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International Journal of Engineering Research

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Editor in Chief : Dr. R.K. Singh

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ISSN : 2319-6890

Volume 2 Issue 6

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0ISSN : 2319-6890(Online) 2347-5013(Print)

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April 01, 2014

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Sept. 01, 2014

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Volume 4 Issue 1 Jan. 01, 2015

Volume 4 issue 2Feb. 01, 2015 Volume 4 Issue 3

March 01, 2015

Volume 4 Issue 4 April 01,2015

March 20, 2015

Volume 4 Issue Special 2

A National Conference on "Recent Advances in Chemical Engineering" GreenChem-15, on March 20, 2015

Organized By Department of Chemical Engg, JDIET, Yavatmal (M.S) India

Editorial Board

Editor in Chief

Dr. R. K. Singh,

Professor and Head,

Department of Electronics and Communication,

KNIT Sultanpur U.P., India

Managing Editor

Mr. J. K. Singh, Managing Editor

Innovative Research Publications, Bhopal M.P. India

Advisory Board

1. Dr. Asha Sharma, Jodhpur, Rajasthan, India

2. Dr. Subhash Chander Dubey, Jammu India

3. Dr. Rajeev Jain, Jabalpur M.P. India

4. Dr. C P Paul, Indore M.P. India

5. Dr. S. Satyanarayana, Guntur, A.P, India.

List of Contents S.No. Manuscript Detail Page No.

1 Synthesis and Characterization of Water Based Silvernanofluids for Heat Transfer Application Abhishek A. Charde,

Durgesh V. Wele, Prashant V. Thorat

63-64

2 Treatment of Fermented Broth for Recovery of Organic Acid Using Integrated Membrane Shubhangi V. Bhande, Dr. V. S. Sapkal

65-67

3 Management of Paper Industry Waste by Energy Generation Using Microbial Fuel Cell Chaitali A. Dore, Dr. R. S. Sapkal

68-71

4 Converting Waste Banana into Bio fuel Using Membrane Technology Lalita S. Shinde, Dr. V. S. Sapkal, Dr. R. S. Sapkal

72-75

5 Study of Average Velocity of Fluids in Baffled Reversed Flow Jet Loop Reactor Rahul D. Mahajan, Amol More, Mahadev Patil, Muralidhar Mundhe, Kunal Patil

76-80

6 Kinetics Study of Transesterification of Karanja and Rice Bran Oil Saurabh Visale, Girish Khuje, Vikash Kumar, Rupesh Tekode, Apeksha Bhonge, Ajay Pardey

81-83

7 Optimization of Biofuel Synthesis Using Lignocellulosic Material Incorporating Pervaporation Technology Ramnath A. Kadam, Dr. V. S. Sapkal, Dr. R. S. Sapkal

84-87

8 Concentration of Aloe Vera Juice By Membrane Technology Shital A. Amrute, R. S. Sapkal

88-91

9 Whey Protein Fractionation by Membrane Technology Swati A. Gurjar, V. S. Sapkal

92-94

10 Lignin Seperation and Purification from Black Liquor Precipitate Shrikant Nanwatkar, Sushama Gawai, Jitendra Shinde

95-98

11 Review on Nanotoxicology and Its Implications Sonal S. Kokate, Avantika S. Patil

99-103

12 Preparation of Fire Retardant Surface Using Lignin Sushama R. Gawai, Shrikant nanwatkar, Jitendra K. Shinde

104-106

13 Indian Rural Energy: Pyrolysis of Cotton stalk in Swept Tubular Pyrolyzer P. R. Tayade, S. H. Amley, A. P. Pardey, S. A. Dharaskar, V. S. Sapkal, R. S. Sapkal

107-109

14 Study of Circulation velocity of liquids in baffled reversed flow Jet loop reactor Mr. Rahul D. Mahajan, Dr. Sameer M.Wagh

110-113

15 Optimization of Treatment of Cleaning In Place Waste from Dairy Industry Using Membrane for Recovery of Caustic Soda and Acid Pradnya H. Athawale, Dr. V. S. Sapkal, Dr. R. S. Sapkal

114-117

16 Textile Dyes Removal: Adsorption of D-Yellow Colour Dye on Pyrolyzed Cotton Stalk Biocha Prashant Tayade, Vaishali Ghoderao, Nilesh Dumore, Nitin Chavan, Ganesh Kakad

118-120

17 Production of Citric Acid by Fermentation of Sugarcane Juice & Study of Effect of Aeration on Process Nilesh S. Dumore, Swapnil A. Dharaskar, Sanjay H. Amaley, Prakash C. Chavan

121-123

18 Carbon Capture and Sequestration for Green House Gas Control Lokesh K. Khotele, Ankita M. Raut, Nihar S. Verma

124-127

19 CO2 capture using 1-Hexyl-3-methylimidazolium based Ionic Liquids Dhaneshwar Devikar, Swapnil Dharaskar, Y. C. Bhattacharyulu, Kailas L. Wasewar

128-131

International Journal of Engineering Research ISSN:2319-6890(online),2347-5013(print)

Volume No.4, Issue Special 2 20 March 2015

NCRACE@JDIET 2015 Page 63

Synthesis and Characterization of Water Based Silver nanofluids for Heat

Transfer Application

Abhishek A. Charde*, Durgesh V. Wele, Dr. Prashant V. Thorat

Department of Chemical engineering, College of Engineering & Technology, Akola-444001, India

Corresponding Author: [email protected]

Abstract — The present research is focus to synthesis water

based silver nanofluids by chemical reduction which increase

the thermal conductivity to enhance the rate of heat transfer

also to characterize the thermal properties and heat transfer

performance of nanofluids over heat exchangers to enhance

the efficiency and overall heat transfer coefficient of heat

exchanger with simultaneous reduction in the area of heat

exchanger. As noted above the basic concept of dispersing

solids in fluids to enhance thermal conductivity. Solid particles

are added because they conduct heat much better than do

liquids. Compared with micro particles, nanoparticles stay

suspended much longer and possess a much higher surface

area. The surface/volume ratio of nanoparticles is 1000 times

larger than that of microparticles. The high surface area of

nanoparticles enhances the heat conduction of nanofluids

since heat transfer occurs on the surface of the particle. The

number of atoms present on the surface of nanoparticles, as

opposed to the interior, is very large. Therefore, these unique

properties of nanoparticles can be exploited to develop

nanofluids.

Keywords— chemical reduction, heat exchanger, nanofluids,

thermal conductivity

I. Int roduct ion

Cooling is one of the most important challenges facing

numerous industrial sectors. Despite the considerable amount of

research and development focusing on industrial heat transfer

requirements, major improvements in cooling capabilities have

been lacking because conventional heat transfer fluids have poor

heat transfer properties. One of the usual methods used to

overcome this problem is to increase the surface area available

for heat exchange, which usually leads to impractical or

unacceptable increases in the size of the heat management

system. Thus there is a current need to improve the heat transfer

capabilities of conventional heat transfer fluids. Crystalline

solids have thermal conductivities that are typically larger than

those of fluids by 1-3 orders of magnitude. Therefore, fluids

containing suspended solid particles can be expected to display

significantly enhanced thermal conductivities relative to those of

pure fluids. Choi of Argonne National Laboratory of USA in

1995 proposed a novel concept of „„nanofluid” by applying

nanotechnology to thermal engineering to meet the cooling

challenges (Bergles et al., 1988). This new class of heat transfer

fluids (nanofluids) is engineered by dispersing nanometer-sized

(one billionth of a meter) solid particles, rods or tubes in

traditional heat transfer fluids. From the investigations in the

past decade, nanofluids were found to exhibit significantly

higher thermal properties, in particular, thermal conductivity,

than those of base fluids. Thus, nanofluids have attracted great

interest from the research community due to their potential

benefits and applications in numerous important fields such as

microelectronics, transportation, manufacturing, medical and

heating, ventilating and air conditioning (HVAC). The impact of

nanofluid technology is expected to be great considering the heat

transfer performance of heat exchangers or cooling devices,

which is vital in numerous industries. For example, the transport

industry has a need to reduce the size and weight of vehicle

thermal management systems and nanofluids can increase the

thermal transport efficiency of coolants and lubricants. When

crystalline solids with nanometer dimensions are suspended in a

suitable base fluid to form stable homogeneous suspensions, and

there is an increase in the thermal conductivity relative to the

base fluid, the resulting suspensions are called nanofluids, as

opposed to nanofluidics, which is concerned with flow in

nanoscale channels.

II. Material and Methodology

125-Ml Borosilicate beaker Silver nitrate (AgNO3) Sodium

borohydride (NaBH4) Water (H2O)

There are various methods available for preparation of

nanofliuds on laboratory as well on large scale. In this project

we select chemical reduction method for preparation of

nanofluids. We found that there is various advantage of chemical

reduction method over other one step as well as two step method

of nanofluids preparation.

It gives good dispersion of nano-particles. Fluid will forms in

one step in this method the processes of drying, storage;

transportation and dispersion of nanoparticles are avoided.

Unique size (10-100nm) & spherical shape particles obtained by

this method. Simplicity low cost of production.

Synthesis of water based silver nanofluid. Characterizations of

silver nanofluid optimizations of the concentrations of raw

materials

Calculation of temperature distribution, log mean temperature

difference, efficiency, of the constructed double pipe heat

exchanger by using Water, nanofluid and commercially

available coolant. Comparison of the data obtained from the

experimental analysis. Take trials of nanofluids on double pipe

heat exchanger.

http://www.coeta.org/departments/chemical_eng/chemical_eng.php



NCRACE@JDIET 2015 4

Figure: Silver Nanofluid

III. Results and Tables

OPTIMUM RESULTS Sr.

no

AgNo3 NaBH4 PVA Remark

1 0.0001M 0.0002M 0.3% Pale yellow colour solution

obtain with stability

2 0.0002M 0.0004M 0.3% Pale yellow colour solution obtain

3 0.0003M 0.0002M 0.3% Pale yellow colour obtained &

black agglomerated particle seen after addition of AgNo3

4 0.0004M 0.0006M 0.3% Pale yellow colour solution

obtained & black agglomerated particles seen after 5days

IV. Conclusion

Most systems/processes whose performance is affected by heat

generation could benefit from nanofluid coolants. Nanofluids

have great potential for thermal management and control

involved in a variety of applications such as double pipe heat

exchanger, car coolant. By changing the various parameters,

reaction condition of AgNO3, NaBH4 & PVA as a stabilizer,

which will give optimum result for synthesis of nanofluids.

While taking run of nanofluids on heat exchanger we observed

that the overall heat transfer coefficient increase than normal

water, which gives the high temperature drop than normal water

as well as

Acknowledgement

It gives me great pleasure to publish the paper on the topic

title “SYNTHESIS AND CHARACTERIZATION OF WATER

BASED SILVERNANOFLUIDS FOR HEAT TRANSFER

APPLICATION”. I wish to take this opportunity to express my

heartiest gratitude with pleasure to College of Engineering &

Technology, Akola, which gave an opportunity fulfilling my

host cherished desire of my goals. I am indebted to a proactive

guide Prof. D. V. Wele, Prof. R. S. Jadhao and Dr. P.V. Thorat,

Head of Chemical Engineering Department because without his

valuable guidance this work would not have a success. His and

her constructive, useful, timely suggestion and encouragement in

every stem helped me to carry out my seminar work. His and

Her valuable presence was a great boosts for me in achieving up

a goal.

References

I) Sarit K. Das Nanofluid (Science & Tech.), Wiley publications (Page

No:1-39, 145-187)

II) M. N. Ozisik, Heat Transfer: A Basic Approach, McGraw-Hill

III) Preparation, Thermal and Rheological Properties of Propylene Glycol and Water Mixture Based Fe3O4 Nanofluids

IV) L. Syam Sundar, E. V. Ramana, Manoj K. Singh, Jose Gracio, and

Antonio C. M. Sousa J. Nanofluids 3, 200-209 (2014) V) Choi, S. Enhancing thermal conductivity of fluids with nanoparticles.

In Development and applications of non-newtonian flows, edited by D.A.

Siginer and H.P. Wang, New York: ASME, 1995, VI) Phelan, P.E.; Bhattacharya, P. & Prasher, R.S. Nanofluids for heat

transfer applications. Annu. Rev. Heat Transfer, 2005,

VII) Xuan, Y. & Le, Q. Heat transfer enhancement of nanofluids. Int. J. Heat Fluid Flow, 2000,

VIII) Keblinski, P.; Phillpot, S. R.; Choi, S. U. S. & Eastman, J. A. Mechanisms of heat flow in suspensions of nanosized particles nanofluids. Int.

J. Heat Mass transfer, 2002,

IX) Chopkar, M.; Kumar, S.; Bhandar, D.R.; Das, P.K. & Manna, I. Development and characterization of Al2O3 and Ag2Al nanoparticle dispersed

water and ethylene glycol based nanofluid., Mat. Sci. Engg. B, 2007,

X) Zhang, X. Effective thermal conductivity and thermal diffusivity of nanofluids containing spherical and cylindrical nanoparticles. J. Appl. Phys.,

2006,




Treatment of Fermented Broth for Recovery of Organic Acid Using Integrated

Membrane

Shubhangi V. Bhande*, Dr. V. S. Sapkal

University Department of Chemical Technology, Sant Gadge Baba Amravati University, Amravati, (444602)

M.S., India,

*Corresponding Author:-:[email protected]

Abstract : During biomass (e.g., crops, animal residues, food

waste) decomposition under an aerobic fermentation process,

organic acids such as acetic acid and butyric acid are

continuously produced from controlled microbial activity.

Since the accumulation of organic acids hinders the microbial

metabolism in the fermentation broths, the organic acids

should be removed by using appropriate separation processes.

The integrated membrane processes proposed here, including

the three steps of (1) clarification of fermentation broth, (2)

organic acid separation, and (3) dewatering, can be applied to

achieve energy-efficient and environmentally friendly organic

acid removal and recovery. First, clarification steps using

microfiltration or ultrafiltration processes. In this study, we

focused only on organic acid separation and dewatering

processes using nanofiltration and forward osmosis membrane

processes. Finally, a low-energyconsuming forward osmosis

process was applied for dewatering in the aqueous organic acid

to obtained concentrated organic acid.

Key Words : Acetobacter pasteurianus, Ultrafiltration,

Nanofiltration , Reverse osmosis , Acetic acid.

I. INTRODUCTION Waste biomass, which has been one of the major environmental

concern in the world to grow environmental awareness. The

conversion of waste into useful chemicals would be an

environmental sound solution to decrease the dependency on

fossil fuels and lower the pollution potential. Biomass

fermentation by microbial activity is a promising

process to extract many valuable organic products. In

fermentation processes the high value product forms is organic

acids such products from various biomass resources such as

crops, animal residues, or even food waste and sewage. The

organic acids alcohols, and methane fermentation processes, and

for these purposes, specific microbes and their metabolic

pathways can be used to produce desirable target as citric acid,

lactic acid, acetic acid, and butyric acid. They found in a living

organism or its metabolites. These organic acids are used in

important applications, including the chemical, pharmaceutical,

food, and cosmetics industries. Moreover, organic acids (e.g.,

acetic acid and butyric acid) from a fermentation process were

successfully converted into biofuels (3,4).

Among them, acetic acid is one of the useful products obtained

from the aerobic fermentation process in control microbial

activity using the acetogenesis of specialty microorganisms such

as Acetobacter pasteurianus. And various carbon sources such as

glucose, xylose, sucrose, and other biomass as feeds for

microorganisms. However, a high concentration of AAc in the

fermentation feed often inhibits bacterial growth, resulting in

lower productivity and selectivity of AAc. In general,

fermentation broths consist of a complex mixture including

various inorganic salts, organic carbons, acids, and other

byproducts, and it is difficult to separate AAc continuously from

fermentation broth while maintaining microbial activity. Thus,

the separation process for AAc recovery is an important factor to

achieve successful fermentation processes.

Several separation processes have been proposed to separate the

target products from the fermentation broth. Not only

conventional separation processes (e.g., distillation and

extraction) but also membrane separation processes (e.g.,

membrane extraction, pervaporation,16 and electrodialysis) have

been studied for energy efficient recovery of organic products

during fermentation. Membrane processes have several

advantages such as process continuity and easy scaleup

compared to conventional technologies(2). Membrane

extraction, commonly considered in this application, is similar to

liquid−liquid extraction in the way that they use organic solvents

to extract organic acids from fermentation broth. Since many

organic extractants are not biocompatible, i.e., toxic, and affect

the microbial activity fatally, the direct contact of extractants and

microorganisms should be prevented from contacting between

two phases, i.e., fermentation broth and extractant. However, an

additional extraction process for recovery of AAc from organic

solvents using strong alkali solution as another extractant is also

required to extract BAc from the solvent followed by energy

intensive concentration and separation processes such as

distillation. Furthermore, biochemical waste from mass

fermentation−separation processes can cause harmful

environmental effluent problems (e.g., discharge, posttreatment).

On the other hand, pressure-driven membrane processes such as

microfiltration (MF), ultrafiltration (UF), nanofiltration (NF),

and reverse osmosis (RO) have gained much attention in

biochemical industry (e.g., pretreatment of fermentation broth or

concentration of downstream) due to their simplicity, high

selectivity, low energy cost, and reduced chemical usage.




MF and UF membranes have pore sizes from a few nanometers

to submicrometers. Large molecules such as proteins, viruses,

and microorganisms in the biological environment can be

selectively removed by these membranes via a size sieving

mechanism. However, such microporous membranes cannot

reject small molecules such as organic acids and salts, and thus

RO or NF membranes should be used to separate them

efficiently. NF and RO membranes have a dense, ultrathin skin

layer on the microporous polymeric supports. In general, NF

membranes have looser porous structures than RO membranes,

but have more charged groups on the membrane surface. The salt

rejection mechanism in NF membranes is the combination of

size sieving, solution−diffusion, and Donnan exclusion.

Numerous studies on the separation of small molecules such as

dyes and organic acids, using NF membrane processes, have

been reported. In general, fermentation broths contain many

different inorganic solutes and organic species. A majority of the

solutes are carbon sources such as glucose, sucrose, and other

biomasses. Microorganisms can digest and then decompose them

into various small organic species such as alcohols and organic

acids that are small enough to pass through many NF

membranes, while large undecomposed or other macromolecular

components are selectively rejected by NF membranes. From

this point of view, NF membranes can be considered as an

efficient separator to permeate water and some organic acids in

continuous fermentation processes. However, only a few studies

on the recovery of organic acids such as lactic acid and succinic

acid from fermentation broth were reported by using NF and or

RO membranes. As such, the purpose of these studies was the

retention of the organic acids or their salts (e.g., lactic acid,

lactate, succinate) by NF or RO membranes.

II. MATERIAL AND METHOD

FERMENTED BROTH

Various carbon sources can be converted to organic acid through

fermentation processes. A number of studies on fermentation

process for organic acid production have been performed with

glucose, xylose, sucrose, and other sources from waste biomass.

In this study, we selected glucose as a model carbon source since

it is one of the final products of biomass hydrolysis. A

defined synthetic medium that has a limited carbon source for

the growth of microorganisms was used to verify the feasibility

of membrane separation processes for organic acid recovery.here

for the formation of acetic acid by aerobic fermentation process

in control microbial activity using the acetogenesis of specialty

microorganisms such as Acetobacter pasteurianus.

INTEGRATED MEMBRANE PROCESSES

Here, we propose integrated membrane processes including

pretreatment, organic acid separation, and dewatering membrane

processes to selectively recover organic acid (e.g., AAc) from

fermentation broth . First, we applied MF or UF for clarification

of fermented broth. And then applied NF or RO process to

selectively recover organic acid and water from fermentation

broth while other organic and inorganic solutes are retained(1).

anticipated that small organic acids can permeate to some extent

through the NF (or RO)membranes by adjusting the pH in the

feed stream. In general, the rejection ratio of organic acids with

carboxylic acid groups is strongly dependent on the pH of the

feed solution. At high pH, the membrane surface is negatively

charged due to carboxylic acid groups on the polyamide

membrane surface. AAc with a carboxylic acid group also

experiences the same effect . Thus, membranes tend to be more

selective to anionic species including organic acids due to

Donnan exclusion. Conversely, the membrane surface charge

becomes positive at low pH since polyamide also has an amine

group. Organic acid molecules can penetrate the positively

charged membrane layer while neutral large organic molecules

are retained (2) .

III. EXPERIMENTAL SETUP

In this work for separation of organic acid first applied MF or

UF for clarification of fermented broth and for separation of

organic acid use NF or RO and then dewatering of organic acid

use forward osmosis membrane .

Forward osmosis membrane

We applied forward osmosis (FO) processes for dewatering of

downstream (i.e., NF/RO permeate) since the additional

concentration processes are needed to obtain a highly

concentrated product. Dewatering by using FO membrane

processes has been studied for desalination, wastewater

treatment, and food processing(5-7). As compared to

conventional distillation processes, FO processes have extremely

low energy requirements to remove water from the mixture

solution. The energy consumption to eliminate the water from

the downstream is high in thermal distillation processes (25−120

kWh/m3), which lowers the economic feasibility.After the

clarification of fermentation broth via NF or RO processes, AAc

and water will be the main components in the downstream. The

main issue in downstream processes is energy consumption. The

most widely used conventional process for downstream

dewatering is the distillation process (600−700 Wh/m3 for

simple distillation), and many engineered distillation processes

such as multieffect distillation, multistage flash distillation, and

vapor compression were proposed to lower the energy

consumption (24−37 kWh/ m3) and the product cost(9).

However, the AAc concentration in downstream is low due to

the limitation of AAc production in fermentation processes

(<6%). Therefore, the required energy and operating cost to

obtain the final product, which is highly concentrated AAc, is

still too high to commercialize.




IV. RESULTS AND DISCUSSION

Fermentation broth The components of a fermentation broth

vary with microbial species, carbon source operation conditions

such as processing time, pH, and temperature in the fermentation

processes. Moreover, the compositions of each species in the

fermentation broth are also changed continuously with microbial

activity especially in batch fermentation processes. Glucose and

yeast extract are organic species commonly used as nutrition and

feed carbon sources for AAc production. There are also other

carbon sources, such as sucrose and waste biomass. Since

glucose obtained from the hydrolysis of other biomass.

V. Conclusion NF and RO processes were investigated for organic acid

recovery from fermentation broth using various NF and RO

membranes at different operating conditions. Both NF and RO

membranes showed Consequently, RO membranes can

successfully retain the solutes in fermentation broth compared to

NF membranes even at low pH condition. However, AAc

recovery was not efficient at low concentration ofAAc due to a

high AAc rejection ratio even at low PH comparison, the AAc

recovery ratios of NF membranes were above 90% even at low

AAc concentration of fermentation broth. The AAc purity was

low in NF membranes due to low rejections to other inorganic

and organic species. However, the AAc purity was increased

with the increase of AAc concentration in the fermentation

broth. Thus, low pH NF processes were thought to be more

attractive to organic acid separation processes due to its high

flux and AAc productivity selective AAc permeation during the

low pH fermentation broth filtration.

ACKNOWLEDGEMENT

Any academic studies would have been impossible without any

technical approach and I am lucky to have an opportunity at

university department of chemical technology, SGBAU

Amravati. The special thanks goes to helpful guide Dr. V.S.

Sapkal, Head of the department, chemical technology,

S.G.B.A.U. Amravati. And I am Thankful to NCL pune ,

provides me required culture , help me to completing the

project. My greatful go to our lab assistant who guided as from

time to time.

REFERENCES i. He, Y. S.; Chen, G.; Ji, Z. J.; Li, S. X. Combined UF-NF membrane

system for filtering erythromycin fermentation broth and concentrating the filtrate to improve the downstream efficiency. Sep. Purif. Technol. 2009, 66 (2),

390−396.

ii. Young Hoon Cho , Hee Dae Lee , and Ho Bum Park June 28, 2012 ; ―Integrated membrane processes for separation and purification of organic acid

from biomass fermentation process‖; I & EC research.

iii. S. Schlosser , R. Kertesz, J. Martak ; 16 Juily 2004 ; ―Recovery and separation of organic acid by membrane based solvent extraction and

pertraction‖; separation and purify. Tech 41. 237 – 266. iv. Chayanon Sawatdeenarunat, Sang Hyoun kim, and Shihwu Sang ;

―Organic acid production from corn stover using cattle manure as an

inoculam‖; envo. Sci. tech. journal. v. Chen, Y. G.; Xu, Q.; Yang, H. Z.; Gu, G. W. Effects of cell

fermentation time and biomass drying strategies on the recovery of poly-3-hydroxyalkanoates from Alcaligenes eutrophus using a surfactant-chelate

aqueous system. Process Biochem. 2001, 36 (8−9), 773−779.

vi. Agenson, K. O.; Oh, J. I.; Urase, T. Retention of a wide variety of organic pollutants by different nanofiltration/reverse osmosis membranes:

controlling parameters of process. J. Membr. Sci. 2003, 225 (1−2), 91−103. vii. Timmer, J. M. K.; Kromkamp, J.; Robbertsen, T. Lactic-Acid

Separation from Fermentation Broths by Reverse-Osmosis and Nanofiltration. J.

Membr. Sci. 1994, 92 (2), 185−197. viii. Kang, S. H.; Chang, Y. K. Removal of organic acid salts from

simulated fermentation broth containing succinate by nanofiltration. J. Membr. Sci. 2005, 246 (1), 49−57.

ix. ix Semiat, R. Energy Issues in Desalination Processes. Environ. Sci.

Technol. 2008, 42 (22), 8193−8201. x. Saur, m. ; Porro,D.; Mattanovich,D.; Branduard, P.; 2008

―Microbial production of organic acids‖ ; expanding the markets. Trand Biotechnology.




Management of Paper Industry Waste by Energy Generation Using Microbial

Fuel Cell

Chaitali A. Dore, Dr. R. S. Sapkal

University Department of Chemical Technology,

Sant Gadge Baba Amravati University, Amravati, (444602) M.S., India,

Corresponding Author:- [email protected]

Abstract : Mediator less dual chamber microbial fuel cell

(MFC) using paper industry waste for energy generation and

wastewater treatment was studied. The potassium

permanganate as a cathode solution with paper industry

wastewater the substrate source to an anodic chamber. Nafion

membrane is used for exchanging proton. MFC was efficient

in the removal of COD (85% removal). Energy generation will

be 0.747 V to 1.12V .

Key words: Microbial fuel cell, MFC Construction,

Electricity generation, wastewater treatment

I .Introduction

Energy is the prime mover of economic growth and is vital to

the sustenance of a modern economy. Future economic growth

crucially depends on the long-term availability of energy from

sources that are affordable, accessible and Environmentally

friendly. It is important find an alternative form of energy

before the world‟s fossil fuels are depleted. A microbial fuel cell

(MFC) is a bio-electrochemical system that harnesses the natural

metabolisms of microbes to produce electrical power. Within the

MFC, microbes consume the nutrients in their surrounding

environment and release a portion of the energy contained in the

food in the form of electricity. The idea of using MFCs for

producing electricity dates back to 1911(M. C. Potter. Recently

the need of renewable and clean forms of energy and the need of

wastewater treatment have triggered wide research interest in

developing the MFC technology to address both of these human

needs. For example, Scientific American had a popular article

introducing the MFC technology In the academic community,

the authors in proposed domestic wastewater treatment using

multi electrode continuous flow MFCs. (Y. Ahn and B. E.

Logan 2013) While renewable energy production and

wastewater treatment are two long term goals of developing the

MFC technology. Efforts are being made to improve the

performance and reduce the construction and operating costs of

MFCs.

MFCs represent a promising technology for sustainable energy

production. A typical MFC is consisting of two chambers, i.e.

the anaerobic anode chamber and the aerobic cathode. The two

chambers are separated by a membrane (e.g., proton exchange

membrane) where protons and other ions are transferred from

the anode chamber to the cathode chamber, while electrons from

the anode chamber are transferred to the cathode chamber

through an external electrical circuit and a resistor for electricity

production. (; Cheng et al., 2006b; Liu et al., 2005b; Liu et al.,

2004; Logan et al., 2006; Min et al., 2008; Zhang et al., 2009).

A variety of readily degradable compounds such as glucose and

acetate, and various types of waste water such as domestic,

starching and paper recycling plant waste water, have operated

successfully as substrate in MFC. Which can benefit cellulose

fermentation and degradation, with the added benefits of

electricity generation rather than power consumption. Several

types of wastewaters have been successfully treated with

simultaneous electricity generation, including municipal, food

processing, brewery, and animal wastewaters. which have been

found to be biocatalysts for directly power generation and waste

treatment in MFC

II Material and Methodology

Methodology

The objectives of the present research were:

1) Collection of waste water from various sources

2) To develop a simple low-cost bacterial fuel cell,

3) To optimize the parameters such as geometry of the biofuel

cell, electrodes, use of resistors, proton exchange membrane, etc.

for optimal electricity generation,

4) To carry out media optimization studies in order to enhance

the growth of bacteria for high efficiency of electricity

production.

5) To test the feasibility of the fuel cell as a method of sewage

treatment with electricity.

6) To give the pure and good quality of water

7) COD will be reduced.

8) Comparative analysis between the various source.

Microbial fuel cell design

Wastewater Sample collection

Sample of paper wastewater was collected from Hardoli paper

mill Bajargaon .

Electrode Materials

Graphite rods from pencils were used as both anode and cathode

(Logan and Regan, 2006; Logan et al., 2007). The arrangement

of the graphite rods was made in such a way as to provide the

maximum surface area for the development of biofilm on anode.

The length and diameter of the graphite rods 15cm

respectively. Pretreatment was not provided for the electrode

materials. The simplest materials for anode electrodes are

graphite plate or rods as they are relatively inexpensive, easy to

handle and have unambiguous surface area. All the indicated

surface area will not necessarily be available to bacteria.

Figure 1: Graphite Rod

mailto:[email protected]




Membrane:

Proton exchange membrane (Naflon 117,) which is collected

from National chemical laboratory Pune .

MFC Reactors:

. The reactors were constructed using nonreactive plastic

containers. The electrodes were connected by using copper wire

as reported by Logan (2005). The electrodes were placed in the

chambers, then were sealed and made air tight. Both the reactors

were checked for water leakage.

Double chambered MFC

Two nonreactive plastic containers were used for

Double chambered MFC.

One plastic container was used as anode chamber (to be

fed with wastewater) and the other as cathode chamber (water is

formed as the only end product).

The cathode and anode chambers were connected using

proton exchange membrane.

Graphite rods were used as the anode, and the cathode

of the same material. The wastewater was fed to the anode

chamber and permegnet (catholyte) was fed to the cathode

chamber

The graphaite rods are connected externally by using

wire. The electrons in the anode are conveyed to a cathode by

external circuit and protons are transferred through the

membrane internally producing potential difference is between

anode and cathode chamber.

For measuring the electric current multimeter is

connected.

Figure 2 : Dual chamber microbial fuel cell

Design criteria of dual chambered mediatorless microbial

fuel cell

Method

Microorganism

Different materials such as anaerobic sludge and cow dung

samples were procured from anaerobic digester plant in

H.V.P.M engineering collage of Amravati.

For inoculation and start up of MFC, the

synthetic wastewater was prepared with NH4Cl (0.5 g/L),

KH2PO4(0.25 g/L), K2HPO4 (0.25 g/L), FeCl3 (0.025 g/L),

NiSO4 (0.016 g/L), MgCl2 (0.3 g/L), CoCl2 (25 mg/L), ZnCl2

(11.5 mg/L), CuCl2 (10.5 mg/L), CaCl2 (5 mg/L), MnCl2 (15

mg/L) and 3 g/L of glucose.The 0.2 g/L potassium per-

manganate solution was used as a cathodic medium during start

up. The waste water was fed into the anode compartment from

the waste water reservoir. Microorganisms present in the waste

water oxidize the substrate and produce electrons and protons in

the anode chamber of MFC.

Anode reaction: C6H12O6 + H2O → 6CO2 + 24e- + 24H

Then the metal reducing bacteria present in the waste water

directly transfer electrons to electrodes (anode), using

electrochemically active redox enzymes. Electrons are

transferred to the cathode compartment through the external

circuit, and the protons through the proton exchange membrane.

The cathode chamber is supplied with oxygen (air) from the air

pump. Electrons and protons are consumed in the cathode

compartment reducing oxygen to water.

The reactions taking place at the cathode chamber is as follows

Cathode reaction:

O2 + 4e- + 4H+ → 2H2O

Overall reaction:

C6H12O6 + 6O2 → 6CO2 + 6H2O +

electricity

Due to the potential difference maintained at both anode and

cathode chambers, and due to the flow of electrons through the

external circuit, electricity is produced which is collected across

the load. The effluent and the subsequent waste water from the

chambers are being drained out and is sent to the sewage

treatment plant for further treatment of waste water.

Again fresh waste water (substrate) is supplied to the anode

chamber from the reservoir. And, thus the process continues. It

was found that a mixed culture of substrates (Industrial waste +

CRITERION DESCRIPTION

Anode chamber Suspended growth

Anode inoculum Aenaerobic sludge

Mediator anode Nil

Mediator cathode Air

Volume of anode and cathode

chamber

1lit

Length of electrode 15cm

Proton conduction pathway Proton exchange

membrane (nafion)




Domestic waste) generated a current that was six fold higher

than that generated by a pure culture.

Experimental work

Microbial fuel cell (MFC) is a device which converts chemical

energy to electrical energy during substrate oxidation with the

help of microorganisms. The work is based on literature review

of studies on research and application of MFC technology in

waste and wastewater treatment areas. Also, some possibilities

of its application for wastewater treatment are outlined based on

basic knowledge about MFC principles and wastewater

treatment processes.

Figure 3. Microbial fuel cell

Microbial Fuel Cell is divided into two halves: aerobic and

anaerobic.

The aerobic half has a positively charged electrode and is

bubbled with oxygen, much like a fishtank.

The anaerobic half does not have oxygen, allowing a negatively

charged electrode to act as the electron receptor for the bacterial

processes. The chambers are separated by a proton exchange

membrane to keep oxygen out of the anaerobic chamber while

still allowing hydrogen ions (H+) pass through.

1. The bacteria on the anode decompose organic matter and free

H+ ions and electrons.

2. The electrons flow from the bacteria to the anode, sometimes

assisted by a mediators molecule.

3. The electrons flow up from the anode, through a wire, and

onto the cathode. While flowing through the wire, an electrical

current is generated that can be used to perform work.

4. The H+ ions flow through the semi-permeable membrane to

the cathode. This process is driven by the electro-chemical

gradient resulting from the high concentration of H+ ions near

the anode

5. The electrons from the cathode combine with dissolved

oxygen and the H+ ions to form pure H2O.

In the anaerobic chamber, a solution containing food for the

bacteria is circulated. This food consists of glucose or acetate,

compounds commonly found in food waste and sewage. The

bacteria metabolize food by first breaking apart the food

molecules into hydrogen ions, carbon dioxide, and electrons. As

shown in Fig. bacteria use the electrons to produce energy by

way of the electron transport chain. The microbial fuel cell

disrupts the electron transport chain using a mediator molecule

to shuttle electrons to the anode. In many ways, a microbial fuel

cell is an extension of the electron transport chain where the

final step of the process (the combination of oxygen, electrons,

and H+ to form water) is transferred outside of the bacterial cell

from which energy can be harvested.

III .Results and discussion

Analytical techniques:

Testing the properties of substrates The quality of waste water is governed by some properties. The

pH-value, conductivity, color, and COD were considered

pH-value: The pH value has a scale of 0 - 14 and pure water has the pH

value of 7 at 27 degree Celsius temperature. If the pH value of a

wastewater lies between 7 - 0 the wastewater becomes more

acidic as the value decreases towards zero. On the contrary if the

pH-value lies within 7 - 14, the water becomes more basic as the

value increases. The pH of the wastewater was measured by a

standard pH meter.

Chemical Oxygen Demand (COD):

The chemical oxygen demand (COD) is a kind of test which is

used in environmental chemistry in order to measure indirectly

the amount of organic compounds in water or wastewater.. The

COD value is expressed in milligrams or grams per liter (mg/L),

which indicates the mass of oxygen consumed per liter of

solution of polluted water or wastewater. It was mentioned in

the background chapter that an MFC can reduce the COD

concentration of a solution. It is very important to measure the

COD of substrates before and after the experiment with MFC in

order to know if the MFC is working accordingly and if the

quality of substrates improving or not. To measure the COD

Reflux condenser method isused.

power recording:

During the MFC-experiment voltage and voltage drop across a

resistor was recorded after every 24 hours. And then current and

power were calculated according to the Ohm‟s law and Joule‟s

law respectively. The experiments were terminated after

reaching the optimal power generation point by the MFC.

Results The effluents used for experimental work are: Paper industry

waste water of Hardoli paper mill ,Bajargaon.

Anaerobic sludge and cow dung samples were procured from

anaerobic digester plant in H.V.P.M engineering collage of

Amravati

Effluent analysis

parameter Pulp and paper

industry

Colour Black

Temperature 27˚c

odour Rotten eggs

PH 5.7

Total dissolilved solid

(ppm)

2360ppm

BOD(mg/l) 670 mg/l

COD(mg/l) 1040 mg/l




Bioelectriciy production: After the anode chamber of mfc is inoculated with anaerobic

sludge,fuel cell is operated with above said of waste water (pulp

and paper industry) as feed. Constant substrate (COD) removal

efficiency and voltage output is considered as indicators to asses

the stable performance. These fuel cells operated continuously

for 10days. Experimental data showed the feasibility of

electricity generation from wastewater treatment. The graph

shows, during the initial stage after inoculation, gradual rise in

voltage is observed .voltage Rapidly increased due to biological

activity and stabilized at 0.747 v .

Figure 4: Variation in voltage during MFC operation

Graph clearly observed that power increases with time until

attaining steady state condition .

Figure 4 : variation of COD during MFC operation

Figure / graph shows the changes in COD values with time

obtained during the operation . It can observed that efficiency of

the treatment improved during the operation and that a steady

state in effluent COD is reached for the values closed.

IV. Conclusion:

There is a quick need to degrade these pollutants in an eco-

friendly way. A significant reduction in the COD during

electricity production from paper industry wastewater may be

considered as the useful feature for clean and green power

generation. Microbial fuel cell is the efficient process for Paper

waste.. After treatment of paper waste water we observed near

about the 85% reduction of COD. And electricity production

near about 0.747 V.

Acknowledgement:

I take this opportunity to express my sense of gratitude Prof. Dr.

V.S.Sapkal, Head of department of chemical technology,

S.G.B.Amravati University and Prof. Dr. R.S.Sapkal, for

suggesting the fascinating problems and for his guidance

throughout this work. I would like to express my sincere

gratitude Mr. Anil Lakhotiya , managing director ,of Hardoli

paper mill Bajargaon for the help which he had provided during

this project.

Referances:

i. M. C. Potter, (1911) ―Electrical Effects Accompanying the De-

composition of Organic Compounds,‖ Royal Society B, Vol. 84, No. 571, 1911, ii. S. Venkata Mohan, G. Mohanakrishna, B. Purushotham Reddy, R.

Saravanan, P.N. Sharma ,(2007) ―Bioelectricity generation from chemical

wastewater treatment in mediatorless (anode) microbial fuel cell (MFC) using selectively enrichedhydrogen producing mixed culture under acidophilic

microenvironment,‖Biochemical Engineering Journal iii. V. Pethkar, Kalyani Kale1 Priyanka Belgaonkar, Vaishali Bagul, V.

S. Kale and Sucheta N. Pati (2012)―A microbiological process for combined

electricity production and waste water treatment using Staphyllococcus Sp‖ Journal of Environmental Research And Development

iv. Jessica Li 2013 ―An Experimental Study of Microbial Fuel Cells for

Electricity Generating: Performance Characterization and Capacity Improvement.‖ Journal of Sustainable Bioenergy Systems,

v. B.M.Mali, C.C. Gavimath, V. R. Hooli, A.B. Patil , D.P.Gaddi,

C.R.Ternikar and B.E.Ravishankera ( 2012) ― Generation of bioelecricity using waste water ‖ International Journal of Advanced Biotechnology and

Research ,

vi. Dr. M. O. Aremu and Dr. S. E. Agarry ―Bioelecricity generation potentials of some Nigerian industrial wastewater through microbial fuel cell

technology.‖ Jouranal of research in science and technology. vii. Liping Huang & Bruce E. Logan (2008) ―The effectiveness of

simultaneous electricity production and treatment of a paper recycling plant

wastewater using microbial fuel cells.‖ Enviornmental biotechnology journal. viii. Hampannavar U.S, Anupama, Pradeep N.V( 2011) International

journal of enviornmental science ix. Abhilasha S Mathuriya, V N Sharma in (2009)― Bioelectricity

production from paper industry waste using amicrobial fuel cell by Clostridium

species ―Jouranal of Biochem Tech x. Y. Ahn and B. E. Logan, (2013) ―Domestic Wastewater Treat- ment

Using Multi-Electrode Continuous Flow MFCs with a Separator Electrode

Assembly Design,‖ Applied Micro- biology and Biotechnology, Vol. 97, No. xi. Z. Du, H. Li and T. Gu, ―A State of the Art Review on Microbial Fuel

Cells: A Promising Technology for Waste- water Treatment and Bioenergy,‖

Biotechnology Advances, Vol. 25, No. 5, xii. Jang J. K., Pham T. H., Chang I.S., Kang K.H., Moon H. and Cho

K.S.,2004 Construction andoperation of a novel mediator and membraneless

microbial fuel cell, Pro. Biochem., 39(8), 1007-1012, xiii. Park D.H. and Zeikus J.G., 2002 Impact of electrodecomposition on

electricity generation insingle compartment fuel cell, Appl.Microbiol.

Biotechnol., 59 (1), 58-61, xiv. Mathuriya, A.S., Sharma, V.N. (2009). ‗Bioelectricity production

from paper industry waste using a microbial fuel cell by Clostridium species‘. J

Biochem Tech 1(2): 49 -52(2008). "Electron-transfer coupling in microbial fuel cells. 2. Performance of fuel cells containing selected microorganism-mediator-

substrate combinations. Journal of Chemical Technology and Biotech- nology.

Biotechnology34:




Converting Waste Banana into Bio fuel Using Membrane Technology

Lalita S. Shinde, Dr. V. S. Sapkal, Dr. R. S. Sapkal

University Deaprtment of chemical Technology, SGBAU, Amravati (M.S) India


ABSTRACT : Combustion of the fossil fuels at the current rate

would contribute to the environmental crisis globally. Bio-fuel

recognized as alternative to fossil fuels, India contributes to

27% of world’s banana production. 25 to 40% bananas wasted

due to bad handling, Waste banana can be used to produce

bio-fuel. Production of bio-fuel is studied by enzymatic

hydrolysis and fermentation by using Saccharomyces

cerevisiae. Utilization of rotten banana is more suitable for

bio-fuel production as renewable energy which could reduce

the cost of initial process. Although several separation

technologies are technically capable of removing volatile

products from fermentation broth, distillation requires more

energy and cost. Pervaporation has been used as an alternative

to classical separation process as distillation. It is an attractive

technology because of the potential to selectively separate

volatile component and water. and energy intensive,

economical, safer separation technology.Hydrophobic PTFE

(Polytetrafluoroethylene) Membrane of porosity 0.2 micron is

used for Pervaporation of Bioethanol-water. The separation

processes have many advantages that can improve the total

efficiency of bioethanol production refineries.

Key Words- Waste Bananas, Enzyme, Baker’s yeast,

Bioethanol, Pervaporation

1. INTRODUCTION

The decreasing reserves and increasing value of petrochemicals

have renewed the interest in the production of bioethanol and its

use as fuel. India imports nearly 70% of its annual crude

petroleum requirement, which is approximately 110 million tons.

The prices are in the range of US$ 50-70 per barrel, and the

expenditure on crude purchase is in the range of Rs.1600 billion

per year, impacting in a big way, the country's foreign exchange

reserves (Ethanol India).Bioethanol can be produced from many

different raw materials, which are grouped according to the type

of carbohydrates they contain, i.e.sugar, starch or cellulose.

Liquid biofuels are being researched mainly to replace

conventional liquid fuels, such as diesel and petrol. Production

of ethanol from lignocellulosic raw material and utilizing it as a

substitute for petrol could help promote rural development,

reduce greenhouse gases, and achieve independence from

outside energy providers (Demirbas, 2005).Bioethanol from

lignocellulosic materials, such as sugar cane, bagasse, has been

studied for the past few decades with great interest, but its

production in industrial scale has not yet become viable Studies

taking into account process integration, increase of fermentation

yields and integration of unit operations are still needed in order

to make hydrolysis a competitive technology (Marina O.S.2009)

The cheapest and easily available source for the production of

bioethanol is fruit wastes. It is a potential energy source, from

which ethanol can be obtained. Fruit waste which is thrown

away has very good antimicrobial and antioxidant potential. In

Australia, approximately 30% of the harvested bananas are

rejected at the packing shed (Clarke et al., 2007). Banana waste

that have been discarded due to the imperfections are normally

dumped as a huge masses of wastes, which ultimately cause

contamination of water source as well as can affect the

environment and health of living microorganisms (Tock et al.,

2009). Banana is the most important fruit crop of India having

great socio-economic significance, and it contributes to 27% of

world‟s banana production. It contributed 31% of the total fruit

production in India. Out of the total production Maharashtra's

share is of 25%. 25 to 40% banana wasted due to bad handling

in Maharashtra. And banana waste during domestic transits is

47% from farm gate to local mandi.21% wastage within District,

16% wastage within state and out of the state.(enRoute transport

corporation of India) To avoid the environmental problem due to

the decomposition of waste, it is usable to make energy from

banana waste as biofuel production source. The composition of

waste banana is 82% moisture, 73.6% sugar, 3.4% starch, 5.2%

ash, 3% cellulose,15% other component (Le Divid ich et

al.1976), To achieve the low cost and sustainable production

objectives for bioethanol, it is important to develope new,

industrially viable technologies at the lowest possible cost. The

use of banana waste has been demonstrated the feasibility of the

fermentation process from this substrate, and other studies are

currently focused on the hydrolysis of the material because it has

been proven that this step involves the highest production cost

(Brooks, 2008, Souza et al., 2011)

The high cost of the distillation from the dilute fermentation

broth often makes the process unviable for industrial-scale

production (Kraemer et al., 2011) membrane separation

processes have been used to replace conventional distillation.

Pervaporation has gained increasing attention in many chemical

processes as an effective and energy saving membrane technique

for separating azeotropes, close boiling mixtures, isomers and

thermally sensitive compounds, and purifying species from

highly concentrated streams. In addition to reducing the

inhibition of ethanol in the production step due to the possibility

of its simultaneous use with fermentation

(Lewandowska,Kujawski,2007), this procedure can replace a

concentration step that is required for recovery because of the

presence of alcohol in small quantities in the broth (Nomura et

al., 2002). Evaluation of the pervaporation of ethanol produced

from banana waste with different ethanol feed composition using

standard solutions (1 to 80 wt%) and fermentation broth (3 and

30wt%) in commercial Polydimethylsiloxane PDMS membranes

were carried out by (R.H.Bello 2013,2014). The results were

considered to be promising and indicate the feasibility of using





pervaporation in the production of bioethanol from banana

waste.

2. MATERIAL AND METHOD

2.1 Raw Materials

Waste bananas collected from local market of Amravati,

Maharashtra.

2.2 Enzymes

Enzymes used in this project are Pectinase,α-Amylase,

Glucoamylase, and Supplied by Chembond Chemicals Ltd.

Mumbai, Jain Food Park,Jalgaon

2.2.1 α-Amylase

α-Amylase is a bacterial α-amylase preparation produced by

submerged fermentation of a selected strain of Bacillus

licheniformis. It is a thermo stable amylase that can randomly

hydrolyze α-1.4 glycosidic bonds of starch and starch derivatives

into soluble dextrin and oligosaccharides. Application pH range

5.5 to 6.5. Optimum 5.8 Application Temperature Range 50-100

°C.

2.2.2. Pectinase

Pectinase is the hydrolytic enzyme of alpha-1, 6 glucosan and

glucose, it is made from Aspergillus niger through cultivation

and extraction technique. It can be used in industry of alcohol,

distillate spirits, beer brewing, and organic acid. It used for

saccharification of starch by hydrolysis of maltodextrin and

amylopectin to glucose. Application pH range 4.0 to

6.5.Optimum 4.6 Application Temperature Range 40-60°C.

2.2.3 Glucoamylase

Glucoamylase is an enzyme which decomposes starch into

glucose by tearing-off glucose units from the non-reduced end of

the polysaccharide chain. It is derived by submerged

fermentation of a specially selected producer strain of Asp.

niger. Optimum PH 4.6 Application Temperature Range 40-

60°C.

2.3 Yeast

Saccharomyces cerevisiae (baker's yeast)

Dry active yeast brought from local market and is rehydrated in

water bath at 40°C, by using clean water and allowed taking to

room temperature before for Fermentation.

2.4 Membrane for Pervaporation

Hydrophobic Polytetrafluoroethylene (PTEF) Membrane is used

of pore size 0.2μm.

2.5 Preparation of the substrate for the fermentation

process

Rotten Bananas were rinsed with distilled water, cut into small

pieces. And then crushed in a mixer and collected in beakers,

50% distilled water was added into the mash. The pretreatment

is usually followed by enzymatic hydrolysis to convert the

Starch to fermentable sugars. it is treated with α-Amylase at 900

C,PH 5.5 for 2hrs.and then hydrolysed by Pectinase and

glucoamylase at 400

C,PH 4 for 2hrs.(0.8Kg/ton of

Starch).Autoclave for 15min at 121 °C and 15psi.

2.6 Fermentation The PH of the pulp was adjusted to 5.0 by the addition of NaOH

solution (0.1 N), dry active yeasts were rehydrated in water bath

at 40°C, by using clean water and allowed taking to room

temperature before adding into the banana mash. and subjected

to anaerobic fermentation at 28-300C for 4days.

During

fermentation process, yeast changes the simple sugars into

ethanol and carbon dioxide when the yeast is submitted to

anaerobic conditions; its metabolic route is deviated to produce

ethanol and CO2. as shown below (Velásquez Arredondo, 2009)

C6H12O6 2 C2H5OH + 2 CO2

2.7 Pervaporation

Pervaporation is a membrane based separation system that

ethanol is selectively separated from the fermentation broth. The

basic pervaporation unit consists of vacuum pump, membrane

and cooling tap. The driving force is the concentration gradient

in PV and it is maintained by vacuum pressure. As the upstream

side of membrane is kept at atmospheric pressure, in

downstream side vacuum is applied. Hence the selective

component which is dissolved on the surface of the membrane,

passes through the membrane and then desorbed as vapor phase.

The pervaporation experiments were conducted by using an

apparatus as shown in Fig.1. The experiments were carried out

with fermented broth and 90-95% ethanol aqueous solutions.

The operation temperatures varied from 40°C to 80°C with

permeate side pressure of 600-650 mm of Hg. And a

Hydrophobic polytetraflouroethylene(PTEF) membrane of

porosity 0.2μm is used, the permeated vapor was condensed and

the composition was analyzed.

Fgure1.Pervaporation Setup

3. Analytical techniques

3.1 PH and TSS

PH was determined by ph meter and TSS was measured by

Refractometer.

3.2 Glucose Estimation

Glucose content was measured by Millers method The 1% of

dinitrosali-cylic acid reagent solution was prepared by adding 10

g of dinitrosalicylic (DNS) acid, 2 g of phenol, 0.5 g of sodium

sulfite, 10 g of sodium hydroxide and mixed; followed by 1 L of

water and mixed well. 3 ml of DNS reagent was added to 3 ml of

glucose sample in a lightly capped test tube. The mixture was

then incubated in water bath for 5 to 15 min at 90°C until the

red-brown color appeared. Then, 1 ml of a 40% potassium

sodium tartrate (Rochelle salt) solution was added to stabilize




the color. The absorbance values of the reducing sugar was

measured using spectrophotometer at 575 nm, after cooling to

room temperature in a cold water bath.

3.3 Bioethanol Concentration

Ethanol concentration was determined according to the method

of Williams and Darwin (1950). Colorimetric method for

determination of ethyl alcohol.

4. Result and Discussion

4.1 Glucose concentration of banana mash treated with

different fermen-tation period

As shown in fig. 2

Fig. 2 Glucose concentration

4.2 Bioethanol concentration

As shown in fig.3

Fig.3 Bioethanol concentration

Total soluble solid of the banana mash before fermentation were

slightly higher than those after fermentation. Initial TSS was

150Brix, after Fermenta- tion it is 10

0Brix, glucose concentration

goes on decreasing as fermentation increases from 7.5-0.4 %.

And Bioethanol concentration goes on increasing from 0-5.1%

with 4 days of anaerobic fermentation. After Pervaporation we

get 99% pure and concentrate Bioethanol. And with

pervaporation more than 40% energy saving can be reach than

for biethanol water separation. (Mario Roza, Eva Maus,2006)

5. Conclusion

Bio-fuel is a noticeable product for future biorefineries, Banana

fruit waste could be used to produce Bioethanol effectively.

Bioethanol from waste banana is sustainable for environment

due to the use of waste raw material for fermentation.

The membrane separation processes have many advantages that

can improve the total efficiency of biofuel production, high

purity of final product, especially bio-fuel can be achieved with

membrane separation processes, the use of Pervaporation for

Bioethanol recovery identified as very attractive to classical

methods such as distillation, Pervaporation seems to be Energy

saving process for bioethaol production.

ACKNOWLEDGMENTS The authors acknowledge the support received from Chembond

Chemicals,Mumbai And Jain Food park, Jalgaon.for providing

enzymes and University Department of Chemical Technology

Amravati For providing necessary facilities for the successful

completion of this project work.

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Study of average velocity of fluids in baffled reversed flow Jet loop reactor

Rahul D. Mahajan1, Dr. Sammer M. Wagh, Amol More

2, Mahadev Patil

3, Muralidhar Mundhe

4, Kunal

Patil5,

1Asst. Professor, Department of Chemical Engineering, D.Y.Patil College of Engineering & Tech. Kolhapur

2Asst. Professor, Laxminarayan Institute of Technology, RTMNU Nagpur (Maharashtra)

2,3,4,5BE Chemical Students, Department of Chemical Engineering, D.Y.Patil College of Engineering & Tech.

Kolhapur


Abstract: Jet loop Bioreactors (JLBR) are being widely

applied in a number of chemical, Biochemical, Petroleum

refineries and Petrochemical industries for the treatment of

the waste water. Some of the advantages of the system are

simple in construction & operation, low investments &

operational cost as well as very fine gas dispersion and high

mixing & mass transfer performance. In JLBR circulation

and fluid dispersion are achieved by a liquid jet. Liquid is

injected into the reactor with high velocity causing a fine

dispersion of different phases. In down flow jet loop reactors

the driving gas is introduced from top of the reactor into a

liquid flowing co currently downward so that the gas bubbles

are forced to move in a direction opposite to their

buoyancy. The reactor consists of a vertical column. A draft

tube was placed axially in the centre of the reactor. The

spray nozzle is located inside the draft tube.

Mixing Characteristics in JLBR will be studied by using

conductivity cell with the tracer particle or Photographic

techniques. To study of the hydrodynamic behavior of fluid

flow inside the reactor, effects of various parameters like

liquid flow rate, gas flow rate Nozzle diameter, Nozzle

heights etc on mixing characteristics are planned to study.

Keywords:, Jet loop Bioreactor, tracer particles, immersion

height, Digital Image processing, Aveg. Velocity

determination, Three phase system, baffled

Introduction

Conventional biological treatment processes have been used for

many years in the treatment of industrial and domestic

wastewaters. However, these processes have some disadvantages

such as larger area requirement, necessity of the transportation

of wastewater to the unpopulated areas due to odour and other

emission problems.

For this reason, some studies have been carried out to develop

smaller and faster wastewater treatment systems. The use of Jet

loop Bioreactor and airlift reactors coupled with membrane

filtration may be seen as examples of such an approach. Among

the different types of loop reactors, it was found that the reactors

where the mixing and flow circulation are achieved through jet

flows had improved performance characteristics (Padmavathi

and Remananda Rao, 1991). This type of loop reactors, normally

referred as jet loop reactors (JLRs), has become increasingly

important in conducting chemical and biochemical reactions.

A JLR is basically an assembly of two concentric cylinders of

which the inner one is known as “draft tube” and the outer one

as “reactor”. A two-fluid nozzle (liquid and gas), also usually

with a structure of concentric cylinders, disperses the gas

delivered in one of the tubes by means of the liquid jet delivered

in the other tube (Dirix and Wiele, 1990; Velan and Ramanujam,

1991, 1992a,b). If wished, the liquid and the gas from their

respective reactor exits can be recirculated back to reactor

through the two fluid nozzles until the liquid is saturated with

the gas. JLRs have found applications in wastewater treatment

processes due to their high mass transfer rates as well as their

intrinsic high turbulence characteristics which also result in the

disintegration of large biomass aggregates thus creating a very

large surface area for greater microbial activity. Aeration

efficiency of conventional activated sludge process is about 8%

with the possibility of upgrading to 20% if pure oxygen is used.

With up flowing gas and liquid, the traditional three phase slurry

reactor has two disadvantages, when used for biochemical

fermentation or biological wastewater treatment i.e. blockage of

the nozzle and low gas phase residence time. While in a jet loop

reactor, when the nozzles are installed at top of the reactor, these

shortcomings can be efficiently eliminated.

Jet loop reactors are widely used to ensure a homogenous

suspension with low power inputs. For an optimal design of loop

reactors with minimal energy consumption, the knowledge of the

pressure drop in three phase mixtures is essential. This is

affected strongly by the liquid circulation velocities and holdup

of the different phases, essentially if particles with different

densities have to be suspended simultaneously. A solid retaining

grid made was fixed just below the outlet to prevent the solid

particles from getting out of the reactor.

In present investigation, we have been used three phase system

in modified Reversed flow jet loop bioreactor. We have been

used liquid-Solid –gas system, for that as a liquid we have been

used tap water, as a solid we have been used acrylic beads

having diameters of 2-3 mm; & as a gas phase compressor air

has been used.

Average liquid circulation velocity is measured for loop

circulation in annular space at different Nozzle heights for

variable parameters of the modified reversed flow jet loop

bioreactor. For this purpose out of various techniques; Digital

image processing.

In present research work, we have been studied Two Phase as

well as Three Phase system. For Two phases we used Liquid-

Solid system and for three phases, we used Gas-Liquid-solid

system. We have been used following Material to carry out the

experimental work.

Compressor air as gas phase.




Acrylic beads as a solid phase.

Tap Water as a liquid phase.

Polystyrene pellets as tracer particles.

Digital camera (5 Megapixel).

Illumination system.

Windows movie maker operating program.

Physical Properties of materials:

Air:

Air (Free from moisture) is supplied from the top of the reactor

through two fluid nozzles to fluidize the mixture of acrylic beads

and water.

Physical properties:

a. Density :1.165

kg/m3

b. Molecular weight : 28.94

c. Thermal Conductivity at (250c, 101kpa) :26.6E-

3W/mok

Acrylic beads:

Acrylic beads having diameter 3mm have been used as a solid

material in two phase a well as three phase system. These beads

are slightly denser than water


a. Density : 1100 kg/m3

Tap Water:

Tap water has been used as a liquid phase in the Two as well as

Three phase System which was pumped through the two fluid

nozzle from top of the reactor.


a. Density : 1000 kg/m3

Polystyrene pellets (SC 206 Polystyrene):

We have been used polystyrene pellets as tracer particles as it is

having density approximately equal to water, so that by

determining the velocity of the polystyrene pellets we can get

the actual corresponding velocity of water within the reactor at

different flow rates of the liquid as well as gas (i.e. Water & air).

The polystyrene pellets were painted with different oil paints in

order to determine the circulation time and velocity of the

polystyrene pellets without any confusion.


MFI = 12.0

technique has been chosen with consideration of the merits &

demerits.

Materials & Method

Materials:

VSP = 101° C

HDT = 83 (Kg/cm2 0

C)

T.S. = 470 (Kg/cm2)

Elongation = 2%

FM = 32.0 (Kg/cm2 × 1000)

Specific gravity = 1.05

From the specific gravity above mentioned, we get the idea

about the density of the material is approximately equal to

density of water. Thus by measuring the velocity of the tracer

particle we can directly determine the value of liquid velocity.

Digital camera (5 Megapixel):

In recent years, Thanks to the continuous development of digital

imaging systems and digital image processing, In present work

we have been used the 5 mega pixel Digital camera made by

leaders in electronics gadget producers, LG electronics. It gives

us really good quality of videos and images so that we could

able to determine the liquid velocities and Bubble images at

different variable parameters.

Illumination System:

Really, an illumination system plays an important role in good

quality picturisation. It helps to distinct the Tracer particles from

the solid phase material and liquid phase at high flow rates of

liquid as well as gases. It is really very difficult to identify the

tracers from the system without proper illumination as

turbulence is takes place at high flow rates of liquid & gas.

The contrasted background is also that much essential as

illumination is. That‟s why we used Black background behind

the reactor as well as Black, Red and Pink colored oil painted

pellets particles, so that it will get visualized & could easily

captured while shooting through digital camera.

We used couple of tube lights and 200 watt bulb which was

covered by white paper in order to reduce the reflection due to

brightness. One 60 watt bulb & series of tube lights were kept

away at proper distances to get a good effect.

Windows movie maker operating program:

This is the key computer program which is bridge between the

videos as well as images captured and the output data of

velocities and circulation time as well as bubble size

determination. It helps to count the actual time in fraction of

seconds, required for the tracer through specific distance of the

reactor. It also helps us to determine the circulation time for the

tracer particle through reactor.

Methods:There are various types of methods which are used for

study of mixing characteristics in jet loop bioreactors, such as

Conductivity Method (Salt addition).

PH change Method.

Thermal Method

Digital Image processing

Technique/photographic method.

Calorimetric chemical reaction method.

The choice of a suitable experimental method for mixing time

measurement as well as study of mixing characteristics has been

a major problem for investigators, in a spite of variety of

reported methods. The major problems of our concern is that

many of the methods previously applied in the literature cause a

significant change in CMC solution viscosity [ e.g. Conductivity

method (salt addition) pH-change method, Thermal Method etc.]

Periodic sampling of the liquid for off- line analysis was not

feasible due to very slow rate of bubble disengagement from

viscous liquids; therefore the dye addition method was dropped

after some unsuccessful preliminary test.

In present investigation we have been used three phase system in

modified Reversed flow jet loop bioreactor. We have been used

liquid-Solid –gas system, for that as a liquid we have been used

tap water, as a solid we have been used acrylic beads having

diameters of 2-3 mm; & as a gas phase compressor air has been

used. The measurements of local liquid circulation velocities in

annular space of the reactor were done by the Digital

image processing technique with help of the oil painted

polystyrene pellets.

Comparatively digital image process technique may well

perform a rigorous and highly detailed assessment of




experimental data and may even be adopted for the analysis of

computational results conveniently expressed into image

graphics as well as tabulate in to graphical form. This technique

provides good visual observation without interfering with the

mixing process. The different techniques for measurement of the

mixing characteristics as well as behavior are already discussed

in literature survey; in spite of that with consideration of all

merits & demerits of all techniques we have been used Digital

Image processing technique / Photographic Method among

them.

A great number of researchers have chosen digital visual

methods to be applied in the field of experimental fluid

dynamics as well as mixing characteristics within the reactor.

These kinds of techniques play a fundamental role in analysis

and data acquisition for multiphase flows such as gas-solid, gas-

liquid, solid-liquid flows, where the observation of inter-phase

boundaries is relatively simple.

Thus Out of above mentioned methods, for the study of mixing

characteristics we have chosen the Digital Image Processing

Technique / photographic method.

Experimental Set Up

Experimental Procedure

The liquid i.e. Water was withdrawn underneath an impact plate

on which the draft tube was fixed and circulated to nozzle via

flow meter (Rotameter) by means of liquid circulation pump.

The gas was fed through an air tube fixed axially in the centre of

two fluid nozzles. Solenoidal valves were fixed in the liquid

inlet, outlet and bypass lines. The desired flow rates were

regulated with the help of these valves. The top neck of reactor

was tightly packed with filter cloth in such manner that it will

allow passing only liquid through the filter cloth. Thus tracer

particles which were painted by different colors of the oil paints

will remain inside the reactor.

After proper arrangement of the illumination, the movement of

the tracer particles which were already dumped into reactor was

captured with the digital camera.

Results & Discussion This Chapter enclosed with all graphical representation against

different operating parameters which gives us the effect on the

average tracer velocity i.e. Liquid Velocity. It gives the idea

about the effect of gas flow rates, liquid flow rates, Diameter of

nozzles as well as different nozzle heights. It also gives the idea

about liquid velocity when it has been determined at ejector

mode and when the air inlet was kept closed to atmosphere.

Effect on Liquid Velocity Profile at Nozzle height =360,450,670

MM When Air Inlet was kept closed to the atmosphere

360, 24.59054

450, 21.265

670, 26.364

0

5

10

15

20

25

30

0 200 400 600 800

av

g.t

race

r v

elo

city

,cm

/se

c

nozzle height,mm

avg.tracer velocity for close to atm.

avg.tracer velocity,cm/sec

Fig. 1- Average Tracer Velocity V/S Nozzle Height At Close

To Atmosphere

Above graph shows that maximum tracer velocity we are getting

at height 670 mm and lowest tracer velocity at nozzle height 450

mm for close to atm.


MM When Air Inlet was kept fully open to the atmosphere.

360, 26.32

450, 27.85

670, 31.59275

0

5

10

15

20

25

30

35

0 200 400 600 800

av

g.t

race

r v

elo

city

,cm

/se

c

nozzle height,mm

avg.tracer velocity for open to atm


Fig. 2- Average Tracer Velocity V/S Nozzle Height At Open

To Atmosphere

Above graph shows that maximum tracer velocity we are

getting at height 670 mm and lowest tracer velocity at nozzle

height 360 mm for open to atm.

Result and discussion for nozzle ht. 18.7 mm





MM When Air Inlet was kept fully Closed to the

atmosphere

360, 14.89175

450, 25.3783

670, 24.3849

0

5

10

15

20

25

30

0 200 400 600 800av

g.t

race

r v

elo

city

,cm

/se

c

nozzle height,mm

avg.tracer velocity profile for all heights at close to atm.


Figure 3- Average Tracer Velocity V/S Nozzle Height At

Close To Atmosphere


at height 670 mm and lowest tracer velocity at nozzle height 360

mm for close to atm.


MM When Air Inlet was kept fully opened to the atmosphere

360, 15.0475

450, 26.3525

670, 21.055

0

5

10

15

20

25

30

0 200 400 600 800

av

g.t

race

r v

elo

city

,cm

/se

c

nozzle height,mm

avg.tracer velocity for all heights at open to atm.


Fig. 4 - Average Tracer Velocity V/S Nozzle Height At Open

To Atmosphere

Above graph shows that maximum tracer circulation velocity

we are getting at height 450 mm and lowest nozzle height = 180

MM. it implies that ther is slightly overlapping of the velocity

profile.

But If we will consider all values of both conditions then we can

concluide that the liquid circulation velocity with higher

concentration gives us comparibly low values. As viscocity of

the liquid phase increases, the resistance of the solid phase also

increases and automatically fluid velocity is also decreaes. We

observed that tracer particles moves very smoothly through the

annulus of reactor. It gaves us the distinct velocities of the solids

and tracers.

Effect On Liquid Velocity Profile At Nozzle Height

=360,450,670 MM For Air Fully Close And Fully Open for

nozzle diameter = 16.5 mm

60, 13.29

80, 19.79

90, 29.96

60, 13.81

80, 27.24

90, 37.91

0

5

10

15

20

25

30

35

40

0 20 40 60 80 100Av

g.

tra

cer

ve

loci

ty,

Cm

/se

c

Liq. Flow rate, LPM

Avg. tracer velocity for 360 mm ht. & 0 LPM Air

Avg.Tracer velocity,cm/sec(CTA)

Avg.Tracer velocity,cm/sec(OTA)

Fig. 5- Average Tracer Velocity V/S Liq.Flow Rate in CTA

& OTA. Above graph shows that maximum tracer velocity we

are getting for open to atm. Condition at height 360 mm and

lowest tracer velocity at nozzle height 360 mm for close to atm.

60, 18.23

80, 26.2190, 29.72

60, 26.87

80, 28.83 90, 31.32

0

5

10

15

20

25

30

35

0 20 40 60 80 100Av

g.

Tra

cer

ve

loci

ty,

cm/

sec

Liq. Flow rate, LPM

Avg. tracer velocity at 0 LPM Air & 450 mm ht.



Fig. 6- Average Tracer Velocity V/S Liquid Flow Rate


for open to atm. Condition at height 450 mm and lowest tracer

velocity at nozzle height 450 mm for close to atm.

60, 17.51

80, 27.8290, 30.9660, 31.58

80, 31.6290, 35

0

5

10

15

20

25

30

35

40

0 20 40 60 80 100Av

g.

Tra

cer

ve

loci

ty,

cm/

sec

Liq. Flow rate, LPM

Avg. tracer velocity at 0 LPM Air at 670 mm ht.



Fig. 7- Average Tracer Velocity V/S Liquid Flow Rate

Above graph shows that maximum tracer velocity we

are getting for open to atm. Condition at height 670 mm and

lowest tracer velocity at nozzle height 670 mm for close to atm.

Effect On Liquid Velocity Profile At Nozzle Height

=360,450,670 MM For Air Fully Close And Fully Open for




nozzle diameter = 18.7 mm

40, 10.1450, 12.5

60, 16.2940, 14.68 50, 13.39

60, 17.07

0

5

10

15

20

0 20 40 60 80Av

g.

Tra

cer

ve

loci

ty,

cm/

sec

Liq. Flow rate, LPM

Avg. tracer velocity at 0 LPM air & 360 mm ht.



Fig. - Average Tracer Velocity V/S Liquid Flow Rate


for open to atm. Condition at height 360 mm and lowest tracer

velocity at nozzle height 360 mm for close to atm.

Conclusion

The Effects of gas and liquid flow rates, Different Nozzle

heights, Different concentration of liquid phase (Change in

viscosity), different operating conditions (i.e. ejector mode, &

By keeping air inlet closed) on the average velocity of fluid

have been investigated in a Three phase (liquid-solid-air)

modified reversed flow jet loop bioreactor. The following

conclusions are made based on the present investigation.

1. Liquid Average velocity in annular space of modified

reversed jet loop reactor increases with increase in liquid flow

rates and the influence of gas flow rate is more pronounced than

liquid flow rate.

2. As Nozzle height immersed more inside the reactor, the

average velocity in annular space of the modified reversed flow

jet loop bioreactor increases.

3. As air is sucked from the air inlet in ejector mode (When air

inlet kept open to atmosphere) into reactor, the average fluid

velocity is increases drastically in this condition and it is

observrd that it became maximum at nozzle height 450 mm.

from top of reactor tube.

4. As air is restricted from the air inlet (When air inlet kept close

to atmosphere) into reactor, the average fluid velocity is

increases drastically in this condition and it is observed that it

became maximum at nozzle height 670mm. from top of reactor

tube

5. In closed loop condition Average velocity of liquid increases

gradually with increase in immersion height.

6. In OTA (Open to Atmosphere) case, Average fluid velocity

profile is found greater than CTA (Close to atmosphere)

Refernences i. Milan k. Popvic and Campbell W. Robinson, 1993, Mixing Characteristics

of External-Loop airlifts: Non Newtonian systems. Chemical engineering science

48, 1405 – 1413. ii. Burhanettin Farizoglu and Bulent keskinler, 2007, Influence of draft tube

cross – sectional geometry on KLa and ε in jet loop Bioreactors (JLB). Chemical

Engineering journal 133,293-299. iii. K Yagna Prasad and T.K. Ramanujam, 1995, Enhancement of gas – liquid

mass transfer in a modified reversed flow jet loop reactor with three- phase

system. Chemical engineering science. 18, 2997-3000.

iv. M. Velan and T. K. Ramanujam, 1992, Gas – Liquid mass transfer in

a down flow jet loop reactor. Chemical engineering science, 47,

2871- 2876. v. Biochemical Engineering: Principles and concept, 149-162.

A. K. Sharma, C.A. Shastri and T.K. Ramanujam, Studies on treatment

of wastewater in Reversed Jet Loop Reactor: Part I – Hydrodynamics and Residence time Distribution studies. IJEP,

12,903-911.

vi. M. Velan and T. K. Ramanujam, 1994, Influence of reactor geometry on mixing characteristics in a down flow jet loop bioreactor:

Newtonian and non-newtonian fluids. Bioprocess Engineering,

11,101-106. vii. M. Velan and T. K. Ramanujam, 1992, Hydrodynamics and mixing in

down flow jet loop bioreactor with a non – Newtonian fluid (b).

Bioprocess Engineering, 7, 193-197. viii. K. Yagna Prasad and T. K. Ramanujam, 1995, overall volumetric

mass transfer coefficient in a modified reversed flow jet loop reactor

with low density particles. Bioprocess Engineering, 12, 209 - 214. ix. B. Kawalec – pietrenko, 2000, Liquid circulation velocity in the

inverse fluidized bed airlift reactor. Bioprocess Engineering, 23, 397

- 402.

x. Ken- ichi kikuchi* et. al, 1999, Hydrodynamic behavior of single

particles in draft tube bubble column, Canadian journal of chemical

engineering, 77, 57 573 - 578. xi. G. Padmavathi and K. Remananda Rao, 1991, Hydrodynamic

characteristics of reversed flow jet loop reactor as a gas-solid- liquid contactor, shorter communications, Chemical Engineering Science,

46, 12, 3293 – 3296.

xii. M. Velan and T. K. Ramanujam, 1995, Mixing time in down-flow jet loop bioreactor, Bioprocess Engineering, 12, 81 - 86.




Kinetics Study of Transesterification of Karanja and Rice Bran Oil .

Saurabh Visale, Girish Khuje, Vikash Kumar, Rupesh Tekode, Apeksha Bhonge, Ajay Pardey

Department of Chemical Engineering

Jawaharlal Darda Institute of Engineering & Technology, Yavatmal (M.S) India.

Corresponding Email: [email protected]

Abstract— Transesterification reaction of Karanja oil and Rice

bran oil with methanol was performed by using ZnO as

catalyst. The reaction was carried out in the batch-type reactor

at 55-65OC and atmospheric pressure. It was consequently

demonstrated that, in a preheating temperature of 55-65OC. It

was observed that with increased in temperature from 55 to

65OC, the concentration of biodiesel increased. It was found

that the highest conversion of biodiesel was obtained at

temperature 65OC and lowest at 55

OC.The kinetic study of

reaction including order and rate of reaction and activation

energy ( Karanja and Rice bran oil ) was calculated.

Keywords- Transesterification, Karanja Oil, Rice bran oil,

Nano-catalyst (ZnO).

INTR OD UCT IO N

The world is presently confronted with the twin crises of fossil

fuel depletion and environmental degradation. The search for

alternative fuels, which promise a harmonious correlation with

sustainable development, energy conservation efficiency and

environmental preservation, has become highly pronounced in

the present context [1].

The fuels of bio-origin can provide a feasible solution to this

worldwide petroleum crisis. Gasoline and diesel-petrol are the

major sources of pollution. The alternative sources of energy

like biodiesel, biomass and biogas are environment friendly and

solved the problems of energy [2]. Biodiesel reduces nearly all

forms of air pollution compared to petroleum diesel. Most

importantly, biodiesel reduces air toxics and cancer-causing

compounds. Using pure biodiesel can reduce the cancer risks by

94%.

Besides coal and natural gas, with the exception of

hydroelectricity and nuclear energy, the petroleum resources

have been supplying the world energy needs [3]. However, with

rising concerns on depleting reserves of these natural resources,

which are predicted to be consumed by the end of the next

century and environmental problems that arise from the use of

fossil fuel. Advantage of transesterification is that it decreases

the viscosity of the vegetable oils and improves the fuel

properties of fatty acid esters [4, 5]. This is because of the fact

that viscosity of vegetable oils is much higher than diesel; there

would have been several problems if these vegetable oils were

directly used in diesel engine as a fuel [6, 7].

Transesterification of vegetable triglycerides with simple

alcohol constitutes common process method for producing

methyl esters. In general, there are two methods of

transesterification [8, 9]. One is the method using a catalyst and

the other is without the assistance of a catalyst. The

transesterification with catalyst can be performed using acid or

alkaline [10]. The latter method without catalyst assistance is

applied in transesterification of vegetable triglycerides in

supercritical methanol [11].

In terms of reaction rate, that an alkaline catalyzed

transesterification proceed at considerably faster rates than acid-

catalyzed [12, 13]. Transesterification is the process of

modifying esters. In more detail, triglycerides such as oils from

vegetables can be transesterified into long chain alkyl esters

known as biodiesel. The reaction between a triglyceride (present

in vegetable oil) and alkyl alcohol produces alkyl esters and

glycerol Examples of triglycerides are vegetable oil, fatty tissues

or tallow obtained from animals. The alkyl alcohols generally

used are methanol and ethanol.

Figure 1 shown in detail the transesterification reaction between

a vegetable oil, such as soya oil, corn oil, etc and methanol.

The objective of the study is to investigate the kinetics

parameters of the transesterification reaction between the

Karanja oil and Rice bran oil based triglycerides with methanol.

Among the parameters studied are order of reaction and the rate

constants at various reaction temperatures as well as the

activation energy. In this paper the transesterification reaction of

Karanja oil and Rice bran oil with methanol was performed by

using catalyst zinc oxide. The effect of temperature on

production of bio-diesel with increase in temperature at interval

of time 5 minutes is evaluated and the optimization of the

production of bio-diesel is evaluated with reference to

temperature. Activation energy of the rice bran and karanja oil is

calculated with help of Arrhenius Law and the rate of the

reaction is also calculated.

MATERIALS AND METHOD

Karanja oil, Rice bran oil, methanol, Nanocatalyst zinc oxide,

sulfuric acid, and distilled water. Isothermal batch reactor tank

reactor bought from K.C. Engineers. In batch reactor the

contents in the reactor are well mixed and have uniform

composition. Thus the exit stream has the same composition as

the fluid within the reactor.

EXPERIMENTAL PROCEDURE

A known quantity of Karanja oil and Rice bran oil was taken

inside the batch reactor and preheated to about 55OC, 60

OC,

65OC respectively. This temperature was maintained throughout

the reaction. Preheating was used to remove unwanted moisture

present in the oil. The transesterification reaction took place in

presence of catalyst zinc oxide. Catalyst was dissolved in

alcohol, once the oil temperature reached to respective

temperature alcohol solution (containing dissolve catalyst) was

added to the batch reactor and equilibrium temperature was

maintained to the batch reactor. The equilibrium temperature





was maintained during the reaction to vaporized alcohol. Once

reaction was over the product were taken out through the outlet

in the lower side of the reactor and the sample is put into

separating funnel for 24 h.

Two phases of different density was formed as a result of

transesterification. Separation of two phases was done using

separating funnel. The Upper layer consists of biodiesel, alcohol

and soap. Lower layer consisted of glycerin, excess alcohol,

catalyst, impurities and traces of unreacted oil. After 24 h, the

sample of the separating funnel is water wash for removing

glycerin and other component.

RESULT AND DISCUSSION

4.1. EFFECT OF REACTION TEMPERATURE

Reaction rate is strongly influenced by the reaction temperature.

Transesterification reaction can even occur at room temperature

provided sufficient time is given for the reaction to occur. The

effect of reaction temperature in this study was investigated.

Several investigators found that although the reaction is usually

carried out nearly boiling point of alcohol but the maximum

yield has been reported at a temperature range of 60-750c.

The effect of reaction temperature on the production of biodiesel

is shown in the Figure 1 and 2. Temperature was changed with

the intervals of 5 0C. It was found that biodiesel produced from

karanja oil, rice bran oil showed maximum yield at 650c. The

figure 1 and 2 showed that the effect of temperature on karanja

and rice bran oil on concentration of the biodiesel with respect to

time. The figure showed that increased in temperature

concentration of biodiesel increased and highest yield obtained

at 650c. As boiling point of methanol is 64.7

oC. So near this

methanol starts boiling and this affects the yield.

Fig.1: Effect on Karanja oil at 55

OC, 60

OC, 65

OC of

temperature on concentration of biodiesel with respect to times.

Fig.2: Effect of rice bran at 55

OC, 60

OC, 65

OC of temperature

on concentration of biodiesel with respect to times.

4.2. DETERMINATION OF RATE AND ORDER OF

REACTION

The differential methods of analysis deals directly with the

differential rate equation to be tested, evaluating all terms in the

equation including the derivative dCA/dt.

The procedure is as follows:

1. Plot the CA vs. t data, and then by eye carefully draw a smooth

curve to represent the data. This curve most likely will not pass

through all the experimental points.

2. Determine the slope of this curve at suitably concentration

values.

These slopes dCA/dt = rA are the rates of reaction at these

compositions.

3. Now search for a rate expression to represent this rA vs CA

data, either by

(a) Picking and testing particular rate form, -rA= kf (CA),

(b) Testing an nth-order form –rA = k CAn by taking logarithms

of the rate equation.

Now carefully draw a smooth curve to represent the data and

draw tangents to the curve, and evaluate to fit an nth-order rate

equation to this data,

-rA= -dCA/dt = kCAn

ln (-dCA/dt) = lnk + n lnCA

ln (-dCA/dt) = y

ln k = intercept

n ln CA= slope(x)

It may be defined as the sum of the powers to which the

concentration terms are raised in a rate law expression.

This is an experimentally determined factor.

For the reaction

Order „n‟ of the reaction = x + y

Rate = k [A]x [B]y

The order „n‟ of the reaction = „x‟ + „y‟ where „a‟ and „b‟ may or

may not be equal to „x‟and „y‟.

y = 1.831x + 1.480R² = 0.926

0

0.5

1

1.5

2

-0.8 -0.6 -0.4 -0.2 0 0.2

ln (

-rA

)

ln (CA)

Fig.3, shows the order of reaction




Figure 3 shows the order of the reaction to calculate the order of

the above reaction, the graph is plotted ln(-rA) Vs ln CA. The

straight line curve is obtained the slope of the curve is nothing

but the order of the reaction which is 1.83 and the value of the

intercept of the curve is 1.48.

4.3. DETERMINATION OF ACTIVATION ENERGY

For many reactions, and particularly elementary reactions, the

reactions, the rate expression can be written as a product of a

temperature dependent term and a composition dependent term,

rA = f1 (temperature). f2 (composition)

= k. f2 (composition)

For such reactions the temperature-dependents term, the reaction

rate constant, has been found in practically all cases to be well

represented by Arrhenius‟ law:

K=k0.e-E/RT

..……(1)

Where, k0 = the frequency or pre-exponential factor

E = the activation energy of the reaction

R = universal gas const.

T = temperature (K)

Fig.4: Represents Rate of reaction in terms of ln(K) Vs 1/T

graph of Karanja Oil.

The figure 4, shows the graph between ln(K) Vs 1/T for karanja

oil, to determine the Activation energy of transesterification

reaction. it is found that from he graph the activation energy for

karanja oil is 185.

Fig. 5: shows ln(K) Vs 1/T graph of Rice bran oil.

Figure 5, shows the graph between ln(K) Vs 1/T for Rice bran

oil, from equation no.1 the activation energy for

transesterfication reaction for rice bran oil is calculated and it is

found 378, which is higher then karanja oil.

CONCLUSION

Two different oils, karanja and rice bran were explored for their

potential use as an alternative source for biodiesel production. It

was observed that increased in temperature, concentration of

biodiesel increased and the maximum yield obtained at 650C.

The activation energy and reaction rate and order of the reaction

were calculated. The catalyst provides a simple and economic

alternative method to produce biodiesel.

REFERENCES

i. Kesse D G Global warming – facts, assessment, countermeasures. J. Petrol Sci Eng 26: 141 – 149, 2000

ii. Johansson, Y. McCarthy S Global warming post Kyoto: continuing impasse

or prospects for progress Energy Dev Rep Energy, pp 69 – 71. iii. A. Demirbas, Biodiesel from vegetable oils via transesterification in

supercritical methanol, Energ. Convers. Manage. 43, 2349-2356, 2002.

iv. Yogesh C. Sharma, Bhaskar Singh, John Korstad, Latest developments on application of heterogeneous basic catalysts for an efficient and eco friendly

synthesis of biodiesel: A review, Fuel 90, 1309–1324, 2011.

v. Dennis Y.C. Leung, Xuan Wu, M.K.H. Leung, A review on biodiesel production using catalyzed transesterification, journal of Applied Energy 87,

1083-1095, 2010.

vi. J. A. Peres, G. P. Mambrini, G. S. Nascimento, C. Ribeiro and L. A. Colnago, Catalytic activity of CaO and ZnO nanoparticles in biodiesel

production, Energy & Fuels, 1777-1781, 2009.

vii. Pankaj Tiwari, Rajeev Kumar and Sanjeev Garg Transesterification, Modeling and Simulation of Batch Kinetics of Non-Edible Vegetable Oils for

Biodiesel Production, Fuel 86, 201–1207, 2009.

viii. Palligarnai T. Vasudevan E, Michael Briggs, Biodiesel production current state of the art and challenges, J Ind Microbial Biotechnology , 421–430, 2008.

ix. Martino Di Serio, Ricardo Tesser, Lu Pengmei, Elio Santacesaria,

Heterogeneous Catalysts for Biodiesel Production, Energy & Fuels, 22, 207–217, 2008.

x. M. Barrios, J. Siles, M.A. Martin, A. Martin, A kinetic study of the

transesterification of free fatty acids (FFA) in sunflower oil, Science direct Fuel 86, 2383–2388, 2007.

xi. M. Kaminski, E. Gilgenast, A. Przyjazny, G. Romanik. Procedure for and

results of simultaneous determination of aromatic hydrocarbons and fatty acid methyl esters in diesel fuels by high performance liquid chromatography, journal

of chromatography A 1122, 153-160, 2006.

xii. Theerayut Leevijit, Worawut Wisutmethangoon, Gumpon Prateepchaikul, Charktir Tongurai and Michael Allen , A Second Order Kinetics of Palm Oil

Transesterification, Sustainable Energy and Environment (SEE), 277-281, 2004.

xiii. Raheman H, Phaveatare AG , Diesel Engine Emission and

Performance from Blends of Karanja Methyl Ester and Diesel, Biomass and

Bioenergy 27, 393-397, 2004.




Optimization of Biofuel Synthesis Using Lignocellulosic Material

Incorporating Pervaporation Technology

Ramnath A. Kadam*, Dr. V. S. Sapkal, Dr. R. S. Sapkal

University Department of Chemical Technology, Sant Gadge Baba Amravati University, Amravati, (444602)

M.S., India,

*Corresponding Author:- [email protected]

Abtract : In present study sugarcane bagasse was used for

production of bioethanol. In enzymatic hydrolysis,

―trichoderma ressi‖ & ―aspergillus‖ were used. Trichoderma

ressi found relatively effective offering conversion up to 14%

glucose in two days compared to three days for aspergillus.

Fermentation carried out under optimized conditions with, S.

cerevisiae produced 11.6% of ethanol. Considering the

limitations of azeotropic mixture, pervaporation was used for

the purification of ethanol. Hydrophobic Poly Tetra

FluroEthylene (PTFE) was used for pervaporation. The study

demonstrated membrane technology as promising, highly

selective, cost & energy saving technology.

Keywords: Lignocellulose, Microorganisms, PTFE

membrane, Pervaporation

Introduction

Today, the transportation sector consumes more than half of the

petroleum used in the world, and the demand for fuel is expected

to increase in the future as vehicle traffic becomes more

abundant. The utilization of fossil fuel has large negative impact

on the environment, and it is of great importance to increase the

production of renewable fuels such as ethanol. First generation

ethanol production from starch and sugar-rich feedstock is

already a mature process.

Unfortunately, these feedstocks cannot meet the increased

demand for fuel, and concerns have been raised about the use of

food crops for fuel production. An alternative is to utilize

lignocellulosic materials as raw material in the fermentation

process for ethanol production, since lignocellulosic materials,

such as residues from agriculture and forestry, are renewable,

abundant and still relatively cheap.

Among the two main kind of hydrolysis (chemical and

enzymatic), enzymatic hydrolysis was more efficient and

“green” for environment, and thus was the focus for many work

[3]. Sugarcane bagasse consists of polymers of mainly two types

of sugars: glucose and xylose. Both sugars can be obtained, in

monomeric forms, with high yield rates from the break-down of

polysaccharide chains using steam pretreatment and subsequent

enzymatic hydrolysis. The monomeric glucose can then be

fermented to ethanol with the help of S. cerevisiae[5].

Ethanol should be waterless to use as fuel. Conventional

purification process such as distillation is a costly process. Also

ethanol and water form azeotrope. It is not possible to go beyond

95-96% purity. When the pervaporation process is applied, both

are better results and more economical operation obtained.

Product which is ethanol concentration is 99,9% can

be obtained by using energy more efficiently. Pervaporation is

membrane aided process which is applied to separation

azeotropes, close boiling mixtures [1]. Solution diffusion

mechanism is mass transport mechanism of the pervaporation

process. This mechanism involves selective sorption of a

component from the feed into membrane, diffusion of selective

component across the membrane, desorption of selective

component as vapor at the permeate side. Membrane and

separation technology might well contribute to making fuel

ethanol production from lignocellulosic material more

economically viable and productive.

II. Material & methods

2.1 Microorganisms

The “trichoderma ressei” & “aspergillus” were used for

hydrolysis of lignocellulosic material. The microorganisms

collected from Thermax Ltd. Pune. Culture were maintained in

incubator at 28 ºC & 120 RPM for 5 days. Initial pH of the

medium was adjusted to 6.5 prior to sterilization at 121 ºC for 30

min. The strain of S. cerevisiae (bakers yeast) purchased from

local market & it was used for fermentation.

2.2 Lignocellulosic material

In this work, sugarcane bagasse was obtained from agriculture.

This is found in abundant form as a residue at air dried condition

containing 22% moisture. The composition of the bagasse used

in all hydrolysis experiments, in terms of cellulose (42%),

hemicelluloses (28%) & lignin (20%).

2.3 Enzymatic Hydrolysis

The enzymatic hydrolysis of pretreated bagasse was performed

in 2000 ml borosil, containing 100 ml trichoderma culture with

medium, 100 gm bagasse & 1 lit water. The initial pH of

enzymatic hydrolysis was kept 5.5 and the hydrolysis

temperature was 45C. The hydrolysis was carried out for 48 hrs.

The same conditions were used for aspergillus Samples were

removed at 0, 6, 12, 24, 48, and 72 h for quantification of the

glucose and total reducing sugar released. All hydrolysis

experiments were carried out in triplicate, and the data were

calculated as means ± standard deviations. The mean values

obtained for each condition were analyzed statistically.

2.4 Fermentation

After completion of hydrolysis the content sterilized at 121 ºC

for 30 min. simultaneously the dry yeast activated at anaerobic

conditions & transferred into the fermentation medium after

gaining room temperature. Fermentation carried out under

optimized conditions (37 ºC & 5.5 pH) Traditionally, baker‟s

yeast (Saccharomyces cerevisiae), has long been used in the


http://en.wikipedia.org/wiki/Saccharomyces_cerevisiae








brewery industry to produce ethanol from glucose. Due to the

complex nature of the carbohydrates present in lignocellulosic

biomass, As a result, the ability of the fermenting

microorganisms to use the whole range of sugars available from

the hydrolysate is vital to increase the economic competitiveness

of cellulosic ethanol and potentially biobased proteins.

2.5 Pervaporation

Pervaporation was used for the purification of ethanol.

Hydrophobic Poly Tetra FluroEthylene (PTFE) membrane was

used for pervaporation having 0.2µm pore size, 65 µm thickness

& 1 inch diameter. In which the one heating mantle from 0 to

100 ºC temp, one three neck vessel, condenser with vacuum

connection & vacuum pump from 0 to 750 mm of Hg were used

for pervaporation of fermented broth.

2.6 Analytical Measurement

Glucose content was determined according to the method of

Miller. The reducing sugars liberated by these reactions were

measured using the 3, 5-dinitrosalicylic acid (DNS) method,

with glucose as standard. 3 ml of DNS reagent was added to 3

ml of glucose sample in a lightly capped test tube. The

absorbance values of the reducing sugar was measured using

spectrophotometer at 575 nm. Total reducing sugar was

calculated as w/v.

Ethanol concentration was determined according to the method

of Williams and Darwin. The 100 ml of potassium dichromate

reagent solution was prepared. On the other hand, saturated s-

Diphenylcarbazide solution was prepared by dissolving 1 g of s-

Diphenylcarbazide to 1 ml of 95% ethanol .The mixture was

then added with 1 ml of a 40% potassium sodium tartrate

(Rochelle salt) solution to stabilize the color. The ethanol

absorbance values were measured at 575 nm. The ethanol % was

calculated as v/v.

III. Experimental

In present study required material collected from different

sources as mentioned above and experiment is carried out in

chemical engineering lab UDCT Amravati. The experimental

work is as follows.

3.1 Pretreatment

Although lignocellulose is the most abundant plant material

resource, its usability is curtailed by its rigid structure. As the

result, an effective pretreatment is needed to liberate the

cellulose from the lignin seal and its crystalline structure so as to

render it accessible for a subsequent hydrolysis step. By far,

pretreatments are done through physical or chemical means. To

achieve higher efficiency, both physical and chemical

pretreatments are done. Physical pretreatment is often called size

reduction to reduce biomass physical size. The lignocellulosic

material crushed in to fine powdered form in crusher.

3.2 Glucose Production

Conversion of Lignocellulosic to glucose requires enzymatic

hydrolysis. The hydrolysis were carried out in 2 lit borosil In

which the one liter water, 100gm bagasse added (10:1) &

incubated culture of trichoderma resie added in hot air isolated

condition. The vessel is kept optimized conditions 45 ºC temp &

5.5 pH in rotary shaker with incubator for reaction upto 48 hrs.

Same procedure was done for aspergillus strain, but the batch

time of aspergillus strain was increased upto 72 hrs for required

conversion. Periodic samples were removed and glucose

analysis done by DNS method.

Enzymatic Hydrolysis

3.3 Ethanol production

Ethanol is produced by fermentation of glucose, which is done in

batch type operation. Saccharomyces cerevisiae (baker's yeast) is

rehydrated in water bath at 40°C, by using clean water and

allowed taking to room temperature before for Fermentation.

The hydrolyzed same batch taken for fermentation and yeast

strain were added in to vessel. Anaerobic fermentation is carried

out at 28-300C for 72 hrs.

During fermentation process, yeast

converts the simple sugars into ethanol and carbon dioxide.

C6H12O6 C2H5OH + 2 CO2

3 C5H10O5 5 C2H5OH + 5 CO2

According to their reactions, the theoretical maximum yield is

0.51 kg ethanol and 0.49 kg carbon dioxide per kg sugar.

Fermentation

Periodic sampling done for analysis of ethanol by Dichromate

colorimetric method.

http://en.wikipedia.org/wiki/Carbohydrate

http://en.wikipedia.org/wiki/Lignocellulosic_biomass






IV. Result & Discussion

In this study enzymatic hydrolysis studied by using trichoderma

reesei and aspergillus. The maximum conversion observed up to

14 % glucose w/v. The yield of enzymatic hydrolysis is achieved

up to 80%. By using trichoderma the 14%conversion achieved in

48 hrs, compared with 72 hrs required for aspergillus. The

graphical presentation of time vs glucose conc shown bellow.

Time in hrs Vs Glucose conc. in % by Trichoderma Reesie

Time in hrs Vs Glucose conc. in % by Aspergillus.

Fermentation of glucose was carried out under optimized

conditions in 72 hrs the conversion achieved up to 11.6%

ethanol v/v. The practical yield achieved upto 85%. Conversion

rate of ethanol is shown in graph

Time in hrs Vs Ethanol Conc. in %

PTFE hydrophobic membrane has studied, in which the

pervaporation temperature increased from 40 to 60 ºC change in

membrane flux is observed as increased at constant ethanol conc

11.6% and constant vacuum 650 mm of Hg.

At constant temperature 50 ºC and vacuum 650 mm of Hg, the

conc of ethanol was increased from 40 to 80%, membrane flux

was also increased as shown in graph.

V. Conclusion

The membrane separation process definitely done a effective

work at the downstream of fermentation for production of

ethanol & increase the productivity. In enzymatic hydrolysis the

practical yield is achieved 20% more than other process so we

can surely say that this is the offering technology for production

of ethanol.

Acknowledgement

I earnestly wish my sincere gratitude to my Guide Dr. V. S.

Sapkal for his valuable guidance and continuous encouragement

that he extended to me without whom my project could not have

been completed successfully. I would also like to thank U.D.C.T

Amravati for providing all required facility which enabled me to

complete this project.

6 References i. Purification of Fuel Bioethanol by Pervaporation, Derya Ünlü,

Nilüfer Durmaz Hilmioğlu, Digital proceeding of ICOEST 18- 21, June -2013. ii. Enzymatic Hydrolysis of Sugarcane Bagasse Using Enzyme Extract

and Whole Solid-state Fermentation Medium of Two Newly Isolated Strains of

Aspergillus Oryzae, Rosangela D.P.B. Pirota, Priscila S. Delabona, Cristiane S. Farinas, ISBN 978-88-95608-29-7; ISSN 2283-9216.

iii. Efficient cellulase production from low-cost substrates by Trichoderma reesei and its application on the enzymatic hydrolysis of corncob,

Lian Xiong, Chao Huang, Wan-feng Peng, Lv-rong Tang, Xiao-yan Yang,

African journal of microbiology research, vol. 7 (43) 5018-5024, 25 oct 2013 iv. Lignocellulose as raw material in fermentation processes, S. I.

Mussatto and J. A. Teixeira, IBB Formatex 2010. v. Pretreatment and hydrolysis of cellulosic agricultural wastes with a

cellulaseproducing Streptomyces for bioethanol production Chuan-Liang Hsua,

Ku-Shang Changb, Yi-Huang Changb, Hung-Der Jangb vi. Huanga, Shri Ramaswamya, U.W. Tschirner, B.V. Ramarao,

Separation and Purification Technology 62 (2008) 1–21. vii. Bioethanol Production in Membrane Bioreactor (MBR) System: A

Review, Anjali Jain and Satyendra P. Chaurasia, International Journal of




Environmental Research and Development. ISSN 2249-3131 Volume 4, Number 4 (2014), pp. 387-394.

viii. Bioethanol Production by Pervaporation Membrane Bioreactor, Filiz Ugur Nigiz, Nilufer Durmaz Hilmioglu, ICOEST, 2013.

ix. Ethanol From Cellulose: A General Review, Badger, P.C. 2002.17–

21. In: J. Janick and A. Whipkey (eds.), Trends in new crops and new uses. ASHS Press, Alexandria, VA.

x. A review of separation technologies in current and future biorefineries, Hua-Jiang Huanga, Shri Ramaswamya, U.W. Tschirner, B.V.

Ramarao, Separation and Purification Technology 62 (2008) 1–21.




Concentration of Aloe Vera Juice By Membrane Technology

Shital A. Amrute

*, Dr. R. S. Sapkal

University Department of Chemical Technology

Sant Gadge Baba Amravati University, Amravati M.S., India


Abstract : Membrane technology is being applied in the food

and beverages industry particularly in fruit juice concentration

all over the world .The major advantages are lesser use of

energy, better taste of products. The study is focus on

experimental investigation of concentration of Aloe Vera juice

through reverse osmosis, membrane distillation

technique,effect of various parameter.The flux of 14-

16Kg/m2/hr achieved and polysaccharide retention was greater

than 60%.

Key words: Aloe Vera ,Reverse Osmosis, Direct Contact

Membrane Distillation, Polysaccharides

I .Introduction

During the last two decades, application of established chemical

engineering principles in food industry has rapidly become an

important branch of chemical engineering. Challenges have been

faced by engineers and technologists in the area of preserving

the original food quality and creating new food structures in

large quantities and at high rates.Aloe Vera have gained more

attention over the last several decades due to its reputable and

valuable cosmetic and medicinal properties. It also finds its

application in the food industry essentially in the formulation of

health food drinks. It's also used in the manufacture of yogurt

and other beverages, including tea. Aloe Vera juices and gels

have found an extensive application in the cosmetic and toiletry

industries, principally due to its valuable moisturizing emollient

effect .Aloe Barbadensis Miller, a succulent tropical or

subtropical plant, is a species of Aloe Vera. The Aloe plant is

96-99% water with an average pH of 4.5, leaving only 1 percent

absorbable solid including over 200 bio-active constituents. The

advantages of the concentration of the liquid foodstuffs include

the reduction in packaging, storage, transport cost and

prevention of deterioration by microorganisms. It therefore

becomes imperative that a simple but efficient processing

technique needs to be developed, especially in the aloe beverage

industry, to improve product quality, to preserve and maintain

almost all of the bioactive chemical entities naturally present in

the plant during processing.

Membrane processes, such as microfiltration (MF), ultra

filtration (UF), reverse osmosis (RO) and membrane distillation

(MD) are interesting potential processes for clarification and

concentration of fruit juices.

In the present work ,reverse osmosis and direct contact

membrane distillation methods are considered. Reverse Osmosis

is a process that utilizes a membrane which selectively restricts

flow of solutes while permitting solvent to flow under pressure

Membrane processes normally operate at ambient temperature.

RO has already widely used in seawater desalination on large

scale.RO is the pressure driven operation and an effective non-

thermal method here for is used to process the Aloe Vera leaf gel

while preserving and maintaining the constituents naturally

present in the Aloe leaf. The RO process protects the heat

sensitive product (vitamins, amino acid, minerals etc) and retain

the color, flavor/aroma and nutritive components of the product.

The experiments are carried out to separate the Aloe water from

Aloe Barbadensis miller using RO technique of membrane

separation processes. It was aimed to remove the water content

from the Aloe juice and concentrate it. It was emphasized to

investigate the influence of various process and operating

parameters which include feed pressure, concentrate and

permeate fluxes, extraction process.

Nevertheless, when concentration is carried out by traditional

multi step vacuum evaporation, a severe loss of the important

components occurs as well as a partial degradation of

polysaccharides and natural antioxidants, accompanied by a

certain discolouration and a consequent qualitative decline.

These effects are mainly attributable to heat transfer to the juice

during evaporation. In order to overcome some of these

problems and to better preserve the properties of the fresh fruits,

several new „„mild” technological processes have been proposed

in the last years for juice production. Membrane Distillation has

many significant advantages, such as high system compactness,

possibility to operate at low temperatures (30–90 0C) which

makes it amenable for use with low temperature heat sources,

including waste or solar heat, and, when compared with say

reverse osmosis or electrodialysis, the simplicity of the

membrane which allows it to be manufactured from a wide

choice of chemically and thermally resistant materials, and much

larger pores than of reverse osmosis membranes (and typically

larger than in ultra-filtration membranes, that aren‟t nearly as

sensitive to fouling.

II Material and Methodology

Methodology

The objectives of the present work were:

1) Extraction of juice from fresh Aloe Vera leaf inner part.

2)To identify an integrated membrane process for the production

of concentrated Aloe Vera juices with high nutritional value.

3) Preconcentration by Reverse osmosis.

4)Concentration By Membrane Distillation of the concentrate

collected from reverse osmosis.

5)To Analyse physic-chemical properties of Aloe Vera

concentrate.

6)To analyse by UV-VIS Spectrophotometer.

Preparation of Aloe Vera juice

Fresh Aloe Vera (Aloe Barbadensis Miller) plants were obtained

from different locations and were used as the raw material in all

experiments. The length of studied leaves was between 25 and

35 cm. The Aloe Vera leaves were washed with water to remove





the dirt and other foreign particles from the surface of the leaves.

Hand-filleting of leaves removed the rind, tips, tails, and spines

from the leaf. The transparent gel slices were collected in a

beaker. Then, the gel was washed with demineralized distilled

water and alkaline solutions (0.1M NaOH) to separate the sap

from Aloe gel slices. Subsequently, the Aloe gel was then

blended to extract the liquid contained in the aloe leaf. A

uniform concentrated solution was obtained. The solution from

blender was filtered to remove the pulp and clear juice of Aloe

Vera was obtained which consists of all the nutritional

constituents present in Aloe Vera.

EXPERIMENTAL WORK

Reverse osmosis unit and procedures: Juices were submitted to a preliminary concentration by RO

using a laboratory unit The equipment consisted of a feed tank, a

cooling coil working with tap water, a high pressure feed pump,

a stainless steel housing, a permeate flowmeter and a pressure

control system. The plant was equipped with an Hydranautics

spiral-wound membrane module (type SWC2-2521, composite

polyamide, salt rejection minimum 99.0%, nominal membrane

area 1.12m 2,pressure operating range 1–69 bar, temperature

operating range 0–45 0C, pH operating range 3–10). All the

experiments were performed according to the batch

concentration mode. The membrane module was rinsed with tap

water for 30 min after the treatment of the juice; then it was

submitted to a cleaning procedure using NaOH The solution was

circulated for 60 min at a temperature of 40 0C and at a TMP of

5 bar. A final rinse of the system with tap water for at least 20

min was carried out. After the cleaning treatment the water

permeability of the membrane module in fixed conditions

(temperature

25 0C) was measured.

Fig. 1: Schematic diagram of RO membrane integrated Aloe

juice processing plant

Direct contact membrane distillation: The retentates coming from the RO unit were submitted

DCMD.The membrane module design for this work is unique in

that it can use flat-sheet membranes . Additionally, the

membrane module and associated apparatus were designed to

achieve relative high feed and permeate within the module.

Concentration of feed solution by DCMD was carried out using

a flat-sheet membrane cell with an effective membrane area.The

membrane cell was made of stainless steel and was placed in a

vertical configuration. The system to be studied consists of a

porous hydrophobic membrane, which is held between two

symmetric channels. Hot feed is circulated through one of the

channels and cold permeate through the other one. The hot and

cold fluids counter-flow tangentially to the membrane surface in

a flat membrane module.

Feed tank with thermostat, pump and temperature and flow

indicator is arrange in feed side, where as pump, and

temperature and flow indicator is arrange in permeate side.

Module is supported with stainless steel holding device. The

schematic arrangement is shown in Fig juice as feed solution and

distilled water as receiving phase were contained in two jacketed

reservoirs and were circulated through the membrane cell by one

two-channel pump. The feed and distillate streams flow counter

currently from the bottom to the upper part of the membrane

cell. Different experiments were carried out for fixed

temperatures in the membrane module. The average feed

temperature Tf varied for the experiments and permeates

temperature Tp varied for the experiment. The linear velocity

feed and permeate was also varied. Different experiments were

carried out applying different recirculation rates.

Figure2 :Flow Diagram of Direct Contact Membrane Distillation


Feed Solution: Weight of aloe Vera leaves = 40 kg Weight of

aloe Vera gel = 3.6 kg Quantity of blended aloe Vera gel = 1.9 L

Analysis of Polysaccharide Content In Aloe Vera

juice:Polysaccharide content was estimated by a colorimetric

analysis. 100 mL of Aloe vera Juice were taken in a beaker and

the samples were vacuum filtered. The filtrate was diluted to

100mL in a beaker according to the methodology suggested by

Hu et al. (2003). Two milliliters of the solution and 10mL of

absolute ethanol were added in plastic tubes; samples were

centrifuged at 2500×g for 30 min, and the supernatant was

removed; the precipitate was dissolved in a final volume of

50mL water. One milliliter of the filtered solution, 1mL of

phenol at 5 g/100 mL, and 5mL of concentrated sulphuric acid

were added to the tops of the tubes. It was allowed to settle for

30 min. Sample absorbance was determined at 490nm

(Spectronic 20 GenesysTM, IL, USA). Total polysaccharide

content was estimated by comparison with a standard curve

generated from d-+-glucose analysis.

Effect Of Operating Pressure On RO Permeate Flux For

Aloe Vera Juice: Experiments were carried out to investigate the influence of

operating pressure on permeate flux of Aloe Vera juice. The RO




membrane was operated at four different transmembrane

pressures e.g. 30, 40, 50 and 60 bars. Similar experiments were

repeated for distilled water as feed. It can be observed from the

graph that permeate flux is a function of applied pressure

difference across the membrane. Permeate flux increases with

the increase of the transmembrane pressure. When the permeate

flux obtained from Aloe Vera as feed is compared with that

obtained from distilled water, it is found that high applied

pressure is required for the concentration of Aloe Vera juice as

compared to permeate flux of distilled water as feed. Thus it can

be envisaged that initially when there is more water content in

Aloe Vera juice, less applied pressure is needed, however, as the

Aloe Vera feed juice is concentrated with the passage of time,

more transmembrane pressure is applied to get the same

permeate flux.

Fig3. Effect of operating pressure on Aloe juice and distilled

water permeate flux.

Effect of Feed Velocity: Effect of feed flow rate on

transmembrane flux for Aloe Vera juice is estimated and

presented in Figure 3.2. During experiments, the feed side flow

rate is varied between 60 to 120 L/hr and permeate side flow rate

(30L/hr), Feed temperature (40 oC), Permeate temperature (20

oC), temperature difference (ΔT = 20 oC), and concentration

was maintained constant (4.4 Bx). The transmembrane flux

increases with increase in flow rate. The increase is mainly due

to the reduction in temperature polarization and fouling

phenomenon. Figure 8.8 shows as the permeate flux increase

when the recirculation rate increases. The effect of high

recirculation rate is to increase the heat transfer coefficient and

thus reduce the effect of temperature polarization. This means

that the temperature at the membrane surface more closely

approximated to the bulk temperature, and thus the

transmembrane temperature difference is greater. This produces

greater driving force and consequently enhanced the flux.

Fig 4: Effect of feed velocity on Transmembrane flux

Effect of Feed concentration

The concentration of orange juice was varied over 4.4 – 8.4 0Brix. During the experiments the feed flow rate (72L/hr),

permeate flow rate (30L/hr), feed temperature (40 0C), permeate

temperature (200C) and temperature difference

(200C) are maintained constant. The values of transmembrane

flux observed at different concentration of feed solution and are

shown in Fig. 5. Thetransmembrane flux decreases with increase

in concentration. This is due to increase in concentration and

temperature polarization and thus decrease the driving force.

Accordingly, concentration polarization may be significant at

high concentration, high temperature and low feed velocity. In

other words, the evaporation rate of water at the membrane

surface decreases with increase in concentration Flux decline

with time was observed, but it was more significant at a high

concentration.

Fig 5: Effect of feed concentration on transmembrane flux

Effect of feed temperature:

The effect of the feed temperature on permeate flux has been

investigated in the DCMD configuration. The feed temperature

has been varied from 30 to 45°C (below the boiling point of the

feed solution) maintaining all other MD

parameters constant. Figure 6 shows that in DCMD

configuration there is an exponential increase of the MD flux

with the increase of the feed temperature. This is due to the

exponential increase of the vapor pressure of the feed

solution with temperature, which increases the transmembrane

vapor pressure (i.e. the driving force) as all the other involved

MD parameters are maintained invariables. It was stated that it is

better to work under high feed temperature as the internal

evaporation efficiency, defined as the ratio of the heat that

contributes to evaporation and the total heat exchanged from the

feed to the permeate side is high although the temperature

polarization effect increases with the feed temperature. On other

hand while deciding feed temperature quality of juice was also

has to be considered.




Fig 6: Effect of feed temperature on transmembrane flux

The key points about quality assurance of aloe vera juice in the

processing include: (1) how to avoid the browning reaction and

maintain the good appearance of the product; (2) how to avoid

the degradations and losses of biological activities of aloe vera

gel to get the nutrient product; (3) how to get aloe vera gel juice

with long shelf life

Table: Physico-chemical properties of Aloe vera juice

Sample TSS

(°Brix)

PH TDS Polysaccharide

(mg/lit)

Fresh Aloe

Vera Juice

4.4 3.71 1050 2700

RO

Concentrate

8.2 4.9 1100 2660

RO

Permeate

3.3 4.1 96ppm -

MD

Concentrate

16 4.2 - 1810

IV. Conclusion:

The results obtained during the study, showed that application of

Membrane technology (RO, MD) to concentrate Aloe Vera juice

could be a better alternative to conventional techniques

(Evaporation, Freeze Drying).The influence of various

parameters such as feed flow rate. It was observed that

transmembrane flux increases with increase in feed flow rate.

The result indicates that concentration up to 60% of

polysaccharides.

Acknowledgement:

I take this opportunity to express my sense of gratitude Prof.

Dr.V.S.Sapkal, Head of department of chemical technology,

S.G.B.Amravati University and Prof. Dr. R.S.Sapkal ,for


throughout this work.

Referances:

i. Josias H. Hamman , Composition and applications of aloe vera leaf gel,

Molecules, 13 (2008). ii. Cassano, B. Jiao, E. Drioli,Integrated membrane process for the production

of highly nutritional kiwifruit juice (2006). iii. S.K. Dershmukh, Dr. V.S. Sapkal, Dr. R.S. Sapkal, Aloe Vera Juice

Concentration by Direct Contact Membrane Distillation, Journal of Pharmacy

Research (2011), iv. A. Cassano, E. Drioli , G. Galaverna , R. Marchelli b, G. Di Silvestro,

P.Cagnasso, Clarification and concentration of citrus and carrot juices by

integrated membrane processes, Journal of Food Engineering (2003). v. B.L. Jiao, V. Calbro and E. Drioli, Concentration of Orange and Kiwi Juice

by integrated Ultrafiltration and Membrane Distillation, Paper presented at ‗IMSTEC‘ 92 held at Sydney Australia, (1992)

vi. Sergey Gunko, Svetlana Verbych, Mykhaylo Bryk, Nidal Hilal,

Concentration of apple juice using direct contact membrane Distillation, Desalination, 190, 2006, 117–124.

vii. R.W. Schofield, A.G. Fane, C.J.D. Fell, ―Heat and mass transfer in membrane distillation‖, Journal of membrane Science 33 (1987) 299–313.

viii. T. Reynolds, A.C. Dweck, ―Aloe vera leaf gel: a review update‖, Journal of

Ethnopharmacology 68 (1999) 3–37. ix. V.D. Alves, I.M. Coelhoso, Orange juice concentration by osmotic

evaporation and membrane distillation: A comparative study, Journal of Food Engineering, 74, 2006, 125–133.

x. Vincenza Calabro, Bi Lin Jiao and Enrico Drioli, Theoretical and

Experimental study on Membrane Distillation in the concentration of Orange Juice, Ind.Eng. Chem. Res, 33, 1994, 1803 – 1808.




Whey Protein Fractionation by Membrane Technology

Swati A. Gurjar*, Dr. V. S. Sapkal




Abstract : Whey protein contains, α lactalbumin, β

lactoglobulin, Bovine serum albumin (BSA),

immunoglobulins, lactoferrin that all are useful as a medicin

.From this study Membrane separation technology involved

UF in continuous diafiltration mode and NF for separation

using different material of membrane gives more pure

product at pH effect. Retentant yield for α lactalbumin ranged

form 43% at pH 4,while for β lactoglobulin,was form 67% at

pH 3.In contrast, and BSA(Bovine serum albumin),

immunoglobulins and lactoferrin were mostly retained ,with

improvement up to 60% in purity at pH9 with respect to

original whey

Key words- Whey protein, Ultrafiltration, Nanofiltration,

polymeric membrane.

I. INTRODUCTION

Whey proteins are commonly used in the food industry due to

their wide range of chemical, physical and functional properties.

The most important functional properties of whey proteins are

solubility, viscosity, water holding capacity, gelation, and

emulsification and foaming. Individual whey proteins have their

own unique nutritional, functional and biological

characteristics. Therefore, whey fractionation for the recovery

and isolation of these proteins has a great scientific and

commercial interest. Separation processes to fractionate whey

proteins reported in the literature fall into a number of

categories, such as selective precipitation, colloidal gas aphrons,

selective adsorption and selective elution. Apart from these

interesting techniques, membrane filtration has also provided

promising results for the fractionation of whey proteins. HPTFF

is based on the proper choice of pH and ionic strength in order to

maximize the differences in the effective hydrodynamic volume

of the different proteins. Following a continuous diafiltration

procedure up to 4 diavolumes, the flux–time profiles and yields

in both retentate and permeate of the individual proteins were

evaluated. For instance,α-lactalbumin has been claimed as a

nutraceutical and a food additive in infant formula owing to its

high content in tryptophan and as a protective against ethanol

and stress-induced gastric mucosal injury β-Lactoglobulinis

commonly used to stabilize food emulsions because of its

surface-active properties . Bovine serum albumin (BSA) has

gelation properties and it is of interest in a number of food and

therapeutic applications, for instance, because of its antioxidant

properties. Bovine immunoglobulins can enhance the

immunological properties of infant formula and they can be used

therapeutically in the treatment of animal neonates and, in the

form of special supplements, they can offer, in many situations,

an important reduction of risk to acquire diarrhoea causing

infections and other illnesses . Bovine lactoferrin, which exists at

relatively low concentrations, has important biological activity.

Lactoferrin has been reported to have antimicrobial,

immunostimulatory and anti-inflammatory activity since it

affects growth and development of a wide range of infectious

agents.

Ultrafilteration is one of the most fascinating technology which

has been introduced for application in the dairy industry.

Ultrafilteration makes it possible to improve the quality of

traditional dairy products, to create new food staffs, to utilize

dairy by product (such as whey) to a much greater extent for

human nutrition and to prepare milk ingredients to be used in the

entire food industry. The performance of ultra and

nanofilteration membranes can be characterized in terms of

permeate flux, membrane retention and yield, which parameters

are determined by pressure, recycle flow rate and temperature.

The results obtained were explained in terms of membrane

protein and protein interaction. The purpose of this work was to

investigate the potential of membrane ultrafiltration and

nanofiltration for the fractionation of clarified whey. Employing

polymeric membrane in a continuous diafiltration mode, the

effect of working pH was evaluated by measuring the flux–time

profiles and the retentate and permeate yields of α-lactalbumin,

β-lactoglobulin, BSA, IgG and lactoferrin.[ M. Carmen

Almecija, Ruben Ibanez, Antonio Guadix, Emilia M. Guadix J.

Membr. Sci. (2007).]

II .Material and Methodology

Methodology

The objectives of the present research were:

1)Collection of whey form dairy.

2)To obtain a relative separation of original α- lactalbumin and

β- lacoglobulin and retentate enriched in BSA,

immunoglobulins and lactoferrin from whey protein.

3)fractionation of protein ultrafilteration, diafiltration mode,

nanofilteraionin process.

4)UF permeats form the sweet whey filtration were further

nanofiltred. Using polymeric membrane.

6) Identification of product by analytical method HPLC, the

content which present in whey protein that was used as a

medicin.

Components Found In Whey Protein:

Whey Components % of Whey Protein

beta-Lactoglobulin 50-55%

alpha-Lactalbumin 20-25%

Immunoglobulins 10-15%

Lactoferrin 1-2%

Bovine Serum Albumin 5-10%




Table no.1 Components Found in Whey Protein.

Molecular Weight Of Proteins:

Protein Molecular weight (kDa)

β-Lactoglobulin 18,277

α-Lactalbumin 14,175

Bovine serum albumin 66,267

Immunoglobulins 25,000

Lactoferrin 80,000

Table no.2 Molecular weight of proteins

Experimental Set-Up :

Fig.1 UF, NF membrane set up.

Ultrafiltration (UF) uses polyethersulfone polymeric membrane ,

which are fully retentive to the whey proteins, to remove main

whey proteins α-Lactalbumin, β-lactoglobulin and bovine serum

albumin , Immunoglobulins, Lactoferrin .yielding a permeate

and retentate stream . The net result is a whey protein

concentrate that is around 60% protein by weight.

The content in whey can be further reduced using a subsequent

diafiltration (DF) in which deionised water is continually added

to the retentate while whey content are simultaneously removed

in the filtrate. This combined UF-DF yields a high value

retentate of about 85% protein.

Nanofiltration polyamide membrane can be used for

concentration of the whey up to 20-24 % w/w solids or

alternatively for concentration of the permeate which penetrates

the membrane during ultrafiltration processing of whey and it

which contains whey protein in the same concentration as in the

water phase of the original fluid.

Experimental The clarified acid bovine whey was adjusted to the working pH

using HCl or NaOH and filtered in order to remove any possible

aggregates. Afterwards, 20 L of whey were added to the feed

tank. While in operation, retentate was recirculated to the feed

tank under the following conditions: transmembrane pressure 1

bar, temperature 30 ◦C, flow rate concentrate 12.5LPM and

permeate 4LPM during ultrafiltration and nanofiltration

membrane pressure is same and flowrate of concentrate was 15.5

and permeate 1.2 LPM . The permeate was collected in the

permeate tank and diafiltration water (at the same pH and

temperature of the feed) was added to the retentate tank at the

same rate of the permeate flow. Permeate and retentate were

collected tank . Permeate flux was calculated from mass

measurements in an analytical balance. Samples of retentate and

permeate were taken at each diavolume for quantification of

individual proteins. And nanofiltreation was done in this UF

concentrate from the sweet whey filtration were further

nanofiltered.


Analytical techniques:

The pH-value, TDS (Total dissolve solid)

HPLC(High-performance liquid chromatography.)

pH-value: The pH value of protein at 9 product purity is more.

TDS(Total dissolve solid) :Total dissolve solid (TDS) more

concentrate is more.

HPLC Analysis:

Individual protein concentrations,including α-lactalbumin,β-

lactoglobulin, BSA, lactoferrin and IgG, were determined by

HPLC. Protein standards for calibration (α-lactalbumin, β-

lactoglobulin A, β-lactoglobulin B, BSA, IgG and lactoferrin)

Results Considering only the molecular weight of the monomer (_α-

lactalbumin, 14 kDa; β lactoglobulin, 18 kDa), it could be

thought that both proteins should pass through the membrane

with ease. However, a variety of permeate yields was obtained at

changes of the electrostatic environment since the extent of the

aggregation of the protein molecules is pH-dependent. For

instance, at pH 4 and 5 both proteins are essentially uncharged,

large aggregates of up to 8 molecules are formed which

results in very low transmissions. At pH in the 7–9 interval,

maximum transmissions were achieved since interactions

between the proteins and the neutral membrane are minimised.

When protein and membrane repel each other (i.e. at pH 3 and

10), permeate yields values were greater than expected, probably

due to the importance of convective transport of solute as a

consequence

of the high permeate flux. Fig. 2 shows Ultrafiltration pearmeate

flux time profile.flux is increases with time. Fig.3.Ultrafiltration

concentrate flux time profile Fig.4.Nanofiltration pearmeate flux

time profile Fig.5.Nanofiltration concentrate flux time profile in

this figure flux increases.

Fig.2. Ultrafiltration pearmeate flux time profile.




6.6

6.8

7

7.2

7.4

7.6

7.8

8

8.2

0 10 20

UF concentrate L/min/M2

UF concentrate L/min/M2

Fig.3.Ultrafiltration concentrate flux time profile

Fig.4.Nanofiltration pearmeate flux time profile

Fig.5.Nanofiltration concentrate flux time profile

IV.Conclusion

whey protein content α-lactalbumin,β-lactoglobulin, BSA,

lactoferrin and IgG, was seprated by ultrafiltration and

nanofiltration in continuous diafiltration mode with more purity

than it original. The diafiltration proposed, the purity of the

retained proteins could be improved . Regarding the permeate

flux, the slowest filtrations occurred at pH 4 and 5. i.e. around

the isoelectric point of α-lactalbumin, β-lactoglobulin and BSA.

Acknowledgement:

I take this opportunity to express my sense of gratitude Prof.

Dr. V.S.Sapkal, Head of department of chemical technology,

S.G.B.Amravati University and for his guidance throughout this

work. I would like to express my sincere gratitude Mr. Yadav

Sir, From Raghuvir Dairy Industry Amravati for the help

which he had provided during this project.

Refrences: i. A. Muller, B. Chaufer, U. Merin, G. Daufin, Prepurification of α-

lactalbumin with ultrafiltration ceramic membranes from acid casein whey: study of operating conditions, Lait 83 (2003) 111.

ii. B. Cheang, A.L. Zydney, A two-stage ultrafiltration process for

fractionation of whey protein isolate, J. Membr. Sci. 231 (2004) 159. iii. M. Carmen Almecija, Ruben Ibanez, Antonio Guadix, Emilia M.

Guadix, Effect of pH on the fractionation of whey proteins with a ceramic ultrafilteration membrane J. Membr. Sci. 288(2007)28.

iv. Mayank Omprakash Nigam, Bipan Bansal, Foling and cieaning of

whey protein concentrate fouled ultrafilteration membranes, desalination 218(2008)313.

v. R. van Reis, J.M. Brake, J. Charkoudian, D.B. Burns, A.L. Zydney, High performance tangential flowfiltration using charged membranes, J. Membr.

Sci. 159 (1999) 133.

vi. R. van Reis, S. Gadam, L.N. Frautschy, S. Orlando, E.M. Goodrich,S. Saksena, R. Kuriyel, C.M. Simpson, S. Pearl, A.L. Zydney,

Highperformance tangential flow filtration, Biotechnol. Bioeng. 56 (1997) vii. R.C. Bottomley, Isolation of immunoglobulin-rich fraction from whey,

Eur.Patent 320,152 (1989).

viii. Ramadan Atraa, Gyula Vataia, Erika Bekassy-Molnara, Agnes Balinta investigation of ultra and nanofilteration for utilization of whey protein

and lactose, J of Food Sci.67(2005)325. ix. S. Bhattacharjee, C. Bhattacharjee, S. Datta, Studies on the

fractionation of β-lactoglobulin from casein whey using ultrafiltration and ion-

exchange membrane chromatography, J. Membr. Sci. 275 (2006) 141. x. SvetlanaButylinaa, SusanaLuqueb, Marianne Nyströma Fractionation

of whey-derived peptides using a combination of ultrafilteration and nanofilteration J of Membr. Sci.280 (2006)418.

http://www.sciencedirect.com/science/article/pii/S0260877404002109?np=y











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Lignin Separation and Purification from Black Liquor Precipitate

Shrikant Nanwatkar*, Sushama Gawai, Jitendra Shinde

Department of Chemical Engineering,

Anuradha Engineering College, Chikhli, Buldhana (M.S) India


Abstract : The spent liquid after the pulping process in pulp

mill, generally known as black liquor contains the degraded

lignin and carbohydrate. The PH and the residual alkali of

black liquor increased with the increase of total alkali used

during the pulping process while the black liquor viscosity

mainly depends on the dissolved lignin. The increase of alkali

charge resulted higher dry solid yield due to the increase of

both inorganic components and dissolved organic components.

Analysis by Fourier transform infrared spectroscopy (FTIR)

showed that the isolated lignin contain in each solvent, while

gas chromatography(GC) analysis showed that black liquor

composition. In this work, lignin precipitation was performed

by the isolation of kraft black liquor at various process

conditions, namely PH, temperature and different solvent and

influences exerted by these parameters on the equilibrium of

lignin increases with decreasing PH and temperature and with

increasing ion strength of the black liquor used. The

concentration of carbohydrates in lignin decreases with

decreasing PH and that an increasing amount of lower

molecular weight lignin is precipitated at a higher precipitation

yield.

Keywords: Black liquor, Lignin, FTIR, Carbohydrate, Gas

chromatography

Introdcution

Lignin has a much more complex structure than the carbohydrate

polymers. The term lignin is derived from the Latin word for

wood lignum. Lignin is a major constituent in structural cell

walls of all higher vascular land plants. Its polyphenolic

structure is well known for its role in woody biomass to give

resistance to biological and chemical degradation. This is due to

its hydrophobic nature and insolubility in aqueous systems

preventing access of degrading chemicals and organisms [1]

. The

monomeric units of phenylpropane in lignin polymers are linked

in a complex network through different types of ether and ester

bonds as well as carbon-carbon bonds. The lignin occurring in

plant cell walls is commonly closely associated with

polysaccharide structures of cellulose and hemicellulose. On

account of the high conyent of Si in straw and the small scale,

many papermaking enterprise have not found a proper method to

treat wastewater in pulping process. With the more tension of

environment protection, those enterprises have confirmed with

the crisis of existence and improvement and they are looking for

a appropriate treatment method, which ought to be not only

suitable for their scales and straw material, but also feasible in

economics [4]

.

In above paper two types of black liquor with pine chips and

coffee been as a row material were treated by isolation krsft

process and reuse. The treatment, the solid material in black

liquor were transferred into two by products (i. e. lignin and

water reducing agent ), which have extensive uses and can bring

economics benefits in good management and marketing.

Fig 6:

Principle monomer

structure of

ligninlignocellulosic

material

cellulose

(%)

hemicellulose

(%)

lignin

(%)

Hardwood steam 40-55 24-40 18-25

Softwood steam 45-50 25-35 25-35

Nut shell 25-30 25-30 30-40

Grasses 25-40 35-50 10-30

Wheat straw 30 50 15

Sorted refuse 60 20 20

Newspaper 40-55 25-40 18-30

Waste paper from

chemical pulps

60-70 10-20 5-10

Solid cattle manure 1.6-4.7 1.4-3.3 2.7-

5.7

Switch grass 45 31.4 12

Table 1. Cellulose, Hemicellulose, and Lignin Contents in

Common Agricultural Residues and Waste

Types of lignin

Gymnosperm lignin, Dicotyledonous lignin, Angiosperm lignin

Lignin Separation Methods

Several techniques are available for the separation and

purification of lignin from black liquor. These techniques are

based on the changes of lignin solubility, the differences

between the molecular weight/size of lignin or a combination of

both. The criteria used for the separation methods are, firstly,

that lignin should be isolated with a high yield, secondly, the

isolated lignin should be free from contaminants and, thirdly, the

procedure should be simple and easy to perform [9]

.

(I) Precipitation

Extracting lignin from black liquor by means of acidification has

been commercialized for a long period of time. In 1942, in the





United States, started to produce lignin from black liquors

obtained from the kraft process; it is still one of the dominant

suppliers of lignin products derived from kraft black liquor, with

an estimated annual production of 27000 metric tons., the

successful lignin extraction process called “LignoBoost”. the

highest yield of precipitated lignin was obtained with a dry solid

content of 27-30% for softwood black liquor and 30-35% for

hardwood black liquor.

(II) Ultrafiltration

Separating lignin from black liquor by membrane ultrafiltration

has also been suggested the ultrafiltration may be considered as

a technically feasible method for the production of kraft lignin.

However, when compared with acidification, this technique

involves higher capital and operating costs. Nevertheless,

ultrafiltration is still an interesting option for separating the

lignin.

(III)The LignoBoost process

Lignin precipitation by the acidification of black liquor is not a

new technique; the lignin extracted from a traditional, single-

stage, dewatering/washing process has a relatively low dry solid

content and high ash content. It also results in severe problems

with a complete or partial plugging of the filter cake and/or the

filter media. The case of virtually complete plugging results in

an extremely low flow of wash liquor through the cake, and a

partial plugging of the filter cakes results in high levels of

impurities in the lignin. Consequently, the novel two-stage

washing/dewatering process called “LignoBoost”, which

extracts lignin efficiently from black liquor, Using this process it

is possible to separate lignin with a low ash content and a high

dry solid content for large-scale industrial production [6]

. In the

LignoBoost process, a stream of black liquor is taken from the

evaporation plant; the lignin in it is precipitated by acidification

(CO2 is preferred) and then filtrated. The difference between this

and the single-stage lignin separation process is that instead of

washing the lignin immediately after filtration, the temperature

is kept equal to that of the final washing liquor and the PH is

decreased. Therefore the change in PH and consequently the

change in lignin solubility.

Experimental section

Chemical and materials

In above experiment following analytical grade chemical is used.

The detail of the chemicals used is as follows What man #4 filter

paper, 0.5 gm of EDTA-2Na+, 2 M H2So4 , 100 ml Black liquor,

9:1 dioxine : water solution, Water, Buckner Funnel, Conical

Flask, Sintered Glass Funnel, Soxhlet Extractor, Rotary

evaporator, Centrifuged machine .

Synthesis of black liquor

Firstly black liquor is collected form Ballarsha pulp and paper

industry of chandrapur district in Maharashtra state of India after

collecting of black liquor black liquor is filtered with what man

#4 filter paper over than 7 days approx. Then purified black

liquor is used for lignin extraction and other filtered contain

organic contain is used for other purposed .

Methodology

Black liquor is first filtered through whatman #4 filter paper

after that 0.5 gm EDTA-2Na was added for every 100 ml black

liquor. The liquor were neutralized with 2M H2SO4 until a PH

of approx 6was reached. Then the solution acidified to a PH of 3

and frozen at -200C. After that solution collected in medium

sintered glass funnel and washed with vigorously at 00C. After

air dried solution soxhlet extractor is used for removing the

sulfur and other impurity and solution is purified with 9:1

dioxine water solution and stirred and dioxine is removed by

rotary evaporation and the purified kraft lignin freezed dried and

purified kraft lignin used for the mankind and industrial used [7]

.

Characterization of lignin

FTIR, GCMS and UV-Spectrometer analyses were carried out

for characterization of lignin extraction

FTIR analysis

The FTIR spectra of lignin are shown in fig 1. The peaks of

wave number of 3100 and3000 cm-1

are the C=C-H Asymmetric

stretching vibration and C-C=C Symmetric stretch vibration at

1600 and 1580cm-1

are due to phenol and alcohols. A broad pick

in the range of 1730-1650cm-1

is due to carboxylic acid

formation with lignin extraction. Peaks at wave number 3400-

2400cm-1

are due to Hydrogen – bonded O-H stretching. This

overall stretching done on FTIR analysis, It was confirmed that a

lignin synthesized contain a Aromatic rings, Phenol &Alcohol

carboxylic acid and cellulosic functional group.

GCMS ANALYSIS

For GCMS analysis, approximately 25 gm of lignin powder are

tested in Anacon laboratory Nagpur Maharashtra state India.

And by qualitative analysis following organic compounds are

obtained in GCMS report that is as fallows.

a-Dodecanol, n-Dodecane ,1-Hexadecanol, n-Tetradecane, 10-

Heneicosane, Octatriacontyl pentafluoropropionate, Propanoic

acid, 2-(3-acetoxy-4,4,14-trimethyl androst-8-en-17-yl),

Acetophenone, 4-hydroxy 3,5-dimethoxy, Erucic acid, Palmitic

acid methyl ester, Ethyl iso-allocate, Linoleic acid methyl ester,

Oleic acid methyl ester.

Result and discussion

We make a different product by using lignin. We are using a

different types solvent like Pentane, Di ethyl ether, Ethanol, Di

chloro methane for making of lignin. One of the key for the

lignin market is its application in a wide range of low volume

responsibility applications. Solubility in water is an important

requirement of lignin in these project work. In addition to this,

lignin can be used in a wide range of applications such as in the

manufacture of vanillin, animal feed, dye dispersants,

micronutrients, Fuels, resins, and cleaning chemicals. There is

an increasing demand for lignin in developing countries such as

China, Russia and India due to the country's expanding industrial

base. With present issues of environmental pollution and

increasing awareness of limited resources, there is growing

opportunity in the use of lignin as a substitute for fossil-based

raw materials which are used in the manufacture of a wide range

of products such as plastics, chemical products, and carbon

fibers. FTIR report as follows

for production of lignin extract with pentane and ethanol [12]

.




FTIR report of lignin

Fig2. FTIR spectra of Lignin removal from pentane

Fig3. FTIR spectra of Lignin removal from Ethanol

Fig4. FTIR spectra of Lignin removal from Di ethyl ether

Fig.5. FTIR spectra of Lignin removal from Di chloro

methane

GCMS report of lignin.

Fig 6.GCMS report of lignin extract with pentane

Table 2: Organic compound present in lignin

Table 3: Quantitative FTIR analysis of lignin sample

extracted with different solvent

Peak

No. Compound Name

1 a-Dodecanol

2 n-Dodecane

3 1-Hexadecanol

4 n-Tetradecane

5 10-Heneicosane

6 Octatriacontyl pentafluoropropionate

7 Propanoic acid, 2-(3-acetoxy-4,4,14-trimethyl androst-8-

en-17-yl)

8 Acetophenone, 4-hydroxy 3,5-dimethoxy

9 Erucic acid

10 Palmitic acid methyl ester

11 Ethyl iso-allocate

12 Linoleic acid methyl ester

13 Oleic acid methyl ester




UV-spectrometer analysis of lignin

The solubility of lignin in 1,4-butanediol/water was determined

by UV-spectroscopy 280 nm. The coefficient of absorbance as

shown below was obtained by measuring the absorbance of UV-

spectra

S=A280 / B

Where S is the solubility of lignin in solvent in solvent (g/L),

A280 is the absorbance at wavelength of 280 nm, B is the

coefficient of absorbance.

Also further work reported that Lignin yield, Ash content, Dry

solid content, Sulphur, Iron oxide, Molecular weight distribution

and solubility analysis of lignin which can find out with the help

of BET analyzer, UV-spactrometer and Cone calorimeter.

Conclusion

We successfully developed a facile route to extract lignin from

black liquor for the use of Fuel, Binders, Dispersants, Activated

carbon, Phenol, Carbon fiber. The developed method was proved

to be efficient and simple, which are believed to be attractive for

the lignin extraction processes from black liquor in pulping

industry. Thermoplastic co polyester based on the extracted

lignin was successfully synthesized as an evident for the

utilization of lignin for eco-friendly material development and

also the mankind and other industrial purposed [11]

.

References:- i. Máté Nagy, Georgia institute of technology, ―Biofuels from lignin and novel

biodiesel analysis‖ December , 2009.

ii. Peter Axegård, STFI-Packforsk AB, Research Director, Division Fiber, Pulp

Energy and Chemicals, Stfi-Packforsk, ―The Kraft Pulp Mill As A Biorefinery‖,1999.

iii. Annie ngsunie, ―Characterization of recovered black liquor and isolated lignin from oil palm empty fruit bunch soda pulping for semichemical and

chemical pulps‖, june 2008

iv. Nguyen Dang Luong ,Nguyen Thi Thanh Binh ,Le Dai Duong • Dong Ouk Kim • Dae-Sik Kim ,Seong Hoon Lee , Baek Jin Kim ,Yong Sang Lee, Jae-Do

Nam , ―An eco-friendly and efficient route of lignin extraction from black liquor and a lignin-based copolyester synthesis‖, 879–890, 17 December 2011

v. Henrik wallmo, Martin wimby, Anders Larsson, Mesto Power AB,

Gothenburg, ―Increase production in your recovery boiler with lignin‖,Sweden,2009

vi. Cecilia Johansson, ―Advent of Biorefinery has developed several new sources of lignin‖,Russia,2005

vii. Sajeev John, Jeoju M.Issac, Roselin Alex, International journal of emerging

technology and advanced engineering, ―Mechanical properties of natural rubber composites reinforced with lignin from caryota fibre‖, volume 4,April 2014

viii. Olugbenga Oludayo Oluwasina, Labunmi Lajide, Bodunde Joseph Owolabi, Department of Chemistry, Federal University of Technology, ―Performance of

bonded boards using lignin-based resins‖, Wood Material Science and

Engineering,18 June 2014 ix. Weizhen Zhu, ―Equilibrium of Lignin Precipitation The Effects of pH,

Temperature, Ion Strength and Wood Origins‖, Forest Products and Chemical Engineering Department of Chemical and Biological Engineering, Chalmers

University of Technology, ISSN 1652-943X, 28 march 2013

x. Mojtaba Zahedifar, ―Uses Of Lignin And Hemicellulosic Sugars From

Acidhydrolysed Lignocellulosic Material‖, University of Tehran,2002

xi. N. P. Kutscha and J. R. Gray, ―The potential of lignin research‖, university of maine orono, Technical bulletin 41,March 1970

xii. Parveen kumar, Diane M. Barrett, Michael J. Delwiche and Pieter

Stroeve, Method for pretreatment of lignocellulosic biomass for efficient hydrolysis and biofuel production, Industrial and Engineering Chemistry

Research, 26 March 2009 xiii. Richard Johannes Antonius Gosselink , ―Lignin as a renewable aromatic

resource for the chemical industry‖ , ISBN: 978-94, 7 December 2011

xiv. Elisabeth Sjöholm, ―Kraft Pulps by Size-exclusion Chromatography and Kraft Lignin Samples by Capillary Zone Electrophoresis‖, Royal Institute of

Technology Department of Pulp and Paper Chemistry and Technology, Division of Wood Chemistry, Stockholm, 1999




Review on Nanotoxicology and Its Implications

Sonal S. Kokate, Avantika S. Patil


Anuradha Engineering College, Chikhli (M.S) India


ABSTRACT :- Nanotechnology, which is the one of the most

rapidly emerging fields of the present day, has shown many

promising applications in the field of electronics,

communication, environmental remediation, medicine,

agriculture and health care among others. However, as is seen

with any technological advancement and innovations, there

are several drawbacks associated with this technology, of

which the most apparent aspect of concern is the toxicity

associated with the several types of nanomaterials and

nanoparticles which are being indiscriminately used in several

fields and industries today. This is felt more so in areas

involving nanomedicine, pharmaceuticals, cosmoceuticals, etc.

which involve direct interaction of these particles with human

and animal cells, tissues and organs. In case of their use in

applications which do not directly affect human health and

welfare, their disposal after use presents a more severe

problem. There are no regulatory authorities which look into

the toxicological aspects of these materials currently and

several of thestatutory bodies which deal with toxicity

assessment issues do not consider a material as different unless

their composition differs. Hence is a bulk material of a

particular composition has been traditionally established as

non toxic, then the corresponding nanomaterial is also

considered safe today. It is yet to be strongly realized that

reduction in particle size lead to alteration in properties of

many materials, and this may have many adverse impacts

compared to bulk material of the same composition. The

different characteristics of nanoparticles such as size, shape,

surface charge, chemical properties, solubility and degree of

agglomeration will determine their effects on biological

systems and human health, and the likelihood of respiratory

hazards. There are a number of new studies about the potential

occupational and environmental effects of nanoparticles and

general precautionary measures are now fully justified.

Keyword:-Nanomaterials, remediation, nanomedicine,

cosmoceuticals, Environmental, Toxicitity INTRODUCTION

The origin of the term „„nanotechnology‟‟ is associated with the

Greek word „„nano,‟‟ which means „dwarf.‟ There has been a

dramatic growth of the nanotechnology industry in the recent

times and nanomaterials are being developed at a rapid rate for

use in innumerable industries. From the physical, chemical and

material science perspective, the improvement of new as well as

established products, with the aid of nanomaterials is very

exciting for a given particle-type, as one scales down to the "10-

9" level, the properties change miraculously, sometimes for

better and at times for worse. For the same mass / volume of a

material, when the number of particles increases, the surface

area proportionately increases and quantum effects also start

dominating. These, in turn, are largely responsible for the

modified properties. For example, "titanium dioxide" particles

lose their white color, seen in their bulk form and convert to

colorless at size ranges below "50 nm" [1].

The large surface area of nanomaterials bestows them with

unusual catalytic properties. This promises to improve their

propellant and fuel catalysis properties, their applications in

automotive catalytic converters and also help in environmental

remediation, where they react with pollutants, for easy

detoxification. However at the same time, the properties of high

reactivity may cause unwanted reactions and hence risks of

production of toxic chemicals or gases which could have serious

repercussions on the environment. Thus may lead to increased

concentration of harmful chemicals causing profound

healthissues and leading also to "genotoxicity" [2].

Nanoparticles are reported to be toxic in general to aquatic life.

However coating them with natural and effluent organic matter

may decrease their toxicity. This has been confirmed with

quantum dots. The hydrophobic nature of these organic matter

may be responsible for mitigation of the toxicity of these

materials [3] Nanoparticles and nano devices are being formed

intentionally, accidentally and manufactured by different

methods and many times, released into the environment directly

or indirectly without any safety tests. These materials are known

to induce cytotoxicity by initiating stress and eliciting

inflammatory responses at the molecular and atomic level.

Nanomaterials can travel more freely and easily as compared to

their larger counterparts and thereby can be more toxic than

larger materials. They can enter the human body through water,

air and skin contact. They can then access the internal body

tissues and organs causing damages which can be even fatal [4].

It has been reported that the smallest nanoparticles show

profound reactivity and exhibit the high levels of vascular

thrombosis as well as the low extravasation. This is observed in

a study wherein a lactic acid based nanoparticle encapsulated a

drug (meso-tetra (carboxyphenyl) porphyrin) with size range

between "121 to 343 nm". The research suggested that large

nanoparticles are more rapidly eliminated from the bloodstream

and are thus effective within a short period of time and with less

harmful effects [5]. Metal based nanoparticles (Ag, Au, and Cu)

are also known to induce toxicity in mammalian cells by

interacting with proteins and enzymes after entering the body.

This imbalances the natural antioxidant defense mechanism,

leading to the generation of reactive oxygen species (ros). The

consequence is the initiation of an inflammatory responses,

along with the perturbation and sometimes even destruction of

the mitochondria. This may in turn lead to cell apoptosis and / or

necrosis. Nanoparticles, which are added to sunscreens to protect

against the uv light, may accumulate on the surface of the skin





and in the stratum corneum among keratinized cells, over a

period of time. This may normally not lead to toxicity, but if the

skin is compromised due to burns and injury, there are chances

of these particles entering the body and causing unfavorable

effects .Sunscreens and other aesthetic products contain either

titanium dioxide or zinc oxide nanoparticles. The photoactive

surfaces of the nanoparticles are susceptible to the formation of

ros. Smaller particles with their greater surface area to volume

ratio have high chemical reactivity as well as biological activity.

The greater chemical reactivity results in large production of ros

which poses several health issues. Ros production has been

reported to occur in a different and diverse range of

nanomaterials which include carbon nanotubes, fullerenes or

bucky balls and nano sized metal oxides. Ros and free radical

production is one of the primary mechanisms of nanoparticle

toxicity which leads to oxidative stress, inflammation, cell injury

and subsequent damage to membranes, protein, cell organelles

and dna. The latter culminates in different types of mutations

which in turn causes production of structural damage to the

protein encoded by it. The protein thus produced can either

malfunction, or be non-functional, causing metabolic blocks in

important metabolic pathways. This catabolic or anabolic block,

can lead to the accumulation of a by-product or an intermediate

which again may lead to certain consequences with varying

degree of effects depending on the type of substance that gets

accumulated. For example, if a nanoparticle reacts with or

damages an enzyme associated with degradation of

phenylalanine making it non-functional, then there may be an

accumulation of a specific intermediate and the deficiency of a

reactant for the next reaction in the chain, hence affecting the

entire phenylalanine metabolism, leading to several metabolic

disorders.

A NEED FOR NANOTOXICOLOGY The branch of

nanotoxicology deals with the study relating to the toxicity of

the nano materials, as it is imperative to know that how toxic a

nano material is before using it for various applications. The

effects and impacts on human health also needs to be assessed

accordingly. The field of nanotoxicology has been growing fast,

and literature reviews show that the results are not only

numerous but also exciting. The International Council on

Nanotechnology (ICON) has formed a database of all the

publications of several nanomaterials along with their impact on

environmental health and safety. This emphasizes on the

interesting trends associated with the field of nanotoxicology[8].

Two consecutive articles were published in 1990, in the Journal

of Aerosol Science analyzing whether inhaled particles, which

are lesser than 100 nm in dia elicits a greater pulmonary

response than the one which is normally expected. When studied

on a mass for mass basis, titanium di oxide and aluminium oxide

particles, which were of the nanometer scale, did elicit a

significantly greater inflammatory response in the lungs of rats

when compared with larger particles of the same chemical

composition. These two studies challenged the long held

presumption that response to a particular type of particle was

dependent only on the chemical composition and not on the size.

The unusual biological activity related with nanometer-scale

materials was noticed for the first time. It was concluded here

that phagocytosis of particles in alveoli, may impede

translocation of particles into the interstitial space. However if

the alveolar macrophages die or dysfunction the translocation

from alveoli into interstitium may be facilitated. "0.02-0.03 nm"

dia particles may penetrate more easily than particles of" 0.2-0.5

nm". Small particles may form aggregates. Their aerodynamic

size is a factor which controls the deposition in the airways.

Deagglomeration may take place after deposition. For primary

particle sizes raging from "0.02- 0.03 nm", deagglomeration may

affect translocation of the particles more than for aggregates

which may consist of larger particles. The ever increasing

manufacture and use of nanomaterial, specifically in the form of

nanoparticles (NPs) of spherical and fibre-like shapes, for

diverse industrial and biomedical applications and other useful

products is on a proportional rise. But we have concerns about

their safety for human health and the environment [9].

TOXICITY TESTING OF NANOMATERIALS

The greatest challenge faced in the field of Nano toxicology

today is the identification as well as the evaluation of the

deleterious effect of various engineered nanomaterials with their

diverse physiochemical properties, which are constantly being

produced and introduced for versatile applications. It is not very

easy to find the hazard denominations of nanoparticles due to

various reasons. In vitro test systems have a lot of limitations in

hazard identification of nanoparticles because of their highly

diverse and versatile physiochemical properties. On the other

hand, conducting in vivo studies on animal models for every new

nanomaterial manufactured is highly impractical. Thus, short

term in vivo studies in rodents, and in vivo and in vitro

investigation, including high throughput proteomics and

genomics studies, to identify toxic pathways of well

characterized reference materials of some class or subclass of

nanomaterials are carried out. This data can be now used as a

reference for any newly manufactured nanomaterial. The hazard

potential of the new nanomaterial can be assessed by only

conducting in vitro high throughput studies and this data can be

compared with reference material of related class or subclass of

nanomaterial[10].

IMMUNOTOXICITY The pharmaceutical industry is researching a number of drugs

and diagnostic procedures based on nanoparticles. Efforts are on

to develop target based drugs which work on the nanoscale and

affect only the cells/organs associated with the disease.

Understanding and evaluating the immune response of nanoscale

drugs is posing a major challenge for scientists. Assessing the

immunotoxicity of nanoparticles, functionalized with small

molecules is regulated by International Conference for

Harmonization"(ICH)-S8" guidelines. During the evaluation

process, two parameters are given highest priority First is the

data of standard toxicity testing evaluated in the organ of

immune system in specific histopathology specimens and also

the changes in white blood cell population. The second factor is

the pharmacological action of the drug. The nanoparticles are

tested for their biodegradable nature and their routes of

elimination from the body [11].




NANOPARTICLES AND THEIR TOXICITY CARBON NANOTUBES (CNT)

Fig.1 Carbon nanotube (CNT)

These are hollow nanostructures derived by rolling graphene

sheets. Research CNT has exploded during the last two decades

after Ijima discovered them in 1991. It can be said safely that

CNT is one of the most widely researched and used

nanomaterial today in electronic and semiconductor industries.

Their health care uses are also being aggressively explored.

However, several workers have reported CNT to be toxic to

mammalian cells. Exposing Wistar rats to multiwalled CNT by

inhalation leads to lesion formation at the upper respiratory tract

and inflammatory changes in the lower tract, at concentrations

"0.03mg/m3". This stated value was put down as no-observed-

adverse -effect-level [12]. Liu et al have reported the foreign

tissue body response caused in the lungs by CNT inhalation and

the distribution of these particles has been observed in vivo in

the target organs along with their time and dose effects. A series

of multiple lesions in the lung tissues is seen to develop in a time

and dose dependent manner, suggesting potential occupational

hazard for workers handling this material [13]. It is not only the

CNT as such, which may lead to deleterious changes at the

organ and cellular level, but the materials and polymers which

are employed to coat and functionalize it may also in turn be

hazardous. CNT, with its high aspect ratio being hydrophobic, it

is quite common to use dispersing agents to overcome its water

repelling character for various biological applications. In such

instances, the dispersing agent may also contribute to the toxic

effects seen in live systems. The effects of such agents like THF,

Triton -X, SDS, etc has been studied on model organisms like

Pseudokirchneriellasubcapitataand Ceriodaphniadubia. The

results certify the variability of the nature of these reagents,

nanomaterials and concentrations in determining the final

toxicity of the overall compound to the living systems [14].

BUCKY BALLS OR FULLERENES

Fig.1 Bulky ball diagram in 3d form

Traditionally, the structure of this nanomaterial has revolved

around a"60 carbon atom "spherical closed cage. However to

suit different applications, its molecular makeup has been

modified and surface chemistry has been altered to provide

versatility to its structure. Further, other small molecules have

also been physically entrapped in its cage to serve diverse

purposes in nanomedicine and other non health care

applications. Its physicochemical characteristics as well the

biological mechanisms which drive the toxicity of fullerenes has

been extensively discussed in the literature and it has been

reported that fullerene toxicity involves genotoxic, oxidative and

cytotoxic responses at cellular level[15]

METAL NANOPARTICLES Nobel and other transition metal nanoparticles have been

extensively employed in medical, medicinal, pharmaceutical,

cosmoceutical and electronic fields. Silver, gold, platinum,

aluminium, zinc, copper and iron nanoparticles, to name a few,

have been used widely applied for diverse applications. The

toxicity associated with these has been reported by several

authors. Aluminium oxide nanoparticles of size "30 and 40 nm"

were seen to cause dose and size dependent genotoxicityin vivo

as compared to bulk material of the same element, in Wistar rats.

Here, micronuclear test and comet assay were used to determine

the % of tail DNA and micronuclei migration in peripheral rat

blood cells, which was taken as a measure of genotoxicity [16].

Aluminium nanoparticles are also implicated in development of

Alzheimer‟s disease although this aspect has not been proved as

yet. It would be relevant to state here that aluminum oxide

nanoparticles are used widely in the manufacture of

antiperspirant and deodorants by several cosmetic manufacturing

companies. Cadmium ions form components of quantum dots

which are utilized for imaging in nanomedicine. The effect of

cadmium ions on caspase 3, mitochondrial membrane potential

and on oxidative stress markers in murine thermocytes has

proved deleterious. DNA damage and apoptogenic potential of

these cells were observed byinternucleosomal fragmentation on

histone and their subsequent detection by ELISA [17].Copper

nanoparticles form part of formulations for the manufacture of

lipsticks where there is a danger of ingesting them, thus

facilitating their entry into the gastrointestinal tract. Excess




copper in the digestive system is known to induce metabolic

alkalosis. Lei et al have proposed an integrated metabolomic

pathway which facilitates in vivo screening for nanotoxicity of

nanomaterials. Copper nanoparticles screened this way in

multiple organs for several biochemical parameters showed the

induction of hepato and nephrotoxicity at dosages of about

"200mg/kg/day," when rats were exposed for five days[18].

Nanocopper suspensions were also found to be toxic to aquatic

biota and the toxicity operates through different mechanisms

which are in turn dependent of the type of organism and

prevailing concentrations [19]. It has been proposed that the size

dependent high reactivity of nanocopper, compared to its ionic

form, may be responsible for inducing high toxicity as evidenced

by in vivo and in vitro tests. The pathological examination of

tissues and biochemical assays attest this fact. The nano copper

ions may themselves per se may not be toxic but may induce

copper ion overload culminating in metabolic alkalosis, as

nanosized copper particles consume hydrogen ions in abdomen

more rapidly than their micron sized particles [20]. These results

indicate the imperative need to relook at the compositional

characteristics of cosmetic products and ensure proper in vitro

and in vivo trials after suitable ethical clearance so that

nanocopper levels are kept well below toxicity standards in

products which are released into market. Gold nanoparticles may

prove to be ideal for studying the size-dependent biological

response of systems to nanoparticles due to their excellent

biocompatibility. Their size can be controlled accurately during

the process of chemical synthesis. The toxicity of gold

nanoparticles in vivohas been reported. When naked particles,

ranging from "3 to 100 nm" intraperitoneally injected into mice

at a dose of 8 mg/kg/week, the particles in the sizes of"3, 5, 50,

and 100 nm" did not elicit any damaging effects. However, the

particles in the size range of"8 to 37 nm" elicited a severe

sickness response in mice. They also exhibited fatigue and

weight less along with loss of appetite and change of fur color. A

number of mice died also within "21 days" [21]. Iron

nanoparticles are used in biomedical devices due to their

magnetic property. A number of biomimetic systems have also

been developed used these particles. However, it has been shown

that intracellular delivery of even small concentrations of iron

nanoparticles may adversely affect cell structure and function.

Specifically it is seen that these particles impair the ability of

"PC12 cells" to differentiate in response to nerve growth factor

[22].Potential lung and cumulative toxicity of iron nanoparticles

have also been reported by Zhu et al [23]. Toxic response of

nickel nanoparticles (Ni NPs) has been observed in lung

epithelial A549 cells when treated at concentrations of"0, 1, 2, 5,

10 and 25 μg/ml for 24h and 48h". Some of the toxicity end

points which were studied included membrane leakage of lactate

dehydrogenase (LDH assay), mitochondrial function (MTT

assay), production of reactive oxygen species (ROS), levels of

reduced glutathione (GSH), caspase-3 activity and peroxidation

of membrane lipids (LPO). Reduction of mitochondrial function

and LDH leakage were seen along with induction of oxidative

stress in a manner which was dose and time-dependent. This was

indicated through the production of ROS and LPO

simultaneously with the depletion of GSH. The activity of the

enzyme caspase-3 which is taken as an indicator of apoptosis

was also measured as appreciably high with time in treated cells

and with Ni NPs dosage[24]. Silver nanoparticles find extensive

applications in the pharmaceutical industries and used in the

treatment of burn injuries. However it has been reported that

these particles may be toxic to organs and may induce

inflammation as observed in spleen of rats [25]. It has been

inferred that in case of titanium toxicity, both crystal structure

and size contribute to the cytotoxicity and the mechanism of cell

death depends on the crystal structure. The anatase structure

induces necrosis and the rutile structure leads to the production

of ROS which in turn initiates apoptosis [26]. Titanium di oxide

particles have been found to be toxic to erythrocytes and when

the latter is treated with nano TiO2, it is found to undergo

abnormalsedimentation. Haemagglutination was also seen along

with dose dependent haemolysis. These changes were not seen

when the cells were treated with micro TiO2 [27]. The effect of

particle agglomeration as well as serum protein adsorption on

influencing the toxicity of amorphous silica nanoparticles has

been reported on a eukaryotic cell model. It has been strongly

inferred that the observed that the toxicity of silica nanoparticles

here is a consequence of physiochemical properties of silica

nanoparticles and not related to silica material as such[28].

NANOTOXICITY RELATED TO BLOOD The developments in nanotechnology have lead to the

indiscriminate production of nanoparticles which accumulates in

the air, water and soil to endanger human and animal health.

Certain methods have been developed to assess the genotoxicity

of such nanoparticles. For example, a study carried out to assess

the toxicity of Aluminum dioxide particles of different sizes,

viz., "30nm and 40nm". The characterization was of these

particles was carried out using modern analytical techniques like

TEM, Doppler velocimetry and light scattering methods. The

micronucleus test and comet assay suggests micronuclei and tail

migration respectively in rat peripheral blood cells and exposure

to the given nanoparticles at varying concentrations. Genotoxic

assay was done in both the male as well as female mice. The

micronuclear test revealed a dose dependent increase in the

frequency of micronuclei, Similarly, the tail DNA showed an

increase with increase in the dosage. The plasma mass

spectrometry studies showed that the penetration of the

nanoparticles into the different organs depended on the size of

nanoparticles as the urine and feces samples where analyzed. It

was concluded that the genotoxicityin-vivo was dose and size

dependent [16].

EFFECTS ON EMBRYONIC BLOOD CELLS Nanotoxicology correlates the risks of nanoparticle exposure to

the organisms. The focus and concern needs to be is directed

towards embryonic blood vessels as they are more vulnerable as

compared to the mature blood vessels. For this reason the study

of nanoparticles needs to be carried out at in-situ level, as such

properties are wholly dependent on the environmental factors.

One such study has examined the dynamics of quantum dots and

polystyrene nanospheres when introduced into the blood vessels

of chicken embryos chorioallantoic membrane. Subsequently,

fluorescence correlation spectroscopy is used to determine the

concentrations and hydrodynamic radii of the injected

nanoparticles[29].




Nanomaterials such as nanotubes, nanowires, fullerene

derivatives and quantum dots are currently being used as new

types of tools in life sciences and also in health technology. But

the geno toxic effect of these have not been clearly established.

A study on the cytotoxic effect of these materials on the male

germ line in vitro shows no significant effect for the

nanomaterials tested except for silver and molybdenum trioxide

nanoparticles. Here too the toxicity was found to be very less

[30]. Nano materials like carbon nanotubes also cause cancer

related to lungs. Experiments performed on mice shows that

CNT can aggravate the inflammation caused by bacterial

lipopolysaccharide (LPS) in rats and lead to the development of

pulmonary fibrosis [31] Nanoparticles are also engineered for

special purposes like targeted drug delivery, imaging and

diagnostic applications etc. and these may have toxic effects too

as they tend to accumulate in the pulmonary arteries and exert

adverse effects on pulmonary structure and function. The

pulmonary applications and lung toxicity related to engineered

nanoparticles has been reviewed [34].It has been shown that

pulmonary nanoparticle exposure impairs dilation of systemic

arterioles. It also affects other endothelium depended responses

because nanoparticle exposure enhances microvascular oxidative

stress by~60%, and also causes a fourfold increase in nitrosative

stress. It decreases the NO production too. In combination with

microvascular dysfunction, nanoparticle exposure reduces NO

bioavailability.

Conclusion Nanotechnology may be useful in the development of a large

number of tools for the advancement in the understanding of the

various chemical, physical and biological phenomenon.

However, its use needs to be scrutinized for deleterious effects

thoroughly before applying them for the service of mankin

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108-114




Preparation of Fire Retardant Surface Using Lignin

Sushama R. Gawai*, Shrikant nanwatkar, Jitendra K. Shinde

Department of Chemical Engineering,

Anuradha Engineering Collge, Chikhli, Buldhana (M.S) India.


Abstract : Fire retardant is prepared from urea, formaldehyde

and lignin for the application of Urea formaldehyde resins was

applied in same concentration by different method like drying.

Retardancy of the treated wood was compared with in terms of

temperature generation.. Beside the flammability results,

temperature generation curve, cellulose-resin reaction

mechanism, thermogravimetry (TG) and FTIR analysis of the

control, treated wood were also compared and commented

condensation polymerization at temperature 90-100ºC and PH

range (7.5-8) was used for the reaction between urea and

formaldehyde to produce polymeric adhesive. UF of resorcinol

are used as bonding catalyst (an adhesion promoter) for UF-

lignin solid waste fibers system as curing binary system of

adhesive for wood/wood laminate. Mechanical properties such

as impact strength, bending test have been measured .The

result shows that all these properties are increased when

percentage of bonding catalyst material is increased for

adhesive-fiber system at different arrangement for solid waste

lignin use as a fire retardant.

Keywords:: Fire retardant, urea, formaldehyde, lignin,

thermogravimetry.

INTRODUCTION

Wood, which mainly consists of cellulose, lignin and

hemicelluloses, catches fire easily and burns primarily because

the cellulose and hemicelluloses polymer undergo pyrolitic and

oxidative reaction with increasing temperature, giving off

flammable gases. The lignin component being more thermally

stable contributes more to char formation than does cellulose and

hemicelluloses [2]

. Increased char formation reduces flammable

gas formation and help insulate wood from further thermal

degradation. Vigorously with flame. As wood is used in

furniture, home decoration and building materials, it will be

essential to make wood products fire resistant/retardant. It is

well known that material made of wood can be treated with

compounds containing urea formaldehyde resin; lignin, HMTA

and resorcinol to increased their fire resistance and accelerate the

formation of a carbonized layer on the material. Wood is an

extensively used material and is present in many places in our

everyday lives [6]

. Not only is wood an integral part of most

structures, especially in India, but is also the main source of

furnishings found in homes, schools, and offices around the

world. As a result, up to ninety percent of any given structure

may contain some form of wood. The often inevitable hazards of

fire make wood a very desirable material for further

investigation [5]

.

Fire retardant method

Chemical action:

This method is in general targeted at interfering with radical

reaction which take place during gas phase and aims to protect

internal material from heating during char creation solid phase.

Physical action:

This method is based on decreasing temperature by endothermic

reaction, reducing the fire distribution by fluxing oxygen with

non combustible gases and promoting the formation of

protective impenetrable surface layer.

Fire retardant theories

Table 1.Fire retardant theories

Sr

no.

Theories Mechanism

1 Barrier theories These theory posit the formation of

glassy layer which impedes the

liberation of volatile gases,

preventing oxygen from reaching the

substrate and protecting the material

surface from the influence of elevated

temperature.

2 Thermal theories Retardant additives enhance the

thermal conductivity of the organic

material and adsorb energy, since an

endothermic reaction is triggered

during their decomposition.

3 Theory of non

combustible gas

In this case mechanism works in the

vapor phase and retardant surface

additives decompose and emit non-

flammable gases available for

reaction.

4 Free radical

theories

These theories operate in the vapor

phase as inhibitors by interrupting the

chain propagation mechanism of

flame by releasing free radicals.

5 Theory of

volatile

reduction

These theories are based on the use of

fire retardant surface chemicals to

reduce the temperature required for

pyrolysis.

Material

1- Urea commercial (NH2CONH2), melting at 35ºC locally

available.

2- Formaldehyde commercially type (37%) (CH2O) of density

1-0.85 at 20ºC.

3- Resorcinol (C6H4(OH)2) , 99% melting at 111ºC ,and density

1.272 g/cm3.

4- Solid waste lignin brown color, and different arrangement of

wood.

Methodology





Preparation of urea-formaldehyde resins:

30 gm of formaldehyde and 20 gm of urea are charged with

agitation in 1 lit water solution, three naked flask equipped with

stirrer, reflux condenser and thermometer. The urea was

dissolved at the temperature range between 20-250c and PH was

adjusted with the range 7.5-8 using 5 N formic acid and sodium

hydroxide. The mixture was heated at the temperature between

90-1000c with vigorous agitation until the reaction was

completed for 2 hrs. The sample was left to cool at room

temperature before measuring PH and viscosity. The PH was

controlled to be 7.5-8 and viscosity was checked every 10 min.

and to obtained a resin is known as urea formaldehyde resin [9]

.

Preparation of composite structures:

The final product resin was treated with a

hexamethylenetetramine (7gm) and various mass ratio adhesion-

promoter resorcinol 12-30 gm/urea formaldehyde to obtained

solid cured product mixed with different types of lignin with a

same proportion and apply as a coating on wood surface and

dried in sun light after drying the wood surface deeps in 9:1

H2SO4 water solution for 3 days to better strength [11]

.

Characterization of fire retardant surface

Impact test:

The capacity of material to absorb energy and hence to predict

failure load under dynamic condition. Izod and Charpy impact

instrument was used for this test.

1. Impact test Sr.

no.

Fire retardant

wood Material with different

types of lignin

Size

(l×b×w)

Izod Impact

value (Energy

absorbed

in joules)

Charpy Impact

value (Energy

absorbed

in joules)

1 Wood 1 10×10×75 5 8

2 Wood 2 10×10×75 5.5 9

3 Wood 3 10×10×75 6 10

4 Wood 4 10×10×75 7.5 9

5 Wood 5 10×10×75 8 18

Graph 1: Izod impact value table

Three point bending test: Three point bending tester was used to determine the resistance

to distortion. This test was carried out according to (ASTM-D-

790) test.

Chemical resistance (Sweling degree):

This type of test was achieved by soaking all composite samples

in both moisture (100% H2O) and acidic solutions (10% H2SO4 )

for 7 days at 50 ºC to estimate the change in weight.

Result and discussion

In this production of different creation which is obtained from

the different types of lignin with mixed with different chemicals.

We are also plan to prepare different types of fire retardant

surface from different lignin which also give better effect in

daily mankind use and industrial use.

Properties to be checked for the fire retardant surface

Pyrolysis test

The main pyrolysis of wood would start at temperature above

2500c and finish below 500

0c. Cellulose, the main component of

wood, generates volatiles in the temperature range from 310 to

3800c and at 500

0c wood is completely burned and formation of

char creates.

Without pyrolysis

After pyrolysis

Burning test

We take different types of fire retardant wood material with

different types of lignin for burning test. When the kerosene is

spray on normal wood surface, it ignited easily and burned to

completion into ashes. On the contrary, with same procedure the

kerosene is spray on fire retardant wood surface it ignited easily

but not completely burned and to form a char layer on the

surface layer.




Graph 2: Fire retardant surface from Acetone lignin

Graph 3: Fire retardant surface from Hexane lignin

Graph 4. Fire retardant surface using Acetone Hexane and

lignin

Graph 5: Fire retardant surface using Acetone Hexane

Water and lignin

Graph 6: Fire retardant surface using Sodium

lignosulfonate

Future scope

The flame retardant treatment significantly improves the fire

safety of wood products by reducing its heat contribution to a

fire. For application where higher level of fire safety is desirable

or necessary, fire-retardant-treated wood products provide a

viable alternative to traditional non-combustible materials. Fire

retardant surface are also used for to avoid the higher flame. Fire

retardant surface also used for the Electronic and electrical

devices, Building and construction material, Furniture and

transportation [12]

.

Reference:- i. TarekH.M, Raghad U. Abass, Falak O. Abas Falak O. Abas, “Use of

solid waste lignin in the reinforcement of UF-R system” National journal of chemistry, vol 23,327-334,2006.

ii. S. Basak*, Kartick. K. Samanta, S. K. Chattopadhyay, R. Narkar, M.

Bhowmick , S. Das & A. H. Saikh, “Fire Retardant and Mosquito Repellent Jute Fabric Treated with Thio-urea”, Chemical and Biochemical processing division

Central Institute for Research on Cotton Technology, jan-feb 2014,273-280.

iii. Lucy Arianie, Ahmad Mulyadi, Wan Arif Abidin, Indra Johansyah Alam, and Afghani Jayuska, “The Inafluence of Urea Modified Lignin from

Palm Empty Bunch toward Vegetative Aspects of Lettuce Leaves”, International

Journal of Chemical Engineering and Applications, Vol. 4, No. 6, December 2013.

iv. Karolos Markesinis, IIias katsampas, “Innovative and competitive

chemical technology for production of fire retardant wood based panels”, 55131,2005.

v. Marina Nikolaeva, timo karki, “A review of fire retardant processes

and chemistry, with discussion of the case of wood-plastic composites”, Baltic forestry, 17(2), 314-326, 2011.

vi. William G. Gosz, Hopkinton, “Fire retardant composition”, united

state patent,(5,064,710), Nov. 12, 1991 . vii. P.R. Hornsby, “The Application of Fire-Retardant Fillers for Use in

Textile Barrier Materials”, http://www.springer.com/978-3-540-71917-5, 2007.

viii. Flame Retardant Research and Materials Fire Testing, University of Dayton research institute, 2013.

ix. Certified Applicators & Manufacturers of Flame Retardant Saturants

& Coating, PH 661/295-3473 (Fire), 28298 Constellation Rd. Valencia, CA 91355.

x. Flame Retardant Basics, North American Flame Retardant Alliance,

2005-2015. xi. Falak O. Abas, Raghad U. Abass “Use of solid waste lignin in the

reinforcement of UF-R system”, Environmental Research centre, University of

Babylon, 4 Feb 2006. xii. United state environmental protection association, “Flame retardant

surface in printed circuit boards”, November 7, 2008.

xiii. vorgelegt von, Diplom-Ingenieur, Henrik Seefeldt, aus Berlin, “Flame retardant surface of wood-plastic composites”, ISSN 1613-4249, Berlin 2012.

http://www.springer.com/978-3-540-71917-5




Indian Rural Energy: Pyrolysis of Cotton stalk in Swept Tubular Pyrolyzer

P. R. Tayade1*, S. H. Amley

1, A. P. Pardey

1, S. A. Dharaskar

1, V. S. Sapkal

2, R. S. Sapkal

2,

1Department of Chemical Engineering,

Jawaharlal Darda Institute of Engg. & Technology, Lohara MIDC, Yavatmal-445001, 2University Department of Chemical Technology,

Sant Gadge Baba Amravati University, Amravati-444602 M.S., India

*Corresponding Email: [email protected]

Abstract— This study was intended to observe the feasibility of

developed swept tubular pyrolyzer for the production of bio-oil

by pyrolysis of biomass such as cotton stalks. To study pyrolysis

parameter, a 628 cm3 (ID 4 cm) swept tubular batch pyrolyzer

was developed itself in our workshop. The effect of

temperature (400 0C to 700

0C), particle size (0.3 mm, 0.35 mm,

0.425 mm, 1 mm) and time of pyrolysis of cotton stalk on the

amount of bio-oil and bio char were investigated at

atmospheric pressure condition with a heating rate of 5 to 6 0C/min and under the constant mild flow of N2. The designed

swept pyrolyzer has given the 42 % bio-oil yield and

temperature and time of pyrolysis of cotton stalk showed

pronounced effect on the yield of bio-oil, whereas particle size

did not shown significant influence on the yield of bio-oil.

Keywords: Swept Tubular Pyrolyzer, Biomass; Cotton

Stalk; Pyrolysis; Bio-oil

I. Int roduct ion

The present global energy scenario is facing the big hurdles of

energy crises, global warming and the environmental pollution,

all resulted because of practice of existing fossil fuels. The

extensive use of fossil fuels to meet the world‟s energy demand

is exposed by increasing concentrations of CO2 in the

atmosphere and concerns over global warming [1, 2]. It is

inevitable to find out the new source of energy to minimize these

problems. The present environmental conditions and energy

crises has created greater impact to rethink on the energy sources

and their effects on the environment. Biomass can be the new

hope in the energy sector to deliver the world energy demand

and cleanliness of energy by maintaining CO2 neutral cycle,

presently estimated to contribute the order of 10–14% of the

world‟s energy supply [3]. The share of renewables in India‟s

energy mix, combining biomass, hydro and other renewables,

was approximately 26% in 2009, of which biomass accounted

for the largest share. Biomass is a third primary energy in India,

produces 450-500 million tones of biomass per year [4],

predominantly used in rural household for cooking and water

heating and delivers most energy for domestic use (Rural 90%

and Urban 40 %) [5, 6]. Among all of the biomasses in India,

cotton stalk biomass contributes 4 % of total amount of residue

having current annual production near about 11.8 metric tons

[7]. Table 1 shows the area wise availability of cotton stalks in

India as per estimate of cotton advisory board.

A possible way to transform this raw biomass into a more

valuable energy source is pyrolysis. It is a thermo chemical

decomposition of organic material at elevated temperatures in

the absence of oxygen. Pyrolysis typically occurs under pressure

and at operating temperatures above 430 °C.

Table 1: Status of area wise availability of cotton stalks in India

Zones States Area(million

ha)

Availability

of Stalks

(million

tonnes)

Northern(Area

1.471 m.ha,

Stalks

4.06 mt)

Haryana

Rajasthan

Punjab

0.533

0.350

0.588

1.60

0.70

1.76

Central(Area

6.205 m.ha,

Stalks

14.86 mt)

Madhya

Pradesh

Gujarat

Maharashtra

Orissa

0.630

2.390

3.124

0.060

1.26

7.17

6.24

0.12

Southern(Area

1.471 m.ha,

Stalks

3.41 mt)

Andhra

Pradesh

Tamil Nadu

Karnataka

Others

0.962

0.133

0.370

0.035

2.4

0.27

0.74

0.07

Total 9.175 22.33

Source: Cotton Advisory Board, 2007

The advantage of pyrolysis of agricultural biomass is the

biochar, which can increase the fertility value of soil at the same

time it helps for the sequestration of CO2 from the environment

[8-13]. Currently, lot of research work has been done for the

production of bio-oil through slow and fast pyrolysis of different

biomasses in fixed bed pyrolyzer, mainly wood, wheat straw,

bagasse, rice husk, cotton stalk, maize stalks and pigeon pea [14-

16]. The main aim of this work was to design the efficient

Pyrolyzer to carry out the slow pyrolysis of different biomasses

and to investigate the effect of the slow pyrolysis conditions

such as pyrolysis temperature, time of pyrolysis and particle size

of cotton stalks on the yield of bio-oil.


2.1 Raw Material – (cotton stalk)

Cotton stalk was used as a raw biomass material, obtained

directly from the farming region of Yavatmal district located in

India. The stalks of cotton were first dried over night in the dryer

at 100 0C to remove the moisture content and then it made into

small pieces by a cutter. The fine particles of cotton stalks was

done in the small home made mixer and separated into different





fractions (0.3 mm, 0.35 mm, 0.425 mm, 1 mm) by standard

sieves. The proximate analysis of cotton stalks was done by

ASTM standards given in Table 2.

Table 2: Proximate and elemental Analysis of Cotton stalks

Biomass Proximate Analysis Elemental Analysis

Cotton

Stalk

%Volatile

Matter

% Fixed

Carbon

content

% Total

Ash

content

%Moistur

e content % C % H % N % O

36.94 51.77 8.21 3.08 50.55 4.90

1.12

44.07

2.2 Experimental Procedure

The pyrolysis of cotton stalks was carried out in well swept

tubular pyrolyzer fabricated itself in our workshop. It comprised

50 cm long stainless steel tube with 4 cm id flanged at both ends,

the outer side of this pyrolyzer wrapped with two 550 W ceramic

band heaters purchased from HBS Technology. The pyrolyzer

tube and both heaters were insulated with thick layer of ceramic

wool. The temperature was read by Pt-100 sensor inserted up to

the centre of pyrolyzer. One end of this pyrolyzer was attached

for N2 inlet with needle valve to control the flow rate of N2 and

other end for product gases with needle valve to maintain the

pressure inside the pyrolyzer as shown in Figure 1. All these

experimental details can be cleared from the photo of

experimental set-up shown in Figure 2. The product gases were

condensed in two condensers at 1 to 2 0C.

Figure 1.Diagrammatic representation of experimental set-up for

the pyrolysis of cotton stalk

Figure 2. Photo of Experimental Set-up


The pyrolysis of cotton stalk was studied to understand the

effects of different operating conditions such as particle size of

cotton stalk, temperature of pyrolysis, pressure inside the

pyrolyzer. Following are the effects of different operating

conditions on the pyrolysis of cotton stalk.

3.1 Biomass Characteristics

Proximate analysis of cotton stalk (wt. %, dry basis) gave 3.08%

moisture, 36.94% volatile matter, 8.21% ash and 51.77% fixed

carbon. Elemental analysis (wt. %, db) gave 50.55% C, 4.90%

H, 1.12% N and 44.07% O. From this elemental analysis it can

be inferred that the total organic matter (C, H, O) of the cotton

stalk is about 98.71% wt./wt. and the heating value is 15.96

MJ/kg. The heat content of cotton stalk was calculated from the

following equation:

Q = 146.58C + 568.78H – 51.53O

where Q is the gross heat content (Btu lb-1

) and C, H, and O are

the amount of carbon,

hydrogen and oxygen (wt.%), respectively [17].

3.2 Effect of Temperature on the yield of Bio-oil

The effect of temperature on the yield of bio-oil was studied in

temperature range of 400 to 700 0C. All these experiments was

done for 25 gm of biomass (cotton stalks) and at atmospheric

pressure under the constant flow of N2. It was observed that

temperature effect gives increase in yield of bio-oil with rise in

temperature, more significant in the temperature range 400-

5000C than beyond 500

0C as shown in Figure 3

Figure 3. Effect of Temperature on the Yield of Bio-oil.

3.3 Effect of Particle size on the Yield of Oil

The effect of particle size on the yield of bio-oil was studied at

500 0C and at atmospheric pressure under the constant flow of

N2. From the graph (Figure 4) it is clear that there is no

significant influence of particle size on the yield of oil and for all

particle sizes bio-oil yield is near about 10.3 gms.

0.0 0.2 0.4 0.6 0.8 1.0

0

2

4

6

8

10

Effect of Cotton Stalk Size

Yie

ld o

f B

io-o

il (

gm

s)

Cotton Stalk Particle Size (mm)




350 400 450 500 550 600 650 700 750

0

2

4

6

8

10

12

Effect of Temperature

Y

ield

of

Bio

-oil

(gm

s)

Temperature (0C)

Figure 4. Effect of Particle size on the Yield of Oil

3.4 Effect of Time of Pyrolysis

The time of pyrolysis of cotton stalk has shown a more influence

on the yield of oil. To study this effect temperature was

maintained constant at 500 0C and at atmospheric pressure under

the constant flow of N2. No bio-oil condensate was observed

during the initial period of pyrolysis and light vapour fractions

start to condense after 300 0C. The maximum yield of bio-oil

(10.48 gms) was observed at 6th

hr of pyrolysis operation as

shown in Figure 5.

3 4 5 6

0

2

4

6

8

10Effect of Pyrolysis Time

Yie

ld o

f B

io-o

il (

gm

s)

Total time of Pyrolysis (hrs)

Figure 5. Effect of time of pyrolysis on yield of Bio-oil.

IV. Conclusion

The most abundantly available Indian cotton stalk was taken as

the biomass for pyrolysis in swept tubular pyrolyzer. The swept

tubular pyrolyzer has given the good performance for the % bio-

oil yield (42 %) at 700 0C and atmospheric pressure under

constant mild flow of N2. The yield of bio-oil is strongly

depends on the temperature and no significant effect was

observed for the cotton stalk particle size. Also, the time of

pyrolysis has substantially affected the yield of bio-oil.

Acknowledgement

The authors are very much thankful to Mr. Kishor Darda,

Chairman, Darda Education Society, Yavatmal, M.S., India and

Dr. Avinash Kolhatkar, Principal, Jawaharlal Darda Institute of

Engineering and Technology, Yavatmal, (MS), India, for their

financial support to this research work.

References

i. Yu J, Corripio AB, Harrison OP,

Copeland RJ. Analysis of the sorbent energy transfer system (SETS) for power generation and CO2 capture. Adv Environ 2003;7:335–45.

ii. Demirbas F, Bozbas K, Balat M. Carbon dioxide emission trends and

environmental problems in Turkey. Energy Explor Exploit 2004;22:355–65. iii. Peter mckendry, Energy production from biomass (part 1): overview

of biomass, Bioresource Technology 83 (2002) 37–46

iv. https://www.iea.org/publications/freepublications/publication/India_study_FINAL_WEB .pdf

v. NCAER (1992). Evaluation survey of household biogas plants set up

during seventh five year plan, National Council for Applied Economic Research, New Delhi.

vi. Shukla P., Biomass Energy in India: Transition from Traditional to

Modern, The Social Engineer, Vol. 6, No. 2, 1-21, (http://www.decisioncraft.com/energy/papers/ecc/re/biomass/bti.pdf).

vii. http://www.icac.org/projects/commonfund/20_ucbvp/papers/15_chan

dra.pdf. viii. Hanisom Abdullah, Kun Aussieanita Mediaswanti, and Hongwei Wu*

Biochar as a Fuel: 2. Significant Differences in Fuel Quality and Ash Properties

of Biochars from Various Biomass Components of Mallee Trees Energy Fuels 2010, 24, 1972–1979 : DOI:10.1021/ef901435f

ix. j o h n l . g a u n t * , † , ‡ a n d j o h a n n e s l e h m a n N † Energy

Balance and Emissions Associated with Biochar Sequestration and Pyrolysis Bioenergy Production Environ. Sci. Technol. 2008, 42, 4152–4158

x. k e l l i g . r o b e r t s , * , † b r e n t a . g l o y , ‡ s t e p h e n j o s e p

h , § norman r . s c o t t , ⊥ a n d j o h a n n e s l e h m a n n † Life Cycle

Assessment of Biochar Systems: Estimating the Energetic, Economic, and Climate Change Potential Environ. Sci. Technol. 2010, 44, 827–833

xi. A N D R E W R . Z I M M E R M A N † Abiotic and Microbial

Oxidation of Laboratory-Produced Black Carbon (Biochar) Environ. Sci. Technol. 2010, 44, 1295–1301

xii. JOHANNES LEHMANN1,∗, JOHN GAUNT2 and MARCO RONDON3 BIO-CHAR SEQUESTRATION IN TERRESTRIAL ECOSYSTEMS –

A REVIEW Mitigation and Adaptation Strategies for Global Change (2006) 11:

403–427

xiii. Kurt A. Spokas1* and Donald C. Reicosky2 IMPACTS OF SIXTEEN

DIFFERENT BIOCHARS ON SOIL GREENHOUSE GAS PRODUCTION Annals of Environmental Science / 2009, Vol 3, 179-193

xiv. Nader Mahinpey,*,† Pulikesi Murugan,‡ Thilakavathi Mani,‡ and

Renata Raina§ Analysis of Bio-Oil, Biogas, and Biochar from Pressurized Pyrolysis of Wheat Straw Using a Tubular Reactor Energy & Fuels 2009, 23,

2736–2742

xv. Putun A.E., Ozbay N., Onal E.P., Putun E., Fixed-bed pyrolysis of cotton stalk for liquid and solid products, Fuel Processing Technology. 2005;

86:1207– 1219.

xvi. Sensoz S., Slow pyrolysis of wood barks from Pinus brutia Ten. And product compositions. Bioresource Technology 2003; 89: 307–311.

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Chemical Engineering, fourth ed., Prentice-Hall, Inc., Englewood Cliffs, NJ, 1982.

https://www.iea.org/publications/freepublications/publication/India_study_FINAL_WEB

https://www.iea.org/publications/freepublications/publication/India_study_FINAL_WEB




Study of Average Circulation velocity of liquids in baffled reversed flow Jet

loop reactor Rahul D. Mahajan

1, Dr. Sameer M.Wagh

2,

1Asst. Professor, Department of Chemical Engineering, D.Y.Patil College of Engineering & Tech. Kolhapur

2Asst. Professor, Laxminarayan Institute of Technology, RTMNU Nagpur (Maharashtra)

Abstract:- Jet loop Bioreactors (JLBR) are being widely

applied in a number of chemical, Biochemical, Petroleum

refineries and Petrochemical industries for the treatment of

the waste water. Some of the advantages of the system are

simple in construction & operation, low investments &

operational cost as well as very fine gas dispersion and high

mixing & mass transfer performance. In JLBR circulation

and fluid dispersion are achieved by a liquid jet. Liquid is

injected into the reactor with high velocity causing a fine

dispersion of different phases. In down flow jet loop reactors

the driving gas is introduced from top of the reactor into a

liquid flowing co currently downward so that the gas bubbles

are forced to move in a direction opposite to their

buoyancy. The reactor consists of a vertical column. A draft

tube was placed axially in the centre of the reactor. The

spray nozzle is located inside the draft tube.

Mixing Characteristics in JLBR will be studied by using

conductivity cell with the tracer particle or Photographic

techniques. To study of the hydrodynamic behavior of fluid

flow inside the reactor, effects of various parameters like

liquid flow rate, gas flow rate Nozzle diameter, Nozzle

heights etc on mixing characteristics are planned to study.

Keywords: Jet loop Bioreactor, tracer particles, immersion

height, Digital Image processing, liquid Circulation Velocity

determination, Three phase system, baffled RFJLR

Introduction

Conventional biological treatment processes have been used for

many years in the treatment of industrial and domestic

wastewaters. However, these processes have some disadvantages

such as larger area requirement, necessity of the transportation

of wastewater to the unpopulated areas due to odour and other

emission problems.

For this reason, some studies have been carried out to develop

smaller and faster wastewater treatment systems. The use of Jet

loop Bioreactor and airlift reactors coupled with membrane

filtration may be seen as examples of such an approach. Among

the different types of loop reactors, it was found that the reactors

where the mixing and flow circulation are achieved through jet

flows had improved performance characteristics (Padmavathi

and Remananda Rao, 1991). This type of loop reactors, normally

referred as jet loop reactors (JLRs), has become increasingly

important in conducting chemical and biochemical reactions.

A JLR is basically an assembly of two concentric cylinders of

which the inner one is known as “draft tube” and the outer one

as “reactor”. A two-fluid nozzle (liquid and gas), also usually

with a structure of concentric cylinders, disperses the gas

delivered in one of the tubes by means of the liquid jet delivered

in the other tube (Dirix and Wiele, 1990; Velan and Ramanujam,

1991, 1992a,b). If wished, the liquid and the gas from their

respective reactor exits can be recirculated back to reactor

through the two fluid nozzles until the liquid is saturated with

the gas. JLRs have found applications in wastewater treatment

processes due to their high mass transfer rates as well as their

intrinsic high turbulence characteristics which also result in the

disintegration of large biomass aggregates thus creating a very

large surface area for greater microbial activity. Aeration

efficiency of conventional activated sludge process is about 8%

with the possibility of upgrading to 20% if pure oxygen is used.

With up flowing gas and liquid, the traditional three phase slurry

reactor has two disadvantages, when used for biochemical

fermentation or biological wastewater treatment i.e. blockage of

the nozzle and low gas phase residence time. While in a jet loop

reactor, when the nozzles are installed at top of the reactor, these

shortcomings can be efficiently eliminated.

Jet loop reactors are widely used to ensure a homogenous

suspension with low power inputs. For an optimal design of loop

reactors with minimal energy consumption, the knowledge of the

pressure drop in three phase mixtures is essential. This is

affected strongly by the liquid circulation velocities and holdup

of the different phases, essentially if particles with different

densities have to be suspended simultaneously. A solid retaining

grid made was fixed just below the outlet to prevent the solid

particles from getting out of the reactor.

In present investigation, we have been used three phase system

in modified Reversed flow jet loop bioreactor. We have been

used liquid-Solid –gas system, for that as a liquid we have been

used tap water, as a solid we have been used acrylic beads

having diameters of 2-3 mm; & as a gas phase compressor air

has been used. Average liquid circulation velocity is measured

for loop circulation in annular space at different Nozzle heights

for variable parameters of the modified reversed flow jet loop

bioreactor. For this purpose out of various techniques; Digital

image processing technique has been chosen with consideration

of the merits & demerits.

In present research work, we have been studied Two Phase as

well as Three Phase system. For Two phases we used Liquid-

Solid system and for three phases, we used Gas-Liquid-solid

system.

We have been used following Material to carry out the

experimental work.

Compressor air as gas phase.

Acrylic beads as a solid phase.

Tap Water as a liquid phase.

Polystyrene pellets as tracer particles.

Digital camera (5 Megapixel).

Illumination system.

Windows movie maker operating program.

Physical Properties of materials:




Air:

Air (Free from moisture) is supplied from the top of the reactor

through two fluid nozzles to fluidize the mixture of acrylic beads

and water.


d. Density : 1.165 kg/m3

e. Molecular weight : 28.94

f. Thermal Conductivity at (250c, 101kpa) :-:26.6E-

3W/mok

Acrylic beads:

Acrylic beads having diameter 3mm have been used as a solid

material in two phase a well as three phase system. These beads

are slightly denser than water


b. Density : 1100 kg/m3

Tap Water:

Tap water has been used as a liquid phase in the Two as well as

Three phase System which was pumped through the two fluid

nozzle from top of the reactor.


b. Density : 1000 kg/m3

Polystyrene pellets (SC 206 Polystyrene):

We have been used polystyrene pellets as tracer particles as it is

having density approximately equal to water, so that by

determining the velocity of the polystyrene pellets we can get

the actual corresponding velocity of water within the reactor at

different flow rates of the liquid as well as gas (i.e. Water & air).

The polystyrene pellets were painted with different oil paints in

order to determine the circulation time and velocity of the

polystyrene pellets without any confusion.


MFI = 12.0

VSP = 101° C

HDT = 83 (Kg/cm2 0

C)

T.S. = 470 (Kg/cm2)

MATERIALS AND METHODS

Elongation = 2%

FM = 32.0 (Kg/cm2 × 1000)

Specific gravity = 1.05

From the specific gravity above mentioned, we get the idea

about the density of the material is approximately equal to

density of water. Thus by measuring the velocity of the tracer

particle we can directly determine the value of liquid velocity.

Digital camera (5 Megapixel):

In recent years, Thanks to the continuous development of digital

imaging systems and digital image processing, In present work

we have been used the 5 mega pixel Digital camera made by

leaders in electronics gadget producers, LG electronics. It gives

us really good quality of videos and images so that we could

able to determine the liquid velocities and Bubble images at

different variable parameters.

Illumination System:

Really, an illumination system plays an important role in good

quality picturisation. It helps to distinct the Tracer particles from

the solid phase material and liquid phase at high flow rates of

liquid as well as gases. It is really very difficult to identify the

tracers from the system without proper illumination as

turbulence is takes place at high flow rates of liquid & gas.

The contrasted background is also that much essential as

illumination is. That‟s why we used Black background behind

the reactor as well as Black, Red and Pink colored oil painted

pellets particles, so that it will get visualized & could easily

captured while shooting through digital camera.

We used couple of tube lights and 200 watt bulb which was

covered by white paper in order to reduce the reflection due to

brightness. One 60 watt bulb & series of tube lights were kept

away at proper distances to get a good effect.

Windows movie maker operating program:

This is the key computer program which is bridge between the

videos as well as images captured and the output data of

velocities and circulation time as well as bubble size

determination. It helps to count the actual time in fraction of

seconds, required for the tracer through specific distance of the

reactor. It also helps us to determine the circulation time for the

tracer particle through reactor.

Methods: There are various types of methods which are used for

study of mixing characteristics in jet loop bioreactors, such as

Conductivity Method (Salt addition).

PH change Method.

Thermal Method

Digital Image processing

Technique/photographic method.

Calorimetric chemical reaction method

The choice of a suitable experimental method for mixing time

measurement as well as study of mixing characteristics has been

a major problem for investigators, in a spite of variety of

reported methods. The major problems of our concern is that

many of the methods previously applied in the literature cause a

significant change in CMC solution viscosity [ e.g. Conductivity

method (salt addition) pH-change method, Thermal Method etc.]

Periodic sampling of the liquid for off- line analysis was not

feasible due to very slow rate of bubble disengagement from

viscous liquids; therefore the dye addition method was dropped

after some unsuccessful preliminary test.

In present investigation we have been used three phase system in

modified Reversed flow jet loop bioreactor. We have been used

liquid-Solid –gas system, for that as a liquid we have been used

tap water, as a solid we have been used acrylic beads having

diameters of 2-3 mm; & as a gas phase compressor air has been

used. The measurements of local liquid circulation velocities in

annular space of the reactor were done by the Digital image

processing technique with help of the oil painted polystyrene

pellets.




EXPERIMENTAL SET UP:

3.1 Experimental Procedure:

Comparatively digital image process technique may well

perform a rigorous and highly detailed assessment of

experimental data and may even be adopted for the analysis of

computational results conveniently expressed into image

graphics as well as tabulate in to graphical form. This technique

provides good visual observation without interfering with the

mixing process. The different techniques for measurement of the

mixing characteristics as well as behavior are already discussed

in literature survey; in spite of that with consideration of all

merits & demerits of all techniques we have been used Digital

Image processing technique / Photographic Method among

them.

A great number of researchers have chosen digital visual

methods to be applied in the field of experimental fluid

dynamics as well as mixing characteristics within the reactor.

These kinds of techniques play a fundamental role in analysis

and data acquisition for multiphase flows such as gas-solid, gas-

liquid, solid-liquid flows, where the observation of inter-phase

boundaries is relatively simple.

Thus Out of above mentioned methods, for the study of mixing

characteristics we have chosen the Digital Image Processing

Technique / photographic method.

The liquid i.e. Water was withdrawn underneath an impact plate

on which the draft tube was fixed and circulated to nozzle via

flow meter (Rotameter) by means of liquid circulation pump.

The gas was fed through an air tube fixed axially in the centre of

two fluid nozzles. Solenoidal valves were fixed in the liquid

inlet, outlet and bypass lines. The desired flow rates were

regulated with the help of these valves. The top neck of reactor

was tightly packed with filter cloth in such manner that it will

allow passing only liquid through the filter cloth. Thus tracer

particles which were painted by different colors of the oil paints

will remain inside the reactor.

After proper arrangement of the illumination, the movement of

the tracer particles which were already dumped into reactor was

captured with the digital camera.

RESULT & DISCUSSION

This Chapter enclosed with all graphical representation against

different operating parameters which gives us the effect on the

average tracer velocity i.e. Liquid Velocity. It gives the idea

about the effect of gas flow rates, liquid flow rates, Diameter of

nozzles as well as different nozzle heights. It also gives the idea

about liquid velocity when it has been determined at ejector

mode and when the air inlet was kept closed to atmosphere.

Effect on Liquid Velocity Profile at Nozzle height =

360,450,670 MM When Air Inlet was kept closed to the

atmosphere

360, 30.2135

450, 34.967

670, 30.56

0

5

10

15

20

25

30

35

40

0 200 400 600 800av

g.c

ircu

lati

on

ve

loci

ty,c

m/

sec

nozzle ht.,mm

avg.circulation velocity for close to atm.

avg.circulation velocity,cm/sec

Figure 1- Average Circulation Velocity V/S Nozzle Height At

Close To Atmosphere

Above graph shows that maximum tracer circulation velocity we

are getting at height 450 mm and lowest tracer velocity at nozzle

height 360 mm for close to atm.

Effect on Liquid Circulation Velocity Profile at Nozzle

height =360,670,450 MM When Air Inlet was kept fully

opened to the atmosphere

360, 37.085

450, 30.132

670, 30.5645

0

5

10

15

20

25

30

35

40

0 200 400 600 800

av

g.c

ircu

lati

on

ve

loci

ty,c

m/

sec

nozzle ht.,mm

avg.circulation velocity for open to atm.


Figure 2- Above graph shows that maximum racer circulation

velocity we are getting at height 360 mm and lowest tracer

velocity at nozzle height 450 mm for open atm.




Effect on Liquid Circulation Velocity Profile at Nozzle

height =360,670,450 MM When Air Inlet was kept fully

Closed to the atmosphere

360, 15.189

450, 35.4167670, 31.5893

0

5

10

15

20

25

30

35

40

0 200 400 600 800

av

g.t

race

r v

elo

city

,cm

/se

c

nozzle height,mm

avg.circulation velocity for all nozzle heights at close to atm.


Figure 3- Average Circulation Velocity V/S Nozzle Height

At Close To Atmosphere.




Effect on Liquid Velocity Profile at Nozzle height

=360,670,450 MM When Air Inlet was kept fully Closed to

the atmosphere.

360, 15.189

450, 35.4167670, 31.5893

0

5

10

15

20

25

30

35

40

0 200 400 600 800

av

g.t

race

r v

elo

city

,cm

/se

c

nozzle height,mm

avg.circulation velocity for all nozzle heights at close to atm.


Figure 4- Average Circulation Velocity V/S Nozzle Height At

Close To Atmosphere




nozzle height = 180 MM. it implies that ther is slightly

overlapping of the velocity profile.

But If we will consider all values of both conditions then we can

concluide that the liquid circulation velocity with higher

concentration gives us comparibly low values. As viscocity of

the liquid phase increases, the resistance of the solid phase also

increases and automatically fluid velocity is also decreaes. We

observed that tracer particles moves very smoothly through the

annulus of reactor. It gaves us the distinct velocities of the solids

and tracers.

Conlcuison

The Effects of gas and liquid flow rates, Different Nozzle

heights, Different concentration of liquid phase (Change in

viscosity), different operating conditions (i.e. ejector mode, &

By keeping air inlet closed) on the liquid circulation velocity

have been investigated in a Three phase (liquid-solid-air)

modified reversed flow jet loop bioreactor. The following

conclusions are made based on the present investigation.

1. Liquid circulation velocity in annular space of modified

reversed jet loop reactor increases with increase in liquid flow

rates and the influence of gas flow rate is more pronounced than

liquid flow rate. (A. K. Sharma et. al, 1992.)

2. As Nozzle height immersed more inside the reactor, the liquid

circulation velocity in annular space of the modified reversed

flow jet loop bioreactor increases gradually. It is observed that in

case of CTA (Close to atmosphere) circulation velocity is

maximum at nozzle immersion height 450 mm from top of

reactor tube.

3. As Nozzle height immersed more inside the reactor, the liquid

circulation velocity in annular space of the modified reversed

flow jet loop bioreactor increases gradually. It is observed that in

case of OTA (Open to atmosphere) circulation velocity is

maximum at nozzle immersion height 360 mm from top of

reactor tube.

4. As air is sucked from the air inlet in ejector mode (When air

inlet kept open to atmosphere) into reactor, the liquid circulation

velocity decreases gradually in this condition.

5. In closed loop condition circulation velocity of liquid

increases initially & decreases gradually.

References i. Milan k. Popvic and Campbell W. Robinson, 1993, Mixing Characteristics of External-Loop airlifts: Non Newtonian systems. Chemical engineering science

48, 1405 – 1413.

ii. Burhanettin Farizoglu and Bulent keskinler, 2007, Influence of draft tube cross – sectional geometry on KLa and ε in jet loop Bioreactors (JLB).

Chemical Engineering journal 133,293-299.

iii. K Yagna Prasad and T.K. Ramanujam, 1995, Enhancement of gas – liquid mass transfer in a modified reversed flow jet loop reactor with three- phase

system. Chemical engineering science. 18, 2997-3000.

iv. M. Velan and T. K. Ramanujam, 1992, Gas – Liquid mass transfer in a down flow jet loop reactor. Chemical engineering science, 47, 2871- 2876.

v. Biochemical Engineering: Principles and concept, 149-162.

vi. K. Sharma, C.A. Shastri and T.K. Ramanujam, Studies on treatment of wastewater in Reversed Jet Loop Reactor: Part I – Hydrodynamics and

Residence time Distribution studies. IJEP, 12,903-911.

vii. M. Velan and T. K. Ramanujam, 1994, Influence of reactor geometry on mixing characteristics in a down flow jet loop bioreactor: Newtonian and

non-newtonian fluids. Bioprocess Engineering, 11,101-106.

viii. M. Velan and T. K. Ramanujam, 1992, Hydrodynamics and mixing in down flow jet loop bioreactor with a non – Newtonian fluid (b). Bioprocess

Engineering, 7, 193-197.

ix. K. Yagna Prasad and T. K. Ramanujam, 1995, overall volumetric mass

transfer coefficient in a modified reversed flow jet loop reactor with low

density particles. Bioprocess Engineering, 12, 209 - 214.

x. B. Kawalec – pietrenko, 2000, Liquid circulation velocity in the inverse fluidized bed airlift reactor. Bioprocess Engineering, 23, 397 - 402.

xi. Ken- ichi kikuchi* et. al, 1999, Hydrodynamic behavior of single particles in draft tube bubble column, Canadian journal of chemical engineering, 77, 57

573 - 578.

xii. G. Padmavathi and K. Remananda Rao, 1991, Hydrodynamic characteristics of reversed flow jet loop reactor as a gas-solid- liquid

contactor, shorter communications, Chemical Engineering Science, 46, 12,

3293 – 3296. xiii. M. Velan and T. K. Ramanujam, 1995, Mixing time in down-flow jet loop

bioreactor, Bioprocess Engineering, 12, 81 - 86.




Optimization of Treatment of Cleaning In Place Waste from Dairy Industry

Using Membrane for Recovery of Caustic Soda and Acid Pradnya H. Athawale, Dr. V. S. Sapkal, Dr. R. S. Sapkal




Abstract : The current issue of responsible environmental

management adds pressure on the dairy industry to reduce

demands for energy, chemicals and water. So from the CIP

solution recover NaOH & HNO3 used membrane filtration

techniques like nanofiltration and after that reconcentration

using reverse osmosis. Nanofiltration reduced the COD

content of the caustic washing solution by 76–90% depending

on the concentration ratio used. The alkaline/acid content of

the nanofiltration permeate was similar to the feed. By reverse

osmosis treatment alkaline NF permeates were concentrate

NaOH.

Key Words: CIP solution, Nanofiltration, Reverse Osmosis,

COD, BOD, NaOH, HNO3

I. Introduction:

CIP procedure are widely used especially in pharmaceutical and

food industry to assure food hygiene and product safety as a

whole use of water and chemical required for those cleaning

operation and have significant economical and environmental

impact.

The operation of regeneration allows reducing the process global

cost in sewage treatment of used solution rejected by CIP unit.

Diluted caustic/acidic streams develop during the CIP cycle

when NaOH/HNO3 solution starts to displace rinsing water in the

pipes and tanks.

Microfiltration, ultrafiltration and nanofiltration are potential

techniques for this purpose depending on the solids content and

the particle size of the solutes .The intention is to purify the

solution and add fresh cleaning chemicals to it when necessary.

[1] More advanced means separate the foulants from the diluted

cleaning solutions and concentrate them back to their original

concentration. This kind of a two step process consists of a

foulant separation step, e.g. ultra- or nanofiltration, and a re-

concentration step of the cleaning solution, i.e. reverse osmosis.

[2-5]

Fig 1. Typical process of CIP solution

For the industrial sector, the regeneration of cleaning solutions

allows to perform economies of water and chemical reactants by

changing the cleaning sequences while maintaining constant the

process efficiency. [6]

The volume of these effluents varies with the type of the process

production and the nature of the treated products. The separation

of caustic and acid is an important field of study for the sake of

industrial safety and environmental protection.[2] However,

there is no information in the literature on the separation of

caustic and acid from dilute aqueous solution by membrane

filtration. So I have take interest in this field to use the

membrane technology for separation. Membrane separation

technology involved NF, RO, UF, MF but I will use NF and RO

for separation for the maximum % yield. And also we will

successfully separate the chemical which is major problem of

wastewater of dairy industries.

II. Materials and methodology

Membranes

Diluted alkaline and acidic washing streams were filtered with

spiral NF membranes. Reverse osmosis measurements were

done with spiral wound membranes (99.0% average NaCl

rejection). The membrane area of the spiral wound elements was

of NF and RO are 1.27*10-4

and 1.85*10-4

. The membranes used

were commercially available membranes.

Dairy washing solutions

Diluted alkaline and acidic washing streams were collected

during 24-h periods from washing cycles of raw milk pipelines

of dairy plant processing 300 m3 raw milk per day. The sodium

hydroxide content in the washing solutions was 0.68% and the

nitric acid content 0.9%. The COD value of the alkaline solution

was 144 mg/L and the total solids content 0.7–1.0%. The pH of

the diluted alkaline solution was 11.5– 12.0 and the conductivity

7–9 mS/cm. The COD of the acidic solution was 80-100mg/L

and the total solids <0.2%. The pH of the diluted acidic solution

was 1.9 and the conductivity 11.7 mS/cm.

Filtration equipment

The spiral wound module tests were carried out with a pilot set-

up equipped with one spiral wound module. Filtration

experiments were run as single stage feed and bleed, i.e. values

for permeate and retentate flows were adjusted in advance.

[3]Permeate and retentate were collected separately.

Filtration experiments




The Nanofiltration measurements were done at low pressures,

and volume concentration ratios were used. Size of one batch

was diluted washing solution. The permeates from NF runs were

collected for re-concentration by RO. Reverse osmosis

measurements were done 6.5kgf/cm2 pressures and volume

concentration ratios were used. The volume concentration ratio

(VCR) is the volume of the feed compared to the volume of the

retentate. All measurements were done at ambient temperatures.

Industrial conditions determined the experimental work. The

diluted washing streams were collected during 24-h periods i.e.

the temperature in the tank was 25–35°C. The low temperatures

of the diluted streams are due to spontaneous cooling during the

collecting period and mixing of flushing water (appr. 8–15°C)

with hot caustic/acidic washing solution. Heating up of the

collected stream was regarded as a waste of energy because the

regenerated solution will be added to the heated washing

solution tank (60– 70°C).

Experimental Work

For NAOH CIP solution experi - ment with NF and RO

Membrane

Fig 2.Membrane setup

The 18 lit of CIP solution containing NAOH, are brought from

the dairy.it is firstly passed through the NF membrane with the

inlet and outlet membrane pressure 8 kgf/cm2 and 5kgf/cm2

respectively. The permeate and concentrate flowrate was the

1.7lpm and 7.5 lpm respectively. and transmembrane pressure

was 6.5kgf/cm2.feed flowrate was 8.39lpm at total flux

5.348*10-4

lit/min cm2.with the PH -11.76,BOD-

54.05mg/l,COD-144mg/l and NAOH concentration of 0.068%

After passing through NF membrane it will pass through RO

membrane with the inlet and outlet membrane pressure 8

kgf/cm2 and 5kgf/cm

2 respectively. The permeate and

concentrate flowrate was the 1lpm and 9 lpm respectively. and

transmembrane pressure was 6.5kgf/cm2. feed flowrate was

7.94lpm at total flux 5.405*10-4

lit/min cm2.

For HNO3 CIP solution experiment with NF and RO

Membrane

The 18 lit of CIP solution containing HNO3, are brought from

the dairy.it is firstly passed through the NF membrane with the

inlet and outlet membrane pressure 8 kgf/cm2 and 5kgf/cm2

respectively. The permeate and concentrate flowrate was the

1lpm and 9lpm respectively.and transmembrane pressure

was6.5kgf/cm2. feed flowrate was 9.46lpm at total flux

5.813*10-4

lit/min cm2 with the PH -11.76,BOD-

63.06mg/l,COD-96mg/land NAOH concentration of 0.945 %

After passing through NF membrane it will pass through RO

membrane with the inlet and outlet membrane pressure 8

kgf/cm2 and 5kgf/cm

2 respectively. The permeate and

concentrate flowrate was the 1.1lpm and 9 lpm respectively. and

transmembrane pressure was 6.5kgf/cm2.feed flowrate was

7.33lpm at total flux 5.45*10-4

lit/min cm2

III .Results and Discussion

Analysis of Dairy Effluent

PH: - It is a term used to express the intensity of the acid or

alkaline condition of a solution. Solutions with a pH less than 7

are said to be acidic and solutions with a pH greater than 7 are

said to be basic or alkaline. Ph can be determining by the ph

meter.

NAOH and HNO3: it can be determine by the titration of

solution with the help of phenelopthelien indicator, or by the

analytical instruments like spectrophotometer AAS respectively.

Chemical Oxygen Demand (COD):- oxygen required for

chemical oxidation of organic matter with the help of strong

chemical oxidant. It is used to measure the pollution of industrial

waste.

Biological oxygen demand (BOD): amount of oxygen required

by microorganisms while stabilizing biological decomposable

organic matter in waste under aerobic condition.

Results

Nanofiltration of diluted caustic washing solution membranes

reduced the COD content 80% in average at volume

concentration ratios. The total solids in the permeate with

membrane Better reductions of the COD content were reached at

lower volume concentration ratios e.g. 90 and 87% respectively.

Actually, in every filtration the permeate was clear in color

compared to the milky retentive. However, differences in caustic

permeation were detected. Retention of

Sodium hydroxide.

1. Recovery of caustic solution with high COD from cleaning of

evaporation plant at a dairy industry. Average flow (feed flow

rate) = 8.39lpm for NF, Average flow (feed flow rate) = 7.94lpm

for RO, COD of permeate=128mg/l Concentrate=112 mg/l.

2. Recovery of acidic solution with high COD from cleaning of

evaporation plant at a dairy industry .Average flow (feed

flowrate) =9.46lpm for NF Average flow (feed flow rate)=

7.33lpm for RO,COD of permeate=32mg/l Concentrate=48mg/l.

3.To purify diluted caustic and acidic streams from dairy CIP

process by NF and reconcentration using RO NF reduce COD

content by 80% .no significant correction of nanofiltered diluted

acidic solution was obtained with RO.

4. To study the cleaning efficiency of reused NAOH CIP

solution after being used for varying number of industrial

cleaning cycle. Cleaning efficiency Nanofiltration and reverse

osmosis 0.94-0.99%.




1. Concentration of NAOH according to various membranes

used

2. Concentration of HNO3 according to various membranes

used

3. Reduction of BOD content in NAOH CIP solution

4.Reduction of BOD content in HNO3 CIP solution

5. Reduction of COD content in NAOH CIP solution

IV. Conclusion

Membrane performances, COD reduction and flux, depended on

origin, history and composition of the CIP solution. The

recovery of different (acid, alkaline) CIP solutions was

performed efficiently by using NF. Besides, membrane

processes are more efficient than centrifugation or decantation to

recover one type of alkaline solution (standardization NAOH).

% NAOH in NF feed is 0.068 %,NF concentrate 0.06%,NF

permeate 0.012 %, RO concentrate 0.048 % ,RO permeate 0.02

%.unit operation recovery % of NAOH at NF

permeate 95% respectively, and total process recovery is 85.5%.

Acknowledgement:

I take this opportunity to express my sense of gratitude Prof. Dr.

V. S .Sapkal, Head of department of chemical technology,

S.G.B.Amravati University and Prof. Dr. R.S.Sapkal, for


throughout this work. I would like to express my sincere

gratitude Mr. Jalamkar Sir, From Government Dairy Industry

congress nagar Amravati for the help which he had provided

during this project.

6. Reduction of COD content in HNO3CIP solution

References: i. Dresch, M., Daufin, G. and Chaufer, B. 1999. Membrane processes

for the recovery of dairy cleaning-in-place solutions. Lait. 79, 245–259.




ii. Dresch, M., Daufin, G. and Chaufer, B. 2001. Integrated membrane regeneration process for dairy cleaning in- place. Separation and Purification

Technology. 22- 23, 181-191. iii. Elina Räsänena, b, Marianne Nyströma, Janne Sahlsteinb, Olli

Tossavainenb.Purification and regeneration of diluted caustic and acidic

washing solutions by membrane filtration Received 1 February 2002; accepted 28 March 2002 Desalination 149 (2002) 185–190

iv. G. Gesan-Guiziou, N. Alvarez, D. Jacob G. Daufin.Cleaning-in-place coupled with membrane regeneration for re-using caustic soda solutions

Separation and Purification Technology 54 (2007) 329–339.

v. G´esan-Guiziou, G., Boyaval, E. and Daufin, G. 2002. Nanofiltration for the recovery of caustic cleaning-in-place solutions: robustness towards large

variations of composition. Journal of Dairy Research. 69, 633-643. vi. Henck, M. 1995. Recycling of used caustic cleaning solutions in the

dairy industry by crossflow filtration. Bulletin of the International Dairy

Federation. 9504, 175-183. vii. Marlène Dresch", Georges Daufin-",Bernard Chaufer"Membrane

processes for the recovery of dairy cleaning-in-place solutions (Received 30 June 1998; accepted 5 October 1998)




Textile Dyes Removal: Adsorption of D-Yellow Colour Dye on Pyrolyzed

Cotton Stalk Biochar

Prashant Tayade*1, Vaishali Ghoderao

1, Nilesh Dumore

1, Nitin Chavan

1, Ganesh Kakad

2

1Department of Chemical Engineering, JIDET, Yavatmal (M.S) India

2Department of Textile Engineering, JIDET, Yavatmal (M.S) India


Abstract Biochar, defined simply as charcoal prepared by

pyrolysis of agricultural waste (Biomass), was investigated

as a low cost adsorbent for wastewater dye removal. The

adsorption of textile D-Yellow dye from aqueous solution was

carried out using cotton stalk bio-char (charcoal) as an

adsorbent. The effects of different operating parameters such

as initial dye concentration, amount of adsorbent (Biochar)

and time of adsorption on removal of dyes were investigated.

For this, liquid phase adsorption experiments were conducted

in batch adsorption mode. The adsorption isotherm was

developed for the effect of initial concentration of dyes. It was

observed that rate of adsorption of dyes on biochar increases

with increase in initial concentration of dyes.

Keywords Colour Dyes, Biochar, Adsorption Isotherm, D-

Yellow Colour.

I. Int roduct ion

The effluent streams from textile, printing and paper-making

industries containing dyes pollutes water on earth surface [1]

underground water [2] and soils by irrigation [3 4]. Methyl violet

is a member of the basic dyes, a group with high brilliance and

intensity of colors and that inhibit photosynthesis of aquatic

plants [5]. Repeated or prolonged exposure to the reactive red

dye can produce eye irritation leading to inflammation and may

produce Conjunctivitis. Some azo dyes may be able to cause

mutations and be associated with the development of bladder

cancer. Therefore, it is necessary to remove these dyes from

wastewater prior to discharge into water bodies.

Removal of dyes and pigments from aqueous solutions via

adsorption processes is a simple method known to be relatively

low-cost, and such effective technology has been adopted widely

by water treatment plants. The removal efficiency of dyes via

adsorption mainly depends on the choice of the adsorbents

employed. Activated carbon [6], natural clay minerals [7], nano-

particles [8], plant biomass [9] and fly ash [10] have been used

to remove methyl violet and other basic dyes from aqueous

solutions. However, recent attention has been given to some

alternative low-cost materials of sufficient suitability and

selectivity for the removal of dyes from aqueous streams. In the

partial or total absence of oxygen, thermal decomposition of

plant-derived biomass (oxygen-limited pyrolysis) has been

manipulated to yield a solid carbon-rich residue generally

referred to as biochar [11].

By using biochar lot of research efforts have been done to

investigate the removal of organic pollutants from water streams

[12]. The biochars having negative charge on their surface can

be used as low-cost adsorbents to remove organic pollutants and

heavy metal cations from water [13].

In this study, biochars from the stalks of cotton were prepared at

500 0C by incomplete combustion in pyrolyzer. Batch

experiments were used to study the adsorption of methyl violet

by these biochars. The objectives were to evaluate the abilities of

biochars generated from cotton stalk to remove methyl violet

from aqueous solutions and to probe the adsorption mechanisms

for the dye on the biochar.


2.1 Adsorbent (Cotton Stalk Biochar) Preparation Cotton stalk was used as a raw biomass material, obtained

directly from the farming region of Yavatmal district located in

India. The stalks of cotton were first dried over night in the dryer

at 100 0C to remove the moisture content and then it made into

small pieces by a cutter. The fine particles of cotton stalks was

done in the small homemade mixer and separated into different

fractions (0.3 mm, 0.35 mm, 0.425 mm, 1 mm) by standard

sieves.

The pyrolysis of cotton stalks for the preparation of

biochar was carried out in well swept tubular pyrolyzer

fabricated itself in our workshop. It comprised 50 cm long

stainless steel tube with 4 cm id flanged at both ends, the outer

side of this pyrolyzer wrapped with two 550 W ceramic band

heaters as shown in Figure 1 and the produced biochar into the

pyrolyzer is shown in Figure 2

2.2 Experimental

Before starting of adsorption experiments a standard solution of

18 mg dye was prepared in 600 ml of distilled water by mixing

completely. Solution of 40 ml, 80 ml, 120 ml, 160 ml and 200

ml was putted in incubator shaker for a 1 hour and absorbance

measured by calorimeter to plot the standard graph.

Batch Adsorption Experiment

Adsorption studies were performed by the batch technique. A

Figure 1. Diagrammatic representation of experimental set-up

for the pyrolysis of cotton stalk




Figure 2 Photo of Biochar prepared from cotton stalk

series of 50-mL plastic conical tubes were used. The tubes were

shaken at room temperature (27±2ºC) and the shaking speed was

125 rpm.


Effect of initial concentration on amount of dye adsorbed: -

To study the effect of initial concentration for D-yellow colour

dye, a solution of known concentration of dye was prepared in a

200 ml of distilled water. The amount of biochar used for each

batch was 100 mg. The mixture was shacked in a shaker for 1 hr

continuously, filtered calibration was done by calorimeter to

calculate optical density and % transmittance. The absorbance

was calculated using following relation

A = 2 – log10* (%T) (1)

It was observed that adsorption of D-yellow colour dye on

biochar becomes constant at 50 mg/lit as shown in Figure 3. For

lower concentration of dye, adsorption was very fast.

20 30 40 50 60

0

2

4

6

8

10

12

1420 30 40 50 60

Effect of Initial Concentration of Dye Solution

Amt of Yellow Dye Adsorbed

Am

ou

nt o

f D

ye A

dso

rbe

d (

mg

)

Initial Concentration of Dye Solution (mg/lit)

Figure 3 Effect of initial concentration of D-yellow on

adsorbance

Effect of time on amount of dye adsorbed:-

To study the effect of time on amount of dye adsorbs, a dye

solution having concentration of 6 mg dye in 200 ml of distilled

water was prepared. From the figure 4, it is clear that adsorption

of dye becomes constant after 40 min. of stirring.

10 20 30 40 50 60

0

5

10

15

20

25

30

35 Effect of Time on Amount of Dye Adsorbed

Am

ount

of D

ye A

dsor

bed

(mg)

Time (min)

Yellow Dye

Figure 4 Effect of time on amount of dye adsorbed

Effect of amount of Biochar:-

For studying the effect of amount of biochar on the extent of

adsorption of dye, the experimental runs were taken on 100 mg,

200 mg, 400mg and 600 mg of biochar for one constant

concentration of dye solution. The results are plotted in figure 5,

it was observed that adsorption increases up to 300 mg and then

it becomes constant.

100 200 300 400 500 600

0

2

4

6

8

10

12Effect of Amount of Biochar

Am

ou

nt o

f D

ye A

dso

rbe

d (

mg

)

Amount of Biochar (mg)

Yellow Dye

Figure 5 Effect of amount of Biochar

Langmuir adsorption isotherm:-

In Langmuir theory, the basic assumption is that sorption takes

place at specific homogeneous sites within the adsorbent. The

linearized forms of Langmuir isotherm is given by Equations (2)

1/qe = 1/Qmax + 1/bQmax x 1/Ce (2)

where Ce is the concentration of dye solution at equilibrium

(mg/lit), q is the amount of dye adsorbed at equilibrium (mg g-1

),

Qmax is the maximum adsorption capacity of the dye(mg g-1

), b

is a constant related to the energy. The isotherm parameters are

given in Table 1.

Table 1 Langmuir Adsorption Isotherm parameters

Concentration(mg/lit) Ce Ce/qe

30 18.5 200




40 20 250.87

60 47.48 378.625

15 20 25 30 35 40 45 50 55 60 65

160

180

200

220

240

260

280

300

320

340

360

380

400

Langmuir Adsorption Isotherm

C e/qe

Ce

Yellow Dye

Red Dye

Figure 6 Longmuir Adsorption Isotherms

IV. Conclusion

The batch adsorption of D-yellow colour dye on biochar was

studied by considering operating conditions such as initial

concentration of dye, time of batch adsorption and amount of

biochar adsorbed. The adsorption of D-yellow was found to be

dependent on the initial concentration, time and amount of

biochar.

References

i. Carneiro, P.A., Umbuzeiro, G.A., Oliveira, D.P., Zanoni, M.V.B.,

2010. Assessment of water contamination caused by a mutagenic textile

effluent/dye house effluent bearing disperse dyes. J. Hazard. Mater. 174, 694–

699.

ii. Dubey, S.K., Yadav, R., Chaturedi, R.K., Yadav, R.K., Sharma, V.K.,

Minhas, P.S., 2010. Contamination of ground water as a consequence of land

disposal of dye waste mixed sewage effluents: a case study of Panipat District of Haryana. India. Bull. Environ. Contam. Toxicol. 85, 295–300.

iii. Topaç, F.O., Dindar, E., Uçarog˘lu, S., Bas_kaya, H.S., 2009. Effect

of a sulfonated azo dye and sulfanilic acid on nitrogen transformation processes in soil. J. Hazard. Mater. 170, 1006–1013.

iv. Zhou, Q.X., Wang, M.E., 2010. Adsorption-desorption characteristics

and pollution behavior of reactive X-3B red dye in four Chinese typical soils. J. Soils Sediments 10, 1324–1334.

v. Hameed, B.H., 2008. Equilibrium and kinetic studies of methyl violet

sorption by vi. agricultural waste. J. Hazard. Mater. 154, 204–212

vii. Soldatkina, L.M., Sagaidak, E.V., 2010. Kinetics of adsorption of

water soluble dyes on activated carbons. J. Water Chem. Technol. 32, 212–217. viii. Guiza, S., Bagane, M., Al-Soudani, A.H., Amore, H.B., 2004.

Adsorption of basic dyes onto natural clay. Adsorption Sci. Technol. 22, 245–

255. ix. Liu, R.C., Zhang, B., Mei, D.D., Zhang, H.Q., Liu, J.D., 2011.

Adsorption of methyl violet from aqueous solution by halloysite nanotubes.

Desalination 268, 111–116.

x. Cengiz, S., Cavas, L., 2010. A promising evaluation method for dead

leaves of Posidonia oceanica (L.) in the adsorption of methyl violet. Mar.

Biotechnol. 12, 728–736. xi. Mall, I.D., Srivastava, V.C., Agarwal, N.K., 2006. Removal of

orange-G and methyl violet dyes by adsorption onto bagasse fly ash-kinetic study

and equilibrium isotherm analyses. Dyes Pigments 69, 210–223. xii. Sohi, S.P., Krull, E., Lopez-Capel, E., Bol, R., 2010. A review of

biochar and its use and function in soil. Adv. Agron. 105, 47–82.

xiii. Cao, X.D., Ma, L.N., Gao, B., Harris, W., 2009. Dairy-manure derived Biochar effectively sorbs lead and atrazine. Environ. Sci. Technol. 43,

3285–3291.

xiv. Inyang, M., Gao, B., Pullammanappallil, P., Ding, W.C., Zimmerman, A.R., 2010. Biochar from anaerobically digested sugarcane bagasse. Bioresour. Technol. 101, 8868–8872.




Production of Citric Acid by Fermentation of Sugarcane Juice & Study of

Effect of Aeration on Process

Nilesh S. Dumore*, Swapnil A. Dharaskar, Sanjay H. Amaley, Prakash C. Chavan

Department of Chemical engineering

Jawaharlal Darda Institute of engineering & Technology, Yavatmal (M.S) India


Abstract: Citric acid is ubiquitous in nature and exists as an

intermediate in the citric acid cycle when carbohydrates are

oxidized to carbon dioxide. It is solid at room temperature, melts

at 153ºC and decomposes at higher temperatures into other

products. It is responsible for the tart taste of various fruits in

which it occurs, i.e. lemons, limes, figs, oranges, pineapples,

pears and goose-berries. Because of its high solubility,

palatability and low toxicity, it can be used in food, biochemical

and pharmaceutical industries. These uses have placed greater

stress on increased citric acid production and search for more

efficient fermentation process. There are many processes for

production of citric acid such as from citrus fruits such as

orange, lemon etc.,by fermentation of corn cobs, fermentation of

apple juice, sugar molasses. But in all of that citric acid from

sugarcane juice or sugar molasses is the most efficient process.

Many microorganisms such as fungi and bacteria can produce

citric acid. The various fungi, which have been found to

accumulate citric acid in their culture media, include strains of

Aspergillus niger, A. awamori, Penicillium restrictum,

Trichoderma viride, Mucor piriformis and Yarrowia lipolytica.

But Aspergillus niger remained the organism of choice for the

production of citric acid.

Keywords: Fermentation, Aspergillus Niger, Sugarcane juice,

Citric acid.

1. Introduction

Although the surface culture process is still being used, most of

the newly built plants have adopted the submerged fermentation

process. Sugarcane juice is a desirable raw material for citric

acid fermentation because of its availability and relatively low

price. As compared to citrous fruits, sugarcane is available in

abundant quantity. Incubation temperature plays an important

role in the production of citric acid. Temperature between 25-

30OC was usually employed for culturing of Aspergillus niger

but temperature above 35OC was inhibitory to citric acid

formation because of the increased the production of by-product

acids and also inhibition of culture development. The

appropriate pH is important for the progress and successful

termination of fermentation. The trace metals such as iron, zinc,

copper, manganese present a critical problem in submerged

fermentation.

The organisms need major elements such as carbon, nitrogen,

phosphorus and sulphur in addition to various trace elements for

growth and citric acid production. Also aeration plays important

role in production of citric acid. The productivity increases by

giving the aeration to the fermentor.

The present work is concerned with the optimization of cultural

conditions for enhanced production of citric acid by mutant

strain of Aspergillus niger in stirred fermentor. Lemons, oranges

and other citrus fruit contain high concentrations of citric acid.

In this work, citric acid was produced by fermentation process

using sugarcane juice and aspergillus nigar as microbial source.

In this process, Study of effect of aeration and change in pH of

solution with respect to time. Reaction of process, Material

balance, energy balance was investigated. Find the feasilbulty

study of fermentation process for confirmation of citric acid

using titration analysis.

2.Material and Methods

Sugarcane juice was purchased from local shop in Yavatmal,

Aspergillus Nigar is available from Diksha Bio-Tech lab

Nagpur. Sugar and potato are purchase from local market.

dextrose agar was brought from Indian scientific chemical (make

Marak).

Experimental Setup

Growth of aspergillus niger culture: Aspergillus niger is the

surface growing culture. So, it is necessary to prepare a surface

for growing the culture. Aspergillus niger is grow only on

surface of potato dextrose agar. For preparing the PDA, we

required potatos, dextrose powder and agar.

Inoculation of aspergillus niger on PDA: As the aspergillus

niger is a surface growing culture, inoculate the aspergillus niger

culture on the slant surface of potato dextrose agar using UV.

inoculation chamber.

Growth of aspergillus niger on PDA: Growth of aspergillus

niger culture takes place in slant surface of PDA because

Aspergillus niger in a surface growing culture. It takes 3 to 4

days for complete growth.

Fermentation Process

Raw materials: For the production of citric acid the main raw

material is required for process is sugar cane juice aspergillus

niger is used as a culture or nutrients.

Experimental Procedure

Take 2.5 kg of sugar cane juice, add 125 gm of sugar in juice.

Keep this sample in autoclave for sterilization. Temperature of

autoclave is maintained at 119oC and pressure at 15lb. after

reaching that temperature, switch off the autoclave and keep it

for cooling. Sterilization is important for killing the unwanted




germs present in juice. Take 100ml of remaining sugarcane juice

in conical flask, add 5gm of sugar and put this sample in

autoclave along with previous sample for sterilization. Before

sterilization how much percentage of citric acid present in

sugarcane juice against 0.1N NaOH solution using

phenolphthalein indicator is find by the titration method.

Production of citric acid by fermentation process is seven days

batch process. Sterilized juice is fed to the fermentor along with

5gm aspergillus niger. Continuous agitation is given to the

fermentor for 7 to 8 hours by induction motor. Compressor is

use for the aeration. Airflow Rotameter is use to control the

aeration. The aeration is given up to 1 to 1.6 kg/cm2.

Temperature required for this process is in between 28oc-35oc,

for maintaining that temperature the water is provided to the

jacketed vessel and then water to drain. Peristaltic pump is used

for taking the sample from the fermentor to check the acidity of

sample.

Two electrode is drawn in the fermentor.

pH electrode:- this electrode is used for measuring the pH which

is indicate by pH controller.

Dissolved oxygen electrode is used for measuring the dissolved

oxygen which is indicate by DO indicator.

Result and Discussion

The production of citric acid from 2.5kg sugarcane juice in

laboratory based fermentor gives the following results during 7

days of fermentation process.

Initial pH=5.55

Eq.weight of citric acid(monohydrate) =70

Initial acidity= 0.417

Aeration

A] With aeration- Following table shows the result of acidity

and pH with aeration citric acid.

Table 3: Result of acidity with aeration

Sr. No. Day Acidity

1 1 0.424

2 2 0.462

3 3 0.812

4 4 1.204

5 5 1.442

6 6 1.703

7 7 1.906

Table 4: Result of pH with aeration

Sr. No. Day pH

1 1 5.55

2 2 5.48

3 3 5.13

4 4 4.89

5 5 4.57

6 6 4.09

7 7 3.84

B] Without aeration:- The following table shows the acidity and

pH of citric acid without aeration.

Table 5: Result of acidity without aeration

Sr. No. Day Acidity

1 1 0.423

2 2 0.448

3 3 0.603

4 4 0.724

5 5 1.153

6 6 1.384

7 7 1.579

Table 3: Result of pH without aeration

Sr. No. Day pH

1 1 5.55

2 2 5.47

3 3 5.21

4 4 4.92

5 5 4.67

6 6 4.47

7 7 4.12

For testing sample without aeration, take the sample of neutrals

solution in a comical Flask and take the result on each day.

Qualitative Test to check the presence of citric acid

Take 3ml of neutral solution, Add 1ml of CaCl2 solution, Heat

the mixture for 1 to 2 min., A heavy white ppt of calcium citrate

is obtained. By performing above test it is clear that citric acid is

present in product solution.

The following fig.1, Shows the graph between No. of days

verses acidity with and without aeration.

Fig.1: acidity with and without Aeration Vs Number of days




Fig. 2: pH with and without Aeration Vs Number of days

Above fig. 2, concluded that as the no. of days increases, the

acidity of product also increases and acidity increases rapidly

with aeration as compared to without aeration. From the above

results it is clear that as increase in number of days acidity goes

on increasing and pH goes on decreasing.

The result of acidity pH by giving aeration shown that the

acidity on day 1 was found to be 1.424 and pH was found 5.55.

The acidity and pH on day 2 was 0.462 & 5.48 respectively on

day 5, the result of acidity and pH was found 1.442 & 4.57

respectively. From the results of acidity and pH shown that the

acidity rapidly increases by giving aeration as compare to

without aeration. The pH was also decreases rapidly by giving

aeration as compared to without aeration.

Conclusion

There are many processes for production of citric acid such as

from citrus fruits such as orange, lemon etc., by fermentation of

corn cobs, fermentation of apple juice, sugar molasses. Among

all of that citric acid from sugarcane juice or sugar molasses is

the most efficient process. A successful fermentation process

depends both on an appropriate strain and optimization of

fermentation parameters. The productivity increases with

aeration without aeration. In the present work, cultural

conditions such as sugar concentration, time profile of citric acid

synthesis, incubation temperature, initial pH, agitation intensity

and air supply were optimized by a mutant strain of Aspergillus

niger in a laboratory scale stirred fermentor. Cultural conditions

for citric acid production by fungi vary from strain to strain and

also depend on the type of process. The optimization of cultural

conditions is the key for high and consistent yields of

metabolites like citric acid. In the present study, the mutant

strain of Aspergillus niger supported maximum production of

citric acid (106.65 g/l) without supplements which was

substantial. The addition of nitrogen sources and minerals like

calcium and phosphate may further increase the production of

citric acid, as required for an industrial process.

Reference

i. Wong P.K.,Trivedyr. K.,Sharma S.,fermentation of citric acid, Asian Journal

of Microbiology , Biotechnology and environmental scienceVol.7.No.2,2005. ii. L. E.Casida,Jr. Indusrial microbiology2005, pp403-407.

iii. A .S.Rao, Introduction to microbiology, 4th Edition 2005. P64-67,148-159.

iv. Adrian Slater; Nigel Scott; Mark Fowler, The genetic manipulation of Plant

Biotechnology, 2005,pp 43-46.

v. Michael J. Pelezer; Microbiology 5th Edition 2005. P 25,110-111,139-

141,360,660-661.

vi. James.M Jay Modern food microbiology, 4th Edition 2006 .p 197,279-

280,372,380. vii. David.L. Nelson; Michael.Mcos. Principal of biochemistry, 4thEdition

2005.p 618.

viii. George.T.Austin, Shreves chemical process industries, 5th Edition 1997.p 597-598.

ix. Octave Lavenspiel, Chemical reaction engineering, 3rd Edition 2004pp.611-

616. x. Smith, J. M., Van Ness,H.C.And Abbott, M. M. Introduction to Chemical

Engineering Thermodynamics. 5th Edition. McGraw-HillSingapore (1996).

xi. Perry, R. H. and Green, D. W. Perrys Chemical Engineers Handbook. McGraw-HillNew York, (1997).

xii. Ali, S.; Haq, I. and Qadeer, M.A. Effect of mineral nutrient on the

production of citric acid by Aspergillus niger. Online Journal of Biological Sciences. April 2001, vol.32, no. 1, p. 31-35.




Carbon Capture and Sequestration for Green House Gas Control Lokesh K. Khotele*, Ankita M. Raut, Nihar S. Verma


Jawaharlal Darda Institute of Engineering & Technology, Yavatmal (M.S) India. 445001


Abstract:- Carbon capture and sequestration (CCS) is a

range of technologies that hold the promise of trapping up to

90% of the carbon-dioxide. CCS involves capturing,

transporting and burying the carbon-dioxide so that it does

not accumulate in the atmosphere and contribute to climate

change. After successfully completing the study we come on

conclusion that CCS involves the responsible utilization of

fossil fuels without endangering the planet. We found that

the CCS technology is garnering attention as a bridging

technology in the new energy society.

Keywords:- Carbon capture and sequestration (CCS), climate

change, enhanced oil recovery (EOR), global warming,

bridging technology.

I. INTRODUCTION

Carbon-dioxide comprises the major portion of GHG emissions,

which is the largest contributor to climate change. There are two

major sources of CO2: Natural source and Human source.Natural

sources of CO2 are more than 20 times greater than sources due

to human activities, but over periods longer than few decades

natural sources are closely balanced by natural sinks.The human

oriented CO2 source is fossil fuel. At present fossil fuels are the

dominant sources of the global primary energy demand, and will

likely remain so far the rest of the century. Fossil fuel supply

over 85% of all primary energy; the rest is made up of nuclear –

hydroelectricity, and renewable energy. Combustion of fossil

fuel produces GHG emissions, which further results in severe

problems such as global warming and ozone layer depletion.

Since the beginning of industrial age in 1880, the CO2

concentration in atmosphere has increased from 280 ppm to 400

ppm in 2015. CCS will play crucial role to attain the required

reduction in GHG emissions.

CCS involves capturing, transporting and burying the carbon-

dioxide so that it does not accumulate in the atmosphere and

contribute to climate change. The most sensible approach of

capturing carbon-dioxide is from large stationary point sources,

such as fossil fuel power plants (Ref fig 1).

The objective of this paper is to present sustainable approach

toward reduction in atmospheric emissions of CO2 from

anthropogenic activities. With the current state of knowledge

concerning technical, scientific and environmental dimensions of

CCS and to place CCS in the context of other options in the

portfolio of potential climate change mitigation measures.

Fig. 1. Schematic representation of CCS

II. NEED OF CCS

During the 21st century emissions of CO2 due to

anthropogenic activities are virtually certain to be the dominant

influence on the trends in atmospheric CO2 concentration. The

global average temperatures as well as sea levels are projected to

rise under all scenarios. This indicates that there is need to take

some major steps toward CO2 mitigation.

The IPCC which includes more than 1,300 scientists from

the United States and other countries gives its synthesis report in

2014.

The findings of the synthesis report are given below:

1. In its first assessment in 1990, the IPCC said observed

temperature increases were “broadly consistent with predictions

of climate models, but it is also of the same magnitude as natural

climate variability.”

2. The second assessment, in 1995, said: “Results indicate that

the observed trend in global mean temperature over the past 100

years is unlikely to be entirely natural in origin.”

3. In 2001, its third assessment reported: “There is new and

stronger evidence that most of the warming observed over the

last 50 years is attributable to human activities.”

4. By2007, the consensus had reached “very high confidence” –

at least a 90 percent chance of being correct – in scientists‟

understanding of how human activities are causing

warming.This fifth assessment puts that certainly at 95 percent

and noted “recent climate changes have had severe, widespread

and irreversible impacts on human and natural systems.”




From above statements we can judge that how necessary it is to

reduce CO2 emissions. Scientists have confidence that global

temperatures will continue to rise for decades to come, largely

due to GHG produced by anthropogenic activities.

The graph below will give us a more clear & concise view of

current scenario of GHG emissions.

Fig. 1. Globally averaged greenhouse gas concentrations.

The above graph shows the relative global concentration of

GHG emissions in atmosphere since 1850s. We can see that how

rapidly the curve deviates upward from 1950s. One remarkable

thing in the graph is CO2 share; it is found comparatively more

than the emissions of CH4 and NOx.

Do we still need any justification for why we need to control the

CO2 emissions?Thus we need a technology which help will us

reduce the CO2 emissions, CCS technologies are currently

available which hold promise of trapping 90 percent of CO2 from

power plants that burn fossil fuels.

Why CCS particularly? There are other options too likewise

reforestation. Following example will give us the better

understanding of our query.

Applied to a 500 MW coal-fired power plant, which emits

roughly 3 million tons of CO2 per year, the amount of GHG

emissions avoided (with 90% reduction efficiency) would be

equivalent to:Planting more than 62 million trees, and waiting at

least 10 years for them to grow.Avoiding annual electricity

related emissions from more than 300,000 homes.

III. OVERVIEW OF CCS

There are three main majors steps involved in CCS:

1. Capture of CO2

2. Compression & Transportation of CO2

3. And, the Storage of captured CO2.

Below the Details of CCS is discussed.

A. Capture Techniques

There are three main approaches for capturing CO2.

i. Pre-combustion capture

ii. Post-combustion capture

iii. Oxyfuel combustion capture

In this section we will discuss about all of them.

a) Pre-combustion capture

Pre-combustion CO2 capture refers to the removal of carbon

from a fuel prior to combustion, so that there will be no

generation of CO2 after combustion. In hydrocarbon fuels (such

as fossil fuels), carbon can be extracted from hydrocarbons as

CO2, and the transformed pure stream of hydrogen can be used as

a clean source of energy. The process diagram below outlines

how pre combustion capture works.

Figure 2 Flow sheet for pre-combustion carbon-dioxide

capture and storage.

The Process:

Initially the pure oxygen is extracted from air in an air

separation unit (ASU).

The oxygen is then sent to the gasifier where it reacts with the

fuel source (coal, oil or biomass) to produce a syngas which is

the mixture of carbon monoxide and hydrogen. The following

reaction takes place in a gasifier to produce syngas:

2CH4 + O2 2CO + 4H2.

The syngas is then fed to the gas water shift reactor provided

with steam. The reaction is carried out at high temperature (upto

1350oC) and pressure. The water gas shift reaction expressed as

follows:

CO + H2O CO2 + H2.

This converts carbon mono-oxide to two pure gas streams of

hydrogen and carbon dioxide, which can then be used as

follows:

The hydrogen can be burned cleanly to generate steam which

can be used to run turbine to produce electricity or be used for

other industrial purposes. Pure CO2 can be captured, compressed

for transportation and storage. All the heat required in the

process can usually be supplied by the partial combustion of the

fuel, so no need of external heat. As we are using pure oxygen




for the gasification purpose, energy is consumed in the

separation of oxygen from air. However, the absence of nitrogen

from the air in the syngas greatly reduces the cost of separation.

b) Post-combustion capture

Post combustion CO2 capture refers to capture of CO2 from an

exhaust gas stream from the combustion of a fuel in the power

plant, boiler, blast furnace or similar combustion environment.

Post combustion can also be applied to a gas stream from an

industrial process likewise hydrocarbon reformation process

which does not actually involve combustion. Post combustion

capture is the most common technique for capturing CO2, the

principle of chemical gas absorption is used for trapping the CO2

coming out from the stack. The best thing about this method is

that we can retrofit this system within any existing plant; this

process is widely deployed by the European countries as well as

United Nations. The process diagram below outlines how post

combustion capture works.

Fig. 4. Flow sheet for post combustion carbon-dioxide


The Process:

After the fossil fuel energy source is combusted with

air, the flue gas coming out from chimney is cooled to efficient

absorption temperature and treated to remove particulate matter,

SO2, NO2 and other trace gases to avoid clogging of the

packing‟s and extra consumption of the solvent.

Once cooled, the gas enters at the bottom of the contact

absorber where the liquid solvent which is typically an aqueous

amine solution (usually a MEA) is sent from the top of the

absorption tower. The amine solution absorbs the CO2.

The CO2 rich solution is then sent to a stripper where it

is heated to 100-140 oC (depending upon the exact solvent in

use). This reverses the absorption process, releasing most of the

CO2 to form a pure stream and the lean solvent is transported

back to the absorber for reuse.

The CO2 stream is then dehydrated, compressed and

transported to its final storage destination.

c) Oxyfuel combustion

At present, the oxy-fuel combustion is the only technology

that has an immediate potential of achieving capture rates very

close to 100%. The advantageous feature of this technique is

substantial reduction in level of NOx produced, because of

removal of nitrogen from air prior to combustion. For the

maximum efficiency of the process high oxygen purity and strict

temperature control are the necessary conditions. Primarily this

technology has industrial application in welding and cutting of

metals, as fuel burns at a significantly higher temperature in O2

than in air. The diagram below outlines how oxyfuel combustion

capture works:

The Process:

For the oxy-fuel combustion capture pure oxygen is

required which is extracted from air using air separation unit

(ASU).

The pure oxygen and hydrocarbon fuel combusted

together.

This results in the formation of a stream of almost pure

carbon dioxide and steam, which can be then used as follows:

Fig. 3. Flow sheet for Oxyfuel combustion carbon-dioxide


The steam produced is used to run the turbine for electricity

generation or we can remove the steam by condensation from

main stream. Then the pure stream of CO2 obtained is

compressed and send for the storage and transportation.

B. Compression & Transportation of Captured CO2

After capturing the CO2 we need to transport it to the storage

site. For convenient transportation of CO2 firstly it is

compressed. If we compress the gas it converts into liquid, so the

same principle is used here. We compress CO2 and convert it

into liquid. Then the liquid CO2 is transported to the storage site

by means of road transport. But the transportation the road

transport again emits CO2, thus the most preferable approach for

transportation is pipelines. Using pipelines the captured CO2 is

delivered at storage site.

C. Storage of Captured CO2

In the previous sections we discussed the technologies for

separating the CO2 from fossil fuel before or after combustion

followed by the transportation of the captured CO2 to the storage

site. In this section we will discuss the various options for

sequestering the captured CO2.

Geological storage:

It is also known as geo-sequestration, this technique involves

injection of captured CO2, commonly in a supercritical form,

directly into underground geological formations. Unremarkably

following sites have been suggested for storage: oil fields, gas

fields, unminable coal seams, saline aquifers. Using brine wells

the compressed CO2 is injected in the geological formations

which lies far beneath the from the earth surface. Various

physical such as highly impermeable cap rock and geochemical

trapping mechanisms prevents the escape of CO2 from the site.

For increased oil recovery sometimes CO2 injection in the

declining oil fields is preferred. According to IPCC we have

enough sites for geological sequestration that we can store the

CO2 at least for 60 years, globally. In the geological

sequestration there might be a threat of leakage, of CO2 back into




the atmosphere but this can be overcome through current

researches done on the trapping mechanisms. This research

shows that the structural trapping, residual trapping, solubility

trapping and mineral trapping can immobilize the CO2

underground, thus it reduces the risk of leakage.

Table 1 lists the estimated worldwide capacities for CO2 storage

in the various media. As a comparison to the storage capacities,

we note that current global anthropogenic emissions amount to

close to 7 GtC per year (1 GtC = 1 billion metric tons of carbon

equivalent = 3.7 Gt CO2).

CO2 for use in algae cultivation

The concept is to grow algae in artificial ponds, it is found that

the algae demands CO2 rich water for boosting the growth, thus

we can fertilize the ponds with CO2 from flue gas. Under such

conditions it is possible to enhance the growth of microalgae,

harvest the algal biomass and turn it to fuel, feed or food.

Mineral Storage

There is another approach for storing the captured CO2 in the

form of stable carbonates. By reacting the metal oxides that are

available in abundant quantity in earth‟s crust such as Calcium

oxides (CaO) and Magnesium oxides (MgO) with the captured

CO2 we can produce the carbonates which are stable in

atmosphere. Following reaction will help us to understand the

concept more clearly.

CaO + CO2 CaCO3 (calcium carbonate)

MgO + CO2 MgCO3 (magnesium carbonate).

Enhanced Oil Recovery (EOR)

EOR is a technique used to increase the extraction of crude

oil from oil fields. In CCS EOR, carbon dioxide is injected into

the gas and oil fields beneath the earth‟s surface around 1 to 3

kms for the recovery oil. CCS EOR, by injecting CO2 into an oil

reservoir it recover the oil which is often never recovered using

more traditional methods.

There are three phases involved in enhanced oil recovery:

primary, secondary and tertiary. During primary recovery we

can recover about 10% of reservoir‟s original oil. Secondary

recovery technique recovers 20 to 40% of original oil, whereas

EOR offers ultimately 40 to 60%, or more recovery of the

reservoir‟s original oil.

IV. Scope of CCS

We are using the concept of an already exist paper in this

study. The rate of emission of carbon-dioxide in the atmosphere

is rising vigorously. The recent report of UNEP, WMO and

IPCC says that the all GHG emissions must fall to zero by 2100;

else the world will face the severe widespread and irreversible

effects from climate change. Carbon-dioxide is the major

component in the climate change through this paper we are

looking toward the carbon-dioxide capture and sequestration

technology as a maestro in reducing CO2 emissions. Today the

CO2 emission is hot issue, if we do not act soon it is our children

and grandchildren who have to pay the price. CCS have

tremendous opportunities and huge potentials, entering into the

field is not easy, as it requires considerable technological

expertise and willingness to take up long term strategies and

research and development efforts appropriate to the particular

industries. By understanding the need of reducing carbon-

dioxide emission this study is carried out. Our main motive is to

deploy this technology for the green and safe future of our

planet.

V. Conclusion

We believe that by adopting this technique we can reduce the

carbon-dioxide contribution in climate change to a huge extent.

This technique will give obvious results immediately. Apart

from the reduction in atmospheric CO2 concentration this

technique is providing us sustainable and long lasting approach

for CO2 management.

VI. ACKNOWLEDGMENT

The authors gratefully acknowledge to Prof. Sanjay H.

Amaley, HOD, Department of Chemical Engineering, JDIET,

Yavatmal for valuable guidance and kind support.

VII.NOMENCLATURES

CCS Carbon Capture & Sequestration

GHG Greenhouse Gas

IPCC Intergovernmental Panel On

Climate Change

WMO World Meteorological Organization

EPA Environmental Protection Agency

UNEP United Nation Environment

Programme

CO2 Carbon dioxide

NOx Nitrogen oxides

SOx Sulphur oxides

CH4 Methane

H2O Water

H2 Hydrogen

O2 Oxygen

CaO Calcium oxide

MgO Magnesium oxides

CaCO3 Calcium carbonate

MgCO3 Magnesium oxides

MEA Mononethanolamine

ASU Air Separation Unit

EOR Enhanced Oil Recovery

CCS EOR Carbon Capture & Sequestration

Enhanced Oil Recovery.

REFERENCES i. Finkenrath, M. 2011 Cost and Performance of Carbon Dioxide Capture

from Power Generation. International Energy Agency.

ii. Center for Climate and Energy Solutions (C2ES). 2009. “In Brief: What the Waxman-Markey Bill Does for Coal.”

iii. U.S. Department of Energy (DOE) and U.S. National Energy Technology Laboratory (NETL). 2010. DOE/NETL Carbon Dioxide Capture and

Storage RD&D Roadmap.

iv. NETL. 2010b. Cost and Performance Baseline for Fossil Energy Plants Volume 1: Bituminous Coal and Natural Gas to Electricity.

v. Taglia, P.2010. Enhanced Oil Recovery (EOR) – Petroleum Resources and Low Carbon Fuel Policy in the Midwest.

vi. Zangeneh, F.T., S. Sahebdelfar, and M. T. Ravanchi, “Conversion of

carbon dioxide to valuable petrochemicals: An approach to clean development mechanism,” Journal of Natural Gas Chemistry. 20 (3): p. 219-

231.2011 vii. IPCC Synthesis Report

viii. M. Songolzadeh, M Takht. Carbon Dioxide Capture and Storage: A

General Review on Adsorbents. ix. “IPCC special report on Carbon Dioxide Capture and Storage summary

for Policymakers” Intergovernmental Panel on Climate Change. x. Mineral carbonation & industrial uses of carbon dioxide. Accelerating the

uptake of CCS: industrial use of the captured carbon dioxide – Appendix

CO2 for use in algae cultivation”.




CO2 capture using 1-Hexyl-3-methylimidazolium based Ionic Liquids

Dhaneshwar Devikar*1, Swapnil Dharaskar

2, Y. C. Bhattacharyulu

2, Kailas L. Wasewar

2

1Department of Chemical Engineering, Anuradha Engineering College, Chikhli (M.S) India

2Department of Chemical Engineering, Jawaharlal Darda Institute of Engineering & Technology, Yavatmal

(M.S) India.


Abstract :- Current post combustion CO2 capture systems in

power plants typically employ amine based solvent, such as

monoethanolamine (MEA), to capture CO2 from flue gas

followed by a desorption (or solvent regeneration) step, usually

a stripping column, to recover the captured CO2 and

regenerate the solvent. The MEA solvent has high heat of

reaction with CO2 that leads to higher stripping energy

consumption during CO2 recovery, thus making amine

scrubbing an energy expensive process. The solvents suggested

for CO2 capture in this work belong to a group of compounds

called ionic liquids (ILs). Many ILs have shown a remarkably

good CO2 solubility. Ionic liquids have also shown good

selective CO2 absorption, thus making ILs a potential

candidate for CO2 capture from flue gas. Since CO2 absorption

in ILs involves physisorption (physical absorption) rather than

chemisorption (chemical absorption) of CO2 in amine based

solvents, there is a potential to develop energy efficient ionic

liquid based absorption-stripping process. The choice of the

ionic liquid, 1-hexyl-3–methylimidazolelium tetrafluoroborate

(HMIM)BF4, has not been optimized but was chosen based on

chemical absorption behaviour and the desire to understand

performance. Engineering design estimates indicate that the

investment for the ionic liquid process will be 11% lower than

the amine based process and provide a 12% reduction in

equipment footprint.

Keywords: CO2 capture, MEA, Ionic liquids, (HMIM)BF4

Introduction

There is growing concern that anthropogenic carbon dioxide

(CO2) emissions are contributing to global climate change

through global warming. Therefore, it is critical to develop

technologies to mitigate this problem. One very promising

approach to reduce CO2 emissions is to capture CO2 at a power

plant, transport to an injection site, and sequestration for long-

term storage in any of a variety of suitable geologic formations.5

The injection site could be a petroleum reservoir and CO2 can be

used in Enhanced oil recovery (EOR) process. Therefore, CO2

capture is expected to become an important part of the future

power production.

Current post combustion CO2 capture systems in power plants

typically employ solvent based absorption followed by a

desorption step, usually a stripping column, to strip off CO2 and

regenerate the solvent. The typical solvents used for this purpose

are the amine based absorption agents, such as

monoethanolamine (MEA).6 The flue gas from power plants

contains normally 12 vol % CO2 besides nitrogen. CO2 from flue

gas is selectively absorbed in MEA solution through a chemical

reaction in the absorption step. After the absorption, CO2 is

desorbed in a stripping column in its pure form, compressed, and

transported in liquid form to the storage place. MEA has high

CO2 carrying capacity, low hydrocarbon solubility, reacts

quickly with CO2 and is relatively inexpensive, thus making it a

popular choice in commercial processes. Besides these

advantages, there are several disadvantages associated with

MEA. It has high vapour pressure which leads to fugitive

emissions during regeneration and its corrosive nature which

limits its use to dilute aqueous solutions. It also forms

degradation products due to side reactions between some minor

constituents of the flue gas. Finally, it has high reaction heat

with CO2 that leads to higher stripping energy consumption, thus

making the process energy expensive.7 Thus there is a need to

develop cost-efficient techniques that have low energy

requirements and that do not cause environmental problems,

such as the release of volatile organic compounds (VOCs) to the

atmosphere. The solvents suggested for CO2 capture in this

project belong to a group of compounds called ionic liquids

(ILs). ILs are molten salts consisting of ions i.e. anions and

cations.

Unlike common salts, ionic liquids are liquid even at

temperature below 100 °C. The terms room temperature ionic

liquid (RTIL), nonaqueous ionic liquid, molten salt, liquid

organic salt and fused salt have also been used to describe these

salts in the liquid phase.8 They are frequently referred to as

“Green Solvents” due to their immeasurably low vapour

pressure. This lack of volatility essentially eliminates the

possibility of solvent release to the atmosphere.8 An important

feature associated with ILs is that their properties (e.g. density,

conductivity, viscosity, Lewis acidity, hydrophobicity, gas

solubility and hydrogen-bonding capability) can be tuned by

varying the structure of the component ions to obtain desired

solvent properties. Due to this reason ILs possesses a large range

of industrial applications. A number of investigations have

shown that CO2 is remarkably soluble in many ionic liquids.9-19

This attractive feature makes ILs a potential candidate for gas

separation. These ionic liquids show a greater tendency to

dissolve CO2 than other gases like methane, ethane, ethane,

oxygen, nitrogen, argon and carbon monoxide, so selective

absorption of CO2 from flue gas is possible.12,15 During

absorption process CO2 is only absorbed physically, therefore

the energy required during desorption process could be smaller

compared to the amine based technology. The objective of this

work is to measure the CO2 solubility in 1-Hexyl-3-

methylimidazolium tetrafluoroborate ionic liquids, using

available facility of High Pressure Reactor.




CO2 Capture Systems

There are three basic systems for capturing CO2 from use of

fossil fuels and/or biomass.36

a) Post-combustion capture

b) Pre-combustion capture

c) Oxy-fuel combustion capture

These systems are shown in simplified form in Figure 3. 2. A

brief description of these systems is given as follows:

a) Post-combustion capture:

Capture of CO2 from flue gases produced by combustion of

fossil fuels and biomass in air is referred to as post-combustion

capture. Instead of being discharged directly to the atmosphere,

flue gas is passed through equipment which separates most of

the CO2. The CO2 is fed to a storage reservoir and the remaining

flue gas is discharged to the atmosphere. In this work we will

focus only on post combustion capture of CO2 from power

generation later in this chapter.

Fig. 1: Different CO2 capture systems in simplified form

b) Pre-combustion capture:

Pre-combustion capture involves reacting a fuel with oxygen or

air and/or steam to give mainly a “synthesis gas (syngas)” or

“fuel gas” composed of carbon monoxide and hydrogen. The

carbon monoxide is reacted with steam in a catalytic reactor,

called a shift converter, to give CO2 and more hydrogen. CO2 is

then separated, usually by a physical or chemical absorption

process, resulting in a hydrogen-rich fuel which can be used in

many applications, such as boilers, furnaces, gas turbines,

engines and fuel cells. Figure 3. 3 shows pre-combustion capture

with some additional equipments to remove particulates and

sulfur before CO2 capture.37 Pure hydrogen is used in gas turbine

and then burnt to produce electricity.

c) Oxy-fuel combustion capture:

In oxy-fuel combustion, nearly pure oxygen is used for

combustion instead of air, resulting in a flue gas that is mainly

CO2 and H2O. If fuel is burnt in pure oxygen, the flame

temperature is excessively high, but CO2 and/or H2O-rich flue

gas can be recycled to the combustor to moderate this. This is

necessary because currently available materials of construction

cannot withstand the high temperatures resulting from coal

combustion in pure oxygen. Oxygen is usually produced by low

temperature (cryogenic) air separation to supply oxygen to the

fuel. For a new unit, it should be possible to use smaller boiler

equipment due to increased efficiency. The main attraction of

this process is that it produces a flue gas which is predominantly

CO2 and water. The water is easily removed by condensation,

and the remaining CO2 can be purified relatively inexpensively.

Figure3. 4 show oxy-fuel combustion capture with some

additional equipments to remove particulates and sulfur before

CO2 capture. 37

Fig. 2: Pre-combustion capture system (Photo Courtesy of

www.kjell-design.com /

Vattenfall)

Fig. 3: Oxy-fuel combustion capture system (Photo Courtesy

of www.kjell-design.com /Vattenfall)

Fig. 4: Post-combustion capture system (Photo Courtesy of

www.kjell-design.com /Vattenfall).




CO2 capture systems for ionic liquids

There are two systems which can be used for CO2 capture using

ionic liquids. Absorption system (absorber and stripper) is one of

the most common techniques for gas purification in which the

flue gas is bubbled through the solvent (e.g. ionic liquid), the

solvent will absorb the gas of interest (e.g. CO2) from flue gas

and the solvent is then regenerated in the stripper to use it again

in the system.125 Supported liquid membrane (SLM) is the

second technique that can be use for CO2 capture medium using

ionic liquids. In SLM system, the pores of a membrane are filled

with the solvent (e.g. ionic liquid). The more soluble gas is able

to permeate across the membrane, while the less soluble gas

remains on the feed side. The major advantage of a supported

liquid membrane system is that a large surface area is achieved

with a small amount of solvent. Another advantage is the

membranes do not require a regeneration step; the gas is

continually desorbing out of the solvent due to a pressure and/or

concentration gradient. However, one of the limiting factors

inhibiting the use of SLM is membrane instability. The flux of

the gas across the membrane is affected by the thickness of the

membrane. A thinner membrane yields a higher flux, but the

thinner the layer of solvent, the quicker the solvent evaporates.

But, due to non volatile nature of ionic liquids this problem can

be eliminated in case of ionic liquids SLM systems.46 However,

the choice of either of the two systems can be made on the basis

of capital cost and energy requirements of the system.

Materials and Methods

Chemical and Materials

Imidazolium based ionic liquid with BF4 cation is used in this

study to measure the solubility of CO2.

1-Hexyl-3-methylimidazolium tetrafluoroborate

[HMIM]BF4 is synthesized by the process given below.

IL used in the experiment was synthesized using analytical

grade chemicals. The details of the chemical used are as

follows: 1-methylimidazole (CAS 616-47-7, Acros, 99%), 1-

bromohexane (CAS 111-25-1, Acros, min 99%), NaBF4 (CAS

237-340-6, Sigma Aldrich, 98%), Acetone (CAS 20003-L25,

SDFCL, 99.5%), Ethyl Acetate (CAS 20108-L25, SDFCL,

99.5%). All chemicals were used without any further

purification.

Synthesis of [HMIM]Br

13.21 g (0.08 mol) of 1- bromohexane and 8.2 g (0.1 mol) of 1-

methyimidizole were mixed in three round neck bottomed flasks

fitted with a reflux condenser for 48 h at 70 0C with stirring until

formation of two phases. The top layer contains unreacted

material which was decanted and 30 ml organic solvent (ethyl

acetate) was added to bottom layer with comprehensive mixing.

Allow the mixture to settle and decant ethyl acetate. The same

procedure was followed by adding fresh ethyl acetate twice.

After the third decantation of ethyl acetate, remaining solvent

was removed by heating at 70 0C. The obtained pale yellow

liquid was vacuum distilled and the intermediate product

(HMIM Br) was placed for vacuum drying at 80 0C in a vacuum

drying oven

Results and Discussion

Ionic liquid, 1-Hexyl-3-methylimidazolium tetrafluoroborate

([HMIM]BF4) has been investigated for its CO2 solubility using

High Pressure Reactor. The purpose of this study is to measure

the CO2solubility in this ionic liquid and to check the

performance and reliability of the setup for these kinds of

measurements. The following section presents various results

obtained in this work.

Solubility Measurements

The details of solubility measurements are presented below.

Carbon Dioxide Solubility. The values of the Henry‟s law

constant for CO2 in the RTILs are presented in Table 1. The

solubility of CO2 in each RTIL at 1 bar CO2 pressure is listed on

both a mole fraction basis as well as in mol CO2/L of RTIL in

Table 2.The above data are plotted in figure 5 and figure 6

Table 1. Experimentally Measured Henry’s Law Constants

(H) for Carbon Dioxide in Ionic Liquid

Ionic Liquid H(bar)

25 0 C 40

0 C

Hmim BF4 52 73.5

Table 2 CO2 Solubility in Ionic Liquids at 1 bar CO2

Pressure

Ionic Liquid Mol CO2/mol IL

25 0 C 40

0 C

Hmim BF4 0.0019 0.0013

Fig. 5. Plot of Henry’s constant versus temperature

Fig. 6. Plot of Mol CO2/mol IL versus temperature




Conclusion

The solubility of CO2 in ionic liquid [hmim][BF4] at 25 oC and

pressure up to 1 bar has been measured and reported. The

measured CO2 solubilities (i.e. Henry‟s constants) is not good

enough and is also not in good agreement with the values

published in the literature. The disagreement in data is due to

some technical problems in the experimental setup used in this

work.

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