ethanol production from crude glycerol
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Transcript of ethanol production from crude glycerol
KKKB 4774BIOPROCESS PLANT DESIGN PROJECT I
Lim Kah HuayA132816Low Bee Chan A132764Sonia Dilip Patel A/P Dilip Kumar A133115Fatin Atikah Binti Kassim A132739Jamilah Binti Ahmad A133159Muhammad Khairil Azim bin Abdullah A133275
PRODUCTION OF BIOETHANOL FROM GLYCEROL USING Enterobacter aerogenes TISTR1468
FEASIBILITY STUDY
Group KB4
Level 1
Level 2
Level 3
Level 4
Feasibility Study Outline
• Process Selection• Chemical reaction• Details for raw material and product
• Design constraint• Site location• Physical / Chemical properties
• Synthesis of Input-Output Structure• Design variable• Design capacity
• Mass balance• Curve of FEP 2
• Number of bioreactor• Limiting reactant balance•Bioreactor selection
• Bioreactor sizing• Cost of bioreactor• Curve of FEP 3
• Disc Stack centrifuge• Distillation column • Molecular sieve
• Storage tank • Curve of FEP 4
• Higher octane number• Reduced particulate and NOx emission• Higher flame speed• Higher heat of vaporization• SO2 & PM emission decreased• Reduce emission of hydrocarbon – depletion of ozone• Lower volatility and photochemical reactivity – smog• Octane enhancer (cancer-causing) – emission reduced by half• Broader flammability limits
Source: Renewable Fuels Association (2008)Level 1
Why Ethanol?
• The United States• Brazil• Canada• Sweden • India• China
Ethanol as Fuel Worldwide
Other Usage• Industries Pharmaceutical Personal care Cleaning products Paint Food Beverage
Product Usage
Property Gasoline Ethanol
Specific gravity 0.73 0.79
30 - 225 78.3
Specific heat (MJ/kg) 43.5 27.0
Heat of vaporization (kJ/kg) 400 900
Octane number 91-100 108
-40 13
300 366
Heat of formation (kcal/mole) -52.78 -51.95
Latent Heat (kcal/kg) 90.82 210.7
Molecular weight (g/mol) 113.228 46.070
Toxicity Toxic Less toxic than gasoline
Solubility in water No Yes
Smoke Produce visible smoke
Does not produce visible smoke
Source: Shah (2010)
GASOLINE & ETHANOLAdvantages of Ethanol Over Gasoline
Exhibits a higher octane number which enables engine to have higher compression
Oxygenated fuel that contains 35% oxygen
Reduced particulate and NOx emission from combustion
Ethanol based on fermentation produces no net increase in carbon dioxide in atmosphere
Octane enhancing additive
Removes free water which can plug fuel lines in cold climates
Broader flammability limits
Higher flame speeds
Higher heat of vaporization
Lower volatility and photochemical reactivity (Reduced smog formation)
Lower toxicity compared to gasoline
Source: Srivastava (2008)
Crude glycerol
Components ConcentrationGlycerin >60%Water < 20 %Sodium Chloride < 5 %Methanol < 1%Ash < 5 %Fatty Acid Ester < 5 %
Table 1.2 Physical and chemical properties of glycerol
Physical Properties Chemical Properties
Amber coloured Density of 1.22-1.24 g/m3
Grain-like odour Melting point of 18 oC
Liquid state Boiling point : >130 oC
Molecular weight of 92.09 Vapour density : 3.17
Specific gravity : 1.26 Flash point : >120 oCRaw Material
Source: Eastridge (2009)
Source: Pangliaro & Rossi (2008)
Table 1.1 Chemical composition of crude glycerolAdvantage over sugar
because of highly reduced nature of
carbon atoms
Bacterial strain Condition Yield of ethanol
Ethanol concentration
Reference
Aerobacter aerogenes 1033
pH 6.5, 35°C, batch culture containing 10% glycerol for 18h.
0.86 mol/mol glycerol
0.54 g/l Megasanik (1953)
Enterobacter aeogenes HU 101
pH of 6.8, 37°C 0.8 mol /mol purified glycerol
0.51 g/l Ito et al (2005)
Enterobacter agglomerans CNCM 1210
pH 7.0, 30°C, 20 g/L of glycerol
0.23mol/0.05mol glycerol
2.91g/l
Barbirato et al(1997)
Klebsiella planticola DR3
Initial pH 7.2 - 7.4, 37°C 10g/L of glycerol for 48h
30 mmol/L 2.76 g/l Jarvis et al(1996)
Clostridium butylicum B593
Initial pH 6.5, 35°C 0.54 mM 0.002 g/l Forsberg (1986)
Klebsiella pneumoniae M5a1
pH 6.8, 37°C 34.0 + 0.4mmol/L
1.57 g/l Lin et al(2005)
Enterobacter aerogenes TISTR 1468
Crude glycerol, 30°C 0.94 mol/mol 24.5 g/l Ciptanto (2009)
BACTERIAL
SELECTION
Kingdom Bacteria
Phylum Proteobacteria
Class Gamma Proteobacteria
Order Enterobacteriales
Family Enterobacteriaceae
Genus EnterobacterFacultative anaerobeGram negativeRod shaped
Enterobacter aerogenes TSISR 1468
Source: Microbial Library (2010)
Biochemical Pathway Mutated pathway to maximize ethanol produced.
Insignificant amount of butanol produced.
Table 1.3 Hierarchy for Enterobacter aerogenes
p/s: The ratings are to the scale of 5.
Factors of Consideration Port Klang Pasir Gudang Pengerang
Availability of raw material 5 5 5
Proximity to market 5 5 4
Labor Availability 5 5 5
Transport and facilities 5 5 5
Effluent Disposal facilities 4 4 4
Product storage availability 3 3 5
Utilities (services) 5 5 4
Political and strategic considerations
4 4 5
Total 36 36 37
Table 1.3 Factors of considerations for site location
SITE LOCATION
Port Klang
Pengerang
Pasir
Gudang
Why Pengerang?Malaysian Federal Government and Johor State Government give full support to develop this area.Located in the middle of oil and gas trading route –Iskandar Malaysia Integrated Development.Potential in becoming major regional manufacturer of oil refinery – attraction of investor for bioethanol plant.Close to major trading hubs – attract investor/customer.Availability of sufficient land 20 000 acres
2013 2014 2015 2016 2017 2018 2019 2020 2021 20220
50
100
150
200
250
300
350
400
World Bioethanol Supply and Demand Capacity from Year 2013 - 2022 (Projections)
demand
supply
Years
Bio
eth
anol
(b
illio
n li
tres
)
Source: OECD-FAO Agricultural Outlook 2013 – 2022 (2013)
Market Analysis
Generation of Productin Capacity Basis
According to OECD-FAO Agricultural Outlook 2013,Shortage = 0.7 million litres / year
= 552.44 tonnes / year
However from Biofuels Digest 2012,Japan’s Toyo Engineering Co. in a joint venture with Glycos Biotechnologies and Malaysian developer Bio-XCell will build a 10,000 ton per year ethanol plant in Johor Bahru by Q2 2013. The facility that will use from crude glycerin from the production of palm methyl ether as feedstock will expand to 30,000 tons per year by 2014.
Therefore, an average of 15,000 tonnes / year of ethanol production will be taken as the plant production capacity basis.
Comparison between Batch & Continuous process
Process
Criteria
Batch Continuous
Capital cost Low High
Rate of production Low High
Raw material product Processed differently in various pieces equipment
Processed in identical fashion/equipment
Workforce More Less
Ease on automation Relatively difficult Relatively easy
Energy efficiency Large peak demand Small but continuous loads
Down time Long Short
INPUT-OUTPUT STRUCTURE
CONTINUOUS PROCESS
Crude glycerol
Ammonia
Carbon dioxide
Biomass
Ethanol
Nitrogen, Oxygen
Water
Process Output DestinationProduct Boiling Point at 1
atm (°C)Class Destination
Ethanol 78.3 Main Product Main product
Biomass N/A Waste Waste treatment
Carbon Dioxide -78.5 Gas byproduct Vent
Water 100 Waste Waste water treatment plant
Price of ethanol – RM 3.06 / kg (Source: OECD-FAO Agricultural Outlook 2013)Price of glycerol – RM 0.64 / kg (Source: Petrosil Glycerin Report 2013)
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
-300.00
-275.00
-250.00
-225.00
-200.00
-175.00
-150.00
-125.00
-100.00
-75.00
-50.00
-25.00
0.00
25.00
50.00
75.00Economic Potential Graph Level 2 vs Glycerol Conversion
552.44 MT/yr10, 000 MT/yr30, 000 MT/yr15, 000 MT/yr
Glycerol Conversion
Eco
nom
ic P
oten
tial
2 (
RM
mill
ion
/yr)
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.10
0.10.20.30.40.50.60.70.80.9
11.1 Yield versus Conversion
ethanol succinic lactic acetic
Conversion
Yie
ld(m
ol/m
ol)
1.05
0.75
Yield (mol/mol)
1.05
Yield (g/g) 0.52
Conversion 75%
Conversion and Stoichiometry
Stoichiometry Equation:𝐶3 𝐻5 (𝑂𝐻)3 + 0.06594 𝑁𝐻3 + 0.047775 𝑂2 →0.27475 𝐶𝐻1.78𝑂0.33𝑁0.24 + 1.05 𝐶2𝐻5𝑂𝐻 + 0.62525𝐶𝑂2 + 0.704382 𝐻2𝑂
Comparison Between 1 Fermenter and 2 Fermenters In Series
0.27 0.49 0.63 0.740
5000
10000
15000
20000
25000
30000
35000Fermenter Volume versus Conversion 2 fermenters 1 fermenter
Conversion
Vol
um
e, L
0.2 0.3 0.4 0.5 0.6 0.7 0.8
-40.00
-30.00
-20.00
-10.00
0.00
10.00
20.00Economic Potential Graph Level 3 Versus Conversion
1 fermenter 2 fermentersConversion
FE
P 3
(R
M m
illio
n/Y
R)
Bioreactor
1 seed fermenter 2 main fermenters in series
8.9
6.7
Diameter of Fermenter, m 1.56
Height of Fermenter, m 4.67
Diameter of impeller, m 0.52
Aeration rate, vvm 0.5
Agitation, rps 0.169
Material SS304
64.77 2.47
48.58 1.85
Diameter of Fermenter, m
3.02 1.02
Height of Fermenter, m 9.05 3.05
Diameter of impeller, m
1.00 0.34
Aeration rate, vvm 0.5 0.5
Agitation, rps 0.083 0.225
Material SS304 SS304
Component Mr Ni
(kmol/h)
Fi (kg/h) No
(kmol/h)
Fo (kg/h) Ni
(kmol/h)
Fi (kg/h) No
(kmol/h)
Fo (kg/h)
Glycerol 92.09 5.05 465 1.24 113.77 51.73 4763.77 12.66 1165.56Ammonia 17 0.25 4.27 0 0 2.51 42.75 0 0Oxygen 32 0.09 2.92 0 0 0.91 29.23 0 0Biomass 22.5 0 0 1.05 23.58 1.05 23.58 11.78 265.11Ethanol 46.07 0 0 4.00 184.48 4.00 184.48 45.03 2074.42Carbon Dioxide
44 0 0 2.32 102.012.32 102.01 26.07 1147.12
Water 18 232.26 4180.73 234.95 4229.08 2614.40 47059.24 2641.92 47554.61∑ 4652.92 4652.92 52205.07 52206.83
Mass Flow Rate(kg/h) Mass Balance Superpro simulation Error %
Total output from fermenters 52205.07 52761.08 1.05
Comparison of mass balance manual calculation with superpro simulation
Mass balance of bioreactor (fermentors)
Seed
Main
rlimiting = Nik /- αkGlycerol flow rate,
Ng(mole/hr)Glycerol limiting,
rg, limitingAmmonia flow
rate, Na(mole/hr)
Ammonia limiting, ra,
limiting
Seed Fermenter 5049.2 5049.2 251.5 3813.8Main Fermenter 51727.4 51727.4 2514.8 38138.0
Excess or Limiting Reactant
Mass Balance
IMSK (recent) IMSD (old)
Fm (material construction
factor)
Fp (pressure factor)
Fi (installation
factor)1512.5 280 3.75 1 1.5
Downstream Separation General Structure
Distillation Column
Disk Stack Centrifuge
Molecular Sieve
Ethanol
Biomass
Water
Biomass
Concentrated Ethanol(99.5%)
Water
Water
Glycerol
Downstream Separation
• Disc-stackSeparation of finely dispersed
particles.Easy to operate and control
through continuous and automatic operation.
Disc split the stream into a large number of very thin layers thereby improving separation.
No filter cloth, additives or flocculants necessary.
Source: Alfa Laval (2008)
Molecular sieves
Minimal labor requirementThe process is inertThe molecular sieve desiccant material used has a very long potential service lifeRegenerable process
Source: Ethanol India (2011)
Source: Doughlas (1988)
Glycerol conversion
K centrifuge K distillation K Molecular sieve
K storage tank K total (in million)
0.0 164 760.42
167 833.8 755 252.2 3 386.23 1.0912
0.1 165 624.54
168 098.5 756 443.1 151 133.90 1.2413
0.2 166 491.86
168 363.2 757 634.6 221 273.00 1.3138
0.3 167 362.37
168 628.2 758 826.7 276 553.20 1.3714
0.4 168 228.79
169 025.8 760 616.2 323 962.70 1.4218
0.5 169 095.98
169 291.1 761 810.1 366 265.10 1.4665
0.6 169 959.11 169 556.6 763 004.6 404 897.60 1.5074
0.7 170 818.21
169 822.2 764 199.7 440 723.20 1.5456
0.8 171 680.53
170 087.9 765 395.6 474 309.20 1.5815
0.9 172 538.85
170 486.8 767 190.6 506 052.30 1.6163
1.0 173 311.67 170 048.8 767 190.6 536 240.30 1.6472
K Values of different unit separation
K Values for Different Types of Separation
0 0.2 0.4 0.6 0.8 1 1.20
100000
200000
300000
400000
500000
600000
700000
800000
900000
Graph of Economy Potential against Glycerol Con-version
Absorber
Storage tank
Centrifuge
Distillation
Glycerol conversion
Eco
nom
y P
oten
tial
(R
M M
illi
on/y
ear)
Comparison of Economic Potential Curve Level 3 (FEP 3) and Level 4 (FEP 4)
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1
-180
-160
-140
-120
-100
-80
-60
-40
-20
0
20
40
FEP 3
FEP 4
Glycerol Conversion
Eco
nom
y P
oten
tial
(R
M M
illi
on/y
ear)
• James M.Douglas. 1988. Conceptual Design of Chemical Process. McGraw-Hill Book.
• Shalabh Srivastava. 2008. Numerical Simulation of a Direct Injection Spark Ignition Engine Using Ethanol As Fuel (2008): 2-5.
• Renewable Fuels Association. 1981. http://www.ethanolrfa.org/pages/philosophy.
• Saon Ray, Smita Miglani & Amrita Godlar. 2011. Ethanol Blending Policy in India: Demand and Supply Issues. ICRIER Policy Series.
• Vishal Shah 2010. Emerging Environmental Technologies: Volume II (2010): 2-5.
• Renewable Fuels Association. 1981. http://www.ethanolrfa.org/pages/philosophy.
• M. Wang, C.Saricks & D.Santini. 1999. Effects of Fuel Ethanol use on Fuel-Cycle Energy and Greenhouse Gas Emission. United States Department of Energy.
REFERENCE
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