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Transcript of “Bio-Inspired heterogeneous catalyst for sustainable biofuel production Prof. (Dr.) Dhanapati Deka...
“Bio-Inspired heterogeneous catalyst for sustainable biofuel production
Prof. (Dr.) Dhanapati DekaDepartment of Energy
Tezpur University, Tezpur, Assam, India
E-mail: [email protected]: +91 3712 27 5301
Contents
1. Zoom on Energy2. Biofuel as Energy Source3. Bio-inspired Catalyst on Biofuel production4. Preparation of Bio-based CaO catalysts 5. Preparation of Carbon based catalyst6. Conclusion
Zoom on energy • High level of energy consumption in developed countries• Growth in demand in emerging economies• Impacts from production and distribution of energy on
biodiversity through• Fuelwood collection• Coal mining• Oil and gas extraction, pipelines / shipping (spills)• Dams (flooding of biodiversity reach areas)• Batteries (production and end of life / waste)
• Impacts from use of fossil energy: Climate change, which in turn, has an impact on biodiversity
Biofuels – an opportunity to reduce impacts or posing new threats??
Petroleum Fuel
Challenges
1.Energy inequality/ Energy Dependence
2.Energy Security
3. Fuels and Chemicals
4.Environmental Issues
Why biofuel ? Why now ?
9-Aug-11 Speaker- Dr. Dhanapati Deka
What are Biofuels ?
Biofuels are fossil fuel substitutes that can be made from a range of
agricultural crops and other sources of biomass. The two most
common current Biofuels are ethanol and biodiesel.
Biofuel: Liquid and gaseous fuels produced from biomass – organic matter derived from
plants or animals. (IEA)
Easy availability from biomass sources BiodegradabilitySustainabilityForeign exchange savings Energy securityOpen up a new income generating path in rural areas etc.
%
1111
21st Century: the beginning of a New Era
Challenge: TO DIVERSIFY ENERGY SOURCESChallenge: TO DIVERSIFY ENERGY SOURCESUp to 2030, the world demand for energy should increase 58%.Up to 2030, the world demand for energy should increase 58%.
Sources: Nakícenovic, Grübler and MaConald, 1998 and US Energy Information Administration Speaker- Dr. Dhanapati Deka
1.One of the main bottlenecks in manufacturing of liquid biofuels are their synthesis routes, which relies on the use of many hazardous and corrosive chemicals such as NaOH, KOH, H2SO4 as catalysts.
2.This not only causes environmental hazards but also adds to the carbon footprint and effects the overall economy of the process.
3.Use of renewables as catalysts or catalysts synthesized from renewabale precursors such as boimass and waste may address these issues.
04/21/23 12
Current Route
Major Liquid Biofuels
(Biodiesel, Bioalcohols
etc.)
Feedstocks (Renewabale
Suorces)
Catalysts/ Reagents used
for synthesis(Non-
renewabale Sources
New stratergy
Major Liquid Biofuels
(Biodiesel, Bioalcohols
etc.)
Feedstocks (Renewabale
Suorces)
Catalysts synthesized from
renewabale Sources
Goals of the study
• Our goal is to obtain a renewable multipurpose heterogeneous catalyst that is faster, active, versatile, and stable under the process conditions capable of competeing with commercialy employed catalysts in the production of major biofuels such as biodiesel and bioalchols with greater emphasis on transesterification.
• It will be capable of substituting corrosive chemicals such as H2SO4, NaOH, KOH etc in various other reactions, there by eliminating the problems associated with their use and consequent environmental hazards.
• Our proposed catalysts will make biofuel production environmentally benign and greener as it will be reusable and derived from renewable/waste materials.
Mechanism of Transesterification Reaction
CH2-OH
CH2-OH
CH2-OH
glycerol
CH2-OOC-R1
CH -OOC-R2
CH2-OOC-R3
+ 3R’OH
R1-COO-R’
R2-COO- R’
R3-COO- R’
+Catalyst
At Temp 60 to 70˚C
Triglyceride + Alcohol Esters +CH
CH2 O
CH2O C
O
C
O
R1
R3
OC
O
R2 + CH3OH
H3CO C
O
R1
H3CO C
O
R2
H3CO C
O
R3
+
++
Refined vegetable oil (Triglycerides)
CH
CH2 OH
CH2OH
HO
Glycerin FAME (biodiesel)
Scheme 1 (Reaction scheme for transesterification of lipids)
Methanol
Catalyst
04/21/23 17
Homogeneous catalytic approach
Drawbacks of conventional heterogeneous catalysts (Alumina, Zeolites, sulfated zirconia etc.)- Expensive- Leaching- Poor activity for the price Solution: Prepare cost effective heterogeneous catalysts
04/21/23
18
Heterogeneous catalytic approach
04/21/23 19
Preparation of Bio-based CaO catalysts with improved reusability for biodiesel production
Advantages of the resources selected
Recycle the waste.
Wide source, low price & favorable biodegradability.
Environment friendly, safer & cheaper.
High active & reusable.21-Mar-2012 Speaker- Dr. Dhanapati Deka
Catalyst 1• Catalyst is prepared from waste shells of
Turbonilla striatula (mollusk)
• Ref:Boro Jutika, Thakur A. J. Deka D. Solid oxide derived from waste shells of Turbonilla striatula as a renewable catalyst for biodiesel production. Fuel Processing Technology 92 (2011) 2061–2067.
21-Mar-2012 Speaker- Dr. Dhanapati Deka
04/21/23 22
The shells were calcined at different temperatures for 4 h and catalyst characterizations were carried out by XRD), scanning electron microscope (SEM), energy dispersive spectrometer (EDS), Fourier transform infrared spectrometer (FT-IR), thermogravimetricanalysis (TGA)/differential scanning calorimetry (DSC) and Brunauer–Emmett–Teller (BET)surface area measurements .
Formation of solid oxide i.e. CaO was confirmed at calcination temperature of 800 °C. The effect of the molar ratio of methanol to oil, the reaction temperature, catalyst calcination temperature and catalyst amount used for transesterification were studied to optimize the reaction conditions.
Biodiesel yield of 9 3. 3% was achieved when transesterification was carried out at 65±5 °C by employing 3.0 wt.% catalyst and 9:1 methanol to oil molar ratio for 6 h. BET surface area indicated that the shells calcined in the temperature range of 700 °C–900 °C exhibited enhanced surface area and higher pore volume than the shells calcined at 600 °C.
Reusability of the catalysts prepared in different temperatures was also studied
21-Mar-2012Speaker- Dr. Dhanapati Deka
04/21/23 24
EDX analysis
04/21/23 25
04/21/23 26
04/21/23 27
FTIR TGA
GC-MS GC analysis of the Biodiesel components
04/21/23 28
04/21/23 29
04/21/23 30
04/21/23 31
Reusability study
XRD pattern of fresh and reused catalysts
04/21/23 32
Fuel properties of biodiesel (in the presence of T-CaO catalyst)
04/21/23 33
04/21/23 34
Li doped waste shell derived CaO
Catalyst 2
Ref: Boro Jutika , Konwar Lakhya Jyoti and Deka Dhanapati. Transesterification of non edible feedstock with lithium incorporated egg shell derived CaO for biodiesel production. Fuel Processing Technology 122 (2014) 72–78.
04/21/23 35
04/21/23 36
A series of Li doped egg shell derived CaO is prepared for biodiesel production from nonedible oil feedstock. The catalyst is characterized by X-ray diffraction (XRD), Fourier transform infrared spectrometer (FT-IR), Brunauer– Emmett–Teller (BET) surface area measurements and their basic strengths were measured by Hammett indicators.
The feedstock for conducting experiments with Li doped waste shell derived CaO to produce biodiesel was waste cooking oil (WCO). Maximum conversion of 94% is observed with 5% of catalyst amount and 2% of Li loading is observed to be optimum for better conversions.
Though the catalyst is not reusable its catalytic activity can be improved by activating it at appropriate temperature and reloading it with Li. NMR studies showed that the final product separated after transesterification is biodiesel
04/21/23 37
XRD pattern of Li doped T-CaO catalyst
From the Figure 4.16, it is seen that peaks of lithium oxide start to appear and the peaks become more intense with higher Li loading. The peaks corresponding to 2θ= 32, 37, 54, 64, 57 corresponds to JCPDS card no. 01-078-0649 which belongs to that of calcium oxide. On the other hand the peaks which appear at 2θ = 19, 29, 30, 47, 51 belongs to lithium oxide (JCPDS file no. 01-073-1640). As the doping increases the peaks of lithium oxide are observed to dominate the XRD pattern and the peaks of CaO are reduced which indicates that the final Li doped catalyst might have overshadowed the peaks of parent catalyst due to overloading.
04/21/23 38
FTIR
Bands appear around 1400 cm-1, 1000cm-1, 850cm-1 correspond to Li=O stretching, Li-O broad band stretching and Li-O-Li group respectively
Basicity and BET analysis
Surface area decreases with increasing Li loading.
Influence of Li loading on methyl ester
transesterification was carried out with 6:1 methanol to oil ratio at 60 °C for 8 h.
1wt. % Li-doped catalyst prepared from T-CaO is considered as optimum concentration for Li
04/21/23 39
Reusability
Fuel properties of biodiesel (in the presence of Li1.0T-CaO catalyst)
04/21/23 40
04/21/23 41
Ba doped waste shell derived CaO
Catalyst 3
Ref: Boro Jutika , Konwar Lakhya Jyoti, Thakur Ashim Jyoti and Deka Dhanapati. Ba doped CaO derived from waste shell of T striatula (Ts-CaO) as heterogeneous catalyst for biodiesel production. Fuel 129 (2014) 182-187.
04/21/23 42
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04/21/23 44
XRD pattern FT-IR
04/21/23 45
04/21/23 46
04/21/23 47
04/21/23 48
EDX analysis
Basicity and surface area
04/21/23 49
04/21/23 50
Reusability
04/21/23 51
04/21/23 52
04/21/23 53
Preparation of Biomass/Carbon based bio-inspired catalyst
Materials and MethodsRaw material selection • The selection of raw material was based on the recent works in literature. The literature in
biomass derived catalytic materials could be classified two distinct classes:
1. Metal oxides or mixed metal oxides derived from alkali rich biomass sources (e.g. CaO prepared from waste shells of egg, shrimps, mollusk etc.). Solid Basic Catalyst.
2. Carbon materials modified with strong acidic groups (such as –SO3H) also known as sulfonated carbons prepared from biomass or products of biomass origin by carbonization
followed by subsequent sulfonation. Solid Acid Catalyst.• Precursor
Materials rich in carbon to prepare supported Active carbon catalysts namely, Turbonilla striatula (TS) shells and de-oiled cake waste from non-edible oil seeds.
04/21/23 54
CaO supported active carbon (AC) catalyst
Turbonilla striatula shells
Drying, grinding
Carbonized at 500 C, Impregnation with aq.
KOH,
Activation at 700 C
@ 10 C/min
Mixing AC and TS (1:1
w/w) followed by activation at 900 C (3 h)
Active carbon (AC)
Supported CaO catalyst (ACaO)
L J Konwar, J Boro and D Deka , Activated carbon supported CaO prepared from waste mollusk shells as heterogeneous catalyst for biodiesel production, Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, (2012, In press) (doi:10.1080/15567036.2012.733483)
•The shells were crushed, dried, sieved and treated as represented below
•AC prepared by two step activation of Shells
•Active phase was formed inside the support by heat treatment of shells at 900 C
CaCO3
Chitin
04/21/23 55
L J Konwar, J Boro and D Deka , Activated carbon supported CaO prepared from waste mollusk shells as heterogeneous catalyst for biodiesel production, Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, (2012, In press) (doi:10.1080/15567036.2012.733483)
Characterization results
10 20 30 40 50 60 70
inte
ns
ity
(a
.u)
2 (degree)
CaO ACaO
Fig. EDX spectrum of ACaO catalyst.
4000 3500 3000 2500 2000 1500 1000 500
50
100
150
200
250
C-Hstrech
(%)
Tra
ns
mit
tan
ce
Wavenumber (cm-1)
CaO BCh-CaO
C-O
Ca-O
O-H
Aromatic C-Hbend
C=O
Fig. XRD (top) and FT-IR (bottom) patterns of CaO in comparison to ACaO.
Fig. SEM images of AC and ACaO particles.
(a)
(b)
04/21/23 56Continued….
04/21/23 57
04/21/23 58
04/21/23 59
Basicity measurements The basicity of the CaO supported ACaO catalyst and shell derived CaO were determined using the hammett indicator tests. It was observed that the catalysts and CaO changed the colour of phenolphthalein (H_ = 8.2) from colorless to pink, the colour of indigo carmine (H_=12.2) from blue to green and the colour of 2,4-dinitroaniline (H_ = 15) from yellow to mauve but failed to change the colour of 4-nitroaniline (H_ = 18.4). Therefore, the catalyst’s basic strength was designated as 15< H_<18.4, and it was considered as a strong base for the transesterification reaction similar to pure CaO.
Optimization results
40 50 60 70 80 90 100 110 120 130 140
20
30
40
50
60
70
80
90
100
Con
vers
ion
(%)
Reaction Temperature (OC)
(a) (b)
0 2 4 6 8 10 12 14 16 18
40
50
60
70
80
90
100
Con
vers
ion
(%)
Catalyst (Wt.%)
(c)
0 1 2 3 4 5 6 7 8 90
20
40
60
80
100
Con
vers
ion
(%)
Reaction time (in h)
(d)
1
2
3
4
5
0 20 40 60 80 100
Conversion (%)
No.
of R
uns
(e)
04/21/23 60
Optimum temp 100-1200C
Optimum 40:1
Optimum 10% Optimum
8 h
No change after 5 run
04/21/23 61
Waste shells of TS were successfully utilized as a raw material for the preparation of both the support (AC) and active phase of a supported CaO catalyst (ACaO). The catalyst was prepared by physical mixing of the finely powdered TS shells with AC followed by a simple heat treatment at 900 C to generate the active CaO particles. The resulting catalyst was successfully employed in the transesterification of used cooking oil. Under optimum reaction conditions of 120 °C, 40:1 methanol to oil ratio, 10/11 wt% catalyst and 7/8 h of reaction time, methyl ester yields as high as 96% could be reached. The catalyst was reusable and it maintained its initial activity upto five cycles. Consequently the reusability issues of the ash catalysts were successfully addressed by employing ACaO catalyst.
Drawbacks and Limitations of ACaO and ash catalyst
Due to such shortcomings in the following chapters the attention of the work was shifted towards solid acid catalysts.
• -SO3H containing AC were synthesized from deoiled-cake wastes (a Lignocellulosic biomass) from non edible seeds, a by-product of biodiesel production and used as catalytic materials in the production of biodiesel and bioethanol.
1. Low surface area
2. Leaching and low stability of supported active species/phase in presence of moisture or hydrophilic molecules. As a result active sites are easily poisoned or leached during reactions.
3. Applicability restricted only to biodiesel production.
04/21/23 62
04/21/23 63
Sulfonated carbon catalysts based on de-oiled cake waste I: Synthesis and applications in biodiesel production
• A sulfonated carbon (Brønsted solid acid) catalyst exhibiting a high surface area and acidity was from de-oiled waste cake residues (DOWC) of Mesua Ferrea Linn. seeds, obtained as a byproduct from biodiesel production.
• In the first step DOWC soaked in 50% phosphoric acid were subjected to activation at 500 C under self generated atmosphere in a muffle furnace to generate the porous AC supports.
• In the 2nd step the AC was subsequently sulfonated with freshly prepared 4-benzenediazonium sulfonate (by diazotization of sulfanilic acid) to generate the catalytic materials under varying conditions.
Konwar L J, Das R, Thakur A J, Salminen E, P Mäki-Arvela, Kumar N, Mikkola J-P and Deka D. Biodiesel production from acid oils using sulfonated carbon catalyst derived from oil-cake waste, Journal of Molecular Catalysis A: Chemical 388–389 (2014) 167–176.
04/21/23 64
Fig. 12; Schematic summary of the work
Konwar L J, Mäki-Arvela P, Thakur A J, Salminen E, Kumar N, Mikkola J-P and Deka D. Towards carbon efficient biorefining: Multifunctional mesoporous solid acids obtained from biodiesel production wastes for biomass conversion. Applied Catalysis B: Environmental 176 (2015) 20–35.
A potential hazardous Waste produced by the processing of Non-edible oil seeds
Toxins includephorbol ester-Jatropha karanjin –PongamiaRicin- Castor
Disposal problems
(ultimately added to
production cost
of biodiesel)
65
Structure of activated carbon /amorphous carbon/amorphous
graphite in compassion to graphite
Graphite
OHOH
COOH
OHO
HOOC
OH
HOOC
COOH
HO
O
Sites for attaching new functional groups(-SO3H, -Ph-SO3H etc.)
Sites for attaching new functional groups(-SO3H, -Ph-SO3H etc.)
04/21/23 66
Scheme used for grafting -Ph-SO3H groups on carbon surface
OHOH
COOH
OHO
HOOC
OH
HOOC
COOH
HO
30-32%aqueous H3PO2 (Method 1)
ON2
+ Cl-HO3S
Hold in 1 M HCl for 12 h (Method 2)
OHOH
COOH
OHO
HOOC
HO3SC6H4
COOH
HO
C6H4SO3H
C6H4SO3H
C6H4SO3H
HO3SC6H4
O
HOOC
OH
Activated Carbon Sulfonated Activated Carbon
Or
4-benzenediazoniumsulfonate
+ N2
Continued….
Catalyst particles in methanol
Product (biodiesel and oil)
Fig. 13; Spontaneous separation of hydrophilic catalyst particles from non-polar product mixture (biodiesel and oil).
Fig. 14; Reaction scheme for simultaneous esterification/transesterification of acid oils using sulfonated carbons as catalysts.
Konwar L J, Das R, Thakur A J, Salminen E, P Mäki-Arvela, Kumar N, Mikkola J-P and Deka D. Biodiesel production from acid oils using sulfonated carbon catalyst derived from oil-cake waste, Journal of Molecular Catalysis A: Chemical 388–389 (2014) 167–176.)
H3PO4
Activation@500 C in air
OHOH
COOH
OHO
HOOC
OH
HOOC
COOH
HO
O
04/21/23 68
Sulfonated CarbonsCHCH2 O
CH2 O CO
CO
R1
R3
OCO
R2
+RCOOH
MeOH
H3CO CO
R2
+
Acid oils (Triglycerides + FFAs)
CHCH2 OH
CH2 OHHO
Glycerin (Trace)FAME + Triglycerides
CHCH2 O
CH2 O CO
CO
R1
R3
OCO
R2 +
+
H2O
OHOH
COOH
OHO
HOOC
HO3SC6H4
COOH
HO
C6H4SO3H
C6H4SO3H
C6H4SO3H
HO3SC6H4
O
HOOC
OH
Table 5
Surface properties of sulfonated carbons and their catalytic activitiesCatalysts Total acid
density a /(mmol g-1)
-SO3H density b (mmol g-1)
Specific Surface area(m2 g-1)
Micro Pore volume (cm3g-
1)
La c
(nm)Esterification
activityCEst
(%)k ( h-1)
MAC 2.032 - 777 0.28 5.47 11 -MAC-SO3H 2.426 0.735 556 0.20 4.89 99 0.65MAC-SO3H (spent) 2.416 0.672 - - - 90 -Starch-SO3H [1] 4.130 1.500 n.r n.r n.r ≤95 n.rOil pitch-SO3H [2] 2.040 2.210 8 n.r n.r 95 n.rCorncob-SO3H [3] n.r 0.160 80 n.r n.r n.r n.ra based on titration,b based on elemental analysis, c average size of polycyclic aromatic carbon sheets (graphitic clusters) n.r = not reported,(spent) = catalyst recovered after fifth cycle of Jatropha oil esterificationReaction conditions: 80 C, 6 h, 43:1 (methanol to oil molar ratio), esterification of crude Jatropha oil (containing 8.17 wt% FFA) Continued….
Characterization resultsTable 4
Elemental analysis of carbon materials Sample C H N Oa S O/S
Mesua ferrea L. OCW 48.63 7.38 3.65 40.34 - -MAC 70.28 2.82 3.19 23.54 - -MAC-SO3H 54. 65 3.73 4.49 34.76 2.35 14.79MAC-SO3H (spent) 55.15 2.98 4.23 35.48 2.15 16.50a by difference (ash free basis) (spent) catalyst recovered after fifth cycle of Jatropha curcas oil esterification
04/21/23 69
(a) (b)
(a)
SEM images of the carbonaceous materials (a) MAC and (b) MAC-SO3H.
The SEM pictures also show that the morphology of the carbon material remains mostly unaffected by sulfonation with 4-benzenediazoniumsulfonate
TEM image of the carbon catalyst MAC-SO3H under different magnifications (a) 100 nm (b) 20 nm. . The presence of randomly
arranged aromatic/graphitic carbon sheets is clearly visible in TEM micrographs of MAC-SO3H samples. The size of the catalyst particles in Fig. is about 348 nm.
(b)
Continued….
L J Konwar, R Das, A J Thakur, E Salminen, P Mäki-Arvela, N Kumar, J-P Mikkola and D Deka, Biodiesel production from acid oils using sulfonated carbon catalyst derived from oil-cake waste, Journal of Molecular Catalysis A: Chemical (2013, In press) (doi:10.1016/j.molcata.2013.09.031)04/21/23 70
3500 3000 2500 2000 1500 1000 500
S=O Streching (*)SO3H Streching (̂ )
^ **
^
^
^
^
% Tr
ansm
ittan
ce
Wavenumber (cm-1)
(a)
(c)(d)
^
**
**(b)
(d) MAC-SO3H(c) MAC-SO3H*(b) Spent MAC-SO3H(a) MAC
Fig. : FT-IR spectra of porous carbons.
20 30 40 50 60 70 80
Inte
nsity
(a.u
)
(c)
(a)
C (002)
C (101)
(b)
(a) MAC(b) MAC-SO3H*(c) MAC-SO3H
Fig. X-ray powder diffraction patterns of carbon materials.
0 100 200 300 400 500 60000
20
40
60
80
100
Wei
ght (
%)
Temperature (oC)
(a)
(b)
(a) MAC(b) MAC-SO3H
Fig. TGA patterns of MAC and MAC-SO3H catalysts.
High thermal stability upto 240 C
Sulfonation increases amorphous character
Presence of SO3H groups confirmed in both spent and fresh materials
Continued….71
C=O, near 1700 cm-1
1580 cm-1 incomplete carbonized ring –aromatic ring
1185 cm−1 (P=O stretching) 1075 cm-1 (P-OC stretching)
The bands appearing at 1185 cm−1 (P=O stretching) and 1075 cm-1 (P-OC stretching) in the non-sulfonated carbons were due to incorporation of H3PO4 in MAC as a result phosphoric acid activation. The appearance of additional bands at 1097 cm−1 and 1008 cm−1 (S=O stretching) and 1176 cm−1, 1171 cm−1 and 1275 cm−1 (stretching in -SO3H along with P=O stretching) in the FT-IR spectra of the sulfonated carbons were consistent with the presence of -SO3H groups .
Catalytic tests
0
20
40
60
80
100
3%
5%
0.02%
H 2SO 4
MAC
MAC-S
O 3H
MAC-S
O 3H
MAC-S
O 3H
MAC-S
O 3H
MAC-S
O 3H
MAC-S
O 3H
FFA
conv
ersio
n (%
)
2%
0%
4%
5% 6.5%
Blank
5%* ( 43.73 wt% FFA )
MAC-S
O 3H
*
MAC-S
O 3H
*
MAC-S
O 3H
*
MAC-S
O 3H
*
MAC-S
O 3H
*
Fig. 19; Effect of catalyst amount on free fatty acid (FFA) conversion. The reaction temperature was 80 °C and the reaction time was 8 hours. Methanol to acid oil molar ratio of 43:1 was applied.
0 1 2 3 4 5 6
0
20
40
60
80
100
Time (h)
FFA
conv
ersio
n (%
)
50 oC, MAC-SO3H
65 oC, MAC-SO3H
80 oC, MAC-SO3H*
80 oC, MAC-SO3H
100 oC, MAC-SO3H
Fig.20; Free fatty acid (FFA) conversion as a function of time. Effect of reaction temperature on free fatty acid (acid oil containing 8.2 wt% of FFA) conversion. The catalyst loading was 5 wt% and methanol to acid oil molar ratio was 43:1.
0 1 2 3 4 5 6
0
20
40
60
80
100
21.5:1, (43.73 wt% FFA) 10.75:1, (43.73 wt% FFA) 6:1, (43.73 wt% FFA)
Time (h)
43:1, (8.17 wt% FFA) 32.2:1, (8.17 wt% FFA) 21.5:1, (8.17 wt% FFA)
FFA
conv
ersio
n (%
)
Fig. 21; Free fatty acid (FFA) conversion as a function of time. The effect of methanol-to-acid oil molar ratio on FFA conversion. The reaction temperature was 80 °C and the catalyst (MAC-SO3H) loading was 5 wt%.
0 1 2 3 4 5 6
0
20
40
60
80
100
Time (h)
FFA
conv
ersio
n (%
) 8.17 wt% FFA (21.5:1) 14.7 wt% FFA (10.75:1) 43.73 wt% FFA (21.5:1) 43.73 wt% FFA (10.75:1)
Fig. 22; Free fatty acid (FFA) conversion as a function of time. Effect of initial FFA level on FFA conversion. The reaction temperature was 80 °C and the catalyst (MAC-SO3H) loading was 5 wt%. Cont….04/21/23 72
With the sulfonated carbon catalysts MAC-SO3H and MAC-SO3H*, the conversion of FFA in acid oils was 99 % and 97 %, respectively at 80 C within 8 h.
1ST JO5SH21-1 (JATROPHA 100).ESP
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
No
rma
lize
d In
ten
sity
3RD USE JO5SH21-1.ESP
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
No
rma
lize
d In
ten
sity
MO5SH.ESP
7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5Chemical Shift (ppm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0N
orm
aliz
ed
Inte
nsi
ty
hydrogen peak of triglyceride
hydrogen peak of triglyceride
hydrogen peak of triglyceride
(a)
(b)
(c)
methyl ester peak
1ST JO5SH21-1 (JATROPHA 100).ESP
2.4 2.3 2.2Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
No
rma
lize
d In
ten
sity
Fig. 23; 1H NMR (a) Showing increased total (esterification + transesterification) yield when using AO with 43.7wt% FFA (b) Effect of reuses on transesterification (reduced yield) at fifth cycle using AO with 43.7wt% FFA (c) Showing low transesterification yield when using AO with 8.17wt% FFA, (insert shows decreased intensity of unmerged FFA triplet at 2.38 ppm); Reaction conditions: 5% MAC-SO3H catalyst, methanol-to-oil
molar ratio 43:1, T = 80 C, t = 8 h.
0102030405060708090
100
43.73 wt% FFA
43.73 wt% FFA
8.17 wt% FFA
MAC-SO3H* MAC-SO3H(5)MAC-SO3H
Met
hyl e
ster
mol
ar y
ield
(%)
Total Esterification Transesterification
MAC-SO3H
8.17 wt% FFA
Fig. 24; Comparison of esterification and transesterification activities. The reaction temperature was 80 °C and the reaction time was 8 h whereas the catalyst loading was 5 wt% and methanol to acid oil molar ratio was 43:1.
1H- NMR also confirmed the non leaching of aromatic species
80
100
FFA
conv
ersi
on (%
) 8.17 wt% FFA 43.73 wt% FFA
51 2 3 4No of Cycles
Fig. 25; Deactivation of the MAC-SO3H catalyst (FFA
conversion was illustrated for five consecutive cycles). The reaction temperature was 80 °C and the reaction time was 8 hours whereas the catalyst loading was 5 wt% and methanol to acid oil molar ratio was 43:1.
Continued….
Tranesterification activity increase with FFA amount
04/21/23 73
Sulfonated carbon catalysts based on de-oiled cake waste II: The effect of carbon source on structure and activity
• C The chapter discusses the effect of carbon source and sulfonation method on the structure and activity of the de-oiled waste cake (DOWC) residue derived sulfonated carbons, obtained from of three different non-edible oil seed wastes (Jatropha Curcas, Pongamia Pinnata and Mesua ferrea Linn), all obtained as by-products from biodiesel production.
• It presents comprehensive characterization of the said materials by means of N2-physisorption, XRD, EDX, XPS, Elemental analysis, FT-IR, Raman analysis, NH3-TPD and acid-base titrations.
• Their catalytic behavior were studied in esterification of fatty acids and saccharification of cellulosic materials, two highly contrasting and important acid catalyzed reactions associated with the production of biofuels.
Konwar L J, Mäki-Arvela P, Thakur A J, Salminen E, Kumar N, Mikkola J-P and Deka D. Towards carbon efficient biorefining: Multifunctional mesoporous solid acids obtained from biodiesel production wastes for biomass conversion. Applied Catalysis B: Environmental 176 (2015) 20–35.
74
Sulfonated Carbons+RCOOH MeOH H3CO C
OR
Fatty acid FAME
+ H2O
OHOH
COOH
OHO
HOOC
HO3SC6H4
COOH
HO
C6H4SO3H
C6H4SO3H
C6H4SO3H
HO3SC6H4
O
HOOC
OH
HOOC
Biomass (Starch, Cellulose or Lignocellulose )
Fermentable sugars
OH
HO
H
HOH
OHOHH
R
H
OH
O
HHO
H
OHH
R OH
O
HHO
H
OHH
R
O
nR= CH2OH or H
R= CH2OH (Glucose)R= H (Xylose)
H2O
OO R
Water soluble Oligomers
R= CH2OH (HMF)R= H (Furfural)
+degradation products
Sulfonated Carbons
OHOH
COOHOHO
COOH
HO3SC6H4
COOH
OH
C6H4SO3H
C6H4SO3HC6H4SO3H
HO3SC6H4
O
HOOC
OH
+H2O
Sulfonated Carbons
OHOH
COOHOHO
COOH
HO3SC6H4
COOH
OH
C6H4SO3H
C6H4SO3HC6H4SO3H
HO3SC6H4
O
HOOC
OH
Reaction scheme for Esterification of long chain fatty acids with methanol
Reaction scheme for Hydrolysis of cellulose/biomass into fermentable sugars
Thermometer
Three neck flask
Hot plate and stirrer
Condenser
Oil bath
Desired product
75
04/21/23 76Continued….
Conclusion and summary
• Three different approaches were successfully applied to transform biogenic wastes into heterogeneous catalysts (both acidic and basic)
• All the base catalysts were successfully employed in transesterification of vegetable oils to FAME (** given that the FFA content in oil was less than 1wt%).
• Highest FAME yields upto 96% was achieved under optimized reaction conditions over the ACaO catalyst.
• ACaO exhibited superior reusability under the investigated reaction conditions when compared to CaO.
• Ash (mixed alkali and alkaline oxide type catalysts) were prone to severe deactivation as the active species (K2O and CaO) were easily leached to the reaction media.
Continued….04/21/23 77
Research area developed—Biomass Conversion laboratory
a) Biodiesel production from locally available oil seeds
b) Development of heterogeneous renewable catalysts for biodiesel production and valorization of wastes.
c) Microemulsion based hybrid Biofuel using locally available vegetable oil.
d) Microbial fuel cell
Research in PlanCatalytic Transformation of microalgae into fuel and chemicals using Nano catalysts/solid acid catalyst-transesterification and hydrotreating, Green Diesel Production.
Exploring Microalgae harvesting method (RAH).
Biodiesel production Micro-emulsion based hybrid biofuel production
• Mesua ferrea (Nahar)
• Pongamia pinnata (Karanja)
• Pongamia glabra (Koroch)
• Thevetia peruviana (Karabi)
• Azadirachta indica (Neem)
• Madhuca longifolia (Mahua)
• Hevea brasiliensis (Rubber)
• Gmelina arborea (Gomari)
• Sapindus mukorossi (Reetha)
• Mesua ferrea (Nahar)
• Thevetia peruviana (Karabi)
• Gmelina arborea (Gomari)
• Acer laurinum Hasskarl (Kathbadam)
• Mimusops elengi Linn (Bokul)
• Waste Cooking Oil
• Refined Soybean Oil
Indigenous vegetable oil feedstock for
Some recent publications of Prof. D.Deka and his group (2014-2015)
1. Konwar LJ, Mäki-Arvela P, Begum P, Kumar N, Thakur AJ, Mikkola J-P, Deka R and Deka D. Shape selectivity and acidity effects in glycerol acetylation with acetic anhydride: Selective synthesis of triacetin over Y-zeolite and sulfonated mesoporous carbons. Journal of Catalysis, 329, 237–247(2015
2. Konwar LJ, Mäki-Arvela P, Salminen E, Kumar N, Thakur AJ, Mikkola J-P and Deka D. Towards carbon efficient biorefining: Multifunctional mesoporous solid acids obtained from biodiesel production wastes for biomass conversion. Applied Catalysis B: Environmental 176, 20–35 (2015).
3. Bora P, Konwar LJ , Boro J, Phukan M M , Deka D and Konwar BB. Hybrid biofuels from non-edible oils: A comparative standpoint with corresponding biodiesel. Applied Energy 135,450–460 (2014).
4. Boro J, Konwar LJ, Thakur AJ and Deka D. Ba doped CaO derived from waste shells of T striatula (TS-CaO) as heterogeneous catalyst for biodiesel production. Fuel, 129, 182–187 (2014).
5. Boro J, Konwar LJ and Deka D. Transesterification of non-edible feedstock with lithium incorporated egg shell derived CaO for biodiesel production. Fuel Processing Technology, 122, 72–78 (2014).
6. Konwar LJ, Das R, Thakur AJ, Salminen E, Mäki-Arvela P, Kumar N, Mikkola J-P and Deka D. Biodiesel production from acid oils using sulfonated carbon catalyst derived from oil-cake waste. Journal of Molecular Catalysis A: Chemical, 388-389, 167-176 (2014).
7. Konwar LJ, Boro J and Deka D. Review on latest developments in biodiesel production using carbon-based catalysts. Renewable and Sustainable Energy Reviews, 29, 546–564 (2014).
8. Das S, Thakur AJ and Deka D. Two-Stage Conversion of High Free Fatty Acid Jatropha curcas Oil to Biodiesel using Brønsted Acidic Ionic Liquid and KOH as Catalysts. The Scientific World Journal, Volume 2014, pp 1-9, Article ID 180983, http://dx.doi.org/10.1155/2014/180983 (2014).
9. Deka D, Sedai P and Chutia RS. Investigating woods and barks of some indigenous tree species in North East. Energy Sources, Part A: 36, 1913-1920 (2014) doi = {10.1080/15567036.2010.538802}.
Research group of Biomass conversion laboratory
Ph.D. Scholar1. Dr. Dipak Sarma- Ph.D. awarded2. Dr. Jutika Boro- Ph.D. awarded3. Dr. Lakhya Jyoti Konwar-Ph.D.awarded (CIMO fellowship)4. Mr. Pitambar Sedai- Ph.D, awarded.5. Mr. Plaban Bora-Ph.D. awarded6.Ms. Anuchya Devi- Ph.D. ongoing7.Ms. Velentina Das– Ph,D ongoing8. Mr. Manash Jyoti Borah-Ph.D. ongoing9. Mr. Swagat Chutia-Ph.D. ongoingM. Tech project students (ongoing)1.Minakshi Gohain2. Sikhamoni Mali3.Jery Lani4. Anjanjyoti Bharali
Contact:Professor D. DekaProfessor & HeadDepartment of EnergyTezpur UniversityTezpur-784028E-mail: [email protected]
Ph. D. awarded : 5Ph.D. ongoing: 4M.Tech. awarded: 26M. Tech ongoing: 4
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Thank you for your attention!