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Biodiesel production based on crude oils using zinc-based catalysts. Shuli Yan. Outline. Background Literature review Objective Experiment Reference. Zinc-based catalysts in transesterification Zinc-based catalysts in esterification Zinc-based catalysts in hydrolysis. - PowerPoint PPT Presentation
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Biodiesel production based on crude oils using zinc-based catalysts
Shuli Yan
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Outline
Background Literature review
Objective Experiment Reference
Zinc-based catalysts in transesterification Zinc-based catalysts in esterification Zinc-based catalysts in hydrolysis
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Background
Biodiesel
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Advantages of using biodiesel Biodegradable
Low emission profile
Low toxicity
Better fuel
Efficiency
High lubricity
Background
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High production Cost
Refined vegetable oils( soybean oil $0.35/lb) FFA content is lower than 0.5 % (wt)
Water content is lower than 0.06% (wt)
Background
Crude oils and yellow grease( about 70 % of refined oils)
FFA content is in the range of 0.5 ~ 15 % (wt)
Water content is higher than 0.06% (wt)
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Long production process (A two-step method)
Strong base
Strong acid
Degumming
Bleaching
Deodorizing and Deacidification
Esterification
Neutralization
Wash
Dehydration
Transeseterification
Neutralization
Wash
Background
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Simultaneous transesterification and esterification
Minimizing hydorlysis
Background
Developing a heterogeneous catalyst with high activity processing feedstock with high FFA and water
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Outline
Background Literature review
Objective Experiment Reference
Zinc-based catalysts in transesterification Zinc-based catalysts in esterification Zinc-based catalysts in hydrolysis
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Literature review
COOHR1 + CH3OH R1COOCH3 + OH2
Catalyst
COOR1 R2 + OH2 COOHR1 + OHR2
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Zinc-based catalysts in transesterification
Literature review
Suppes et al: Zinc Oxide and zinc carbonate, 120 oC, 24hr, yield 80 % Xie et al: KF/ZnOLi et al: I2/ZnO
Sreeprasanth et al: Fe-Zn oxidesEsterfip － H process: Al-Zn oxides
The activity of catalyst is related with its basicity
The activity of catalyst is related with its acidity
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Literature review
Zinc-based catalysts in esterification
Catalysts Esterificaiton Reaction ReferenceZinc acetate palmitic acid with isopropanol 12-14
Supported zinc acetate palmitic acid with isopropanol 15-17
Zinc carboxylate glycerol with fatty acid 18
Zinc oxide, Zinc Chloride
glycerol with fatty acid 19
Zinc carboxylate glycerol with fatty acid 20
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Zinc-based catalysts in hydrolysis
Literature review
Markley, K. S. In Fatty Acids, 2nd ed.; Markley, K. S., Ed.; Interscience Publishers Ltd.: London, 1961; Part 2, Chapters 8 and 9. Hui, Y.H.; Bailey's industrial oil and fat products, 4th ed. (In Chinese); Shu, W. Y.; Manual of oil technology; (In Chinese);
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My previous work
Literature review
120 135 150 165 180 195 210 225 240
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15
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60
75
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Oil
conv
ersi
on
%
Temperature oC
No cat al yst 1
ZnO 2
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My previous work
Literature review
-50 0 50 100 150 200 250 300 350 400
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No cat al yst 4
ZnO 5
H2SO4 3
ZnO 2
NaOH 1
Oil
conv
ersi
on
%
Time min
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My previous work
Literature review
-50 0 50 100 150 200 250 300 350 400
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20
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O
il co
nver
sion
%
Time min
Crude lard Refined rapeseed oil Refined rapeseed oil with 3.8 % FFA and 5% water addition Crude peanut oil Crude rapeseed oil Crude coconut oil
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Outline
Background Literature review
Objective Experiment Reference
Zinc-based catalysts in transesterification Zinc-based catalysts in esterification Zinc-based catalysts in hydrolysis
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The overall objective is to develop an effective zinc-based catalyst for both transeseterification and esterification, while limiting hydrolysis of oil.
Objective
This zinc-based catalyst will be used directly to catalyze some crude oils which contain FFA and water in the range of 0.5 ~ 15 % for the purpose of biodiesel production.
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Two aspects:
Objective
Confirm the reaction pathway for methyl esters production
Crude Oils
Transesterification Hydrolysis Esterification Hydrolysis
Triglyceride Water FFA
Fatty acid methyl esters
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Enhance the active sites on the surface of zinc-based catalysts
Objective
By alloying (i.e. La2O3) Preparation conditions
─Calcination temperature─Molar ratio─Preparation method
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Outline
Background Literature review
Objective Experiment Reference
Zinc-based catalysts in transesterification Zinc-based catalysts in esterification Zinc-based catalysts in hydrolysis
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Experiment
Synthesis of zinc-based catalysts
Precipitation method
Zn: La = 1:0, 1:1, 3:1, 9:1, 0:1
Drying condition: 100 oC for 8 hr.
Calcining condition: 200 ~700 oC for 8hr
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Experiment
Characterization of zinc-based catalysts
• Surface composition (AES and XPS)
• Bulk composition (XRD and AAS)
• Surface area (BET)
• Pore structure ( mercury porosimetry )
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Experiment
Activity test of zinc-based catalysts
• Transesterification of refined oil with methanol
• Esterification of oleic acid with methanol
• Hydrolysis of refined oil, hydrolysis of methyl esters
• Simultaneous catalysis process, i.e. using zinc catalysts in some natural crude oils, refined oil with FFA addition, refined oil with water addition, refined oil with both FFA and water addition, respectively.
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Experiment
Activity test of zinc-based catalysts
Temperature(100 ~ 230 oC), Time(0 ~ 6 hr), Molar ratio of methanol to oil(3:1 ~60:1), Catalyst dosage(0 ~ 25 % wt. ), Particle size of catalyst(10 ~ 200 mesh), Sti
r speed (100 ~ 600 rpm )
At elevated temperature and pressure in a batch reactor
No mass transfer limitation Reaction conditions:
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To understand the impact of bulk structure, surface structure, and the interaction between zinc oxide and support on the yield of methyl esters.
Summary
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References
[1] Clark S. J., Wagner L., Schrock MD. Methyl and ethyl esters as renewable fuels for diesel engines. J. Am. Oil Chem. Soc. 1984, 61, 1632-1638. [2] Muniyappa PR, Brammer SC, Noureddini H. Improved conversion of plant oils and animal fates into biodiesel and co-product. Bioresour. Technol. 1996, 6, 19-24. [3] Nelson, R. G., Hower, S. A. Potential feedstock supply and costs for biodiesel production. In Bioenergy’ 94, Proceedings of the Sixth National Bioenergy Conference, Reno/Sparks, NV, 1994 [4] Canakci, M.; Gerpen, J. V. Biodiesel production from oils and fats with high free fatty acids. Trans. ASAE 2001, 44, 1429-1436. [5] Kusdiana, D.; Saka, S. Effects of water on biodiesel fuel production by supercritical methanol treatment. Bioresour. Technol. 2004, 91, 289-295. [6] Saka, S.; Kusdiana, D.; Minami, E. Non-catalytic biodiesel fuel production with supercritical methanol technologies. J. Sci. Ind. Res. 2006, 65, 420-425. [7] Wang C.; Sun Y.; Hu L., Poly (ethylene naphthalate) formation 1. Transesterification of dimethylnaphthalate with ethylene glycol. J. Polymer. Res. 1994, 1, 131–139.
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References [12] J. Chen, L. Chen, J. Appl. Polym. Sci. 73 (1999) 35–40. [13] E. Santacesaria, F. Trulli, L. Minervini, M. Di Serio, R. Tesser, S. Contessa, J. Appl. Polym. Sci. 54 (1994) 1371–1384. [14] C. Wang, Y. Sun, L. Hu, J. Polym. Res. 1 (1994) 131–139. [15] R. Nava, T. Halachev, R. Rodriguez, V.M. Castano, Catal. A: Gen. 231, (2002) 131–149. [16] R. Nava, T. Halachev, R. Rodriguez, V.M. Castano, Microporous Mesoporous, Mater. 78 (2005) 91–96. [17] R. Aafaqi, A.R. Mohamed, S. Bhatia, J. Chem. Technol. Biotechnol. 79, (2004) 1127–1134. [18] M. Adam and Szelaü g H. Ind. Eng. Chem. Res. 43, (2004), 7744-7753 [19] Pouilloux, Y.; Me´tayer, S.; Barrault, J. Synthesis of Glycerol Monooctadecanoate from Octadecanoic Acid and Glycerol. Influence of Solvent on the Catalytic Properties of Basic Oxides. C. R. Acad. Sci. Paris, Ser. IIc, Chim. 2000, 3, 589. [20] Szelaü g, H.; Macierzanka, A. Tenside Surf. Det. 2001, 38, 377.
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Thank you!
