Transcript Using zinc oxide catalysts in biodiesel production basing

Biodiesel production based on
crude oils using zinc-based catalysts
Shuli Yan
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Outline

Background

Literature review
 Zinc-based catalysts in transesterification
 Zinc-based catalysts in esterification
 Zinc-based catalysts in hydrolysis

Objective

Experiment

Reference
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Background

Biodiesel
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Background

Advantages of using biodiesel
 Biodegradable
 Low emission profile
 Low toxicity
 Better fuel
 Efficiency
 High lubricity
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Background

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)
 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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6
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Background
 Long production process (A two-step method)
Degumming
Bleaching
Deodorizing and Deacidification
Esterification
Strong acid
Neutralization
Wash
Dehydration
Transeseterification
Strong base
Neutralization
Wash
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Background
 Developing a heterogeneous catalyst
with high activity processing feedstock
with high FFA and water


Simultaneous transesterification and
esterification
Minimizing hydorlysis
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Outline

Background

Literature review
 Zinc-based catalysts in transesterification
 Zinc-based catalysts in esterification
 Zinc-based catalysts in hydrolysis

Objective

Experiment

Reference
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Literature review
Cataly st
R1COOH + CH 3OH
R1COO R2
+
H2O
R1COOCH 3 + H2O
R1COOH
+
R2OH
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Literature review

Zinc-based catalysts in transesterification
Suppes et al: Zinc Oxide and zinc carbonate, 120 oC, 24hr,
yield 80 %
Xie et al: KF/ZnO
Li et al: I2/ZnO
Sreeprasanth et al: Fe-Zn oxides
Esterfip－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
Reference
Zinc acetate
palmitic acid with isopropanol
12-14
Supported zinc acetate
palmitic acid with isopropanol
15-17
Zinc carboxylate
glycerol with fatty acid
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Zinc oxide, Zinc
Chloride
glycerol with fatty acid
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Zinc carboxylate
glycerol with fatty acid
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Literature review

Zinc-based catalysts in hydrolysis
 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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Literature review

My previous work
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Literature review
Oil conversion %

My previous work
NaOH
1
100
80
ZnO
2
60
40
3
H2SO4
20
No catalyst
0
ZnO
-50
0
50
100
150
200
Time min
250
300
4
5
350
400
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Literature review
My previous work
100
80
Oil conversion %

60
40
20
0
-50
0
50
100
150
200
250
300
350
400
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
 Zinc-based catalysts in transesterification
 Zinc-based catalysts in esterification
 Zinc-based catalysts in hydrolysis

Objective

Experiment

Reference
18
Objective

The overall objective is to develop an
effective zinc-based catalyst for both
transeseterification and esterification,
while limiting hydrolysis of oil.
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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Objective

Two aspects:
 Confirm the reaction pathway for methyl esters production
Crude Oils
Triglyceride
Transesterification
Water
Hydrolysis
FFA
Esterification
Hydrolysis
Fatty acid methyl esters
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Objective

Enhance the active sites on the
surface of zinc-based catalysts
 By alloying (i.e. La2O3)
 Preparation conditions
─Calcination temperature
─Molar ratio
─Preparation method
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Outline

Background

Literature review
 Zinc-based catalysts in transesterification
 Zinc-based catalysts in esterification
 Zinc-based catalysts in hydrolysis

Objective

Experiment

Reference
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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
 At elevated temperature and pressure in a batch
reactor
 No mass transfer limitation
 Reaction conditions:
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),
Stir speed (100 ~ 600 rpm )
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Summary

To understand the impact of bulk
structure, surface structure, and the
interaction between zinc oxide and
support on the yield of methyl
esters.
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References
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[1] Clark S. J., Wagner L., Schrock MD. Methyl and ethyl esters as renewable
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[2] Muniyappa PR, Brammer SC, Noureddini H. Improved conversion of plant
oils and animal fates into biodiesel and co-product. Bioresour. Technol. 1996,
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[4] Canakci, M.; Gerpen, J. V. Biodiesel production from oils and fats with
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[7] Wang C.; Sun Y.; Hu L., Poly (ethylene naphthalate) formation 1.
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References
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Thank you!
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