Biodiesel production based on

crude oils using zinc-based catalysts

Shuli Yan

Outline

Background

Literature review
Zinc-based catalysts in transesterification
Zinc-based catalysts in esterification
Zinc-based catalysts in hydrolysis

Objective

Experiment

Reference
2

Background

Biodiesel

Background

Advantages of using biodiesel

Biodegradable
Low emission profile
Low toxicity
Better fuel
Efficiency
High lubricity
4

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)

Background
Long production process (A two-step method)
Degumming
Bleaching
Deodorizing and Deacidification
Esterification

Strong acid

Neutralization
Wash
Dehydration
Transeseterification

Strong base

Neutralization
Wash

Background
Developing a heterogeneous catalyst
with high activity processing feedstock
with high FFA and water
Simultaneous transesterification and
esterification
Minimizing hydorlysis

Outline

Background

Literature review
Zinc-based catalysts in transesterification
Zinc-based catalysts in esterification
Zinc-based catalysts in hydrolysis

Objective

Experiment

Reference
10

Literature review

R1COOH + CH3OH
R1COO R2

H2 O

Catalyst

R1COOCH 3 + H2O
R1COOH

R2OH
11

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
12

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

18

Zinc oxide, Zinc

Chloride

glycerol with fatty acid

19

Zinc carboxylate

glycerol with fatty acid

20
13

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);

14

Literature review
My previous work
90

ZnO

75

Oil conversion %

60

45

30

No catalyst

15

0
1 20

13 5

150

165

1 80

Temperature

19 5
o

21 0

225

240

15

Literature review

Oil conversion %

My previous work
NaOH

100

80

ZnO

60

40
3

H 2SO 4
20

No catalyst
0

ZnO
-50

50

100

150

200

Time min

250

300

350

400

16

Literature review
My previous work
100

80

Oil conversion %

60

40

20

0
-50

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

17

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.

19

Objective

Two aspects:

Confirm the reaction pathway for methyl esters production

Crude Oils

Triglyceride

Transesterification

Water

Hydrolysis

FFA

Esterification

Hydrolysis

Fatty acid methyl esters

20

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

21

Outline

Background

Literature review
Zinc-based catalysts in transesterification
Zinc-based catalysts in esterification
Zinc-based catalysts in hydrolysis

Objective

Experiment

Reference
22

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

23

Experiment

Characterization of zinc-based catalysts

Surface composition (AES and XPS)
Bulk composition (XRD and AAS)
Surface area (BET)
Pore structure ( mercury porosimetry )

24

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.
25

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 )
26

Summary

To understand the impact of bulk

structure, surface structure, and the
interaction between zinc oxide and
support on the yield of methyl
esters.

27

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, 131139.

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References

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[13] E. Santacesaria, F. Trulli, L. Minervini, M. Di Serio, R. Tesser, S. Contessa,
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[18] M. Adam and Szela g H. Ind. Eng. Chem. Res. 43, (2004), 7744-7753
[19] Pouilloux, Y.; Metayer, 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.
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Thank you!
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