1

Biodiesel production based on crude oils using zinc-based catalysts

Shuli Yan

2

Outline

Background Literature review

Objective Experiment Reference

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

3

Background

Biodiesel

4

Advantages of using biodiesel Biodegradable

Low emission profile

Low toxicity

Better fuel

Efficiency

High lubricity

Background

5

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)

6

7

8

Long production process (A two-step method)

Strong base

Strong acid

Degumming

Bleaching

Deodorizing and Deacidification

Esterification

Neutralization

Wash

Dehydration

Transeseterification

Neutralization

Wash

Background

9

Simultaneous transesterification and esterification

Minimizing hydorlysis

Background

Developing a heterogeneous catalyst with high activity processing feedstock with high FFA and water

10

Outline

Background Literature review

Objective Experiment Reference

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

11

Literature review

COOHR1 + CH3OH R1COOCH3 + OH2

Catalyst

COOR1 R2 + OH2 COOHR1 + OHR2

12

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

13

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

14

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);

15

My previous work

Literature review

120 135 150 165 180 195 210 225 240

0

15

30

45

60

75

90

Oil

conv

ersi

on

%

Temperature oC

No cat al yst 1

ZnO 2

16

My previous work

Literature review

-50 0 50 100 150 200 250 300 350 400

0

20

40

60

80

100

No cat al yst 4

ZnO 5

H2SO4 3

ZnO 2

NaOH 1

Oil

conv

ersi

on

%

Time min

17

My previous work

Literature review

-50 0 50 100 150 200 250 300 350 400

0

20

40

60

80

100

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

18

Outline

Background Literature review

Objective Experiment Reference

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

19

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.

20

Two aspects:

Objective

Confirm the reaction pathway for methyl esters production

Crude Oils

Transesterification Hydrolysis Esterification Hydrolysis

Triglyceride Water FFA

Fatty acid methyl esters

21

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

22

Outline

Background Literature review

Objective Experiment Reference

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

23

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

24

Experiment

Characterization of zinc-based catalysts

• Surface composition (AES and XPS)

• Bulk composition (XRD and AAS)

• Surface area (BET)

• Pore structure ( mercury porosimetry )

25

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.

26

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:

27

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

Summary

28

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.

29

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.

30

Thank you!