AIChEAbstract 2 CaLa

7/31/2019 AIChEAbstract 2 CaLa

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Biodiesel from Waste or UnrefinedOils Using Calcium Oxide-based

Catalysts

Shuli Yan, Manhoe Kim, Steve O. Salley and K. Y. Simon Ng

National Biofuels Energy LaboratoryNextEnergy/Wayne State University

Detroit, MI 48202

AICHe Meeting at Nov. 16 , 2008


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Content Introduction

Biodiesel Traditional Processes for Biodiesel Production Literature Review

Experiment Results and Discussion

Catalyst Activity Catalyst Structure Effect of Water and FFA in Oil Feedstock Effect of H2O and CO2 in Air Effect of Reaction Conditions Transesterification Mechanism

Conclusion


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Introduction Biodiesel

A mixture of fatty acid esters

Derived from vegetable oils, animal fats, waste oils


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IntroductionBiodiesel - Advantages

BiodegradableLow emission profileLow toxicityEfficiencyHigh lubricity

0

50

100

150

200

250

M i l l i o n

G a

l l o n s

1 2 3 4 5 6 7 8

Year

U.S. Biodiesel Production

99 00 01 02 03 04 05 06


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IntroductionTraditional Processes for Biodiesel Production

Refined oils as feedstock (food-grade vegetable oils)

Homogeneous strong base or acid catalysts (NaOH, H 2SO 4)

FFA content is lower than 0.5 % (wt)

Water content is lower than 0.06% (wt)High price

Highly corrosive

Long oil pretreatment processLong product purification process

Large amount of waste water

Long time for phase separation

High process cost


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IntroductionDecrease of Feedstock Cost

Decrease of Process Cost

Using inexpensive oils as feedstock Crude vegetable oils, recycled cooking oils, trap grease etc.

Simplifying the oil pretreatment process Simplifying the product purification process

o Replace homogeneous catalysts by heterogeneous catalysts


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Solid Base Catalysts

Goal

Catalyst T Time(h) Conv.(%) Ref.

KNO 3/Al 2O3 65

C 7 87 1

ZnO 120

C 24 80 2

HT (Mg-Al) 180

C 1 92 3

SO 42-/ZrO 2 200

C 4 95.7 4

I2/Zn 65

C 24 96 5

Nafion acid resins 60

C 8 50 6


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Solid Base CatalystsCatalyst T Time(h) Conv.(%) Ref.

Nano-CaO Roomtemperature

6-24 95 10

CaO 65 C 24 93 11

CaO 65

C 3 60 12

CaO, Ca(OH) 2,CaCO 3

65

C 24 95.7 13

1. Catalytic activities much lower than NaOH.

2. Conducted at elevated temperature and pressure.

3. Low tolerant to water and FFA in feedstocks.


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Research Goal

Develop an effective biodiesel process catalyst

with high activityUsing solid catalysts to replace homogeneous NaOH

An improved property in tolerance to water and FFA

Using solid catalysts in food-grade, unrefined and waste oils.


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Experiment Oil Feedstock

Fatty Acid

Components

Food-grade Soybean Oil

(%)

Crude Soybean Oil

(%)

Crude Palm Oil

(%)

Waste Cooking Oil

(%)

C 14: 0 0 0.27 0.21 0

C 16: 0 11.07 13.05 41.92 11.58

C 16: 1 0.09 0.39 0.23 0.18

C 18: 0 3.62 4.17 3.85 4.26

C 18: 1 20.26 22.75 42.44 24.84

C 18: 2 57.60 52.78 11.30 53.55

C 18: 3 7.36 6.59 0.04 5.60

FFA Content 0.02 3.31 0.24 3.78

Water Content 0.02 0.27 0.04 0.06


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Experiment Catalyst Preparation Ca and La nitrate salts

transparent solution

Stirring for 3h at 60o

C

Placing for 48h at RM

Filter and Wash

Drying for 24h at 100 oC

Calcining for 8h at 750 oC

Activation

Ethanol 3 N Ammonia; CO 2, 4vol %, each hours

Ammonia-CarbonDioxide

Precipitate

Method


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Experiment Catalyst Characterization

Basic Property

Hammett indicator method;

Hammett indicator-benzene carboxylic acid titration method;

Specific surface area

Micromeritics model ASAP 2010 surface area analyzer (North Huntingdon, PA)

TG/DTG

Perkin Elmer Pyris-1 (Waltham, MA)

XRD

Rigaku RU2000 rotating anode powder diffractometer (Woodlands, TX)

FTIR

Perkin Elmer Spectrum 400 spectrometer (Waltham, MA)


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Experiments

Transesterification

Product analysis

10.0 g of soybean oil and 7.6 g of methanoland 0.5 g activated catalyst

GC-MSKarl Fischer (Water Content)

titration (Fatty Acid Content)


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Catalyst Activity

0 20 40 60 80 100 120

0

20

40

60

80

100

Y i e l d o

f F A M E

%

Time min

NaOH H2SO

4Ca3La1 Ca1La0 Ca0La1

Figure 1 Transesterification activities of Ca3La1, Ca1La0,

Ca0La1, NaOH, and H2SO4 at 64.5o

C and 1 atm.


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Catalyst Structure XRD

2 0 3 0 4 0 5 0 6 0 7 0 8 0

4

3

2

2 T h e t a

1

Figure 2 XRD spectra of Ca3La1 (curve 1), fresh Ca3La1 (curve 2),Ca0La1 (curve 3) and the Ca3La1 exposed to air for 30 days (curve 4).


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Catalyst StructureTable 3 Specific surface areas, XRD, basicity and catalytic activity of

Ca1La0, Ca0La1, Ca3La1 and the Ca3La1 adsorbed water (Ca3La1-water)and Ca3La1 adsorbed FFA (Ca3La1-FFA).

Basicity mmol/gCatalyst Specific Surface

Area m 2 /g

X-ray Structure

4.2


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Catalyst Structure FTIR

4500 4000 3500 3000 2500 2000 1500 1000 500

Frequence cm -1

1

2

3

Figure 3 FTIR analysis of Ca3La1 (1), Ca3La1 adsorbed

water (2) and Ca3La1 adsorbed FFA (3)


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Effect of Water and FFA in Oil

Feedstock

0 20 40 60 80 100 120 140 1600

20

40

60

80

100

01 %2 %4 %10 %

F A M E Y i e l d

%

Time min

Water addition

0 1 2 3 4 5 6 7 8 9 10 110

20

40

60

80

100

NaOH

H2SO

4

Ca3La1 Y i e l d o

f F A M E %

Water content %

Figure 4 Effect of water addition on transesterification..

a b


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Effect of Water and FFA in Oil

Feedstock

0 20 40 60 80 100 1200

20

40

60

80

100

00.51.11.63.65.17.0 F

A M E Y i e l d %

Time min

FFA Addition %

Figure 5 Yield of FAME in the presence of different FFA addition.


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Single Step Conversion of Unrefined

and Waste Oil

Figure 6 Yield of FAME using unrefined and

waste oils (a) and diluted unrefined oils (b).

0 20 40 60 80 100 120 140 160 180 2000

20

40

60

80

100

Y i e l d o

f F A M E

%

Time min


Crude Soybean Oil

Crude Palm Oil

Waste Cooking Oil

0 20 40 60 80 100 1200

20

40

60

80

100


Diluted Crude Soybean Oil

Diluted Crude Palm Oil

Diluted Waste Cooking Oil

Y i e l d o

f F A M E

%

Time min

a b


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Effect of Water and FFA on Catalyst

Structure Basic Property

FTIR


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Effect of H 2O and CO 2 in Air

Storage conditions Pretreatment conditions Total Basicity mmol/g Yield of FAME1 %

Air for 12 hr \ 1.5 34.5

Air for 12 hr 200 oC, N 2, 1.5 hr 1.5 38.3

Air for 12 hr 430 oC, N 2, 1.5 hr 3.1 51.4

Air for 12 hr 750 oC, N 2, 1.5 hr 14.2 97.2

Air for 12 hr 950o

C, N 2, 1.5 hr 13.1 89.0

N2 flow with 10 (vol) % CO 2, 4 (vol) % H 2O \ 1.5 23.9

N2 flow with 10 (vol) % CO 2, 4 (vol) % H 2O 750oC, N 2, 1.5 hr 14.0 96.8

Table 4 Effects of storage and pretreatment conditions on the catalyticactivity of Ca3La1.


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Effect of H 2O and CO 2 on Catalyst

Structure XRD FTIR

4500 4000 3500 3000 2500 2000 1500 1000 500

5

4

Wavenumber cm -1

1

2

3

Figure 7 FTIR spectra of Ca3La1 exposed to air about 3

min (1), 5 min (2), 8 min (3), 15 min (4) and 30 min (5).


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Effect of H 2O and CO 2 on Catalyst

Structure TG/DTG

200 400 600 800

TG Curve

DTG Curve

Temperature o C

8 %

1 6 %

Figure 8 TG/DTG curves of Ca3La1 exposed to air for 12 hours.


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Effect of Reaction Conditions

0 20 40 60 80 100 120 140 160 180 2000

10

20

30

40

50

60

70

80

90

100

Y i e l d o

f F A M E

%

Time min

610152024

Molar ratio of methanol to oil

Figure 9 FAME yields with different mass ratio of catalyst tooil (a), with different mole ratio of methanol to oil (b), and

with different reaction temperatures (c).


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Effect of Reaction Conditions

Figure 9 FAME yields with different mass ratio of catalyst tooil (a), with different mole ratio of methanol to oil (b), and

with different reaction temperatures (c).

0 100 200 300 400 500

0

20

40

60

80

100

Y i e l d o

f F A M E

%

Time min

35oC

45oC

50oC

58oC


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Transesterification Mechanism Adsorption Sites

4500 4000 3500 3000 2500 2000 1500 1000 500

c

b

Frequence cm -1

a

11621097 718

Figure 10 FTIR spectra; (a) Ca3La1 adsorbed triglyceride (curve1), free triglyceride (curve 2) and the fresh Ca3La1 (curve 3);


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Transesterification Mechanism Adsorption Sites

4500 4000 3500 3000 2500 2000 1500 1000 500

Frequence cm -1

1

2

3

12181365

1735

Figure 10 FTIR spectra;(b) free methanol (curve 1), the Ca3La1 adsorbed methanol(curve 2) and the fresh Ca3La1 (curve 3).

O O


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CH 3

O

H

CH 3 OH

OH - /O 2 - OH - /O 2 -

CH 3

O-

OH - /O 2 -

H

OH - /O 2 -

CH 3-O

C

O

R 1O

R 2

H

Ca 2+ /La 3+ Ca 2+ /La 3+

C

O

R 1OR 2O

R1

OR2 +

Ca 2+ /La 3+

CH 3

O

C

O

R 1O

R 2

-

CHO

C

O

R 1R 2 O

-

OH - /O 2 -

H

OH - /O 2 -

H

O R 2

OH - /O 2 -

R 2 OH

+ +

+

R1: alkyl group of fatty acidR2: alkyl esters of triglyceride

Figure 11 Schematic representation of possible mechanism for transesterification of triglyceride with methanol.


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Conclusion A single-step method using unrefined oils and

calcium and lanthanum mixed oxides

strong base strength, large amount of basicity andhigh surface area

A strong interaction between Ca and La species

Highly tolerant to water and FFA in oil feedstock


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Acknowledgement

Financial support of this research by the Department

of Energy (DE12344458) and Michigan's 21stCentury Job Fund program is gratefully

acknowledged


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Thanks!

AIChEAbstract 2 CaLa

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