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Biodiesel from Waste or Unrefined Oils 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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Introduction Biodiesel - Advantages
Biodegradable Low emission profile Low toxicity Efficiency High lubricity
0
50
100
150
200
250M
illio
n G
allo
ns
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, H2SO4)
FFA content is lower than 0.5 % (wt)
Water content is lower than 0.06% (wt)
High price
Highly corrosive
Long oil pretreatment process
Long product purification process
Large amount of waste water
Long time for phase separation
High process cost
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Introduction
Decrease 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.
KNO3/Al2O3 65°C 7 87 1
ZnO 120°C 24 80 2
HT (Mg-Al) 180°C 1 92 3
SO42-/ZrO2 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 Catalysts
Catalyst T Time(h) Conv.(%) Ref.
Nano-CaO Room temperature
6-24 95 10
CaO 65°C 24 93 11
CaO 65°C 3 60 12
CaO, Ca(OH)2, CaCO3
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 activity
Using 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
1
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Experiment• Catalyst Preparation Ca and La nitrate salts
transparent solution
Stirring for 3h at 60 oC
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; CO2, 4 vol %, each hours
Ammonia-Carbon Dioxide
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 methanol and 0.5 g activated catalyst
GC-MS
Karl Fischer (Water Content)
titration (Fatty Acid Content)
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Catalyst Activity
0 20 40 60 80 100 1200
20
40
60
80
100
Yie
ld o
f FA
ME
%
Time min
NaOH H2SO
4 Ca3La1 Ca1La0 Ca0La1
Figure 1 Transesterification activities of Ca3La1, Ca1La0, Ca0La1, NaOH, and H2SO4 at 64.5 oC and 1 atm.
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Catalyst Structure• XRD
20 30 40 50 60 70 80
4
3
2
2 T heta
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/g Catalyst Specific Surface
Area m2/g
X-ray Structure
4.2<H-
<6.8
6.8<H-
<7.2
7.2<H-
<9.8
9.8<H-
<15
Total Basicity
mmol/g
Yield of
FAME % 1
Ca1La0 10.4 CaO, CaCO3,
Ca(OH)2
0.3 0.1 \ \ 0.4 18.7
Ca0La1 9.9 La2CO5, LaOOH 0.1 \ \ \ 0.1 3.2
Ca3La1 62.6 CaCO3, Ca(OH)2,
La2CO5, LaOOH
0.6 2.0 10.4 1.0 14.0 95.3
Ca3La1-
water 2
\ \ 0.1 6.0 4.6 0.8 15.4 96.1
Ca3La1-
FFA 3
\ \ 0.1 \ \ \ 0.1 47.5
1
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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
0 1 % 2 % 4 % 10 %
FA
ME
Yie
ld
%
Time min
Water addition
0 1 2 3 4 5 6 7 8 9 10 110
20
40
60
80
100
NaOH
H2SO
4
Ca3La1Yie
ld o
f FA
ME
%
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
0 0.5 1.1 1.6 3.6 5.1 7.0F
AM
E Y
ield
%
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
Yie
ld o
f FA
ME
%
Time min
Food-grade Soybean Oil
Crude Soybean Oil
Crude Palm Oil
Waste Cooking Oil
0 20 40 60 80 100 1200
20
40
60
80
100
Food-grade Soybean Oil
Diluted Crude Soybean Oil
Diluted Crude Palm Oil
Diluted Waste Cooking Oil
Yie
ld o
f FA
ME
%
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 H2O and CO2 in Air 1
Storage conditions Pretreatment conditions Total Basicity mmol/g Yield of FAME 1 %
Air for 12 hr \ 1.5 34.5
Air for 12 hr 200 oC, N2, 1.5 hr 1.5 38.3
Air for 12 hr 430 oC, N2, 1.5 hr 3.1 51.4
Air for 12 hr 750 oC, N2, 1.5 hr 14.2 97.2
Air for 12 hr 950 oC, N2, 1.5 hr 13.1 89.0
N2 flow with 10 (vol) % CO2, 4 (vol) % H2O \ 1.5 23.9
N2 flow with 10 (vol) % CO2, 4 (vol) % H2O 750 oC, N2, 1.5 hr 14.0 96.8
Table 4 Effects of storage and pretreatment conditions on the catalytic activity of Ca3La1.
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Effect of H2O and CO2 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 H2O and CO2 on Catalyst Structure
• TG/DTG
200 400 600 800
TG Curve
DTG Curve
Temperature oC
8 %
16 %
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
Yie
ld o
f FA
ME
%
Time min
6 10 15 20 24
Molar ratio of methanol to oil
Figure 9 FAME yields with different mass ratio of catalyst to oil (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 to oil (a), with different mole ratio of methanol to oil (b), and
with different reaction temperatures (c).
0 100 200 300 400 5000
20
40
60
80
100
Yie
ld o
f FA
ME
%
Time min
35 oC
45 oC
50 oC
58 oC
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Transesterification Mechanism• Adsorption Sites
4500 4000 3500 3000 2500 2000 1500 1000 500
c
b
Frequence cm-1
a
1162
1097 718
Figure 10 FTIR spectra; (a) Ca3La1 adsorbed triglyceride (curve 1), 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).
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CH3
O
H
CH3OH
O H -/O 2- O H -/O 2-
CH3
O-
O H -/O 2-
H
O H -/O 2-
CH3
-O
C
OR1
O
R2
H
C a 2+ /L a 3+ C a 2+ /L a 3+
C
O
R1OR2O
R1OR2 +
C a 2+ /L a 3+
CH3
O
C
OR1
O
R2
-
CH3
O
C
OR1
R2 O -
O H -/O 2-
H
O H -/O 2-
H
O R2
O H -/O 2-
R2 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 and high 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 21st
Century Job Fund program is gratefully
acknowledged
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Thanks!