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“Use of Portland Pozzolana Cement for the
Production of Biodiesel
”

Presented by
Sunny Soni
DEPARTMENT OF CHEMICAL ENGINEERING
MALAVIYA NATIONAL INSTITUTE OF TECHNOLOGY
JAIPUR -302017

1
Contents
Introduction
Experiments
Result & discussion
Conclusion

References
2
Introduction

Biodiesel
Chemically, biodiesel refers to a non-petroleum-based
diesel fuel consisting of short chain alkyl (methyl or ethyl)
esters, made by transesterification of vegetable oil or
animal fat (tallow), which can be used (alone, or blended
with conventional petro diesel) in unmodified dieselengine vehicles.
B100 or “neat” fuel: Biodiesel is pure or 100%
BXX : Biodiesel blends
XX indicates the amount of biodiesel in the blend
(i.e., a B80 blend is 80% biodiesel and 20% petrodiesel)
3
Transesterification
In the transesterification of vegetable oils, a triglyceride reacts
with an alcohol in the presence of a strong acid or base,
producing a mixture of fatty acids alkyl esters and glycerol.
Triglyceride + ROH

Diglyceride + RCOOR1

Diglyceride + ROH

Monoglyceride + RCOOR2

Monoglyceride + ROH

Glycerol + RCOOR3

Transesterification reaction can be either carried out via noncatalytic or catalytic processes.
4
Transesterification
Acid-Catalyzed Processes
Base-Catalyzed Processes

5
Catalysts for transesterification
Catalyst used for the transesterification of triglycerides is
classified as
Alkali catalyst,
acid catalyst,
enzyme or heterogeneous catalysts

6
Why should we use Heterogeneous catalysts for transesterification ?
Problems associated with the homogeneous catalysts
The high consumption of energy,
form unwanted soap by-product by reaction of the FFA,
Expensive separation of the homogeneous catalyst from the
reaction mixture ,
Generation large amount of wastewater during separation
and cleaning of the catalyst and the products

7
Heterogeneous catalysts:
Many heterogeneous catalysts, based on Metal hydroxides, metal
complexes, metal oxides such as calcium oxide, magnesium
oxide, zirconium oxide and supported catalysts have been
investigated as solid catalysts.
Heterogeneous catalysts can be more easily separated
higher quality of ester products and glycerol by product
obtain, without expensive refining operations
catalysts are not consumed or dissolved in the reaction and
therefore can be easily separated from the products
catalysts can also be readily regenerated and reused
more environmentally benign because there is no need for
acid or water treatment in the separation step
8
Details Of Work Done
Following work has been done
Characterization of cement
Characterizations of thumba oil & soybean oil
Synthesis of catalyst
Production of biodiesel
Characterization of biodiesel

9
Experimental
Materials
Soybean oil and Thumba oil used for the preparation of biodiesel was purchased from Jaipur and Jodhpur.
CH3OH, KOH & all the chemicals were purchased from companies Ranbaxy fine chemicals (Renkem)
Laboratory, Hi-media Laboratory Limited & MERCK Limited. The Portland pozzolana cement was
collected from J.K. Lakshmi Cement Ltd., Jaykaypuram-Sirohi (Rajasthan).

Characterization of raw material
Characterization of soybean oil and Thumba oil
S.No.

Parameter

Soybean oil

Thumba oil

1.

Density(kg/L)

0.843 kg/L

0.924

2.

Kinematic viscosity (mm2/sec. at 400C)

28.97

34.95

3.

Iodine value (gI2/100gm)

141

101

4.

Cloud point (0C)

-2

-1

5.

Pour point (0C)

-3

-3

6.

Flash point (0C)

265

263

7.

Fire point (0C)

270

269

8.

Acid value (mg KOH/g)

2.15

11.25

9.

Free fatty acid

1.075

5.625

Table 1 Characterization of soybean oil and Thumba oil
10
Characterization of Portland pozzolana cement
The characterization of Portland pozzolana cement has been done by XRF at JK Lakshmi Cement Ltd., which
have shown in table 2. The Portland pozzolana cement has composition of 65% clinker, 29% fly ash and 6%
gypsum.
S.NO.
1

Content
Na2O

Composition of clinker (%)
0.37

Composition of fly ash (%)
1.12

2
3

MgO
Al2O3

3.03
5.72

1.80
25.60

4

SiO2

20.99

51.50

5

SO3

1.29

1.7

6
7

ClƟ
K2O

0.69

0.56

8
9

CaO
TiO2

63.98
-

8.25
-

10

Fe2O3

3.71

5.4

11
12
13

A/F
S/R
LSF

1.54
2.23
94

14
15

F/CaO
Tricalcium Silicate (Ca3SiO5), C3S

1.84
46.11

-

16

Dicalcium Silicate (Ca2SiO4), C2S

25.4

-

17

Tricalcium Aluminate (Ca3Al2O6), C3A

8.87

-

18

Tetracalcium Aluminoferrite
(Ca2AlFeO5), C4AF

11.3

-

19

Table 2 Characterization of Portland pozzolana cement
28.1
Liquid

-

11
Preparation of catalyst
The solid base catalysts were prepared by chemical synthesis methods as follows.
1. Preparation of hydrated Portland pozzolana cement pellets.
Portland pozzolana cement and deionised water solution were mixed in a 1000
ml beaker. The mixture was stirred vigorously at 90 oC for 3 h. After the mixture
was cooled to room temperature, the paste of Portland pozzolana cement was
collected and prepared pellets.
2. Generation of the solid pellets.
The hydrated Portland pozzolana cement pellets were dried at 100 oC for 24h in
an oven and then it immersed in water and kept at room temperature for 7 days to
provide strength. Then it was extracted and dried.
3. Generation of the solid base catalyst.
15gm of solid pellets & 4 gm of aq. KOH solution solution were mixed in a
beaker. The mixture was stirred vigorously at 20 rpm and 90 oC till it dried. It was
dried in oven at 1000C for a night. Thereafter, the dried pellets were calcined at
8500C for 7 hrs. The catalyst, thus, obtained with KOH loading as 21.05 wt%
KOH/ Portland pozzolana cement.
12
Reaction Procedure

13
Reaction Procedure

14
Result & Discussion

15
Optimization of reaction conditions
In this study, the new prepared solid base catalyst was employed to catalyze the transesterification of soybean
oil and thumba oil with methanol to produce biodiesel. The variables affecting the transesterification, such as
methanol-to-oil molar ratio (3:1–9:1), catalyst amount (2.0–5.0 wt. % of oil), reaction temperature (55–70 oC),
and reaction time (50–65 minutes), were investigated.
Effect of mole ratio of methanol/oil

Figure (a)
Figure (b)
(a) Effect of methanol/soybean oil molar ratio on the methyl ester content at 65 OC, with 4 wt.% catalyst and for 65 minutes
(b) Effect of methanol/thumba oil molar ratio on the methyl ester content at 65 OC, with 4 wt.% catalyst and for 65 minutes
16
Effect of catalyst amount

Figure (a)

Figure (b)

(a) Effect of the amount of catalyst on the soybean oil methyl ester content at 65 OC, with 6:1 M ratio and for 65 minutes
(b) Effect of the amount of catalyst on the thumba oil methyl ester content at 65 OC, with 6:1 M ratio and for 65 minutes
17
Effect of reaction temperature

Figure (a)
Figure (b)
(a) Effect of reaction temperature on the soybean oil methyl ester content with 6:1 M ratio, 4 wt.% catalyst and for 65 minutes.
(b) Effect of reaction temperature on the thumba oil methyl ester content with 6:1 M ratio, 4 wt.% catalyst and for 65 minutes
18
Characterization of biodiesel
S.No.

Parameter

soybean oil methyl ester

thumba oil methyl ester

1.

Density(kg/L)

0.801

0.805

2.

Kinematic viscosity
(mm2/sec. at 400C)

4.25

4.95

3.

Iodine value (gI2/100gm)

136

104

4.

Acid value (mg KOH/g)

0.15

0.24

5.

Cloud point (0C)

-6

-4

6.

Pour point (0C)

-10

-9

7.

Flash point (0C)

170

174

8.

Fire point (0C)

175

179

9.

Yield (%)

94.52

90

Table 3 Characterization of soybean oil methyl ester and thumba oil methyl ester

19
Conclusions
In this study,

A novel solid base catalyst which contains KOH is prepared by simple steps and
is inexpensive.
 The experimental results show that 21 wt. % KOH/ Portland pozzolana cement
as catalyst has excellent catalytic activity and outstanding stability in the
transesterification of soybean oil and thumba oil with methanol to produce
biodiesel.
The optimal transesterification conditions are obtained as follows: methanol/oil
molar ratio 6:1, the amount of catalyst 4 wt. %, reaction temperature 65oC.
The results demonstrate that the Portland pozzolana cement catalyst shows high
catalytic performance & it was found that the yield of biodiesel can reach as high
as 94.52% with soybean oil & 90% with thumba oil under the optimal conditions.
Moreover, the catalyst is used repeatedly for at least 3 cycles with sustained
activity and with decreasing the methyl ester content, which sufficiently shows its
good stability.
20
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21
22

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162 sunny soni

  • 1. “Use of Portland Pozzolana Cement for the Production of Biodiesel ” Presented by Sunny Soni DEPARTMENT OF CHEMICAL ENGINEERING MALAVIYA NATIONAL INSTITUTE OF TECHNOLOGY JAIPUR -302017 1
  • 3. Introduction Biodiesel Chemically, biodiesel refers to a non-petroleum-based diesel fuel consisting of short chain alkyl (methyl or ethyl) esters, made by transesterification of vegetable oil or animal fat (tallow), which can be used (alone, or blended with conventional petro diesel) in unmodified dieselengine vehicles. B100 or “neat” fuel: Biodiesel is pure or 100% BXX : Biodiesel blends XX indicates the amount of biodiesel in the blend (i.e., a B80 blend is 80% biodiesel and 20% petrodiesel) 3
  • 4. Transesterification In the transesterification of vegetable oils, a triglyceride reacts with an alcohol in the presence of a strong acid or base, producing a mixture of fatty acids alkyl esters and glycerol. Triglyceride + ROH Diglyceride + RCOOR1 Diglyceride + ROH Monoglyceride + RCOOR2 Monoglyceride + ROH Glycerol + RCOOR3 Transesterification reaction can be either carried out via noncatalytic or catalytic processes. 4
  • 6. Catalysts for transesterification Catalyst used for the transesterification of triglycerides is classified as Alkali catalyst, acid catalyst, enzyme or heterogeneous catalysts 6
  • 7. Why should we use Heterogeneous catalysts for transesterification ? Problems associated with the homogeneous catalysts The high consumption of energy, form unwanted soap by-product by reaction of the FFA, Expensive separation of the homogeneous catalyst from the reaction mixture , Generation large amount of wastewater during separation and cleaning of the catalyst and the products 7
  • 8. Heterogeneous catalysts: Many heterogeneous catalysts, based on Metal hydroxides, metal complexes, metal oxides such as calcium oxide, magnesium oxide, zirconium oxide and supported catalysts have been investigated as solid catalysts. Heterogeneous catalysts can be more easily separated higher quality of ester products and glycerol by product obtain, without expensive refining operations catalysts are not consumed or dissolved in the reaction and therefore can be easily separated from the products catalysts can also be readily regenerated and reused more environmentally benign because there is no need for acid or water treatment in the separation step 8
  • 9. Details Of Work Done Following work has been done Characterization of cement Characterizations of thumba oil & soybean oil Synthesis of catalyst Production of biodiesel Characterization of biodiesel 9
  • 10. Experimental Materials Soybean oil and Thumba oil used for the preparation of biodiesel was purchased from Jaipur and Jodhpur. CH3OH, KOH & all the chemicals were purchased from companies Ranbaxy fine chemicals (Renkem) Laboratory, Hi-media Laboratory Limited & MERCK Limited. The Portland pozzolana cement was collected from J.K. Lakshmi Cement Ltd., Jaykaypuram-Sirohi (Rajasthan). Characterization of raw material Characterization of soybean oil and Thumba oil S.No. Parameter Soybean oil Thumba oil 1. Density(kg/L) 0.843 kg/L 0.924 2. Kinematic viscosity (mm2/sec. at 400C) 28.97 34.95 3. Iodine value (gI2/100gm) 141 101 4. Cloud point (0C) -2 -1 5. Pour point (0C) -3 -3 6. Flash point (0C) 265 263 7. Fire point (0C) 270 269 8. Acid value (mg KOH/g) 2.15 11.25 9. Free fatty acid 1.075 5.625 Table 1 Characterization of soybean oil and Thumba oil 10
  • 11. Characterization of Portland pozzolana cement The characterization of Portland pozzolana cement has been done by XRF at JK Lakshmi Cement Ltd., which have shown in table 2. The Portland pozzolana cement has composition of 65% clinker, 29% fly ash and 6% gypsum. S.NO. 1 Content Na2O Composition of clinker (%) 0.37 Composition of fly ash (%) 1.12 2 3 MgO Al2O3 3.03 5.72 1.80 25.60 4 SiO2 20.99 51.50 5 SO3 1.29 1.7 6 7 ClƟ K2O 0.69 0.56 8 9 CaO TiO2 63.98 - 8.25 - 10 Fe2O3 3.71 5.4 11 12 13 A/F S/R LSF 1.54 2.23 94 14 15 F/CaO Tricalcium Silicate (Ca3SiO5), C3S 1.84 46.11 - 16 Dicalcium Silicate (Ca2SiO4), C2S 25.4 - 17 Tricalcium Aluminate (Ca3Al2O6), C3A 8.87 - 18 Tetracalcium Aluminoferrite (Ca2AlFeO5), C4AF 11.3 - 19 Table 2 Characterization of Portland pozzolana cement 28.1 Liquid - 11
  • 12. Preparation of catalyst The solid base catalysts were prepared by chemical synthesis methods as follows. 1. Preparation of hydrated Portland pozzolana cement pellets. Portland pozzolana cement and deionised water solution were mixed in a 1000 ml beaker. The mixture was stirred vigorously at 90 oC for 3 h. After the mixture was cooled to room temperature, the paste of Portland pozzolana cement was collected and prepared pellets. 2. Generation of the solid pellets. The hydrated Portland pozzolana cement pellets were dried at 100 oC for 24h in an oven and then it immersed in water and kept at room temperature for 7 days to provide strength. Then it was extracted and dried. 3. Generation of the solid base catalyst. 15gm of solid pellets & 4 gm of aq. KOH solution solution were mixed in a beaker. The mixture was stirred vigorously at 20 rpm and 90 oC till it dried. It was dried in oven at 1000C for a night. Thereafter, the dried pellets were calcined at 8500C for 7 hrs. The catalyst, thus, obtained with KOH loading as 21.05 wt% KOH/ Portland pozzolana cement. 12
  • 16. Optimization of reaction conditions In this study, the new prepared solid base catalyst was employed to catalyze the transesterification of soybean oil and thumba oil with methanol to produce biodiesel. The variables affecting the transesterification, such as methanol-to-oil molar ratio (3:1–9:1), catalyst amount (2.0–5.0 wt. % of oil), reaction temperature (55–70 oC), and reaction time (50–65 minutes), were investigated. Effect of mole ratio of methanol/oil Figure (a) Figure (b) (a) Effect of methanol/soybean oil molar ratio on the methyl ester content at 65 OC, with 4 wt.% catalyst and for 65 minutes (b) Effect of methanol/thumba oil molar ratio on the methyl ester content at 65 OC, with 4 wt.% catalyst and for 65 minutes 16
  • 17. Effect of catalyst amount Figure (a) Figure (b) (a) Effect of the amount of catalyst on the soybean oil methyl ester content at 65 OC, with 6:1 M ratio and for 65 minutes (b) Effect of the amount of catalyst on the thumba oil methyl ester content at 65 OC, with 6:1 M ratio and for 65 minutes 17
  • 18. Effect of reaction temperature Figure (a) Figure (b) (a) Effect of reaction temperature on the soybean oil methyl ester content with 6:1 M ratio, 4 wt.% catalyst and for 65 minutes. (b) Effect of reaction temperature on the thumba oil methyl ester content with 6:1 M ratio, 4 wt.% catalyst and for 65 minutes 18
  • 19. Characterization of biodiesel S.No. Parameter soybean oil methyl ester thumba oil methyl ester 1. Density(kg/L) 0.801 0.805 2. Kinematic viscosity (mm2/sec. at 400C) 4.25 4.95 3. Iodine value (gI2/100gm) 136 104 4. Acid value (mg KOH/g) 0.15 0.24 5. Cloud point (0C) -6 -4 6. Pour point (0C) -10 -9 7. Flash point (0C) 170 174 8. Fire point (0C) 175 179 9. Yield (%) 94.52 90 Table 3 Characterization of soybean oil methyl ester and thumba oil methyl ester 19
  • 20. Conclusions In this study, A novel solid base catalyst which contains KOH is prepared by simple steps and is inexpensive.  The experimental results show that 21 wt. % KOH/ Portland pozzolana cement as catalyst has excellent catalytic activity and outstanding stability in the transesterification of soybean oil and thumba oil with methanol to produce biodiesel. The optimal transesterification conditions are obtained as follows: methanol/oil molar ratio 6:1, the amount of catalyst 4 wt. %, reaction temperature 65oC. The results demonstrate that the Portland pozzolana cement catalyst shows high catalytic performance & it was found that the yield of biodiesel can reach as high as 94.52% with soybean oil & 90% with thumba oil under the optimal conditions. Moreover, the catalyst is used repeatedly for at least 3 cycles with sustained activity and with decreasing the methyl ester content, which sufficiently shows its good stability. 20
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