Automating Google Workspace (GWS) & more with Apps Script
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
21. References
•Marchetti J.M.,, Miguel V.U., Errazu A.F. (2007) Heterogeneous esterification of oil with high amount of free fatty acids, Fuel 86, pp. 906–910.
•Srivastava A. and Prasad R. (2000) Triglycerides based diesel fuels, Renew Sustain Energy Rev 4, pp. 111–33.
•Murugesan A., Umarani C., Chinnusamy T.R., Krishnan M., Subramanian R., Neduzchezhain N. (2008) Production and analysis of bio-diesel from non-edible oils—A review,
Energy Rev, doi:10.1016/j.rser.
•Dubé M.A., Tremblay A.Y., Liu J. (2007) Biodiesel production using a membrane reactor, Bioresource Technology, 98, pp. 639–647.
•Xie W. and Yang Z. (2007) Ba-ZnO catalysts for soybean oil transesterification, Catalysis Letters 117, pp.159–165.
•Eckey E.W. (1956) Esterification and interesterification, JAOCS, 33, pp. 575–579.
•Dizge N., Aydiner C., Imer D.Y., Bayramoglu M., Tanriseven A., Keskinler B. (2009) Biodiesel production from sunflower, soybean, and waste cooking oils by
transesterification using lipase immobilized onto a novel microporous polymer, Bioresource Technology, 100, pp. 1983–1991.
•Sivozhelezova V., Bruzzeseb D., Pastorinoa L., Pechkova E., Nicolini C. (2009) Increase of catalytic activity of lipase towards olive oil by Langmuir-film immobilization of
lipase, Enzyme and Microbial Technology, 44, pp. 72–76.
•Freedman B., Pryde E.H., Mounts T.L. (1984) Variables affecting the yields of fatty esters from transesterified vegetable oils, Journal of the American Oil Chemists Society, 61,
pp. 1638–1643.
•Canakci M. and Gerpen J.V. (1999) Biodiesel production via acid catalysis, Transactions of the American Society of Agricultural Engineers, 42, pp. 1203–1210.
•Dmytryshyn S.L., Dalai A.K., Chaudhari S.T. (2004) Synthesis and characterization of vegetable oil derived esters: evaluation for their diesel additive properties, Bioresource
Technology, 92, pp. 55–64.
•Alamu O.J., Waheed M.A., Jekayinfa S.O. (2008) Effect of ethanol–palm kernel oil ratio on alkali-catalyzed biodiesel yields, Fuel, 87, pp. 1529–1533.
•Formo M.W. (1954) Ester reactions of fatty material, J Am Oil Chem Soc., 31(11), pp. 548–59.
•Feuge R.U. and Gros At., Modification of vegetable oils, VII Alkali catalyzed interesterification of peanut oil with ethanol, J Am Oil Chem Soc., 26 (3), pp.97.
•Krishangkura K. and Simamaharnnop R.(1992) Continuous transmethylation of palm oil in an organic solvent,. J Am Oil Chem Soc., 69(2), pp. 166–9.
•Saka S. and Dadan K. (2001) Bio diesel fuel, from rapeseed oil as prepared in supercritical methanol, Fuel, 80, pp. 22.
•Vicente G., Martínez M., Aracil J. (2007) Optimization of integrated biodiesel production, part I. a study of the biodiesel purity and yields, Bioresource Technology, 98, pp.
1724–1733.
•Ma F. and Hanna M. (1999) Biodiesel production :A review, Bioresour. Technol, 70, pp. 1-15.
•Dalai A.K., Kulkarni M.G., Meher L.C. (2006) Biodiesel productions from vegetable oils using heterogeneous catalysts and their applications as lubricity additives, IEEE EIC
Climate Change Technology Conference EICCCC art 4057358.
•Abreu F.R., Lima D.G., Hamú E.H., Einloft S., Rubim J.C., Suarez P.A.Z. (2003) New metal catalysts for soybean oil transesterification, Journal of the American Oil Chemists'
Society, 80, pp. 601–604.
•Granados M.L., Poves M.D.Z., Alonso D.M., Mariscal R., Galisteo F.C., Tost R. M., Santamaría J., Fierro J.L.G. (2007) Biodiesel from sunflower oil by using activated calcium
oxide, Applied Catalysis B: Environmental, 73, pp.317–326.
•Wang L. and Yang J. (2007) Transesterification of soybean oil with nano-MgO or not in supercritical and subcritical methanol, Fuel, 86, pp. 328–333.
•Jitputti J., Kitiyanan B., Rangsunvigit P., Bunyakiat K., Attanatho L., Jenvanitpan- jakul P. (2006) Transesterification of crude palm kernel oil and crude coconut oil by different
solid catalysts, Chemical Engineering Journal 116, pp. 61–66.
•Xie W. and Huang X. (2006) Synthesis of biodiesel from soybean oil using heterogeneous KF/ZnO catalyst, Catalysis Letters, 107, pp. 53–59.
•Dossin T.F., Reyniers M.F., Berger R.J., Marin G.B. (2006) Simulation of heterogeneously MgO-catalyzed transesterification for fine chemical and biodiesel industrial
production, Applied Catalysis B, 67, pp.136–148.
•Lu Y.J., Gong Y.S. Zhang L.F. (2004) Oil detection technology. 1st ed. Beijing: Chemical Industry.
•Ma H.B., Li S.F., Wang .Y., Wang R.H., Tian S.J. (2008) Transesterification of rapeseed oil for synthesizing biodiesel by K/KOH/c-Al2O 3as heterogeneous base catalyst, J Am
Oil Chem Soc, 2008, 85, pp. 263–70.
21