“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

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Contents

Introduction

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References

Experiments

Result & discussion

Conclusion

BiodieselChemically, 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 diesel-engine vehicles. B100 or “neat” fuel: Biodiesel is pure or 100%BXX : Biodiesel blendsXX indicates the amount of biodiesel in the blend(i.e., a B80 blend is 80% biodiesel and 20% petrodiesel) 3

Introduction

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.

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Transesterification reaction can be either carried out via non-catalytic or catalytic processes.

Transesterification

Triglyceride + ROH Diglyceride + RCOOR1

Diglyceride + ROH Monoglyceride + RCOOR2

Monoglyceride + ROH Glycerol + RCOOR3

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Acid-Catalyzed Processes

Base-Catalyzed Processes

Transesterification

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

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Catalysts for transesterification

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Why should we use Heterogeneous catalysts for transesterification ?

Problems associated with the homogeneous catalystsThe 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

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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 separatedhigher quality of ester products and glycerol by product obtain, without expensive refining operationscatalysts are not consumed or dissolved in the reaction and therefore can be easily separated from the productscatalysts can also be readily regenerated and reusedmore environmentally benign because there is no need for acid or water treatment in the separation step

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Details Of Work Done

Following work has been done

Characterization of cementCharacterizations of thumba oil & soybean oilSynthesis of catalystProduction of biodieselCharacterization of biodiesel

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Experimental

MaterialsSoybean 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).

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

Characterization of raw materialCharacterization of soybean oil and Thumba oil

Table 1 Characterization of soybean oil and Thumba oil

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S.NO. Content Composition of clinker (%) Composition of fly ash (%)1 Na2O 0.37 1.12

2 MgO 3.03 1.803 Al2O3 5.72 25.60

4 SiO2 20.99 51.50

5 SO3 1.29 1.7

6 ClƟ - -7 K2O 0.69 0.56

8 CaO 63.98 8.259 TiO2 - -

10 Fe2O3 3.71 5.4

11 A/F 1.54 -12 S/R 2.23 -13 LSF 94 -14 F/CaO 1.84 -15 Tricalcium Silicate (Ca3SiO5), C3S 46.11 -

16 Dicalcium Silicate (Ca2SiO4), C2S 25.4 -

17 Tricalcium Aluminate (Ca3Al2O6), C3A 8.87 -

18 Tetracalcium Aluminoferrite

(Ca2AlFeO5), C4AF

11.3 -

19 Liquid 28.1 -

Characterization of Portland pozzolana cementThe 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.

Table 2 Characterization of Portland pozzolana cement

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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 90oC 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 100oC 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 90oC 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.

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Reaction Procedure

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Reaction Procedure

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Result & Discussion

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Optimization of reaction conditionsIn 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 65OC, with 4 wt.% catalyst and for 65 minutes(b) Effect of methanol/thumba oil molar ratio on the methyl ester content at 65OC, with 4 wt.% catalyst and for 65 minutes

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Effect of catalyst amount

Figure (a) Figure (b)

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

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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

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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

Characterization of biodiesel

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

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ConclusionsIn 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.

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