BIODIESEL PRODUCTION FROM RESIDUAL ANIMAL FAT USING VARIOUS CATALYSTS.
Waste animal fat is considered a promising cheap alternative feedstock for biodiesel production that does not compete with food items. The objective of the study was to utilize waste animal fat (beef and mutton) for biodiesel production using different catalysts (Na, NaOHand KOH). Oil extracted from beef and mutton fat was analyzed by Gas Layer Chromatography for its fatty acids composition. Both mutton and beef fat showed 50-93% conversion rate of oil to biodiesel with 3:1 methanol to oil molar ratio with addition of 1% by weight of different catalysts (Na, NaOHand KOH) at 60oC. Transesterification of animal fat with KOH catalyst produced biodiesel of high quality with good conversion rate. Biodiesel produced after transesterification reaction was analyzed for flash point (less then)145oC each, kinematic viscosity 2.74 and 2.59cSt, density 0.88 and 0.87kg/L, pour point 59 oF and 57.2oF, calorific value 11568.7 and 10907.4BTU/lb and water content 0.03 and 0.04%vol for mutton and beef respectively.
Properties of biodiesel were comparable to ASTM standards so it can be used as a fuel in vehicles.
Key words: Biodiesel, Catalyst, Transesterification, Animal fat, Mutton and Beef.
Fossil fuel consumption was increased in the last 25 years as well as petrochemical products due to high dependence on the fossil fuel (Bunnell, 2007). In 1985, 2807 million tons of petroleum was consumed worldwide. Average growth rate of consumption of fossil fuel is found to be 1.5% per year so it is becoming more expensive day by day due to its finite or scarce nature (Balat and Balat, 2010).
Currently, world primary energy demand of petroleum is 35% which is fulfilled by petro-diesel.
This demand was 84 million barrels per day in 2009 but in 2014 demand will increase to 90 million barrels per day. Demand of petroleum in China and Asia is higher because these are non oil producing countries. There is threat for depletion of remaining resources of oil which are only for 53 years (Ito et al., 2012).
It is estimated that the oil would exhaust in 41 years and gas would be depleted in 63 years. In USA demand will reach from 84.40 million barrels to 116 million barrels per day by 2030. Consumption is increasing day by day, the exhaustion time span will also decrease by increasing demand. Due to increasing demand of fuel, European countries planned to use 10% of biofuel by the 2020 (Shahid and Jamal, 2011).
Increase energy demand worries the experts about petroleum resources, because these resources are only available for few decades to come. Fossil resources like liquid petroleum gas, gasoline, natural gas and petro diesel are all used in the transport sector.
The major benefit of biodiesel is that its raw material is easily available and environmental friendly which are non toxic, biodegaradeable. Levels of emissions are also improved by the biodiesel (Demirbas, 2007).
Biodiesel has a list of advantages which are as follows; (i) fossil fuel alternative, which reduces dependence on foreign import of petro-diesel or fossil fuel (ii) Achieve the target of renewable energy of European Union (iii) Balance energy crisis (iv) Reduces green house gasses emissions (v) Reduces harmful emissions (vi) Is environment friendly fuel (Vicente et al., 2011).
The objective of the current study was to collect pure fat and residual fat from slaughter house for its conversion to oil by heating process. Extracted oil was transesterified to biodiesel using various catalysts. Prepared biodiesel was analyzed for various parameters by GC-MS using ASTM standard methods. Properties of biodiesel were compared with international standards to measure its quality. Catalytic efficiencies were also compared to find the best catalyst for biodiesel production.
MATERIALS AND METHODS
Collection of beef and mutton fats: Samples of animal fats were collected from slaughter house at Bakarmandi, Lahore, in plastic bags and transferred in the laboratory for further process.
Analysis and processing of fats:
Washing and heating: Collected fats were washed with water to remove dust and other extra materials than it was heated at 1000C for 90 minutes on hot plate to extract oil from animal fats and residual waste was separated from oil.
Filtration: The extracted oil was filtered to remove impurities such as protein contents and residual meat pieces.
Composition of fatty acids: Fatty acids profile was analyzed by Gas Chromatography Mass Spectrometry (GC-MS).
Preparation of Catalysts: Sodium hydroxide and potassium hydroxide were present in the form of pellets and sodium metal was present in the solidified form. Catalysts were converted into powder form by using pestle and mortar. Three grams of sodium hydroxide, potassium hydroxide and sodium metal were dissolved in 10 ml of methanol and stirred for 10-15 minutes.
Transesterification process: Transesterification reaction was carried out using 3:1 molar ratio of methanol to oil. Hundred mililitre of extracted oil from animal fats (beef and mutton) were mixed with 300 ml of methanol (analytical reagent) and stirred continuously for 90 minutes at 60 0C. Ten mililitre of each catalyst (sodium methoxide, potassium hydroxide and Na metal) were added to initiate the reaction. After reaction, sample was put in separating funnel for 16 hours to separate biodiesel from residual glycerin. Upper layer was distinguished as biodiesel while lower layer was of glycerin.
Biodiesel production and analysis: Upper layer of biodiesel was separated by separating funnel and its properties such as Kinematic viscosity at 37.80C, Flash point, Density at 150C, Pour point, Calorific value (Gross) and Water content were measured to analyze the quality of biodiesel by ASTM D-445, D-93, D-1298, D-97, D-240 and Karl Fischer titration respectively.
RESULTS AND DISCUSSION
Oil extraction from fats: Two different animal fats (beef and mutton) were taken, in pure form and residual form which consist of meat and other parts too. The percentage extraction of oil was different for each sample. In case of pure fats one kilogram pure fat of mutton and beef were converted into oil up to 77.27 % and 89.01 % respectively. In other case, residual fats of mutton and beef were also converted into the oil and its conversion ratio is totally different from pure fats because there were several impurities are present in it. One kilogram of residual fat of mutton and beef converted oil up to 68.76% and 51.43 % respectively (Figure 1). Demirbas (2009) conducted study to use animal fat oil for biodiesel production because it was not compete in the food market. Bozbas (2008) studied that vegetable oil is not good for biodiesel production because it is expensive and on the other side the biodiesel production from animal fat oil is better as compare to vegetable oil.
Residual waste of the oil extract: Oil was extracted from the collected animal fats and residue was left after its extraction. It was observed that the production of waste from pure fats was less as compared to the residual fats (Figure 2). The waste production from pure fat of mutton and beef were 11.4% and 11.1% respectively and waste from residual fat of mutton and beef was higher which were 14.5% and 28.07% respectively because quantity of impurities was greater in residual fat.
Effect of catalysts on biodiesel production:
Efficiency of different catalyst was also measured in this research work. This result showed that the percent yield of biodiesel with potassium hydroxide was greater as compared to others that were 93% of mutton oil and 91% of beef oil. While efficiency of sodium metal was lesser as compared to potassium hydroxide and greater than sodium hydroxide, that were 72% for mutton oil and 62% for beef oil. Efficiency of sodium hydroxide was very low as compared to both catalysts i.e. sodium metal and potassium hydroxide, which were 53% for mutton oil and 48% for beef oil (Figure 3). Mutrejaet al (2011) conducted study to use potassium hydroxide as a catalyst and conversion rate of mutton oil into biodiesel was observed up to 98%. Dias et al (2011) stated that the selection of the catalyst is most important for biodiesel production. Oner and Altun (2009) conducted study for biodiesel production in which sodium hydroxide was used as a catalyst and stated that it is better than other catalysts.
Vicente et al (2011) selected commonly used homogenous catalysts biodiesel production which was sodium methoxide, potassium methoxide, sodium hydroxide and potassium hydroxide. It was concluded that all the catalysts were suitable for biodiesel production.
Fatty acid composition:
Fatty acid composition of mutton oil: Fatty acid composition of mutton oil was determined by Gas Chromatography which showed different carbon chain compounds were present in the sample. It was found that mutton biodiesel contained 1.15 wt. % lauric acid, 8.12 wt. % Myristic acid, 3.51 wt. % Palmitic acid, 0.64 wt. % Palmitoleic acid, 49.70 wt. % Stearic acid, 27.66 wt. % Oleic acid, 7.82 wt. % Linoleic acid and 1.17 wt. % Linolenic acid (Table 1). Morales et al (2011) reported fatty acid of mixed fats were Myristate acid (C14:0) wt. % 2.1, Palmitate acid (C16:0) wt. % 26.6, Palmitoleate acid (C16:1) wt. % 3.4, Stearate acid (C18:0) wt. % 16.7, Oleic acid (C18:1) wt. % 42.1, Linoleic acid (C18:2) wt. % 7.6 and Linolennic acid (C18:3) wt. % 0.57.
Fatty acid composition of beef oil: Fatty acid composition of beef oil was determined by Gas Chromatography which show different carbon chain compound was present in this sample. It was found that beef biodiesel contained 1.49 wt. % lauric acid, 26.87 wt. % Myristic acid, 2.50 wt. % Palmitic acid, 1.69 wt.
% Palmitoleic acid, 0.57 wt. % Stearic acid, 19.98 wt.
% Oleic acid, 38.06 wt. % Linoleic acid, 3.75 wt. % Linolenic acid and 4.24 wt. % Arachidic acid (Table 1). Encinaret al (2011) reported the percentage of different faty acid which was 1.5 wt. % Myristic acid, 28.1 wt. % Palmitic acid, 4.0 wt. % Palmitoleic acid, 12.0 wt. % Stearic acid, 44.6 % Oleic acid, 9.4 wt. % Linoleic acid and 0.5 wt. % Linolenic acid. Dias et al (2011) reported fatty acid content in pork lard which was Myristate acid (C14:0) wt. % 1.5, Palmitate acid (C16:0) wt. % 23.9, Palmitoleate acid (C16:1) wt. % 2.1, Stearate acid (C18:0) wt. % 12.2, Oleic acid (C18:1) wt. % 42.5, Linoleic acid (C18:2) wt. % 15.1 and Linolennic acid (C18:3) wt. % 0.9. Ma et al (1998) stated that percentage of fatty acid of beef tallow was 0.1 wt. % lauric acid, 2.8 wt. % Myristic acid, 23.3 wt. % Palmitic acid, 19.4 wt. % Stearic acid, 42.4 wt. % Linoleic acid, 2.9 wt. % Oleic acid and 0.9 wt. % Linolenic acid.
Table 1: Percentage composition of mutton and beef oil fatty acids from GLC spectrum.
Fatty Acid Profile###Mutton oil###Beef oil
Biodiesel analysis: The produced biodiesel was analyzed for the following properties:
Kinematic Viscosity: The kinematic viscosity at 37.80C value of mutton and beef were 2.74cSt and 2.59cSt respectively and the ASTM standard of kinematic viscosity is 1.9-6.0 (Table 2). Liu et al (2011) determined the viscosity of biodiesel from beef tallow that was 5.23cSt. Cunha et al (2009) also measured the kinematic viscosity of beef tallow was 5.3cSt. Morales et al (2011) reported that the viscosity of mixed fat was 5.2 cSt at 400C.
Flash point: Flash point value of both mutton and beef biodiesel were less than 145 0C. The ASTM standard of flash point for biodiesel is greater than 1300C (Table 2). Cunha et al (2009) measured the flash point of pure biodiesel from beef tallow was 156.070C.
Density: Density at 150C of mutton and beef biodiesel was 0.88 Kg/Liter and 0.87 Kg/Liter respectively. The ASTM standard for density of biodiesel is 0.86-0.9 (Table 2). Cunha et al (2009) determined density of pure biodiesel from beef tallow was 0.872 Kg/Liter. Morales et al (2011) reported the density of mixed fat was 0.892 Kg/L at 400C.
Water content: The water content in mutton and beef derived biodiesel were 0.03%volume and 0.04% volume respectively. The ASTM standard for biodiesel is 0.05% volume (Table 2). Mutrejaet al (2011) conducted the study to find the moisture content in biodiesel was 0.02%. Ramalhoet al (2012) conducted the study to find the moisture content in biodiesel was 0.09 %.
Pour point: The pour point value of mutton and beef derived biodiesel that were 59.0 0F and 57.2 0F respectively. There is no standard of pour point in ASTM standards list of biodiesel (Table 2).
Calorific value (Gross): Calorific values were different for mutton and beef biodiesel that were 11568.7 BTU/Lb and 10907.4 BTU/Lb respectively. There is no ASTM standard of calorific value too (Table 2).
Table 2: Properties of biodiesel derived from oil extracted from mutton and beef fats.
Kinematics Viscosity at 37.8oC###cSt###ASTM D-445###2.74###2.59###1.9-6.0
Flash Point (PMCC)###Deg. C###ASTM D-93###(less then)145 (less then)145###(less then)130
Density at 15 0C###Kg / Ltr ASTM D-1298###0.88###0.87###0.86-0.9
Water Content###% Vol.###KF - Titration###0.03###0.04###0.05
Pour point###Deg. F###ASTM D-97###59.0###57.2###-
Calorific Value (Gross)###BTU /Lb###ASTM D-240###11568.7###10907.4###--
Conclusions: Exploitation of fossil fuels and their increasing prices forced researchers to find alternatives. Biofuels can be the good alternatives as these are produced from renewable raw material. Animal fats are produced as waste in slaughter houses and butcher shops. A small quantity of these fats is used by soap industry, rest is dumped in landfills. Biodiesel production from animal fat is economical as the raw material is cheaper and easily available. In the current study it was observed that percentage of oil and biodiesel production was higher with mutton fat as compared to the beef fat. Comparison of catalyst indicated that KOH given higher yield of biodiesel after transesterification reaction than NaOH and Na metal. Properties of biodiesel indicated that it can be suitable fuel for vehicle.
Acknowledgements: The authors acknowledge Sustainable Development Study Centre at Government College University Lahore for providing funding for the current study and Director General, Pakistan Council of Scientific and Industrial Research (PCSIR), Director, Applied Chemistry Research Center (ACRC) and Dr. Zeeshan Ali and Miss SaimaSiddique at ACRC, PCSIR laboratories Lahore for providing testing facilities of oil and biodiesel.
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GC University, Sustainable Development Study Centre, Lahore, Pakistan, Forman Christian College (A Chartered University) Lahore, Pakistan, Corresponding Author email: firstname.lastname@example.org
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|Author:||Ali, A. S.; Ahmad, F.; Farhan, M.; Ahmad, M.|
|Publication:||Pakistan Journal of Science|
|Date:||Dec 31, 2012|
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