FORM 2
THE PATENTS ACT 1970
(39 of 1970)
&
The Patents [Amendment] Rules, 2006
PROVISIONAL SPECIFICATION
(See section 10 and rule 13)
1. TITLE OF THE INVENTION
Novel Catalyst Composition for Biodiesel Production and a Process for Producing Biodiesel and the Product Thereof

2. APPLICANT
NAME : Indian Oil Corporation Limited
NATIONALITY : IN
ADDRESS : G-9, Ali Yavar Jung Marg, Bandra (East), Mumbai-400 051 (IN)
3. PREAMBLE TO THE DESCRIPTION
PROVISIONAL
The following specification describes the invention :

FIELD OF THE INVENTION
This invention, in general, relates to a novel catalyst composition for production of biodiesel and a process for the preparation of biodiesel. More specifically; but without restriction to the particular embodiments hereinafter described in accordance with the best mode of practice, this invention relates to a novel catalyst composition, prepared from natural waste materials. More particularly, the catalyst composition is prepared from seashells and eggshells.
BACKGROUND OF THE INVENTION
Environmental problems coupled with petroleum reserve depletion stimulated research to develop the renewable transportation fuels. Biodiesel is one of the candidates, which has similar combustion properties as diesel and is being used in a view to reduce the air pollution, to
support agriculture and to reduce dependence on the fossil fuel, which are limited resources and
localized to some specific regions.
The use of biodiesel in conventional diesel engines results, in substantial reduction of un-burnt hydrocarbons, carbon monoxide and particulate matters. Biodiesel is considered as a clean fuel as it has almost no sulphur, no aromatics and has about 10% built-in oxygen, which helps it to burn fully. Its higher cetane number improves the igrntion quality even in blends with petroleum diesel.
Fatty Acid Methyl Esters (FAME) have properties very similar to petroleum diesel and so known as biofuel or Biodiesel. These esters can be made from virgin or used vegetable oils or animal fats and can be used as a blend in petroleum diesel.
Processes for producing biodiesel employing different catalysts have been reported in the prior art. These catalysts could be basic, e.g. sodium hydroxide, potassium hydroxide, sodium methoxide, potassium ethoxide or acidic, e.g. sulfuric acid Biocatalysts like lipases have also been employed for biodiesel synthesis. Solid acid catalysts like alumina, metal salts and clay have also been used as catalysts in the biodiesel production Different experimental parameters have been used to develop the process for production of biodiesel.
30 MAR 2009

United States Patent No. 5,525,126 to Basu et al. discloses esterification of a mixture of fats and oils using a calcium acetate-barium acetate catalyst. However, the matter requires elevated temperature, in excess of 200°C, and elevated pressure of approx. 500 psi. These conditions render the esterification process impractical and uneconomical for industrial scale production.
PCT International Application WO 00/05327 to Ginosar et al. discloses use of a critical fluid, high temperature and high pressure to affect a transesterification process. PCT International Application WO 03/022961 to Bioclean fuels Inc., discloses a process and an apparatus for producing biodiesel by esterifying waste oil with alcohols using static pressure, continuous flow through reaction vessels and specialized reaction tanks with vertical rotating feed tubes.
United States Patent Application Serial No. 2003/0032826 of Henna discloses a process for the production of fatty acid esters from triglyceride feeds stocks by a process in which the alcohol introduced is being characterized in that having a Reynolds No. of at least about 2100.
United States Patent No. 6,712,867 to Boocock et al. discloses a process for the esterification of triglyceride. The disclosed process comprises of forming a single phase solution of said triglyceride, an alcohol, a base catalyst (Sodium or Potassium hydroxide) for the esterification reaction and a co-solvent at a temperature that is less than the boiling point of the solution. The alcohol employed in the process is selected from the group consisting of methanol and ethanol, and mixtures thereof. The ratio of the alcohol to triglyceride is in the range of 15:1 to 35:1. The co-solvent is in an amount sufficient to effect formation of the single phase; permitting esterification to occur in said solution and recovering ester from said solution. The co-solvent is selected from the group consisting of tetrahydrofuran, 1,4-dioxane, diethyl ether, methyl-tertiarybutyl ether and diisopropyl ether.
United States Patent No. 6,642,399 to Boocock et al. discloses a single liquid phase process for the esterification of a mixture of fatty acids and triglycerides. The disclosed process comprises of forming a solution of the fatty acids and triglycerides, an alcohol, an acid catalyst (anhydrous sulfuric acid), a base catalyst (Sodium or potassium hydroxide) and a co-solvent at a temperature that is less than the boiling point of the solution. The alcohol is selected from the group consisting of methanol, ethanol, and mixtures thereof. The molar ratio of the alcohol to the triglycerides plus one third of the fatty acids is in the range of 15:1 to 35:1. The co-solvent is in an amount to effect formation of a single liquid phase.
United States Patent No. 6,489,496 to Barnhorst et al. discloses that the reaction zone can be any type of vessel commonly used for transesterification reactions, as for example, a reaction
3 0 MAR 2009

vessel having a stirrer or agitator, a vessel having a recirculation loop, or a static mixer within a pipe or a similar container.
United States Patent No. 6,399,800 to Haas et al. discloses a method for producing fatty acid alkyl esters from a feedstock, involving first saponifying the feedstock and then drying the saponified feedstock, and esterifying the dried saponified feedstock with an alcohol in the presence of an inorganic acid catalyst (sulfuric acid) to form fatty acid alkyl esters.
United States Patent No. 6,364,917 to Matsumura, et al. discloses a method and equipment of refining virgin plant oil and/or waste vegetable oil into fuel, preferably diesel engine fuel, by heating the oil, mixing the oil with water and/or ozone and agitating the mixture of oil and water and/or dissipating the ozone. United States Patent No. 6,768,015 to Luxem et al. discloses a method for making biodiesel from a vegetable oil source, simultaneously reacting the free fatty acids and glycerides of the oil source with methanol, in presence of an acid at temperatures between about 80°C to about 200°C and under pressure up to 500 psi.
United States Patent No. 5,302,746 to Koono et al. discloses a process for producing a carboxylic acid ester by reacting a carboxylic acid with an alcohol in the presence of an acid catalyst to produce a reaction solution and neutralizing the reaction solution, using range of aqueous alkali for neutralization.
European Patent No. 0924185 discloses a three stage transesterication process by using a heterogeneous catalyst based upon zinc or bismuth, titanium oxide and alumina followed by vacuum distillation at reduced pressure to separate the product. The vacuum distillation used for the separation of the ester is energy intensive and could also deteriorate the residue material due to high temperature.
German Patent No. DEI 0245758 to Rethmann Klemens et al. discloses a process for production of biodiesel by reacting a branched monohydric alcohol with a fat having a low unsaturated fatty acid content in the presence of sodium hydroxide or potassium hydroxide. European Patent EP-B-0 198 243 discloses a transesterification catalyst, comprising alumina or a mixture of alumina and ferrous oxide. The catalyst works at very low space velocity and also the glycerin generated in the process is far less than that of the theoretical value. It may be that glycerin ethers are formed as reported on US Patent 5,908,946.
English Patent GB795 573 (A) discloses formation of alkyl esters from vegetable or animal oils by catalytically treating the materials under superatmospheric pressure and elevated

temperature with an excess of a monohydroxy aliphatic alcohol so that the fatty materials are converted to glycerin and alkyl esters of the acids present in the fatty materials.
US Patent 5,908,946 discloses a process for production of alkyl ester and high purity glycerin with a catalyst that is selected from among zinc oxide, mixtures of zinc oxide and aluminum oxide, and zinc aluminates. The 90 -95 % conversion is achieved in two-stage process. The glycerin is removed from the ester after first step. The patent also discussed the detrimental effect of the presence of water, which encourages the formation of fatty acids, which may react to form soaps.
US Patent 6,712,867 discloses a transesterification process by using a co-solvent to form a single-phase solution of triglyceride in an alcohol selected from methanol and ethanol. The reaction is carried out below the lower of the boiling points of the solvent and co-solvent and the co-solvent removed after the reaction by distillation. Tetrahydrofuran (THF) and 1,4-dioxane, diethyl ether, methyl tertiary butyl ether and diisopropyl ether are reported to be used in an amount to effect formation of the single phase and a base catalyst for the esterification reaction.
US Patent 7,145,026 discloses a transesterification process, in a continuous, plug-flow environment using a 7-foot of 3/8" coiled copper pipe with a low residence time of about 10 seconds, single-pass in a temperature range of 80-180 C and a pressure of 1-30 atm. The coiled copper tubes are coated with metallic catalyst or a caustic and achieves about 70% conversion.
US Patent 7,193,097 describes a process using a third component like carbon dioxide, propane, butane, pentane, and hexane in a super critical or a sub critical state using catalysts sodium carbonate; sodium bicarbonate; titanium aluminum sulfate; and a salt containing titanium, zirconium, and phosphorous.
US Patent 7,122,688 discloses a method to prepare a fatty acid lower alkyl esters from a reaction of vegetable or animal oil, with a lower alcohol using acidic mesoporous silicate as catalyst. In this patent the various acidic mesoporous silicates have been prepared and activities of different acidic catalysts such as H2S04, SBA-15-S03H-P123, Nafion, SBA-15-S03H-L64, SBA-15-phS03H-P123, CDAB-S03H-C16 have been compared by esterification of palmitic acid in soybean oil
US Patents 7,138,536 and 6,878,837 discloses a process for producing fatty acid alkyl esters
3 0 MAR 2009

and glycerol from vegetable and/or animal oil and an alcohol, in the presence of a heterogeneous zinc aluminate catalyst. The process requires the control of the water in the reaction medium and is achieved by employing water/methanol separation steps by evaporation steps or through a series of nanofiltration membrane modules, maintained at a pressure close to 6 MPa.
EP 2000522 patent publication has described a novel method for the production of diesel oil by transesterifying fatty acid esters present in vegetable oils and fats, using a novel catalyst consisting of the oxide of a group V metal and having the formula X 2 O 5, such as niobium pentoxide (Nb2O5). Unlike in the methods used traditionally according to the prior art, the oils are converted here into high-purity products, including glycerol, in yields of the order of 100%, while using significantly less catalyst for a quantity of oil processed, when e.g. soya-bean oil, cotton-seed oil and canola oil are processed by the method according to the invention.
CN 101249431 & CN 101249449 patent publications disclose a novel solid base catalyst prepared by loading potassium carbonate or potassium flouride as an active component on a support and calcining at a high temperature. The catalyst has the advantages of high yield, cheap catalyst, small catalyst consumption, mild reaction conditions, short reaction time, reutilization of the catalyst, environment friendliness and low requirement for the raw material.
In CN 101250105 patent publication, p-toluene sulphonic acid formaldehyde condensate polymer has been used as solid catalyst to ptoduce biodiesel. The method has the advantages of high yield, cheap catalyst, low catalyst consumption, mild reaction conditions, short reaction time, reutilization of the catalyst, environment friendliness and non side reaction as saponification.
In general, heterogeneous catalysts are preferred, due to their recyclability, easy work up and high purity of glycerol obtained. However, majority of catalysts work under high temperatures and pressure condition. In addition, these catalysts are expensive. The present invention involve preparation of a transesterification catalyst, from natural inexpensive easily available waste materials, particularly seashells and eggshells and the catalyst developed produces biodiesel under atmospheric pressure and at 60-80°C temperature. The developed process is very convenient and fast. The catalyst developed retains its activity even after 5-6 cycles of reuse.


DETAILED DESCRIPTION OF THE INVENTION
It is an object of the present invention to develop an efficient and easy process for production of biodiesel from inexpensive recyclable catalyst. These and other objects are attained in accordance with the present invention wherein there is provided several embodiments of the process for the production of biodiesel by transesterification of vegetable oils and animal fats, utilizing a catalyst composition prepared from waste or fresh natural seashells. and eggshells.
According to the present invention, there is provided a process for preparation of catalyst composition by calcination of mixture of waste or fresh natural seashells and eggshells.
According to the present invention, there is provided a process for the production of biodiesel, in which catalyst is used as a fixed bed. The process comprises of reacting vegetable oil or animal fats with methanol, with catalyst of the present invention packed on a fixed bed, for effective conversion of the oils to biodiesel.
Cost is the one of the major factors slowing the commercialization of biodiesel. Replacement of homogeneous catalyst by solid catalysts eliminates the processing costs associated with the homogenous catalysis. Furthermore, the cost can be further reduced by production of solid catalysts from natural resources. The present invention involves the selection and identification of natural resources, capable of giving catalytic properties, for tranesterification of vegetable oils and animal fats, to produce biodiesel.
Disclosed natural resources include seashells and eggshells, which are available in plenty and very economic. The disclosed embodiment of the present invention deals with a optimum combination of seashell and eggshell, for production of catalyst for biodiesel synthesis.
The present invention further provides a process for the preparation of a novel transesterification catalyst by calcination of a optimum combination of seashell and eggshell. This combination contains seashells between 10-90% and eggshells between 90-10%. Furthermore, the calcination is carried out at 550-1000 °C.
The ratio between vegetable oils / animal fats and methanol is best selected so that, a distinct molar excess of methanol is provided relative to the triglycerides to be trans-esterified. Preferably a molar ratio of about 5:1 to 20:1 is employed. Larger quantities of methanol have a positive effect upon the rate and completeness of the esterification reaction. Even though the solubility of methanol in natural triglycerides is constant for a given reaction temperature, it has
30 MAR 2009

been found that, to a certain extent, an increase in the quantity of methanol used produces more rapid and more complete trans-esterification of the triglycerides.
The reaction temperature can be varied upto 200°C above the boiling point of alcohol used. For example, when methanol is used, the reaction temperature should be within the range of about 65°C to 265°C.
Although the present invention is not intended to be limited to any particular procedure for transesterifying the vegetable oils, the anhydrous triglycerides are subjected to atmospheric novel natural catalyst, prepared by calcination of optimum combination of seashell and eggshell, at a reaction temperature in the range of from about 65°C to 265°C in a known manner with a lower monoalcohol, e.g., an alkanol having 1 to 5 carbon atoms. The reaction is conducted at atmospheric pressure and it is prefened to carry out the reaction at the reflux temperature of the alcohol employed, e.g., for methanol, at about 65 C, reaction times between about 1 to 5 hours, being typical. The preferred monoalcohol is methanol. The transesterifi cation reaction can be carried out batch wise or continuously in any of the many known pressurized or non-pressurized reaction systems. In general, the methanol is used in a 50% to 150% excess over the stoichiometric quantity required for the transesterification reactions. The transesterification reaction should be carried out with substantially anhydrous methanol. The catalysts are used in quantities of from about 0.1 to 4.0 percent by weight based on the triglycerides. Preferred are catalyst quantities of from about 1 to 2 percent by weight, with about 1.5 percent by weight being most preferred.
Feed Stocks
The triglycerides derived from various plants and animals such as jatropha curcas oil, castor oil, sunflower oil, soybean oil, rapeseed oil, cotton oil, corn oil, coconut oil, ground nut oil, olive oil, palm kernel oil, fish oil, lard, tallow etc. may be used. In the present invention the triglycerides derived particularly from non-edible oils available in India such as jatropha curcas oil, castor oil, and karanjia oils have been used.
EXPERIMENTAL
Catalyst preparation
The sea shells are collected from sea beach. The seashells were washed thoroughly with water to remove any impurity or interfering materials. The washed shells were dried in oven at 110°C for 6hrs to remove traces of water. The shells are grounded to fine powder and sieved through


150 micron mesh and then calcined in muffle furnace at 550°C, for three hours. The eggshells are also washed thoroughly with water to remove traces of impurities and gelatin mass. The washed shells are grounded to fine powder and then dried at 110 °C. Subsequently, the dried eggshells are calcined at 300°C. Calcined seashells are admixed with calcined eggshell in desired ratio and the composition is then calcined at 550-1000 °C for four hours. This composition is then used as catalyst for transesterification.
Catalyst characterization
XRD studies were carried out in a 18 KW X Ray Diffractometer (Rigalcu, Japan) having copper rotating anode. XRD patterns were recorded at 50 KV & 250mA, at a scan rate of 2 deg / min with a step size of 0.01 deg in the temperature range of 2 to 75 deg 2-Theta. The XRD patterns were processed and peak search was conducted by search match to find out different phases present in the sample. The X-ray diffraction pattern exhibit calcium carbonate as the major phase in samples calcined below 750°C where as in samples calcined at temperatures above 750°C due to loss of CO2 calcium oxide becomes the major phase and caicium carbonate as the minor phase.
The average particle size was measured using analyzer of make Cilas model number 1180.The average particle size is 20-30 microns. SEM micrographs were performed to view textural structure changes in sea shells with change in calcinations temperature using a Hitachi S3400N scanning electron microscope. The S3400N SEM utilizes an electron beam accelerated at 300V to 30 KV. The SEM images show that the structure of shell changed with change of calcinations temperature. At 850°C the shape of particle became more regular. Accelerated surface area and porosity was measured on micrometricis instrument as per ASAP-2010 method.
The thermal stability was measured using TGA model 2960 thermal analyzing machine (TA instruments, USA) under a flow of nitrogen. Weight calibration was carried out using certified weighing stones. ~ 5-10 mg of the sample was taken in the Platinum pan and heated in air at the heating rate of 10 deg / min up to 900 deg C. The TGA results show loss of weight below 600°C , due to loss of water and other volatile matter, major loss in temperature range above 650°C , due to loss of C02 i.e., change of calcium carbonate phase to calcium oxide the effective phase.
Process for preparation of Fatty acid methyl ester (FAME) or Biodiesel


Trans-esterification reactions were carried out in a multi-necked round bottom flask fitted with condenser, heating mantle and mechanical stirrer. In a typical experiment to 1 mole of vegetable oil and 6 mole of methanol and 4% of catalyst composition. The reaction progress was monitored with thin layer chromatography using mixture of petroleum ether, diethyl ether and glacial acetic acid (85:13.5:1.5) as eluent and analytical techniques like GPC & NMR spectroscopy.
After completion of reaction the mixture was filtered to remove the catalyst. The catalyst was washed with methanol twice to remove residual ester and glycerol. The catalyst was vacuum dried at 80C for 4 hrs and further reused. The filtrate was allowed to equilibrate which resulted in separation of two phases. The upper phase consisted ester in methanol and lower layer consisted of glycerol and excess methanol. After separating the upper layer, it was passed through the column of acidic alumina followed by alcohol recovery to yield biodiesel. Biodiesel produced was tested for various properties as per American Society for Testing and Materials (ASTM)/Indian Specifications. The catalyst showed no change in activity even after 5 cycles of reuse.
The following examples are illustrative of the invention and should not be construed as limiting the scope of the invention in any manner. It is understood that the variations of the process described below are possible without departing from the scope and spirit of the invention;
EXAMPLE-1
The grounded & sieved egg shells (90 gram) and sea shells (10 gram) were properly mixed physically and the mixture calcined in a muffle furnace at 550°C for 3 hrs. under static air to obtain composition I (96 gram). The catalyst was characterized using TGA, SEM and XRD spectroscopy. The XRD diffraction patterns and scanning micrograph images show the composition to have calcium carbonate characteristics.
EXAMPLE-2
The physical mixture (lOOgram) as taken in Example-1 was calcined at 700°C for 3 hrs. under static air to obtain composition II (88 gram). The XRD diffraction patterns and scanning micrograph images show the composition to have calcium carbonate as the major phase and calcium oxide as the minor phase.
EXAMPLE-3
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A 100 gram mixture as described in Example-1 was calcined at 750°C for 3hrs. in muffle furnace under static air to obtain composition III (62 gram). The diffraction patterns and scanning micrograph images show the composition to have calcium oxide as the major phase and calcium carbonate as the minor phase.
EXAMPLE-4
A 100 gram mixture as described in Example-1 was calcined at 850°C for 3hrs. in muffle
furnace under static air to obtain composition IV (59 gram). The diffraction patterns and
scanning micrograph images show particle shape to be more regular due to complete change in
composition to calcium oxide. ,
EXAMPLE-5
80 gram of egg shells and 20 gram of sea shells were calcined in a muffle furnace at 850°C for 3 hrs. under static air to obtain composition V (54 gram). The catalyst was characterized using TGA, SEM and XRD spectroscopy. The XRD diffraction patterns and scanning micrograph images show the composition to have calcium oxide characteristics. Accelerated surface area and porosity measurement showed 3.5 m2/gm BET, 0.008 total pore volume and 140.4 A average pore size.
EXAMPLE 6
The catalyst composition VI was prepared in dry (pellet) form by using equivalent weight of catalyst composition (IV) and aluminium oxide (acidic), with PSB Alumina as binder, under mild acidic conditions. 14 gram of formic acid, 200gm of distilled water and 108 gm of PSB alumina binder are taken in a flask and stirred for 30 minutes at room temperature. In another flask, 100 gm of catalyst composition (IV), l00gm of acidic alumina and 20 ml of distilled water are taken. The contents of both the flasks are mixed and stirred for 15 minutes. The mixture is dried at 120-130°C for 2 hours. The dried material is crushed to power form and calcined at 400°C for 8 hrs, to yield Catalyst composition VI
EXAMPLE-7
4.0 gm of catalyst composition (1) was taken in a 250 ml three necked round bottom flask fitted with stirrer, condenser and thermometer.. 100 gm of sunflower oil and 30 gm methanol were then added into the flask and stirring was started. Subsequently the reaction mixture was heated to 70°C under reflux and stirred at this temperature for 8 hrs. Progress of the reaction was monitored by thin layer chromatography using mixture of hexane, diethyl ether and acetic acid as eluent. in the ratio of 85:13.5:1.5 and analytical techniques like GPC and 1HNMR

analysis. The analytical analysis of the product formed showed 10-12 % conversion of vegetable oil to fatty acid methyl ester( FAME) after 8 hrs. of reaction time.
EXAMPLE-8
The reaction was carried out as per exampIe-6 using catalyst composition (II, prepared as per example-2). The analytical analysis of the product formed showed 28% conversion of vegetable oil to FAME after 8 hrs. of reaction time.
EXAMPLE-9
The reaction was carried out as per example-6 using catalyst composition (III, prepared as per example-3). TLC indicated the completion of reaction after 5 Hrs reflux time. The contents were cooled after 5 hrs to room temperature, filtered to remove solid catalyst and washed with 15 ml of methanol. The filtered contents were passed through acidic alumina column and subsequently methanol was distilled off on rotavapor. Traces of methanol was removed at 70-80 Deg C under 10-50 mbar pressure. The resultant mixture of biodiesel & glycerine product was transferred to the separating funnel to remove the lower layer of glycerine. The reaction yielded 98 gram (-98.6% conversion) of biodiesel ( upper layer) and 7.4 grams of glycerine. The physico-chemical characteristics of the biodiesel obtained were: Ester content: 98.6%, specific gravity at 25°C: 0.8610, kinematic viscosity at 40°C: , 4.4 centistokes; total acid number: 0.42
EXAMPLE-10
This example demonstrates preparation of biodiesel using 8 gram of catalyst composition (IV) as prepared in exampIe-4, 200 gram of sunflower oil and 55 gram methanol in a 500 ml three necked flask equipped with condenser, stirrer and thermocouple. Reaction was carried out at reflux temperature of 70°C and TLC monitoring indicated the completion of rection in 3 Hrs. After the reaction completion the contents were cooled to room temperature. Catalyst was filtered and washed with 15 ml of methanol and dried at 70°C for 3hrs. for reuse. The filtered mixture was passed through column of acidic alumina and the excess alcohol was recovered on rotavapours initially at atmospheric pressure and then at reduced pressure to yield biodiesel and glycerol. The contents after methanol removal were transferred to separating funnel for removal of upper biodiesel layer & lower glycerine layer. The reaction yielded 196.1 gram (-98.6% conversion) of biodiesel and 15 grams of glycerol. The synthesized biodiesel was found to be meeting IS-15607: 2005 & ASTM D6751 specifications.
3 OMAR 2009

EXAMPLE-11
This example demonstrates preparation of biodiesel as per example 9 but using Jatropha oil in place of sunflower oil as reactants. TLC monitoring indicated the completion of reaction in 4 hrs. The reaction was worked up after 4 hrs. as described in EXAMPLE-9 to yield 198.2 gram (-99% conversion) of biodiesel and 15.1 grams of glycerine. The biodiesel thus produced was found to have 0.886 specific gravity at 25 deg C, 4.6 centistokes kinematic viscosity at 40 deg C and the total acid number of 0.45% by weight.
EXAMPLE-12
The reaction was carried out as per example-9 but using catalyst composition V, prepared as per exampIe-5 . TLC indicated completion of reaction in 3.5 hrs. Work up of the reaction mixture yielded 197.5 gram (98.8% conversion) of biodiesel and 15.2 gram of glycerol. The biodiesel thus produced was found to meet desired specifications.
EXAMPLE-13
A catalyst complex (A) was prepared under inert conditions by mixing 22 gram of catalyst composition (V) and 18 gm of methanol in a 100 ml round bottom flask fitted with stirrer and condenser. Stir the contents at the temperature to 65° C for 2 hrs. Then the reaction mixture was cooled to room temperature. The catalyst complex thus produced was filtered and dried at 100°C for 2 hrs and stored in a desiccator. 200 gram of sunflower oil, 55 gram methanol and 6 gram of catalyst complex (A) were taken in 500 ml three necked flask and reaction was carried out at at reflux temperature of 70°C as described in Example -11. The reaction completion was observed in 3 hours. Work up of the reaction mixture yielded 198.6 gram (-98.9 % conversion) of biodiesel and 15.2 gram of glycerine. The catalyst was washed with 15 ml of methanol and dried at 70 deg C for 3hrs. for reuse.
EXAMPLE-14
In a similar set up as described above to 25.8 gram of catalyst composition (V) added 42.4 gram of absolute ethanol. The contents were stirred under reflux at 70 °C for 2.5 hrs. to get catalyst complex (B). The catalyst complex B was filtered and dried at 100°C for 2 hrs. before use. The reaction was carried out as described in example-12 using catalyst complex B and Jatropha oil. The completion of reaction was observed in 3,5 Hrs by TLC. Work up of the reaction mixture yielded 197.8 gram (-98.5% conversion) of biodiesel and 15.3 grams of glycerol. The biodiesel thus produced has 0.8830 specific gravity at 25°C 4.4 centistokes kinematic viscosity at 40 ° C and the total acid number of 0.43% by weight.

EXAMPLE-15
This example demonstrates laboratory preparation of catalyst complex (C) formed by reaction of 5.6 gm catalyst composition (V) with 44 gm of p-nonyl phenol at 85° C for 3 hrs. Cooled the contents to room temperature, filtered and dried at 100°C for 2 hrs. Reaction was carried out as described in example -13 using catalyst complex C and Palm oil. The yield of biodiesel was 197 (~ 98.5 conversion) gram and of glycerol was 15.8 gram. The biodiesel thus produced from the reaction has specific gravity at 25° C of 0,8870, 4.5 centistokes kinematic viscosity at 40°C and the total acid number of 0.45% by weight.
EXAMPLE-16
In a similar set up a catalyst complex D was prepared from shell mixture and cardanol from cashew nut shell liquid. 44 gram of shell mixture taken in 1000 ml round bottom flask fitted with stirrer and condenser was reacted with 473 gram of hydrogenated CNSL under inert conditions. Stir the reaction mixture and carry out the complex formation at 100 C for 2 I2 hrs. The catalyst complex (D) thus formed was filtered and dried at 100°C for 3 hrs. A 250 ml three necked flask was equipped with condenser, stirrer and thermocouple was charged with 14 grams of the catalyst complex (D), 100 gm of neem oil and 55 gm of Ethanol. The reaction mixture was stirred and temperature was raised to reflux at 70°C. Conversion of oil to fatty acid methyl ester got completed in 51/2 hrs. The reaction mixture was passed through column of alumina and the excess alcohol was recovered under reduced pressure to yield biodiesel and glycerol. The layers were transferred and separated in a separatory funnel. The upper layer contains the biodiesel and the lower is the glycerine layer. The yield of biodiesel is 98.7 gram (98.9% conversion) and glycerol is 7.6 gram.
EXAMPLE-17
100 gm of Jatropha oil, 40 gm of methanol and 10 gm of catalyst (Composition VI), are taken in a high pressure reactor. The reactor is pressurized with nitrogen to 52 bar of pressure. The contents are stirred at 170° C and reaction monitored by TLC. Reaction completion was observed in 8 hrs. Work up of the reaction mixture yielded 98.8 gram (-98.5% conversion) of biodiesel and 8.1 grams of glycerol. The biodiesel thus produced has 0.8830 specific gravity at 25°C 4.4 centistokes kinematic viscosity at 40 ° C and the total acid number of 0.43% by weight.

EXAMPLE-18
The catalyst, of composition VI, is charged on a fixed bed reactor, and Jatropha oil and methanol are pumped through the catalyst, at 70 bar pressure and 180 C temperature. The flow of reactants and their ratio is controlled to get the maximum conversion. The reaction products are cooled and isolated after separation through a high pressure separator. Glycerol layer is separated and methanol is distifted off from -upper layer. The reaction is monitored by TLC. The product mixture contains 97% fatty acid methyl esters and traces of glycerol. The reaction mixture is distilled off, to get cut of 300-360 C, to remove unreacted diglycerides and triglycerides, and to meet the international standards of biodiesel. The biodiesel thus produced has 0.885 specific gravity at 25° C, 4.42 centistokes kinematic viscosity at 40°C and the total acid number of 0.12% by weight.
Comparative Example
200 gram of sunflower oil, 55 gram methanol and 8.2 gram of calcium oxide was taken in 500 ml three necked flask, equipped with condenser, stirrer and thermocouple. Reaction was carried out at reflux temperature of 70°C. The reaction completion was observed in six hours. Work up of the reaction mixture yielded 185 gram (97.9% conversion) of biodiesel and 8.8 gram of glycerol. The biodiesel yield and purity was found to be inferior as compared to the reactions carried out with catalyst composition of the present invention.
While this provisional patent application contains the description of the principal inventive concepts, the complete patent application pursuant hereto, will fully and particularly describe the preferred embodiments of the present invention.

MANISHA SINGH NAIR
Agent for the Applicant [IN/PA-740]
LEX ORBIS
Intellectual Property Practice
709 / 710, Tolstoy House,
15-17, Tolstoy Marg,
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Dated this 27th Day of March, 2009