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WO2010113011A2 - Novel catalyst composition for biodiesel production and process for preparing the same - Google Patents

Novel catalyst composition for biodiesel production and process for preparing the same Download PDF

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Publication number
WO2010113011A2
WO2010113011A2 PCT/IB2010/000708 IB2010000708W WO2010113011A2 WO 2010113011 A2 WO2010113011 A2 WO 2010113011A2 IB 2010000708 W IB2010000708 W IB 2010000708W WO 2010113011 A2 WO2010113011 A2 WO 2010113011A2
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WIPO (PCT)
Prior art keywords
process according
catalyst
catalyst composition
biodiesel
oil
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PCT/IB2010/000708
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French (fr)
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WO2010113011A3 (en
Inventor
R. Sarin
A. K. Arora
S. K. Puri
Shanti Prakash
Rajeev Ranjan
J. Christopher
D. K. Tuli
R. K. Malhotra
Anand Kumar
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Indian Oil Corporation Limited
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Publication of WO2010113011A2 publication Critical patent/WO2010113011A2/en
Publication of WO2010113011A3 publication Critical patent/WO2010113011A3/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • This invention in general, relates to a novel catalyst composition for production 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 for production of biodiesel, wherein the catalyst is prepared using natural waste materials preferably fresh or waste natural seashell and eggshells alone or in complex with alcohol or phenol. Further, the present invention provides process for producing biodiesel.
  • 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.
  • Biodiesel no sulphur, no aromatics and has about 10% built-in oxygen, which helps'it to burn fully. Its higher cetane number improves the ignition quality even in blends with petroleum diesel.
  • FAME Fatty Acid Methyl Esters
  • PCT International Application WOO.0/05327 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 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 ?an#(a ⁇ co-solvent at a temperature that is less than the boiling point of'the'so'ktfwxfi ⁇ hbalcdriol employed in the process is selected from the group consisting of methanol and elHa'nol, 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 ⁇ stfeel ⁇ 'cj ⁇ d '' from the group consisting of methanol, ethanol, and mixtures thereof* fl ⁇ lk ⁇ t ⁇ kf ⁇ f 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.
  • the reaction zone can be any type of vessel commonly used for transesterification reactions, as for example, a reaction vessel having a stirrer or agitator, a vessel having a recirculation loop, or a static .fruxer withiiv a pipe or a similar container.
  • 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 8O 0 C to about 200 ⁇ 1 #&dVnW ⁇ ressure up to 500 psi.
  • United States Patent NbIVf 5 302#4 ⁇ sftkKoono 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. DE 10245758 to Rethmann Klemens et al. discloses a process for production of biodiesel by reaction of a branched monohydric alcohol with a fat having low unsaturated fatty acid content in 'the presence of sodium hydroxide or potassium hydroxide.
  • European 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 in US Patent 5,908,946.
  • English Patent GB 795 573 (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
  • 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 ' an#at$' ⁇ S#taly sfc for the esterification reaction.
  • 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.
  • acidic mesoporous silicates have been prepared and activities of different acidic catalysts such as H2SO4, SBA- 15-SO3H-P123, Nafion, SBA-15-SO3H-L64, SBA-15-phSO3H-P123, CDAB-SO3H-
  • 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 pil processed, when e.g. soya-bean oil, cotton-seed oil and canola oil aB&pr6Ws1 ⁇ etl?0yfthe method according to the invention.
  • CN 101249431 & cWk' ⁇ i ⁇ tiwi ⁇ fcm ⁇ t 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, environment friendliness and low requirement for the raw material.
  • 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.
  • heterogeneous catalysts are preferred, due to their recyclability, work under high temperatures ⁇ rra pr ⁇ &ur ⁇ di ⁇ ridition. In addition, these catalysts expensive.
  • Still another object of the present invention to provide a catalyst composition, wherein the composition is derived from inexpensive easily available natural waste materials.
  • Yet another object of the present invention is to provide an easy and fast transesterification process to produce biodiesel with excellent yields and conversion. It is another object of the present invention, wherein the catalyst is recyclable and reusable.
  • Still another object of the present invention is to provide a transesterification process for producing biodiesel under atmospheric pressure and low temperature.
  • a catalyst composition for producing biodiesel wherein said composition is prepared by calcinations of natural waste materials.
  • a catalyst composition for producing biodiesel wherein said catalyst is prepared by calcinations of natural waste materials. Preferably fresh natural seashell and eggshells alone or in complex with alcohol or phenol.
  • a process for the preparation of catalyst composition for trans esterif ⁇ ation is provided.
  • a process for producing a biodiesel by reacting triglycerides with an alcohol in presence of the catalyst composition derived from natural waste materials in accordance with another embodiment of the present invention, there is provided a process for producing a biodiesel by reacting triglycerides with an alcohol in presence of the catalyst composition derived from natural waste materials, wherein said catalyst composition retains its activity even after 5-6 cycles of reuse.
  • the combination contains seashells between 10-90% and eggshells between 90-10% i.e. the ration varies from 90:10 to 10:90.
  • the catalyst composition according to the invention is having surface area preferably in the range 50 to 200 m 2 /g. According to the invention the catalyst composition is preferably having poi l e Volume ranging from 0.0001 to 0.6 cc/g and an
  • the preparation of catalyst composition for producing biodiesel comprises washing and drying of seashells/eggshells folloAved by grounding and sieving, calcining the sieved and dried seashell/eggshells, grinding to fine particles a composition of calcined seashells and eggshells homogenously, calcining the dried extrudated material in a furnace at a temperature ranging from 750 to 1000 0 C for a prime period of 3 to 12 hours, resulting in an in situ generation of the active components; and obtaining final catalyst composition.
  • washing and drying of seashells and eggshell is preferably carried out at a temperature of HO 0 C.
  • the calcinations of sieved and dried seashell and eggshells is preferably earned out at a temperature of 55O 0 C and 300 0 C respectively.
  • 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.
  • a molar ratio of about 5:1 to 20:1 is employed.
  • the ratio of alcohol to oil ranges from 1 to 20, preferably 1 to 5 molar ration. 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 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 upt ⁇ 200 0 C above the boiling point of alcohol used.
  • wh& ⁇ Aetl$Jri ⁇ l W ⁇ sed
  • the reaction temperature should be within the range of about 65 Wffi ⁇ fa ' ⁇ ife ' $' % '
  • the present invention is not intended to be limited to any particular procedure for transesterifying the vegetable oils to produce biodiesel, wherein the
  • reaction temperature in the range from about 65 0 C to 265 0 C in a known manner.
  • the reaction is conducted at atmospheric pressure and it is preferred to carry out the reaction at the reflux temperature of the alcohol employed, e.g., for methanol, at about 65 0 C, reaction times between about 1 to 5 hours, being typical.
  • the preferred monoalcohol is methanol, ethanol, propanol, butanol or mixture thereof. In general, the methanol is used in a 50% to 150% excess over the stoichiometric quantity required for the transesterification reactions .
  • the transesterification reaction can be carried out batch wise or continuously in any of the many known pressurized or non-pressurized reaction systems.
  • the substantially anhydrous reaction can be carried out batch wise or continuously in any of the many known pressurized or non-pressurized reaction systems.
  • catalyst quantities from about 1 to 2 percent by weight, with about 1.5 percent by weight being most preferred.
  • the triglycerides are derived from various plants, particularly vegetable oils and animal fats such as jatropha curcas oil, castor oil, sunflower oil, soybean oil, rapeseed oil, mustard oils, canola oil, cotton oil, corn oil, coconut oil, ground nut oil, olive oil, palm kernel oil, fish oil, lard, tallow etc. may be used.
  • the vegetable oils include both edible and non-edible vegetable oils.
  • the non-edible oils available in India such as jatropha curcas oil, Pongamia, Madhuca indica, Neem, Niger and Rice bran oil, castor oil and karanjia oils have been used.
  • shells were dried in oven at 1 10 0 C for 6hrs to remove traces of water.
  • the shells grounded to fine powder and sieved through 150 micron mesh and then calcined in muffle furnace at 55O 0 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 0 C.
  • the dried eggshells are calcined at 300° C.
  • Calcined seashells are admixed Avith calcined eggshell in desired ratio and the composition is then calcined at 550-1000 0 C for four hours.
  • 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 CO 2 calcium oxide becomes the major phase and calcium 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 s compftitr ⁇ b ' han ⁇ eV ⁇ fesea shells with change in calcinations temperature using a Hitachi electron microscope.
  • the S3400N SEM utilizes an electron beam accel rated at 300V to 30 KV.
  • the SEM images show that the structure of shell changed with change of calcinations temperature. At 85O 0 C the shape of particle became more regular. Accelerated surface area and porosity was measured on micrometricis instrument as per AS AP-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
  • TGA results show loss of weight below 600 0 C is due to loss of water and other volatile matter, major loss in temperature range above 650°C is due to loss of CO2 i.e. change of calcium carbonate phase'to calcium oxide the effective phase.
  • the catalyst was washed with methanol twice to remove residual ester and glycerol.
  • the catalyst was vacuum dried at 8O 0 C for 4 hrs and further reused.
  • the filtrate was allowed to equilibrate which resulted in separation of two phases.
  • Example-1 is 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:
  • the grounded & sieved egg .shells (90 grarn) and sea shells (10 gram) were properly mixed physically and ilMnife ⁇ fa ⁇ al ⁇ ined in a muffle furnace at 55O°C for using TGA, SEM and XRD spectroscopy.
  • the XRD diffraction patterns and scanning micrograph images show the composition to have calcium carbonate characteristics.
  • composition II 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.
  • 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.
  • 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.
  • 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. Im another flask, 100 gm of catalyst composition
  • catalyst composition prepared as per example 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 7O 0 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 arid analytical techniques like GPC and IPINMR 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.
  • FAME fatty acid methyl ester
  • reaction was carried out as per example-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.
  • 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 .coojed, 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 lotavapor. 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.
  • This example demonstrates preparation of biodiesel using 8 gram of catalyst composition (IV) as prepared in example-4, 200 gram of sunflower oil and 55 gram methanol in a 500 ml equipped with condenser, stirrer and thermocouple. Reaction 'reflux temperature of 7O 0 C and TLC monitoring indicated the completion 'of reaction 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 7O 0 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.
  • 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. The contents were stirred at the temperature to 65 0 C for 2 hrs. Then the reaction mixture was cooled to room temperature. The catalyst complex thus produced was filtered and dried at 100 0 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 flask and reaction was carried out at reflux temperature of 7O 0 C as 'ttesdiibetPirf 'Example - 11. The reaction completion was observed in 3 hours.
  • 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 0 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 0 C, 4.4 centistokes kinematic viscosity at 40 ° C and the total acid number of 0.43% by weight.
  • This example demonstrates Jaboratpry 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 and dried at 100 0 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 4O 0 C and the total acid number of 0.45% by weight.
  • Example-16 shows Jaboratpry 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 and dried at 100 0 C
  • 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.
  • the catalyst composition VI is charged on a fixed bed reactor, and Jatropha oil and methanol are pumped through the catalyst, at 70 bar pressure and 18O 0 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 distilled 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

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Abstract

Disclosed herein is a catalyst composition for producing biodiesel, wherein the catalyst composition comprising calcined natural waste materials. Further, the present invention also provides process for producing biodiesel.

Description

NOVEL CATALYST COMPOSITION FOR BIODIESEL PRODUCTION AND PROCESS FOR PREPARING THE SAME
Field of the Invention This invention, in general, relates to a novel catalyst composition for production 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 for production of biodiesel, wherein the catalyst is prepared using natural waste materials preferably fresh or waste natural seashell and eggshells alone or in complex with alcohol or phenol. Further, the present invention provides process for producing biodiesel.
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-burnfr hydiOca^ofj&^-^fk©^ monoxide and particulate matters. Biodiesel no sulphur, no aromatics and
Figure imgf000002_0001
has about 10% built-in oxygen, which helps'it to burn fully. Its higher cetane number improves the ignition 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 btøφe'setyi; 'έtøf btø> ' 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 >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 WOO.0/05327 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 piocess 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 ?an#(a\co-solvent at a temperature that is less than the boiling point of'the'so'ktfwxfi^hbalcdriol employed in the process is selected from the group consisting of methanol and elHa'nol, 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 ^stfeel^'cjød ''from the group consisting of methanol, ethanol, and mixtures
Figure imgf000003_0001
thereof* fl^ψψβlkψtϊkfό^f 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 vessel having a stirrer or agitator, a vessel having a recirculation loop, or a static .fruxer withiiv a pipe or a similar container. United
States Patent No. 6,399,800 to HaasietW: discloses a method for producing fatty acid
* ι t i l ' > "> P T l 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 8O0C to about 200^1 #&dVnWφressure up to 500 psi. United States Patent NbIVf5302#4δsftkKoono 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. DE 10245758 to Rethmann Klemens et al. discloses a process for production of biodiesel by reaction of a branched monohydric alcohol with a fat having low unsaturated fatty acid content in 'the presence of sodium hydroxide or potassium hydroxide.
European
Figure imgf000004_0001
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 in US Patent 5,908,946. English Patent GB 795 573 (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
Figure imgf000005_0001
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' an#at$'ά^S#taly sfc for the esterification reaction.
US Patent 7,145,026, fdifέteiέs«Φ#aiφsterification 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 0C 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 H2SO4, SBA- 15-SO3H-P123, Nafion, SBA-15-SO3H-L64, SBA-15-phSO3H-P123, CDAB-SO3H-
Figure imgf000006_0001
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 (Nb 2 O 5 ). 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 pil processed, when e.g. soya-bean oil, cotton-seed oil and canola oil aB&pr6Ws1§etl?0yfthe method according to the invention.
CN 101249431 & cWk'όiϊtiwiΦfcmήt 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, 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,
Figure imgf000006_0002
work under high temperatures ^rra pr^&ur^diβridition. In addition, these catalysts expensive.
Therefore there still exists a need for development a catalyst composition that is inexpensive, recyclable and works under normal temperature and pressure conditions.
Objects and Summary of the Invention
It is a principal object of the present invention to provide a catalyst composition suitable for transesterification of vegetable oil or animal fats to produce
for the
Figure imgf000007_0001
preparation of an efficient, iήexpeήsive<''and:i't'asily available heterogeneous catalyst composition for transesterification reactions. Still another object of the present invention to provide a catalyst composition, wherein the composition is derived from inexpensive easily available natural waste materials.
Yet another object of the present invention is to provide an easy and fast transesterification process to produce biodiesel with excellent yields and conversion. It is another object of the present invention, wherein the catalyst is recyclable and reusable.
Still another object of the present invention is to provide a transesterification process for producing biodiesel under atmospheric pressure and low temperature.
The above and other objects' are attained in accordance with the following embodiments of the pre^έϊαVivfib4έ"rtϊi^j'-ιfillvVever5 'the described embodiments hereinafter is in accordance witlf'lhe' ''4BeSt ϊiϊYcfde of practice and the invention is not restricted to the particular embodiments.
In accordance with one preferred embodiment of the present invention, there is provided a catalyst composition for producing biodiesel, wherein said composition is prepared by calcinations of natural waste materials.
In accordance with one preferred embodiment of the present invention, there is provided a catalyst composition for producing biodiesel, wherein said catalyst is prepared by calcinations of natural waste materials. Preferably fresh natural seashell and eggshells alone or in complex with alcohol or phenol. In accordance with another embodiment of the present invention, there is provided a process for the preparation of catalyst composition for trans esterifϊation
Figure imgf000007_0002
sieved and dried seashell, washing and drying of eggshell followed by grounding and sieving, calcining the dried and sieved eggshells, grinding to fine particles of composition of calcined seashellβ and eggshells homogenously, calcining the dried from 750 to 10000C for a generation of the active
Figure imgf000008_0001
components and obtaining final' catalyst' c'oηiposition.
In accordance with another embodiment of the present invention, there is provided a process for producing a biodiesel by reacting triglycerides with an alcohol in presence of the catalyst composition derived from natural waste materials. In accordance with still another embodiment of the present invention, there is provided a process for producing a biodiesel by reacting triglycerides with an alcohol in presence of the catalyst composition derived from natural waste materials, wherein said catalyst composition retains its activity even after 5-6 cycles of reuse.
Detailed Description of the Invention While this specification concludes with claims particularly pointing out and distinctly claiming that, which is regarded as the invention, it is anticipated that the invention can be more readily ^ndfeFstøQ&hthrough reading the following detailed
Figure imgf000008_0002
Cost is the one of the! 'l'rkjόr'lWfors 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 waste materials. The present invention involves the selection and identification of natural waste materials capable of giving catalytic properties for transesterification of vegetable oils and animal fats to produce biodiesel. The natural waste materials include natural waste or fresh natural seashell and eggshells.
Disclosed herein are natural waste materials including seashells and eggshells, which are available in plenty and are very economic. The disclosed embodiment of the present invention deals with an optimiim combination of seashell and eggshell for
Figure imgf000008_0003
eggshell. The combination contains seashells between 10-90% and eggshells between 90-10% i.e. the ration varies from 90:10 to 10:90.
The catalyst composition according to the invention is having surface area preferably in the range 50 to 200 m2/g. According to the invention the catalyst composition is preferably having poile Volume ranging from 0.0001 to 0.6 cc/g and an
the preparation of catalyst
Figure imgf000009_0001
composition for producing biodiesel comprises washing and drying of seashells/eggshells folloAved by grounding and sieving, calcining the sieved and dried seashell/eggshells, grinding to fine particles a composition of calcined seashells and eggshells homogenously, calcining the dried extrudated material in a furnace at a temperature ranging from 750 to 10000C for a prime period of 3 to 12 hours, resulting in an in situ generation of the active components; and obtaining final catalyst composition. In accordance with the invention washing and drying of seashells and eggshell is preferably carried out at a temperature of HO0C. In accordance with the present invention, the calcinations of sieved and dried seashell and eggshells is preferably earned out at a temperature of 55O0C and 3000C respectively.
Figure imgf000009_0002
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. The ratio of alcohol to oil ranges from 1 to 20, preferably 1 to 5 molar ration. 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 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 uptό 2000C above the boiling point of alcohol used. For example, wh&ώ(Aetl$Jri©l Wύsed, the reaction temperature should be within the range of about 65 Wffiέfa'βife ' $' % ' Although the present invention is not intended to be limited to any particular procedure for transesterifying the vegetable oils to produce biodiesel, wherein the
Figure imgf000010_0001
optimum combination of seashell an'd eggshell, at a reaction temperature in the range from about 650C to 2650C in a known manner. The reaction is conducted at atmospheric pressure and it is preferred to carry out the reaction at the reflux temperature of the alcohol employed, e.g., for methanol, at about 650C, reaction times between about 1 to 5 hours, being typical. The preferred monoalcohol is methanol, ethanol, propanol, butanol or mixture thereof. In general, the methanol is used in a 50% to 150% excess over the stoichiometric quantity required for the transesterification reactions .
The transesterification reaction can be carried out batch wise or continuously in any of the many known pressurized or non-pressurized reaction systems. The substantially anhydrous
to 4.0 percent by weight
Figure imgf000010_0002
based on the triglycerides. Preferred are catalyst quantities from about 1 to 2 percent by weight, with about 1.5 percent by weight being most preferred. Feed Stocks
The triglycerides are derived from various plants, particularly vegetable oils and animal fats such as jatropha curcas oil, castor oil, sunflower oil, soybean oil, rapeseed oil, mustard oils, canola oil, cotton oil, corn oil, coconut oil, ground nut oil, olive oil, palm kernel oil, fish oil, lard, tallow etc. may be used. The vegetable oils include both edible and non-edible vegetable oils. The non-edible oils available in India such as jatropha curcas oil, Pongamia, Madhuca indica, Neem, Niger and Rice bran oil, castor oil and karanjia oils have been used.
Figure imgf000010_0003
shells were dried in oven at 1 100C for 6hrs to remove traces of water. The shells grounded to fine powder and sieved through 150 micron mesh and then calcined in muffle furnace at 55O0C, 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 0C. Subsequently, the dried eggshells are calcined at 300° C. Calcined seashells are admixed Avith calcined eggshell in desired ratio and the composition is then calcined at 550-10000C for four hours.
Figure imgf000011_0001
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 calcium 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 s
Figure imgf000011_0002
trucftitrøb'han^eV^fesea shells with change in calcinations temperature using a Hitachi
Figure imgf000011_0003
electron microscope. The S3400N SEM utilizes an electron beam accel rated at 300V to 30 KV. The SEM images show that the structure of shell changed with change of calcinations temperature. At 85O0C the shape of particle became more regular. Accelerated surface area and porosity was measured on micrometricis instrument as per AS AP-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 6000C is due to loss of water and other volatile matter, major loss in temperature range above 650°C is due to loss of CO2 i.e. change of calcium carbonate phase'to calcium oxide the effective phase.
Process for preparation^f^ai^iiijbjifethyl estέr (FAME) or Biodiesel Trans-esterification rea^!ioW^v£r$ drifted out in a multi-necked round bottom flask fitted with condenser, heating mantle1 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 8O0C for 4 hrs and further reused. The filtrate was allowed to equilibrate which resulted in separation of two phases. The upper phase
Figure imgf000012_0001
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 grarn) and sea shells (10 gram) were properly mixed physically and ilMnife^fa^al^ined in a muffle furnace at 55O°C for
Figure imgf000012_0002
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
A 100 gram mixture as described in Example-1 was calcined at 75O0C 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 'arid
Figure imgf000013_0001
sea shells were calcined in a muffle furnace at 850°C for 3 hrs under static, fair- '(<? 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. Im another flask, 100 gm of catalyst composition
(IV), 100gm of acidic alumina and 20 ml of distilled water are taken. The contents of both the flasks are mixed
Figure imgf000013_0002
The mixture is dried at 120-
13O0C for 2 hours. The dried"*ιmate"iϊa-l <1& blushed to powder form and calcined at
4000C for 8 hrs, to yield Catalyst composition VI Example-7
4.0 gm of catalyst composition (prepared as per example 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 7O0C 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 arid analytical techniques like GPC and IPINMR 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 example-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 .coojed, 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 lotavapor. 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 250C : 0.8610, kinematic viscosity at 4O0C : , 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 example-4, 200 gram of sunflower oil and 55 gram methanol in a 500 ml equipped with condenser, stirrer and thermocouple. Reaction 'reflux temperature of 7O0C and TLC
Figure imgf000014_0001
monitoring indicated the completion 'of reaction 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 7O0C 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.
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
250C, 4.6 centistokes kinematic viscosity at 4O0C, and the total acid number of 0.45% by weight.
" ExampleU'2
The reaction was canned out as per example-9 but using catalyst composition
V (prepared as per example-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. The contents were stirred at the temperature to 650C for 2 hrs. Then the reaction mixture was cooled to room temperature. The catalyst complex thus produced was filtered and dried at 1000C 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
Figure imgf000015_0001
flask and reaction was carried out at reflux temperature of 7O0C as 'ttesdiibetPirf '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 7O0C 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 0C 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 250C, 4.4 centistokes kinematic viscosity at 40 ° C and the total acid number of 0.43% by weight.
Example-15
This example demonstrates Jaboratpry 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 and dried at 1000C 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 4O0C 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 cany out the complex formation at 100° C for^'/^rir^Tne catalyst complex (D) thus formed was filtered and dried at 100oC'll3r^^|j'f^c^<?^:lllthfee necked flask was equipped with
Figure imgf000016_0001
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 7O0C. Conversion of oil to fatty acid methyl ester got completed in 5V2 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 pressurized with
Figure imgf000016_0002
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 250C 4.4 acid number of 0.43% by weight.
Figure imgf000017_0001
The catalyst composition VI is charged on a fixed bed reactor, and Jatropha oil and methanol are pumped through the catalyst, at 70 bar pressure and 18O0C 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 distilled 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
Figure imgf000017_0002
200 gram of sunflower oil; 55^glmϊViletnanol 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 7O0C. 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. Certain modifications and improvements of the disclosed invention will occur to those skilled in the art without departing from the scope of invention, which is limited only by the appended claims.

Claims

We Claim;
1. A catalyst biodiesel, wherein said
Figure imgf000018_0001
composition comprising calcined natural waste materials.
2. The composition according to claim 1, wherein said natural waste materials are natural waste or fresh natural seashell and eggshells alone or in complex with alcohol or phenol.
3. The catalyst composition according to claim 1, wherein the ratio of seashells to eggshell varies from 90:10 to 10:90.
4. The catalyst composition according to claim 1, wherein said catalyst is having surface area ranging from 50 to 200 m"/g.
5. The catalyst composition according to claim 1, wherein said catalyst is having pore volume ranging from 0.0001 to 0.6 cc/g.
6. The catalyst composition of claim 1, wherein said catalyst is having an average pore size ranging
Figure imgf000018_0002
7. A process for 'tl^i^tbpAψi^iC of J catalyst composition of claim 1 for producing biodiesel comprising: ' a) washing and drying of seashells followed by grounding and sieving; b) calcining the sieved and dried seashell; c) washing and drying of eggshell followed by grounding and sieving; d) calcining the dried and sieved eggshells; e) grinding to fine particles a composition of calcined seashells and eggshells homogenously; f) calcining the dried extrudated material of step (e) in a furnace at a temperature ranging from 750 to 10000C for a time period of 3 to 12 hours, resultiήj^in -$riii$; 'si ^Ui1 generation of the active components; and g) obtaining final catalyst composition.
8. The process according to claim 7, wherein the washing and drying of seashells and eggshell is carried out at a temperature of HO0C.
9. The process according to claim 7, wherein the calcinations of sieved and dried seashell is carried out at a temperature of 55O0C.
Figure imgf000019_0001
5
1 1. A process for producing a biddiesel by reacting triglycerides with an alcohol in presence of a catalyst composition derived from natural waste materials.
12. The process according to claim 11, wherein said natural waste materials are natural waste or fresh natural seashell and eggshells.
13. The process according to claim 11, wherein the triglycerides are 10 obtained from vegetable oils or animal fats.
14. The process according to claim 13, wherein the vegetable oils are edible vegetable oils.
15. The process according to claim 14, wherein the edible vegetable oil are obtained from plant sources selected from a group consisting of soybean, rapeseed,
15 palm, mustard, or canola oils.
16. The process according, tb'claitfft '15, wherein the vegetable oils are non- edible vegetable oils. > ' ! nit dϊ Ή U-mjieruiuf ■
17. The process according" to claim 16, wherein the non-edible vegetable oil sources are plant species selected from the group comprising Jatropha, Pongamia,
20 Madhuca indica, Neem, Niger and Rice bran oil.
18. The process according to claim 11, wherein the alcohol is methanol, ethanol, propanol, butanol or mixture thereof.
19. The process according to claim 11, wherein the process is carried out at a pressure ranges from atmospheric to 90 bar.
25 20. The process according to claim 11, wherein the process is carried out at a pressure ranges between 3 to 15 bar.
21. The process according to claim 1 1 , wherein the molar ratio of alcohol to oil ranges from 20 to 1 and preferably 5 to 1.
22. The process according )to '-d lai'tn wherein the process is carried out " 0 at a
Figure imgf000019_0002
23. The process according to cl&im 11, wherein the vegetable oil is in the form of feed stocks containing 10 to 10000 ppm of water.
24. The process according to claim 11, wherein the vegetable oil is in the form of feed stocks containing 0-5% of free fatty acids.
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WO2011113827A1 (en) * 2010-03-16 2011-09-22 Albemarle Europe Sprl Metal carbonate containing catalysts and their use in solid basic catalyst-catalyzed reactions
WO2015036714A1 (en) * 2013-09-12 2015-03-19 Centre National De La Recherche Scientifique Use of certain organic materials, containing alkali or alkaline-earth metals, for implementing organic chemical reactions
US9643163B2 (en) 2014-10-10 2017-05-09 Crystaphase Products, Inc. Heterogeneous catalyst for transesterification and method of preparing same
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