[go: up one dir, main page]

WO2010113011A2 - Nouvelle composition de catalyseur pour la production de biodiesel et procédé pour le préparer - Google Patents

Nouvelle composition de catalyseur pour la production de biodiesel et procédé pour le préparer Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
process according
catalyst
catalyst composition
biodiesel
oil
Prior art date
Application number
PCT/IB2010/000708
Other languages
English (en)
Other versions
WO2010113011A3 (fr
Inventor
R. Sarin
A. K. Arora
S. K. Puri
Shanti Prakash
Rajeev Ranjan
J. Christopher
D. K. Tuli
R. K. Malhotra
Anand Kumar
Original Assignee
Indian Oil Corporation Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Indian Oil Corporation Limited filed Critical Indian Oil Corporation Limited
Publication of WO2010113011A2 publication Critical patent/WO2010113011A2/fr
Publication of WO2010113011A3 publication Critical patent/WO2010113011A3/fr

Links

Classifications

    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Processing Of Solid Wastes (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)

Abstract

L'invention concerne une composition de catalyseur pour la production de biodiesel, la composition de catalyseur comprenant des matériaux de déchets naturels calcinés. En outre, la présente invention concerne également un procédé de production de biodiesel.
PCT/IB2010/000708 2009-03-30 2010-03-30 Nouvelle composition de catalyseur pour la production de biodiesel et procédé pour le préparer WO2010113011A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN809MU2009 2009-03-30
IN809/MUM/2009 2009-03-30

Publications (2)

Publication Number Publication Date
WO2010113011A2 true WO2010113011A2 (fr) 2010-10-07
WO2010113011A3 WO2010113011A3 (fr) 2010-11-25

Family

ID=42828767

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2010/000708 WO2010113011A2 (fr) 2009-03-30 2010-03-30 Nouvelle composition de catalyseur pour la production de biodiesel et procédé pour le préparer

Country Status (1)

Country Link
WO (1) WO2010113011A2 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011113827A1 (fr) * 2010-03-16 2011-09-22 Albemarle Europe Sprl Catalyseurs contenant des carbonates métalliques et leur utilisation dans les réactions catalysées par un catalyseur basique solide
WO2015036714A1 (fr) * 2013-09-12 2015-03-19 Centre National De La Recherche Scientifique Utilisation de certains materiaux d'origine organique contenant des metaux alcalins ou alcalino-terreux pour la mise en oeuvre de reactions de chimie organique
US9643163B2 (en) 2014-10-10 2017-05-09 Crystaphase Products, Inc. Heterogeneous catalyst for transesterification and method of preparing same
US10144696B2 (en) 2015-04-17 2018-12-04 Crystaphase Products, Inc. Heterogeneous catalyst for transesterification and method of preparing same
CN114797906A (zh) * 2021-01-27 2022-07-29 湖南工程学院 一种BiOCl@Bi2S3复合材料的原位合成方法及其应用
KR102840691B1 (ko) * 2025-02-14 2025-07-30 조원상 바이오 중유 제조방법

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080110082A1 (en) * 2006-09-19 2008-05-15 Maliszewski Thomas A Biodiesel production with enhanced alkanol recovery

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011113827A1 (fr) * 2010-03-16 2011-09-22 Albemarle Europe Sprl Catalyseurs contenant des carbonates métalliques et leur utilisation dans les réactions catalysées par un catalyseur basique solide
WO2015036714A1 (fr) * 2013-09-12 2015-03-19 Centre National De La Recherche Scientifique Utilisation de certains materiaux d'origine organique contenant des metaux alcalins ou alcalino-terreux pour la mise en oeuvre de reactions de chimie organique
US9643163B2 (en) 2014-10-10 2017-05-09 Crystaphase Products, Inc. Heterogeneous catalyst for transesterification and method of preparing same
US9770707B2 (en) 2014-10-10 2017-09-26 Crystaphase Products, Inc. Heterogeneous catalyst for transesterification and method of preparing same
US10183281B2 (en) 2014-10-10 2019-01-22 Crystaphase Products, Inc. Heterogeneous catalyst for transesterification and method of preparing same
USRE49551E1 (en) 2014-10-10 2023-06-13 Crystaphase Products, Inc Heterogeneous catalyst for transesterification and method of preparing same
US10144696B2 (en) 2015-04-17 2018-12-04 Crystaphase Products, Inc. Heterogeneous catalyst for transesterification and method of preparing same
USRE49610E1 (en) 2015-04-17 2023-08-15 Crystaphase Products, Inc. Heterogeneous catalyst for transesterification and method of preparing same
CN114797906A (zh) * 2021-01-27 2022-07-29 湖南工程学院 一种BiOCl@Bi2S3复合材料的原位合成方法及其应用
KR102840691B1 (ko) * 2025-02-14 2025-07-30 조원상 바이오 중유 제조방법

Also Published As

Publication number Publication date
WO2010113011A3 (fr) 2010-11-25

Similar Documents

Publication Publication Date Title
Borah et al. Biodiesel production from waste cooking oil catalyzed by in-situ decorated TiO2 on reduced graphene oxide nanocomposite
Guldhe et al. Conversion of microalgal lipids to biodiesel using chromium-aluminum mixed oxide as a heterogeneous solid acid catalyst
Fereidooni et al. Experimental assessment of electrolysis method in production of biodiesel from waste cooking oil using zeolite/chitosan catalyst with a focus on waste biorefinery
Shu et al. Synthesis of biodiesel from soybean oil and methanol catalyzed by zeolite beta modified with La3+
Teo et al. Methoxy-functionalized mesostructured stable carbon catalysts for effective biodiesel production from non-edible feedstock
Mohadesi et al. Biodiesel production using alkali earth metal oxides catalysts synthesized by sol-gel method
Saini Conversion of waste cooking oil to biodiesel
Basumatary Transesterification with heterogeneous catalyst in production of biodiesel: A Review
JP5470382B2 (ja) 脂肪酸アルキルエステルの製法
WO2010113011A2 (fr) Nouvelle composition de catalyseur pour la production de biodiesel et procédé pour le préparer
EP2043972A1 (fr) Nouveaux catalyseurs à base de composite pour la production de biocarburant
Kowthaman et al. Synthesis, characterization, and optimization of Schizochytrium biodiesel production using Na+‐doped nanohydroxyapatite
Faba et al. Thermo-chemically tuning of active basic sites on nanoarchitectured silica for biodiesel production
Warrier Production of biodiesel from waste cooking oil using MgO nanocatalyst
Guerrero-Ruiz et al. Use of biobased crude glycerol, obtained biocatalytically, to obtain biofuel additives by catalytic acetalization of furfural using SAPO catalysts
Reinoso et al. Synthesis of biodiesel from soybean oil using zinc layered hydroxide salts as heterogeneous catalysts
Roschat et al. Kinetics study of biodiesel production at room temperature based on eggshell-derived CaO as basic heterogeneous catalyst
Mahmood et al. Microwave assisted production of biodiesel using CaO nano-catalyst produced from mango fallen leaves extract
Alanis et al. Methyl esters production from Waste Cooking Oil catalysed by iron oxides supported on CaO: Cost and environmental impacts
Savaliya et al. Eco-friendly process for preparation of biodiesel from WFO over MTSA-Si catalyst: An innovative approach for the utilization of side product
Fereidooni et al. Evaluation of methyl ester production using cement as a heterogeneous catalyst
Ruatpuia et al. Biodiesel production through heterogeneous catalysis route: A review
Brito et al. Reuse of fried oil to obtain biodiesel: Zeolites Y as a catalyst
Harreh et al. Production of karanja methyl ester from crude karanja oil using Meretrix Lyrata synthesised active Cao catalyst
Semwal et al. Preparation of novel catalyst composition from natural waste for biodiesel production

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10758120

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10758120

Country of ref document: EP

Kind code of ref document: A2