US20050108927A1 - Process for the preparation of bio-diesel - Google Patents

Process for the preparation of bio-diesel Download PDF

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Publication number
US20050108927A1
US20050108927A1 US10/718,559 US71855903A US2005108927A1 US 20050108927 A1 US20050108927 A1 US 20050108927A1 US 71855903 A US71855903 A US 71855903A US 2005108927 A1 US2005108927 A1 US 2005108927A1
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Prior art keywords
oil
less
biodiesel
hrs
diesel
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US10/718,559
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Kandukalpatti Velappan
Subramani Saravanan
Nagarajan Vedaraman
Paruchuri Rao
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Council of Scientific and Industrial Research CSIR
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Council of Scientific and Industrial Research CSIR
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Priority to PCT/IB2003/005349 priority Critical patent/WO2005052103A1/en
Priority to US10/718,559 priority patent/US20050108927A1/en
Assigned to COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH reassignment COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: RAO, PARUCHURI GANGADHAR, SARAVANAN, SUBRAMANI, VEDARAMAN, NAGARAJAN, VELAPPAN, KANDUKALPATTI CHINNARAJ
Assigned to COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH reassignment COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GANGADHAR RAO, PARUCHURI, SARAVANAN, SUBRAMANI, VEDARAMAN, NAGARAJAN, VELAPPAN, KANDUKALPATTI CHINNARAJ
Publication of US20050108927A1 publication Critical patent/US20050108927A1/en
Abandoned legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11CFATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/03Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/02Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11CFATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10Ester interchange
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel

Definitions

  • the present invention relates to an improved process for the preparation of bio-diesel. It has enormous potential application in automobile industry as a substitute fuel for diesel.
  • Biodiesel has of late been recognized as an efficient fuel substitute. As reported by Anjana Srivastava and Ram Prasad (Renewable & Sustainable Energy Reviews—4, 2000, p111-133,) renewable sources such as vegetable oils, animal fats and used cooking oils are normally used as the starting material for preparing this alternate source of fuel. There are also reports that, the engine problems due to carbonization of combustion chamber and wax deposits & engine failure.
  • biodiesel is prepared from oil by reacting with alcohol using a acid/alkali/enzyme catalyst in the temperature range of 40-80° C. under constant stirring for a period of 2-6 hrs.
  • a acid/alkali/enzyme catalyst in the temperature range of 40-80° C. under constant stirring for a period of 2-6 hrs.
  • 1-3 moles per moles of oil in excess to stoichemetric quantity of alcohol is normally used and the unreacted alcohol is removed in the subsequent process steps.
  • the ester obtained is separated from glycerine by suitable separation process and the ester is washed with mild acid.
  • the product is purified further by evaporation to remove unreacted alcohol and traces of moisture.
  • the final product is normally used in combination with regular petroleum fuels to overcome the viscosity and related problems.
  • the main object of the present invention is to provide an improved process for the preparation of bio-diesel which obviates the limitations as stated above.
  • Another object of the present invention is to provide a chemical process for biodiesel with renewable sources of energy.
  • Still another object of the present invention is to provide a chemical process for biodiesel oil preparation from extracted from agricultural edible and non-edible products.
  • Yet another object of the present invention is to provide an environmentally friendly fuel.
  • Still yet another object of the present invention is to provide an improved quality of biodiesel can be used with out any alteration in the diesel engine.
  • the present invention provides an improved process for the preparation of bio-diesel, which comprises
  • the oil used may be selected from ricebran oil, cottonseed oil , soybean oil, sunflower oil, castor oil, coconut oil.
  • the alcohol used may be selected from methanol, ethanol, n-propanol, n-butanol, n-pentanol
  • the catalyst used may be selected from sodium hydroxide, potassium hydroxide.
  • the known method of separation used may be such as decanting, centrifuging, gravity separation, settling.
  • the conventional method of purification used may be selected from bubble washing involving bubble size of 1-3 mm, micro filtration with not less than 5 micron filter, centrifuging, either alone or in any combination.
  • the Reynolds number (N Re ) used for maintaining turbulence may be adjusted at not less than 4000 irrespective of the type of reactor.
  • Oil having specific gravity in the range of 0.85-0.96 and iodine value not exceeding 208 is heated to a temperature not exceeding 120° C. for not less than 2 hrs and is transesterified using 8 to 42% w/w, of alcohol of general formula R-OH, where R represents (C n H 2n+1 ), n being any integer between 1 and 5, by known method in presence of not more than 0.5% w/w, of a known catalyst, at a temperature higher than the boiling point of the alcohol but not exceeding 215° C. for not less than 30 minutes under continuous turbulent condition at rpm in the range of 100-150 to get a mixture of ester and glycerol.
  • the Reynolds number (N Re ) is maintained at not less than 4000 irrespective of the type of the reactor.
  • the mixture of ester and glycerol is subjected to separation by known method for a period of not less than 4 hrs and the top layer ester is purified by conventional method for a period of not less than 8 hrs.
  • the process of separation as well as purification is repeated for not less than three times in succession to get biodiesel.
  • the inventive step of the present invention lies not only in selecting the temperature of transesterification at higher than the boiling point of the alcohol while not exceeding 215° C., but also in maintaining turbulence monitored by adjusting the Reynolds number (N Re ) at not less than 4000 irrespective of the type of the reactor, to ensure about 97% conversion of the oil into ester within a period of as low as 30 minutes, thereby enhancing the formation of fuel properties in the resulting product called biodiesel.
  • the resulting solution was taken in separating funnel, and two layers were found to form. The mixture was allowed to settle for 4 hrs and the top layer was taken for further processing.
  • This oil was taken in the specially modified batch Continuous Stirred Tank Reactor (CSTR) with provision for alcohol recycle/recovery system, condenser, thermometer and feeding funnel.
  • CSTR Continuous Stirred Tank Reactor
  • 40 ml of butanol was taken in a beaker and 0.5 gm sodium hydroxide was added to it under continuous stirring.
  • the resulting solution was then added to the reactor rapidly.
  • the reactor system maintained at turbulent condition by stirring at 100-rpm in order to maintaining the Reynolds number (N Re ) at the minimum of 4000.
  • the reaction was continued for 30 minutes.
  • the excess butanol of 8.3 ml used for above reaction was later is recovered by the special recovery system.
  • the resulting solution was taken in separating funnel, and two layers were found to form. The mixture was allowed to settle for 4 hrs and the top layer was taken for further processing.
  • This oil was taken in the specially modified batch Continuous Stirred Tank Reactor (CSTR) with provision for alcohol recycle/recovery system, condenser, thermometer and feeding funnel. 47 ml of methanol was taken in a beaker and 1 gm sodium hydroxide was added to it under continuous stirring. The resulting solution was then added to the reactor rapidly. The reactor system maintained at turbulent condition by stirring at 100-rpm in order to maintaining the Reynolds number (N Re ) at the minimum of 4000. The reaction was continued for 60 minutes. The excess methanol of 10 ml used for above reaction was later is recovered by the special recovery system.
  • CSTR Continuous Stirred Tank Reactor
  • the resulting solution was taken in separating funnel, and two layers were found to form. The mixture was allowed to settle for 8 hrs and the top layer was taken for further processing.
  • This oil was taken in the specially modified batch Continuous Stirred Tank Reactor (CSTR) with provision for alcohol recycle/recovery system, condenser, thermometer and feeding funnel.
  • CSTR Continuous Stirred Tank Reactor
  • 35 ml of ethanol was taken in a beaker and 0.5 gm sodium hydroxide was added to it under continuous stirring.
  • the resulting solution was then added to the reactor rapidly.
  • the reactor system maintained at turbulent condition by stirring at 100-rpm in order to maintaining the Reynolds number (N Re ) at the minimum of 4000.
  • the reaction was continued for 45 minutes.
  • the excess ethanol of 8 ml used for above reaction was later is recovered by the special recovery system.
  • the resulting solution was taken in separating funnel, and two layers were found to form. The mixture was allowed to settle for 8 hrs and the top layer was taken for further processing.
  • This oil was taken in the specially modified batch Continuous Stirred Tank Reactor (CSTR) with provision for alcohol recycle/recovery system, condenser, thermometer and feeding funnel.
  • 20 ml of methanol was taken in a beaker and 0.5 gm sodium hydroxide was added to it under continuous stirring.
  • the resulting solution was then added to the reactor rapidly.
  • the reactor system maintained at turbulent condition by stirring at 100-rpm in order to maintaining the Reynolds number (N Re ) at the minimum of 4000.
  • the reaction was continued for 30 minutes.
  • the excess methanol of 4 ml used for above reaction was later is recovered by the special recovery system.
  • the resulting solution was taken in separating funnel, and two layers were found to form. The mixture was allowed to settle for 4 hrs and the top layer was taken for further processing.
  • This oil was taken in the specially modified batch Continuous Stirred Tank Reactor (CSTR) with provision for alcohol recycle/recovery system, condenser, thermometer and feeding funnel. 25 ml of ethanol was taken in a beaker and 0.5 gm sodium hydroxide was added to it under continuous stirring. The resulting solution was then added to the reactor rapidly. The reactor system maintained at turbulent condition by stirring at 100-rpm in order to maintaining the Reynolds number (N Re ) at the minimum of 4000. The reaction was continued for 30 minutes. The excess ethanol of 8 ml used for above reaction was later is recovered by the special recovery system.
  • CSTR Continuous Stirred Tank Reactor
  • the resulting solution was taken in separating funnel, and two layers were found to form. The mixture was allowed to settle for 4 hrs and the top layer was taken for further processing.
  • Un-reacted methanol removal Un-reacted methanol has separated immediately by an addition process step of after the reaction by a specially modified flash recovery system (in a provision built within on within the reactor separate reactor) 6.
  • Fixed bed/Plug flow reactor Batch reactor 7.
  • Multiple reactor Single reactor consists of special provision for excess alcohol recovery 8.
  • Continuous process Batch process 9.
  • Increased final product The final product contains only higher fatty acid volume due to blending of esters. higher fatty acid ester with glyceryl ether. 10.
  • Oxidative process Base catalysed transesterification 12.
  • Product is Mixture of Bio-
  • the final product contains higher fatty acid diesel and Ester glycerol esters. 13. Transesterifying at least a Almost all portion. portion only 14.
  • This step ensures that no blending, as described in the U.S. Patent document.

Abstract

A process is disclosed for the preparation of biodiesel, whereby oil is subjected to catalytical transesterification, settling, separation, bubble washing and micro filtration at controlled conditions of temperature and turbulence. The process enables production of high quality fuel, termed as biodisel, within a period of as low as 50 hrs. The fuel can be used without blending with any conventional fuel.

Description

    FIELD OF THE INVENTION
  • The present invention relates to an improved process for the preparation of bio-diesel. It has enormous potential application in automobile industry as a substitute fuel for diesel.
  • BACKGROUND OF THE INVENTION
  • Biodiesel has of late been recognized as an efficient fuel substitute. As reported by Anjana Srivastava and Ram Prasad (Renewable & Sustainable Energy Reviews—4, 2000, p111-133,) renewable sources such as vegetable oils, animal fats and used cooking oils are normally used as the starting material for preparing this alternate source of fuel. There are also reports that, the engine problems due to carbonization of combustion chamber and wax deposits & engine failure.
  • As reported by Gerhard Vellguth (Society of Automobile Engines No. 831358, 1983), the fuel injector modifications are needed in standard diesel engines while using vegetable oil as a fuel , otherwise forms deposits on the injectors and in the cylinder head, leading to poor performance, higher emissions and reduces engine life. This limitation has to some extent been resolved by way of transesterification. Reference may be made to Antolin et al., (Bioresource Technology 83, 2002, p 111-114), who transesterified sunflower oil with methanol at a temperature in the range of 40-70° C. under constant stirring for a period of 2-6 hrs. Similar efforts have been made by different research groups to prepare biodiesel from multiple oil sources. As reported by Alcantara et al., (Biomass Bioenergy 18,p515-527,2000) several oils such as soybean, frying oil, tallow have been tried as substitutes for diesel. As reported by Widyan and Shyoukh (Bioresource Technology 85, p253-256,2002), palm oil has also been tried as substitutes.
  • Conventionally, biodiesel is prepared from oil by reacting with alcohol using a acid/alkali/enzyme catalyst in the temperature range of 40-80° C. under constant stirring for a period of 2-6 hrs. In order to achieve higher product conversion, 1-3 moles per moles of oil in excess to stoichemetric quantity of alcohol is normally used and the unreacted alcohol is removed in the subsequent process steps. The ester obtained is separated from glycerine by suitable separation process and the ester is washed with mild acid. The product is purified further by evaporation to remove unreacted alcohol and traces of moisture. The final product is normally used in combination with regular petroleum fuels to overcome the viscosity and related problems.
  • The major limitation associated with all these processes is that the overall product conversion in most of the cases is limited to 60-85% only. Moreover, the temperature range limited up to 60° C. results in prolonged time, which may be as high as 6 hrs and thereby enhancing the cost of the process significantly.
  • Another limitation associated with these processes is that the resulting product exhibits higher viscosity compared with conventional petroleum fuels, thereby necessitating it is blending with petroleum fuels for the use in diesel engines.
  • OBJECTS OF THE INVENTION
  • The main object of the present invention is to provide an improved process for the preparation of bio-diesel which obviates the limitations as stated above.
  • Another object of the present invention is to provide a chemical process for biodiesel with renewable sources of energy.
  • Still another object of the present invention is to provide a chemical process for biodiesel oil preparation from extracted from agricultural edible and non-edible products.
  • Yet another object of the present invention is to provide an environmentally friendly fuel.
  • Still yet another object of the present invention is to provide an improved quality of biodiesel can be used with out any alteration in the diesel engine.
  • Accordingly the present invention provides an improved process for the preparation of bio-diesel, which comprises
      • i) heating oil, characterized by specific gravity in the range of 0.85-0.96 and iodine value not exceeding 208, to a temperature not exceeding 120° C. for not less than 2 hrs followed by transesterification with 8 to 42% w/w, of alcohol of general formula R-OH, where R represents (CnH2n+1), n being any integer between 1 and 5, by known method in presence of not more than 0.55% w/w, of a known catalyst, at a temperature higher than the boiling point of the alcohol but not exceeding 215° C. for a period of not less than 30 minutes under continuous turbulent condition to get mixture of ester and glycerol,
      • ii) subjecting the mixture, as formed in step(i) to separation of the esterified oil by known method for a period of not less than 4 hrs followed by conventional purification for a period of not less than 8 hrs. and repeating the process of separation as well as purification in succession for not less than three times to get biodiesel.
  • In an embodiment of the present invention the oil used may be selected from ricebran oil, cottonseed oil , soybean oil, sunflower oil, castor oil, coconut oil.
  • In another embodiment of the present invention the alcohol used may be selected from methanol, ethanol, n-propanol, n-butanol, n-pentanol
  • In yet another embodiment of the present invention the catalyst used may be selected from sodium hydroxide, potassium hydroxide.
  • In still another embodiment of the present invention, the known method of separation used may be such as decanting, centrifuging, gravity separation, settling.
  • In yet another embodiment of the present invention the conventional method of purification used may be selected from bubble washing involving bubble size of 1-3 mm, micro filtration with not less than 5 micron filter, centrifuging, either alone or in any combination.
  • In still another embodiment of the present invention, the Reynolds number (NRe) used for maintaining turbulence may be adjusted at not less than 4000 irrespective of the type of reactor.
  • The process of the present invention is described below in detail.
  • Oil having specific gravity in the range of 0.85-0.96 and iodine value not exceeding 208 is heated to a temperature not exceeding 120° C. for not less than 2 hrs and is transesterified using 8 to 42% w/w, of alcohol of general formula R-OH, where R represents (CnH2n+1), n being any integer between 1 and 5, by known method in presence of not more than 0.5% w/w, of a known catalyst, at a temperature higher than the boiling point of the alcohol but not exceeding 215° C. for not less than 30 minutes under continuous turbulent condition at rpm in the range of 100-150 to get a mixture of ester and glycerol. The Reynolds number (NRe) is maintained at not less than 4000 irrespective of the type of the reactor.
  • The mixture of ester and glycerol is subjected to separation by known method for a period of not less than 4 hrs and the top layer ester is purified by conventional method for a period of not less than 8 hrs. The process of separation as well as purification is repeated for not less than three times in succession to get biodiesel.
  • The inventive step of the present invention lies not only in selecting the temperature of transesterification at higher than the boiling point of the alcohol while not exceeding 215° C., but also in maintaining turbulence monitored by adjusting the Reynolds number (NRe) at not less than 4000 irrespective of the type of the reactor, to ensure about 97% conversion of the oil into ester within a period of as low as 30 minutes, thereby enhancing the formation of fuel properties in the resulting product called biodiesel.
  • The following examples are given by way of illustration only and therefore should not be construed to limit the scope of the present invention.
  • EXAMPLE 1
  • 100 ml of rice bran oil having a moisture content of 3% was heated at 120° C. for a period of 2 hrs. Later the moisture content of the oil was found to be 0.5%. This oil was taken in the specially modified batch Continuous Stirred Tank Reactor (CSTR) with provision for alcohol recycle/recovery system, condenser, thermometer and feeding funnel. 20 ml of methanol was taken in a beaker and 0.5 gm sodium hydroxide was added to it under continuous stirring. The resulting solution was then added to the reactor rapidly. The reactor system was maintained at turbulent condition by stirring at 100 rpm in order to maintaining the Reynolds number (NRe) at the minimum of 4000. The reaction was continued for 30 minutes. The excess methanol of 4 ml used for above reaction was later is recovered.
  • The resulting solution was taken in separating funnel, and two layers were found to form. The mixture was allowed to settle for 4 hrs and the top layer was taken for further processing.
  • This was then subjected to bubble washing by aeration with 15 ml of distilled water for a period of 8 hrs and the resulting material was allowed to settle for 8 hrs. It was taken for micro filtration to remove the micro particles present in the product. The bubble washing, settling and filtration operations were repeated for two more times to attain improved fuel properties. The resulting biodiesel was stored.
  • 97% of rice bran oil was estimated to has been converted into biodiesel, which was found to meet the specifications of conventional petroleum fuel. The biodiesel was used for running a test engines. The emission properties of this biodiesel were found to be better than of the conventional fuels.
  • EXAMPLE 2
  • 100 ml of rice bran oil having a moisture content of 3% was heated at 120° C. for a period of 2 hrs. Later the moisture content of the oil was found to be 0.5%. This oil was taken in the specially modified batch Continuous Stirred Tank Reactor (CSTR) with provision for alcohol recycle/recovery system, condenser, thermometer and feeding funnel. 32 ml of propanol was taken in a beaker and 0.5 gm sodium hydroxide was added to it under continuous stirring. The resulting solution was then added to the reactor rapidly. The reactor system maintained at turbulent condition by stirring at 100-rpm in order to maintaining the Reynolds number (NRe) at the minimum of 4000. The reaction was continued for 30 minutes. The excess methanol of 7 ml used for above reaction was later is recovered by the special recovery system. The resulting solution was taken in separating funnel, and two layers were found to form. The mixture was allowed to settle for 4 hrs and the top layer was taken for further processing.
  • This was then subjected to bubble washing by aeration with 25 ml of distilled water for a period of 8 hrs and the resulting material was allowed to settle for 8 hrs. It was taken for micro filtration to remove the micro particles present in the product. The bubble washing, settling and filtration operations were repeated for two more times to attain improved fuel properties. The resulting biodiesel was stored.
  • 95% of rice bran oil was estimated to has been converted into biodiesel, which was found to meet the specifications of conventional petroleum fuel. The biodiesel was used for running a test engines. The emission properties of this biodiesel were found to be better than of the conventional fuels.
  • EXAMPLE 3
  • 100 ml of sunflower oil having a moisture content of 1.5% was heated at 120° C. for a period of 2 hrs. Later the moisture content of the oil was found to be 0.5%.
  • This oil was taken in the specially modified batch Continuous Stirred Tank Reactor (CSTR) with provision for alcohol recycle/recovery system, condenser, thermometer and feeding funnel. 40 ml of butanol was taken in a beaker and 0.5 gm sodium hydroxide was added to it under continuous stirring. The resulting solution was then added to the reactor rapidly. The reactor system maintained at turbulent condition by stirring at 100-rpm in order to maintaining the Reynolds number (NRe) at the minimum of 4000. The reaction was continued for 30 minutes. The excess butanol of 8.3 ml used for above reaction was later is recovered by the special recovery system.
  • The resulting solution was taken in separating funnel, and two layers were found to form. The mixture was allowed to settle for 4 hrs and the top layer was taken for further processing.
  • This was then subjected to bubble washing by aeration with 15 ml of distilled water for a period of 8 hrs and the resulting material was allowed to settle for 8 hrs. It was taken for micro filtration to remove the micro particles present in the product. The bubble washing, settling and filtration operations were repeated for two more times to attain improved fuel properties. The resulting biodiesel was stored.
  • 98.0% of sunflower oil was estimated to have been converted into biodiesel, which was found to meet the specifications of conventional petroleum fuel. The biodiesel was used for running a test engines. The emission properties of this biodiesel were found to be better than of the conventional fuels.
  • EXAMPLE 4
  • 200 ml of coconut oil having a moisture content of 2% was heated at 120° C. for a period of 2 hrs. Later the moisture content of the oil was found to be 0.5%.
  • This oil was taken in the specially modified batch Continuous Stirred Tank Reactor (CSTR) with provision for alcohol recycle/recovery system, condenser, thermometer and feeding funnel. 47 ml of methanol was taken in a beaker and 1 gm sodium hydroxide was added to it under continuous stirring. The resulting solution was then added to the reactor rapidly. The reactor system maintained at turbulent condition by stirring at 100-rpm in order to maintaining the Reynolds number (NRe) at the minimum of 4000. The reaction was continued for 60 minutes. The excess methanol of 10 ml used for above reaction was later is recovered by the special recovery system.
  • The resulting solution was taken in separating funnel, and two layers were found to form. The mixture was allowed to settle for 8 hrs and the top layer was taken for further processing.
  • This was then subjected to bubble washing by aeration with 15 ml of distilled water for a period of 8 hrs and the resulting material was allowed to settle for 8 hrs. It was taken for micro filtration to remove the micro particles present in the product. The bubble washing, settling and filtration operations were repeated for two more times to attain improved fuel properties. The resulting biodiesel was stored.
  • 98.0% of coconut oil was estimated to have been converted into biodiesel, which was found to meet the specifications of conventional petroleum fuel. The biodiesel was used for running a test engines. The emission properties of this biodiesel were found to be better than of the conventional fuels.
  • EXAMPLE 5
  • 100 ml of coconut oil having a moisture content of 2% was heated at 120° C. for a period of 2 hrs. Later the moisture content of the oil was found to be 0.5%.
  • This oil was taken in the specially modified batch Continuous Stirred Tank Reactor (CSTR) with provision for alcohol recycle/recovery system, condenser, thermometer and feeding funnel. 35 ml of ethanol was taken in a beaker and 0.5 gm sodium hydroxide was added to it under continuous stirring. The resulting solution was then added to the reactor rapidly. The reactor system maintained at turbulent condition by stirring at 100-rpm in order to maintaining the Reynolds number (NRe) at the minimum of 4000. The reaction was continued for 45 minutes. The excess ethanol of 8 ml used for above reaction was later is recovered by the special recovery system.
  • The resulting solution was taken in separating funnel, and two layers were found to form. The mixture was allowed to settle for 8 hrs and the top layer was taken for further processing.
  • This was then subjected to bubble washing by aeration with 15 ml of distilled water for a period of 8 hrs and the resulting material was allowed to settle for 8 hrs. It was taken for micro filtration to remove the micro particles present in the product. The bubble washing, settling and filtration operations were repeated for two more times to attain improved fuel properties. The resulting biodiesel was stored.
  • 97.0% of coconut oil was estimated to have been converted into biodiesel, which was found to meet the specifications of conventional petroleum fuel. The biodiesel was used for running a test engines. The emission properties of this biodiesel were found to be better than of the conventional fuels.
  • EXAMPLE 6
  • 100 ml of sunflower oil having a moisture content of 1.5% was heated at 120° C. for a period of 2 hrs. Later the moisture content of the oil was found to be 0.5%.
  • This oil was taken in the specially modified batch Continuous Stirred Tank Reactor (CSTR) with provision for alcohol recycle/recovery system, condenser, thermometer and feeding funnel. 20 ml of methanol was taken in a beaker and 0.5 gm sodium hydroxide was added to it under continuous stirring. The resulting solution was then added to the reactor rapidly. The reactor system maintained at turbulent condition by stirring at 100-rpm in order to maintaining the Reynolds number (NRe) at the minimum of 4000. The reaction was continued for 30 minutes. The excess methanol of 4 ml used for above reaction was later is recovered by the special recovery system. The resulting solution was taken in separating funnel, and two layers were found to form. The mixture was allowed to settle for 4 hrs and the top layer was taken for further processing.
  • This was then subjected to bubble washing by aeration with 15 ml of distilled water for a period of 8 hrs and the resulting material was allowed to settle for 8 hrs. It was taken for micro filtration to remove the micro particles present in the product. The bubble washing, settling and filtration operations were repeated for two more times to attain improved fuel properties. The resulting biodiesel was stored.
  • 98.0% of sunflower oil was estimated to have been converted into biodiesel, which was found to meet the specifications of conventional petroleum fuel. The biodiesel was used for running a test engines. The emission properties of this biodiesel were found to be better than of the conventional fuels.
  • EXAMPLE 7
  • 100 ml of sunflower oil having a moisture content of 1.5% was heated at 120° C. for a period of 2 hrs. Later the moisture content of the oil was found to be 0.5%.
  • This oil was taken in the specially modified batch Continuous Stirred Tank Reactor (CSTR) with provision for alcohol recycle/recovery system, condenser, thermometer and feeding funnel. 25 ml of ethanol was taken in a beaker and 0.5 gm sodium hydroxide was added to it under continuous stirring. The resulting solution was then added to the reactor rapidly. The reactor system maintained at turbulent condition by stirring at 100-rpm in order to maintaining the Reynolds number (NRe) at the minimum of 4000. The reaction was continued for 30 minutes. The excess ethanol of 8 ml used for above reaction was later is recovered by the special recovery system.
  • The resulting solution was taken in separating funnel, and two layers were found to form. The mixture was allowed to settle for 4 hrs and the top layer was taken for further processing.
  • This was then subjected to bubble washing by aeration with 15 ml of distilled water for a period of 8 hrs and the resulting material was allowed to settle for 8 hrs. It was taken for micro filtration to remove the micro particles present in the product. The bubble washing, settling and filtration operations were repeated for two more times to attain improved fuel properties. The resulting biodiesel was stored.
  • 98.0% of sunflower oil was estimated to have been converted into biodiesel, which was found to meet the specifications of conventional petroleum fuel. The biodiesel was used for running a test engines. The emission properties of this biodiesel were found to be better than of the conventional fuels.
  • Emission Analysis of Diesel, Biodiesel and Various Blends
  • Load Time for CO CO2 HC O2 NOx Noise Texh
    KW Sample 10 cc(sec) (% vol) (% vol) (ppm) (% VOL) (ppm) (db) (° c.)
    0 Diesel 65 0.08 2.1 28 17.53 180 145 140
    Biodiesel 65 0.04 2.55 10 17.10 111 116 182
    BS1 66 0.02 2.31 0 17.30 154 145 153
    BS2 71 0.02 2.14 0 17.50 96 112 154
    BS3 69 0.03 2.13 0 17.36 125 113 145
    BS4 69 0.03 2.42 5 17.28 113 120 170
    BS5 78 0.04 2.09 0 17.47 84 115 169
    4 Diesel 49 0.12 3.5 43 15.62 397 145 210
    Biodiesel 45 0.04 3.95 20 15.27 118 119 202
    BS1 51 0.03 3.61 0 15.70 369 120 190
    BS2 49 0.03 3.49 27.5 15.57 277 112 196
    BS3 48 0.03 3.84 20 14.94 300 115 180
    BS4 49 0.04 3.90 17.5 16.39 283 129 245
    BS5 48 0.045 4.02 2.5 14.99 300 116 242
    7 Diesel 42 0.13 4.3 63 14.68 582 146 243
    Biodiesel 36 0.03 5.06 10 13.53 525 121 277
    BS1 46 0.04 4.11 35 14.73 473 117 210
    BS2 39 0.04 4.87 12.5 13.56 502 114 225
    BS3 38 0.05 5.44 10 12.67 479 116 243
    BS4 38 0.05 5.20 10 13.18 496 126 285
    BS5 38 0.06 5.46 32.5 12.85 451 119 315
    11 Diesel 32 0.2 6.3 85 11.2 689 159 287
    Biodiesel 30 0.05 6.74 20 10.99 727 123 329
    BS1 32 0.06 6.79 37.5 10.53 800 119 250
    BS2 29 0.06 6.91 15 10.43 728 118 240
    BS3 30 0.10 7.05 15 10.15 608 119 285
    BS4 30 0.10 7.35 45 9.83 605 126 296
    BS5 30 0.11 7.01 30 10.36 616 121 362
    14 Diesel 27 0.34 7.7 89 9.12 942 169 294
    Biodiesel 25 0.09 8.30 35 8.74 904 124 411
    BS1 27 0.07 7.58 35 9.24 977 120 266
    BS2 26 0.18 8.04 47.5 8.54 858 119 363
    BS3 23 0.27 9.03 52.5 6.86 782 122 342
    BS4 27 0.14 8.10 45 8.60 782 127 395
    BS5 24 0.24 8.30 45 8.22 660 123 380

    Note:

    BS—Blended with Diesel

    BS1-B20, BS2-B80, BS3-B50, BS4-B40, BS5-B60
  • Oil Specification
    • Specific gravity: 0.916-0.912
    • Refractive Index: 1.470-1.473
    • Iodine value: 99-108
    • Saponification value: 181-189
    • Acid value: 4-120
    • Titer: 24-28° C.
    • Unsaponifiable matter: 3.5%
    • Tocopherols average: 400 mg/kg of oil
    Fuel Properties
  • Property DIESEL Biodiesel (RBOE)
    Density (gm/cc) 0.82 0.865
    Viscosity (Cst) 2.4 3.46
    Heat Of Combustion 42.57 45.09
    (MJ/Kg)
    Flash Point (° C.) 74 182
    Fire Point (° C.) 87 194
    Copper strip Corrosion No. 3 <No. 1
    @ 100 (° C.)
  • Engine Efficiency
  • Specific Fuel Break Thermal Mechanical Indicative Thermal
    Load Consumption (kWh) Efficiency (%) Efficiency (%) Efficiency (%)
    (kW) Diesel Biodiesel Diesel Biodiesel Diesel Biodiesel Diesel Biodiesel
    0 0 0 0 0 20.65 30.22
    4 0.556 0.611 15.07 14.01 47.41 37.54 31.77 37.33
    7 0.378 0.419 22.17 20.08 62.22 51.27 36.22 40.46
    11 0.314 0.333 26.67 25.69 71.26 62.31 37.42 41.23
    14 0.292 0.328 28.65 26.07 75.94 67.78 37.73 38.45
  • A comparative study of the Complete specification relating to P03ce04 (an improved process for the preparation of bio-diesel) and the U.S. Pat. No. 6,015,440 apparently reveals the following differences.
    Sl. No U.S. Pat. No. 6,015,440 Bio-diesel Process - Ref No. P03ce04/CLRI
    1. Temperature range of the More than the boiling point of the alcohol but
    reaction 70-80° C. less than 215° C.
    2. Pressure at 20 psig Atmospheric pressure
    3. Separation alkali using ion Separation of alkali using water
    exchange column
    4. Top layer approximately 80% More than 80%
    5. Un-reacted methanol removal Un-reacted methanol has separated immediately
    by an addition process step of after the reaction by a specially modified
    flash recovery system (in a provision built within on within the reactor
    separate reactor)
    6. Fixed bed/Plug flow reactor Batch reactor
    7. Multiple reactor Single reactor consists of special provision for
    excess alcohol recovery
    8. Continuous process Batch process
    9. Increased final product The final product contains only higher fatty acid
    volume due to blending of esters.
    higher fatty acid ester with
    glyceryl ether.
    10. Reaction with isobutylene No such reaction
    11. Oxidative process Base catalysed transesterification
    12. Product is Mixture of Bio- The final product contains higher fatty acid
    diesel and Ester glycerol esters.
    13. Transesterifying at least a Almost all portion.
    portion only
    14. This end product of this The end product is bio-diesel, no mixing with
    process is a mixture of ester glycerol. In fact glycerol is obtained as by-
    and the etherified glycerol, product
    which is converted into bio-
    diesel by blending.
    15. Only by mixing the etherified This is a bio-diesel process, without mixing the
    glycerol to the esterified oil glycerol, with all required bio-diesel properties
    may gives the viscosity and emission norms similar to the normal diesel
    reduction. fuel.
    16. Strong acid catalyst process Alkali/base catalyst process
    17. Approximately 80% of the More than 95% in pure form
    bio-diesel is in pure form
    18. Effect of mixing of etherified No engine difficulties. No need of any change in
    crude glycerol's effect in the the engine needed, no engine block etc.
    engine is not defined, shown
    only the viscosity reduction
    19. Low waste process, not More than 95% conversion. Glycerol formed as
    separating the 20% crude a by-product can be used in other industries.
    glycerol formed.
    20. Formation of 20% glycerol, Glycerol formed as a by-product can be used in
    for economical purpose, after other industries.
    reacting with isobutylene
    mixing with the bio-diesel
    21. After mixing the crude The final product after the reaction is similar to
    glycerol only, the product diesel fuel
    gives properties closely
    resembling to have of diesel
    fuel
  • In our opinion, the inventive step of the present invention visa-vis the aforesaid U.S. Patent document, however, essentially lies in conducting the reaction at a temperature higher than the boiling point of the alcohol used, besides maintaining the turbulence (NRe=4000 or more), that is applicable irrespective of the type of the reactor used, to enhance the fuel properties of the resulting product. This step ensures that no blending, as described in the U.S. Patent document.
  • Following are some of the advantages of the present invention:
      • 1. The high temperature with turbulent condition (Reynolds number more than 4000), reduces the reaction time significantly.
      • 2. The special provision in the reactor enables the effective recovery of excess alcohol added for the reaction.
      • 3. Bubble washing and microfiltration achieved the high quality of the biodiesel.
      • 4. The product is based on renewable source.
      • 5. The product can be used as substitute fuel for diesel engines without any major modification of engines.
      • 6. The final product is a substitute fuel for diesel without blending with other conventional petroleum fuels.
      • 7. The products fuel properties and the engine efficiency are comparable with normal diesel engine fuels.
      • 8. The emission characteristics are like those of normal fuels.

Claims (7)

1. An improved process for the preparation of bio-diesel, which comprises
i) heating oil having by specific gravity in the range of 0.85-0.96 and iodine value not exceeding 208, to a temperature not exceeding 120° C. for not less than 2 hrs followed by transesterification with 8 to 42% w/w, of alcohol of general formula R-OH, where R represents (CnH2n+1), n being any integer between 1 and 5, in presence of not more than 0.55% w/w, of a catalyst, at a temperature higher than the boiling point of the alcohol but not exceeding 215° C. for a period of not less than 30 minutes under continuous turbulent conditions to obtain a mixture of ester and glycerol,
ii) Subjecting the mixture, as formed in step (i) to separation of the esterified oil for a period of not less than 4 hrs followed by purification for a period of not less than 8 hrs. and repeating the process of separation as well as purification in succession for not less than three times to obtain biodiesel.
2. A process, as claimed in claim 1 wherein the oil is selected from ricebran oil, cottonseed oil , soybean oil, sunflower oil , castor oil, coconut oil.
3. A process, as claimed in claim 1, wherein the alcohol is selected from methanol, ethanol, n-propanol, n-butanol, and n-pentanol
4. A process, as claimed in claim 1 wherein the catalyst is selected from sodium hydroxide, potassium hydroxide.
5. A process, as claimed in claim 1 wherein the esterified oil is separated by decanting, centrifuging, gravity separation, settling, either alone or in any combination.
6. A process, as claimed in claim 1 wherein the purification of the mixture is by bubble washing involving bubble size of 1-3 mm, micro filtration with not less than 5 micron filter, centrifuging, either alone or in any combination.
7. A process, as claimed in claim 1 wherein the Reynolds number (NRe) for maintaining turbulence is adjusted at not less than 4000 irrespective of the type of reactor.
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WO2007062480A1 (en) * 2005-12-02 2007-06-07 Acqua International Group Inc Method and apparatus for manufacturing and purifying bio-diesel
US20080028675A1 (en) * 2005-05-10 2008-02-07 Nbe,Llc Biomass treatment of organic waste materials in fuel production processes to increase energy efficiency
CN100375779C (en) * 2005-06-24 2008-03-19 清华大学 Technical method for preparing biodiesel using reactive separation process coupling technique
WO2008049154A1 (en) * 2006-10-23 2008-05-02 Blue Diesel Pty Ltd Process and apparatus for biofuel production
CN100402631C (en) * 2006-05-22 2008-07-16 暨南大学 Method for synthesizing biodiesel
US20080234398A1 (en) * 2007-02-24 2008-09-25 Reinhold Klipper Monodisperse weakly acidic cation exchangers
WO2009047793A1 (en) 2007-10-09 2009-04-16 Council Of Scientific & Industrial Research An improved process for the preparation of biodiesel from vegetable oils containing high ffa
DE102007026654A1 (en) 2007-06-08 2010-01-07 Hölter, Heinrich, Prof. Dr. sc. Dr.-Ing. Dr. hc Preparing fatty acid alkyl esters and glycerin comprises preparing a catalyst containing a basic component and alcohol, making an activated catalyst, mixing triglycerides with the activated catalyst and contacting the reactants
EP2197989A1 (en) * 2007-09-27 2010-06-23 11 Good's Energy, Ltd. Fuel composition
US20100218734A1 (en) * 2006-01-17 2010-09-02 Tetuo Sugioka Bio-diesel fuel engine system and bio-diesel fuel engine operating method
RU2618715C2 (en) * 2015-10-07 2017-05-11 Федеральное Государственное Бюджетное Научное Учреждение "Аграрный Научный Центр "Донской" Method of continuous component dispensing during liquid biofuel production and device for its implementation
WO2018214997A1 (en) * 2017-05-24 2018-11-29 3-102-735843 Sociedad De Responsabilidad Limitada Organic method for enhancing conventional diesel and biodiesel with emissions reduction
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US20080028675A1 (en) * 2005-05-10 2008-02-07 Nbe,Llc Biomass treatment of organic waste materials in fuel production processes to increase energy efficiency
CN100375779C (en) * 2005-06-24 2008-03-19 清华大学 Technical method for preparing biodiesel using reactive separation process coupling technique
US20090223118A1 (en) * 2005-12-02 2009-09-10 Acqua International Group Inc Method and Apparatus for Manufacturing and Purifying Bio-Diesel
WO2007062480A1 (en) * 2005-12-02 2007-06-07 Acqua International Group Inc Method and apparatus for manufacturing and purifying bio-diesel
US8381701B2 (en) * 2006-01-17 2013-02-26 Tetuo Sugioka Bio-diesel fuel engine system and bio-diesel fuel engine operating method
US20100218734A1 (en) * 2006-01-17 2010-09-02 Tetuo Sugioka Bio-diesel fuel engine system and bio-diesel fuel engine operating method
CN100402631C (en) * 2006-05-22 2008-07-16 暨南大学 Method for synthesizing biodiesel
WO2008049154A1 (en) * 2006-10-23 2008-05-02 Blue Diesel Pty Ltd Process and apparatus for biofuel production
US20080234398A1 (en) * 2007-02-24 2008-09-25 Reinhold Klipper Monodisperse weakly acidic cation exchangers
DE102007026654A1 (en) 2007-06-08 2010-01-07 Hölter, Heinrich, Prof. Dr. sc. Dr.-Ing. Dr. hc Preparing fatty acid alkyl esters and glycerin comprises preparing a catalyst containing a basic component and alcohol, making an activated catalyst, mixing triglycerides with the activated catalyst and contacting the reactants
EP2197989A1 (en) * 2007-09-27 2010-06-23 11 Good's Energy, Ltd. Fuel composition
EP2197989A4 (en) * 2007-09-27 2011-08-10 11 Good S Energy Ltd Fuel composition
WO2009047793A1 (en) 2007-10-09 2009-04-16 Council Of Scientific & Industrial Research An improved process for the preparation of biodiesel from vegetable oils containing high ffa
RU2618715C2 (en) * 2015-10-07 2017-05-11 Федеральное Государственное Бюджетное Научное Учреждение "Аграрный Научный Центр "Донской" Method of continuous component dispensing during liquid biofuel production and device for its implementation
WO2018214997A1 (en) * 2017-05-24 2018-11-29 3-102-735843 Sociedad De Responsabilidad Limitada Organic method for enhancing conventional diesel and biodiesel with emissions reduction
WO2018214998A1 (en) * 2017-05-24 2018-11-29 3-102-735873 Sociedad De Responsabilidad Limitada Organic process for preventing corrosion and extreme temperatures in internal combustion engines and industrial processes cooled by liquids
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