WO2005052103A1 - An improved process for the preparation of bio-diesel - Google Patents

An improved process for the preparation of bio-diesel Download PDF

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Publication number
WO2005052103A1
WO2005052103A1 PCT/IB2003/005349 IB0305349W WO2005052103A1 WO 2005052103 A1 WO2005052103 A1 WO 2005052103A1 IB 0305349 W IB0305349 W IB 0305349W WO 2005052103 A1 WO2005052103 A1 WO 2005052103A1
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Prior art keywords
oil
less
biodiesel
period
hrs
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PCT/IB2003/005349
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French (fr)
Inventor
Kandukalpatti Chinnaraj Velappan
Subramani Saravanan
Nagarajan Vedaraman
Paruchuri Gangadhar Rao
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Council Of Scientific And Industrial Research
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Application filed by Council Of Scientific And Industrial Research filed Critical Council Of Scientific And Industrial Research
Priority to PCT/IB2003/005349 priority Critical patent/WO2005052103A1/en
Priority to AU2003282270A priority patent/AU2003282270B2/en
Priority to US10/718,559 priority patent/US20050108927A1/en
Publication of WO2005052103A1 publication Critical patent/WO2005052103A1/en

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • 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
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange
    • 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

  • 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, pi 11- 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.
  • the present invention provides an improved process for the preparation of biodiesel, 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 2hrs followed by transesterification with 8 to 42% w/w, of alcohol of general formula R-OH, where R represents (C n H n+ ⁇ ), 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.
  • the oil used may be selected from ricebraii 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 l ⁇ iown 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 l-3mm, micro filtration with not less than 5micron filter, centrifuging, either alone or in any combination.
  • the Reynolds number (N e ) 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 2hrs and is transesterified using 8 to 42% w/w, of alcohol of general formula R-OH, where R represents (C n H 2n+ ⁇ ) , n being any integer between 1 and 5, by l ⁇ iown 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.
  • N Re (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 l ⁇ iown 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 8hrs.
  • 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
  • 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
  • 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 7 ml used for above reaction was later is recovered by the special recovery system.
  • 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 0.5gm 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 R ⁇ ) 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 lgm 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. 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.
  • CSTR Continuous Stirred Tank Reactor
  • 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 0.5gm sodium hydroxide was added to it under continuous stirring.
  • CSTR Continuous Stirred Tank Reactor
  • 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 e ) 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.
  • 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 0.5gm sodium hydroxide was added to it under continuous stirring.
  • CSTR Continuous Stirred Tank Reactor
  • 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 (NR ⁇ ) 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 nrocessin ⁇ . This was then subjected to bubble washing by aeration with 15ml of distilled water for a period of 8 hrs and the resulting material was allowed to settle for 8hrs. 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.
  • the mixture was allowed to settle for 4 hrs and the top layer was taken for further processing.
  • This step ensures that no blending, as described in the US Patent document.
  • Bubble washing and micro filtration achieved the high quality of the biodiesel.
  • the product is based on renewable source.
  • 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.
  • the emission characteristics are like those of normal fuels.

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

AN IMPROVED PROCESS FOR THE PREPARATION OF BIO-DIESEL 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, pi 11- 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, pi 11-114), 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 idyan 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 biodiesel, 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 2hrs followed by transesterification with 8 to 42% w/w, of alcohol of general formula R-OH, where R represents (CnH n+ι), 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 ricebraii 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 lαiown 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 l-3mm, micro filtration with not less than 5micron filter, centrifuging, either alone or in any combination.
In still another embodiment of the present invention, the Reynolds number (N e) 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 2hrs and is transesterified using 8 to 42% w/w, of alcohol of general formula R-OH, where R represents (CnH2n+ι) , n being any integer between 1 and 5, by lαiown 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 lαiown 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 8hrs. 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%o. 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. 20ml of methanol was taken in a beaker and 0.5gm 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 (NRJ.) 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 15ml of distilled water for a period of 8 hrs and the resulting material was allowed to settle for 8hrs. 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. 32ml of propanol as taken in a beaker and 0.5gm 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 25ml of distilled water for a period of 8 hrs and the resulting material was allowed to settle for 8hrs. 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 0.5gm 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 (NRβ) 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 15ml of distilled water for a period of 8 hrs and the resulting material was allowed to settle for 8hrs. 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 lgm 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 15ml of distilled water for a period of 8 hrs and the resulting material was allowed to settle for 8hrs. 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 0.5gm 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 e) 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 15ml of distilled water for a period of 8 hrs and the resulting material was allowed to settle for 8hrs. 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 0.5gm 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 (NRβ) 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 nrocessinε. This was then subjected to bubble washing by aeration with 15ml of distilled water for a period of 8 hrs and the resulting material was allowed to settle for 8hrs. 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 0.5gm 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 8ml 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 15ml of distilled water for a period of 8 hrs and the resulting material was allowed to settle for 8hrs. 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
Figure imgf000010_0001
Note: BS- Blended with Diesel BSl- 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 ofoil Fuel properties
Figure imgf000011_0001
Engine Efficiency
Figure imgf000011_0002
A comparative study of the Complete specification relating to P03ce04 ( an improved process for the preparation of bio-diesel) and the US patent No. 6,015,440 apparently reveals the following differences.
Figure imgf000011_0003
Figure imgf000012_0001
In our opinion, the inventive step of the present invention vis-a-vis the aforesaid US 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 US 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 micro filtration 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

Claims:
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 2hrs followed by transesterification with 8 to 42% w/w, of alcohol of general formula R-OH, where R represents (C„H n+ι), 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 l-3mm, micro filtration with not less than 5micron 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.
PCT/IB2003/005349 2003-11-24 2003-11-24 An improved process for the preparation of bio-diesel WO2005052103A1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100335595C (en) * 2005-09-09 2007-09-05 清华大学 Continuous biological diesel oil preparing process
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WO2008011731A2 (en) * 2006-07-27 2008-01-31 Forest Bioproducts Inc. A device for the transesterification of animal and plant glycerides into fatty acid alkyl esters for small scale production of biodiesel and value added products
CN101982530A (en) * 2010-11-02 2011-03-02 中国农业大学 Biological ethanol/diesel blended fuel and preparation method thereof

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080028675A1 (en) * 2005-05-10 2008-02-07 Nbe,Llc Biomass treatment of organic waste materials in fuel production processes to increase energy efficiency
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CN100402631C (en) * 2006-05-22 2008-07-16 暨南大学 Method for synthesizing biodiesel
AU2007308739A1 (en) * 2006-10-23 2008-05-02 Blue Diesel Pty Ltd Process and apparatus for biofuel production
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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
CA2607478A1 (en) * 2007-09-27 2009-03-27 11 Good's Energy Ltd. Fuel composition
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4324875A1 (en) * 1992-07-28 1994-02-03 Prometeo Tecnoambiente Srl Prepn. of alkyl ester(s) from tri:glyceride vegetable oils - by reacting the oil with a low mol.wt. alcohol in the presence of an alkali catalyst
US5354878A (en) * 1992-03-26 1994-10-11 Joosten Connemann Process for the continuous production of lower alkyl esters of higher fatty acids
US5514820A (en) * 1989-09-29 1996-05-07 Henkel Kommanditgesellschaft Auf Aktien Continuous process for the production of lower alkyl esters
US5773636A (en) * 1993-11-08 1998-06-30 Henkel Kommanditgesellschaft Auf Aktien Process for the production of fatty acid lower alkyl esters
US20030032826A1 (en) * 2001-07-20 2003-02-13 The Board Of Regents Of The University Of Nebraska Transesterification process for production of biodiesel
KR20030049614A (en) * 2001-12-15 2003-06-25 이기영 Manufacturing method of biodiesel fuel using animal fats

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3421217A1 (en) * 1984-06-07 1985-09-05 Hoechst Ag, 6230 Frankfurt METHOD FOR PRODUCING FATTY ACID ESTERS OF SHORT-CHAIN ALCOHOLS
DE69005501T2 (en) * 1989-04-05 1994-05-11 Unilever Nv Process for the preparation of lower alkyl fatty acid monoesters.
US6127560A (en) * 1998-12-29 2000-10-03 West Central Cooperative Method for preparing a lower alkyl ester product from vegetable oil
JP2000219886A (en) * 1999-02-01 2000-08-08 Masatoshi Matsumura Method and apparatus for conversion of vegetable oil (virgin) or waste vegetable oil to fuel for diesel engine

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5514820A (en) * 1989-09-29 1996-05-07 Henkel Kommanditgesellschaft Auf Aktien Continuous process for the production of lower alkyl esters
US5354878A (en) * 1992-03-26 1994-10-11 Joosten Connemann Process for the continuous production of lower alkyl esters of higher fatty acids
DE4324875A1 (en) * 1992-07-28 1994-02-03 Prometeo Tecnoambiente Srl Prepn. of alkyl ester(s) from tri:glyceride vegetable oils - by reacting the oil with a low mol.wt. alcohol in the presence of an alkali catalyst
US5773636A (en) * 1993-11-08 1998-06-30 Henkel Kommanditgesellschaft Auf Aktien Process for the production of fatty acid lower alkyl esters
US20030032826A1 (en) * 2001-07-20 2003-02-13 The Board Of Regents Of The University Of Nebraska Transesterification process for production of biodiesel
KR20030049614A (en) * 2001-12-15 2003-06-25 이기영 Manufacturing method of biodiesel fuel using animal fats

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
A.P.HARVEY ET AL.: "Process intensification of biodiesel production using a continuous oscillatory flow reactor", JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY. (INTERNATIONAL JOURNAL OF BIOTECHNICAL AND CHEMICAL PROCESSES), vol. 78, no. 2-3, 2003, GBELSEVIER APPLIED SCIENCE PUBLISHERS. BARKING., pages 338 - 341, XP001145053 *
DATABASE WPI Section Ch Week 200371, Derwent World Patents Index; Class H06, AN 2003-753689, XP002286048 *
G. ANTOLIN ET AL.: "Optimisation of biodiesel production by sunflower oil transesterification", BIORESOURCE TECHNOLOGY., vol. 83, no. 2, 2002, GBELSEVIER., pages 111 - 114, XP002286047 *
R. ALCANTARA ET AL.: "Catalytic production of biodiesel from soy-bean oil, used frying oil and tallow", BIOMASS AND BIOENERGY., vol. 18, no. 6, 2000, GBPERGAMON, OXFORD., pages 515 - 527, XP002286046 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100335595C (en) * 2005-09-09 2007-09-05 清华大学 Continuous biological diesel oil preparing process
CN100363464C (en) * 2005-11-23 2008-01-23 陈锦清 Application of high erucic acid rapeseed oil as raw material to prepare biodiesel oil and methyl erueidate
WO2008011731A2 (en) * 2006-07-27 2008-01-31 Forest Bioproducts Inc. A device for the transesterification of animal and plant glycerides into fatty acid alkyl esters for small scale production of biodiesel and value added products
WO2008011731A3 (en) * 2006-07-27 2008-05-08 Forest Bioproducts Inc A device for the transesterification of animal and plant glycerides into fatty acid alkyl esters for small scale production of biodiesel and value added products
CN101982530A (en) * 2010-11-02 2011-03-02 中国农业大学 Biological ethanol/diesel blended fuel and preparation method thereof
CN101982530B (en) * 2010-11-02 2014-02-19 中国农业大学 Biological ethanol/diesel blended fuel and preparation method thereof

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