WO2007143803A1 - Method for transesterification of vegetable oils and animal fats, catalyzed by modified strong base for the production of alkyl esters - Google Patents

Method for transesterification of vegetable oils and animal fats, catalyzed by modified strong base for the production of alkyl esters Download PDF

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Publication number
WO2007143803A1
WO2007143803A1 PCT/BR2007/000132 BR2007000132W WO2007143803A1 WO 2007143803 A1 WO2007143803 A1 WO 2007143803A1 BR 2007000132 W BR2007000132 W BR 2007000132W WO 2007143803 A1 WO2007143803 A1 WO 2007143803A1
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guanidine
vegetable oils
transesterification
animal fats
fact
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PCT/BR2007/000132
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French (fr)
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Osvaldo Lopes Candido
Antonio José DA SILVA MACIEL
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Universidade Estadual De Campinas - Unicamp
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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
    • 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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • This present invention refers to a method for producing alkyl esters, such as biodiesel (methyl and ethyl esters) and other alkyl esters, from vegetable oils and animal fats by non- conventional catalysts (not containing metal in their chemical structure): guanidine hydroxides and quaternary ammonium hydroxide and alkoxides (alcoholates), dissolved in methanol, ethanol and others, representing the catalysts in homogeneous form, also cause the transesterification reaction when linked or anchored to polymers or resins, representing the heterogeneous form, which simplify the production process and provides a high yield, obtaining products with a high degree of purity.
  • non- conventional catalysts not containing metal in their chemical structure
  • guanidine hydroxides and quaternary ammonium hydroxide and alkoxides (alcoholates) dissolved in methanol, ethanol and others, representing the catalysts in homogeneous form, also cause the transesterification reaction when linked or anchored to
  • the transesterification reaction of vegetable oils and animal fats (triglycerides) plus methyl or ethyl alcohol can be catalyzed by: NaOH (sodium hydroxide), KOH (potassium hydroxide), NaOCH 3 (sodium methoxide), NaOCH 2 CH 3 (sodium ethoxide), KOCH 3 (potassium methoxide), KOCH 2 CH 3 (potassium ethoxide), H 2 SO 4 (sulphuric acid), HCL (hydrochloric acid), in the industrial production process almost always a conventional strong base is used - Lopes, O. C.
  • Reaction stoichiometry points to a molar ratio of 6 to 1 ethanol to vegetable oil or fat, that is, twice the stoichiometry to be able to displace the equilibrium towards products - Freedman, B.; Pryde, E.H.; Mounts, T.L., Variables Affecting the Yields of Fatty Esters from Transesterified vegetable Oils, JAOCS,vol61 n 10 1984.
  • the solubility of NaOH in ethanol is much harder to achieve than in methanol, because the formation of sodium or potassium ethoxide is more difficult.
  • the transesterification reaction is carried out at around 50 degrees Celsius to minimize the formation of soap, with a reaction time of around one hour using 1% catalyst in relation to the vegetable oil mass - Zhou, Weiyang; Konar, S. K., Boocock, G.B. Ethyl Esters from the Single-Phase Base-catalyzed Ethanolysis of Vegetable Oils., JAOCS,vol80,n4 2003.
  • Patent of invention n 0 PI0105888-6 describes a process consisting of promoting a transesterification reaction wherein the seeds themselves react with dry ethanol in the presence of an alkaline catalyst to generate ethyl esters that will later be separated by settling and neutralized to serve as fuel for diesel engines, co-solvents for mixtures of diesel and gasoline with dry or hydrated ethanol and as solid fractions that can be used as fertilizer in animal fodder and as raw material for the production of ethanol.
  • this patent does not include the catalysts that are the subject matter of this present patent.
  • Patent of invention n 0 PI0301183-6 discloses a method for producing ethyl ester from fatty acids and equipment for carrying it out, designed to enable the technical and economic production of biodiesel including compositions of saturated and unsaturated fatty acids at least one of which is of vegetable and animal origin with at least one C 1 to C 5 chained alcohol preferably C 2 H 5 OH in the presence of a catalyst or co-catalyst that can be acidic, enzymatic, alkaline or lipase, preferably alkaline.
  • the method also includes a pump(5) having the function of suction, stirring and injection, which method of transesterification of said mixture occurs internally therein, being injected under high pressure into a spraying nozzle 30 located internally in a reactor(3) the already transesterificated mixture internally in the pump(5) and injected into the spraying nozzle 30 when going from a high pressure environment to a lower pressure environment immediately separates into phases, one bottom phase containing glycerine and a top one containing a monoester in this process the alcohol performs the extra function of atomizing liquid of the fatty acids.
  • Said method enables the production of esters having a high conversion rate in an extremely short time.
  • this patent does not include the catalysts that are the subject matter of this present application.
  • Patent of invention n 0 PI0404243-3 discloses a continuous method for producing biodiesel which was developed to produce monoesters of fatty acids (biodiesel) on a continuous basis having a higher quality international standard from semi- refined vegetable oil and dry alcohol by a method of transesterification in characteristic reactors with continuous separation of the residual alcohol by evaporation and the glycerine (obtained as reaction byproduct) through centrifuges also used in the washing and final purification of the biodiesel.
  • This patent includes a continuous method that involves centrifuges and reactors, but bears no claim to protect the catalysts in question. Therefore, it would be useful to develop a method of producing biodiesel (alkyl esters) with catalysts capable of producing ethyl biodiesel with a high degree of purity over 99%, without the drawbacks of the conventional catalysts.
  • the present invention refers to a method of obtaining methyl or ethyl biodiesel and other alkyl esters, by the transesterification reaction of vegetable oils and/or animal fats, catalyzed by modified strong base, which does not contain metallic ions in its structure. Therefore, they do not form soap or emulsion, either in homogeneous or heterogeneous form, and produce esters with a high yield in a shorter time than the traditional methods.
  • the present invention offers a solution for the catalytic problems involved in the production of biodiesel, as it does not contain metallic ions in its chemical composition, it does not form soap in the method of transesterification of vegetable oils and animal fats. Accordingly, the concentration of the catalyst is maintained at levels near to that added at the start of the transesterification reaction. For this reason, the alkyl esters yield is above 99%, even using a temperature lower than the boiling point of alcohols, with spontaneous settling of glycerine, dispensing with the use of centrifuges.
  • the system has a similar behavior to that of methanol or ethanol, obtaining the guanidine hydroxides and hydroxides and quaternary ammonium alkoxides, is from the salts of the same in an alcoholic means in the solutilization process of sodium or potassium hydroxide, resulting in a complete transfer reaction of the guanidine and quaternary ammonium cations.
  • the title of this invention is thus justified, as the true catalyst is the OH " or alkoxides, causing the precipitation of sodium or potassium salts.
  • This reaction is preferably conducted by stirring and at temperatures lower tan the boiling point of the alcohols used and in the approximate time of 10 to 50 minutes, preferably between 15 and 30 minutes, depending on the quantity and type of alcohol and the form and quantity of the salt used in the transesterification reaction. It is important to emphasize that the reaction can be used at temperatures above the boiling point of the alcohols.
  • the transesterification reaction of vegetable oil or animal fat is conducted with the catalysts, preferably using 1% or more, depending on the reaction conditions, dissolved in methanol or ethanol in homogeneous or solvate form, when the form is used, that will generate the methoxide or ethoxide, with the respective guanidine or quaternary ammonium counter-ions, in a sufficient quantity to produce the high-yield esters, preferably at a temperature below the boiling point of the alcohols (and may also be above).
  • the method proposed herein provides for the use of derivates of guanidine salts or quaternary ammonium salts transformed into the respective guanidine hydroxides and ammonium quaternary hydroxides or alkoxides (alcoholates), wherein the chemical family of guanidines is: non-substituted guanidine and substituted guanidines, such as:
  • N,N - dialkyl guanidine N,N' ,N " - trialkyl guanidine;
  • substituted quaternary ammonium salts wherein Ri ; R 2, R 3, R 4 , may represent the alkyl or aryl groups, or another chemical function, linked to the counter-ions, chlorate, bromate, sulphate, carbonate, phosphate or any other negative ions.
  • the catalysts referred to herein do not produce soap in the process, because they do not have metallic cations arid have a greater tolerance to the quantity of water in the process, allowing the use of alcohol with a higher water content;
  • the new catalysts have no restrictions to the use of vegetable oils or fats
  • esters require only the recovery of alcohol and neutralization of the catalyst excess and subsequent purification, thus producing a biodiesel in conformity to the standards laid down in the ANP resolution and international standards described above;
  • the new catalysts can be recovered in the process when used in heterogeneous form;
  • the glycerine obtained by this process presents crystalline form with low impurity content;
  • the new catalysts are active when anchored or linked to polymers or resins, producing heterogeneous catalysis in continuous reactors or in batch.
  • the basic quaternary ammonium resins are already produced on a commercial scale for various purposes. However, with such a . structure, they present practically no catalyst activity in the transesterification reaction. Yet by using the principle of nanotechnology for structural change, these resins or basic polymers will have a high catalytic activity in the transesterification reaction, present common advantages of heterogeneous catalysis.
  • the catalysts that are the subject matter of this present invention can be used for fast preparation of small samples of methyl fatty esters from oils and fats, to determine their fatty acid composition. Therefore, since these catalysts contain no metals in their chemical composition, they do not cause isomerization of the double links and have a series of advantages over the official American method (AOCS Ce-266) that uses 20% boron trifluoride dissolved in methanol.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Fats And Perfumes (AREA)

Abstract

The present invention comprises the production of alkyl esters, such as biodiesel, from any vegetable oils or animal fat, on the methyl or ethyl routes, catalyzed by a modified strong base, both in the homogeneous phase, where a high yield is obtained, as well as in the transesterification reaction, causing spontaneous decantation of glycerol. After withdrawing the excess alcohol by reaction means, the catalyst neutralization and purification, (biodiesel) esters are obtained having a purity over 99%. The catalysts of this present invention allow both the batch and continuous processes, where it is possible to use the entire industrial plant engineering that already operates with methanol to operate on the ethyl route. Heterogeneous phase catalysts simplify the process because they do not contaminate the products, do not require the alkyl ester neutralization and purification stages, and are not consumed during the transesterification process.

Description

"METHOD FOR TRANSESTERIFICATION OF VEGETABLE OILS AND ANIMAL FATS, CATALYZED BY MODIFIED STRONG BASE FOR THE PRODUCTION OF ALKYL ESTERS" FIELD OF THE INVENTION
This present invention refers to a method for producing alkyl esters, such as biodiesel (methyl and ethyl esters) and other alkyl esters, from vegetable oils and animal fats by non- conventional catalysts (not containing metal in their chemical structure): guanidine hydroxides and quaternary ammonium hydroxide and alkoxides (alcoholates), dissolved in methanol, ethanol and others, representing the catalysts in homogeneous form, also cause the transesterification reaction when linked or anchored to polymers or resins, representing the heterogeneous form, which simplify the production process and provides a high yield, obtaining products with a high degree of purity.
BACKGROUND OF THE INVENTION The transesterification reaction of vegetable oils and animal fats (triglycerides) plus methyl or ethyl alcohol can be catalyzed by: NaOH (sodium hydroxide), KOH (potassium hydroxide), NaOCH3 (sodium methoxide), NaOCH2CH3 (sodium ethoxide), KOCH3 (potassium methoxide), KOCH2CH3 (potassium ethoxide), H2SO4 (sulphuric acid), HCL (hydrochloric acid), in the industrial production process almost always a conventional strong base is used - Lopes, O. C. L - Novos catalisadores para transesterificaςdo de όleos vegetais, Thesis for Master's Degree in Chemistry at Campinas State University, page 98, 1983. However, other catalysts can be used at laboratory level such as: CH2N2 (Diazomethane), BF3 (boron trifluoride) and CN3H5 (guanidine) with a free base - Shuchardt, U.; Lopes, O. C. Method of preparing methyl esters, with organic catalysts and method of rapid determination of composition of oils and fats BR n° 3830236-6, May 6, 1983. More specifically, the industrial processes nowadays use almost exclusively NaOH(sodium hydroxide) and KOH (potassium hydroxide) as catalysts due to availability and price, because the bases are more efficient as catalysts in the process of transesterification - Shuchardt, U.; Sercheli, R.; Vargas, R.M. Transesterification of Vegetable oils: a Review in:Braz.Chem.Soc, 1998,9,19Op.
The production of biodiesel with methanol is already a well-established technology, because methanol is the most acidic of alcohols - Bhattacharyya, S.; Reddy,C,S.: Vegetable Oils as Fuels for Internal Combustion Engines: A review J. Agric.EngngRes. 1994 57, 157-166, with pKa = 15.5 with water content around 0.0723%, and for this reason, the reaction with the presence of about 1% strong base, easily forms sodium ' or potassium methoxide, forming the methyl esters and with a certain percentage of saponification - Freedman, B.; Pryde, E.H.; Mounts, T.L.J.Am.Oil.Chem. Soc. 1984, 61, 1638.
The yield from this process is over 96%, and this technology has been established for over 20 years. Glycerine is spontaneously decanted due to the low percentage of mono glycerides and only a small percentage of soap. This reaction is performed by mechanical or hydraulic stirring for less than one hour at a temperature from 60 to 65 degrees - Dorado, M.P.; Ballesteros, J.M.A, Gomes, J.; Jimenez, F.J.L., Testing Waste Olive Oil Methyl Ester as a Fuel a Diesel Engine, Energy & Fuels 2003, .17, 1560-1565.
The production of biodiesel with ethanol presents a rather different scenario, because commercial ethanol has 0.557% water and, therefore, it is necessary to use dry ethanol with 99.98% alcohol or more - Ferrari, R.A.; Oliveira, V.S.; Scabio, A. Biodiesel de soja- taxa de conversdo em esteres etilicos, caracterizaςdo fisico-quimica e consumo em gerador de energia. Quim.Nova, vol 28 n0 1, 19-23,2005.
Reaction stoichiometry points to a molar ratio of 6 to 1 ethanol to vegetable oil or fat, that is, twice the stoichiometry to be able to displace the equilibrium towards products - Freedman, B.; Pryde, E.H.; Mounts, T.L., Variables Affecting the Yields of Fatty Esters from Transesterified vegetable Oils, JAOCS,vol61 n 10 1984. The solubility of NaOH in ethanol is much harder to achieve than in methanol, because the formation of sodium or potassium ethoxide is more difficult. The transesterification reaction is carried out at around 50 degrees Celsius to minimize the formation of soap, with a reaction time of around one hour using 1% catalyst in relation to the vegetable oil mass - Zhou, Weiyang; Konar, S. K., Boocock, G.B. Ethyl Esters from the Single-Phase Base-catalyzed Ethanolysis of Vegetable Oils., JAOCS,vol80,n4 2003.
As the pKa of ethanol is 15.9 and that of water is 15.7, hydrolysis is preferred with the consequent formation of soap. This reaction is not complete, having reasonable percentages of mono-, di- and even triglycerides, the interaction between the mono- and diglyceride soaps and water, plus glycerine, and forms a stable microemulsion that will prevent spontaneous settling of glycerine. Obtaining ethyl biodiesel depends on the purity of the esters and, therefore, the settling of glycerine on an industrial scale can be obtained by using continuous centrifuges or acidification of the means to transform the soaps into free acids, breaking the microemulsion and with consequent settling of glycerine. In these processes in both cases there is a need for strong acid washing and subsequent drying of the biodiesel. The yield from this process is lower than 95% and the final product does not meet the standards required by National Petroleum Agency Resolution n0 42 (ANP 42) dated September 15, 2003, and international standards (EN 14214:2003), mainly related to water content, mono-, di- and tri-glycerides, free and linked glycerol content, viscosity, appearance, carbon residue, corrosion resistance to copper, density and others.
Patent of invention n0 PI0105888-6 describes a process consisting of promoting a transesterification reaction wherein the seeds themselves react with dry ethanol in the presence of an alkaline catalyst to generate ethyl esters that will later be separated by settling and neutralized to serve as fuel for diesel engines, co-solvents for mixtures of diesel and gasoline with dry or hydrated ethanol and as solid fractions that can be used as fertilizer in animal fodder and as raw material for the production of ethanol. However, this patent does not include the catalysts that are the subject matter of this present patent.
Patent of invention n0 PI0301183-6 discloses a method for producing ethyl ester from fatty acids and equipment for carrying it out, designed to enable the technical and economic production of biodiesel including compositions of saturated and unsaturated fatty acids at least one of which is of vegetable and animal origin with at least one C1 to C5 chained alcohol preferably C2H5OH in the presence of a catalyst or co-catalyst that can be acidic, enzymatic, alkaline or lipase, preferably alkaline. The method also includes a pump(5) having the function of suction, stirring and injection, which method of transesterification of said mixture occurs internally therein, being injected under high pressure into a spraying nozzle 30 located internally in a reactor(3) the already transesterificated mixture internally in the pump(5) and injected into the spraying nozzle 30 when going from a high pressure environment to a lower pressure environment immediately separates into phases, one bottom phase containing glycerine and a top one containing a monoester in this process the alcohol performs the extra function of atomizing liquid of the fatty acids. Said method enables the production of esters having a high conversion rate in an extremely short time. However, this patent does not include the catalysts that are the subject matter of this present application.
Patent of invention n0 PI0404243-3 discloses a continuous method for producing biodiesel which was developed to produce monoesters of fatty acids (biodiesel) on a continuous basis having a higher quality international standard from semi- refined vegetable oil and dry alcohol by a method of transesterification in characteristic reactors with continuous separation of the residual alcohol by evaporation and the glycerine (obtained as reaction byproduct) through centrifuges also used in the washing and final purification of the biodiesel. This patent includes a continuous method that involves centrifuges and reactors, but bears no claim to protect the catalysts in question. Therefore, it would be useful to develop a method of producing biodiesel (alkyl esters) with catalysts capable of producing ethyl biodiesel with a high degree of purity over 99%, without the drawbacks of the conventional catalysts.
BRIEF DESCRIPTION OF THE INVENTION The present invention refers to a method of obtaining methyl or ethyl biodiesel and other alkyl esters, by the transesterification reaction of vegetable oils and/or animal fats, catalyzed by modified strong base, which does not contain metallic ions in its structure. Therefore, they do not form soap or emulsion, either in homogeneous or heterogeneous form, and produce esters with a high yield in a shorter time than the traditional methods.
It is important to emphasize that the method of this present invention can use dry ethanol replacing methanol without any drawback. Accordingly, ethyl biodiesel is obtained, without the need for petroleum derivatives, rendering it even more environmentally friendly.
DETAILED DESCRIPTION OF THE INVENTION The present invention offers a solution for the catalytic problems involved in the production of biodiesel, as it does not contain metallic ions in its chemical composition, it does not form soap in the method of transesterification of vegetable oils and animal fats. Accordingly, the concentration of the catalyst is maintained at levels near to that added at the start of the transesterification reaction. For this reason, the alkyl esters yield is above 99%, even using a temperature lower than the boiling point of alcohols, with spontaneous settling of glycerine, dispensing with the use of centrifuges. Following the Federal Government's decision to replace up to 5% of diesel oil by methyl or ethyl biodiesel, the need has arisen to produce 800 million liters per year to supply 2% of the domestic demand. So, an efficient method of transesterification is required, having a yield above 99% - Yolanda, Cadernos de Altos estudos e Inclusao Social. Brazil is the largest producer of ethanol, but imports methanol which besides being toxic, has a more complex industrial plant compared to ethanol plants. In view of the government's social inclusion goals, family farming will increase in the production process of biodiesel, not least because ethanol is a renewable and non-toxic fuel - Pacheco, F. Biodiesel: Sera o combustivel do futuro? Conjuntura e planejamento, Salvador,Ba.nl22,p.26-31 July 2004.
Along these lines, the new, non-conventional catalysts were developed. They have not yet been described in literature for this purpose, using strong bases whose counter-ions substitute sodium or potassium maintaining the OH" or alkoxides (alcoholates) available for catalytic action. These bases are guanidine hydroxides with pKa of around 13.6 - 13.9 and hydroxide and quaternary ammonium hydroxide and that are totally ionic and equivalent to sodium or potassium hydroxide in terms of basicity. In the production process, the system has a similar behavior to that of methanol or ethanol, obtaining the guanidine hydroxides and hydroxides and quaternary ammonium alkoxides, is from the salts of the same in an alcoholic means in the solutilization process of sodium or potassium hydroxide, resulting in a complete transfer reaction of the guanidine and quaternary ammonium cations. The title of this invention is thus justified, as the true catalyst is the OH" or alkoxides, causing the precipitation of sodium or potassium salts. This reaction is preferably conducted by stirring and at temperatures lower tan the boiling point of the alcohols used and in the approximate time of 10 to 50 minutes, preferably between 15 and 30 minutes, depending on the quantity and type of alcohol and the form and quantity of the salt used in the transesterification reaction. It is important to emphasize that the reaction can be used at temperatures above the boiling point of the alcohols.
The transesterification reaction of vegetable oil or animal fat is conducted with the catalysts, preferably using 1% or more, depending on the reaction conditions, dissolved in methanol or ethanol in homogeneous or solvate form, when the form is used, that will generate the methoxide or ethoxide, with the respective guanidine or quaternary ammonium counter-ions, in a sufficient quantity to produce the high-yield esters, preferably at a temperature below the boiling point of the alcohols (and may also be above). In other words, a yield above 99%, confirmed by proton magnetic resonance; infra-red spectroscopy; gaseous chromatography; high performance liquid chromatography (HPLC), and reaction time under thirty-five minutes (included here as an example). The glycerine is spontaneously settled and the excess alcohol is withdrawn from the ester phase, the resulting esters are neutralized and purified.
The method proposed herein provides for the use of derivates of guanidine salts or quaternary ammonium salts transformed into the respective guanidine hydroxides and ammonium quaternary hydroxides or alkoxides (alcoholates), wherein the chemical family of guanidines is: non-substituted guanidine and substituted guanidines, such as:
N- alkyl guanidine, N5N' -de alkyl guanidine;
N,N - dialkyl guanidine; N,N' ,N" - trialkyl guanidine;
N, N, N'- trialkyl guanidine;
N, N, N', N tetraalkyl guanidine;
N, N, N', N tetraalkyl guanidine;
N, N, N', N , N" pentaalkyl guanidine; And the substituted quaternary ammonium salts, wherein Ri ; R2, R3, R4, may represent the alkyl or aryl groups, or another chemical function, linked to the counter-ions, chlorate, bromate, sulphate, carbonate, phosphate or any other negative ions. The transesterification of the vegetable oils and fats with guanidine hydroxide and quaternary ammonium hydroxide and alkoxide (alcoholate) strong bases, have the following advantages over the state of the art:
The catalysts referred to herein do not produce soap in the process, because they do not have metallic cations arid have a greater tolerance to the quantity of water in the process, allowing the use of alcohol with a higher water content;
They are more efficient and have a yield above 99%; Since the glycerine is spontaneously settled, it is not necessary to use centrifuges in the process, thus reducing the cost of implantation of plants in the different scales;
Their characteristics enable the process to be continuous;
The new catalysts have no restrictions to the use of vegetable oils or fats;
The purification of esters requires only the recovery of alcohol and neutralization of the catalyst excess and subsequent purification, thus producing a biodiesel in conformity to the standards laid down in the ANP resolution and international standards described above;
When catalysts are used in heterogeneous form, the process is simplified because the catalyst does not contaminate the product, therefore, it requires no neutralization and final purification.
The advantages of these new catalysts are the ethyl or methyl route;
Industrial production of these new catalysts is based on low-cost raw materials which today are produced on a large scale in the country, namely guanidine salts from urea and ammonium nitrate and quaternary salts from ammonia and alkyl halates;
The new catalysts can be recovered in the process when used in heterogeneous form; The glycerine obtained by this process presents crystalline form with low impurity content;
The new catalysts are active when anchored or linked to polymers or resins, producing heterogeneous catalysis in continuous reactors or in batch.
The basic quaternary ammonium resins are already produced on a commercial scale for various purposes. However, with such a. structure, they present practically no catalyst activity in the transesterification reaction. Yet by using the principle of nanotechnology for structural change, these resins or basic polymers will have a high catalytic activity in the transesterification reaction, present common advantages of heterogeneous catalysis.
The catalysts that are the subject matter of this present invention can be used for fast preparation of small samples of methyl fatty esters from oils and fats, to determine their fatty acid composition. Therefore, since these catalysts contain no metals in their chemical composition, they do not cause isomerization of the double links and have a series of advantages over the official American method (AOCS Ce-266) that uses 20% boron trifluoride dissolved in methanol.
The above description of the present invention is set forth for purposes of illustration and description.
Additionally, the description is not designed to limit the invention to the form disclosed herein. Consequently, variations and changes compatible with the teachings above and the capability or knowledge of the relevant art, are within the scope of this present invention.
The embodiments described above are intended to provide a better explanation of the known modes for carrying out this invention in order to allow a person skilled in the art to use the invention in reference, or other embodiments and with various changes necessary for specific applications or uses of this present invention. The present invention is designed to include all modifications and variations thereof, within the scope described in the specification.

Claims

1. METHOD FOR TRANSESTERIFICATION OF VEGETABLE OILS AND ANIMAL FATS5 CATALYZED BY MODIFIED STRONG BASE FOR THE PRODUCTION OF ALKYL ESTERS characterized by providing for the use of guanidine salt derivatives or quatenary ammonium salts transformed into the respective hydroxides and alcoxides (alcoholates), the substituted quaternary ammonium salts, wherein Ri t R2, Rβ, R4, may represent alkyl or aryl groups, or any other chemical groups, linked to the counter-ions: chlorate, bromate, sulphate, carbonate, phosphate or any other negative ions.
2. METHOD FOR TRANSESTERIFICATION OF VEGETABLE OILS AND ANIMAL FATS, according to claim 1, characterized by the fact that the guanidine chemical family encompasses non-substituted guanidine and substituted guanidine.
3. METHOD FOR TRANSESTERIFICATION OF VEGETABLE OILS AND ANIMAL FATS, according to claim 2, characterized by the fact that the substituted guanidines may be selected from among: N-alkyl guanidine, N,N'-de alkyl guanidine; N,N - dialkyl guanidine; N,N',N" - trialkyl guanidine; N, N, N'- trialkyl guanidine; N5 N, N', N tetraalkyl guanidine; N5 N, N',N' tetraalkyl guanidine; and N, N, N', N ' N" pentaalkyl guanidine.
4. METHOD FOR TRANSESTERIFICATION
OF VEGETABLE OILS AND ANIMAL FATS5 according to all the claims above, characterized by providing for guanidine hydroxides or ammonium quaternary hydroxide or alcoxides (alcoholates) in homogeneous or heterogeneous form, anchored to polymers or resins.
5. METHOD FOR TRANSESTERIFIC ATION
OF VEGETABLE OILS AND ANIMAL FATS, according to claims 1 and 4, characterized by providing for the use of guanidine hydroxides or ammonium quaternary hydroxides and alcoxides for vegetable oils or animal fats, having any acidity or water content.
6. METHOD FOR TRANSESTERIFICATION OF VEGETABLE OILS AND ANIMAL FATS, according to all the claims above, characterized by the fact that it may be applied in any industrial scale, from mini-pilot plants to semi-industrial or industrial plants, with any kind of oil or fat, in any reaction time, any temperature and any kind of alcohol and in any proportion, capable of carrying out the process described in the claims above.
7. METHOD FOR TRANSESTERIFICATION OF VEGETABLE OILS AND ANIMAL FATS according to all the claims above, characterized by the fact that it may be applied for rapid preparation of small samples of vegetable oils or animal fats in chromatographic analyses for the production of methyl esters and the determination of their composition in fatty acids.
8. METHOD FOR TRANSESTERIFICATION OF VEGETABLE OILS AND ANIMAL FATS, according to claim 1, characterized by the fact that the preferred salt is guanidine carbonate because it performs best in the transesterification reaction due to the generation of two catalysts: guanidine hydroxide and sodium carbonate or potassium.
9. METHOD FOR TRANSESTERIFICATION OF VEGETABLE OILS AND ANIMAL FATS5 according to all the claims above, characterized by the fact that tetramethylammonium is the preferred salt for the formation of hydroxide or alcoxide (alcoholate) by having a more suitable molecular weight and volume to act as catalyst in the transesterification of vegetable oils and fats.
PCT/BR2007/000132 2006-06-14 2007-05-30 Method for transesterification of vegetable oils and animal fats, catalyzed by modified strong base for the production of alkyl esters WO2007143803A1 (en)

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