WO2015188233A1 - A process for the preparation of fatty acid alkyl esters - Google Patents
A process for the preparation of fatty acid alkyl esters Download PDFInfo
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- WO2015188233A1 WO2015188233A1 PCT/AU2015/050324 AU2015050324W WO2015188233A1 WO 2015188233 A1 WO2015188233 A1 WO 2015188233A1 AU 2015050324 W AU2015050324 W AU 2015050324W WO 2015188233 A1 WO2015188233 A1 WO 2015188233A1
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- fatty acid
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- alkyl esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/02—Preparation of carboxylic acid esters by interreacting ester groups, i.e. transesterification
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/003—Esters of saturated alcohols having the esterified hydroxy group bound to an acyclic carbon atom
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- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/02—Refining fats or fatty oils by chemical reaction
- C11B3/04—Refining fats or fatty oils by chemical reaction with acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/02—Refining fats or fatty oils by chemical reaction
- C11B3/08—Refining fats or fatty oils by chemical reaction with oxidising agents
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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
- 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
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- 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
- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0461—Fractions defined by their origin
- C10L2200/0469—Renewables or materials of biological origin
- C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
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- 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 broadly relates to a process for preparing fatty acid alkyl esters from fat-containing feedstocks.
- Fatty acid alkyl esters find use in a number of industries, for example mining (as collectors), agriculture (as adjuvants) and energy (biodiesel).
- Fatty acid alkyl esters are typically prepared from feedstocks including vegetable oil, animal fat and used cooking oil by converting the constituent fatty acid triglycerides and any free fatty acids.
- the esters are short-chain esters such as methyl esters.
- the present inventors have surprisingly discovered that fat-containing feedstocks having a broad range of free fatty acid contents can be efficiently esterified and transesterified under aqueous conditions by use of selected sulfonated fatty acid derivatives as catalysts.
- the present invention provides a process for preparing fatty acid alkyl esters comprising:
- n is an integer between 0 and 7
- n is an integer between 0 and 17,
- R is hydrogen or methyl
- R 1 is hydrogen or C C 6 alkyl
- step ii) allowing the mixture in step i) to react so as to produce a mixture comprising fatty acid alkyl esters
- the fat-containing feedstock may comprise at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95%, by weight of free fatty acids.
- the fat-containing feedstock may be a triglyceride-containing feedstock, for example a triglyceride-containing oil.
- the alcohol may be present in the mixture in an amount between about 10% and about 60%, or in an amount between about 15% and about 60%, or in an amount between about 15% and about 40%, or in an amount between about 15% and about 30%, by weight.
- the sulfonated fatty acid derivative may be present in the mixture in an amount between about 0.05% and about 5%, or in an amount between about 0.5% and about 2.5%, or in an amount between about 0.1 % and about 5%, or in an amount between about 0.1 % and 2%, by weight.
- the mixture in step i) may further comprise an acid.
- the acid may be present in the mixture in an amount between about 0.5% and about 5%, or in an amount between about 0.5% and about 3%, or in an amount between about 0.5% and about 2.5%, or in an amount between about 1 % and about 2%, by weight.
- the mixture in step i) may further comprise water.
- Water may be present in an amount of up to about 10%, or in an amount of up to about 5%, or in an amount of up to about 2%, or in an amount of up to about 1 %, by weight. In some embodiments water may be present in an amount between about 0.5% and about 5%, or in an amount between about 1 % and about 5%, or in an amount between about 1 % and about 2%, by weight.
- the fatty acid alkyl esters may be C C 12 alkyl esters or mixtures thereof. In some embodiments the fatty acid alkyl esters are Ci-C 6 alkyl esters, or mixtures thereof. In one embodiment the fatty acid alkyl esters are methyl esters.
- the alcohol may be a CrC ⁇ alcohol, or a mixture thereof. In some embodiments the alcohol is a C C 6 alcohol, or a mixture thereof. In one embodiment the alcohol is methanol.
- the acid may be a strong acid, for example, sulfuric acid.
- Step ii) may comprise heating the mixture.
- the process is performed at atmospheric pressure.
- m may be an integer between 6 and 17, or an integer between 8 and 17, or an integer between 10 and 17 or an integer between 1 1 and 15.
- n may be an integer between 0 and 6, 0 and 4, or 0 and 3. In one embodiment n is 0, 1 or 2. In another embodiment n is 0 or 1 .
- R 1 may be Ci-C 6 alkyl. In one embodiment R 1 is methyl.
- R may be methyl
- n is 0, 1 or 2 and R and R 1 are methyl.
- n is 0 and R and R 1 are methyl.
- n is 0 and R and R 1 are methyl.
- the mixture in step i) may comprise a plurality of sulfonated fatty acid derivatives of the formula (I).
- the mixture comprises a plurality of C 14 -C 18 a-sulfonated fatty acid methyl esters.
- the sulfonated fatty acid derivative is Ci 6 - i 8 alkylCH(S0 3 H)COOCH 3 or a salt thereof, for example a-MES.
- the process may further comprise pre-treatment of the fat-containing feedstock used in step i), for example the fat-containing feedstock may be bleached and/or degummed prior to use in step i).
- step iv) forming a mixture comprising the fatty acid alkyl esters obtained following step iii), unreacted triglycerides or unreacted free fatty acids, an alcohol and a sulfonated fatty acid derivative of the formula (I) as defined above; v) allowing the mixture in step iv) to react such that at least some of the triglycerides or at least some of the free fatty acids are converted into fatty acid alkyl esters;
- the alcohol may be an anhydrous alcohol and the mixture in step iv) may further comprise an acid.
- Step v) may comprise heating the mixture.
- step vii) treating the fatty acid alkyl esters obtained following step iii) or step vi) with a base so as to neutralise residual acid.
- the process further comprises:
- the fatty acid alkyl esters obtained following steps iii), vi) or ix) may be suitable for use as biodiesel with, or without further purification.
- the process may further comprise distilling the fatty acid alkyl esters obtained following steps iii), vi) or ix).
- fatty acid alkyl esters isolated in one or more of steps iii), vi) or ix) may not be subjected to further purification.
- the present invention provides fatty acid alkyl esters whenever prepared by the process of the first aspect.
- the present invention provides use of fatty acid alkyl esters of the second aspect as biodiesel.
- an element means one element or more than one element.
- C C 12 alcohols include, but are not limited to, methanol, ethanol, 1 - propanol, 2-propanol, isopropanol, 1 -butanol, 2-butanol, isobutanol, ferf-butanol, isopentanol, 1 -pentanol, 2-pentanol, 2-methyl-1 -pentanol, 4-methyl-1 -pentanol, 3- methyl-2-pentanol, 1 -hexanol, 2-hexanol, 3-hexanol, 1 -heptanol, 3,4-dimethyl-1 - heptanol, 2-octanol, 1 -decanol, 3-d
- CrC 12 alkyl and C C 6 alkyl are taken to mean straight chain or branched chain monovalent saturated hydrocarbon groups having between 1 and 12 or 1 and 6 carbon atoms.
- Examples of C 1 -C 12 alkyl groups include, but are not limited to, methyl, ethyl, 1 -propyl, isopropyl, 1 -butyl, 2-butyl, isobutyl, ferf-butyl, amyl, 1 ,2-dimethylpropyl, 1 ,1 -dimethylpropyl, pentyl, isopentyl, hexyl, 4- methylpentyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 3,3- dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 1 ,2,2-trimethylpropyl, 1
- the present invention provides a process for preparing fatty acid alkyl esters comprising or consisting essentially of: i) forming a mixture comprising a fat-containing feedstock, an alcohol and a sulfonated fatty acid derivative of the formula (I), or a salt thereof:
- n is an integer between 0 and 7
- n is an integer between 0 and 17,
- R is hydrogen or methyl
- R 1 is hydrogen or C C 6 alkyl
- step ii) allowing the mixture in step i) to react so as to produce a mixture comprising fatty acid alkyl esters
- the present invention is predicated on the surprising finding by the inventors that fat- containing feedstocks having a broad range of free fatty acid content can be efficiently esterified and transesterified under aqueous conditions by use of selected sulfonated fatty acid derivatives as catalysts. With some feedstocks it is possible to achieve at least 90% conversion in a single reaction step. Current processes used for preparing fatty acid alkyl esters at atmospheric pressure typically only tolerate free fatty acid levels of up to about 30% in the feedstock. Where the free fatty acid content rises above about 30% water generated from esterification retards the rate of further esterification. In addition, little if any transesterification occurs.
- fatty acid alkyl esters having acceptable acid values and triglyceride levels can be obtained in less steps and in less time compared to when the catalyst is absent, and in some embodiments, in a single reaction step.
- the inventors postulate that the catalytic activity of the sulfonated fatty acid derivatives of formula (I) are not inhibited by the presence of water, meaning that the catalyst performs effectively in aqueous conditions. It was also surprisingly discovered that the presence of water is actually beneficial because it reduces colouration of the oil during the process.
- the process of the present invention enables the use of a much wider range of fat-containing feedstocks for preparing fatty acid alkyl esters compared to prior art processes, including very low quality, cheap feedstocks containing high amounts of free fatty acids (for example palm sludge oil and grease trap waste).
- Non-limiting examples of fat-containing feedstocks suitable for use in the present invention include palm oil sludge, vegetable oils (for example corn oil, peanut oil, soybean oil, cotton seed oil, rice bran oil, jatropha oil, sunflower oil, coconut oil, rapeseed oil, linseed oil, palm seed oil, canola oil and the like), animal fats (for example tallow and lard), waste cooking oil, grease trap waste, fish oil and microbial oil (for example yeast or algal oil).
- vegetable oils for example corn oil, peanut oil, soybean oil, cotton seed oil, rice bran oil, jatropha oil, sunflower oil, coconut oil, rapeseed oil, linseed oil, palm seed oil, canola oil and the like
- animal fats for example tallow and lard
- waste cooking oil for example tallow and lard
- waste cooking oil for example yeast or algal oil
- the fat-containing feedstock comprises at least 20%, or at least 25%, or at least 30%, or at least 35%, or at least 40%, or at least 45%, or at least 50%, or at least 55%, or at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 95%, or at least 99%, by weight of free fatty acids.
- the fat- containing feedstock is a triglyceride-containing feedstock, for example a triglyceride- containing oil.
- the triglyceride-containing feedstock may comprise free fatty acids in any of the amounts noted above.
- the fat-containing feedstock used in the process may be pretreated.
- Pre-treatment may be appropriate where the feedstock is contaminated with gums, odourous or intractable matter and/or where the feedstock is very dark in colour.
- Grease trap waste and palm oil sludge are examples of feedstocks that may require pre- treatment.
- pre-treatment involves bleaching and/or degumming. Degumming may be achieved by, for example, treating the feedstock with phosphoric acid and water. Bleaching may be carried out by, for example, treating the feedstock with chlorite. Those skilled in the art will be familiar with alternative methods for degumming and bleaching fat-containing feedstocks.
- Fatty acid alkyl esters prepared in accordance with the process of the invention may be Ci-Ci 2 alkyl esters or mixtures thereof.
- the fatty acid alkyl esters are Ci-C 6 alkyl esters for example, methyl, ethyl, propyl, isopropyl, butyl, f-butyl etc. esters or mixtures thereof, such as for example fusel alcohol esters.
- fatty acid alkyl esters prepared in accordance with the process are methyl or ethyl esters.
- the alcohol used in the process of the present invention is dependent on the type of fatty acid alkyl esters that are to be prepared. For example, if it is desired to prepare fatty acid methyl esters then the alcohol will be methanol. In some embodiments the alcohol is a C 1 -C 12 alcohol or a mixture thereof. In other embodiments the alcohol is a C C 6 alcohol, for example, methanol, ethanol, propanol, isopropanol, butanol, f-butanol, pentanol etc., or a mixture thereof, such as for example fusel alcohol. Typically, the alcohol is methanol or ethanol.
- the process of the present invention does not require anhydrous conditions, and therefore permits the use of aqueous alcohols in step i), such as fusel alcohol or waste ethanol. Because aqueous alcohols are considerably cheaper than anhydrous alcohols the process of the present invention offers significant costs savings compared to known processes that require careful control over the amount of water present during esterification.
- the inventors have found that low-cost mixed aqueous alcohols such as fusel alcohol are suitable for use in the process. It has also been found that the alcohol can be recovered at the completion of the process and then re-used, in some instances without purification. Alternatively, the recovered alcohol can be distilled until it reaches a concentration of about 80% and then re-used in the process.
- the alcohol may be present in the mixture in step i) in an amount between about 10% and about 60%, or in an amount between about 15% and about 60%, or in an amount between about 15% and about 40%, or in an amount between about 20% and about 40%, or in an amount between about 20% and about 30% by weight.
- the weight ratio of fat-containing feedstock to alcohol may be in the range of about 2:1 to about 10:1 , preferably about 5:1 .
- the process may be performed using anhydrous alcohols in step i), however as will be appreciated by those skilled in the art this will add considerably to the cost of performing the process thereby reducing its economic viability.
- the water may be present in an amount of up to about 10%, or in an amount of up to about 8%, or in an amount of up to about 6%, or in an amount of up to about 5%, or in an amount of up to about 2%, or in an amount of up to about 1 %, by weight. In some embodiments water is present in an amount between about 0.05% and about 10%, or in an amount between about 0.05% and about 5%, or in an amount between about 0.5% and about 3%, or in an amount between about 1 % and about 6%, or in an amount between about 1 % and about 5%, or in an amount between about 1% and about 3%, or in an amount between about 1 % and about 2%, by weight.
- step i) water may be introduced into the mixture as part of an aqueous alcohol mixture and/or may be added to the mixture neat.
- the acid may be present in the mixture in an amount between about 0.05% and about 5%, or in an amount between about 0.5% and about 5%, or in an amount between about 0.5% and about 3%, or in an amount between about 0.5% and about 2.5%, or in an amount between about 1 % and about 2%, by weight.
- acids that are suitable for use in the process, for example hydroiodic acid, hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid and the like.
- the acid is a strong acid.
- the acid is sulfuric acid.
- the sulfonated fatty acid derivative of the formula (I) has the following structure:
- n is an integer between 0 and 7
- m is an integer between 0 and 17
- R is hydrogen or methyl
- R 1 is hydrogen or C C 6 alkyl, or a salt thereof.
- Exemplary salts of the sulfonated fatty acid derivatives include alkali metal salts (i.e lithium, potassium, sodium and caesium) and ammonium salts. Other suitable salts will be readily apparent to those skilled in the art.
- the sulfonated fatty acid derivatives are present in salt form, for example as sodium salts.
- Sulfonated fatty acid derivatives of the formula (I) may be prepared by methods known to those skilled in the art, for example by a-sulfonation of the corresponding fatty acid derivatives. Sulfonated fatty acid derivatives of the formula (I) are also commercially available.
- the catalyst is recovered when the process is completed.
- the sulfonated fatty acid ester derivative of the formula (I) or salt thereof may be present in the mixture in steps i) and iv) in an amount between about 0.05% and about 5%, or in an amount between about 0.2% and about 5%, or in an amount between about 0.5% and about 5%, or in an amount between about 0.5% and about 3%, or in an amount between about 0.5% and about 2%, by weight.
- the sulfonated fatty acid ester derivative of the formula (I) or salt thereof may be present in the mixture in an amount up to about 5%, 4%, 3%, 2% or 1 %, by weight.
- Step ii) may comprise heating the mixture so as to increase the rate of reaction.
- the mixture is heated at the boiling point of the alcohol or mixture of alcohols.
- the mixture is heated at a temperature that is about 5 to 10 °C below the boiling point of the alcohol or mixture of alcohols.
- step ii) may comprise heating the mixture at a temperature between about 40 and 100 °C, or at a temperature between about 50 and 90 °C.
- Step ii) may comprise heating the mixture for a period of time between about 1 hour and about 50 hours, or between about 1 hour and about 30 hours, or between about 5 hours and about 20 hours, or between about 4 hours and about 24 hours, or between about 4 hours and about 22 hours, or between about 4 hours and about 30 hours, or between about 1 hour and about 5 hours, or between about 1 hour and about 4 hours, or between about 1 hour and about 3 hours, or between about 1 hour and about 2 hours, or between about 12 hours and about 24 hours, or between about 12 hours and about 30 hours.
- the fatty acid alkyl esters obtained in step iii) may be recycled through the process.
- this recycling serves to convert at least some of the unreacted triglycerides and/or at least some of the unreacted free fatty acids present with the fatty acid alkyl esters obtained following step iii), into fatty acid alkyl esters.
- the recycling serves to enrich the purity of the fatty acid alkyl esters.
- the process may further comprise:
- step iv) forming a mixture comprising the fatty acid alkyl esters obtained following step iii), unreacted triglycerides or unreacted free fatty acids, an alcohol and a sulfonated fatty acid derivative of the formula (I) as defined above;
- step iv) allowing the mixture in step iv) to react such that at least some of the triglycerides or at least some of the free fatty acids are converted into fatty acid alkyl esters;
- the mixture in step iv) may further comprise an acid as described above for step i).
- Step v) may comprise heating the mixture as described above for step ii).
- step v) is performed at atmospheric pressure.
- the amounts of sulfonated fatty acid derivative of the formula (I), acid and alcohol may be as defined above for step i).
- the alcohol used in step iv) is anhydrous so as to optimise the conversion of triglycerides and/or free fatty acids to fatty acid alkyl esters.
- the mixture in step iv) may further comprise water as described above for step i).
- the fatty acid alkyl esters obtained following steps iii) and vi) are treated with a base (such as for example methoxide) to neutralise residual acid.
- a base such as for example methoxide
- this step also reduces the water content of the fatty acid alkyl esters, which is advantageous where a base-catalysed transesterification step is to be performed.
- the process further comprises:
- Step viii) may be performed by conventional methods known to those skilled in the art, for example treatment with an alcoholate anion in an alcohol solvent, for example sodium methoxide in methanol.
- an alcoholate anion in an alcohol solvent for example sodium methoxide in methanol.
- the process may comprise steps iv) to vi) where the feedstock comprises a significant amount of intractable foreign matter that must be removed.
- steps i) to iii) produce a mixture that readily separates into a top phase, a small intermediate sludge phase and a bottom aqueous phase.
- the aqueous phase may be retained for subsequent re-use.
- the sludge phase containing the intractable foreign matter is disposed or used for composting.
- the desirable top phase can then be subjected to steps iv) to vi).
- the top phase comprising the esters can be used without further purification or washed with water.
- the top phase may be subjected to steps viii) and ix) using minimal amounts of alkaline catalyst and methanol to produce very high purity esters.
- Isolation of the fatty acid alkyl esters may be performed by methods known to those skilled in the art.
- an oil layer comprising the fatty acid alkyl esters is separated from an aqueous layer after completion and washed with water.
- the oil may then be dried under vacuum so as to remove low molecular weight volatiles, such as alcohols, ethers, aldehydes and/or ketones.
- steps i) to iii) utilising feedstocks with high free fatty acid content provides fatty acid alkyl esters at conversion rates above about 95%. Accordingly, steps iv) to ix) may only be required where the feedstock comprises very high amounts of free fatty acids (for example greater than 80%) and/or where the intended use requires very high purity fatty acid alkyl esters, such as for example in biodiesel applications.
- the Australian Biodiesel Standard requires an ester content of at least 96.5% (based on the EU Standard: prEN 14214).
- Fatty acid alkyl esters isolated in steps iii) and/or vi) may have a purity of at least about 60%, or at least about 70%, or at least about 80%, or at least about 85%, or at least about 90%, or at least about 95%, or a purity in the range of about 80% and 85%, 85% and 90%, 90% and 99%, or 95% and 99%.
- the purity of the fatty acid alkyl esters obtained will be dependent on the quality of the fat-containing feedstock.
- Fatty acid alkyl esters isolated in steps iii), step vi) or step ix) may have an acid value in the range of about 0.1 and 10 mg KOH / g, or in the range of about 0.1 and 5 mg KOH / g, or in the range of about 0.1 and 2 mg KOH / g of oil.
- Fatty acid alkyl esters find use in, or are precursors to compounds used in, many industrial applications for example in graffiti removal products, as adjuvants for herbicides, as collectors in the mining industry and in biodiesel applications.
- Fatty acid alkyl ester compositions will require different levels of purity depending on their intended use. For example, strict limits are set on the amount of free fatty acids present in fatty acid alkyl ester compositions intended for use in biodiesel applications. In contrast, the presence of up to 20% of free fatty acids in fatty acid alkyl ester compositions intended for use as collectors is desirable.
- the process of the present invention is sufficiently flexible so as to allow efficient and cost effective preparation of fatty acid alkyl esters that are suitable for use across a range of different applications.
- the process may be used to prepare fatty acid alkyl esters suitable for use as collectors from grease trap waste by performing steps i), ii) and iii) (and optionally steps (iv), (v) and (vi)) using a cheap aqueous alcohol, such as fusel alcohol or waste ethanol.
- a cheap aqueous alcohol such as fusel alcohol or waste ethanol.
- the extent of esterification and transesterification is such that no further purification of the fatty acid alkyl esters is required prior to use. If it is desried to provide higher purity fatty acid alkyl esters, steps i) to iii) can be followed by steps iv) to vi).
- the process may be used to prepare fatty acid alkyl esters suitable for use as biodiesel from grease trap oil by performing steps i), ii) and iii) using aqueous methanol and distilling the resultant fatty acid alkyl esters obtained.
- the distilled esters may be used as biodiesel.
- Feedstocks of this type include high purity acid oils derived from purification of edible vegetable oils.
- the process may be used to prepare fatty acid alkyl esters suitable for use as biodiesel from palm oil sludge by performing steps i) to iii), vii), viii) and ix). No further purification is required.
- step viii) is preferably performed by base-catalysed transesterification using methoxide and methanol. Base- catalysed transesterification calls for the use of anhydrous alcohols. Because considerable transesterification occurs in step ii) of the process, the amount of anhydrous methanol required in order to convert any remaining triglycerides to fatty acid alkyl esters is much less than known processes, thereby further minimising costs associated with performing the process.
- the process may be used to prepare fatty acid alkyl esters suitable for use as biodiesel from palm sludge oil utilising steps i) to ix).
- the catalyst used was a mixture of C 14 -C 18 a-sulfonated fatty acid methyl esters.
- the upper layer comprising the esters was separated. To this upper layer was added 53.7 grams of 20% sulfuric acid in methanol and 43.0 grams of dry methanol. The mixture in the flask was heated to a temperature of 71 °C for a period of
- Example 3 Conventional transeste ification of the product obtained in Example 2
- Example 2 The product from Example 2 was subjected to a neutralisation step followed by a conventional transesterification as follows.
- Example 4 Conventional transesterification of the product obtained in Example 1
- Example 1 The product from Example 1 was subjected to a neutralisation step followed by a conventional transesterification as follows.
- Example 5 Preparation of fatty acid alkyl esters from grease trap oil having high free fatty acid content utilising a catalyst of formula (I) and low cost mixed aqueous alcohols
- Example 6 Preparation of fatty acid alkyl esters from grease trap oil having high free fatty acid content in the absence of a catalyst of formula (I) and low cost mixed aqueous alcohols
- Example 7 Preparation of fatty acid alkyl esters from palm sludge oil having medium free fatty acid content utilising a catalyst of formula (I) and low cost mixed aqueous alcohols
- the upper layer comprising the esters was separated. To this upper layer was added 50.0 grams of 20% sulfuric acid in methanol, 60 grams of dry methanol, 5.0 grams of catalyst and 5.0 grams of water. The mixture was heated to a temperature of 77 °C for a period of 2 hours. The upper layer comprising the esters was bleached with 10.0 grams of sodium chlorite. The recovered product has an acid value of 6.2. Thin layer chromatography analysis of the product shows moderate esters with some triglycerides and low free fatty acids.
Abstract
Description
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Priority Applications (6)
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AU2015274247A AU2015274247B2 (en) | 2014-06-13 | 2015-06-12 | A process for the preparation of fatty acid alkyl esters |
US15/317,232 US10233141B2 (en) | 2014-06-13 | 2015-06-12 | Process for the preparation of fatty acid alkyl esters |
EP15806513.6A EP3154935A4 (en) | 2014-06-13 | 2015-06-12 | A process for the preparation of fatty acid alkyl esters |
JP2017517149A JP2017518377A (en) | 2014-06-13 | 2015-06-12 | Process for preparing fatty acid alkyl esters |
CA2950748A CA2950748A1 (en) | 2014-06-13 | 2015-06-12 | A process for the preparation of fatty acid alkyl esters |
US16/355,458 US20190210953A1 (en) | 2014-06-13 | 2019-03-15 | Process For The Preparation of Fatty Acid Alkyl Esters |
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AU2014902260A AU2014902260A0 (en) | 2014-06-13 | A process for the preparation of fatty acid alkyl esters | |
AU2014902260 | 2014-06-13 |
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US15/317,232 A-371-Of-International US10233141B2 (en) | 2014-06-13 | 2015-06-12 | Process for the preparation of fatty acid alkyl esters |
US16/355,458 Continuation US20190210953A1 (en) | 2014-06-13 | 2019-03-15 | Process For The Preparation of Fatty Acid Alkyl Esters |
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US (2) | US10233141B2 (en) |
EP (1) | EP3154935A4 (en) |
JP (1) | JP2017518377A (en) |
AU (1) | AU2015274247B2 (en) |
CA (1) | CA2950748A1 (en) |
WO (1) | WO2015188233A1 (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US2371284A (en) * | 1945-03-13 | Preparation of sulphated fatty | ||
US3128294A (en) * | 1961-06-09 | 1964-04-07 | Alexander J Stirton | Salts of alpha-sulfonated fatty acid esters |
US3172905A (en) * | 1965-03-09 | Catalytic preparation of esters from tertiary olefins and carboxylic acids | ||
WO2006095134A1 (en) * | 2005-03-11 | 2006-09-14 | The Queen's University Of Belfast | Production of bio-diesel |
CN101343245A (en) * | 2008-08-22 | 2009-01-14 | 江南大学 | Method for preparing fatty acid methyl ester sulphonic salt with low-disodium salt content by using earlier sulfonation and later esterification technique |
EP2316913A1 (en) * | 2009-10-29 | 2011-05-04 | Malaysian Palm Oil Board | A Method Of Converting Free Fatty Acid (FFA) From Oil To Methyl Ester |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2467095A (en) * | 1947-07-08 | 1949-04-12 | Carbide & Carbon Chem Corp | Acylation with enol esters |
-
2015
- 2015-06-12 AU AU2015274247A patent/AU2015274247B2/en not_active Ceased
- 2015-06-12 US US15/317,232 patent/US10233141B2/en not_active Expired - Fee Related
- 2015-06-12 JP JP2017517149A patent/JP2017518377A/en active Pending
- 2015-06-12 WO PCT/AU2015/050324 patent/WO2015188233A1/en active Application Filing
- 2015-06-12 CA CA2950748A patent/CA2950748A1/en not_active Abandoned
- 2015-06-12 EP EP15806513.6A patent/EP3154935A4/en not_active Withdrawn
-
2019
- 2019-03-15 US US16/355,458 patent/US20190210953A1/en not_active Abandoned
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2371284A (en) * | 1945-03-13 | Preparation of sulphated fatty | ||
US3172905A (en) * | 1965-03-09 | Catalytic preparation of esters from tertiary olefins and carboxylic acids | ||
US3128294A (en) * | 1961-06-09 | 1964-04-07 | Alexander J Stirton | Salts of alpha-sulfonated fatty acid esters |
WO2006095134A1 (en) * | 2005-03-11 | 2006-09-14 | The Queen's University Of Belfast | Production of bio-diesel |
CN101343245A (en) * | 2008-08-22 | 2009-01-14 | 江南大学 | Method for preparing fatty acid methyl ester sulphonic salt with low-disodium salt content by using earlier sulfonation and later esterification technique |
EP2316913A1 (en) * | 2009-10-29 | 2011-05-04 | Malaysian Palm Oil Board | A Method Of Converting Free Fatty Acid (FFA) From Oil To Methyl Ester |
Non-Patent Citations (2)
Title |
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HAYYAN A. ET AL.: "Ethanesulfonic acid-based esterification of industrial acidic crude palm oil for biodiesel production", BIORESOURCE TECHNOLOGY, vol. 102, no. 20, 2011, pages 9564 - 9570, XP028290101 * |
See also references of EP3154935A4 * |
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Publication number | Publication date |
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AU2015274247B2 (en) | 2019-02-07 |
US10233141B2 (en) | 2019-03-19 |
EP3154935A4 (en) | 2018-03-07 |
CA2950748A1 (en) | 2015-12-17 |
JP2017518377A (en) | 2017-07-06 |
US20170113996A1 (en) | 2017-04-27 |
EP3154935A1 (en) | 2017-04-19 |
AU2015274247A1 (en) | 2017-01-05 |
US20190210953A1 (en) | 2019-07-11 |
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