WO2018096248A1 - Composition acide pour le traitement d'acides gras - Google Patents
Composition acide pour le traitement d'acides gras Download PDFInfo
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- WO2018096248A1 WO2018096248A1 PCT/FR2017/053172 FR2017053172W WO2018096248A1 WO 2018096248 A1 WO2018096248 A1 WO 2018096248A1 FR 2017053172 W FR2017053172 W FR 2017053172W WO 2018096248 A1 WO2018096248 A1 WO 2018096248A1
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- Prior art keywords
- acid
- composition according
- catalyst
- weight
- fatty acids
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
-
- 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
- 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
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
Definitions
- the invention relates to the treatment of fatty acids, and more particularly the esterification of fatty acids.
- the fatty acid esters obtained can thus serve as raw materials in various fields such as cosmetics or biofuel production.
- the invention relates to an acid composition which can in particular be used as a catalyst in the processes for the esterification of fatty acids.
- patent EP1951852 B1 provides a process for the manufacture of alkyl esters of fatty acids from "tall oil” containing sulfur compounds in the presence of a strong acid catalyst such as sulfuric acid in particular.
- Sulfuric acid is known for its oxidizing and dehydrating power causing side reactions that can compete with the main esterification reaction.
- WO2006081644 and WO2015134495 describe the use of methanesulfonic acid in fatty acid esterification processes.
- alkanesulphonic acids being relatively expensive compounds, it is sought to optimize their use. In addition, it may be useful to further improve the efficiency of the esterification catalysts.
- the present invention relates to a composition
- a composition comprising: at least one alkanesulphonic acid of formula R-SO3H in which R represents a linear or branched, saturated hydrocarbon-based chain containing from 1 to 4 carbon atoms, which may or may not be substituted with at least one halogen atom;
- the proportion by weight of alkane-sulphonic acid relative to the total weight of alkane-sulphonic acid and of sulfuric acid is between 40% and 90%, preferably between 44% and 89%;
- the proportion by weight of sulfuric acid relative to the total weight of alkanesulphonic acid and of sulfuric acid is between 10% and 60%, preferably between 11% and 56%.
- the solvent may be of any type known to those skilled in the art and for example water, an organic solvent, a mixture of organic solvents or a mixture of water and one or more organic solvents.
- the solvent is chosen from water, an alcohol and an ether, preferably water and a C 1 -C 3 alcohol, and more particularly water and methanol, taken alone. or in combination.
- the proportion by weight of solvent relative to the total weight of the composition is generally between 0% and 50%, preferably between 5% and 35%.
- halogen atom is preferably selected from fluorine, chlorine and bromine, preferably fluorine.
- the alkanesulfonic acid of formula R-SO3H defined above, usable in the context of the present invention is advantageously selected from methanesulfonic acid, ethanesulfonic acid, n-propane acid. sulfonic acid, / 'n-propane-sulfonic acid, n-butane-sulfonic acid, the acid / sulfonic n-butane, sec-butane-sulphonic acid, tert-butane acid sulfonic acid, trifluoro methanesulfonic acid (also known as triflic acid), and mixtures of two or more of them in all Most preferably, the alkanesulfonic acid is methanesulfonic acid.
- the acidic composition according to the present invention may comprise one or more additive (s) and / or charge (s), which are well known to those skilled in the art, such as those chosen, for example, from the inhibitors of corrosion, perfumes, odorants, and others.
- additives such as those chosen, for example, from the inhibitors of corrosion, perfumes, odorants, and others.
- the present invention also relates to the use of said composition as an esterification catalyst, and more particularly to esterification of fatty acid (s).
- the invention relates to a process for producing fatty acid esters comprising the steps of:
- step d may be performed simultaneously with step a and / or b, preferably at the same time as steps a and / or b.
- the molar ratio catalyst / fatty acid is between 0.001 and 1, preferably between 0.01 and 0.5 and more particularly between 0.02 and 0.2.
- Figure 1 represents the percentage of residual fatty acids (y-axis) in the organic phase after esterification reaction depending on the nature of the acid catalyst used.
- Figure 2 shows the kinetics of conversion of residual fatty acids during the esterification step depending on the nature of the acid catalyst used.
- AMS means that the catalyst used contains 70% pure methanesulfonic acid and 30% water
- - 70 AMS / 30 H2SO 4 means that the catalyst used is a catalyst according to the invention and that it comprises:
- - 60 AMS / 40 H2SO 4 means that the catalyst used is a catalyst according to the invention and that it comprises:
- the AMS used is an AMS diluted to 70% by weight in water and the sulfuric acid used is a sulfuric acid diluted to 97% by weight in water.
- composition comprising:
- the proportion by weight of pure alkanesulphonic acid relative to the total weight of alkanesulphonic acid and of sulfuric acid is between 40% and 90%;
- the proportion by weight of pure sulfuric acid relative to the total weight of alkanesulphonic acid and of sulfuric acid is between 10% and 60%.
- the proportion by weight of pure alkanesulphonic acid relative to the total weight of alkanesulphonic acid and of sulfuric acid is between 44% and 89%; the proportion by weight of pure sulfuric acid relative to the total weight of alkanesulphonic acid and of sulfuric acid is between 11% and 56%.
- pure is meant a compound undiluted in water or a solvent.
- composition may also comprise one or more solvents, and optionally one or more additives.
- solvent means aqueous, organic or water-soluble products.
- the solvent may be water, an alcohol or an ether, taken alone or in combination.
- the solvent is water and / or a C1 to C3 alcohol.
- the solvent is water, methanol or a water / methanol mixture.
- the content by weight of solvent relative to the total weight of the composition is between 0 and 50%, and preferably between 5% and 35%.
- halogen atom is chosen from fluorine, chlorine and bromine, preferably fluorine.
- the alkanesulphonic acid included in the composition according to the invention is chosen from methanesulfonic acid, ethanesulfonic acid, n-propanesulfonic acid, acid and / or propionic acid .
- the alkanesulfonic acid is methanesulfonic acid.
- Said alkanesulphonic acid may be used as such, or in combination with one or more other components, that is to say in formulation.
- Any type of formulation comprising at least one alkanesulphonic acid may be suitable.
- the formulation comprises from 0.01% to 100% by weight of alkanesulfonic acid, more generally from 0.05% to 90% by weight, in particular from 0.5% to 75% by weight, inclusive limits, of alkane-sulfonic acid (s), based on the total weight of said alkanesulfonic acid formulation.
- the formulation is for example an aqueous, organic or even hydro-organic formulation.
- the formulation may be prepared as a concentrated mixture, wherein the concentrated mixture may be diluted prior to use.
- the formulation may be a pure alkanesulphonic acid, or a mixture of pure alkanesulphonic acids, that is to say that the formulation may contain only one or more acids.
- alkane sulfonic acid (s) without any other formulation additive or other solvent or diluent.
- the alkanesulfonic acid may be diluted to 70% in a solvent, preferably in water.
- the alkanesulfonic acid is methanesulfonic acid diluted to 70% by weight in water, such as that found commercially.
- anhydrous methanesulfonic acid or AMSA ascronym for "anhydrous methane sulphonic acid” in the English language
- methanesulfonic acid in aqueous solution for example a methanesulfonic acid solution.
- 70% by weight in water and marketed by Arkema under the name Scaleva ® It is also possible to use the methanesulfonic acid marketed by Arkema under the name AMS LC ("MSA LC" in English).
- methanesulfonic acid in aqueous solution, as marketed by BASF under the name Lutropur ® MSA ready for use or diluted with water in the proportions indicated above.
- the formulation comprises from 0.01% to 100% by weight of sulfuric acid, more generally from 0.05% to 98% by weight, in particular from 74% to 97% by weight, inclusive limits, d sulfuric acid, based on the total weight of said formulation.
- the formulation is for example an aqueous, organic, or alternatively hydro-organic formulation.
- the formulation can be a concentrated mixture.
- the formulation may also be a ready-to-use formulation, i.e., it does not need to be diluted.
- the formulation may be pure sulfuric acid without other formulation additive or other solvent or diluent.
- the sulfuric acid is 97% diluted weight in water, such as that marketed by Arkema or sulfuric acid diluted to 96% by weight in water marketed by BASF.
- the composition according to the invention is used as an acid esterification catalyst, and preferably as an acidic esterification catalyst for fatty acids.
- the present invention also relates to an acidic esterification catalyst, preferably fatty acid esterification comprising, and preferably consisting of, the acid composition as defined above.
- composition according to the invention finds a particularly advantageous use as a catalyst, for example as a catalyst for esterification of pure fatty acids or in a mixture in oils or fats, which are then called "fatty acids free ", as opposed to the fatty acids present in the form of mono-, di- and / or tri-glycerides present in said oils and / or fats.
- the fatty acid esterification reaction allows, from the condensation of an alcohol on a fatty carboxylic acid, obtaining a fatty ester and a molecule of water.
- fatty acid is understood to mean a carboxylic acid with an aliphatic chain, in particular a C 4 -C 36 chain.
- the natural fatty acids generally have a carbon chain of 4 to 36 carbon atoms, said carbon chain may be saturated or unsaturated, linear or branched.
- the fatty acids may, preferably, be fatty acids present in the oils.
- the esterification reaction may be followed by a transesterification reaction in the presence of a light alcohol, generally comprising from 1 to 4 carbon atoms, in order to obtain fatty acid esters and glycerol, said fatty acid esters can then be used as fuel, called "biodiesel".
- the Applicant has thus demonstrated that, with respect to an alkanesulfonic acid used alone as a catalyst or with respect to the sulfuric acid used alone as a catalyst, the mixture of at least one alkane-sulfonic acid with the acid sulfuric in the proportions claimed, allows, after an esterification step, to lower the level of residual fatty acids in the organic phase below 1.1% by weight, preferably 1% by weight, and more particularly 0.95% by weight; which is very difficult to achieve with an alkane-sulfonic acid used alone or sulfuric acid used alone.
- This low content of residual fatty acids in particular has an advantage over the final purity of the ester or during the transesterification step, often carried out later, since the latter will consume less catalyst, generally basic catalyst, often expensive. , and will limit the formation of soaps that disrupt the reaction.
- the use of the acid composition according to the invention as an esterification catalyst makes it possible to obtain a smaller amount of residual catalyst in the organic phase than that obtained with the alkane-acid catalyst.
- sulfonic acid alone or sulfuric acid catalyst alone makes it possible to reduce the consumption of basic catalyst during a possible subsequent transesterification step in order to prepare, for example, biodiesel.
- composition according to the invention makes it possible to improve the conversion kinetics of fatty acids with respect to the use of an alkane-sulphonic acid used alone. or sulfuric acid used alone.
- the composition according to the invention is an esterification and transesterification catalyst thus making it possible to carry out, in a single step, the esterification and transesterification of free fatty acids and of fatty acids present in the form of mono-, di- and / or tri-glycerides.
- the composition according to the invention may comprise one or more additives well known to those skilled in the art, such as those chosen from corrosion inhibitors, perfumes, odorants, and other well-known additives. of the skilled person.
- the composition according to the invention comprises at least one corrosion inhibitor.
- the composition comprises at least one perfume and / or an odorant.
- composition according to the invention may be prepared by mixing the alkane-sulfonic acid (s) and sulfuric acid, according to any method known to those skilled in the art such as, for example, the method described below, said process not being limiting.
- the alkane sulfonic acid is introduced.
- the sulfuric acid is then added according to any technique known to those skilled in the art, so as to limit the possible exotherm of the reaction.
- the addition of sulfuric acid will be carried out so that the temperature does not exceed 90 ° C, preferably 80 ° C and more particularly 60 ° C.
- the rate of addition of the sulfuric acid will be carried out so as not to reach a temperature of the mixture greater than 90 ° C, preferably 80 ° C and more particularly 60 ° C.
- the present application also relates to a process for the production of fatty acid esters in which the fatty acids are esterified in the presence of the composition according to the invention.
- the esterification process consists of introducing a fatty acid or a mixture of fatty acids into a reactor.
- the alcohol is then added and the medium is heated to a temperature generally between 50 ° C and 200 ° C, more generally between 60 ° C and 120 ° C, preferably between 60 ° C and 80 ° C.
- the introduction of the composition according to the invention is preferably carried out at the esterification temperature. According to another embodiment of the invention, said composition can be added before heating.
- the alcohol and said composition may be added continuously, together or separately, when the medium has reached the esterification temperature.
- said composition may be added with the fatty acid or the mixture of fatty acids.
- the fatty acid or the mixture of fatty acids, the alcohol and the said composition are added together before heating. The esterification reaction is then carried out in the temperature range indicated above.
- composition according to the invention acts as a catalyst.
- the fatty acids may be of any type selected from fatty acids and mixtures of fatty acids known to those skilled in the art, including fatty acids from the plant or animal medium, including algae, and more generally of the vegetable kingdom. These said acids generally and advantageously comprise at least one olefinic unsaturation.
- oils extracted from various oleaginous plants such as, in a non-limiting manner, peanuts, sunflower, rapeseed, castor oil, lesquerella, olive, soya, oil palm, avocado, walnut, hazelnut, almond, sesame, sea buckthorn and limanthus, including algae.
- the acids present in these oils are placed in the presence of an alcohol.
- the alcohol may be of any type known to those skilled in the art such as mono-alcohols, diols, triols, tetrols, and the like, used alone or in combination.
- the alcohol used has a molar mass of between 30 and 200 g. mol "1 .
- the alcohol is of the type R 1 -OH where R 1 is an alkyl or aromatic linear or branched chain, saturated or unsaturated, comprising from 1 to 20 carbon atoms.
- R 1 is an alkyl chain containing from 1 to 10 carbon (s), in particular from 1 to 4.
- the alcohol has more than one -OH function, as by for example two or three -OH functions, and, for example, the alcohol may be glycerol (propane-1,2,3-triol).
- the molar ratio catalyst according to the invention / fatty acid is between 0.001 and 1, preferably between 0.01 and 0.5 and more particularly between 0.02 and 0.2.
- the number of moles of fatty acids is measured by acid-base assay by potentiometry and is expressed in moles per gram of fatty acids present in the starting material. This value is then multiplied by the catalyst / fatty acid molar ratio to determine the amount of catalyst to be added.
- the molar ratio alcohol / fatty acids is between 1 and 20, preferably between 4 and 10.
- the esterification reaction of the fatty acids can be carried out at any temperature but preferably at temperatures between 50 ° C and 200 ° C, more generally at temperatures between 60 ° C and 120 ° C, preferably between 60 ° C and 80 ° C.
- the esterification reaction of the fatty acids may be carried out at any pressure but preferably at a pressure of between 10 3 Pa (0.01 bar absolute) and 2.10 6 Pa ( 20 bar absolute), more generally between atmospheric pressure and 10 6 Pa (10 bar absolute) and very particularly preferably at atmospheric pressure.
- the reaction time for the esterification of fatty acids can vary in large proportions and is generally between a few minutes and a few hours, for example between 10 minutes and 6 hours, typically between 30 minutes and 180 minutes.
- the esterification reaction may be carried out batchwise or continuously.
- the catalyst according to the invention is added to the mixture or separately in the reaction medium. It can be added alone or co-fed with the source of fatty acids (oil, animal fat, etc.) and / or alcohol.
- the reaction can be carried out in one or more reactors, between 2 and 15, more generally 2 to 10 reactors, more generally still from 2 to 5 reactors, arranged in parallel or in cascade. According to one particular embodiment, the batch process with several cascaded reactors is preferred.
- the water formed can be removed by any method well known to those skilled in the art, for example as it is formed, for example by heating. In one embodiment of the invention, removal of water may result in removal of all or part of the solvent, particularly when the solvent is an alcohol.
- the free fatty acids used come from vegetable oil to obtain biofuel, including biodiesel.
- the biodiesel is obtained after a transesterification step, as described above. If a step of neutralizing this biodiesel is necessary, it is possible to use the acidic aqueous phase obtained at the end of the esterification reaction of the free fatty acids.
- the alcohol is removed before using said acid phase.
- the esterification reaction of the fatty acids according to the invention also provides products that can be used in various fields such as cosmetics, lubricants, agrochemicals, pharmacy, cleaning, etc.
- composition comprising:
- the above composition is prepared from a 70% by weight aqueous solution of AMS LC from Arkema, introduced into a jacketed reactor cooled by a thermostatic bath regulated at 10 ° C. 97% by weight sulfuric acid is added, dropwise, to a dropping funnel attached to the jacketed reactor cap, being careful not to exceed 60 ° C.
- composition thus obtained contains, per 100 g of composition, 0.8355 moles of acids (42/96 + 39/98 (96 being the molar mass of the AMS and 98 being the molar mass of H 2 SO 4 ). ).
- composition thus prepared is used as esterification catalyst in the example below.
- An industrial mixture comprising an oil comprising triglycerides and 94% by weight of free fatty acids (FFA for "Free Fatty Acids") with an average molecular weight of fatty acids at 268 ⁇ 1 g / mol is used.
- FFA Free Fatty Acids
- the methanol / FFA molar ratio is equal to 8.
- the catalyst / FFA molar ratio is equal to 0.175.
- a temperature probe and a refrigerant 451 g of said industrial mixture comprising triglycerides and 94% by weight of FFA are introduced. or 1. 582 moles of fatty acid.
- the reaction mixture is heated to 70 ° C and then introduced the catalyst prepared above.
- the reaction medium is stirred for 2 hours at 70 ° C. and then decanted and left overnight at 70 ° C.
- the aqueous and organic phases are analyzed according to the methods described below. Methods of analysis:
- the FFA and the catalyst in the organic phase are determined by potentiometry in the following manner: in a beaker, about 1.5 g of organic phase are introduced, then the mixture is made up to 50 ml with the toluene mixture. isopropanol / water in the proportions 500/495/5 by volume.
- the potentiometric assay is carried out with 0.1 mol.L -1 KOH in ethanol with a DG1 13-SC # 2 electrode and a T50 titrator, both from Mettler Toledo.
- the determination makes it possible to accurately determine, on the one hand, the amount of residual catalyst in the organic phase in moles per gram and, on the other hand, the residual fatty acid content in the organic phase in% by weight.
- the acid-base dosage makes it possible to obtain 2 potential jumps: the first jump corresponds to the catalyst and the second jump corresponds to the residual fatty acids.
- the FFA conversion kinetics is improved with respect to the use of each single acid, as shown in FIG. 2.
- a kinetics of conversion to a faster ester and, at the same time (1 h) a better conversion of FFA (98% with the composition according to the invention and 97% with AMS alone and H 2 SO alone) .
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Abstract
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201780073006.3A CN109963832A (zh) | 2016-11-25 | 2017-11-20 | 用于加工脂肪酸的酸组合物 |
BR112019009473-3A BR112019009473B1 (pt) | 2016-11-25 | 2017-11-20 | Composição ácida para o tratamento de ácidos graxos, utilização da composição e processo para a produção de ésteres de ácidos graxos |
US16/463,534 US11534743B2 (en) | 2016-11-25 | 2017-11-20 | Acid composition for processing fatty acids |
KR1020197017950A KR102278977B1 (ko) | 2016-11-25 | 2017-11-20 | 지방산 처리용 산 조성물 |
EP17812006.9A EP3544948A1 (fr) | 2016-11-25 | 2017-11-20 | Composition acide pour le traitement d'acides gras |
PH12019501024A PH12019501024A1 (en) | 2016-11-25 | 2019-05-08 | Acid composition for processing fatty acids |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201662426334P | 2016-11-25 | 2016-11-25 | |
FR1661482A FR3059327B1 (fr) | 2016-11-25 | 2016-11-25 | Composition acide pour le traitement d'acides gras |
US62/426,334 | 2016-11-25 | ||
FR1661482 | 2016-11-25 |
Publications (1)
Publication Number | Publication Date |
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WO2018096248A1 true WO2018096248A1 (fr) | 2018-05-31 |
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Application Number | Title | Priority Date | Filing Date |
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PCT/FR2017/053172 WO2018096248A1 (fr) | 2016-11-25 | 2017-11-20 | Composition acide pour le traitement d'acides gras |
Country Status (8)
Country | Link |
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US (1) | US11534743B2 (fr) |
EP (1) | EP3544948A1 (fr) |
KR (1) | KR102278977B1 (fr) |
CN (1) | CN109963832A (fr) |
AR (2) | AR110242A1 (fr) |
FR (1) | FR3059327B1 (fr) |
PH (1) | PH12019501024A1 (fr) |
WO (1) | WO2018096248A1 (fr) |
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CN1830949A (zh) * | 2005-03-09 | 2006-09-13 | 四川古杉油脂化学有限公司 | 一种利用菜籽油下脚料生产芥酸甲酯的方法 |
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DE102006054519A1 (de) * | 2006-11-20 | 2008-05-21 | Evonik Degussa Gmbh | Verfahren zur Herstellung von Fettsäurealkylestern und Acrolein aus Triglyceriden |
CN100526427C (zh) * | 2007-07-19 | 2009-08-12 | 山东省花生研究所 | 用高酸值油脂生产生物柴油的催化剂及生物柴油生产方法 |
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US8957242B2 (en) * | 2013-03-15 | 2015-02-17 | Renewable Energy Group, Inc. | Dual catalyst esterification |
FR3012138B1 (fr) * | 2013-10-22 | 2015-10-30 | Arkema France | Utilisation d'acide alcane-sulfonique pour la preparation d'alcool phenolique |
KR20160001054A (ko) * | 2014-06-26 | 2016-01-06 | 대구가톨릭대학교산학협력단 | 술폰산 또는 술폰산염 촉매를 이용한 에스테르 화합물의 제조방법 |
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2016
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2017
- 2017-11-20 KR KR1020197017950A patent/KR102278977B1/ko active IP Right Grant
- 2017-11-20 EP EP17812006.9A patent/EP3544948A1/fr active Pending
- 2017-11-20 US US16/463,534 patent/US11534743B2/en active Active
- 2017-11-20 CN CN201780073006.3A patent/CN109963832A/zh active Pending
- 2017-11-20 WO PCT/FR2017/053172 patent/WO2018096248A1/fr unknown
- 2017-11-27 AR ARP170103294A patent/AR110242A1/es active IP Right Grant
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Also Published As
Publication number | Publication date |
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FR3059327A1 (fr) | 2018-06-01 |
AR124039A2 (es) | 2023-02-08 |
US20190374931A1 (en) | 2019-12-12 |
KR102278977B1 (ko) | 2021-07-16 |
BR112019009473A2 (pt) | 2019-07-30 |
EP3544948A1 (fr) | 2019-10-02 |
US11534743B2 (en) | 2022-12-27 |
AR110242A1 (es) | 2019-03-13 |
FR3059327B1 (fr) | 2021-10-15 |
CN109963832A (zh) | 2019-07-02 |
KR20190082953A (ko) | 2019-07-10 |
PH12019501024A1 (en) | 2020-01-20 |
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