EP3544948A1 - Acid composition for the treatment of fatty acids - Google Patents

Acid composition for the treatment of fatty acids

Info

Publication number
EP3544948A1
EP3544948A1 EP17812006.9A EP17812006A EP3544948A1 EP 3544948 A1 EP3544948 A1 EP 3544948A1 EP 17812006 A EP17812006 A EP 17812006A EP 3544948 A1 EP3544948 A1 EP 3544948A1
Authority
EP
European Patent Office
Prior art keywords
acid
composition according
catalyst
weight
fatty acids
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP17812006.9A
Other languages
German (de)
French (fr)
Inventor
Jean-Alex Laffitte
Bernard Monguillon
Vijay Srinivas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP3544948A1 publication Critical patent/EP3544948A1/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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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  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

The invention relates to a composition comprising: at least one alkanesulfonic acid of formula R-SO3H, in which R is a linear or branched saturated hydrocarbon chain of 1 to 4 carbon atoms, optionally substituted with at least one halogen atom; sulfuric acid; and, optionally, at least one solvent; the proportions thereof being as defined in the description. The invention also relates to the use of the composition as a catalyst for esterifying fatty acids.

Description

COMPOSITION ACIDE POUR LE TRAITEMENT D'ACIDES GRAS  ACIDIC COMPOSITION FOR THE TREATMENT OF FATTY ACIDS
[0001] L'invention concerne le traitement des acides gras, et plus particulièrement l'estérification des acides gras. Les esters d'acides gras obtenus peuvent ainsi servir de matières premières dans divers domaines tels que la cosmétique ou la production de biocarburant. En particulier, l'invention concerne une composition d'acides pouvant notamment servir de catalyseur dans les procédés d'estérification des acides gras. 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. In particular, 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.
[0002] Lors de l'estérification des acides gras, il est souvent nécessaire d'utiliser un catalyseur, par exemple acide. Parmi les catalyseurs acides utilisés, on connaît notamment l'utilisation de l'acide sulfurique.  During the esterification of fatty acids, it is often necessary to use a catalyst, for example acid. Among the acid catalysts used, the use of sulfuric acid is particularly known.
[0003] Par exemple, le brevet EP1951852 B1 prévoit un procédé de fabrication d'esters alkyliques d'acides gras à partir de « tall oil » contenant des composés soufrés en présence d'un catalyseur acide fort tel que notamment l'acide sulfurique.  For example, 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.
[0004] L'acide sulfurique est connu pour son pouvoir oxydant et déshydratant entraînant des réactions secondaires qui peuvent entrer en compétition avec la réaction principale d'estérification. Sulfuric acid is known for its oxidizing and dehydrating power causing side reactions that can compete with the main esterification reaction.
[0005] Il est également connu l'utilisation d'acide alcane-sulfonique comme catalyseur acide de réactions d'estérification des acides gras. Ainsi, les documents It is also known the use of alkane-sulfonic acid as an acid catalyst for esterification reactions of fatty acids. Thus, the documents
WO2006081644 et WO2015134495 décrivent l'utilisation d'acide méthane sulfonique dans les procédés d'estérification des acides gras. WO2006081644 and WO2015134495 describe the use of methanesulfonic acid in fatty acid esterification processes.
[0006] Cependant, les acides alcane-sulfoniques étant des composés relativement chers, on cherche à en optimiser leur utilisation. De plus, il peut être utile de pouvoir améliorer encore l'efficacité des catalyseurs d'estérification.  However, 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.
[0007] Il convient donc de trouver un catalyseur acide qui soit plus efficace, aussi bien au niveau du degré conversion des acides gras en esters que du point de vue de la cinétique d'estérification, et qui soit peu onéreux. Pour cela, la Demanderesse a démontré qu'un catalyseur comprenant au moins une composition acide particulière permet, entre autres, de pallier ces inconvénients.  It is therefore necessary to find an acid catalyst that is more effective, both in terms of the degree of conversion of fatty acids into esters than from the point of view of the esterification kinetics, and which is inexpensive. For this, the Applicant has demonstrated that a catalyst comprising at least one particular acid composition makes it possible, among other things, to overcome these disadvantages.
[0008] Ainsi, et selon un premier aspect, la présente invention concerne une composition comprenant : - au moins un acide alcane-sulfonique de formule R-SO3H dans laquelle R représente une chaîne hydrocarbonée saturée, linéaire ou ramifiée, comportant de 1 à 4 atomes de carbone, pouvant ou non, être substituée par au moins un atome d'halogène ; Thus, and according to a first aspect, the present invention relates to 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;
- de l'acide sulfurique ;  - sulfuric acid;
- et éventuellement, au moins un solvant ;  and optionally, at least one solvent;
dans laquelle : in which :
- la proportion en poids en acide alcane-sulfonique par rapport au poids total d'acide alcane-sulfonique et d'acide sulfurique est comprise entre 40% et 90%, de préférence entre 44% et 89% ;  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%;
- la proportion en poids en acide sulfurique par rapport au poids total d'acide alcane-sulfonique et d'acide sulfurique est comprise entre 10% et 60%, de préférence entre 1 1 % et 56%.  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%.
[0009] Le solvant peut être de tout type connu de l'homme du métier et par exemple l'eau, un solvant organique, un mélange de solvants organiques ou encore un mélange d'eau et d'un ou plusieurs solvants organiques.  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.
[0010] Dans un mode de réalisation, le solvant est choisi parmi l'eau, un alcool et un éther, de préférence l'eau et un alcool en Ci à C3, et plus particulièrement, l'eau et le méthanol, pris seuls ou en combinaison. La proportion en poids de solvant par rapport au poids total de la composition est généralement comprise entre 0% et 50%, de préférence entre 5% et 35%. In one embodiment, 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%.
[0011] Lorsque la chaîne hydrocarbonée du groupement R ci-dessus est substituée par au moins un atome d'halogène, ledit atome d'halogène est de préférence choisi parmi le fluor, le chlore et le brome, de préférence le fluor.  When the hydrocarbon chain of the R group above is substituted by at least one halogen atom, said halogen atom is preferably selected from fluorine, chlorine and bromine, preferably fluorine.
[0012] L'acide alcane-sulfonique, de formule R-SO3H définie précédemment, utilisable dans le cadre de la présente invention est avantageusement choisi parmi l'acide méthane-sulfonique, l'acide éthane-sulfonique, l'acide n-propane-sulfonique, l'acide /'so-propane-sulfonique, l'acide n-butane-sulfonique, l'acide /'so-butane- sulfonique, l'acide sec-butane-sulfonique, l'acide terf-butane-sulfonique, l'acide trifluoro méthane-sulfonique (aussi connu sous le nom d'acide triflique), et les mélanges de deux ou plusieurs d'entre eux en toutes proportions, et de manière tout particulièrement préférée, l'acide alcane-sulfonique est l'acide méthane- sulfonique. 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.
[0013] En outre la composition acide selon la présente invention peut comprendre un ou plusieurs additif(s) et/ou charge(s), bien connus de l'homme du métier, tels que ceux choisis, par exemple, parmi les inhibiteurs de corrosion, les parfums, les agents odorants, et autres.  In addition, 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.
[0014] La présente invention se rapporte également à l'utilisation de ladite composition en tant que catalyseur d'estérification, et plus particulièrement d'estérification d'acide(s) gras.  The present invention also relates to the use of said composition as an esterification catalyst, and more particularly to esterification of fatty acid (s).
[0015] Enfin, l'invention concerne un procédé de fabrication d'esters d'acides gras comprenant les étapes de :  Finally, the invention relates to a process for producing fatty acid esters comprising the steps of:
a/ introduire au moins un acide gras dans un réacteur ; a / introducing at least one fatty acid into a reactor;
b/ ajouter au moins un alcool ; b / add at least one alcohol;
c/ chauffer le milieu réactionnel ; c / heating the reaction medium;
d/ introduire une composition acide définie précédemment, comme catalyseur ; e/ optionnellement, éliminer l'eau formée au cours de la réaction d'estérification ; et f/ récupérer l'ester d'acide gras ; d / introducing an acid composition defined above, as a catalyst; e / optionally, removing the water formed during the esterification reaction; and recovering the fatty acid ester;
l'étape d pouvant être réalisée en même temps que l'étape a et/ou b, de préférence en même temps que les étapes a et/ou b. step d may be performed simultaneously with step a and / or b, preferably at the same time as steps a and / or b.
[0016] Dans ledit procédé, le ratio molaire catalyseur/acide gras est compris entre 0,001 et 1 , de préférence entre 0,01 et 0,5 et plus particulièrement entre 0,02 et 0,2.  In said process, 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.
[0017] L'invention sera mieux comprise au regard de la description, des figures et des exemples qui suivent mais n'est en aucun cas limitée aux dits figures et exemples. The invention will be better understood from the description, figures and examples which follow but is in no way limited to said figures and examples.
[0018] La figure 1 représente le pourcentage d'acides gras résiduels (axe des ordonnées) dans la phase organique après réaction d'estérification en fonction de la nature du catalyseur acide utilisé.  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.
[0019] La figure 2 représente la cinétique de conversion des acides gras résiduels lors de l'étape d'estérification en fonction de la nature du catalyseur acide utilisé.  Figure 2 shows the kinetics of conversion of residual fatty acids during the esterification step depending on the nature of the acid catalyst used.
[0020] Dans les dites figures 1 et 2 : In said FIGS. 1 and 2:
- 100 AMS signifie que le catalyseur utilisé contient 70% d'acide méthane- sulfonique pur et 30% d'eau, - 70 AMS/30 H2SO4 signifie que le catalyseur utilisé est un catalyseur selon l'invention et qu'il comprend : 100 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:
o 49% en poids d'acide méthane sulfonique pur par rapport au poids total du mélange,  49% by weight of pure methanesulfonic acid relative to the total weight of the mixture,
o 29,1 % en poids d'acide sulfurique pur par rapport au poids total du mélange et,  29.1% by weight of pure sulfuric acid relative to the total weight of the mixture and,
o 21 ,9% d'eau.  o 21.9% water.
- 60 AMS/40 H2SO4 signifie que le catalyseur utilisé est un catalyseur selon l'invention et qu'il comprend : - 60 AMS / 40 H2SO 4 means that the catalyst used is a catalyst according to the invention and that it comprises:
o 42% en poids d'acide méthane sulfonique pur par rapport au poids total de mélange,  o 42% by weight of pure methanesulfonic acid relative to the total weight of the mixture,
o 38,8% en poids d'acide sulfurique pur par rapport au poids total du mélange et,  38.8% by weight of pure sulfuric acid relative to the total weight of the mixture and,
o 19,2% d'eau.  o 19.2% water.
- 100 H2SO4 signifie que le catalyseur utilisé comprend 97% d'acide sulfurique pur et 3% d'eau. - 100 H2SO 4 means that the catalyst used comprises 97% pure sulfuric acid and 3% water.
[0021] L'AMS utilisé est un AMS dilué à 70% en poids dans l'eau et l'acide sulfurique utilisé est un acide sulfurique dilué à 97% en poids dans l'eau.  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.
[0022] Plus spécifiquement, l'invention est relative à une composition comprenant : More specifically, the invention relates to a composition comprising:
- au moins un acide alcane-sulfonique de formule R-SO3H dans laquelle R représente une chaîne hydrocarbonée saturée, linéaire ou ramifiée, comportant de 1 à 4 atomes de carbone, pouvant ou non, être substituée par au moins un atome d'halogène, et 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, and
- de l'acide sulfurique.  - sulfuric acid.
[0023] Dans la composition selon l'invention :  In the composition according to the invention:
- la proportion en poids d'acide alcane sulfonique pur par rapport au poids total d'acide alcane-sulfonique et d'acide sulfurique est comprise entre 40% et 90% ; 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%;
- la proportion en poids en acide sulfurique pur par rapport au poids total d'acide alcane-sulfonique et d'acide sulfurique est comprise entre 10% et 60%. 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%.
[0024] De façon préférée :  [0024] In a preferred manner:
- la proportion en poids d'acide alcane sulfonique pur par rapport au poids total d'acide alcane-sulfonique et d'acide sulfurique est comprise entre 44% et 89% ; - la proportion en poids en acide sulfurique pur par rapport au poids total d'acide alcane-sulfonique et d'acide sulfurique est comprise entre 1 1 % et 56%. 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%.
[0025] Par « pur », on entend un composé non dilué dans l'eau ou un solvant. By "pure" is meant a compound undiluted in water or a solvent.
[0026] Grâce à la composition selon l'invention, la Demanderesse a démontré des résultats surprenants, tels que ceux cités en exemples dans la présente demande. With the composition according to the invention, the Applicant has shown surprising results, such as those cited in examples in the present application.
[0027] Il est à noter que ladite composition peut également comprendre un ou plusieurs solvants, et éventuellement un ou plusieurs additifs. It should be noted that said composition may also comprise one or more solvents, and optionally one or more additives.
[0028] Par « solvant », on entend des produits aqueux, organiques ou hydrosolubles. De préférence, le solvant peut être de l'eau, un alcool ou un éther, pris seul ou en combinaison. De manière préférée, le solvant est de l'eau et/ou un alcool en C1 à C3. Et plus particulièrement, le solvant est de l'eau, du méthanol ou un mélange eau/méthanol. La teneur en poids de solvant par rapport au poids total de la composition est comprise entre 0 et 50%, et de manière préférée entre 5% et 35%. The term "solvent" means aqueous, organic or water-soluble products. Preferably, the solvent may be water, an alcohol or an ether, taken alone or in combination. Preferably, the solvent is water and / or a C1 to C3 alcohol. And more particularly, 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%.
[0029] Lorsque la chaîne hydrocarbonée du groupement R ci-dessus est substituée par au moins un atome d'halogène, ledit atome d'halogène est choisi parmi le fluor, le chlore et le brome, de préférence le fluor.  When the hydrocarbon chain of the R group above is substituted by at least one halogen atom, said halogen atom is chosen from fluorine, chlorine and bromine, preferably fluorine.
[0030] De préférence, l'acide alcane sulfonique compris dans la composition selon l'invention est choisi parmi l'acide méthane-sulfonique, l'acide éthane-sulfonique, l'acide n-propane-sulfonique, l'acide /'so-propane-sulfonique, l'acide n-butane- sulfonique, l'acide /'so-butane-sulfonique, l'acide sec-butane-sulfonique, l'acide tert- butane-sulfonique, l'acide trifluoro-méthane-sulfonique (aussi connu sous le nom d'acide triflique), et les mélanges de deux ou plusieurs d'entre eux en toutes proportions. De manière préférée, l'acide alcane sulfonique est l'acide méthane sulfonique. Preferably, 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 . n-propane-sulfonic acid, n-butane sulfonic acid, / 'n-butane-sulfonic acid, sec-butane-sulphonic acid, tert-butane-sulphonic acid, trifluoro-methanesulfonic acid sulphonic acid (also known as triflic acid), and mixtures of two or more of them in all proportions. Preferably, the alkanesulfonic acid is methanesulfonic acid.
[0031] Ledit acide alcane-sulfonique peut être utilisé tel quel, ou en association avec un ou plusieurs autres composants, c'est-à-dire en formulation. Tout type de formulation comprenant au moins un acide alcane-sulfonique peut convenir. En règle générale, la formulation comprend de 0,01 % à 100% en poids d'acide alcane- sulfonique, plus généralement de 0,05% à 90% en poids, en particulier de 0,5% à 75% en poids, bornes incluses, d'acide(s) alcane-sulfonique(s), par rapport au poids total de ladite formulation d'acide alcane-sulfonique. [0032] La formulation est par exemple une formulation aqueuse, organique, ou encore hydro-organique. La formulation peut être préparée sous forme de mélange concentré, ledit mélange concentré pouvant être dilué avant utilisation. Enfin, au sens de la présente invention, la formulation peut être un acide alcane-sulfonique pur, ou encore un mélange d'acides alcane-sulfoniques purs, c'est-à-dire que la formulation peut ne contenir que un ou plusieurs acide(s) alcane-sulfonique(s), sans autre additif de formulation ou autre solvant ou diluant. 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. As a rule, 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. Finally, within the meaning of the present invention, 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. (s) alkane sulfonic acid (s), without any other formulation additive or other solvent or diluent.
[0033] Selon un mode de réalisation de l'invention, l'acide alcane sulfonique peut être dilué à 70% dans un solvant, de préférence dans l'eau. De manière préférée, l'acide alcane sulfonique est l'acide méthane sulfonique dilué à 70% en poids dans l'eau, tel que celui trouvé dans le commerce. On peut par exemple utiliser de l'acide méthane-sulfonique anhydre ou AMSA (acronyme pour « anhydrous méthane sulphonic acid » en langue anglaise) ou encore de l'acide méthane-sulfonique en solution aqueuse par exemple une solution d'acide méthane-sulfonique à 70% en poids dans l'eau et commercialisé par la société Arkema sous la dénomination Scaleva®. On peut également utiliser l'acide méthane sulfonique commercialisé par la société Arkema sous la dénomination AMS LC (« MSA LC » en langue anglaise). According to one embodiment of the invention, the alkanesulfonic acid may be diluted to 70% in a solvent, preferably in water. Preferably, the alkanesulfonic acid is methanesulfonic acid diluted to 70% by weight in water, such as that found commercially. It is possible, for example, to use anhydrous methanesulfonic acid or AMSA (acronym for "anhydrous methane sulphonic acid" in the English language) or even 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).
[0034] On peut encore utiliser de l'acide méthane-sulfonique en solution aqueuse, telle que commercialisée par B.A.S.F sous la dénomination Lutropur®MSA prête à l'emploi ou diluée à l'eau dans les proportions indiquées ci-dessus. It is also possible to use 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.
[0035] Concernant la formulation d'acide sulfurique, tout type de formulation peut convenir. En règle générale, la formulation comprend de 0,01 % à 100% en poids d'acide sulfurique, plus généralement de 0,05% à 98% en poids, en particulier de 74% à 97% en poids, bornes incluses, d'acide sulfurique, par rapport au poids total de ladite formulation. Regarding the sulfuric acid formulation, any type of formulation may be suitable. As a general rule, 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.
[0036] La formulation est par exemple une formulation aqueuse, organique, ou encore hydro-organique. La formulation peut être un mélange concentré. En variante, la formulation peut également être une formulation prête à l'emploi, c'est- à-dire qu'elle ne nécessite pas d'être diluée. Enfin, au sens de la présente invention, la formulation peut être de l'acide sulfurique pur sans autre additif de formulation ou autre solvant ou diluant. De manière préférée, l'acide sulfurique est dilué à 97% en poids dans l'eau, tel que celui commercialisé par la société Arkema ou l'acide sulfurique dilué à 96% en poids dans l'eau commercialisé par la société BASF. The formulation is for example an aqueous, organic, or alternatively hydro-organic formulation. The formulation can be a concentrated mixture. Alternatively, the formulation may also be a ready-to-use formulation, i.e., it does not need to be diluted. Finally, within the meaning of the present invention, the formulation may be pure sulfuric acid without other formulation additive or other solvent or diluent. In a preferred manner, 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.
[0037] Selon un mode de réalisation préféré, la composition selon l'invention est utilisée en tant que catalyseur acide d'estérification, et de préférence en tant que catalyseur acide d'estérification d'acides gras. According to a preferred embodiment, the composition according to the invention is used as an acid esterification catalyst, and preferably as an acidic esterification catalyst for fatty acids.
[0038] La présente invention concerne également un catalyseur acide d'estérification, de préférence d'estérification d'acide gras comprenant, et de préférence consistant en, la composition acide telle que définie précédemment.  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.
[0039] La composition selon l'invention trouve une utilisation tout particulièrement intéressante en tant que catalyseur, par exemple comme catalyseur d'estérification d'acides gras purs ou en mélange dans les huiles ou graisses, que l'on dénomme alors « acides gras libres », par opposition aux acides gras présents sous la forme de mono-, di- et/ou tri-glycérides présents dans lesdites huiles et/ou graisses. The 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.
[0040] La réaction d'estérification des acides gras permet, à partir de la condensation d'un alcool sur un acide carboxylique gras, l'obtention d'un ester gras et d'une molécule d'eau. On entend par acide gras, un acide carboxylique à chaîne aliphatique notamment en C4-C36. Les acides gras naturels possèdent généralement une chaîne carbonée de 4 à 36 atomes de carbone, ladite chaîne carbonée pouvant être saturée ou insaturée, linéaire ou ramifiée. 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. The term "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.
[0041] Selon l'invention, les acides gras peuvent, de préférence, être des acides gras présents dans les huiles. Dans ce cas, la réaction d'estérification peut être suivie d'une réaction de transestérification en présence d'un alcool léger, comprenant généralement de 1 à 4 atomes de carbone, afin d'obtenir des esters d'acides gras et du glycérol, lesdits esters d'acides gras pouvant alors être utilisés comme carburant, dit « biodiesel ». According to the invention, the fatty acids may, preferably, be fatty acids present in the oils. In this case, 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".
[0042] Typiquement, lors de la préparation de biodiesel, si le taux d'acides gras résiduels présents dans l'huile ou la graisse est supérieur à 1 %, il existe un risque de saponification desdits acides gras résiduels par réaction avec les catalyseurs de transestérification. Ceci peut notamment présenter un inconvénient lors de la production de biodiesel, les savons formés pouvant créer une émulsion et rendre la séparation du biodiésel et du glycérol difficile, voire impossible. [0043] La Demanderesse a ainsi démontré que, par rapport à un acide alcane- sulfonique utilisé seul comme catalyseur ou par rapport à l'acide sulfurique utilisé seul comme catalyseur, le mélange d'au moins un acide alcane-sulfonique avec l'acide sulfurique dans les proportions revendiquées, permet, à l'issue d'une étape d'estérification, d'abaisser le taux d'acides gras résiduels en phase organique en- dessous de 1 ,1 % poids, de préférence 1 % poids, et plus particulièrement 0,95% poids ; ce qui est très difficile à réaliser avec un acide alcane-sulfonique utilisé seul ou l'acide sulfurique utilisé seul. Typically, during the preparation of biodiesel, if the level of residual fatty acids present in the oil or fat is greater than 1%, there is a risk of saponification of said residual fatty acids by reaction with the catalysts of transesterification. This can be particularly disadvantageous in the production of biodiesel, the formed soaps can create an emulsion and make the separation of biodiesel and glycerol difficult or impossible. 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.
[0044] Cette faible teneur en acides gras résiduels présente notamment un avantage sur la pureté finale de l'ester ou lors de l'étape de transestérification, souvent réalisée ultérieurement, puisque que cette dernière consommera moins de catalyseur, généralement catalyseur basique, souvent onéreux, et limitera la formation de savons qui perturbent la réaction.  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.
[0045] Il a également été démontré que l'utilisation de la composition d'acides selon l'invention comme catalyseur d'estérification permet d'obtenir une quantité de catalyseur résiduel moindre dans la phase organique que celle obtenue avec le catalyseur acide alcane-sulfonique seul ou le catalyseur acide sulfurique seul. Ceci permet de réduire la consommation de catalyseur basique lors d'une éventuelle étape ultérieure transestérification dans le but de préparer par exemple du biodiesel.  It has also been demonstrated that 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. This makes it possible to reduce the consumption of basic catalyst during a possible subsequent transesterification step in order to prepare, for example, biodiesel.
[0046] De manière surprenante, il a en outre été démontré que l'utilisation de la composition selon l'invention permet d'améliorer la cinétique de conversion des acides gras par rapport à l'utilisation d'un acide alcane-sulfonique utilisé seul ou l'acide sulfurique utilisé seul. Surprisingly, it has furthermore been demonstrated that the use of the 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.
[0047] Selon un mode de réalisation de l'invention, la composition selon l'invention est un catalyseur d'estérification et de transestérification permettant ainsi de réaliser, en une seule étape, l'estérification et la transestérification d'acides gras libres et d'acides gras présents sous la forme de mono-, di- et/ou tri-glycérides.  According to one embodiment of the invention, 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.
[0048] De façon optionnelle, la composition selon l'invention peut comprendre un ou plusieurs additifs bien connus de l'homme du métier, tels que ceux choisis parmi les inhibiteurs de corrosion, les parfums, les agents odorants, et autres additifs bien connus de l'homme du métier. [0049] Selon un mode de réalisation préféré, la composition selon l'invention comprend au moins un inhibiteur de corrosion. Selon un autre mode de réalisation préféré, la composition comprend au moins un parfum et/ou un agent odorant. Optionally, 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. According to a preferred embodiment, the composition according to the invention comprises at least one corrosion inhibitor. According to another preferred embodiment, the composition comprises at least one perfume and / or an odorant.
[0050] La composition selon l'invention peut être préparée par mélange des acides alcane-sulfonique(s) et sulfurique, selon toute méthode connue de l'homme du métier telle que, par exemple, le procédé décrit ci-après, ledit procédé n'étant pas limitatif. The 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.
[0051] Dans un récipient refroidi à environ 10°C, on introduit l'acide alcane sulfonique. L'acide sulfurique est ensuite ajouté selon toute technique connue de l'homme du métier, de sorte à limiter l'exothermie éventuelle de la réaction. De manière générale, l'addition de l'acide sulfurique sera effectuée de façon que la température n'excède pas 90°C, de préférence 80°C et plus particulièrement 60°C. Dans le cas où un solvant et d'éventuels additifs sont utilisés, il est préférable de les pré-mélanger avec l'acide alcane sulfonique avant d'ajouter lentement l'acide sulfurique. En fonction du solvant et des additifs utilisés, la vitesse d'addition de l'acide sulfurique sera effectuée de manière à ne pas atteindre une température du mélange supérieure à 90°C, de préférence 80°C et plus particulièrement 60°C.  In a container cooled to about 10 ° C, 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. In general, 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. In the case where a solvent and any additives are used, it is preferable to premix them with the alkanesulfonic acid before slowly adding the sulfuric acid. Depending on the solvent and the additives used, 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.
[0052] La présente demande concerne également un procédé de fabrication d'esters d'acides gras dans lequel les acides gras sont estérifiés en présence de la composition selon l'invention. 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.
[0053] Le procédé d'estérification consiste à introduire un acide gras ou un mélange d'acides gras dans un réacteur. L'alcool est ensuite ajouté puis le milieu est chauffé à une température généralement comprise entre 50°C et 200°C, plus généralement entre 60°C et 120°C, de préférence entre 60°C et 80°C. L'introduction de la composition selon l'invention se fait préférentiellement à la température d'estérification. Selon un autre mode de réalisation de l'invention, ladite composition peut être ajoutée avant le chauffage.  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.
[0054] Selon encore un autre mode de réalisation de l'invention, l'alcool et ladite composition peuvent être ajoutés de manière continue, ensemble ou séparément, lorsque le milieu a atteint la température d'estérification. Selon un mode de réalisation de l'invention, ladite composition peut être ajoutée avec l'acide gras ou le mélange d'acides gras. [0055] Selon un mode de réalisation préféré de l'invention, l'acide gras ou le mélange d'acides gras, l'alcool et ladite composition sont ajoutés ensemble avant le chauffage. La réaction d'estérification est alors réalisée dans la gamme de température indiquée précédemment. According to yet another embodiment of the invention, the alcohol and said composition may be added continuously, together or separately, when the medium has reached the esterification temperature. According to one embodiment of the invention, said composition may be added with the fatty acid or the mixture of fatty acids. According to a preferred embodiment of the invention, 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.
[0056] Au cours de ce procédé d'estérification, la composition selon l'invention joue le rôle de catalyseur.  During this esterification process, the composition according to the invention acts as a catalyst.
[0057] Les acides gras peuvent être de tout type choisis parmi les acides gras et les mélanges d'acides gras connus de l'homme du métier parmi lesquels les acides gras issus du milieu végétal ou animal, y compris les algues, et plus généralement du règne végétal. Ces dits acides comportent généralement et avantageusement au moins une insaturation oléfinique.  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.
[0058] Ces dits acides sont le plus souvent présents dans les huiles végétales extraites de diverses plantes oléagineuses telles que, de manière non limitative, les arachides, le tournesol, le colza, le ricin, le lesquerella, l'olive, le soja, le palmier à huile, l'avocat, la noix, la noisette, l'amande, le sésame, l'argousier et la limanthe, y compris les algues.  These so-called acids are most often present in vegetable 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.
[0059] Ils peuvent également être issus du monde animal terrestre ou marin, et dans ce dernier cas, ils peuvent être issus de graisses de poissons ou de graisses de mammifères, telles que, par exemple et de manière non limitative, les graisses provenant de bovins, de la morue, des baleines ou des phoques. Enfin, lesdits acides peuvent provenir d'huiles usagées recyclées telles que, de manière non limitative, les huiles de friture (« used cooking oil » en anglais).  They may also be from the terrestrial or marine animal world, and in the latter case, they may be derived from fish fats or mammalian fats, such as, for example and without limitation, fats derived from cattle, cod, whales or seals. Finally, said acids can come from recycled used oils such as, in a non-limiting manner, cooking oils ("used cooking oil" in English).
[0060] Comme décrit précédemment, les acides présents dans ces huiles sont mis en présence d'un alcool. L'alcool peut être de tout type connu de l'homme du métier tel que les mono-alcools, les diols, les triols, les tétrols, et autres, utilisés seuls ou en combinaison. De manière préférée, l'alcool utilisé a une masse molaire comprise 30 et 200 g. mol"1. As described above, 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. In a preferred manner, the alcohol used has a molar mass of between 30 and 200 g. mol "1 .
[0061] Selon un mode de réalisation de l'invention l'alcool est de type R1-OH où R1 est une chaîne alkyle ou aromatique, linéaire ou ramifiée, saturée ou insaturée, comprenant de 1 à 20 atomes de carbone. De manière préférée, R1 est une chaîne alkyle contenant de 1 à 10 carbone(s), en particulier de 1 à 4. Selon un autre mode de réalisation de l'invention, l'alcool possède plus de une fonction -OH, comme par exemple deux ou trois fonctions -OH, et, par exemple, l'alcool peut être le glycérol (propane-1 ,2,3-triol). According to one embodiment of the invention 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. Preferably, R 1 is an alkyl chain containing from 1 to 10 carbon (s), in particular from 1 to 4. According to another embodiment of the invention, 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).
[0062] Dans un mode de réalisation de l'invention où la composition d'acides est utilisée comme catalyseur de réaction d'estérification d'acides gras, et en particulier d'acides gras libres présents dans des huiles, le ratio molaire catalyseur selon l'invention/acides gras est compris entre 0,001 et 1 , de manière préférée entre 0,01 et 0,5 et plus particulièrement entre 0,02 à 0,2. Le nombre de moles d'acides gras est mesuré par dosage acido-basique par potentiométrie et est exprimé en moles par gramme d'acides gras présents dans le produit de départ. Cette valeur est ensuite multipliée par le ratio molaire catalyseur/acides gras, pour déterminer la quantité de catalyseur à ajouter.  In one embodiment of the invention wherein the acid composition is used as an esterification reaction catalyst for fatty acids, and in particular free fatty acids present in oils, 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.
[0063] Selon un mode de réalisation du procédé d'estérification selon l'invention, le ratio molaire alcool /acides gras est compris entre 1 et 20, de manière préférée entre 4 et 10.  According to one embodiment of the esterification process according to the invention, the molar ratio alcohol / fatty acids is between 1 and 20, preferably between 4 and 10.
[0064] Selon un mode de réalisation de l'invention, la réaction d'estérification des acides gras peut être effectuée à toute température mais de préférence à des températures comprises entre 50°C et 200°C, plus généralement à des températures comprises entre 60°C et 120°C, de préférence entre 60°C et 80°C.  According to one embodiment of the invention, 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.
[0065] Selon un mode de réalisation de l'invention, la réaction d'estérification des acides gras peut être réalisée à toute pression mais de préférence sous une pression comprise entre 103 Pa (0,01 bars absolus) et 2.106 Pa (20 bars absolus), plus généralement entre la pression atmosphérique et 106 Pa (10 bars absolus) et de manière tout particulièrement préférée sous pression atmosphérique. According to one embodiment of the invention, 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.
[0066] Le temps de réaction pour l'estérification des acides gras peut varier dans de grandes proportions et est généralement compris entre quelques minutes et quelques heures, par exemple entre 10 minutes et 6 heures, typiquement entre 30 minutes et 180 minutes. 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.
[0067] La réaction d'estérification peut être effectuée en batch ou en continu. Le catalyseur selon l'invention est ajouté au mélange ou de manière séparée dans le milieu réactionnel. Il peut être ajouté seul ou en co-alimentation avec la source d'acides gras (huile, graisse animale, etc..) et/ou l'alcool. La réaction peut être effectuée dans un ou plusieurs réacteurs, entre 2 et 15, plus généralement 2 à 10 réacteurs, plus généralement encore de 2 à 5 réacteurs, disposés en parallèle ou en cascade. Selon un mode particulier, on préfère le procédé en batch avec plusieurs réacteurs disposés en cascade. 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.
[0068] Il peut être avantageux d'opérer des séparations de phases organique et aqueuse entre deux réacteurs. Afin d'améliorer le rendement de la réaction, l'eau formée peut être éliminée selon toute méthode bien connue de l'homme du métier, par exemple au fur et à mesure de sa formation, et par exemple par chauffage. Dans un mode de réalisation de l'invention, l'élimination de l'eau peut entraîner l'élimination de tout ou partie du solvant, en particulier lorsque le solvant est un alcool.  It may be advantageous to carry out organic and aqueous phase separations between two reactors. In order to improve the efficiency of the reaction, 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.
[0069] Selon un mode de réalisation de l'invention, les acides gras libres utilisés proviennent d'huile d'origine végétale afin d'obtenir du biocarburant, notamment du biodiesel. Dans ce cas-là, le biodiesel est obtenu après une étape de transestérification, comme décrit ci-dessus. Si une étape de neutralisation de ce biodiesel est nécessaire, il est possible d'utiliser la phase aqueuse acide obtenue à la fin de la réaction d'estérification des acides gras libres. Selon un mode de réalisation de l'invention, l'alcool est éliminé avant d'utiliser ladite phase acide.  According to one embodiment of the invention, the free fatty acids used come from vegetable oil to obtain biofuel, including biodiesel. In this case, 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. According to one embodiment of the invention, the alcohol is removed before using said acid phase.
[0070] La réaction d'estérification des acides gras selon l'invention permet également d'obtenir des produits pouvant être utilisés dans divers domaines tels que la cosmétique, les lubrifiants, l'agrochimie, la pharmacie, le nettoyage, etc. 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.
Exemples Examples
[0071] Les exemples qui suivent permettent d'illustrer la présente invention mais ne sont en aucun cas limitatifs. The following examples illustrate the present invention but are in no way limiting.
Mode de préparation d'une composition selon l'invention : Mode of preparation of a composition according to the invention
[0072] On prépare une composition comprenant : A composition is prepared comprising:
• 60% en poids d'acide méthane-sulfonique dilué à 70% dans l'eau (soit 42% en poids d'acide méthane-sulfonique pur) ;  60% by weight of methanesulfonic acid diluted to 70% in water (ie 42% by weight of pure methanesulfonic acid);
• 40% en poids d'acide sulfurique dilué à 97% dans l'eau (soit 39% en poids d'acide sulfurique pur). [0073] La composition ci-dessus est préparée à partir d'une solution aqueuse à 70% en poids d'AMS LC de la société Arkema, introduite dans un réacteur double enveloppe refroidi par un bain thermostatique régulé à 10°C. L'acide sulfurique à 97% en poids est ajouté, goutte à goutte, par une ampoule de coulée fixé sur le chapeau du réacteur double enveloppe en faisant attention à ne pas dépasser 60°C. 40% by weight of sulfuric acid diluted to 97% in water (ie 39% by weight of pure sulfuric acid). 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.
[0074] La composition ainsi obtenue contient, pour 100 g de composition, 0,8355 moles d'acides (42/96 + 39/98 (96 étant la masse molaire de l'AMS et 98 étant la masse molaire de H2SO4)). La masse molaire du mélange d'acide est de 1 19,7 g/mole (= 100/0,8355). The 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 ). ). The molar mass of the acid mixture is 1 19.7 g / mol (= 100 / 0.8355).
[0075] La composition ainsi préparée est utilisée comme catalyseur d'estérification dans l'exemple ci-dessous.  The composition thus prepared is used as esterification catalyst in the example below.
Exemple d'estérification d'une huile : Example of esterification of an oil:
[0076] On utilise un mélange industriel comprenant une huile comprenant des triglycérides et 94% en poids d'acides gras libres (FFA pour « Free Fatty Acids ») avec un poids moléculaire moyen des acides gras à 268 ± 1 g/mol.  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.
[0077] Le ratio molaire méthanol/FFA est égal à 8. Le ratio molaire catalyseur/FFA est égal à 0,175. The methanol / FFA molar ratio is equal to 8. The catalyst / FFA molar ratio is equal to 0.175.
[0078] Dans un réacteur double enveloppe préchauffé à 50°C et équipé d'une agitation mécanique, d'une sonde de température et d'un réfrigérant, on introduit 451 g dudit mélange industriel comprenant des triglycérides et 94% en poids de FFA, soit 1 ,582 moles d'acide gras. La quantité de méthanol introduite est déterminée comme suit : 1 ,582 x 8 x 32 = 405 g de méthanol (8 équivalents molaire/FAA).  In a double jacket reactor preheated to 50 ° C. and equipped with mechanical stirring, 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 quantity of methanol introduced is determined as follows: 1. 582 × 8 × 32 = 405 g of methanol (8 molar equivalents / FAA).
[0079] Le mélange réactionnel est chauffé à 70°C et on introduit alors le catalyseur préparé ci-dessus. La quantité de catalyseur à ajouter est calculée comme suit : 1 ,582 x 0,175 x 1 19,7 = 33,14 g de composition (0,175 équivalent molaire/FFA). Le milieu réactionnel est agité 2 heures à 70°C, puis mis à décanter et laissé une nuit à 70°C. Les phases aqueuse et organique sont analysées suivant les méthodes décrites ci-dessous. Méthodes d'analyse : The reaction mixture is heated to 70 ° C and then introduced the catalyst prepared above. The amount of catalyst to be added is calculated as follows: 1. 582 x 0.175 x 19.7 = 33.14 g of composition (0.175 molar equivalents / FFA). 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:
[0080] Les FFA et le catalyseur, dans la phase organique, sont dosés par potentiométrie de la manière suivante : dans un bêcher, on introduit environ 1 ,5 g de phase organique, puis on complète jusqu'à 50 mL avec le mélange toluène/isopropanol/eau dans les proportions 500/495/5 en volume.  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.
[0081] Le dosage potentiométrique est effectué avec du KOH 0,1 mol.L"1 dans l'éthanol avec une électrode DG1 13-SC n°2 et un titrateur T50, tous les deux de chez Mettler Toledo. 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.
[0082] Le dosage permet de déterminer de manière précise, d'une part la quantité de catalyseur résiduel dans la phase organique en moles par gramme et, d'autre part, la teneur en acide gras résiduels dans la phase organique en % poids.  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.
[0083] Le dosage acido-basique permet d'obtenir 2 sauts de potentiels : le premier saut correspond au catalyseur et le second saut correspond aux acides gras résiduels. 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.
Résultats : Results:
[0084] Les dosages décrits précédemment permettent de mesurer le pourcentage de FFA résiduels dans la phase organique. The assays described above make it possible to measure the percentage of residual FFA in the organic phase.
[0085] Ces résultats, représentés sur la Figure 1 , montrent que le pourcentage massique de FFA résiduels est de 1 ,2 avec l'AMS seul, de 1 ,05 avec le H2SO4 seul, de 0,89 avec la composition 70 AMS/30 H2SO4 selon l'invention, et de 0,9 avec la composition 60 AMS/40 H2SO4 selon l'invention. These results, represented in FIG. 1, show that the mass percentage of residual FFA is 1, 2 with AMS alone, of 1, 05 with H2SO 4 alone, of 0.89 with composition 70 AMS. H 2 SO 4 according to the invention, and 0.9 with the composition 60 AMS / 40 H 2 SO 4 according to the invention.
[0086] Grâce à la composition selon l'invention, on obtient donc un pourcentage de FFA résiduels inférieur à ceux obtenus avec les autres compositions.  With the composition according to the invention, therefore, a percentage of residual FFA is obtained that is lower than those obtained with the other compositions.
[0087] Par ailleurs, la cinétique de conversion des FFA est améliorée par rapport à l'utilisation de chaque acide seul, telle que représentée sur la figure 2. En effet, on remarque, avec la composition selon l'invention, une cinétique de conversion en ester plus rapide et, au bout d'un même temps donné (1 h), une meilleure conversion des FFA (98% avec la composition selon l'invention et 97% avec l'AMS seul et le H2SO seul). Furthermore, the FFA conversion kinetics is improved with respect to the use of each single acid, as shown in FIG. 2. In fact, it is noted, with the composition according to the invention, 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) .

Claims

REVENDICATIONS
1. Composition comprenant : 1. Composition comprising:
- au moins un acide alcane-sulfonique de formule R-SO3H dans laquelle R représente une chaîne hydrocarbonée saturée, linéaire ou ramifiée, comportant de 1 à 4 atomes de carbone, pouvant ou non, être substituée par au moins un atome d'halogène ;  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;
- de l'acide sulfurique ;  - sulfuric acid;
- et éventuellement, au moins un solvant ;  and optionally, at least one solvent;
dans laquelle : in which :
- la proportion en poids en acide alcane-sulfonique par rapport au poids total d'acide alcane-sulfonique et d'acide sulfurique est comprise entre 40% et 90%, de préférence entre 44% et 89% ;  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%;
- la proportion en poids en acide sulfurique par rapport au poids total d'acide alcane-sulfonique et d'acide sulfurique est comprise entre 10% et 60%, de préférence entre 1 1 % et 56%.  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%.
2. Composition selon la revendication 1 dans laquelle le solvant est choisi parmi l'eau, un alcool et un éther, pris seuls ou en combinaison. 2. Composition according to claim 1 wherein the solvent is selected from water, an alcohol and an ether, taken alone or in combination.
3. Composition selon l'une des revendications précédentes dans laquelle le solvant est l'eau ou un alcool en Ci à C3, pris seuls ou en combinaison. 3. Composition according to one of the preceding claims wherein the solvent is water or a C 1 -C 3 alcohol, taken alone or in combination.
4. Composition selon l'une des revendications précédentes dans laquelle le solvant est l'eau ou le méthanol, pris seuls ou en combinaison. 4. Composition according to one of the preceding claims wherein the solvent is water or methanol, alone or in combination.
5. Composition selon l'un des revendications précédentes dans laquelle la proportion en poids de solvant par rapport au poids total de la composition est comprise entre 0% et 50%, de préférence entre 5% et 35%. 5. Composition according to one of the preceding claims wherein the proportion by weight of solvent relative to the total weight of the composition is between 0% and 50%, preferably between 5% and 35%.
6. Composition selon l'une des revendications précédentes dans laquelle l'acide alcane-sulfonique est choisi parmi l'acide méthane-sulfonique, l'acide éthane-sulfonique, l'acide n-propane-sulfonique, l'acide /'so-propane-sulfonique, l'acide n-butane-sulfonique, l'acide /'so-butane-sulfonique, l'acide sec-butane- sulfonique, l'acide terf-butane-sulfonique, l'acide trifluoro méthane-sulfonique, et les mélanges de deux ou plusieurs d'entre eux en toutes proportions. 6. Composition according to one of the preceding claims wherein the alkane sulfonic acid is selected from methanesulfonic acid, ethanesulfonic acid, n-propane-sulfonic acid, / 'so -propane-sulphonic acid, n-butane-sulfonic acid, / 'n-butane sulfonic acid, sulfonic sec-butane acid, tert-butane-sulfonic acid, trifluoro methane sulfonic acid , and mixtures of two or more of them in all proportions.
7. Composition selon l'une des revendications précédentes dans laquelle l'acide alcane-sulfonique est l'acide méthane-sulfonique. 7. Composition according to one of the preceding claims wherein the alkanesulfonic acid is methanesulfonic acid.
8. Composition selon l'une des revendications précédentes comprenant au moins un inhibiteur de corrosion. 8. Composition according to one of the preceding claims comprising at least one corrosion inhibitor.
9. Composition selon l'une des revendications précédentes comprenant au moins un parfum ou un agent odorant, pris seul ou en combinaison. 9. Composition according to one of the preceding claims comprising at least one perfume or an odorant, taken alone or in combination.
10. Utilisation de la composition selon l'une des revendications 1 à 9 comme catalyseur d'estérification, de préférence d'estérification d'acide gras. 10. Use of the composition according to one of claims 1 to 9 as esterification catalyst, preferably esterification of fatty acid.
11. Procédé de fabrication d'esters d'acides gras comprenant les étapes de : a/ introduire au moins un acides gras dans un réacteur ; 11. A process for producing fatty acid esters comprising the steps of: a / introducing at least one fatty acid into a reactor;
b/ ajouter au moins un alcool ; b / add at least one alcohol;
c/ chauffer le milieu réactionnel ; c / heating the reaction medium;
d/ introduire la composition selon l'une quelconque des revendications 1 à 9 comme catalyseur ; d / introducing the composition according to any one of claims 1 to 9 as a catalyst;
e/ optionnellement, éliminer l'eau formée au cours de la réaction d'estérification ; f/ récupérer les esters d'acides gras ; e / optionally, removing the water formed during the esterification reaction; f / recovering fatty acid esters;
l'étape d pouvant être réalisée en même temps que l'étape a et/ou b, de préférence en même temps que les étapes a et/ou b. step d may be performed simultaneously with step a and / or b, preferably at the same time as steps a and / or b.
12. Procédé selon la revendication 1 1 dans lequel le ratio molaire catalyseur/acides gras est compris entre 0,001 et 1 , de préférence entre 0,01 et 0,5 et plus particulièrement entre 0,02 à 0,2. 12. The method of claim 1 1 wherein 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 to 0.2.
EP17812006.9A 2016-11-25 2017-11-20 Acid composition for the treatment of fatty acids Pending EP3544948A1 (en)

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US201662426334P 2016-11-25 2016-11-25
FR1661482A FR3059327B1 (en) 2016-11-25 2016-11-25 ACID COMPOSITION FOR TREATMENT OF FATTY ACIDS
PCT/FR2017/053172 WO2018096248A1 (en) 2016-11-25 2017-11-20 Acid composition for the treatment of fatty acids

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WO2018096248A1 (en) 2018-05-31
US20190374931A1 (en) 2019-12-12
FR3059327A1 (en) 2018-06-01
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