Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
  • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
  • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
  • C07C219/08—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of an acyclic unsaturated carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
  • C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
  • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
  • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
  • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
• • 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
  • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
  • C07C69/54—Acrylic acid esters; Methacrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

• R represents a linear or branched alkyl radical comprising from 1 to 18 carbon atoms and comprising, where appropriate a heteroatom such as nitrogen.
• the esters of acrylic acid, acrylates are widely used in the industry. The range of uses for the manufacture of polymers is extensive. However, some of them require the acrylate used as monomer or as monomer co in the manufacture of copolymers or terpolymers the respect of standards for purity. These standards of purity vis-à-vis certain compounds are specific and directly related to the polymer of the final application. It is difficult to achieve these standards without resorting to expensive fractionation and purification techniques.
• the acrylates are prepared from acrylic acid either by simple esterification, or by a trans-esterification reaction of a light acrylate of methyl, ethyl, propyl or butyl acrylate type, with the necessary hydroxylated compound. the synthesis of the polymer constituting or forming part of the final ester.
• the 2-ethylhexyl acrylate ester of formula CH 2 CH-COO-
• R 0 OH R 0 being either CH 3 or C 2 H 5 , or C 3 H 7 , or C 4 H 9 .
• Butyl acrylate (ABu), ester of formula CH 2 CH-COO-C 4 H 9 , very often used in copolymerization processes to give the copolymer an elastomeric character is most often synthesized by direct esterification of the acrylic acid with n-butanol.
• This oxidation process which is very efficient, however, has the disadvantage of forming by-products, impurities, such as in particular furfural, cyclic aldehyde, maleic anhydride or maleic acid which are very difficult to separate. of the main product even after all the conventional purification process.
• this reaction is generally conducted in the vapor phase, usually in two steps, which can be conducted in two separate reactors or a single reactor:
• the first step achieves the substantially quantitative oxidation of propylene to a mixture rich in acrolein (ACO), in which the AA is a minority * the second step completes the conversion of the ACO into AA.
• ACO acrolein
• the gaseous mixture resulting from the 2nd oxidation reaction stage consists, apart from acrylic acid:
• incondensable light compounds under usual temperature and pressure conditions (unconverted nitrogen, oxygen and propylene, propane in reactive propylene, carbon monoxide and carbon dioxide formed in small quantities by ultimate oxidation),
• condensable light compounds in particular water, generated by the oxidation reaction of propylene, unconverted acrolein, light aldehydes, such as formaldehyde and acetaldehyde, and acetic acid main impurity generated in the reaction section ,
• the second stage of fabrication is to recover the AA from the gas mixture from the 2nd stage, by introducing this gas in the foot of an absorption column where it meets against the current solvent introduced at the top of column.
• the solvent used in this column is water or a hydrophobic solvent with a high boiling point.
• the complementary purification steps comprise a dehydration step, generally carried out in the presence of water-immiscible solvent, in a heteroazeotropic extraction or distillation column. then a light removal step, in particular acetic acid and formic acid, and a step of separating the heavy compounds.
• furfuraldehyde even if present in trace amounts in acrylic acid, with a concentration greater than 0.01% by weight, may in certain subsequent transformations have major drawbacks having a high negative impact.
• the degree of polymerization required for the product in the intended application In a similar way it has been observed that this process also has the disadvantage of synthesizing also as a by-product, anhydride or maleic acid which, at a concentration greater than 0.1% by weight, may in certain applications be a drawback important because of the acidity generated in the monomer.
• the presence of the iso isomer, isobutyl acrylate can modify the Tg (glass transition temperature) of the final polymers.
• furfuraldehyde is a troublesome impurity for the manufacture of ADAME and the subsequent use of this monomer as a cationic flocculant precursor.
• the object of the invention is to overcome these drawbacks by proposing a new mode of synthesis of these esters by implementing another process for the synthesis of acrylic acid, which is the subject of more recent developments, using as raw material glycerol in place of propylene.
• the use of alcohols, themselves of vegetable and / or animal origin will make it possible to consolidate the "bioressourced" nature of the process by essentially consuming renewable raw materials.
• the process for synthesizing acrylic acid by this route is a two-step process consisting in a first step of dehydrating glycerol to acrolein and then in a second step of oxidizing acrolein to acrylic acid according to the following reaction process:
• Glycerol can lead to acrolein.
• Glycerol also called glycerin
• Glycerol is derived from the methanolysis of vegetable and / or animal oils at the same time as the methyl esters which are used in particular as fuels or fuels in diesel and heating oil.
• Glycerol can also derive from the hydrolysis of vegetable and / or animal oils leading to the formation of fatty acids, or the saponification of vegetable and / or animal oils leading to the formation of soaps. It is a natural product that has a "green" aura, is available in large quantities and can be stored and transported without difficulty. Many studies are devoted to the valorisation of glycerol according to its degree of purity, and the dehydration of glycerol to acrolein is one of the ways envisaged.
• the above-mentioned reaction involved in obtaining acrolein from glycerol is a balanced reaction.
• the hydration reaction is favored at low temperatures, and dehydration is favored at high temperatures.
• the reaction can be carried out in the liquid phase or in the gas phase. This type of reaction is known to be catalyzed by acids.
• the oxidation reaction of acrolein is usually carried out in the gaseous phase in the presence of an oxidation catalyst.
• US Pat. No. 5,387,720 describes a process for producing acrolein by dehydration of glycerol, in the liquid phase or in the gas phase, on acidic solid catalysts defined by their Hammett acidity.
• an aqueous solution comprising from 10 to 40% of glycerol is used and is carried out at temperatures of between 180 ° and 340 ° C. in the liquid phase and between 250 ° and 340 ° C. in the gas phase.
• the reaction in the gas phase is preferable because it makes it possible to have a glycerol conversion rate close to 100%.
• This reaction leads after condensation to an aqueous solution of acrolein containing secondary products such as hydroxypropanone, propanaldehyde, acetaldehyde, acetone, adducts of acrolein on glycerol.
• secondary products such as hydroxypropanone, propanaldehyde, acetaldehyde, acetone, adducts of acrolein on glycerol.
• About 10% of the glycerol is converted to hydroxypropanone, which is found as a major by-product in the acrolein solution.
• Acrolein is recovered and purified by distillation or fractional condensation.
• a conversion of 15-25% can not be exceeded, under penalty of forming the secondary products in an unacceptable quantity and to obtain a quality of monomer (acrolein or acrylic acid) incompatible with the desired quality.
• the dehydration reaction of glycerol in the gas phase is carried out in the presence of molecular
• the document WO 06/087084 recommends the use of strongly acidic solid catalysts having a Hammett Ho acidity of between -9 and -18 for the dehydration of glycerol in the gas phase.
• the glycerol used as raw material of the dehydration reaction is an aqueous solution
• a preferred variant of the two-step process consists in carrying out a partial condensation of water in the reaction gases resulting from the first step of dehydration of glycerol, before introducing the gas into the second stage oxidation reactor in acrylic acid.
• This additional condensation step consists in cooling the gas stream to a temperature such that a portion of the water is condensed in the liquid phase and all of the acrolein remains in gaseous form.
• WO 06/114506 discloses a process for the preparation of acrylic acid in one step by reaction of oxy dehydration of glycerol in the presence of molecular oxygen with the 2 consecutive reactions of dehydration and oxidation.
• the invention aims to overcome the aforementioned drawbacks by proposing to manufacture esters to use an acrylic acid obtained by a different mode of synthesis, using as main raw material glycerol.
• the third step is carried out in two sub-steps, the first consisting in esterifying acrylic acid with a light alcohol having 1 to 4 carbon atoms and then in the second converting the ester of the alcohol. selected light, usually methyl or ethyl, to the desired ester by transesterification with alcohol ROH.
• the alcohol ROH comprises a heteroatom such as nitrogen.
• the first two steps can be carried out, as described in the application WO 06/114506, in a single reactor by reaction of oxy dehydration of glycerol in the presence of molecular oxygen using the 2 consecutive reactions of dehydration and oxidation.
• an intermediate step of condensation of the water contained in the stream resulting from the first glycerol dehydration step is carried out before introduction into the second stage oxidation reactor in acrylic acid.
• the first step of dehydration of glycerol is carried out in the gas phase in the reactor in the presence of a catalyst at a temperature ranging from 150 ° C. to 500 ° C., preferably between 250 ° C. and 350 ° C., and a pressure comprised between 10 5 to 5.10 5 Pa.
• the reactor used can be operated in a fixed bed, fluidized bed or circulating fluidized bed, or in a configuration in modules (plates or baskets) in the presence of solid acid catalysts.
• Suitable catalysts are homogeneous or multiphase materials, insoluble in the reaction medium which have a Hammett acidity, denoted Ho less than +2 as indicated in US Pat. No. 5,387,720, which refers to the article by K. Tanabe et al in "Studies in Surface Science and Catalysis", Vol 51, 1989, Chapters 1 and 2; the acidity of Hammett is determined by amine titration using indicators or adsorption of a base in the gas phase.
• the catalysts meeting the acidity criterion Ho of less than +2 may be chosen from natural or synthetic siliceous materials or acidic zeolites; inorganic carriers, such as oxides, coated with inorganic acids, mono, di, tri or polyacids; oxides or mixed oxides or heteropolyacids. These catalysts can generally be constituted by a heteropoly acid salt in which protons of said heteropoly acid are exchanged with at least one cation chosen from the elements belonging to Groups I to XVI of the
• mixed oxides mention may also be made of those based on iron and phosphorus and those based on cesium, phosphorus and tungsten.
• the catalysts are chosen from zeolites, Nafion ® composites (based on sulfo nic acid of fluorinated polymers), chlorinated aluminas, phosphotungstic acid and salts of acids and / or silicotungstic, and different oxide type solid metals such as Ta 2 Os tantalum oxide, Nb 2 Os niobium oxide, Al 2 O 3 alumina, TiO 2 titanium oxide, ZrO 2 zirconia, SnO 2 tin oxide, silica SiO 2 or silico-aluminate SiO 2 -Al 2 Os, impregnated with acid functions such as BO3 borate, SO 4 sulfate, WO3 tungstate, PO 4 phosphate, SiO 2 silicate, or MOO3 molybdate. According to data from the literature these catalysts all have a Hammett's acidity of less than +2.
• the foregoing catalysts may further comprise a promoter such as Au, Ag, Cu, Pt, Rh, Pd, Ru, Sm, Ce, Yt, Sc, La, Zn, Mg, Fe, Co, Ni, or montmorillonite.
• the preferred catalysts are zirconium phosphates, tungsten zirconias, zirconium silicates, titanium or tin oxides impregnated with tungstate or phosphotungstate, phosphated aluminas or silicas, heteropolyacids or salts of heteropolyacids, iron phosphates and phosphates. iron phosphates comprising a promoter.
• the second step of the process according to the invention is carried out under the following conditions.
• the oxidation reaction of the acrolein-rich stream generated during the first step (concentration of acrolein generally from 2 to 15% by volume) is carried out in the presence of molecular oxygen which can also be introduced in the form of air or in the form of enriched or diluted with molecular oxygen at a concentration of 1
• inert gases such as N 2 , CO 2 , methane, ethane, propane or other light alkanes and water.
• the inert gases necessary for the process, in order to prevent the reaction mixture from being in the flammable range, may possibly consist wholly or partly of the gases obtained at the top of the separation column placed downstream of the second reactor. step.
• the oxidation reaction is carried out at a temperature ranging from 200 ° C. to 350 ° C., preferably from 250 ° C. to 320 ° C., and at a pressure ranging from 10 5 to 5 ⁇ 10 5 Pa.
• oxidation catalyst all types of catalysts well known to those skilled in the art are used for this reaction. Generally solids containing at least one element selected from the list Mo, V, W, Re, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, are used.
• Te, Sb, Bi, Pt, Pd, Ru, Rh present in the metal form or in oxide, sulphate or phosphate form.
• the formulations containing, in the form of mixed oxides, Mo and / or V and / or W and / or Cu and / or Sb and / or Fe as main constituents are used.
• the reactor can operate in a fixed bed, in a fluidized bed or in a circulating fluidized bed. It is also possible to use a plate heat exchanger with a modular arrangement of the catalyst such as those described in the patents cited below: EP 995 491, EP 1 147 807 or US 2005/0020851.
• the third esterification step carried out to synthesize the esters is carried out under the following standard conditions.
• the catalytic reaction is carried out under the following temperature and pressure conditions: temperature of 60 to 90 ° C. and pressure of 1.2 ⁇ 10 5 Pa at 2.10 5 Pa.
• the catalysts of the esterification reaction are acidic. They may be chosen from mineral acids, such as sulfuric acid, sulphonic acids, phosphoric acid or p-toluene sufonic, benzene sulphonic, methanesulfonic or dodecyl sulphonic derivatives, the reaction taking place in a homogeneous monophasic medium. .
• the catalysts can also be solid polymers (acid ion exchange resins), and in this case, the reaction takes place in a biphasic heterogeneous medium.
• catalysts will generally be sulfonated styrene-divinylbenzene (DVB) copolymers called "acid resins" of the gel or macroporous type whose DVB content may vary from 2 to 25% by weight and whose acidity is expressed in terms of eq H + / l. of resins is between 1 and 2. They are for example provided by Lanxess under the name
• the catalysts used are preferably acidic ion exchange resins of the Amberlyst 131 and Lewatit K1461 type.
• the reaction is conducted in a reactor operating continuously.
• the conditions of the transesterification are as follows.
• the transesterification reaction is carried out batchwise or continuously as described in patents FR 2 617 840, FR 2 777 561 and FR 2 876 375.
• the transesterification process consists in reacting, under bubbling with air, in the presence of a catalyst and at least one polymerization inhibitor, at a temperature of between 20 and 120 ° C. and at a pressure equal to atmospheric pressure. or lower than atmospheric pressure, the light acrylic ester with the target alcohol, usually a dialkyl amino alcohol, in a molar ratio of light acrylic ester to amino alcohol of between 1.3 and 5 in the presence of a catalyst, and during the reaction to withdraw the azeotropic mixture light ester / light alcohol, and at the end of the reaction to separate the dialkylamino alkyl acrylate generally by distillation.
• dialkylamino alkyl acrylate is meant dimethylaminoethyl acrylate and diethylaminoethyl acrylate.
• alkyl titanates for example ethyl titanate, tin derivatives such as dibutyltin oxide or distannoxanes, zirconium derivatives such as zirconium acetylacetonate or derivatives thereof.
• magnesium such as magnesium ethoxide, calcium derivatives such as calcium acetylacetonate.
• a light acrylic ester molar ratio on dialkyl amino alcohol of between 1.5 and 2.5 is chosen.
• the temperature is preferably maintained between 80 and
• the pressure is preferably maintained between 50 and 85 kPa, i.e. the reaction is conducted under slightly reduced pressure.
• dialkyl amino alcohols suitable for the present invention mention may be made of diethylaminoethanol and dimethylaminoethanol, with dimethylaminoethanol being preferred.
• phenothiazine hydroquinone methyl ether, hydroquinone, ditertiobutylmethylhydroxytoluene, 4-hydroxy-Tempo alone or in admixture are used at a rate of 500 to 2500 ppm relative to the total charge. .
• esters of acrylic acid having a high level of purity, that is to say in this case a furfural content ⁇ 3 ppm, particularly troublesome compound for the subsequent application of the ester in question.
• these compounds are especially intended to be converted into quaternary salts, so-called "ADAME quats” by action, for example, CH 3 Cl.
• ADAME quats may enter into the constitution of flocculants for the treatment of water under form of ADAME-quats / acrylamide copolymers.
• the variant of the process consists in a first step of subjecting glycerol to a dehydration reaction in the presence of an acid catalyst having a Hammett Ho acidity of less than +2 and then, in a second step, to oxidize acrolein formed in acrylic acid. by oxidation in the presence of a catalyst containing in the form of mixed oxides the following metals Mo and / or V and / or W and / or
• the transesterification of the light acrylate with the aminoalcohol of formula (CH 2 ) 2 -N-CH 2 -CH 2 OH is preferably carried out in the presence of a catalyst consisting of a titanate of tetrabutyl, tetraethyl and tetra (2-ethylhexyl) at a temperature between 90 and 120 0 C in a stirred reactor at a pressure of between 0.5.10 5 Pa and 10 5 Pa
• the furfural content of acrolein, after condensation of water, which represents the major part of the reaction medium (it should be remembered that the glycerol is treated in the form of an aqueous solution) before its introduction in the second step is of the order of a few tens of ppm to compare with a few hundred ppm of the first stage effluent of the propylene process.
• ADAME a slightly lower concentration in the technical AA (AAT), of the order of ten or so.
• AAT technical AA
• the ADAME obtained is quaternized by the action of methyl chloride according to method described for example in EP 1144356, EP 1144357 or WO 00/43348 to lead to an aqueous solution of ADAMQUAT MC 80% active ingredient.
• AD AMQUAT TM is then polymerized with acrylamide and the resulting polymer is characterized by measuring the viscosity at room temperature of a molar aqueous solution of NaCl containing 0.1% of the copolymer manufactured as illustrated in patent FR 2,815,036.
• the synthesis is directed to the synthesis of an ester of formula
• CH 2 CH-COO-CH 2 -CH (C 2 H S ) - (CH 2 ) S -CH 3 (A2EH) with a low residual acidity content.
• the equilibrium reaction must be displaced to the ester formation by removal of water, generally by stripping with a water-forming solvent a heteroazeotropic mixture, or more simply and preferentially in the form of a mixture of the alcohol, the ester and the water, which also forms a heteroazeotropic mixture. After decantation, the aqueous phase is removed and the organic phase is recycled to the reaction stage.
• the following purification steps, to obtain the pure acrylic ester consist in carrying out an elimination of the light compounds (mainly excess alcohol, unconverted acrylic acid and residual water) at the head of a top-loading column, and then elimination of the compounds heavy at the bottom of a tailing column, the pure product being recovered at the head of this column.
• the light compounds mainly excess alcohol, unconverted acrylic acid and residual water
• the problem posed by the manufacture of the acrylic ester A2EH from an acrylic acid manufactured according to a conventional process of the petrochemical type and then esterified with 2-ethyl hexanol using a process based on acid resins is the presence in the The ester produces a high level of certain impurities, in particular maleic-type compounds, which take the latter out of the specifications allowed for their marketing in most fields, in particular in the adhesives and leather and textile processing industries where the presence of acidity slows down the polymerization process.
• the residual acidity of the purified monomer can come from two main sources: the presence of acrylic acid and that of maleic anhydride contained as an impurity in the acrylic acid used for the esterification.
• the maleic anhydride is a compound with a volatility close to that of 1 ⁇ 2EH.
• the maleic anhydride may be derived from the incomplete conversion of this compound to mono (2-ethylhexyl) maleate and di (2-ethylhexyl) maleate by esterification with the alcohol. Indeed, mono (2-ethyl hexyl) maleate is a thermally unstable compound, which undergoes in the purification columns a disproportionation of di (2-ethyl hexyl) anhydride and maleate.
• the maleic anhydride generated by this disproportionation reaction and / or present as the impurity of the unconverted acrylic acid by esterification can not be easily removed by distillation, because of its boiling point close to that of monomer, and is responsible for an acidity of the synthesized ester, which is troublesome for the manufacture of polymers from this ester.
• the maleic anhydride content at the outlet of the oxidation reactor of acrolein in AA from propylene is of the order of 1% by weight, after purification to the so-called technical grade AA (AAT) content. is very generally of the order of 1000 to 1500 ppm.
• AAT technical grade AA
• the maleic anhydride present in the AAT will unfortunately remain in the medium during the esterification step of AAT with ethyl-2-hexanol to form esters, ethyl-2-hexanol monomaleate and mostly (ten times more) the dimaleate of this alcohol.
• the separation of the latter which is a heavy product is relatively easy by distillation.
• the first two stages, dehydration and oxidation, are carried out as described above and the esterification reaction is carried out in the liquid phase at a temperature of between 50 and 150 ° C. in the presence of a solid acid catalyst, for example of the resin type.
• a solid acid catalyst for example of the resin type.
• Lewatit K2621 or Amberlyst 15 at a pressure of between 1 and 3.10 5 Pa.
• One of the main objects of the invention is to use raw materials of natural and renewable origin, that is to say bioressourcées. Regardless of the manufacture of acrylic acid from “natural” glycerol, the invention extends to the use, during the esterification, of ROH alcohols of natural origin renewable or derived from biomass, in other words biobased. If light alcohols are on an industrial scale, most often of natural origin, the same goes for higher alcohols.
• ROH alcohols which is produced by hydroformylation of propylene to n-butyraldehyde, followed by hydrogenation to n-butanol.
• the invention also relates to a process for synthesizing butyl acrylate in which the acrylic acid is manufactured as described above from glycerol and then esterified with n-butanol obtained by aerobic fermentation of bio mass in the presence of bacterium.
• the fermentation of renewable materials leading to the production of butanol generally with the presence of acetone is carried out in the presence of one or more suitable microorganisms, this microorganism may possibly have been modified naturally by a chemical or physical constraint, or genetically on then speaks of mutant.
• the microorganism used is a Clostridium, advantageously it will be Clostridium acetobutylicum or one of its mutants.
• the lists presented above are not exhaustive.
• the fermentation step may also be preceded by a step of hydrolysis of the raw materials by means of a cellulase enzyme or a complex of several cellulase enzyme.
• plant materials can be used; materials of animal origin or materials from recovered materials of plant or animal origin (recycled materials).
• low quality raw materials may be used such as frozen potatoes, cereals contaminated with mycotoxins or surplus sugar beet, or cheese whey.
• renewable raw materials are plant materials.
• the fermentation step is generally followed by an isolation step of butanol.
• This isolation of butanol consists of a separation of the different products of the reaction for example by heteroazeotropic distillation. This separation can also be followed by distillation to obtain butanol in more concentrated form.
• a step for separating n-butanol from other isomers can also be provided. Nevertheless, fermentation leads to a smaller number of isomers of butanol than the chemical route of hydroformylation of propylene.
• the table below illustrates the analysis of butanol from fermenting renewable raw materials and butanol from fossil raw materials.
• N-butanol resulting from a fermentation of renewable raw materials has a lower ratio of isobutanol / n-butanol to purified butanol from fossil raw materials, even before the possible step of isolating n-butanol.
• Isobutanol and n-butanol have very similar physicochemical properties, so that separation of these products is expensive.
• the use of n-butanol, low in isobutanol and other by-products therefore constitutes a major economic advantage for the process which is the subject of the invention, since it makes it possible to produce butyl acrylate of purity higher than that of a petrochemical ex-butanol ABu at a lower cost.
• the 14 C / 12 C ratio is kept constant by the metabolism because the carbon is continuously exchanged with the environment.
• the proportion of 14 C is substantially constant in the atmosphere, it is the same in the body, as long as it is alive, since it absorbs 14 C as it absorbs 12 C.
• the average ratio of 14 C / 12 C is equal to 1, 2xl ⁇ ⁇ 12 .
• 12 C is stable, that is to say that the number of atoms of 12 C in a given sample is constant over time.
• the half-life of 14 C is 5730 years.
• a product or polymer is derived from renewable raw materials it contains at least 15% (0.2.10 "12 / 1.2.10 ⁇ 12 ⁇ by weight of C RES on the total weight of carbon, preferably at least 50% by weight of C of renewable origin on the total mass of carbon, that is, a product or a polymer is derived from renewable raw materials, ie a product or a polymer is boiressourcé, if it contains at least 0.2.10 "10 % by mass of 14 C, preferably 0.6.10 " 10 % by mass of 14 C on the total mass of carbon. bioressourced if it contains from 0.2.10 "10 % to 1.2 10 " 10 % by mass of 14 C.
• this method consists of counting 'Beta' particles resulting from the decay of 14 C Beta radiation from a sample of known mass (number of known carbon atoms) is measured over a period of time. This 'radioactivity' is proportional to the number of 14 C atoms, which can be determined.
• the 14 C present in the sample emits ⁇ - radiation, which, in contact with the scintillating liquid (scintillator), give rise to photons.
• the analysis relates to the CO 2 previously produced by combustion of the carbon sample in an appropriate absorbent solution, or on benzene after prior conversion of the carbon sample to benzene.
• mass spectrometry the sample is reduced to graphite or gaseous CO 2 , analyzed in a mass spectrometer. This technique uses an accelerator and a mass spectrometer to separate 14 C ions and 12 C and thus determine the ratio of the two isotopes.
• the measurement method preferably used is the mass spectrometry described in the ASTM D6866-06 standard ("accelerator mass spectroscopy").
• the invention also relates to the use of esters containing at least 0.2 ⁇ 10 10 mass% of 14 C obtained according to the process of the invention in its various variants as monomers or co-monomers for the polymerization of polymer or copolymer compounds with a purpose. industrial. It also relates to polymers or copolymers made from esters synthesized according to the methods of the invention.
• the process consists in a first step in synthesizing acrolein by oxidation of propylene. This step is carried out in the gaseous phase in the presence of a catalyst based on molybdenum oxides and bismuth, at a temperature in the region of 320 ° C. and at atmospheric pressure.
• a catalyst based on molybdenum oxides and bismuth based on molybdenum oxides and bismuth
• acrylic acid in the presence of molecular oxygen and a catalyst composed of a mixed molybdenum-vanadium oxide. containing copper and antimony, at a temperature of the order of 260 0 C and at atmospheric pressure.
• the reactions are carried out in fixed bed laboratory reactors.
• the first oxidation reactor consists of a 22mm diameter reaction tube filled with 500 ml of acrolein propylene oxidation catalyst, immersed in a salt bath (KNO3 eutectic mixture, NaNO 3 , NaNO 2 ) maintained at room temperature. temperature of 320 ° C. it is fed with a gaseous mixture consisting of 8 mol% of propylene, 8 mol% of water, air in the amount necessary to obtain a molar ratio O 2 / propylene of 1.8 / 1 , and nitrogen in addition.
• KNO3 eutectic mixture NaNO 3 , NaNO 2
• the outgoing gaseous mixture is then fed to a second acrylic acid acrolein oxidation reactor, consisting of a 30mm diameter reaction tube filled with 500ml of catalyst, immersed in a heat-transfer salt bath of the same type. the same as that of the first reaction stage, maintained at a temperature of 260 ° C.
• a second acrylic acid acrolein oxidation reactor consisting of a 30mm diameter reaction tube filled with 500ml of catalyst, immersed in a heat-transfer salt bath of the same type. the same as that of the first reaction stage, maintained at a temperature of 260 ° C.
• the gaseous mixture is introduced at the bottom of an absorption column, against the flow of a stream of water introduced into the reactor. column head.
• the column filled with ProPack packing is equipped with a condensing section, at the top of which is recycled a portion of the condensed mixture recovered at the bottom of the column, after cooling in an external exchanger.
• the next step is to purify the acrylic acid to obtain the technical acrylic acid grade.
• the aqueous solution obtained is subjected to distillation in the presence of methyl isobutyl ketone solvent (MIBK), which makes it possible to remove the water at the top of the column, after decantation of the MIBK-water heteroazeotropic mixture, and reflux of the solvent at the top.
• MIBK methyl isobutyl ketone solvent
• the dehydrated acrylic acid recovered at the bottom of the column is fed to a header column, which makes it possible to eliminate light compounds, mainly acetic acid, at the top.
• the acrylic acid headless recovered at the bottom of this column is fed to a tailing column, which removes heavy compounds in the foot.
• the acrylic acid obtained at the top of the column constitutes technical acrylic acid (AAT).
• the technical acrylic acid is esterified with ethanol in the presence of a catalyst consisting of Lewatit acid resins Kl 461 with the following temperature and pressure conditions: T: 80 0 C and P: 1.5.10 5 Pa.
• the reaction is conducted by continuously feeding the reactants (AAT, Ethanol) in a first reaction stage consisting of two reactors connected in parallel containing resins.
• the stream leaving the 1 st floor enters a 2nd reaction stage consisting of a reactor containing resins.
• the two reaction stages are in series.
• excess ethanol is carried out with an Ethanol / AA molar ratio of 2
• the process is carried out in excess of AAT by injection of AAT from the base of the first column.
• Distillate which separates the AAT from the mixture AE / Ethanol / Water (in this case the molar ratio AAT / Ethanol is 2.
• the flow at the outlet of the 2nd stage reaction is purified by distillation and liquid-liquid extraction.
• the distillation train comprises 4 other distillation columns and a liquid-liquid extraction column.
• the top of the first column containing the AE / ethanol / water mixture is sent to a distillation column which serves to concentrate this mixture as a head towards a value as close as possible to the theoretical AE / ethanol / water azeotropic mixture.
• a stream containing mainly water is sent to a liquid extraction column which separates the EA from the Ethanol / Water mixture. This mixture is treated on a distillation column to leave: - at the top the Ethanol / concentrated water mixture which is recycled to the reaction.
• the head of the extraction column consisting of a mixture AE / light compounds / heavy compounds is sent to a distillation column which leaves: at the top the light compounds (essentially ethyl acetate) - in the foot AE and heavy compounds (furfural, various additives like stabilizers ...)
• the transesterification of the ethyl acrylate is carried out with the aminoalcohol of formula (CH 2 ) 2 -N-CH 2 -CH 2 OH in the presence of a catalyst consisting of a tetraethyl titanate at a temperature of 115 ° C. in a reactor stirred at a pressure of 8.67 ⁇ 10 4 Pa.
• the levels of furfural measured by visible UV spectrophotometry in the presence of aniline were 300 ppm in the first stage acrolein, 120 ppm in the AAT, 10 ppm in ethyl acrylate and finally 3 ppm in the final ester.
• EXAMPLE 2 Synthesis of ADAME from AAT ex glycerol
• the experiment of Example 1 is reproduced by using as raw material during the first two stages, the glycerol subjected first to a dehydration to acrolein and then an oxidation of the latter to acrylic acid, the last two steps being identical.
• the dehydration reaction is carried out in the gas phase in a fixed bed reactor in the presence of a solid catalyst consisting of a ZrO 2 -WO 3 tungsten zirconia at a temperature of 320 ° C. under atmospheric pressure.
• a mixture of glycerol (20% by mass) and water (80% by mass) is sent into a vaporizer, in the presence of air, in an O 2 / glycerol molar ratio of 0.6 / 1.
• the gaseous medium leaving the vaporizer at 290 ° C is introduced into the reactor, consisting of a 30mm diameter tube charged with 400 ml of catalyst, immersed in a salt bath (eutectic mixture KNO 3 , NaNO 3 , NaNO 2 ) maintained at a temperature of 320 ° C.
• a salt bath eutectic mixture KNO 3 , NaNO 3 , NaNO 2
• the gaseous reaction mixture is sent at the bottom of a condensation column.
• This column consists of a lower section filled with raschig rings, surmounted by a condenser circulated by a cold heat transfer fluid.
• the cooling temperature in the exchangers is adapted so as to obtain at the top of the column a vapor temperature of 72 ° C. under atmospheric pressure. Under these conditions, the loss of acrolein at the bottom of the condensation column is less than 5%
• This gaseous mixture is introduced, after addition of air (molar ratio O 2 / acrolein 0.8 / 1) and nitrogen in an amount necessary to obtain a concentration of acrolein of 6.5 mol%, in reactor feed of oxidation of acrolein to acrylic acid.
• This oxidation reactor consists of a 30mm diameter tube filled with mixed oxide catalyst 480ml Mo / V, immersed in a salt bath identical to that described above, maintained at a temperature of 250 0 C. Before introduction on the catalytic bed, the gaseous mixture is preheated in a tube also immersed in the salt bath. On leaving the reaction, the gaseous mixture is subjected to a purification treatment identical to that of Comparative Example 1.
• the furfural content measured in the UV visible spectrophotometry fluxes at the various stages were such that the mass ratio of furfural to acrolein was 70 ppm in the acidic acid feed of the acrolein oxidation reactor. acrylic, after condensation of water, 30 ppm in AAT and 3 ppm in ethyl acrylate and finally ⁇ 0.5 ppm in the final ester.
• Example 3 (Comparative): Synthesis of 1 ⁇ 2EH from petrochemical AAT The first two steps of Example 1 are repeated and the technical acrylic acid obtained after the purification steps described in Example 1 is subjected to esterification with the alcohol of formula CH S - (CH 2 ) S -CH (C 2 H 5 ) -CH 2 OH conducted under the following conditions.
• the esterification reaction is carried out in the liquid phase at a temperature of 95 ° C. in a slight excess of AAT and in the presence of a Lewatit K2621 resin under a pressure of 0.65 ⁇ 10 5 Pa.
• the maleic anhydride content is measured by reverse phase high performance liquid chromatography.
• the chromatography column is a Lichrosphère 100 RP 18 with a length of 250 mm and an internal diameter of 4 mm.
• the eluent is a mixture of water and methanol.
• the detector is a UV detector operating at 225 nm.
• the acrylic acid has a maleic anhydride content of 1% by weight.
• the AAT has a maleic anhydride content of 1500 ppm; and after the esterification step and the purification by distillation follows the acidity in the purified product is reduced to 150 ppm.
• Example 4 Synthesis of 1 ⁇ 2EH from AAT ex glycerol
• the first two steps of Example 2 are repeated and the technical acrylic acid obtained is subjected to esterification with the alcohol of formula CH 3 - (CH 2 ) 3 CH (C 2 H 5 ) -CH 2 OH, conducted under the conditions described in Example 3.
• the concentration by weight of maleic anhydride relative to acrolein is less than 1% by weight of feed 2 nd reaction stage, after condensation of the water, the content in the technical acrylic acid is of the order of 500 ppm and the final acidity in purified 1 ⁇ 2EH is ⁇ 40 ppm.

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