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    • 专利摘要:
    The invention relates to a conversion process fed with a diol charge comprising at least 90% by weight of diol and a carboxylic acid charge comprising at least 80% by weight of carboxylic acid, said process comprising at least: an esterification step, fed with at least said diol charge and at least said carboxylic acid charge, the feed rates being adjusted so that the carboxylic acid / diol molar ratio at the inlet of said esterification step is between 2 and 6, said step esterification composition comprising at least one reactive distillation column operated at a temperature between 40 and 280 ° C, at a pressure of between 0.01 and 0.5 MPa, with a molar reflux ratio of between 0.5 and 10 and a molar reboiling rate in the range 0.5 to 10, consisting of a mixed reaction / separation zone located between two separation zones, each of said separation zones having an efficiency of at least two theoretical stages, said mixed zone comprising an acidic heterogeneous catalyst, said esterification step producing at least one distillate comprising water and a diol diester residue; a step of removing the water supplied by said distillate comprising water and producing at least one water effluent.
    公开号:FR3032707A1
    申请号:FR1551354
    申请日:2015-02-18
    公开日:2016-08-19
    发明作者:Romain Richard；Le Cocq Damien Leinekugel；Marc Jacquin；Margarita Dorato；Nuno Pacheco；Claire Rannoux
    申请人:Michelin Recherche et Technique SA Switzerland ；Compagnie Generale des Etablissements Michelin SCA；IFP Energies Nouvelles IFPEN；Michelin Recherche et Technique SA France；
    IPC主号:
    专利说明:

    [0001] TECHNICAL FIELD OF THE INVENTION The invention relates to the production of diesters and diolefins from diols. The invention is particularly well suited to the production of 1,3-butadiene from 1,4-butanediol, 1,3-butanediol and 2,3-butanediol.
    [0002] PRIOR ART Today, 95% of the production of 1,3-butadiene is provided by the steam-cracking of hydrocarbons and the subsequent extraction of the diolefins in a C4 distillation cut by extractive distillation processes.
    [0003] The evolution of the price of raw materials leads to operate the steam cracking units with increasingly light loads, because less expensive, resulting in the decrease in production of C4 cut, and therefore 1,3-butadiene.
    [0004] Other methods make it possible to produce butadiene on an industrial scale. We can mention the dehydrogenation processes of butenes and butanes, which start from a C4 hydrocarbon resource. We can also mention the Lebedev process, which makes it possible to obtain 1,3-butadiene from ethanol.
    [0005] Another method for producing 1,3-butadiene operated on a pilot scale in the 1945's in the USA is described, for example, in patents FR 859902, US 2383205, US 2372221 and in Industrial & Engineering Chemistry, 37 (9). , 1945, p.865 to 908. This process consists of three main stages: - the fermentation of sugar in 2,3-butanediol; esterifying 2,3-butanediol with a carboxylic acid to form the corresponding diester; pyrolysis of the diester to produce 1,3-butadiene and carboxylic acid, the latter being recycled to the esterification step.
    [0006] This process is particularly advantageous because the pyrolysis step of the diester can be carried out with very good yields (typically more than 80 mol%), and the 1,3-butadiene obtained is of high purity (typically more than 99% by weight). , which is crucial for its use in various applications (fine chemistry, elastomer).
    [0007] In addition, different diols can be obtained by fermentation. In particular, production of 2,3-butanediol from sugar can be achieved at the laboratory stage with Klebsiella pneumoniae with excellent performance, at a final concentration of 2,3-butanediol in the must of 3032707 2 fermentation of 160 gr . Klebsiella oxytoca has also been used in pilot stage fermentations. Nevertheless, Klebsiella is involved in serious lung diseases, making its use for the production of 2,3-butanediol very problematic.
    [0008] Other non-pathogenic microorganisms make it possible to obtain 04 diols. For example, patent WO 12058508 describes the production of ethanol and 2,3-butanediol by synthesis gas fermentation. WO 10141780 discloses the production of 1,4-butanediol by fermentation of sugar. The esterification step of 2,3-butanediol with acetic acid is described in the articles "Esterification of 2,3-butylene glycol with acetic acid" and "Continuous process for acetylation of 2,3-butylene glycol" from Industrial and Engineering Chemistry Vol.
    [0009] 37 No.9 p. 900-905 and p. 872-877 respectively. This step is critical in the process since the diester product must be of high purity, that is to say not contain diol and diol monoester, in order to obtain good yields of butadiene production in the process. pyrolysis step. Moreover, the diester yield at the esterification stage must be maximum, so as not to penalize the overall yield of the process. In the process of the prior art, the esterification step of 2,3-butanediol is carried out by reactive distillation with a homogeneous catalyst (sulfuric acid). The diol is introduced to an intermediate plate located in the upper part of the distillation column, and the acetic acid is introduced into the reboiler of the distillation column. The water produced is drawn off at the head with a portion of the acetic acid introduced in excess, and the diester product is drawn off in the bottom. The homogeneous catalyst is introduced with the diol, and recovered in the bottom with the diester. Nevertheless, the embodiment of the prior art has many disadvantages. Indeed, the boiling point of the diester is 204 ° C. at atmospheric pressure. A reactive distillation column operating at atmospheric pressure producing a water-acetic acid mixture at the top and a pure bottom diester would therefore have a thermal profile ranging from 100-110 ° C. at the top to 204 ° C. in the bottom. However, above a temperature of 150 ° C., the presence of the homogeneous catalyst causes secondary reactions of degradation of 2,3-butanediol, especially methyl ethyl ketone (MEK). These side reactions indirectly induce a loss of butadiene yield that must be avoided at all costs. To minimize these degradation reactions, the solution retained in the prior art is to introduce a large excess of acetic acid into the reboiler of the distillation column - thereby reducing the bubble temperature of the acetic acid / diester mixture withdrawn as a bottom - And therefore the entire thermal profile in the column.
    [0010] A first disadvantage of the solution retained in the prior art is that the acetic acid is introduced with a large excess relative to the diol, greater than the excess that would be necessary to produce a diester of sufficient purity for the stage. pyrolysis. The introduction of this high excess of acetic acid induces oversizing of the equipment, and an increase in energy consumption to separate the produced water from the acetic acid not consumed. A second disadvantage of the solution retained in the prior art is that the acetic acid / diester / homogeneous catalyst mixture withdrawn in the bottom must be separated, before sending the diester to the pyrolysis step. This separation is achieved by first distillation under high vacuum to minimize the operating temperature and then a second distillation at atmospheric pressure. The first vacuum distillation column makes it possible to recover the homogeneous catalyst which is recycled to the reactive distillation column, and at the top a mixture of acetic acid and diester. The latter is separated in the second distillation column at atmospheric pressure, producing acetic acid at the top and at the bottom the diester. Acetic acid is recycled to the reactive distillation column, and the diester is sent to the pyrolysis step. Overall, these separation operations are costly both from an investment point of view (column to be distilled under vacuum) and operating costs (vacuum, total vaporization of the acetic acid / diester mixture, etc.). In addition, the MEK, inevitably produced by the degradation reaction, is recovered in the effluent withdrawn at the top of the reactive distillation column, with the water produced and the acetic acid introduced in excess. This water and acetic acid must then be separated: the water is removed from the process, and the acetic acid is recycled to the esterification step. It is well known to those skilled in the art that the separation of water and acetic acid can be achieved by simple distillation. Indeed, the presence of a nip in the liquid-vapor balance curves does not effectively eliminate all the acetic acid in an aqueous effluent. Water and acetic acid are separated by carrying out a heterogeneous azeotropic distillation, which employs a trainer. The trainer forms an azeotrope with water, which is withdrawn at the top of two distillation columns: one that produces a residue consisting of water, and the other that produces a residue consisting of acetic acid. The distillate of these two distillation columns is condensed in a settling tank. Due to immiscibility between the entrainer and the water, phase separation occurs: a water-rich phase is obtained which is refluxed in the column producing the water residue, and a coach-rich phase which is returned as reflux to the column producing the acetic acid residue. The acetic acid which could have been entrained in the distillates is preferentially partitioned in the rich phase of the carrier, and is therefore preferentially returned to the column producing the residue consisting of acetic acid. The presence of MEK in this heterogeneous azeotropic distillation is extremely problematic. Indeed, the MEK being more volatile than the azeotrope water / trainer, it goes to the top of the distillation columns, and accumulates in the decanter tank. Beyond a certain content, the MEK renders the mixture water / acetic acid / monophasic carrier: water and acetic acid can then no longer be separated. To overcome this problem, the solution adopted in the prior art consists of distilling the rich phase of the carrier to remove the MEK, before returning it to the distillation column which produces a residue consisting of acetic acid. Nevertheless, it is not obvious to find a high performance trainer for the water / acetic acid separation which is easily separable from the MEK. The operation of separating water and acetic acid is therefore made more complex because of the presence of MEK. Finally, a last problem of the solution retained in the prior art is related to equipment corrosion. Acetic acid is slightly corrosive, except at high concentrations and high temperatures found at the bottom of the column. These corrosion problems are exacerbated by the presence of a homogeneous inorganic catalyst such as sulfuric acid which was used in the prior art. It should be noted that the problems mentioned above are not specific to the case of 2,3-butanediol. For example, if it is desired to esterify 1,4-butanediol or 1,3-butanediol with acetic acid, the thermal profiles within the reactive distillation column would be similar to those observed in the reaction column. case of the esterification of 2,3-butanediol, the position of oxygen functions on the carbon skeleton having little impact on boiling temperatures. Moreover, the presence of temperature-activated side reactions in the presence of the homogeneous catalyst is inevitable regardless of the diol, even if the nature of the by-products varies. In fact, with 1,4-butanediol or 1,3-butanediol, the predominantly formed by-product would not be MEK but tetrahydrofuran. The latter is just as problematic as the MEK within the heterogeneous azeotropic distillation section separating the water produced from the acetic acid introduced in excess. The present invention makes it possible to remedy one or more problems of the prior art. Indeed, the Applicant has discovered an implementation of the reactive distillation of a diol with a carboxylic acid which makes it possible to produce a high-purity diester, while minimizing the excess carboxylic acid, and the degradative reactions. . OBJECT AND INTEREST OF THE INVENTION The invention relates to a conversion process fed with a diol charge comprising at least 90% by weight of diol and a carboxylic acid charge comprising at least 80% by weight of carboxylic acid, said process comprising at least an esterification step, fed with at least said diol charge and at least said carboxylic acid charge, the feed rates being adjusted so that the carboxylic acid / diol molar ratio at the inlet of said esterification step is between 2 and 6, said esterification step comprising at least one reactive distillation column operated at a temperature between 40 and 280 ° C, at a concentration between 0.01 and 0.5 MPa, with a rate of molar reflux ratio of between 0.5 and 10 and a molar reboiling rate of between 0.5 and 10, consisting of a mixed reaction / separation zone located between two separation zones, each of said separation zones having an efficiency of at least two theoretical stages, said mixed zone comprising an acidic heterogeneous catalyst, said esterification step producing at least one distillate comprising water and a diol diester residue; a step of removing the water supplied by said distillate comprising water and producing at least one water effluent.
    [0011] An advantage of the invention is to be able to minimize the operating and investment costs related to the esterification step of the diol in diester. Another advantage of the invention and to be able to minimize the degradation reactions of the diol charge, and therefore to improve the yield of the esterification process. The use of a heterogeneous catalyst in place of a homogeneous catalyst also makes it possible to solve the effluent / catalyst separation problem.
    [0012] DETAILED DESCRIPTION OF THE INVENTION FILLING In accordance with the invention, the conversion process is fed with a diol feedstock comprising at least 90% by weight of diol. Said diol filler may also comprise water. Said diol filler may in particular come from a process for treating the effluents of a fermentation of sugars or of synthesis gas or of hydrogenolysis of a compound derived from renewable resources such as sorbitol for example, and producing a diol.
    [0013] Said diol is advantageously chosen from butanediols, pentanediols and hexanediols, taken alone or as a mixture, preferably butanediols. Preferably, said diol is chosen from 2,3-butanediol, 1,3-butanediol and 1,4-butanediol, very preferably said diol is 2,3-butanediol.
    [0014] According to the invention, the conversion process is also fed with a carboxylic acid charge comprising at least 80% by weight of carboxylic acid, and preferably more than 95% by weight of carboxylic acid. Said carboxylic acid charge may comprise water, preferably less than 5% by weight of water, preferably less than 1% by weight of water, and very preferably less than 0.1% by weight of water. Said carboxylic acid filler may comprise organic impurities. Said carboxylic acid charge advantageously comprises the liquid pyrolysis effluent from the pyrolysis step when this is carried out.
    [0015] The carboxylic acid charge advantageously comprises the carboxylic acid residue from the water removal step when this is carried out in a heterogeneous azeotropic distillation uncoupled from the azeotropic distillation step.
    [0016] Said carboxylic acid is advantageously chosen from aliphatic carboxylic acids. In a preferred manner, the carboxylic acid is chosen from formic acid, acetic acid, propanoic acid and butanoic acid. Preferably, the carboxylic acid is acetic acid.
    [0017] In a preferred arrangement of the invention, the conversion process can also be fed with a carboxylic anhydride feed. This carboxylic anhydride filler does not contain water by definition, but may contain the corresponding carboxylic acid. The carboxylic anhydride used in the conversion process according to the invention is the carboxylic anhydride corresponding to the carboxylic acid of said carboxylic acid charge. Preferably, the acetic anhydride is acetic anhydride. The acetic anhydride feed is introduced into the process so as to partially or completely compensate for the losses of carboxylic acid in the pyrolysis step. The flow rate of the carboxylic anhydride charge is therefore very low compared with the flow rate of the carboxylic acid charge.
    [0018] Esterification step According to the invention, the esterification process comprises at least one esterification step, fed by said diol charge and by said carboxylic acid charge, the feed rates being adjusted so that the ratio The carboxylic acid / diol molar at the inlet of the esterification step 25 is between 2 and 6, preferably between 2 and 4, very preferably between 2 and 3.5. In a preferred arrangement of the invention, the esterification process is also fed by the carboxylic anhydride feed. Said esterification step produces at least one distillate comprising water and a diester residue of diol. It comprises at least one reactive distillation column operated at a pressure of between 0.01 and 0.5 MPa, and preferably at atmospheric pressure and at a temperature of between 40 ° C. and 280 ° C., said reactive ditillation column. comprising a mixed reaction / separation zone located between two separation zones.
    [0019] Said diol feed, optionally pre-esterified, is introduced into said reactive distillation column at an intermediate stage, preferably between the mixed zone and the separation zone situated above the mixed zone. At least a portion of said carboxylic acid charge is introduced into said reactive distillation column at one or more intermediate stages below the diol charge injection stage. Preferably, said fraction of said carboxylic acid charge is introduced into the intermediate-stage reactive distillation column, located between the mixed zone and the separation zone situated below. In a preferred arrangement of the invention, the carboxylic anhydride feedstock is introduced into the reactive distillation column with the carboxylic acid feedstock or into a single intermediate stage, below the carboxylic acid feed stage. Intermediate stage means a stage of the reactive distillation column which is neither the reboiler nor the condenser. Above or above means in the direction of the condenser. By 10 below or below is meant in the direction of the reboiler. According to the invention, the molar reflux ratio (equal to the molar reflux rate of the condenser to the column head divided by the molar rate of distillate) is between 0.5 and 10, preferably between 0.5 and 4, very preferably between 1 and 2. According to the invention, the molar reboiling rate (equal to the molar flow rate of reflux of the reboiler to the bottom of the column divided by the molar flow rate of the residue) is between 0, 5 and 10, preferably between 4 and 10, most preferably between 5 and 6. Each of said separation zones comprises interns known to those skilled in the art such as trays, loose or structured packing, or combination of these types of internals, said internals or said association having overall a separation efficiency for each of said separation zones of at least two theoretical stages, preferably between two and ten stages theo and preferably between two and four theoretical stages so as to ensure a minimum of yield and purity of the diol diester produced.
    [0020] Said mixed zone comprises an acidic heterogeneous catalyst. In a first particular arrangement, said mixed zone consists of trays and catalytic sections, which are located outside the distillation column, each catalytic section being connected to the trays of said mixed zone by means of a liquid withdrawal. on a plateau of said mixed zone, with reinjection to the lower plate after passing through said catalytic section. Said mixed zone advantageously comprises at most 20, preferably at most 15 catalytic sections. In a second particular arrangement, said mixed zone consists of internals holding said catalyst. Said catalyst is then maintained in said mixed zone by means known to those skilled in the art. In a nonlimiting manner, the heterogeneous catalyst can be maintained between the plates of a structured packing, be trapped in metal grids deposited on the distillation trays, be trapped in a fabric shaped so as to serve as packing and establish the transfer between the gas phase and the liquid phase, or alternatively in a particular dispensing device for the liquid and vapor phases as described in patent FR 2,737,131. In a preferred manner, said mixed zone uses the particular dispensing device for the liquid and vapor phases as described in patent FR 2,737,131. This device is preferred because it generates a lower pressure drop within the column, the gas phase being short-circuited from the catalytic zone. This device therefore makes it possible to maintain a lower pressure at the bottom of the column, and therefore a lower temperature. When a particular dispensing device of the liquid and vapor phases as described in FR 2,737,131 is used to maintain the heterogeneous catalyst in the column, the mixed zone consists of an alternation of reaction sections and separation sections. Advantageously, said mixed zone comprises, according to this embodiment, at most 20, preferably at most 15 reaction sections. The residence time of the liquid phase in each catalytic section according to the first particular arrangement, or in each reaction section in the second particular setting is advantageously between 5 and 30 minutes, preferably between 15 and 25 minutes. In addition, the superficial velocity of the liquid phase in the fixed bed of catalyst is advantageously between 0.05 and 0.5 cm / s and preferably between 0.1 and 0.3 cm / s. Said heterogeneous acidic catalyst is, in a nonlimiting manner, an acidic ion exchange resin (Amberlyst type, Amberlite, Dowex, and in particular Amberlyst 35, Amberlyst 36 or Amberlyst 70), a mixed oxide (ZrO 2, SnO) or an acidic zeolite (H-MOR, H-MFI, H-FAU and H-BEA). Preferably, said heterogeneous acid catalyst is stable at a temperature above 130 ° C, preferably above 150 ° C, very preferably higher than 170 ° C. The residence time in said reactive distillation column, defined as the volume of the reactive distillation divided by the volume flow rate of said diol charge and of said carboxylic acid charge, is advantageously between 0.5 h and 10 h, preferably between 0.5 h and 5 h, and preferably between 1 h and 2 h. Preferably, the MMH (Mole per Mole per Hour, corresponding to the molar flow rate of diol in the diol charge divided by the number of moles of catalyst present within said mixed zone) is between 0.05 and 25 h. 1, preferably between 0.15 and 2011-1. In a preferred arrangement, said esterification step also comprises a pre-esterification section fed by said diol charge and a fraction of said carboxylic acid charge and producing a pre-esterified diol charge consisting of unconverted diol, diol monoester , diol diester, unconverted carboxylic acid and water, implemented in a fixed bed in the presence of a heterogeneous acid catalyst which may be identical or different from that which is used in the mixed zone of the esterification step. Said pre-esterification section is carried out at a pressure of between 0.01 and 0.5 MPa, and preferably at atmospheric pressure, and at a temperature of between 80 ° C. and 170 ° C., preferably of a preferred manner. between 100 ° C and 140 ° C. Preferably, the MMH (corresponding to the molar flow rate of diol in the diol feedstock divided by the number of moles of catalyst present in said pre-esterification step) is between 0.05 and 25 h -1, preferably between 0.15 and 20 h-1. The purpose of the pre-esterification section is to convert all or part of the diol included in said diol charge at least to monoester. This section has a particularly interesting effect when the conversion reaction of diol to monoester is slow compared to the conversion reaction of the monoester to diester. The carboxylic acid feed fraction feeding said pre-esterification section is adjusted to obtain the desired conversion to a monoester, preferably to obtain the conversion of 50% of the diol included in said diol charge, preferably 60% of the diol, very preferably 70% of the diol.
    [0021] Said reactive distillation column is then fed with said pre-esterified diol charge and with the fraction of said carboxylic acid charge which does not supply said pre-esterification section. Water Removal Step In accordance with the invention, the method of esterifying a diol filler according to the invention comprises at least one step of removing the water produced by the esterification reaction. In one embodiment of the invention, said step of removing water comprises at least one heterogeneous azeotropic distillation section, decoupled from the esterification step, comprising at least two heterogeneous azeotropic distilling distillation columns. and a decanter. Said distillate comprising water produced by said esterification step feeds a first distillation column in which a trainer is present. The trainer forms an azeotrope with water, which is withdrawn at the top of said first distillation column, which thus produces a carboxylic acid residue in the bottom. The water / entrainer azeotrope withdrawn at the top of said first distillation column is condensed in a settling tank. Because of the low miscibility between the trainer and water, a phase separation occurs: a rich water phase is obtained which is returned as reflux in the second distillation column, and a rich phase in a trainer. which is returned as reflux in the first distillation column producing the carboxylic acid residue. Preferably, the carboxylic acid which is entrained in the distillate of the first distillation column is preferentially partitioned in the coach-rich phase, and is therefore returned to the first distillation column. The second distillation column produces a bottom water residue, which is removed from the process, and at the head a distillate consisting of water / coach azeotrope, which is condensed in the settling tank.
    [0022] In this embodiment of the invention, said water removal step may also advantageously comprise liquid-liquid extraction section located upstream of said first heterogeneous azeotropic distilling distillation column. Said distillate produced by said esterification step 5 feeds said liquid-liquid extraction section, which is fed at the bottom by the trainer. Said liquid-liquid extraction section produces at the top an extract which feeds said first heterogeneous azeotropic distilling distillation column and at the bottom a raffinate which feeds said second heterogeneous azeotropic distillation column.
    [0023] The entrainer used in said water removal step is an ether such as diethyl ether, methyl tert-butyl ether, diisopropyl ether, an ester such as methyl acetate, acetate. ethyl, isopropyl acetate, a ketone such as MEK, or a hydrocarbon such as hexane, cyclohexane or benzene. In a very preferred manner, said trainer is the MEK. In the case where the MEK is used as a trainer, the MEK by-product generated in the esterification step and in the pyrolysis step can advantageously be used. In another embodiment of the invention, said water removal step is coupled to said esterification step. By coupled is meant that the first heterogeneous azeotropic distillation column is common with the reactive distillation column of said esterification step. In this embodiment of the invention, the makeup booster is fed directly into said esterification step in the condenser of the reactive distillation column. Because of the presence of the trainer, demixing takes place in the condenser of the reactive distillation column between a rich phase in a trainer and a water-rich phase. The coach-rich phase is returned as reflux to the reactive distillation column. The water-rich phase is sent to a distillation column, which produces a bottom water residue, and at the top of the vapors which are sent to the condenser of said reactive distillation column. The carboxylic acid entrained at the top of said reactive distillation column and condensed in the condenser is preferentially partitioned in the coach-rich phase, and is therefore returned to said reactive distillation column. In this embodiment, the trainer must be stable under the operating conditions of the reactive distillation column, especially in the presence of the heterogeneous catalyst and water. The trainer used in this embodiment is an ether such as diethyl ether, methyl tert-butyl ether, diisopropyl ether, a ketone such as MEK, or a hydrocarbon such as hexane, cyclohexane or benzene. . Most preferably, said trainer is MEK. In the case where the MEK is used as a trainer, it is advantageous to use the by-product MEK generated in the esterification step and in the pyrolysis step. In this case, the carboxylic acid / diol molar ratio at the inlet of the esterification step is preferably between 2 and 2.5.
    [0024] Optional Pyrolysis Step The conversion process according to the invention advantageously comprises a pyrolysis step comprising a pyrolysis reactor fed by said diol diester residue from the esterification step, operated at a temperature of between 500 and 500.degree. 650 ° C to produce a pyrolysis effluent, said pyrolysis step also comprising at least one separation section in which said pyrolysis effluent is cooled to a temperature below 100 ° C so as to produce at least one liquid pyrolysis effluent which is advantageously recycled to the esterification stage in admixture with the carboxylic acid charge, and a steam pyrolysis effluent. The pyrolysis reaction mainly converts one mole of diol diester to one mole of diolefin and thus releases two moles of carboxylic acid. By mainly, it is meant that more than 70 mol% of the diester is converted to diolefin. Preferably more than 80 mol% of the diester is converted to diolefin. Said pyrolysis reactor, called pyrolysis furnace, is operated at a temperature between 500 and 650 ° C, preferably between 59D and 600 ° C, preferably between 575 and 585 ° C. The optimum contact time within the pyrolysis furnace is a function of the partial pressure of the diol diester injected into the pyrolysis furnace. It is typically 1 second for a diol diester partial pressure of 0.1 MPa, and 7 seconds for a diol diester partial pressure of 0.04 MPa. The effluent from said pyrolysis reactor is rapidly cooled to a temperature below 100 ° C., preferably below 50 ° C., so as to reduce the formation of degradation products, for example by Diels-Alder reaction of diolefins on them. -Same. By way of illustration, in the case where the diolefin is 1,3-butadiene, such a degradation product is vinylcyclohexene. The cooling of the effluent generates a liquid phase and a vapor phase which can be easily separated within a gas-liquid separator tank into a liquid pyrolysis effluent and a steam pyrolysis effluent.
    [0025] Said steam pyrolysis effluent comprises more than 90% by weight, preferably more than 95% by weight of diolefins (without considering the optional inert diluent used to lower the diol diester partial pressure within the pyrolysis furnace). Said steam pyrolysis effluent may also contain light organic compounds derived from the pyrolysis of the carboxylic acid, for example in the case where the carboxylic acid is acetic acid, methane, carbon monoxide, carbon monoxide, Carbon dioxide, ketene, hydrogen or ethane. Said steam pyrolysis effluent may be compressed and / or cooled so as to condense the diolefins. Non-condensable organic compounds resulting from the pyrolysis of the carboxylic acid are thus removed at the top of a gas-liquid separator in the form of an effluent of light compounds. The diolefins, which are recovered at the bottom of the column, can then undergo one or more final purification steps well known to those skilled in the art. Non-limiting examples include sieve or clay purification. This makes it possible to eliminate the impurities and to obtain a diolefin effluent, which comprises more than 99%, preferably more than 99.5% of diolefins.
    [0026] Said liquid pyrolysis effluent is predominantly composed of carboxylic acid. By a majority, we mean at least 50% by weight, and preferably at least 70% by weight. It also includes other organic compounds such as unconverted diol diester, pyrolysis intermediates such as methyl vinyl carbinol acetate (MVCA), methyl ethyl ketone enol acetate (MEKEA) and crotyl acetate (CA ) and by-products such as vinylcyclohexene, methyl ethyl ketone (MEK) or methylacetylacetone (MAA), in the case where the carboxylic acid is acetic acid and the diol is 2,3-butanediol. Among the pyrolysis intermediates (that is to say the diester molecules having lost a carboxylic acid moiety on both necessary for the formation of diolefin), some allow to increase the overall yield of diolefin of the unit. if they are recycled to the pyrolysis stage, and others not. By way of illustration, in the case where the carboxylic acid is acetic acid and the diol is 2,3-butanediol, the methyl vinyl carbinol acetate (MVCA) and the crotyl acetate (CA) make it possible to increase the butadiene yield if recycled to the pyrolysis step, while this is not the case of methyl ethyl ketone enol acetate (MEKEA). However, these pyrolysis intermediates are isomers, and therefore have very close physicochemical properties. Moreover, these pyrolysis intermediates are strongly diluted in the carboxylic acid. It turns out that when the diol charge is butanediol, regardless of the carboxylic acid considered, the relative volatility between the carboxylic acid and the pyrolysis intermediates is very close to unity. All of these elements make the extraction of pyrolysis intermediates in the liquid pyrolysis effluent very difficult. The liquid pyrolysis effluent is advantageously recycled to the esterification stage in admixture with the carboxylic acid charge. Surprisingly, the use of the liquid pyrolysis effluent to form part of the carboxylic acid charge of the esterification step does not degrade the performance of the esterification of the diol and has several unexpected advantages.
    [0027] First of all, it is not necessary to separate the diester present in the liquid pyrolysis effluent from the other compounds. Indeed, during its recycling to the esterification step, the liquid pyrolysis effluent is introduced into an intermediate plateau located between the mixed zone and the lower zone of separation, mixed with the carboxylic acid charge. The diester then falls directly to the bottom of the reactive distillation column with the freshly produced diester in the reactive distillation column. The recycling of the liquid pyrolysis effluent thus makes it possible to dispense with a distillation column in order to separate the unconverted diester from the other constituents of the liquid pyrolysis effluent, and associated operation costs (vaporization of about 80.degree. % wt of the pyrolysis liquid effluent, mainly consisting of carboxylic acid). In addition, in the case where the diol is 2,3-butanediol and the carboxylic acid is acetic acid, within the reactive distillation column described above, the MEKEA pyrolysis intermediate, and the sub-10 MAA products are hydrolyzed to MEK, while other pyrolysis intermediates such as, methyl vinyl carbinol acetate (MVCA), and crotyl acetate (CA) are not or little converted. This difference in reactivity between the pyrolysis intermediates is particularly interesting, since the MEKEA - which would not have produced butadiene if recycled to the pyrolysis furnace - can thus be easily separated from the other pyrolysis intermediates that are methyl vinyl carbinol Acetate (MVCA) and crotyl acetate (CA) - which produce butadiene if recycled to the pyrolysis furnace. Furthermore, the hydrolysis of one mole of the by-product MAA releases one mole of acetic acid, which makes it possible to limit the additions of acetic acid within the process. Finally, another unexpected effect is related to the production of MEK within the reactive distillation column, from non-recoverable by-products or pyrolysis intermediates. In the esterification process according to the invention, the molar ratio of acetic acid / diol has been greatly reduced compared with that of the esterification process of the prior art. A direct consequence is that the distillate withdrawn at the top of the reactive distillation column is much richer in water and therefore much less rich in acetic acid. Indeed, for an initial molar ratio carboxylic acid / diol of less than 2.5 which is equivalent to having a final molar ratio water / AA greater than 4, the distillate obtained at the head of the water / acetic acid / MEK column is diphasic. . The MEK thus produced within the reactive distillation column acts as a trainer to separate water and acetic acid. It can thus be seen that the direct recycling of the liquid pyrolysis effluent to the esterification step makes it possible to valorize certain by-products and pyrolysis intermediates (which are not recoverable in butadiene) in order to form in situ the entrainer necessary for the separation. water and acetic acid. This unexpected effect makes it possible to dispense with the purchase of coaching supplements within the esterification process. Description of the Figures - Figure 1 shows a possible overall arrangement of the method according to the invention. A diol (1) feedstock and a carboxylic acid (2) feed, in an esterification step (A), a reaction-separation section in which the diol converted to the diol diester. The distillate comprising water (3) is removed from the process and the diol diester residue (4) feeds a pyrolysis step (B). Said pyrolysis step (B), which comprises a pyrolysis reactor and at least one separation section, produces a liquid pyrolysis effluent (5), which is recycled in the esterification step (A), an effluent consisting of light compounds (6) and a diolefin effluent (7) which is the main product of the process according to the invention, when the pyrolysis step is present in the process. Another main product is the diol diester. FIG. 2 shows a reactive distillation column (DR1) according to a first embodiment of the invention, which makes it possible to carry out the esterification step. The alcohol charge (101) is introduced above the mixed reaction-separation zone of the column (DR1) while the carboxylic acid charge (102) is introduced below this mixed reaction-separation zone. The mixed zone is flanked by two separation sections (S1) and (S2) respectively at the head and at the bottom of the column (DR1). At the top of the column (DR1), the distillate comprising water (103) is an effluent composed essentially of water and carboxylic acid. Part of this distillate (104) is returned to the top plate of the column (DR1) as reflux. A diester residue of diol (105) is recovered at the bottom of the column, which is constituted for the most part by a diol diester. Part of this residue (106) is returned to the bottoms level of the column (DR1) as a reboil. - Figure 3 shows another embodiment of the invention, wherein the esterification step comprises a column (DR2) preceded by a pre-esterification section (E). The diol charge (201) and a fraction of the carboxylic acid charge (202) are introduced into the pre-esterification reactor (E). This results in a pre-esterified diol filler (203) consisting of diol diester, diol monoester, diol, water and carboxylic acid. This charge is introduced between the upper separation zone (S1) and the mixed reaction zone (ZM) of the column (DR2). The remaining portion of the carboxylic acid charge (204) is introduced between the mixed reaction-separation zone (ZM) and the lower separation zone (S2) of the column (DR2). At the top of the column, the distillate comprising water (205) is an effluent composed essentially of water and acetic acid. Part of this distillate (206) is returned to the top plate of the column (DR2) as reflux. At the bottom of the column (207), a diol diester residue is recovered which consists, for the most part, of diol diester. Part of this residue (208) is returned to the bottom tray of the column (DR2) as a reboil.
    [0028] Example 1 - Esterification carried out by reactive distillation (comparative) This example shows the performance of an esterification process by reactive distillation carried out according to the teaching of the prior art.
    [0029] Esterification of 2,3-butadediol (2,3-BDO) with acetic acid is catalyzed by sulfuric acid. This esterification is carried out in a reactive distillation under the operating conditions described in "Continuous process for acetylation of 2,3-butylene glycol", Industrial and Engineering Chemistry, 1945, Vol.
    [0030] 37 No.9 p. 872-877.
    [0031] The reactive distillation column comprises 13 trays numbered from top to bottom. 50.46 kmol / h of feed at 110 ° C, including 2,3-BDO and 1 '/ 0 mass of sulfuric acid relative to 2,3-BDO, is introduced at the plateau 3. 300 kmol Acetic acid at 110 ° C. is injected at the bottom of the column (plate 13). The reflux of the distillate is fed back to the plate 1, with a molar reflux ratio of 1, and the reflux of residue is reinjected to the plate 13, with a molar reboiling rate of 5.3. The column is operated with a pressure and head temperature of 0.1 MPa and 103.5 ° C, and a bottom pressure and temperature of 0.11 MPa and 149.9 ° C.
    [0032] The residence time in the column is 2h. The residence time per tray is 9.23 min (the homogeneous catalyst is distributed throughout the column, it is considered that the residence time is distributed equitably on all trays).
    [0033] The molar ratio of Acetic Acid / 2,3-BDO in the column is 6. Under these conditions, the column produces 259.8 kmol / h of distillate and 90.66 kmol / h of residue. 2.3-BDO diester is obtained at a purity of 99.9 mol% (diester flow in the residue / diol + monoester + diol flow in the residue), with a yield of 2,3-BDO diester. 99.2 mol% (diester flow in the residue / input diol flow). Losses of diol, monoester and distillate diester are 0.7% (flow of diol + monoester + diester in the distillate / diol flow input).
    [0034] It may be noted that in the process according to the prior art, the addition of a large excess of acid at the bottom of the column makes it possible to maintain the temperature at around 150 ° C., in order to limit the degradation reactions. 2,3-butanediol to MEK. The addition of this large excess of acetic acid has two adverse consequences: a high circulation of acetic acid within the process the need to separate the diester from acetic acid, after removing the homogeneous catalyst under vacuum. Example 2 - Esterification carried out by reactive distillation (invention) This example shows the performance of an esterification process by reactive distillation carried out according to the invention.
    [0035] The reactive distillation column comprises 20 trays numbered from top to bottom. 50 kmol / h of feed, consisting of 2,3-BDO at 110 ° C, is introduced at the plateau 5. 150 kmol / h of acetic acid at 110 ° C is injected at the plateau 15. The reflux of The distillate is re-injected to tray 1, with a molar reflux ratio of 1, and the residue reflux is fed back to tray 20, with a molar reboiling rate of 5.3. The column is operated with a pressure and head temperature of 0.1 MPa and 90.9 ° C, and a bottom pressure and temperature of 0.11 MPa and 206.3 ° C.
    [0036] The residence time in the column is 2h. The residence time per reagent tray is 24 min. The column comprises 5 reactive trays containing an acidic ion exchange resin (Dry Amberlyst 35), these trays being numbered 6, 8, 10, 12 and 14. The molar ratio Acetic Acid / 2,3-BDO in the column is 3.
    [0037] Under these conditions, the column produced 150.0 kmol / h of distillate and 50.0 kmol / h of residue. 2.3-BDO diester is obtained with a purity of 99.3 mol% (diester flow in the residue / diol + monoester + diol flow rate in the residue), with a yield of 2,3-BDO diester of 99.3 mol% (diester flow in the residue / diol flow rate at the inlet). Losses of diol, monoester and distillate diester are 0.4 mol% (flow of diol + monoester + diester in the distillate / diol flow input).
    [0038] The process according to the invention makes it possible to considerably reduce the flow rate of acetic acid relative to the flow rate of 2,3-butanediol without significantly reducing the performance of the reactive distillation (purity of 99.3% mol according to the invention against 99 9% mol according to the prior art, yield of 99.3 mol% according to the invention versus 99.2 mol% according to the prior art). The temperature in the column used in the process according to the invention increases significantly only at the bottom of the column, in the zone consisting only of separation stages (trays 15 to 20) which makes it possible to carry out the separation between the diol / monoester / diester species on the one hand and acetic acid / water on the other hand. Since the catalyst is located above this zone, where the temperature does not exceed 135 ° C., the degradation reactions of 2,3-butanediol in MEK are very substantially limited.
    [0039] EXAMPLE 3 Recycling of the Pyrolysis Liquid Effluent This example shows the possibility of recycling the liquid pyrolysis effluent according to the invention.
    [0040] The residue of Example 2 feeds a pyrolysis step, which comprises a pyrolysis oven operated at 580 ° C with a contact time of about 2s. The pyrolysis effluent is rapidly cooled to 45 ° C and condenses into a liquid pyrolysis effluent. The non-condensed portion, which constitutes the steam pyrolysis effluent, comprises 97.5% by weight of 1,3-butadiene. The composition of the liquid pyrolysis effluent is indicated in Table 1. Table 1: Mass and molar composition of the liquid pyrolysis effluent. 2,3-BDODiAc = 2,3-butanediol diacetate, BDE-butadiene, VCH = vinylcyclohexene, MEK = methyl ethyl ketone, MAA-methylacetylacetone, MVCA-methyl vinyl carbinol acetate, MEKEA = methyl ethyl ketone enol acetate, CA = crotyl acetate. % by mass% molar AA 79.60% 83.54% 2,3-BDOdiAc 2,81% 1,02% BDE 9,01% 10,51% VCH 0,62% 0,36% MEK 0,57% 0 , 50% MVCA 0.95% 0.52% MEKEA 3.49% 1.93% CA 2.64% 1.46% MAA 0.31% 0.17% Two esterification tests for 2,3-butanediol by acetic acid were made. One test was performed with pure acetic acid and the other the liquid pyrolysis effluent described above. These tests were conducted in a batch reactor with a volume of 30 mL at atmospheric pressure, equipped with a condenser. The temperature is constant and regulated at 110 ° C thanks to a heat transfer fluid in a double jacket. The reactions are carried out in the presence of an ion exchange resin (Dry Amberlyst 35) present at a concentration of 2.2 mol% relative to 2,3-butanediol. These reactions were carried out with a molar ratio of acetic acid / 2,3-butanediol of 6. These tests made it possible to follow the kinetics of the esterification reaction, but also the evolution of the various impurities and pyrolysis intermediates during the course of the reaction. time. The comparison of the results of these two tests is presented in Table 2 below: Table 2: Results of the two esterification tests of 2,3-BDO with pure acetic acid and with a liquid pyrolysis effluent Acetic acid Pyrolysis liquid Time (h) 20 XAA 65.9% 69.1% XH2O 20.1% 15.6% X2.3-BDO 0.8% 0.7% X2.3-BDOmonoAc 6.1 % 6.2% X2.3-BDOdiAc 7.1% 8.5% (L.mo1-1.11-1) 0.0500 0.0500 k_, (L.mo1-1.11-) 0.0217 0.0238 kb (L.mo1-1.11-1) 0.0200 0.0200 k_2 (L. mol-T.11-1) 0.0571 K1 = k1 / k_1 2.3 0.0645 2.1 K2 = k2 / k- 2 0.35 0.1n1 iae (M011 0.31 C ince (mol.L)) BDE 1.2551 0.3256 VCH 0.0864 0.0542 MEK 0.0794 0.6371 0.1333 MVCA 0.1407 MEKEA 0.4862 0 , 0117 0.3678 CA 0.2905 MAA 0.0432 0 0.0000 With AA = acetic acid, 2,3-BDO = 2,3-BDO, 2,3-BDOmonoAc = 2,3-butanediol monoester, 2,3-BDOdiAc = 2,3-butanediol diester and = = kinetic constant of the esterification reaction of the diol as monoester = kinetic constant of the hydrolysis reaction of the monoester in diol 10 k2 = kinetic constant of the esterification reaction of the monoester in diester k_2 = kinetic constant of the hydrolysis reaction of the diester in monoester = thermodynamic constant of the esterification reaction of the diol in monoester K2 = thermodynamic constant of the esterification reaction of the monoester in the diester It can be seen that the esterification kinetics and the thermodynamic equilibria are practically unaffected by the use of the liquid pyrolysis effluent obtained by pyrolysis of the 2,3-butanediol diester . With regard to the impurities present in the liquid pyrolysis effluent, some have evolved over time. The butadiene concentration was almost divided by 4 between the beginning of the reaction and the end, this is explained by its low boiling point of -4.4 ° C. at atmospheric pressure: butadiene was not condensed by the refrigerant overcoming the batch reactor and was thus lost. Since the concentrations of VCH and MVCA are relatively low, it is possible to say that these concentrations have evolved little with differences of -37.3% and + 6.3%, respectively. The CA, in greater quantity initially, also does not evolve significantly during the reaction (-21.0%). On the other hand, it is shown here that MEKEA (-97.6%) and MAA (-100%) disappear almost completely during the reaction to give MEK. Indeed, the disappearance of MEKEA and MAA corresponds to 0.5176 mol.L-1 and the formation of MEK corresponds to 0.5577 mol.L-1.
    [0041] It is thus demonstrated that it is possible to use the liquid pyrolysis effluent directly at the esterification stage of 2,3-BDO. Intermediates that can lead to butadiene by pyrolysis furnace recycling (MVCA, CA) are little impacted under the test conditions, while the MEKEA intermediate likely to give MEK by pyrolysis furnace recycling and by-product MAA are converted to MEK. 10
    权利要求:
    Claims (14)
    [0001]
    REVENDICATIONS1. A conversion process fed with a diol charge comprising at least 90% by weight of diol and a carboxylic acid charge comprising at least 80% by weight of carboxylic acid, said process comprising at least: an esterification step, fed by at least said charge diol and at least said carboxylic acid charge, the feed rates being adjusted so that the carboxylic acid / diol molar ratio at the inlet of said esterification step is between 2 and 6, said esterification step comprising at least a reactive distillation column operated at a temperature between 40 and 280 ° C, at a concentration between 0.01 and 0.5 MPa, with a molar reflux ratio of between 0.5 and 10 and a molar reboiling rate between 0.5 and 10, consisting of a mixed reaction / separation zone located between two separation zones, each of said separation zones having an efficiency of at least two stages theo said mixed zone comprising an acidic heterogeneous catalyst, said esterification step producing at least one distillate comprising water and a diol diester residue; a step of removing the water supplied by said distillate comprising water and producing at least one water effluent.
    [0002]
    2. Conversion process according to claim 1 wherein the carboxylic acid / diol molar ratio at the inlet of said esterification step is between 2 and 4.
    [0003]
    3. Conversion process according to one of claims 1 to 2 wherein the residence time in said reactive distillation column, defined as the volume of the reactive distillation divided by the volume flow of said diol charge and said carboxylic acid charge , is between 0.5 h and 10 h.
    [0004]
    4. Conversion process according to one of claims 1 to 3 wherein said step of removing water comprises a heterogeneous azeotropic distillation section operated in the presence of an ether, ester, ketone or hydrocarbon type entrainer comprising: a first heterogeneous azeotropic distillation column fed by said distillate comprising water and producing a distillate comprising the water / entrainer azeotrope and a carboxylic acid residue; a settler fed by said distillate comprising the water / entrainer azeotrope and producing a water-rich phase and a train-rich phase, said train-rich phase being recycled as reflux of said first heterogeneous azeotropic distillation column; A second heterogeneous azeotropic distillation column fed by said water-rich phase, which produces a distillate recycled to said decanter and a water residue.
    [0005]
    5. Conversion process according to one of claims 1 to 3 wherein said step of removing water 5 comprises: a liquid-liquid extraction section fed at the top by said distillate comprising water and in the bottom by an ether, ester, ketone or hydrocarbon type entrainer and producing at the top an extract and in the bottom a raffinate: a first heterogeneous azeotropic distillation column supplied with said extract and producing a distillate comprising the water / entrainer azeotrope and a residue carboxylic acid; a second heterogeneous azeotropic distillation column fed by said raffinate and producing a distillate comprising the water / entrainer azeotrope and a water residue; a settler fed by said distillate comprising the water / entrainer azeotrope derived from said first column and by said distillate comprising the water / entrainer azeotrope derived from said second column and producing a water-rich phase and a train-rich phase, said a train-rich phase being recycled as reflux of said first column and said water-rich phase being recycled as reflux of said second column.
    [0006]
    6. Conversion process according to one of claims 1 to 3 wherein said esterification step and said step of removing water are coupled, said esterification step being also fed by a trainer, which causes a demixing in the condenser of said reactive distillation column between a water-rich phase and a coach-rich phase, said water-rich phase feeding a distillation column which produces a water residue and a distillate, which is recycled in said condenser of said reactive distillation column, said entrainer being an ether, a ketone or a hydrocarbon.
    [0007]
    7. Conversion method according to one of claims 1 to 6 wherein said trainer is the MEK. 30
    [0008]
    8. Conversion process according to one of claims 1 to 7 further comprising a pyrolysis step comprising: a pyrolysis reactor fed by said diol diester residue of said esterification step operated at a temperature between 500 and 650 ° This producing a pyrolysis effluent; at least one separation section in which said pyrolysis effluent is cooled to a temperature below 100 ° C so as to produce at least one liquid pyrolysis effluent and a steam pyrolysis effluent, which is separated into a light compound effluent and a diolefin effluent. 3032707 22
    [0009]
    9. Conversion process according to claim 8 wherein said liquid pyrolysis effluent is mixed with said carboxylic acid feed supplying said conversion process. 5
    [0010]
    10. Conversion process according to one of claims 1 to 9 wherein said diol is selected from butanediols, pentanediols and hexanediols.
    [0011]
    11. Conversion process according to one of claims 1 to 10 wherein said diol is selected from 2,3-butanediol, 1,3-butanediol and 1,4-butanediol. 10
    [0012]
    12. Conversion process according to one of claims 1 to 11 wherein said esterification step also comprises a pre-esterification section fed by said diol charge and a fraction of said carboxylic acid charge and producing a pre-esterified diol charge implemented in a fixed bed in the presence of a heterogeneous acid catalyst, said pre-esterification section being operated at a pressure of between 0.01 and 0.5 MPa, and at a temperature of between 80 ° C. and 170 ° C. ° C.
    [0013]
    13. Conversion process according to one of claims 1 to 12 wherein said carboxylic acid is selected from aliphatic carboxylic acids. 20
    [0014]
    14. The conversion method according to claim 13 wherein said carboxylic acid is selected from formic acid, acetic acid, propanoic acid and butanoic acid.
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    同族专利:
    公开号 | 公开日
    WO2016131845A1|2016-08-25|
    US10421706B2|2019-09-24|
    BR112017017640A2|2018-05-08|
    US20180022682A1|2018-01-25|
    FR3032707B1|2017-03-10|
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    法律状态:
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    2016-08-19| PLSC| Publication of the preliminary search report|Effective date: 20160819 |
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1551354A|FR3032707B1|2015-02-18|2015-02-18|METHOD FOR ESTERIFYING A DIOL IMPLEMENTING A REACTIVE DISTILLATION|FR1551354A| FR3032707B1|2015-02-18|2015-02-18|METHOD FOR ESTERIFYING A DIOL IMPLEMENTING A REACTIVE DISTILLATION|
    BR112017017640-8A| BR112017017640B1|2015-02-18|2016-02-17|CONVERSION PROCESS POWERED BY A LOAD OF DIOL COMPRISING AT LEAST 90% BY WEIGHT OF DIOL AND A LOAD OF CARBOXYLIC ACID COMPRISING AT LEAST 80% BY WEIGHT OF CARBOXYLIC ACID|
    PCT/EP2016/053300| WO2016131845A1|2015-02-18|2016-02-17|Process for esterification of a diol using a reactive distillation|
    US15/551,754| US10421706B2|2015-02-18|2016-02-17|Method for esterification of a diol using a reactive distillation|
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