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    • 专利摘要:
    The invention relates to a process for producing 1,3-butanediene from a butanediol feedstock comprising at least: a) a step of esterifying butanediol with a carboxylic acid to form the corresponding diester fed with said butanediol feed and by a carboxylic acid feed comprising a carboxylic acid feedstock and the liquid pyrolysis effluent from step b), and producing at least one carboxylic acid effluent and a diester effluent; b) a step of pyrolysis of the diester effluent from step a) comprising a reaction section and a separation section and producing at least one liquid pyrolysis effluent comprising at least 50% by weight of carboxylic acid and an effluent steam pyrolysis method comprising more than 90% by weight of butadiene; c) a distillation step fed by at least the carboxylic acid effluent from step a) and producing an aqueous distillate and a carboxylic acid residue; d) a step of drying the carboxylic acid fed at least by the carboxylic acid residue from step c) and producing a water effluent and a carboxylic acid product feeding step a).
    公开号:FR3045599A1
    申请号:FR1562859
    申请日:2015-12-18
    公开日:2017-06-23
    发明作者:Nuno Pacheco；Margarita Dorato；Marc Jacquin；Rejane Dastillung；Sophie Couderc
    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:

    FIELD OF THE INVENTION The invention relates to the process for producing 1,3-butadiene from a butanediol filler comprising at least one butanediol chosen from the list consisting of 1,4-butanediol and 2,3-butanediol. 1,3-butanediol and mixtures thereof.
    PRIOR ART
    Today, 95% of 1,3-butadiene production is provided by the steam cracking of hydrocarbons and the subsequent extraction of diolefins in a C4 distillation cut by extractive distillation processes. The evolution of the price of raw materials has led to operating steam cracking units with increasingly light loads, because less expensive, resulting in reduced production of C4 cut, and therefore 1,3-butadiene. Other methods make it possible to produce butadiene on an industrial scale. We can mention the dehydrogenation processes of butenes and butanes, from a C4 hydrocarbon resource. We can also mention the Lebedev process, which makes it possible to obtain 1,3-butadiene from ethanol.
    Another process for the production of 1,3-butadiene was carried out on a pilot scale in the 1945s in the USA, and described, for example, in patents FR 859902, US 2383205, US 2372221 and in Industrial & Engineering Chemistry, 37 (9), 1945, pp. 865-908. This process consists of 2 main steps: - esterification of 2,3-butanediol with a carboxylic acid to form the corresponding diester - pyrolysis of the diester for produce 1,3-butadiene and the carboxylic acid which is recycled to the esterification step.
    This process has been developed because the direct dehydration of 2,3-butanediol leads to the very predominant formation of methyl-ethyl-ketone (MEK), and MEK can not be dehydrated to 1,3-butadiene. This process is particularly advantageous since the pyrolysis step of the diester can be carried out with very good yields (typically more than 80%), and the 1,3-butadiene obtained is of high purity (typically more than 99%), which is crucial for its use in various applications (fine chemistry, elastomer).
    A difficulty raised by the process for producing 1,3-butadiene from one of the isomers of butanediol (1,4-butanediol, 2,3-butanediol and 1,3-butanediol) by esterification and then pyrolysis is the purification of the carboxylic acid for recycling. The heterogeneous azeotropic distillation used to dry the carboxylic acid, that is to say to remove the water produced in the esterification step, is difficult to operate, particularly because of the accumulation of organic compounds in the carboxylic acid.
    Indeed, these organic compounds, accumulating in the carboxylic acid, disturb the liquid-liquid equilibrium of the water / carboxylic acid / carrier system, or even homogenize a system that is two-phase in their absence, and therefore make the drying of the carboxylic acid by inoperative heterogeneous azeotropic distillation.
    The organic compounds in question may be: 1. Butanediol dehydration by-products (THF for 1,4-butanediol feed, MEK for 2,3-butanediol feed, and 1-buten-4-ol for feedstock. 1,3-butanediol) formed especially in the esterification step; 2. pyrolysis intermediates and by-products formed in the pyrolysis step (for example vinylcyclohexene, methylvinylcarbinol acetate (MVCA), methyl ethyl ketoneenol acetate (MEKEA), crotylacetate (CA), VCH, MEK or methylacetylacetone (MAA)), which are difficult to separate from the carboxylic acid released in the pyrolysis step, and which can therefore be returned, totally or partially, to the esterification step.
    These numerous pyrolysis intermediates have a boiling point close to that of acetic acid, and form homogeneous azeotropes (maximum and minimum) with the latter. The purification of acetic acid can therefore be done by simple distillation. US Pat. No. 2,372,221 describes the use of the pyrolytic liquid without prior purification directly to the esterification step, and the catastrophic consequences on heterogeneous azeotropic distillation implemented (coach = benzene in this case) for drying the carboxylic acid.
    In the process of the prior art (Industrial & Engineering Chemistry, 37 (9), 1945, p.865-908), the drying of the acetic acid introduced in excess at the esterification stage is carried out with a variant of the heterogeneous azeotropic distillation well known to those skilled in the art, in which a distillation column makes it possible to eliminate the MEK and the other organic compounds which accumulate in the entrainer. Esterification of butanediol with acetic acid is carried out in a reactive distillation column. The diester is withdrawn at the bottom of the column while the excess acetic acid and the water produced by the esterification reaction are recovered in the distillate.
    A first distillation column is fed by this distillate essentially composed of acetic acid, water, but also MEK and other organic compounds. The residue of this first column consists of dry and pure acetic acid, the latter being returned to the esterification step of 2,3-butanediol. The distillate of this first column to be distilled, a mixture consisting of entrainer (in this case isopropyl acetate), acetic acid, water and MEK and other organic compounds is withdrawn and sent to a decanter.
    This settler makes it possible to separate an aqueous phase containing mainly water, and an organic phase containing predominantly the trainer.
    The aqueous phase from the decanter is sent as reflux of a second column to be distilled. At the bottom of this second column, pure water, ie without a trainer is obtained and eliminated from the process. At the head of this second distillation column, the heterogeneous azeotrope composed of water and entrainer is recovered and returned to the decanter.
    The organic phase from the clarifier feeds as reflux a third column to be distilled. This third column makes it possible to produce at the top the MEK and organic compounds which are eliminated from the process, and in bottom a mixture of entrainer, water and acetic acid which is returned as reflux in the first distillation column. .
    This solution, to be operable, assumes that the third column to be distilled is extremely effective and maintains the amount of MEK and other organic compounds in the system to a level that does not disturb the liquid-liquid equilibrium in the decanter. However, the liquid-vapor equilibrium between the MEK and the isopropyl acetate are such that it is difficult to envisage a good separation of the MEK and the trainer, even with a large number of theoretical distillation plates. Other coaches that are more easily separable from MEK, such as butyl acetate, have been envisaged. Nevertheless, the latter does not effectively separate water and acetic acid. In conclusion, it is difficult to find a trainer that allows both a good separation of water and acetic acid, and is easily separable from the MEK.
    The present invention overcomes the problem of accumulation of dehydration by-products of butanediol in the carboxylic acid, in a process for producing butadiene from butanediol by esterification and pyrolysis. In addition, the present invention is also applicable for a process for producing butadiene from the different isomers of butanediol. Indeed, the applicant has discovered that a particular sequence of distillation columns could be implemented to effectively remove the water produced in the esterification step and the organic compounds that can accumulate in the carboxylic acid. .
    The Applicant has discovered that his invention for drying the carboxylic acid and removing organic compounds was particularly robust, and could be implemented even if the pyrolytic liquid was recycled without prior purification to the esterification step. In addition, the Applicant has discovered that the fact of using the pyrolytic liquid without purification prior to the esterification step according to its invention made it possible not to accumulate in the carboxylic acid, the pyrolysis intermediates and the by-products formed. in the pyrolysis step.
    Thus, the Applicant has discovered that a particular sequence of distillation columns, by judicious management of the separations of the by-products and the addition of the entrainer used in the azeotropic distillations, different from that of the process of the art. previous, could be implemented to: • dry the carboxylic acid and recycle it to the esterification step • effectively remove the water • effectively remove the by-products of dehydration whatever the butanediol used in filler (2,3-butanediol, 1,4-butanediol and / or 1,3-butanediol) • remove pyrolysis intermediates and pyrolysis by-products from 2,3-butanediol diester, diester of 1, 4-butanediol and 1,3-butanediol diester. The invention thus makes it possible to simplify the process according to the prior art and thus reduce operating costs and investment costs, while retaining flexibility on the nature of the butanediol feed supplying the process (1,4-butanediol 2,3-butanediol, 1,3-butanediol and mixtures thereof).
    OBJECT AND INTEREST OF THE INVENTION The invention relates to a process for producing 1,3-butanediene from a butanediol feedstock comprising at least: a) a step of esterifying butanediol with a carboxylic acid to form the corresponding diester fed by said butanediol feed and by a carboxylic acid feed comprising a carboxylic acid feedstock and the liquid pyrolysis effluent from step b), and producing at least one carboxylic acid effluent and a diester effluent, carried out in distillation reactive in the presence of a homogeneous or heterogeneous acid catalyst operated at a pressure of between 0.01 and 1 MPa; b) a step of pyrolysis of the diester effluent from step a) comprising a reaction section and a separation section and producing at least one liquid pyrolysis effluent comprising at least 50% by weight of carboxylic acid and an effluent vapor pyrolysis process comprising more than 90% by weight of butadiene, said reaction section being operated at a temperature between 500 and 650 ° C, the effluent of said reaction section being cooled to a temperature below 100 ° C before feeding said separation section; c) a distillation step fed by at least the carboxylic acid effluent from step a), carried out in a distillation column at a pressure of at most 1 MPa, with a head temperature of between 0 and 110 ° C and a bottom temperature of 100 to 120 ° C, and producing an aqueous distillate and a carboxylic acid residue; d) a step of drying the carboxylic acid fed at least by the carboxylic acid residue from step c) and producing a water effluent and a carboxylic acid product supplying step a).
    An advantage of the invention is the possibility of treating all isomers of butanediol (1,4-butanediol, 2,3-butanediol, 1,3-butanediol and mixtures thereof), to produce 1,3-butadiene with a yield of high, above 70%.
    Another advantage of the invention is the ability to remove the various dehydration by-products of butanediols, pyrolysis intermediates and pyrolysis by-products with a reduced number of equipment, thereby reducing operating costs, reducing investment costs and increasing the process flexibility with respect to the load.
    DETAILED DESCRIPTION OF THE INVENTION
    Charge
    According to the invention, the process is fed with a butanediol feedstock comprising at least butanediol, advantageously at least 90% by weight of butanediol. Said butanediol is an isomer of butanediol selected from the list consisting of 1,4-butanediol, 2,3-butanediol, 1,3-butanediol and mixtures thereof. Said butanediol filler may also comprise water. Said butanediol feed can come from a sugar fermentation process or synthesis gas. Said butanediol feed may be derived from a process for synthesizing butanediol from acetylene and formaldehyde.
    Preferably for the purposes of the invention, the carboxylic acid is acetic acid. Step a) esterification of butanediol
    According to the invention, the process for the production of 1,3-butadiene comprises a step a) of esterifying butanediol with a carboxylic acid to form the corresponding diester fed at least by said butanediol feedstock and by a carboxylic acid charge and producing at least one carboxylic acid effluent and a diester effluent, implemented in reactive distillation in the presence of a homogeneous or heterogeneous acid catalyst, preferably heterogeneous.
    This esterification step can be carried out by any implementation in reactive distillation well known to those skilled in the art.
    The butanediol feedstock is introduced into the upper portion of the reactive distillation, and the carboxylic acid feedstock comprising the carboxylic acid feedstock, the liquid pyrolysis effluent from step b), advantageously also the carboxylic acid product derived from the step d), is introduced into the lower part of the reactive distillation.
    Said reactive distillation is carried out at a pressure of between 0.01 and 1 MPa, preferably at a pressure slightly above 0.1 MPa. The temperature of the reactive distillation is between the boiling temperature of the water produced at the head and that of the diester produced in the bottom. In the case where the carboxylic acid used is acetic acid, the temperature between the head and the bottom of the reactive distillation typically varies between 100 and 230 ° C.
    Reactive distillation produces at the top a distillate constituting the carboxylic acid effluent. Said carboxylic acid effluent mainly comprises the water produced by the esterification reaction, the excess carboxylic acid introduced and the dehydration by-products generated. Said carboxylic acid effluent may also comprise organic impurities from the liquid pyrolysis effluent from step b) fed in admixture with the carboxylic acid charge.
    Reactive distillation produces in bottom a residue constituting the diester effluent and mainly comprising the butanediol diester product.
    Said esterification step a) is carried out in such a way that the conversion of butanediol to butanediol diester is greater than 95 mol%, preferably greater than 99 mol%. These performances are achieved by adjusting the operating parameters of the reactive distillation, such as the reflux and reboil rates, and the butanediol charge / carboxylic acid load ratio of said step a), as known to those skilled in the art. .
    The feed rates of butanediol and carboxylic acid feed are adjusted so that the carboxylic acid / diol molar ratio at the inlet of the esterification step is between 2 and 6, preferably between 2 and 4, very preferably. preferred between 2 and 3.5.
    The molar reflux ratio (equal to the molar reflux rate of the condenser to the column head divided by the molar flow 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 residue) is between 0.5 and 10, preferably between 4 and 10, very preferably between 5 and 6.
    In a preferred arrangement, said reactive distillation comprises a mixed reaction / separation zone located between two separation zones.
    In this arrangement, said butanediol feed 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. Said carboxylic acid feed is introduced into said reactive distillation column at one or more intermediate stages located below the butanediol feed injection stage. Preferably, said carboxylic acid charge is introduced into the reactive distillation column at a single intermediate stage, located between the mixed zone and the separation zone situated below.
    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. Below or below is meant in the direction of the reboiler.
    Each of said separation zones comprises interns known to those skilled in the art such as trays, bulk or structured packing, or a combination of these types of internals, said internals or said combination having overall a separation efficiency for each said separation zones of at least two theoretical stages, preferably between two and ten theoretical stages, and preferably between two and four theoretical stages, so as to guarantee a minimum of yield and purity of the diol diester product .
    Preferably, said mixed zone comprises a heterogeneous acidic 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 plate 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 even in a particular distribution device of the liquid and vapor phases as described in patent FR 2,737,131. Preferably, said mixed zone implements the particular dispensing device of 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 within 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.
    Regardless of the embodiment, the heterogeneous acidic catalyst is chosen from an acidic ion exchange resin (Amberlyst type, Amberlite, Dowex, and in particular an 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 above 170 ° C.
    The acid catalysts used to catalyze the esterification reaction also activate the dehydration reactions, especially at the operating temperatures of said step a), producing MEK or THF or 2-buten-1-ol depending on the isomer butanediol present in the butanediol feed.
    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 filler 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 20 h-1. Step b) pyrolysis of the butanediol diester
    According to the invention, the process for producing 1,3-butanediene comprises a step b) of pyrolysis of the diester effluent from step a) comprising a reaction section and a separation section and producing at least one liquid pyrolysis effluent comprising at least 50% by weight of carboxylic acid and a steam pyrolysis effluent comprising more than 90% by weight of butadiene, said reaction section being carried out at a temperature of between 500 and 650 ° C., the effluent of said reaction section being cooled to a temperature below 100 ° C before feeding said separation section.
    The pyrolysis reaction converts one mole of butanediol diester to one mole of 1,3-butadiene and thereby releases two moles of carboxylic acid. More than 70 mol% of the butanediol diester is converted to 1,3-butadiene. Preferably, more than 80 mol% of the butanediol diester is converted to 1,3-butadiene. Said pyrolysis reactor is operated at a temperature between 500 and 650 ° C, preferably between 550 and 600 ° C, preferably between 575 and 585 ° C. The optimal contact time within said reactor is a function of the partial pressure of the butanediol diester injected into said reactor. 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.
    Said pyrolysis step b) according to the invention also comprising at least one separation section fed by said pyrolysis effluent, cooled to a temperature of less than 100 ° C., so as to produce at least one liquid pyrolysis effluent and an effluent of steam pyrolysis which can be easily separated within a gas-liquid separator tank. The pyrolysis effluent from said pyrolysis reactor is cooled rapidly to a temperature of less than 100 ° C., preferably less than 50 ° C., so as to limit the formation of degradation products, for example by Diels-Alder reaction of 1 , 3-butadiene on itself to form VinylCycloHexene (VCH).
    Said steam pyrolysis effluent comprises more than 90% by weight, preferably more than 95% by weight of 1,3-butadiene (without considering the optional inert diluent used to lower the butanediol diester partial pressure in the pyrolysis reactor) . 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 to condense 1,3-butadiene. 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. 1,3-Butadiene may then undergo one or more ultimate purification steps well known to those skilled in the art. Non-limiting mention may be made of sieve or clay purification, or washing with water. This makes it possible to eliminate the last traces of impurities and to obtain a 1,3-butadiene effluent, which comprises more than 99%, preferably more than 99.5% of 1,3-butadiene, which is the product of the process.
    Said liquid pyrolysis effluent is mainly composed of carboxylic acid. By a majority, we mean at least 50% by weight, and preferably at least 70% by weight. It may also include other organic compounds, such as unconverted butanediol diester, pyrolysis intermediates (i.e., butanediol diester molecules having lost a carboxylic acid moiety on both necessary to the formation of 1,3-butadiene), and possible pyrolysis byproducts. The nature of these by-products obviously depends on the nature of the feed introduced into the pyrolysis reactor.
    Many pyrolysis intermediates and impurities are produced. By way of illustration, in the case where acetic acid is used to carry out the esterification of 2,3-butanediol in step a), the liquid pyrolysis effluent comprises 2,3-butanediol diacetate. (1.5% wt.), Pyrolysis intermediates such as, methylvinylcarbinol acetate (MVCA 0.8% wt.), Methyl ethyl ketoneenol acetate (MEKEA 2.4% wt.) And crotylacetate (CA 3.3% wt.) and by-products such as HCV (2.2% wt), MEK (1.4% wt.) or methylacetylacetone (MAA 0.9% wt.). The liquid pyrolysis effluent thus contains many pyrolysis intermediates having a boiling point close to that of acetic acid, and forming homogeneous azeotropes (maximum and minimum) with the latter. Purification of the acetic acid before recycling to the esterification step can therefore be done by simple distillation.
    In a first embodiment of the invention, the liquid pyrolysis effluent is purified before being recycled to the esterification step a) in admixture with the carboxylic acid charge. This purification makes it possible to eliminate the pyrolysis intermediates and by-products formed in stage b). The liquid pyrolysis effluent is purified by any mode well known to those skilled in the art. It can for example be purified by heterogeneous azeotropic distillation, using water as a carrier, as described in the document "Pilot-plant conversion of 2,3-butylene glycol diacetate to 1,3-butadiene" in the newspaper "Industrial and Engineering Chemistry »volume 37, No. 9.
    In a second embodiment of the invention, the liquid pyrolysis effluent is directly recycled to the esterification step a) in admixture with the carboxylic acid charge, without purification. The non-converted butanediol diester at the end of the pyrolysis step b) is thus recovered at the bottom of said reactive distillation column and returned to the feed of said pyrolysis step b), improving the overall yield in 1, 3-butadiene of the process.
    In this second embodiment of the invention, the pyrolysis intermediates and certain pyrolysis by-products which are difficult to separate from the carboxylic acid are converted totally or partially under the operating conditions of the esterification step a). other products more easily separable from the carboxylic acid and which evacuate at the top of said reactive distillation column to the distillation step c). For example, in the case where the carboxylic acid used is acetic acid for esterifying 2,3-butanediol, the methylacetylacetone (MAA) and the methylacetylacetone (MEKEA) formed in the pyrolysis step b) are hydrolysed in the conditions of the esterification step a) to acetic acid and MEK, which evacuate at the top of said reactive distillation column to the distillation step c). Step c) Distillation
    According to the invention, the distillation step c) is fed with the carboxylic acid effluent from step a). The distillation step (c) produces an aqueous distillate comprising the by-products of dehydration and pyrolysis and comprising not more than 10% by weight of carboxylic acid which is removed from the process and a carboxylic acid residue which is dried at room temperature. step d). The feed of step c) comprises water produced by the esterification reaction, the carboxylic acid and organic compounds derived from the dehydration of the butanediol feed, such as, for example, THF or MEK or 2-buten-1-ol. Said feed may also comprise pyrolysis intermediates, pyrolysis by-products formed in step b) of pyrolysis, recycled and not converted in the esterification step a), as well as organic compounds which are derived from the conversion of the pyrolysis intermediates and pyrolysis byproducts in the esterification step a).
    Said distillation step c) is carried out in a distillation column at a pressure at most equal to 1 MPa, and preferably at a pressure of between 0.1 and 0.2 MPa. The temperature of the column head is between 0 and 110 ° C, preferably between 50 ° C and 100 ° C. Under these conditions, the aqueous distillate produced at the top of said distillation column is composed mainly of water and organic by-products. For the most part, it is meant that the carboxylic acid content does not exceed 10% by weight, preferably not more than 5% by weight. The bottom temperature of the column is from 100 to 120 ° C, preferably from 100 ° C to 115 ° C. Thus, the carboxylic acid residue produced at the bottom of this first column is depleted in organic by-products and consisting mainly of water and carboxylic acid.
    Surprisingly, the arrangement of the esterification step a) and the pyrolysis step b) with recycling of the liquid pyrolysis effluent from step b) to said step a) leads, because of different reactions occurring in step a) and step b), the production of a carboxylic acid effluent from step a) can be separated on the one hand into an aqueous distillate comprising water and by-products of dehydration and pyrolysis and on the other hand a carboxylic acid residue consisting of water and carboxylic acid.
    The carboxylic acid residue produced at the bottom of this column is free of organic compounds and consists of water and acetic acid. It constitutes the load of step d). This operating mode of the column makes it possible to eliminate more than 98% of the organic by-products and to limit the losses of acetic acid between 0 and 10% by weight, preferably between 0 and 5%, and very preferably between 0 and 5%. and 1% by weight.
    Depending on the isomer or isomers of butanediol present in said butanediol feedstock, demixing may occur in the condenser of the distillation column used in the distillation step c). In the case where demixing occurs, the skilled person can increase the reflux ratio to be outside the demixing zone and again to a homogeneous mixture. However, in an advantageous arrangement where demixing occurs, the aqueous phase is refluxed to the column and the organic-rich phase is withdrawn as the distillate. Step d) drying the carboxylic acid
    According to the invention, a step d) of drying the carboxylic acid is fed by the carboxylic acid residue from distillation step c) and produces a water effluent and a carboxylic acid product.
    Said drying step d) is a water / carboxylic acid separation and may be carried out for example by heterogeneous azeotropic distillation in the presence of a trainer. The trainer which forms a heteroazeotrope with the carboxylic acid-water mixture is preferably selected from the group consisting of alkanes, aromatic compounds, ketones, esters, and mixtures thereof. Preferably, the entrainer is selected from the group consisting of n-dodecane, mesitylene, 3-pentanone, 2-hexanone, 4-methyl-2-pentanone, 2-pentanone, cyclopentanone, cyclohexanone , diisobutyl ketone, isopropyl acetate, n-propyl acetate, ethyl acetate, n-butyl acetate, iso-butyl acetate and mixtures thereof.
    According to a preferred arrangement, step d) comprises, at the outlet of the azeotropic distillation, a step of decanting the water-carboxylic acid-entrainer mixture, making it possible to separate the aqueous phase (water) from the organic phase comprising the entrainer and the carboxylic acid; the organic phase being returned to the azeotropic distillation column. This preferred arrangement is particularly suitable in the case where the trainer is very poorly miscible with water. Preferably, particularly when the carboxylic acid is acetic acid, the entrainer is isopropyl acetate.
    According to another preferred arrangement, some are the carboxylic acid and the trainer, it is possible to use a distillation column at the outlet of the decanter, to separate the entrainer remaining in the aqueous phase during decantation, this trainer being returned to the decanter.
    The carboxylic acid product is recycled to the esterification step a) in admixture with the carboxylic acid charge.
    EXAMPLES
    Example 1 [Comparative] Drying of acetic acid by heterogeneous azeotropic distillation and elimination of MEK
    This example shows that an arrangement according to the prior art, in which a carrier is added to the carboxylic acid effluent resulting from the esterification step, this trainer being easily separable from the carboxylic acid, causes problems in MEK / trainer separation level.
    A carboxylic acid effluent from an esterification step conducted in a reactive distillation feeds a heterogeneous azeotropic distillation column. The trainer used is isopropyl acetate. This carboxylic acid effluent contains MEK, acetic acid and water. The coach is added to the load.
    The heterogeneous azeotropic distillation column is operated at atmospheric pressure, with 30 theoretical stages a mass reboiling rate of 7.57. The feeding is carried out in the upper third of the column.
    The organic phase of the condenser of this column is withdrawn and contains 96.2% of the MEK fed into said column and the trainer. This organic phase feeds a second column intended to separate the MEK from the trainer.
    This separation is very difficult because the dew and bubble curves of the MEK / isopropyl-acetate mixture are very close and a very large number of stages (more than 50 theoretical stages) are necessary.
    Table 1: Material balance with the heterogeneous azeotropic distillation column for drying acetic acid according to the prior art
    Example 2 [in conformity] recycling of liquid pyrolysis effluent in esterification
    This example shows that the sequence of esterification and pyrolysis steps, with recycling of the liquid pyrolysis effluent leads to the transformation of certain pyrolysis by-products into readily separable products (MEK) in the separation steps of the pyrolysis. carboxylic acid effluent according to the invention. These by-products would have otherwise required dedicated treatment. There is thus synergy between the esterification / pyrolysis sequence and the recycling of the liquid pyrolysis effluent and the sequence of separation steps fed by the carboxylic acid effluent according to the invention.
    This example shows the possibility of recycling the liquid pyrolysis effluent according to the invention.
    A butanediol feed consisting of 2,3-butanediol feeds an estification step. The diester effluent comprises the 2,3-butanediol diacetate formed. The diester effluent feeds a pyrolysis step, which comprises a pyrolysis furnace operated at 580 ° C with a contact time of about 2 s. 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 shown in Table 2.
    Table 2: 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.
    Two esterification tests of 2,3-butanediol with acetic acid were carried out. One test was carried out with pure acetic acid and the other with 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 Amberlyst 36 catalyst, with a number of H + acid function 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 over time. .
    The results presented in the table below also show that the impurities present in the liquid pyrolysis effluent, some have evolved over time.
    Table 3: Results of the two esterification tests of 2,3-BDO with pure acetic acid and with a liquid pyrolysis effluent
    Concentrations of VCH and MVCA have changed little. The turnover also does not change significantly. On the other hand, it is shown here that MEKEA and MAA disappear almost completely under the conditions of esterification to give MEK. Indeed, the disappearance of MEKEA and MAA corresponds to 0.5177 mol.L-1 and the formation of MEK corresponds to 0.5577 mol.L-1, which is in the measurement error.
    It is thus demonstrated that certain pyrolysis intermediates and pyrolysis by-products are partially or completely converted into other products under the conditions of esterification, which are more easily separable from acetic acid, which makes it possible to avoid their accumulation. Thus, the sequencing of the esterification / pyrolysis steps with recycling of the liquid pyrolysis effluent according to the invention makes it possible, by the induced transformation of certain by-products, to improve the operation of the separation steps carried out on the acid effluent. carboxylic acid.
    Example 3 [Compliant] Elimination of MEK by-products of pyrolysis before drying of acetic acid by heterogeneous azeotropic distillation
    This example shows that in the absence of a trainer, the by-products included in the carboxylic acid effluent can be separated by distillation by producing a carboxylic acid residue comprising almost only carboxylic acid and water. which residue can be treated by heterogeneous azeotropic distillation without difficulty.
    The table below shows the material balance of a distillation column, operated at atmospheric pressure, with 15 theoretical equilibrium stages a mass reflux ratio of 1.48 and a mass reboiling rate of 0.47 where feeding is done on the floor 5.
    Table 4: Material balance at the MEK elimination azeotropic distillation column (step c)), before drying of the acetic acid by heterogeneous azeotropic distillation (step d)).
    MEK is 99% eliminated, MVCA 100%, CA 72%, VCH 100%, water 17%. This simulation reveals a loss of acetic acid of 3% which is quite acceptable.
    The MEK-free residue can be efficiently distilled by heterogeneous azeotropic distillation.
    EXAMPLE 4 [Conforming] Elimination of MEK, by-products of pyrolysis before drying of acetic acid by heterogeneous azeotropic distillation
    This example shows that in the absence of a trainer, the by-products included in the carboxylic acid effluent can be separated by distillation by producing a carboxylic acid residue comprising almost only carboxylic acid and water. which residue can be treated by heterogeneous azeotropic distillation without difficulty. In this example, the column is operated in such a way that demixing takes place in the condenser.
    The table below shows the material balance of a distillation column, operated between 1 and 2 bar, with 25 theoretical equilibrium stages a mass reflux ratio of 2.15 and a mass reboiling rate of 0.9 where the supply is made to stage 13, knowing that the first stage is at the top of the column.
    The overhead vapors of the column are condensed to 86 ° C. and sent to a reflux flask in which two liquid phases coexist. The organic phase is withdrawn as distillate and is free of acetic acid. The aqueous phase (of composition Water 96% wt, MEK 1.6% wt, MVCA 1.1% wt) is refluxed to the distillation column.
    Table 5: Material balance at the azeotropic distillation column of elimination of the MEK, before drying of acetic acid.
    The MEK is 100% eliminated, the MVCA 100%, the AC 100%, the VCH 100%, water 28%. This simulation reveals a loss of acetic acid of 0.003% which is quite negligible.
    The residue free from MEK, CA, MVCA can be efficiently distilled by heterogeneous azeotropic distillation and all of the acetic acid can be recovered for recycling and recovery.
    Example 5 [in conformity] Elimination of THF, by-products of pyrolysis before drying of acetic acid by heterogeneous azeotropic distillation
    This example shows that in the absence of a trainer, the by-products included in the carboxylic acid effluent can be separated by distillation by producing a carboxylic acid residue comprising almost only carboxylic acid and water. which residue can be treated by heterogeneous azeotropic distillation without difficulty.
    This example shows the simulation of the process for removing THF and pyrolysis byproducts before the drying of acetic acid by heterogeneous azeotropic distillation, according to the invention.
    The table below shows the material balance of a distillation column, operated at atmospheric pressure, with 15 equilibrium theoretical stages a mass reflux ratio of 10 and a mass reboil rate of 0.42 where feed is made on the floor 5.
    Table 6: Material balance at the azeotropic distillation column for removal of THF and the by-product of pyrolysis, before drying of acetic acid.
    THF is removed to 100%, the monoacetylated from pyrolysis is eliminated to 100%, it is also eliminated VCH 100%, water 3%. This simulation reveals a loss of acetic acid of 2% which is quite acceptable.
    The residue is mainly composed of water and acetic acid. Thus, this residue can be effectively distilled by heterogeneous azeotropic distillation in the presence of a trainer.
    权利要求:
    Claims (12)
    [1" id="c-fr-0001]
    A process for producing 1,3-butanediene from a butanediol feedstock comprising at least: a) a step of esterifying butanediol with a carboxylic acid to form the corresponding diester fed by said butanediol feed and by a feed carboxylic acid comprising a carboxylic acid charge and the liquid pyrolysis effluent from step b), and producing at least one carboxylic acid effluent and a diester effluent, carried out in reactive distillation in the presence of a homogeneous acid catalyst or heterogeneous, operated at a pressure of between 0.01 and 1 MPa; b) a step of pyrolysis of the diester effluent from step a) comprising a reaction section and a separation section and producing at least one liquid pyrolysis effluent comprising at least 50% by weight of carboxylic acid and an effluent steam pyrolysis process comprising more than 90% by weight of butadiene, said reaction section being operated at a temperature between 500 and 650 ° C, the effluent of said reaction section being cooled to a temperature below 100 ° C before feeding said separation section; c) a distillation step fed by at least the carboxylic acid effluent from step a), carried out in a distillation column at a pressure of at most 1 MPa, with a head temperature of between 0 and 110 ° C and a bottom temperature of between 100 and 120 ° C, and producing an aqueous distillate comprising by-products of step a) and step b) on the one hand, and a carboxylic acid residue on the other hand ; d) a step of drying the carboxylic acid fed at least by the carboxylic acid residue from step c) and producing a water effluent and a carboxylic acid product supplying step a).
    [2" id="c-fr-0002]
    2. Process according to claim 1, wherein said butanediol feedstock comprises at least 90% by weight of butanediol chosen from the list consisting of 1,4-butanediol, 1,3-butanediol and 2,3-butanediol taken alone or in part. mixed.
    [3" id="c-fr-0003]
    3. Method according to one of the preceding claims wherein said carobxylic acid is acetic acid.
    [4" id="c-fr-0004]
    4. Method according to one of the preceding claims wherein the reactive distillation of step a) comprises a mixed reaction / separation zone located between two separation zones.
    [5" id="c-fr-0005]
    5. Method according to the preceding claim wherein said mixed zone comprises a heterogeneous acid catalyst selected from an acidic ion exchange resin, a mixed oxide or an acidic zeolite.
    [6" id="c-fr-0006]
    6. Method according to one of the preceding claims wherein the residence time in said reactive distillation column of step a), defined as the volume of the reactive distillation divided by the volume flow rate of said diol charge and said charge. carboxylic acid, is between 0.5 h and 10 h.
    [7" id="c-fr-0007]
    7. Method according to one of claims 4 to 6 wherein the MMH, corresponding to the molar rate of diol in the diol charge divided by the number of moles of catalyst present in said mixed zone, is between 0.05 and 25 h-1.
    [8" id="c-fr-0008]
    8. Method according to one of the preceding claims wherein said liquid pyrolysis effluent of step b) is purified before being recycled to step a) in admixture with the carboxylic acid charge.
    [9" id="c-fr-0009]
    9. The process according to one of the preceding claims wherein said aqueous distillate of said step c) comprises not more than 10% by weight of carboxylic acid.
    [10" id="c-fr-0010]
    10. Method according to one of the preceding claims wherein step c) is carried out in a distillation column whose temperature of the column head is between 50 ° C and 100 ° C, and the bottom temperature of the column is between 100 ° C and 115 ° C.
    [11" id="c-fr-0011]
    11. Method according to one of the preceding claims wherein said step d) is carried out by heterogeneous azeotropic distillation in the presence of a trainer.
    [12" id="c-fr-0012]
    12. Method according to the preceding claim wherein said trainer of step d) is isopropyl acetate.
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    同族专利:
    公开号 | 公开日
    FR3045599B1|2018-01-12|
    US10647624B2|2020-05-12|
    EP3390326B1|2019-11-20|
    US20180370869A1|2018-12-27|
    WO2017102743A1|2017-06-22|
    EP3390326A1|2018-10-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2383205A|1942-11-16|1945-08-21|Universal Oil Prod Co|Manufacture of butadiene|
    FR859902A|1939-06-03|1941-01-02|Cie Nat Matieres Colorantes|Process for the preparation of butadiene|
    US2372221A|1943-09-14|1945-03-27|Samuel A Morell|Process of acetylating 2,3-butylene glycol with the impure acetic acid obtained from the pyrolytic decomposition of 2,3-butylene glycol diacetate to butadiene|
    FR2737131B3|1995-07-24|1997-09-05|Inst Francais Du Petrole|PROCESS AND DEVICE FOR REACTIVE DISTILLATION WITH PARTICULAR DISTRIBUTION OF LIQUID AND VAPOR PHASES|
    FR2737132B1|1995-07-24|1997-09-19|Inst Francais Du Petrole|PROCESS AND DEVICE FOR REACTIVE DISTILLATION WITH PARTICULAR DISTRIBUTION OF LIQUID AND VAPOR PHASES|FR3051467B1|2016-05-17|2018-06-01|IFP Energies Nouvelles|CONVERSION OF BUTANEDIOL TO BUTADIENE WITH DIESTER WASH|
    CN109879712B|2019-03-04|2020-06-02|浙江大学|Synthesis method of 1, 9-decadiene|
    CN110128241B|2019-06-16|2021-10-22|宁波永顺精细化工有限公司|Method for co-producing 1, 9-decadiene and 9-decaen-1-ol in fixed bed reactor|
    CN110128237B|2019-06-16|2021-11-05|宁波永顺精细化工有限公司|Method for preparing 1, 9-decadiene by using fixed bed reactor|
    法律状态:
    2016-12-12| PLFP| Fee payment|Year of fee payment: 2 |
    2017-06-23| PLSC| Publication of the preliminary search report|Effective date: 20170623 |
    2017-12-14| PLFP| Fee payment|Year of fee payment: 3 |
    2019-12-23| PLFP| Fee payment|Year of fee payment: 5 |
    2021-09-10| ST| Notification of lapse|Effective date: 20210806 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1562859A|FR3045599B1|2015-12-18|2015-12-18|PROCESS FOR PRODUCING BUTADIENE FROM BUTANEDIOLS|
    FR1562859|2015-12-18|FR1562859A| FR3045599B1|2015-12-18|2015-12-18|PROCESS FOR PRODUCING BUTADIENE FROM BUTANEDIOLS|
    EP16809088.4A| EP3390326B1|2015-12-18|2016-12-13|Method for producing butadiene from butanediols|
    PCT/EP2016/080824| WO2017102743A1|2015-12-18|2016-12-13|Method for producing butadiene from butanediols|
    US16/063,595| US10647624B2|2015-12-18|2016-12-13|Method for producing butadiene from butanediols|
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