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    • 专利摘要:
    The invention relates to a process for producing 1,3-butadiene from a feed rich in ethanol, that is to say in which ethanol represents more than 50% of the total weight of said feed, comprising at least minus: A) a step of converting at least said ethanol rich feedstock and the ethanol effluent from the separation step B into a conversion effluent comprising predominantly 1,3-butadiene, water and ethylene, and a hydrogen effluent, operating at a pressure of between 0.1 and 1.0 MPa, at a temperature between 300 and 500 ° C in the presence of at least one catalyst; B) a step of separating at least said conversion effluent from A and the hydration effluent from C into at least one ethanol effluent, a butadiene effluent, a water effluent and an ethylene effluent; C) a hydration step fed at least by said ethylene effluent and said effluent water from the separation step B, to produce a hydration effluent comprising ethanol, said hydration effluent then being recycled to step B of separation.
    公开号:FR3014097A1
    申请号:FR1361831
    申请日:2013-11-29
    公开日:2015-06-05
    发明作者:Rejane Dastillung；Nicolas Cadran；Marc Jacquin；Raphael Huyghe；Beatrice Fischer
    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 The invention relates to the field of the production of unsaturated hydrocarbons, in particular the production of diolefins, such as, for example, the production of diolefins. 1,3-butadiene, the latter may be used as polymerization monomer, or converted into another chemical intermediate, such as for example 1,6-hexanediamine. State of the Prior Art The production of 1,3-butadiene from ethanol is well known to those skilled in the art. Two processes have been industrialized on a large scale: the "S.K." process, in which 1,3-butadiene is produced from ethanol in one reaction step, with a single catalyst; the "Carbide" process, in which the ethanol is converted to acetaldehyde in a first reaction step on a first catalyst consisting of a mixture of chromium oxide and copper oxide, followed by a second reaction step on a second catalyst in which the ethanol-acetaldehyde mixture is converted to 1,3-butadiene (see for example US 2,439,587). The catalyst used in the "S.K." process is dehydrogenating, and therefore produces a large amount of acetaldehyde when fed with ethanol. As early as the 1940s, the product acetaldehyde was recycled to the catalytic unit, allowing a significant improvement in yields. Through this recycling, the catalytic unit of the process "S.K." therefore received an ethanol-acetaldehyde mixture. The overall balance of the conversion reaction of ethanol to 1,3-butadiene is written as follows: ## STR2 ## For the sake of simplification, we will therefore speak later of "Ethanol-rich feedstock", the term designating the ethanol-acetaldehyde mixture comprising more than 50% by weight of ethanol sent to the single catalyst of the "SK" process or to the second catalyst of the "Carbide" process. Whatever the process (one or two steps), the selectivity of the conversion of the feed rich in ethanol to 1,3-butadiene is low, said transformation leading to the formation of numerous by-products. By-product means constituents formed other than those produced or consumed by the main reaction (ie other than 1,3-butadiene, H2, H2O products and ethanol and acetaldehyde consumed). Toussaint et al., Industrial and Engineering Chemistry Vol. 39, No. 2, p. 120-125 1947 give as an illustration the distribution of the by-products formed on an industrial unit "Carbide": diethyl ether (23% by-products), ethylene (11% by weight of by-products), hexenes and hexadienes (11% by weight of by-products). Nevertheless, the distribution of the by-products may vary considerably depending on the operating conditions and the nature of the catalyst used for the conversion of the feed rich in ethanol to 1,3-butadiene.
    [0002] In addition, the conversion of the feed rich in ethanol to 1,3-butadiene is low. Unconverted reagents must therefore be separated from the products before being recycled. By way of illustration, US Pat. No. 2,393,381 describes the recycling of unconverted ethanol and acetaldehyde in the second catalytic section of the "Carbide" process. US Pat. No. 2,393,381 also describes the elimination of gaseous and liquid by-products generated by the catalytic process.
    [0003] Many improvements have been made to the basic processes, in order to valorize certain by-products of this type of process. Indeed, the by-products can be extracted by various separation processes and then: - or recycled to the catalytic unit producing 1,3-butadiene from the feed rich in ethanol. or sent to a dedicated catalytic unit to be converted into other compounds. Thus, in US Pat. No. 2,439,587 concerning the "Carbide" process, the ethyl acetate - a minor impurity in the process - is recovered by recycling to the catalytic unit producing 1,3-butadiene.
    [0004] Ethyl acetate can be formed by different mechanisms within the catalytic unit, but can also produce 1,3-butadiene. Indeed, under the conditions gathered within the catalytic unit, ethyl acetate can be substituted for ethanol to produce 1,3-butadiene and acetic acid.
    [0005] Another example well known to those skilled in the art is the case of diethyl ether (DEE), a major by-product of the process. In the process "S. K." DEE is returned to the catalytic section with the ethanol-rich feedstock. The recycling of the DEE to the catalytic unit makes it possible to improve the yield of 1,3-butadiene, and also causes an increase in the amount of ethylene produced. Indeed, under the conditions gathered within the catalytic unit, DEE can substitute for ethanol to produce 1,3-butadiene and ethylene. On the other hand, in the "Carbide" process, the recycling of the DEE towards the catalytic unit did not lead to an increase in the yield of 1,3-butadiene. This difference in behavior can be explained both by the nature of the catalyst and by the thermal levels, which are different for the two processes. Within the "Carbide" process (US Pat. No. 2,474,874), the DEE is separated and sent to a dedicated catalytic unit in order to be converted into another valuable compound, for example ethylene. Indeed, ethylene can be used as a raw material for the synthesis of styrene, which can itself be used as a raw material for the production of butadiene - styrene copolymer.
    [0006] Another example of recovery mentioned in US Pat. No. 2,474,874 is the formation of ethanol by hydration of DEE. The ethanol produced can be recycled on site to the 1,3-butadiene production process, so as to increase the overall yield.
    [0007] The hydration of ethylene to ethanol corresponds to the following reaction: CH 2 = CH 2 + H 2 O -> CH 3 CH 2 OH The processes for hydration of ethylene into ethanol are well known to those skilled in the art and are divided into two major groups. categories: direct and indirect hydration (Weissermel and Arpe, Industrial Organic Chemistry and Publishing, Wiley-VCH 2003). Indirect hydration is characterized by the formation of reaction intermediates formed by the addition of an acid to the olefin, followed by hydrolysis to alcohol. This type of process can be carried out in the presence of concentrated sulfuric acid which, in the presence of gas containing ethylene, forms mono- and diethyl sulphates, which decompose into ethanol after addition of water in the medium. The advantages of this type of process are the low reaction temperatures (50-150 ° C) and a high pass conversion level. The main disadvantage is the use of concentrated acid, which poses corrosion problems as well as significant operating costs for the reconcentration / reuse of the acid. Indirect hydration is carried out in two-phase gas / liquid medium. Direct hydration is characterized by the formation in a single reaction step of the alcohol. For the hydration of ethylene, the reaction is in the gas phase. Reaction temperatures are higher (200-400 ° C) and low pass conversions (<10%) which require significant recycling. This process uses heterogeneous catalysts based on inorganic acids such as phosphoric acid deposited for example on silicic or silica-based supports (kieselguhr ..) which makes it possible to eliminate the problems associated with the use of a concentrated acid necessary for the indirect hydration process. The disadvantages of this type of process are its low pass conversion and its need to work with high purity ethylene (especially to avoid the accumulation of inert during recycle). Hydration processes of ethylene, direct or indirect, require working with a very pure ethylene. Indeed, the presence of impurities is problematic for the proper functioning of these processes. This can be illustrated with two conventional impurities of the "C2" distillation cup which are ethane and acetylene. In a direct hydration process, ethane accumulates because it is not converted. In a direct or indirect hydration process, acetylene is converted to acetaldehyde, which must be managed and removed within the process.
    [0008] Moreover, even with high purity ethylene, the ethanol produced must be purified. Indeed, side reactions can occur and generate by-products such as acetaldehyde or diethyl ether.
    [0009] However, it has been discovered that it is possible to judiciously combine a step of conversion of ethanol to 1,3-butadiene and a step of hydration of ethylene to ethanol so as to increase the overall yield in 1 , 3-butadiene, despite a decrease in the conversion and selectivity in the hydration step due to the use of a less pure ethylene than taught in the prior art.
    [0010] Said association, through the use of recycling and synergies, makes it possible to valorize common by-products, whereas these by-products (for example DEE and acetaldehyde) must be eliminated when these stages are operated independently of one another. the other. SUMMARY AND INTEREST OF THE INVENTION One aspect of the invention is to enhance the ethylene by-product produced during the conversion of the ethanol-rich feedstock to 1,3-butadiene to maximize the yield of 1,3-butadiene. . The ethylene by-product produced with 1,3-butadiene is concentrated in a gas stream that is hydrated in a dedicated catalytic section to produce predominantly ethanol. The effluent thus obtained is returned within the step of conversion to 1,3-butadiene via a separation step capable of separating the various constituents, for example ethanol, water, DEE, acetaldehyde and ethylene. Thus, the ethylene impurity is valued, which allows to maximize the overall yield of 1,3-butadiene.
    [0011] This invention is particularly suitable when, for example because of the operating conditions, or of the catalyst used, or of the recycling of diethyl ether within the unit for transforming the feedstock rich in ethanol into 1,3-butadiene, the amount of ethylene produced is important. Another aspect of the invention is to supply all or part of the hydration unit of ethylene with another source of ethylene, in order to ensure greater flexibility for the operator of the unit of ethylene. production of 1,3-butadiene as a function of changes in the cost of raw materials, market prices of products and energy prices. This other source of ethylene may for example be a fossil hydrocarbon steam cracking unit or a fluid catalytic cracking type unit, or Fluid Catalytic Cracking in the language of Shakespeare.
    [0012] Finally, another aspect of the invention is to use, in whole or in part, water coproduced with 1,3-butadiene to hydrate ethylene, that it is a by-product generated within the process or come from another source.
    [0013] The Applicant has discovered that it is possible to feed the hydration unit with less pure ethylene than is usually done in the prior art, obtaining, despite hydration not working optimally, an improvement in the overall performance of the 1,3-butadiene production process.
    [0014] The invention has a downward impact on the level of investments and consumption of utilities compared to prior art (water, steam, electricity). In fact: The ethanol produced by step C of hydration of ethylene does not need to be purified to 94.5% by mass, as commonly done in the prior art, because it is recycled as a filler. in conversion step A, where the purity constraint is lower. The stages of separation and treatment of the effluents of conversion steps A and C of hydration are shared. There is therefore no need for a dedicated train for purification of the hydration effluent. Acetaldehyde and DEE produced by the hydration reaction of ethylene are, in the state of the art, separated from ethanol and most often flared, ie burned at a loss. Since these products are also reagents and by-products of the conversion step A, it is no longer necessary to have dedicated columns for withdrawing ethanol produced from ethylene. The integration of step A of conversion and step C of hydration of ethylene makes it possible to valorize acetaldehyde and DEE.
    [0015] The ethylene produced by conversion step A and sent to the hydration unit does not need to be purified to the level of 99.9% wt, which limits the losses produced and the investment levels. The water produced by the conversion step A is used totally or partially in the hydration step C, which limits the rejections of the unit, and therefore the size and the consumption of utilities of the treatment unit. downstream waters. DESCRIPTION OF THE INVENTION The invention relates to a process for producing 1,3-butadiene from a feed rich in ethanol, that is to say in which ethanol represents more than 50% of the total weight of said feedstock, comprising at least: A) a step of converting at least said feed rich in ethanol and the ethanol effluent from the separation step B into a conversion effluent comprising predominantly 1,3-butadiene, water and ethylene, and a hydrogen effluent, operating at a pressure of between 0.1 and 1.0 MPa, at a temperature between 300 and 500 ° C in the presence of at least one catalyst; B) a step of separating at least said conversion effluent from A and the hydration effluent from C into at least one ethanol effluent, a butadiene effluent, a water effluent and an ethylene effluent; C) a hydration step fed at least by said ethylene effluent and said effluent water from the separation step B, to produce a hydration effluent comprising ethanol, said hydration effluent then being recycled to step B of separation.
    [0016] Charge rich in ethanol According to the invention, the feedstock sent to the 1,3-butadiene production unit is a feed rich in ethanol. By ethanol-rich filler is meant a filler in which ethanol accounts for more than 50% of the total weight of said filler.
    [0017] Said filler rich in ethanol may advantageously comprise acetaldehyde. When said feed rich in ethanol comprises acetaldehyde, the mass ratio of ethanol to acetaldehyde is preferably between 2: 1 and 4: 1, preferably between 2.5: 1 and 3.5: 1 and very preferably from 3: 1.
    [0018] Said filler rich in ethanol may also comprise impurities, such as, for example, ethers (diethyl ether, vinylethyl ether, methylethyl ether, butyl ethyl ether, etc.), esters (for example ethyl acetate), acetals (for example ethyl acetal), aldehydes other than acetaldehyde and ketones (for example crotonaldehyde, butyraldehyde and acetone), alcohols (for example butanol, hexanol, etc.), and saturated or unsaturated hydrocarbons. The content of these impurities is between 0% and 20% of the total weight of the filler, preferably between 0 and 10% by weight. Finally, said feed rich in ethanol may also comprise water. The water content is advantageously between 0 and 30% of the total weight of the filler. Preferably, the water content is between 4 and 15% by weight. Step A of Converting the Ethanol-rich Filler to 1,3-Butadiene According to the invention, said ethanol-rich feed feeds a conversion step A.
    [0019] According to a preferred embodiment, said conversion step A is carried out in a reaction step ("S.K." process). In this mode, said feed rich in ethanol is mixed with the ethanol effluent from the separation step B before supplying said conversion step A. According to another preferred embodiment, said step A is carried out in two reaction steps, the first step making it possible to convert ethanol to acetaldehyde in the presence of a catalyst consisting of a mixture of chromium oxide and copper oxide, or any other suitable catalyst. The mass ratio of ethanol to acetaldehyde in the effluent of said first reaction stage is preferably between 2: 1 and 4: 1, preferably between 2.5: 1 and 3.5: 1 and very preferably 3: 1. In this mode, said feed rich in ethanol feeds the first reaction stage and the ethanol effluent from the separation stage B feeds the second reaction stage, mixed with said effluent of the first reaction stage. Said ethanol-rich feedstock and the ethanol effluent from step B undergo, in a conversion step A, a chemical conversion so as to produce a conversion effluent and a hydrogen effluent. Said step A completely or partially converts the ethanol-rich feedstock and the ethanol effluent from step B to at least butadiene, ethylene, hydrogen, water, and acetaldehyde, most of which 1,3-butadiene. For the most part, it is meant that more than 50% by weight of the products formed (excluding production of water, hydrogen and acetaldehyde) at the end of stage A are 1,3-butadiene, preferably more than 60% wt. Nevertheless, since the conversion of the feedstock rich in ethanol and the ethanol effluent from stage B may be partial, 1,3-butadiene may represent less than 50% by weight of the conversion effluent (excluding water, hydrogen and acetaldehyde) due, for example, to the presence of unconverted ethanol. Said conversion effluent comprises between 1 and 8% by weight of ethylene (excluding water, ethanol, hydrogen and acetaldehyde).
    [0020] Step A is carried out at a pressure of between 0.1 and 1.0 MPa, preferably between 0.1 and 0.5 MPa, preferably between 0.1 and 0.3 MPa. Step A is carried out at a temperature between 300 and 500 ° C.
    [0021] In the case where step A is carried out in a reaction step, it is carried out in the presence of a zinc aluminate catalyst, or MgO-SiO 2 doped with chromium, as that used in the "S.K." process. (see for example Bhattacharyya, Ganguly Journal of Applied Chemistry Volume 12, Issue 3, pages 97-110, March 1962). Step A is then preferably carried out at a temperature between 380 and 430 ° C.
    [0022] In the case where step A is carried out in two reaction stages, the second reaction stage of said step A is carried out in the presence of a silica-type catalyst with a tantalum oxide, zirconium oxide or columbium oxide, preferably with 2% d Tantalum oxide, such as that used in the "Carbide" process (see for example Corson, Jones, Welling, Hincbley, Stahly, Ind. Eng Chem., 1950, 42, 2, 359-373). The second reaction stage of step A is then preferably carried out at a temperature of between 320 and 370 ° C. The first reaction step of said step A is carried out according to the prior art, at a temperature between 200 and 300 ° C. A hydrogen effluent, mainly comprising hydrogen, is separated at the end of the reaction by means known to those skilled in the art (gas-liquid separator for example). When the conversion step A is carried out with two reaction stages (conversion according to the "Carbide" method), the hydrogen is mainly produced in the first reaction stage of the process. It is then separated between the two reaction stages. Separation stage B In accordance with the invention, the conversion effluent resulting from stage A as well as the hydration effluent resulting from stage C feed a separation stage B so as to produce at least one ethanol effluent , a butadiene effluent, a water effluent, and an ethylene effluent.
    [0023] Said step B makes it possible to separate butadiene, the main product of the process according to the invention, as well as to produce an ethanol effluent that can be recycled in conversion step A. By ethanol effluent is meant an effluent comprising more than 50% by weight of ethanol. This effluent may contain up to 30% by weight of acetaldehyde. This effluent may also comprise impurities, such as, for example, ethers (for example diethyl ether, vinyl ethyl ether, methyl ethyl ether, butyl ethyl ether, etc.), esters (for example ethyl acetate), acetals (eg ethyl acetal), aldehydes and ketones (eg crotonaldehyde, butyraldehyde and acetone), alcohols (eg butanol, hexanol, ...), and saturated hydrocarbons or unsaturated. The total content of these impurities is between 0% and 20% by weight, preferably between 0 and 10% by weight. This effluent may also contain water. The water content can be between 0 and 30 wt%. Preferably, the water content is between 4 and 15% by weight. The acetaldehyde may advantageously subsequently be separated from the ethanol effluent.
    [0024] Said ethanol effluent is recycled in step A as a mixture with said ethanol-rich feedstock. By butadiene effluent is meant an effluent comprising more than 80% by weight, preferably more than 90% by weight, and more preferably more than 99% by weight of 1,3-butadiene.
    [0025] By effluent water is meant an effluent comprising more than 90% by weight of water, preferably more than 99% by weight of water. This effluent may especially contain very polar impurities and less volatile than water, especially acetic acid. By ethylene effluent is meant a gaseous effluent at a temperature below 50 ° C and a pressure of less than 0.8 MPa, comprising at least 50% by weight of ethylene. It may also include traces of hydrogen, carbon monoxide, carbon dioxide, propylene, acetylene, light alkanes (eg methane, ethane, propane), DEE, which may be formed by reactions secondary.
    [0026] The separation step B also advantageously produces a heavy gas effluent, that is to say a gaseous effluent at a temperature below 50 ° C. and a pressure of less than 0.8 MPa, comprising the constituents other than those included in FIG. ethylene effluent.
    [0027] The separation step B also advantageously produces an oils effluent, that is to say an effluent comprising a mixture of saturated and unsaturated hydrocarbon compounds, and oxygenated compounds: esters, ethers, acetals, aldehydes, ketones, alcohols which can be saturated or unsaturated. This effluent is characterized by being composed only of carbon, oxygen and hydrogen, and having a boiling temperature ranging from 20 ° C to 500 ° C. It can be used as a fuel for the generation of utilities (heat, electricity) necessary for the proper functioning of the process according to the invention, or it can be processed for separation operations in order to extract recoverable products.
    [0028] The separation step B is carried out by a set of unitary operations well known to those skilled in the art, for example and without limitation by distillation, cryogenic distillation, solvent washing (for example water or ethanol), extractive distillation. , liquid-liquid extraction, sieving, membrane separation.
    [0029] In a nonlimiting manner, an example of a sequence of these unit operations may be the following. The conversion effluent resulting from stage A is cooled and sent to an ethanol washing column: an ethylene effluent, comprising ethylene, ethanol and possibly traces of hydrogen, is evacuated head of the washing column. The liquid effluent obtained at the bottom of the washing column is sent to a distillation column, in order to obtain a rich butadiene effluent at the top of the distillation column. This effluent rich in butadiene is then washed with water to remove volatile polar compounds. Finally, the rich butadiene effluent having been washed with water is sent to an extractive distillation unit using a polar solvent (for example DMF, NMP or ACN) in order to eliminate the butenes and possibly other impurities. to produce a butadiene effluent. The bottom of the distillation column and washing columns are sent to a distillation train which produces a water effluent, an ethanol effluent, and an effluent oils. The ethanol effluent can be recycled to the conversion step A, mixed with the ethanol-rich feedstock. Hydration Step C In accordance with the invention, at least a portion of the ethylene effluent and at least a portion of the water effluent from the separation step B feed a hydration step C to produce a hydration effluent. Said step C is advantageously powered by another external source of ethylene. Said other external source of ethylene may be, for example, a steam cracker or an FCC type unit. Said step C may also advantageously be powered by an external source of water. The purity of the ethylene flow feeding the hydration step C is therefore variable depending on the ethylene source used. The purity of the ethylene is between 50 and 100%, preferably between 65 and 99.9% by weight, and very preferably between 65 and 75% by weight.
    [0030] In a preferred embodiment, said hydration step C is indirect hydration. In a first step, the ethylene reacts in the presence of concentrated sulfuric acid at a reaction temperature of between 50 and 150 ° C. in a two-phase gas / liquid medium. In a second step, the products formed in the first step are hydrolysed to predominantly form ethanol at a temperature between 70 and 100 ° C. Finally, sulfuric acid is reconcentrated for reuse. In another preferred embodiment, said hydration step C is a direct hydration, carried out in the gas phase, at a reaction temperature of between 200 and 400 ° C., in the presence of a heterogeneous catalyst based on inorganic acids such as phosphoric acid deposited for example on silicic or silica-based supports (kieselguhr ..). According to the invention, said hydration effluent is recycled to the separation step B. It can either be mixed directly with the conversion effluent from conversion stage A or be treated by a dedicated unit operation of separation stage B. This recycling ultimately allows the recycling of ethanol to conversion stage A. Said hydration effluent comprises, in addition to ethanol, DEE produced according to the following reaction: ## STR2 ## %), the hydration effluent comprises on the one hand gaseous by-products that have not completely reacted in the catalytic unit C (propylene acetylene, DEE), and on the other hand non-reactive gaseous by-products. not (carbon monoxide, carbon dioxide, methane, ethane, propane) which are sent to the separation step B so as to keep constant the concentration of non-reactive gaseous by-products in the feed of step C In a preferred embodiment, all the ethylene fed to the catalytic unit C is produced by the conversion step A, after passing through the separation step B. That is, there is no input from an external source of ethylene. In this mode, the amount of water produced in step A is sufficient to hydrate the ethylene produced in step A. Therefore, all of the water feeding step C of hydration can from the conversion step A, after separation in the separation step B.
    [0031] The hydration step C is also advantageously fed with ethylene from an external source.
    [0032] If the amount of water produced in step A is not sufficient to hydrate the ethylene supplying step C of hydration, then an additional external source of water supply of step C is also used. The portion of water from said external source represents less than 20% by weight, preferably less than 10% by weight of the water supplying the hydration stage C.
    [0033] When the process according to the invention is carried out in a site comprising other processes, the flows of said site comprising acetylene or DEE can advantageously be treated in the hydration step C of the process according to the invention. .
    [0034] DESCRIPTION OF THE FIGURES FIG. 1 schematically describes the process for producing 1,3-butadiene from a feed rich in ethanol according to the invention. The feed rich in ethanol 1 is mixed with the effluent ethanol 6 so as to form a conversion charge 2. Said conversion charge 2 is sent to the conversion step A to produce a conversion effluent 4 and an effluent hydrogen 3. The conversion effluent 4 from step A and the hydration effluent 13 from step C feed the separation step B in which an ethanol effluent 6, a butadiene effluent 5, are separated. a water effluent 7, an ethylene effluent 8, a heavy gas effluent 9, and an effluent oils 10. A fraction 7a of the effluent water 7 is purged. A fraction 8a of the ethylene effluent 8 is purged. Part of the water effluent 7 and a portion of the ethylene effluent 8 feed the hydration step C. An external source of ethylene 11 and an external source of water 12 also feed into said step C. Step C produces a hydration effluent 13, which feeds the separation step B. The following examples illustrate the invention without limiting its scope. Examples In the following examples, the performances of the processes are evaluated on the basis of the overall yield of 1,3-butadiene defined as follows: mass flow rate of 1,3-butadiene in the butadiene effluent divided by the mass flow rate of ethanol in the feed rich in ethanol. Example 1 - Non-Conforming Example 1 illustrates the operation of the Lebedev process according to the prior art. After a conversion step, the unconverted ethanol and acetaldehyde are separated and recycled upstream of said converting step. An ethanol-rich feed consisting of 93.3 wt.% Ethanol and 6.7 wt.% Water feeds conversion step A. Unconverted ethanol and acetaldehyde present in the conversion effluent are separated in a separation step B and recycled upstream of step A.
    [0035] The separation step B is carried out in such a way that 99% of the ethanol and 100% of the acetaldehyde included in the conversion effluent are recycled to stage A. The overall yield of 1,3-butadiene of the process is 0.383.
    [0036] Example 2 - Non-Conforming This example is based on Example 1. After the conversion step, an ethylene effluent which is hydrated is further separated in a hydration process as known to those skilled in the art so that produce a hydration effluent comprising ethanol. Said ethanol effluent is then recycled upstream of the conversion step (after separation of the ethylene and a part of the water).
    [0037] The conversion step A is fed with a feedstock rich in ethanol identical to that of Example 1, as well as with an ethanol effluent from the separation step B. The separation step B is carried out in such a way that 99% of the ethanol and 100% of the acetaldehyde included in the conversion effluent are recycled to stage A. As is known to those skilled in the art the ethylene sent to the hydration unit must be very pure (Weissermel and Arpe, Industrial Organic Chemistry 4th edition, Wiley-VCH 2003). The separation and purification of the ethylene contained in said conversion effluent into an ethylene effluent comprising 99.9% by weight of ethylene induces 15% loss of ethylene. Thus, the separation step B makes it possible to recover 85% of the ethylene included in said conversion effluent. Said ethylene effluent, as well as a water flow of origin external to the process, are converted into ethanol in a hydration process as known to those skilled in the art. At the end of the hydration reaction step, the ethanol is purified in a dedicated separation unit typical of prior art hydration processes, which produces 94.5% ethanol and recycled. to the feed of conversion step A. The overall yield of the process is 0.395, which is 3.1% more than in Example 1.
    [0038] Example 3 - Conform In this example, according to the invention, the conversion effluent is treated in a separation step B to produce at least one butadiene effluent, an ethanol effluent, an ethylene effluent and a water effluent. The purity specification on the ethylene effluent is less, and an internal process water flow is used for the hydration step. The conversion step A is fed with a feedstock rich in ethanol identical to that of Example 1, as well as with an ethanol effluent from the separation step B. The separation step B, fed by the conversion effluent from said step A, as well as by the hydration effluent from said step C, makes it possible to produce at least one butadiene effluent, an ethanol effluent, an effluent ethylene and a water effluent. It is operated in such a way that 99% of the ethanol and 100% of the acetaldehyde included in the feed of said stage B are recycled to stage A. 99% of the ethylene included in said conversion effluent is separated in said ethylene effluent. The purity of the ethylene in this effluent is 73% by weight. It is sent, as well as said water effluent, to a step C of hydration The overall yield of the process is 0.397, 0.5% better than Example 2 and 3.7% better than Example 1 With reference to Example 2, the overall performance of the process could be maintained, or even improved by 0.5%, whereas the purity of the ethylene sent to the hydration stage is much lower (73% wt. instead of 99.9% by weight). The separation of the ethylene contained in the conversion effluent resulting from stage A is therefore, because of a constraint of less severe purity, facilitated in the example according to the invention, which allows a better recovery of said ethylene (99% instead of 85%). This lower purity also leads to a more energy-efficient separation. The pooling of the treatment of the conversion effluent resulting from stage A and the hydration effluent resulting from stage C makes it possible to reduce by 40% the number of equipment required. The process according to the invention thus allows a better valorization of the ethylene co-product in the conversion step A, since 16.4% of ethylene is valorized in addition with respect to Example 2 (99% / 85%).
    [0039] The hydration of an ethylene effluent of low purity, contrary to the known uses of the prior art, has, surprisingly, not the effect of impacting the overall yield of 1,3-butadiene process. Indeed, even if the effluent water and the ethylene effluent that feed said hydration step include impurities, such as for example acetic acid, acetaldehyde, acetylene, propylene and diethyl ether, the setting in common of the separation step B capable of separating these compounds and the recycling to the conversion step A, which converts some of these impurities, they compensate for the degradation of performance of the hydration step C due to the use of the charge (ethylene effluent and water) less pure than those commonly used in the prior art.
    权利要求:
    Claims (7)
    [0001]
    REVENDICATIONS1. A process for producing 1,3-butadiene from a feed rich in ethanol, that is to say in which the ethanol represents more than 50% of the total weight of said feedstock, comprising at least: A) A step of converting at least said ethanol-rich feedstock and the ethanol effluent from the separation step B into a conversion effluent comprising predominantly 1,3-butadiene, water and ethylene, and a hydrogen effluent, operating at a pressure of between 0.1 and 1.0 MPa, at a temperature between 300 and 500 ° C in the presence of at least one catalyst; B) a step of separating at least said conversion effluent from A and the hydration effluent from C into at least one ethanol effluent, a butadiene effluent, a water effluent and an ethylene effluent; C) a hydration step fed at least by said ethylene effluent and said effluent water from the separation step B, to produce a hydration effluent comprising ethanol, said hydration effluent then being recycled to step B of separation.
    [0002]
    The process according to claim 1 wherein said step C is indirect hydration, wherein in a first reaction step the ethylene reacts in the presence of concentrated sulfuric acid at a reaction temperature of between 50 and 150 ° C. in two-phase gas / liquid medium, and in a second step, the products formed in the first reaction stage are hydrolysed to predominantly form ethanol at a temperature between 70 and 100 ° C.
    [0003]
    3. Process according to claim 1, in which said step C is a direct hydration operating in the gas phase, at a reaction temperature of between 200 and 400 ° C., in the presence of a heterogeneous catalyst based on inorganic acids such as phosphoric acid deposited on silica-based supports.
    [0004]
    4. Method according to one of claims 1 to 3 wherein the purity of the ethylene flow feeding the hydration step C is between 65 and 99.9% by weight.
    [0005]
    5. Method according to one of claims 1 to 3 wherein the purity of the flow of ethylene feeding step C hydration is between 65 and 75% by weight
    [0006]
    6. Method according to one of claims 1 to 5 wherein step A) is carried out in the presence of a silica type catalyst with 2% tantalum oxide, at a temperature between 320 and 370 ° C.
    [0007]
    7. Method according to one of claims 1 to 6 wherein step A) is carried out in the presence of a catalyst of zinc aluminate type, or MgO-SiO 2 doped with chromium at a temperature between 380 and 430 ° C .
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    同族专利:
    公开号 | 公开日
    FR3014097B1|2016-01-01|
    BR112016011953B1|2020-12-29|
    US20160376206A1|2016-12-29|
    WO2015079040A1|2015-06-04|
    US9776933B2|2017-10-03|
    CN105980338B|2019-02-15|
    EP3074367A1|2016-10-05|
    CN105980338A|2016-09-28|
    EP3074367B1|2018-08-01|
    PL3074367T3|2019-07-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2374433A|1942-06-08|1945-04-24|Universal Oil Prod Co|Production of butadiene|
    US2474874A|1945-11-09|1949-07-05|Koppers Co Inc|Recovery of by-product ether|
    EP1052234A1|1998-01-30|2000-11-15|Kabushiki Kaisha Sangi|Process for the synthesis of chemical industrial feedstock and high-octane fuel, and high-octane fuel composition|
    US2386324A|1943-04-16|1945-10-09|Air Reduction|Production of butadiene|
    US3686334A|1969-01-13|1972-08-22|Exxon Research Engineering Co|Direct hydration of ethylene to ethanol|WO2016043209A1|2014-09-16|2016-03-24|積水化学工業株式会社|Method for producing butadiene and device for producing butadiene|
    FR3053332B1|2016-06-29|2018-08-03|IFP Energies Nouvelles|PROCESS FOR THE PRODUCTION OF BUTADIENE FROM ETHANOL COMPRISING A PURIFICATION OF A BUTADIENE-RICH EFFLUENT BY EXTRACTIVE DISTILLATION|
    FR3053331B1|2016-06-29|2018-08-03|IFP Energies Nouvelles|PROCESS FOR PRODUCING BUTADIENE FROM INTEGRATED ETHANOL WITH EXTRACTIVE DISTILLATION|
    FR3057467B1|2016-10-17|2018-12-07|IFP Energies Nouvelles|PROCESS FOR PURIFYING AQUEOUS SOLUTION COMPRISING DIETHYLACETAL|
    FR3060559A1|2016-12-21|2018-06-22|IFP Energies Nouvelles|PROCESS FOR TREATING AN AQUEOUS SOLUTION COMPRISING ETHANOL USING A COLUMN|
    WO2021193457A1|2020-03-23|2021-09-30|積水化学工業株式会社|Method for producing 1,3-butadiene and device for producing 1,3-butadiene|
    法律状态:
    2015-11-05| PLFP| Fee payment|Year of fee payment: 3 |
    2016-11-21| PLFP| Fee payment|Year of fee payment: 4 |
    2017-11-28| PLFP| Fee payment|Year of fee payment: 5 |
    2019-11-28| PLFP| Fee payment|Year of fee payment: 7 |
    2020-11-26| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1361831A|FR3014097B1|2013-11-29|2013-11-29|PROCESS FOR PRODUCING 1,3-BUTADIENE FROM A CHARGE COMPRISING ETHANOL|FR1361831A| FR3014097B1|2013-11-29|2013-11-29|PROCESS FOR PRODUCING 1,3-BUTADIENE FROM A CHARGE COMPRISING ETHANOL|
    PL14805885T| PL3074367T3|2013-11-29|2014-11-28|Process for producing 1,3-butadiene from a feedstock comprising ethanol|
    PCT/EP2014/076002| WO2015079040A1|2013-11-29|2014-11-28|Process for producing 1,3-butadiene from a feedstock comprising ethanol|
    EP14805885.2A| EP3074367B1|2013-11-29|2014-11-28|Process for producing 1,3-butadiene from a feedstock comprising ethanol|
    CN201480065247.XA| CN105980338B|2013-11-29|2014-11-28|By the method for the raw material production 1,3-butadiene comprising ethyl alcohol|
    BR112016011953-3A| BR112016011953B1|2013-11-29|2014-11-28|PRODUCTION PROCESS OF 1,3-BUTADIENE FROM A LOAD UNDERSTANDING ETHANOL|
    US15/039,881| US9776933B2|2013-11-29|2014-11-28|Process for producing 1,3-butadiene from a feedstock comprising ethanol|
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