EP3411348A1 - Procédé de préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydative - Google Patents

Procédé de préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydative

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Publication number
EP3411348A1
EP3411348A1 EP17702600.2A EP17702600A EP3411348A1 EP 3411348 A1 EP3411348 A1 EP 3411348A1 EP 17702600 A EP17702600 A EP 17702600A EP 3411348 A1 EP3411348 A1 EP 3411348A1
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EP
European Patent Office
Prior art keywords
stream
gas stream
butenes
butadiene
hydrocarbons
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP17702600.2A
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German (de)
English (en)
Inventor
Jan Pablo JOSCH
Ragavendra Prasad Balegedde Ramachandran
Ulrike Wenning
Hendrik Reyneke
Anton Wellenhofer
Christel TOEGEL
Heinz Boelt
Christine TOEGEL
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BASF SE
Linde GmbH
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BASF SE
Linde GmbH
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Application filed by BASF SE, Linde GmbH filed Critical BASF SE
Publication of EP3411348A1 publication Critical patent/EP3411348A1/fr
Withdrawn legal-status Critical Current

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    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • C07C11/00Aliphatic unsaturated hydrocarbons
    • C07C11/12Alkadienes
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    • C07C11/1671, 3-Butadiene
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    • C07C7/00Purification; Separation; Use of additives
    • C07C7/11Purification; Separation; Use of additives by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/10Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
    • B01J2523/13Potassium
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/40Constitutive chemical elements of heterogeneous catalysts of Group IV (IVA or IVB) of the Periodic Table
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    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/50Constitutive chemical elements of heterogeneous catalysts of Group V (VA or VB) of the Periodic Table
    • B01J2523/54Bismuth
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    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
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    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/80Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
    • B01J2523/84Metals of the iron group
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    • B01J2523/80Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
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    • C07C2523/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85Chromium, molybdenum or tungsten
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    • C07C2523/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85Chromium, molybdenum or tungsten
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    • C07C2523/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85Chromium, molybdenum or tungsten
    • C07C2523/88Molybdenum
    • C07C2523/881Molybdenum and iron

Definitions

  • the invention relates to a process for the preparation of 1, 3-butadiene from n-butenes by oxidative dehydrogenation (ODH).
  • Butadiene is an important basic chemical and is used for example for the production of synthetic rubbers (butadiene homopolymers, styrene-butadiene rubber or nitrile rubber) or for the production of thermoplastic terpolymers (acrylonitrile-butadiene-styrene copolymers).
  • Butadiene is further converted to sulfolane, chloroprene and 1, 4-hexamethylenediamine (over 1, 4-dichlorobutene and adiponitrile).
  • dimerization of butadiene vinylcyclohexene can also be produced, which can be dehydrogenated to styrene.
  • Butadiene can be prepared by thermal cracking (steam cracking) of saturated hydrocarbons, usually starting from naphtha as the raw material. Steam cracking of naphtha produces a hydrocarbon mixture of methane, ethane, ethene, acetylene, propane, propene, propyne, allenes, butanes, butenes, butadiene, butynes, methylalls, Cs and higher hydrocarbons.
  • Butadiene can also be obtained by oxidative dehydrogenation of n-butenes (1-butene and / or 2-butene).
  • ODH oxidative dehydrogenation
  • any n-butenes containing mixture can be used.
  • a fraction containing n-butenes (1-butene and / or 2-butene) as a main component and obtained from the C 4 fraction of a naphtha cracker by separating butadiene and isobutene can be used.
  • gas mixtures which comprise 1-butene, cis-2-butene, trans-2-butene or mixtures thereof and which have been obtained by dimerization of ethylene can also be used as the starting gas.
  • n-butenes containing gas mixtures can be used as the starting gas, which were obtained by catalytic fluid catalytic cracking (FCC).
  • FCC catalytic fluid catalytic cracking
  • Hydrocarbons comprising butadiene and n-butenes in an absorbent to obtain an absorbent stream laden with C 4 hydrocarbons and the gas stream d2, and Db) subsequent desorption of the C 4 hydrocarbons from the loaded absorbent stream in a desorption column, wherein a C 4 - Product gas flow d1 is obtained.
  • US 2012 / 0130137A1 describes a process for the oxidative dehydrogenation of butenes to butadiene using catalysts containing oxides of molybdenum, bismuth and, as a rule, other metals.
  • Paragraph [0122] also refers to the problem of by-products.
  • phthalic anhydride, anthraquinone and fluorenone are mentioned, which are typically present in concentrations of 0.001 to 0.10 vol .-% in the product gas.
  • a cooling liquid quench tower
  • cooling liquids are called water or aqueous alkali solutions.
  • the product discharge gas of the oxidative dehydrogenation is first adjusted to a temperature between 300 and 221 ° C and then further cooled to a temperature between 99 and 21 ° C.
  • paragraphs [0066] ff. It is described that for adjusting the temperature between 300 and 221 ° C preferably heat exchangers are used, but also a part of the high boilers from the product gas could fail in these heat exchangers.
  • JP201 1 -001341 A therefore, an occasional washing out of deposits from the heat exchangers with organic or aqueous solvents is described.
  • the solvent for example, aromatic hydrocarbons such as toluene or xylene or an alkaline aqueous solvent such as the aqueous solution of sodium hydroxide are described.
  • JP 201 1 -001341A describes a structure with two heat exchangers arranged in parallel, each of which is operated or purged alternately (so-called A / B mode of operation).
  • a separation of isobutene or its reaction product methacrolein, of acetaldehyde or acrolein is not mentioned.
  • JP 201 1 -132218 limits the iso-butene content in the feed since it is known that isobutene forms oxy genates. The separation of the oxygenates is not described.
  • JP 2012-240963 describes a process for butadiene production in which the gas stream containing C 4 -hydrocarbons is brought into contact with an absorbent b in an absorption stage b 'in order to absorb the C 4 components.
  • JP 2010-090083 limits the amount of aldehydes and, in Table 1, also discloses the formation of methacrolein, but makes no proposals for its separation;
  • Iso-butene is present in almost all C 4 hydrocarbon streams that can be used for the ODH process.
  • C 4 hydrocarbon streams from FC crackers contain iso-butene in amounts of up to 15% by volume.
  • the isoButene entering the ODH reactor is converted into methacrolein by about 50%, depending on the catalyst used and the reaction conditions. This accumulates in the recycle stream of the absorption / desorption part of the C 4 -hydrocarbon separation and can cause side reactions such as oligomerizations and polymerizations, deposits on the column internals and in particular on evaporators and condensers as well as a deterioration of the separation performance.
  • Cycle water contained secondary components formed, inter alia, by coking or polymerization and divorced in the steam generator and in the underlying lines.
  • the object of the invention is to provide an improved process for the preparation of butadiene by oxidative dehydrogenation of n-butenes and subsequent workup of the ⁇ -hydrocarbons and by-products containing product gas stream, which remedies the disadvantages described above.
  • the object is achieved by a process for the preparation of butadiene from n-butenes with the following steps:
  • the water vapor condensate is separated from the absorbent in a phase separator and evaporated in a steam generator and re-provided as stripping gas in the desorption column, characterized in that the steam condensate is subjected to a pretreatment before evaporation in a steam generator in a further process step ,
  • This pretreatment of the aqueous condensate stream counteracts solid formation in the steam generator.
  • the separation of the secondary components by stripping with nitrogen, preferably at a temperature in the range of 20 to 80 ° C and a pressure of 0.1 to 15 bar. The obtained at the top of the low boiler separation column containing the minor components
  • Gas flow can be utilized thermally.
  • the concentration of the low-boiling secondary components that is, the minor components with lower boiling point than water, after carrying out the separation step according to the invention from 0.1 to 1000 ppm, preferably 10 to 100 ppm.
  • the content of the minor components acrylic acid, methacrylic acid and 3-propanal total is generally 0.1 to 500 ppm, preferably 1 to 100 ppm.
  • steps E) and F) are carried out:
  • an organic solvent is used in the cooling stage Ca.
  • These generally have a much higher solubility for the high-boiling by-products, which can lead to deposits and blockages in the downstream of the ODH reactor, as water or alkaline aqueous solutions.
  • Preferred organic solvents used as coolants are aromatic hydrocarbons, for example toluene, o-xylene, m-xylene, p-xylene, diethylbenzenes, triethylbenzenes, diisopropylbenzenes, triisopropylbenzenes and mesitylene or mixtures thereof. Particularly preferred is mesitylene.
  • the stage Ca) is carried out in several stages in stages Ca1) to Can), preferably in two stages in two stages Ca1) and Ca2). In this case, it is particularly preferred that at least part of the solvent, after passing through the second stage Ca2), be supplied as cooling agent to the first stage Ca1).
  • the stage Cb) generally comprises at least one compression stage Cba) and at least one cooling stage Cbb). At least one cooling stage Cbb) in which the gas compressed in the compression stage Cba) is brought into contact with a cooling agent is preferred. More preferably, the cooling agent of the cooling step Cbb) contains the same organic solvent used in step Ca) as a cooling agent. In a particularly preferred variant, at least part of this cooling agent is fed after passing through the at least one cooling stage Cbb) as cooling agent of the stage Ca).
  • the stage Cb) comprises a plurality of compression stages Cba1) to Cban) and cooling stages Cbb1) to Cbbn), for example four compression stages Cba1) to Cba4) and four cooling stages Cbb1) to Cbb4).
  • step D) comprises the steps Da1), Da2) and Db): Da1) absorption of the C4 hydrocarbons comprising butadiene and n-butenes in a high-boiling absorbent to obtain a C4 hydrocarbon-laden absorbent stream and the gas stream d2,
  • the high-boiling absorbent used in step Da) is an aromatic hydrocarbon solvent, more preferably it is the aromatic hydrocarbon solvent used in step Ca), in particular mesitylene. Diethylbenzenes, trietylbenzenes, diisopropylbenzenes and triisopropylbenzenes can also be used.
  • the gas stream d2 contained in step Da) is recycled to at least 30%, preferably at least 40%, in step B). This can be useful if only a small purge of electricity has to be removed from the gas stream d2.
  • the feed gas stream used is n-butenes (1-butene and / or cis- / trans-2-butene) and isobutene-containing gas mixtures.
  • n-butenes (1-butene and / or cis- / trans-2-butene) and isobutene-containing gas mixtures.
  • Such a gas mixture can be obtained, for example, by non-oxidative dehydrogenation of n-butane.
  • n-butenes (1-butene and cis- / trans-2-butene)
  • gas mixtures which comprise 1-butene, cis-2-butene, trans-2-butene or mixtures thereof and which have been obtained by dimerization of ethylene can also be used as the input gas stream.
  • n-butenes containing gas mixtures can be used, which were obtained by catalytic fluid cracking (FCC).
  • the starting gas mixture containing n-butenes is obtained by non-oxidative dehydrogenation of n-butane.
  • a non-oxidative catalytic dehydrogenation with the oxidative dehydrogenation of the n-butenes formed, a high yield of butadiene, based on n-butane used, can be obtained.
  • a gas mixture is obtained which, in addition to butadiene 1-butene, 2-butene and unreacted n-butane, contains minor constituents.
  • Common secondary constituents are hydrogen, water vapor, nitrogen, CO and CO2, methane, ethane, ethene, propane and propene.
  • the composition of the gas mixture leaving the first hydrogenation zone can vary greatly depending on the mode of operation of the dehydrogenation.
  • the product gas mixture has a comparatively high content of water vapor and carbon oxides.
  • the product gas mixture of the non-oxidative dehydrogenation has a comparatively high content of hydrogen.
  • step B the n-butenes-containing feed gas stream and an oxygen-containing gas are fed into at least one dehydrogenation zone (the ODH reactor A) and the butenes contained in the gas mixture are oxidatively oxidized to butadiene in the presence of an oxydehydrogenation catalyst.
  • an oxygen-containing gas containing more than 10% by volume, preferably more than 15% by volume and more preferably more than 20% by volume of molecular oxygen.
  • air is used as the oxygen-containing gas.
  • the upper limit of the content of molecular oxygen in the oxygen-containing gas is then generally 50% by volume or less, preferably 30% by volume or less, and more preferably 25% by volume or less.
  • any inert gases may be contained in the molecular oxygen-containing gas. Possible inert gases include nitrogen, argon, neon, helium, CO, CO2 and water.
  • the amount of inert gases in the oxygen-containing gas for nitrogen is generally 90% by volume or less, preferably 85% by volume or less and even more preferably 80% by volume or less. ger. In the case of components other than nitrogen in the oxygen-containing gas, it is generally 10% by volume or less, preferably 1% by volume or less.
  • Catalysts suitable for oxydehydrogenation are generally based on a Mo-Bi-O-containing multimetal oxide system, which generally additionally contains iron.
  • the catalyst system contains other additional components, such as potassium, cesium, magnesium, zirconium, chromium, nickel, cobalt, cadmium, tin, lead, germanium, lanthanum, manganese, tungsten, phosphorus, cerium, aluminum or silicon.
  • Iron-containing ferrites have also been proposed as catalysts.
  • the multimetal oxide contains cobalt and / or nickel. In a further preferred embodiment, the multimetal oxide contains chromium. In a further preferred embodiment, the multimetal oxide contains manganese.
  • Mo-Bi-Fe-O-containing multimetal oxides are Mo-Bi-Fe-Cr-O or Mo-Bi-Fe-Zr-O-containing multimetal oxides. Preferred systems are described, for example, in US 4,547,615 (Moi2BiFeo, iNi 8 ZrCr 3 Ko, 20x and Moi2BiFeo, iNi 8 AICr 3 Ko, 20x), US 4,424,141
  • Particularly preferred catalytically active, molybdenum and at least one further metal-containing multimetal oxides have the general formula (Ia):
  • X 2 Li, Na, K, Cs and / or Rb,
  • y a number determined on the assumption of charge neutrality by the valence and frequency of the elements other than oxygen in (1a).
  • Preference is given to catalysts whose catalytically active oxide composition of the two metals Co and Ni has only Co (d 0).
  • a gas mixture which has a molar oxygen: n-butenes ratio of at least 0.5.
  • the starting material gas can be mixed with oxygen or an oxygen-containing gas and optionally additional inert gas, methane or steam.
  • the resulting oxygen-containing gas mixture is then fed to the oxydehydrogenation.
  • the reaction temperature of the oxydehydrogenation is generally controlled by a heat exchange medium located around the reaction tubes.
  • liquid heat exchange agents come z.
  • metals such as sodium, mercury and alloys of various metals into consideration.
  • ionic liquids or heat transfer oils are used.
  • the temperature of the heat exchange medium is between 220 to 490 ° C and preferably between 300 to 450 ° C and more preferably between 350 and 420 ° C.
  • the temperature in certain sections of the interior of the reactor during the reaction may be higher than that of the heat exchange medium, and a so-called hotspot is formed.
  • the location and height of the hotspot is determined by the reaction conditions, but it may also be regulated by the dilution ratio of the catalyst layer or the flow rate of mixed gas.
  • the difference between hotspot temperature and the temperature of the heat exchange medium is generally between 1 to 150 ° C, preferably between 10 to 100 ° C and more preferably between 20 to 80 ° C.
  • the temperature at the end of the catalyst bed is generally between 0 to 100 ° C, preferably between 0.1 to 50 ° C, more preferably between 1 to 25 ° C above the temperature of the heat exchange medium.
  • the oxydehydrogenation can be carried out in all fixed-bed reactors known from the prior art, such as, for example, in the hearth furnace, in the fixed-bed tubular reactor or tube bundle reactor or in the plate heat exchanger reactor.
  • a tube bundle reactor is preferred.
  • the oxidative dehydrogenation is carried out in fixed bed tubular reactors or fixed bed bundle bundle reactors.
  • the reaction tubes are (as well as the other elements of the Tube bundle reactor) usually made of steel.
  • the wall thickness of the reaction tubes is typically 1 to 3 mm. Their inner diameter is usually (uniformly) at 10 to 50 mm or 15 to 40 mm, often 20 to 30 mm.
  • the number of reaction tubes accommodated in the tube bundle reactor is generally at least 1000, or 3000, or 5000, preferably at least 10,000. Frequently, the number of reaction tubes accommodated in the tube bundle reactor is 15,000 to 30,000 or 40,000 or 50 000.
  • the length of the reaction tubes normally extends to a few meters, typical is a reaction tube length in the range of 1 to 8 m, often 2 to 7 m, often 2.5 to 6 m.
  • the catalyst layer which is set up in the ODH reactor A, can consist of a single layer or of 2 or more layers. These layers may be pure catalyst or diluted with a material that does not react with the source gas or components of the product gas of the reaction. Furthermore, the catalyst layers may consist of solid material and / or supported shell catalysts.
  • the product gas stream 2 leaving the oxidative dehydrogenation contains, in addition to butadiene, generally unreacted 1-butene and 2-butene, oxygen and water vapor.
  • it furthermore generally contains carbon monoxide, carbon dioxide, inert gases (mainly nitrogen), low-boiling hydrocarbons such as methane, ethane, ethene, propane and propene, butane and isobutane, optionally hydrogen and optionally oxygen-containing hydrocarbons, so-called oxygenates.
  • Oxygenates may be, for example, formaldehyde, furan, acetic acid, maleic anhydride, formic acid, methacrolein, methacrylic acid, crotonaldehyde, crotonic acid, propionic acid, acrylic acid, methyl vinyl ketone, styrene, benzaldehyde, benzoic acid, phthalic anhydride, fluorenone, anthraquinone and butyraldehyde.
  • the product gas stream 2 at the reactor exit is characterized by a temperature near the temperature at the end of the catalyst bed.
  • the product gas stream is then brought to a temperature of from 150 to 400.degree. C., preferably from 160 to 300.degree. C., particularly preferably from 170 to 250.degree. It is possible to isolate the line through which the product gas stream flows to maintain the temperature in the desired range, or to use a heat exchanger. This heat exchanger system is arbitrary as long as the temperature of the product gas can be maintained at the desired level with this system.
  • heat exchangers there may be mentioned spiral heat exchangers, plate heat exchangers, double tube heat exchangers, multi-tube heat exchangers, boiler spiral heat exchangers, shell-shell heat exchangers, liquid-liquid contact heat exchangers, air heat exchangers, direct-contact heat exchangers and finned tube heat exchangers.
  • the heat exchanger system should preferably have two or more heat exchangers.
  • the two or more intended heat exchangers may be arranged in parallel.
  • the product gas is supplied to one or more, but not all, heat exchangers, which are replaced after a certain period of operation of other heat exchangers. In this method, the cooling can be continued, a portion of the heat of reaction recovered and in parallel, the deposited in one of the heat exchangers high-boiling by-products can be removed.
  • a solvent can be used as long as it is capable of dissolving the high-boiling by-products.
  • aromatic hydrocarbon solvents such as toluene, xylenes, diethylbenzenes, trietylbenzenes, diisopropylbenzenes and triisopropylbenzenes.
  • mesitylene is particularly preferred.
  • aqueous solvents These can be made both acidic and alkaline, such as an aqueous solution of sodium hydroxide.
  • Cooling is by contacting with a coolant.
  • This stage is also referred to below as quench.
  • This quench can consist of only one stage or of several stages (for example B, C in FIG. 1).
  • the product gas stream 2 is thus brought into direct contact with the organic cooling medium 3b and 9b and thereby cooled.
  • Suitable cooling media are aqueous coolants or organic solvents, preferably aromatic hydrocarbons, more preferably toluene, o-xylene, m-xylene, p-xylene or mesitylene, or mixtures thereof.
  • stage Ca comprises two cooling stages Ca1) and Ca2), in which the product gas stream 2 is brought into contact with the organic solvent.
  • the product gas depending on the presence and temperature level of a heat exchanger before the quench B, a temperature of 100 to 440 ° C.
  • the product gas is in the 1.
  • Quenching stage B brought into contact with the cooling medium of organic solvent.
  • the cooling medium can be introduced through a nozzle in order to achieve the most efficient possible mixing with the product gas.
  • internals such as further nozzles, which pass through the product gas and the cooling medium together, can be introduced into the quenching stage.
  • the coolant inlet into the quench is designed to minimize clogging due to deposits in the area of the coolant inlet.
  • the product gas 2 in the first quenching stage B is cooled to 5 to 180.degree. C., preferably to 30 to 130.degree. C. and even more preferably to 60 to 110.degree.
  • the temperature of the coolant medium 3b at the inlet may generally be 25 to 200 ° C, preferably 40 to 120 ° C, particularly preferably 50 to 90 ° C.
  • the pressure in the first quenching stage B is not particularly limited, but is generally 0.01 to 4 bar (g), preferably 0.1 to 2 bar (g) and more preferably 0.2 to 1 bar (g).
  • the quenching stage B is designed as a cooling tower.
  • the cooling medium 3b used in the cooling tower is often used in a circulating manner.
  • the recycle flow of the cooling medium in liters per hour, based on the mass flow of butadiene in grams per hour, can generally 0.0001 to 5 l / g, preferably 0.001 to 1 l / g and more preferably 0.002 to 0.2 l / g be.
  • the temperature of the cooling medium 3 in the bottom can generally be 27 to 210 ° C, preferably 45 to 130 ° C, particularly preferably 55 to 95 ° C. Since the loading of the cooling medium 4 with secondary components increases over time, a part of the loaded cooling medium can be withdrawn from the circulation as Purgestrom 3a and the circulating amount can be kept constant by adding unladen cooling medium 6. The ratio of effluent amount and added amount depends on the vapor load of the product gas and the product gas temperature at the end of the first quench stage.
  • the cooled and possibly depleted in secondary components product gas stream 4 can now be a second quenching C are supplied. In this he can now be brought into contact again with a cooling medium 9b.
  • the product gas is cooled to 5 to 100 ° C, preferably 15 to 85 ° C and even more preferably 30 to 70 ° C, until the gas outlet of the second quenching stage C is reached.
  • the coolant can be supplied in countercurrent to the product gas.
  • the pressure in the second quenching stage C is not particularly limited, but is generally 0.01 to 4 bar (g), preferably 0.1 to 2 bar (g) and more preferably 0.2 to 1 bar (g).
  • the second quenching stage is preferably designed as a cooling tower.
  • the cooling medium 9b used in the cooling tower is frequently used in a circulating manner. The circulation flow of the cooling medium 9b in liters per hour, based on the
  • the flow rate of butadiene in grams per hour may be from 0.0001 to 5 l / g, preferably from 0.001 to 1 l / g, and more preferably from 0.002 to 0.2 l / g.
  • the temperature of the cooling medium 9 in the bottom can generally be from 20 to 210 ° C., preferably from 35 to 120 ° C., particularly preferably from 45 to 85 ° C. Since the loading of the cooling medium 9 with secondary components increases over time, part of the loaded cooling medium can be withdrawn from the circulation as purge stream 9a, and the circulation amount can be kept constant by adding unladen cooling medium 10.
  • internals in the second quenching stage C may be present.
  • Such internals include, for example, bell, centrifugal and / or sieve trays, structured packing columns, e.g. B. Sheet metal packings with a specific surface area of 100 to 1000 m 2 / m 3 as Mellapak® 250 Y, and packed columns.
  • the solvent circulations of the two quench stages can be both separated from each other and also connected to each other.
  • the current 9a can be supplied to the current 3b or replace it.
  • the desired temperature of the circulating streams can be adjusted by means of suitable heat exchangers.
  • the cooling stage Ca) is carried out in two stages, wherein the solvent of the second stage Ca2) loaded with secondary components is passed into the first stage Ca1).
  • the solvent taken from the second stage Ca2) contains less secondary components than the solvent removed from the first stage Ca1).
  • suitable structural measures such as the installation of a demister, can be taken.
  • high-boiling substances which are not separated from the product gas in the quench, can be removed from the product gas by further structural measures, such as further gas scrubbing.
  • the gas stream b from the cooling step Ca which is depleted in high-boiling secondary components, is cooled in step Cb) in at least one compression stage Cba) and preferably in at least one cooling stage Cbb) by contacting with an organic solvent as the cooling agent.
  • the product gas stream 5 from the solvent quench is compressed in at least one compression stage E and subsequently cooled further in the cooling apparatus F, with at least one condensate stream 14 being formed.
  • gas stream 12 containing butadiene, 1-butene, 2-butenes, oxygen, water vapor, optionally low-boiling hydrocarbons such as methane, ethane, ethene, propane and propene, butane and isobutane, optionally carbon oxides and optionally inert gases. Furthermore, this product gas stream may still contain traces of high-boiling components.
  • the compression and cooling of the gas stream 5 can be carried out in one or more stages (n-stage). Generally, a total pressure is compressed in the range of 1.0 to 4.0 bar (absolute) to a pressure in the range of 3.5 to 20 bar (absolute).
  • the condensate stream can therefore also comprise a plurality of streams in the case of multistage compression.
  • the condensate stream consists to a large extent of water and the solvent used in the quench. Both streams (aqueous and organic phase) may also contain minor components such as low boilers, C4 hydrocarbons, oxygenates and carbon oxides.
  • the condensed quench solvent can be cooled in a heat exchanger and recycled as a coolant into the apparatus F. Since the loading of this cooling medium 13b with secondary components increases over time, a portion of the loaded cooling medium can be withdrawn from the circulation (13a) and the circulation rate of the cooling medium can be kept constant by adding unladen solvent (15).
  • the solvent 15 added as a cooling medium may be an aqueous coolant or an organic solvent.
  • aromatic hydrocarbons particular preference is given to toluene, o-xylene, m-xylene, p-xylene, diethylbenzene, triethylbenzene, diisopropylpolybenzene, triisopropylbenzene, mesitylene or mixtures thereof.
  • mesylene is especially preferred.
  • the condensate stream 13a may be recycled to the recycle stream 3b and / or 9b of the quench. As a result, the C4 components absorbed in the condensate stream 13a can be brought back into the gas stream and thus the yield can be increased.
  • Suitable compressors are, for example, turbo, rotary piston and reciprocating compressors.
  • the compressors can be driven, for example, with an electric motor, an expander or a gas or steam turbine.
  • the inlet pressure into the first compressor stage is 0.5 to 3 bar absolute, preferably 1 to 2 bar absolute.
  • Typical compression ratios (outlet pressure: inlet pressure) per compressor stage are between 1, 5 and 3.0, depending on the design.
  • the cooling of the compressed gas takes place in flushed with coolant heat exchangers or organic quench, which can be performed, for example, as a tube bundle, spiral or plate heat exchanger.
  • Suitable coolants may be aqueous or the above-mentioned organic solvents. In this case, cooling water or heat transfer oils or organic solvents are used as the coolant in the heat exchangers.
  • air cooling is preferably used using blowers.
  • step D) are non-condensable and low-boiling gas constituents, oxygen, low-boiling hydrocarbons (methane, ethane, ethene, propane, propene), carbon oxides and inert gases in an absorption column G as gas stream 16 from the process gas stream 12 by absorption of C4 hydrocarbons in a high-boiling absorbent (21 b and / or 26) and subsequent desorption of the C4 hydrocarbons separated.
  • step D) as shown in FIG. 1, comprises the steps Da1), Da2) and Db):
  • step Da2) removal of oxygen from the C4 hydrocarbons-laden absorbent stream from step Da1) by stripping with a non-condensable gas stream 18, wherein a C4 hydrocarbons laden absorbent stream 17 is obtained, and
  • a C4 product gas stream 27 is obtained, which consists essentially of C4 hydrocarbons.
  • the gas stream 12 is brought into contact with an absorbent and the C4 hydrocarbons are absorbed in the absorbent, whereby an adsorbent loaded with C4 hydrocarbons and an exhaust gas 16 containing the other gas constituents are obtained.
  • the C4 hydrocarbons are released from the high-boiling absorbent again.
  • the absorption stage can be carried out in any suitable absorption column known to the person skilled in the art. Absorption can be accomplished by simply passing the product gas stream through the absorbent. But it can also be done in columns or in rotational absorbers. In doing so, one can work in direct current, countercurrent or cross current. Preferably, the absorption is carried out in countercurrent. Suitable absorption columns are z. B. tray columns with bell, centrifugal and / or sieve tray, columns with structured packings, eg. B. Sheet metal packings with a specific surface area of 100 to 1000 m 2 / m 3 as Mellapak® 250 Y, and packed columns.
  • Inert absorbent used in the absorption stage are generally high-boiling non-polar solvents in which the C4-hydrocarbon mixture to be separated has a significantly higher solubility than the other gas constituents to be separated off.
  • Suitable absorbents are comparatively nonpolar organic solvents, for example aliphatic Cs to Cis alkanes, or aromatic hydrocarbons, such as the paraffin distillation from the paraffin distillation, toluene or ethers with bulky groups, or mixtures of these solvents, these being a polar solvent such as 1, 2 Dimethyl phthalate may be added.
  • Suitable absorbents are also esters of benzoic acid and phthalic acid with straight-chain C 1 to C 1 alkanols, as well as so-called heat transfer oils, such as biphenyl and diphenyl ether, their chlorinated derivatives and triaryl alkenes.
  • a suitable absorbent is a mixture of biphenyl and diphenyl ether, preferably in the azeotropic composition, for example, the commercially available Diphyl ®. Frequently, this solvent mixture contains dimethyl phthalate in an amount of 0.1 to 25 wt .-%.
  • the same solvent as in the cooling stage Ca) is used.
  • Preferred absorbents are solvents which have a solubility for organic peroxides of at least 1000 ppm (mg active oxygen / kg solvent). Preference is given to aromatic hydrocarbons, particularly preferably toluene, o-xylene, p-xylene and mesitylene, or mixtures thereof. Diethylbenzene, triethylbenzene, diisopropylbenzene and triisopropylbenzene can also be used.
  • a stream 16 is withdrawn, which essentially oxygen, low-boiling hydrocarbons (methane, ethane, ethene, propane, propene), optionally C4 hydrocarbons (butane, butenes, butadiene), optionally inert gases, optionally carbon oxides and optionally still contains water vapor.
  • This stream can be partially fed to the ODH reactor.
  • the inlet flow of the ODH reactor can be adjusted to the desired C4 hydrocarbon content.
  • the stripping out of the oxygen in step Db) can be carried out in any suitable column known to the person skilled in the art.
  • the stripping can be carried out by simply passing non-condensable gases, preferably not or only weakly in the absorption tion medium flow 21 b and / or 26 absorbable gases such as methane, carried by the loaded absorption solution. With stripped C4 hydrocarbons are washed in the upper part of the column G back into the absorption solution by the gas stream is passed back into this absorption column. This can be done both by a piping of the stripping column and a direct assembly of the stripping column below the absorber column. Since the pressure in the stripping column part and the absorption column part is the same, this direct coupling can take place.
  • Suitable Stippkolonnen are z. B. tray columns with bell, centrifugal and / or sieve tray, columns with structured packings, eg. B. Sheet metal packings with a specific surface area of 100 to 1000 m 2 / m 3 as Mellapak® 250 Y, and Gunnen. But there are also trickle and spray towers and rotary columns, dishwashers, cross-flow scrubbers and rotary scrubbers into consideration. Suitable gases are for example nitrogen or methane.
  • the stream 17 may optionally be cooled or heated and enters the desorption column as stream 19.
  • the entry point is generally 0 to 10 theoretical plates, preferably 2 to 8, more preferably 3 to 5 theoretical plates below the top of the column.
  • the absorbent regenerated in the desorption stage is removed in a mixture with the condensed stripping water vapor as stream 20 of the desorption column H at the bottom of the column.
  • This biphasic mixture can be cooled in a heat exchanger and is fed as stream 21 to a phase separator I designed as a decanter. There, the stream 21 in an aqueous stream 21 a and an organic Absorptionsstoffstorm 21 b is separated. The regenerated absorbent stream 21 b is fed back to the absorption column G.
  • Low boilers in the process gas stream such as ethane or propane and high-boiling components such as benzaldehyde, maleic anhydride and phthalic anhydride can accumulate in the absorption medium circulation stream.
  • a purge stream 25 can be deducted.
  • the resulting condensate stream 21 a from the dehydrogenation plant is completely or partially supplied to a sewage treatment plant.
  • the treatment plant which may include a chemical and / or a biological treatment stage, the condensate stream is cleaned and disposed of according to local conditions throughout the wastewater stream.
  • a volume flow of suitable raw water equivalent to the discharged condensate stream is fed into the dehydrogenating plant after any necessary treatment (such as, for example, demineralization) and then evaporated in the steam generator.
  • the aqueous stream 21a for the treatment of water prior to its evaporation is fed according to the invention only into a low boiler separation column L.
  • Suitable columns are, for example, tray columns with bells, centrifugal and / or sieve trays, columns with structured packings, for example sheet metal packings with a specific surface area of 100 to 1000 m 2 / m 3 such as Mellapak® 250 Y, and packed columns.
  • aqueous stream 21 a contained low boilers, in particular acrolein, as stream 21 d separated.
  • the water stream 21 c thus obtained, which is depleted of low-boiling components, is evaporated in the steam generator M, the stripping steam thus generated is fed as stream 23 into the desorption column.
  • a fresh water stream 24 can also be fed into the steam generator 23. It is also possible for only part of the stream 21 c to be vaporized and for the other part to be taken off as stream 22 and fed, for example, to the wastewater treatment.
  • the C4 product gas stream 27 consisting essentially of n-butane, n-butenes and butadiene generally contains from 20 to 80% by volume of butadiene, from 0 to 80% by volume of n-butane, from 0 to 10% by volume 1 - Butene and 0 to 50% by volume of 2-butenes, the total amount being 100% by volume. Furthermore, small amounts of iso-butane may be included.
  • a portion of the condensed, mainly C4 hydrocarbons containing overhead discharge of the desorption column H is recycled as stream 30 in the top of the column to increase the separation efficiency of the column.
  • Desorption step H can be carried out in any suitable desorption column known to the person skilled in the art.
  • the desorption can be effected by lowering the pressure and / or heating the desorption stage.
  • Suitable desorption columns are, for example, tray columns with bells, centrifugal and / or sieve trays, columns with structured packings, eg sheet metal packings with a specific surface area of 100 to 1000 m 2 / m 3 such as Mellapak® 250 Y, and packed columns.
  • the desorption column H can, as shown in FIG. 1, be taken off a methacrolein-containing side draw-off stream 31 in order to prevent the accumulation of methacrolein in the absorbent circulation stream.
  • the side draw stream 31 can be both liquid and gaseous, preferably it is gaseous.
  • the desorption column preferably has from 5 to 30, particularly preferably from 10 to 20, theoretical plates.
  • the side draw stream 31 is preferably removed in the lower third of the desorption column.
  • the liquid side draw stream 31 generally contains from 0.1 to 2% by weight of methacrolein. In addition, it contains 5 to 15 wt .-% water, 0 to 3 wt .-% C 4 -hydrocarbons and 70 to 90 wt .-% of the absorbent.
  • the gaseous side draw stream 31 generally contains from 1 to 10% by weight of methacrolein. In addition, it contains 30 to 60 wt .-% water, 0 to 6 wt .-% C 4 hydrocarbons and 30 to 60 wt .-% of the absorbent.
  • the gaseous C4 hydrocarbon-containing stream 29 is returned to the compressor.
  • the liquid C4 product stream 28 leaving the condenser is then separated in step E) by extractive distillation with a butadiene-selective solvent into a butadiene and the material stream 35 containing the selective solvent and a stream 36 comprising butanes and n-butenes.
  • the stream 28 may be previously washed in a liquid-liquid washing with polyalcohols such as ethylene glycol and glycerol or even methanol and thus furan be partially separated.
  • the stream 28 may be previously freed of other minor components, such as aldehydes, in a gas-liquid wash with water.
  • the extractive distillation may, for example, as described in "petroleum and coal - natural gas - petrochemistry", Volume 34 (8), pages 343 to 346 or “Ullmann's Encyclopedia of Industrial Chemistry", Volume 9, 4th edition 1975, pages 1 to 18, be performed.
  • the C 4 product gas stream with an extractant preferably an N-methylpyrrolidone
  • the extraction zone is generally carried out in the form of a wash column, which soils, packing or
  • Packs contains as internals. This generally has 30 to 70 theoretical plates, so that a sufficiently good release effect is achieved.
  • the wash column has a backwash zone in the column head. This backwash zone serves to recover the extractant contained in the gas phase by means of a liquid hydrocarbon recirculation, for which purpose the overhead fraction is condensed beforehand.
  • the mass ratio extractant to C 4 product gas stream in the feed of the extraction zone is generally from 10: 1 to 20: 1.
  • the extractive distillation is preferably carried out at a bottom temperature in the range from 100 to 250 ° C., in particular at a temperature in the range from 110 to 210 ° C., a top temperature in the range from 10 to 100 ° C., in particular in the range from 20 to 70 ° C. ° C and a pressure in the range of 1 to 15 bar, in particular operated in the range of 3 to 8 bar.
  • the extractive distillation column preferably has from 5 to 70 theoretical plates.
  • Suitable extractants are butyrolactone, nitriles such as acetonitrile, propionitrile, methoxypropionitrile, ketones such as acetone, furfural, N-alkyl-substituted lower aliphatic acid amides such as dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, N-formylmorpholine, N-alkyl-substituted cyclic acid amides (lactams) such as N Alkylpyrrolidones, especially N-methylpyrrolidone (NMP).
  • NMP N-methylpyrrolidone
  • alkyl-substituted lower aliphatic acid amides or N-alkyl substituted cyclic acid amides are used.
  • Particularly advantageous are dimethylformamide, acetonitrile, furfural and in particular NMP.
  • mixtures of these extractants with one another for example NMP and acetonitrile
  • mixtures of these extractants with cosolvents and / or tert-butyl ethers for example methyl tert-butyl ether, ethyl tert-butyl ether, propyl tert-butyl ether, n- or iso-butyl tert-butyl ether
  • NMP preferably in aqueous solution, preferably with 0 to 20 wt .-% water, particularly preferably with 7 to 10 wt .-% water, in particular with 8.3 wt .-% water.
  • the overhead product stream 36 of the extractive distillation column J contains essentially butane and butenes and small amounts of butadiene and is taken off in gaseous or liquid form.
  • the stream consisting essentially of n-butane and 2-butene contains up to 100% by volume of n-butane, 0 to 50% by volume of 2-butene and 0 to 3% by volume of further constituents, such as isobutane, isobutene , Propane, propene and Cs + hydrocarbons.
  • n-butane and 2-butene and optionally methane stream 36 can be supplied in whole or in part or not in the C 4 feed of the ODH reactor. Since the butene isomers of this recycle stream consist essentially of 2-butenes, and 2-butenes are generally more slowly dehydrogenated to butadiene than 1-butene, this recycle stream can be catalytically isomerized prior to being fed to the ODH reactor. Thereby, the isomer distribution can be adjusted according to the isomer distribution present in the thermodynamic equilibrium. Furthermore, the stream can also be fed to a further work-up to separate butanes and butenes from one another and to return the butenes in whole or in part to the oxydehydrogenation. The stream can also go into maleic anhydride production.
  • the material stream 35 containing the butadiene and the selective solvent is fractionated by distillation into a stream 37 consisting essentially of the selective solvent and a stream 38 containing butadiene.
  • the material stream 35 obtained at the bottom of the extractive distillation column J generally contains the extractant, water, butadiene and in small proportions butenes and butane and is fed to a distillation column K. In this can be obtained overhead or as a side take butadiene.
  • a distillation column K In this can be obtained overhead or as a side take butadiene.
  • an extractant and optionally water-containing stream 37 is obtained, wherein the composition of the extractant and water-containing stream corresponds to the composition as it is added to the extraction.
  • the extractant and water-containing stream 37 is preferably returned to the extractive distillation.
  • the extraction solution thus withdrawn is transferred to a desorption zone, wherein the butadiene is desorbed again from the extraction solution and washed back.
  • the desorption zone can be embodied, for example, in the form of a wash column which has 2 to 30, preferably 5 to 20 theoretical stages and optionally a backwashing zone with, for example, 4 theoretical stages. This backwash zone is used to recover the extractant contained in the gas phase by means of a liquid hydrocarbon reflux, to which the top fraction is condensed beforehand.
  • internals packings, trays or packing are provided.
  • the Des- Tilling is preferably carried out at a bottom temperature in the range of 100 to 300 ° C, in particular in the range of 150 to 200 ° C and a top temperature in the range of 0 to 70 ° C, in particular in the range of 10 to 50 ° C.
  • the pressure in the distillation column is preferably in the range of 1 to 10 bar. In general, in the desorption zone relative to the extraction zone, a reduced pressure and / or an elevated temperature prevail.
  • the product stream 38 obtained at the top of the column generally contains 90 to 100% by volume of butadiene, 0 to 10% by volume of 2-butene and 0 to 10% by volume of n-butane and isobutane.
  • a further distillation according to the prior art can be carried out.
  • the claimed technical solution was developed by thermodynamic equilibrium step simulations and tested in a pilot plant.
  • the salt bath reactor, the organic quench, the compressor unit and the C4 absorption / desorption were mapped.
  • the scale of the pilot plant was chosen so that an up-scaling to the large plant was possible. Accordingly representative, for example, the internals of the columns were selected and the returns were closed.
  • the pilot plant was able to produce between 500 and 1500 grams of butadiene per hour.
  • BUTAN% by weight 0.00 0.01 0.00 0.00 0.00 0.01 l BUTANE 0.00 0.00 0.00 0.00 0.00 0.00 0.00
  • Example 1 As in Example 1 a nitrogen was introduced as stripping gas in the column L. However, the amount of nitrogen was reduced to 40%. Depletion of the low-boiling secondary components was thus also still possible. The proportion of separated secondary components, however, decreases.
  • Table 3 The composition of the streams is shown in Table 3 below.
  • BUTAN% by weight 0.00 0.01 0.00 0.00 0.00 0.01 l BUTANE 0.00 0.00 0.00 0.00 0.00 0.00 0.00
  • BUTAN% by weight 0.00 0.01 0.00 0.00 0.00 0.01 l BUTANE 0.00 0.00 0.00 0.00 0.00 0.00 0.00

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Abstract

La présente invention concerne un procédé de préparation de butadiène à partir de n-butènes, comprenant les étapes consistant : A) à produire un flux de gaz de départ a contenant des n-butènes ; B) à introduire le flux de gaz de départ a contenant des n-butènes, et un gaz contenant de l'oxygène, dans au moins une zone de déshydrogénation oxydative, et à effectuer une déshydrogénation oxydative des n-butènes en butadiène pour obtenir un flux de gaz b contenant du butadiène, des n-butènes n'ayant pas réagi, de la vapeur d'eau, de l'oxygène, des hydrocarbures à bas point d'ébullition, des constituants secondaires à point d'ébullition élevé, éventuellement des oxydes de carbone et éventuellement des gaz inertes ; Ca) à refroidir le flux de gaz obtenu b en le mettant en contact avec un agent de refroidissement et à effectuer la condensation d'au moins une partie des constituants secondaires à point d'ébullition élevé ; Cb) à comprimer, dans au moins un étage de compression, le flux de gaz b restant, pour obtenir au moins un flux de condensat aqueux c1 et un flux de gaz c2 contenant du butadiène, des n-butènes, de la vapeur d'eau, de l'oxygène, des hydrocarbures à bas point d'ébullition, éventuellement des oxydes de carbone et éventuellement des gaz inertes ; Da) à séparer, du flux de gaz c2, les constituants gazeux non condensables et à bas point d'ébullition, contenant de l'oxygène, des hydrocarbures à bas point d'ébullition, éventuellement des oxydes de carbone et éventuellement des gaz inertes, sous la forme d'un flux de gaz d2, par absorption, dans un absorbant, des hydrocarbures C4 contenant du butadiène et des n-butènes, pour obtenir un flux d'absorbant chargé en hydrocarbures C4 et le flux de gaz d2, puis Db) à effectuer la désorption, dans une colonne de désorption, des hydrocarbures C4 présents dans le flux d'absorbant chargé, pour obtenir un flux de gaz C4 d1, De) à séparer, de l'absorbant, le condensat de vapeur d'eau dans un séparateur de phases, et à le vaporiser dans un générateur de vapeur, puis à le réintroduire dans la colonne de désorption en tant que gaz d'épuration. L'invention est caractérisée en ce qu'avant la vaporisation, dans un générateur de vapeur, le condensat de vapeur d'eau est soumis à un prétraitement, dans une autre étape du procédé.
EP17702600.2A 2016-02-04 2017-01-30 Procédé de préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydative Withdrawn EP3411348A1 (fr)

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WO2021044919A1 (fr) * 2019-09-02 2021-03-11 Jsr株式会社 Procédé de production de 1,3-butadiène

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PH12128A (en) 1973-09-04 1978-11-07 Standard Oil Co Chromium-containing catalysts useful for oxidation reactions
US3932551A (en) 1973-10-12 1976-01-13 The Standard Oil Company Process for the preparation of diolefins from olefins
US3911039A (en) 1974-01-23 1975-10-07 Standard Oil Co Ohio Process for the preparation of botadiene from N-butene
GB1523772A (en) 1974-07-22 1978-09-06 Standard Oil Co Oxidation catalysts
US4162234A (en) 1974-07-22 1979-07-24 The Standard Oil Company Oxidation catalysts
US4397771A (en) 1975-01-13 1983-08-09 The Standard Oil Co. Oxidation catalysts
IN145044B (fr) 1975-01-13 1978-08-19 Standard Oil Co Ohio
JPS56140931A (en) 1980-04-04 1981-11-04 Nippon Zeon Co Ltd Preparation of conjugated diolefin
JPS56150023A (en) 1980-04-22 1981-11-20 Nippon Zeon Co Ltd Preparation of conjugated diolefin
US4424141A (en) 1981-01-05 1984-01-03 The Standard Oil Co. Process for producing an oxide complex catalyst containing molybdenum and one of bismuth and tellurium
US4547615A (en) 1983-06-16 1985-10-15 Nippon Zeon Co. Ltd. Process for producing conjugated diolefins
JP2010090083A (ja) 2008-10-10 2010-04-22 Mitsubishi Chemicals Corp 共役ジエンの製造方法
JP5621304B2 (ja) 2009-05-21 2014-11-12 三菱化学株式会社 共役ジエンの製造方法
JP5648319B2 (ja) * 2009-05-29 2015-01-07 三菱化学株式会社 共役ジエンの製造方法
JP2011132218A (ja) 2009-11-27 2011-07-07 Mitsubishi Chemicals Corp 共役ジエンの製造方法
JP2012240963A (ja) 2011-05-19 2012-12-10 Mitsubishi Chemicals Corp 共役ジエンの製造方法
CN103539300B (zh) * 2012-07-13 2016-12-21 中国石油化工股份有限公司 一种处理丁烯氧化脱氢制丁二烯废水的方法
EP2945923B1 (fr) 2013-01-15 2017-03-15 Basf Se Procédé de déshydrogénation oxydative de n-butènes en butadiène
WO2014111409A1 (fr) 2013-01-15 2014-07-24 Basf Se Procédé de préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydative
WO2016023892A1 (fr) 2014-08-12 2016-02-18 Basf Se Procédé de production de 1,3-butadiène à partir de n-butène par déshydrogénation oxydative
WO2016046009A1 (fr) 2014-09-26 2016-03-31 Basf Se Procédé de préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydative
JP6625634B2 (ja) 2014-11-03 2019-12-25 ビーエーエスエフ ソシエタス・ヨーロピアBasf Se 酸化的脱水素化によりn−ブテン類から1,3−ブタジエンを製造するための方法
EP3218334B1 (fr) 2014-11-14 2018-09-26 Basf Se Procédé de fabrication de 1,3 butadiène par la déshydratation de n-butènes par préparation d'un flux de matière contenant du butane et de 2-butène
KR101785146B1 (ko) * 2015-03-24 2017-10-12 주식회사 엘지화학 공액디엔의 제조방법 및 제조장치
WO2016151074A1 (fr) 2015-03-26 2016-09-29 Basf Se Procédé de préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydative
US20180072638A1 (en) 2015-03-26 2018-03-15 Basf Se Process for preparing 1,3-butadiene from n-butenes by oxidative dehydrogenation
WO2016151033A1 (fr) 2015-03-26 2016-09-29 Basf Se Procédé de préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydative
KR20170133404A (ko) 2015-03-26 2017-12-05 바스프 에스이 산화성 탈수소화에 의한 n-부텐으로부터의 1,3-부타디엔의 제조
WO2016150940A1 (fr) 2015-03-26 2016-09-29 Basf Se Procédé de préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydative

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US20190039971A1 (en) 2019-02-07
US10647639B2 (en) 2020-05-12

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