WO2018095840A1 - Procédé pour la préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydante comprenant une séparation de furanne lors du traitement - Google Patents

Procédé pour la préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydante comprenant une séparation de furanne lors du traitement Download PDF

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Publication number
WO2018095840A1
WO2018095840A1 PCT/EP2017/079718 EP2017079718W WO2018095840A1 WO 2018095840 A1 WO2018095840 A1 WO 2018095840A1 EP 2017079718 W EP2017079718 W EP 2017079718W WO 2018095840 A1 WO2018095840 A1 WO 2018095840A1
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stream
butadiene
butenes
water
hydrocarbons
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PCT/EP2017/079718
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German (de)
English (en)
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Ragavendra Prasad Balegedde Ramachandran
Stephan DEUBLEIN
Jan Pablo Josch
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
    • B01D3/343—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances the substance being a gas
    • B01D3/346—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances the substance being a gas the gas being used for removing vapours, e.g. transport gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
    • B01D3/40—Extractive distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
    • C07C7/08—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds by extractive distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/10—Purification; Separation; Use of additives by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/11—Purification; Separation; Use of additives by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids

Definitions

  • the invention relates to a process for the preparation of 1, 3-butadiene from n-butenes by oxidative dehydrogenation (ODH) comprising a furan separation in the workup of the product gas mixture of the dehydrogenation.
  • ODH oxidative dehydrogenation
  • 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 added to sulfolane, chloroprene and 1, 4-
  • 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 starting gas.
  • n-butenes containing gas mixtures can be used as the starting gas, which were obtained by catalytic fluid catalytic cracking (FCC).
  • Processes for the oxidative dehydrogenation of butenes to butadiene are known in principle. Such processes often include the following steps: A) providing a feed gas stream a containing n-butenes;
  • Cooling the product gas stream b by contacting it with a coolant and condensing at least part of the high-boiling secondary components;
  • At least one aqueous condensate stream c1 and a gas stream c2 containing butadiene, n-butenes, water vapor, oxygen, low-boiling hydrocarbons, optionally carbon oxides and optionally inert gases is obtained;
  • non-condensable and low-boiling gas components comprising oxygen, low-boiling hydrocarbons, optionally carbon oxides and optionally inert gases as gas stream d2 from the gas stream c2 by absorption of the C 4 hydrocarbons comprising butadiene and n-butenes in an absorbent, one with C 4 - Hydrocarbons-laden absorbent stream and a gas stream d2 are obtained, and subsequent desorption of the C 4 hydrocarbons from the loaded absorbent stream in a desorption column, wherein a C 4 product gas stream 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 indicates the problem of by-products.
  • phthalic anhydride, anthraquinone and fluorenone are mentioned, which would typically be present at 0.001 to 0.10 vol% in the product gas.
  • cooling liquids are called water or aqueous alkali solutions.
  • the problem of blockages in the quench by high boilers from the product gas or by polymerization polymerization is expressly mentioned.
  • JP 201 1 -132218 limits the iso-butene content in the feed since it is known that isobutene forms oxy genates. However, the separation of oxygenates formed from isobutene or n-butenes is not described.
  • Furan is formed in oxidative dehydrogenations of n-butenes to butadiene. It can be formed during the dehydrogenation of n-butenes to butadiene in the presence of oxygen from n-butenes or 1,3-butadiene. Furan can accumulate in the extractive distillation and lead to fouling in high concentrations.
  • 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 C4 hydrocarbon and byproducts containing product gas stream, in which the accumulation of furan is avoided in the workup.
  • Cooling the product gas stream b in one or more cooling stages by bringing into contact with a circulating coolant, wherein water vapor and at least a portion of the high-boiling secondary components condense and an aqueous condensate d a is obtained;
  • a stream essentially consisting of butadiene f2 is taken from an extractive distillation column as a side draw stream.
  • this is further purified in a further distillation column (butadiene purifying distillation column).
  • the stream f2 may contain as secondary components water, the extractant and furan.
  • the butadiene content of stream f2 is generally> 98% by weight.
  • the further distillation column (butadiene pure distillation column) is a butadiene having a purity of generally> 99 wt .-% removed as a product stream, generally as a top draw stream.
  • water, extraction agent and furan are enriched with respect to the feed stream f2.
  • the bottom draw stream of the further distillation column is recycled, generally as side feed stream, into the extractive distillation column.
  • the extractive distillation column is preferably at a bottom temperature in the range of 100 to 250 ° C, in particular at a temperature in the range of 1 10 to 210 ° C, a head temperature in the range of 10 to 100 ° C, in particular in the range of 20 to 70 ° 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.
  • the further distillation column (butadiene pure distillation column) generally has 10 to 50, preferably 15 to 30 theoretical plates and is generally at a bottom temperature in the range of 30 to 80 ° C, preferably in the range of 40 to 70 ° C and a head temperature in the range of generally 30 to 50 ° C, preferably operated from 30 to 40 ° C.
  • the pressure in the distillation column is generally in the range from 1 to 6 bar, preferably from 3 to 5 bar.
  • step G the stream gl is obtained as Soabzugs- ström a distillation column and the water-containing extractant as the bottom draw stream of this distillation column.
  • the stream f3 recovered at the bottom of the extractive distillation column generally contains the extractant, water, butadiene and small amounts of furan and is fed to a distillation column (extractant recovery column).
  • the stream gl containing butadiene, water and extractant, which is highly enriched in furan is recovered as a side draw stream.
  • the furan content of the side draw stream is generally> 5% by weight and may be> 10% by weight.
  • an extractant and water-containing stream is added, which is added to the extractive distillation column.
  • the gaseous top draw stream has approximately the composition of the bottom draw stream of the extractive distillation column and is recycled to the bottom of the extractive distillation column.
  • the extractant recovery column is operated at a lower pressure than the extractive distillation column. Then, the gaseous top draw stream is compressed with a compressor before it is fed to the bottom of the extractive distillation column.
  • This distillation column (extractant recovery column) generally has 5 to 40, preferably 10 to 25 theoretical plates and is generally at a bottom temperature in the range of 60 to 230 ° C, preferably from 120 to 190 ° C and a head temperature in Range of generally 60 to 160 ° C, preferably operated from 80 to 130 ° C.
  • the pressure in the distillation column is generally in the range of 2 to 10 bar, preferably from 2.5 to 6 bar.
  • the process according to the invention preferably has the additional step H):
  • step H) in a wash column from the stream g the extractant is separated by washing with water and from the top draw stream of Wash column of the furan and water-containing stream h1 condensed, leaving the butadiene-containing stream h2 remains.
  • the stream g1 is fed into a washing column in which the extractant is backwashed with a stream of water.
  • the mass ratio of stream gl to the washing water stream is generally 10: 1 to 0.1: 1.
  • a stream of butadiene, water and furan is obtained.
  • a stream of water and extractant is obtained, which is fed to the extractant recovery column.
  • the scrubbing column Q is preferably at a bottom temperature in the range of 100 to 180 ° C, in particular from 120 to 150 ° C, a top temperature in the range of 20 to 180 ° C, in particular from 100 to 150 ° C and a pressure in the range of 2 operated to 10 bar, in particular from 2.5 to 6 bar.
  • the scrubbing column Q generally has 2 to 20, preferably 3 to 7 theoretical plates.
  • the top draw stream of the wash column generally contains from 10 to 50% by weight of butadiene, from 30 to 80% by weight of water and from 1 to 20% by weight of furan.
  • water and furan are condensed out of this stream, resulting in a liquid stream h1, which consists essentially of water and furan, and a gaseous butadiene stream h2.
  • the gaseous butadiene stream h2 may still contain furan, higher boiling point (e.g., pentane), and water.
  • the liquid stream generally contains 10 to 25% by weight of furan and 75 to 90% by weight of water.
  • the gaseous butadiene stream h2 generally contains 90 to 98% by weight of butadiene, 0.5 to 5% by weight of furan, 0.5 to 5% by weight of high boilers and 0.1 to 2
  • the butadiene-containing stream h2 is recycled in step G). In a further embodiment of the process, the butadiene-containing stream h2 is recycled to step Cb).
  • an organic solvent is preferably used.
  • Organic solvents generally have a much higher solvent power 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. Especially preferred is mesitylene.
  • the following embodiments are preferred or particularly preferred variants of the method according to the invention.
  • 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).
  • aqueous condensates c1 b can be produced on each of the compression stages Cba1) to Cban) and of each of the cooling stages Cbb1) to Cbbn).
  • the aqueous phase c1a obtained in the cooling step Ca) is preferably used in the optional washing step E).
  • step D) comprises the steps Da1), Da2) and Db):
  • the high-boiling absorbent used in step Da) is an aromatic hydrocarbon solvent, particularly 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.
  • FIGS. 1 and 2 Embodiments of the method according to the invention are illustrated in FIGS. 1 and 2 and will be described in detail below.
  • Feed gas stream 1 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 catalytic 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 unconverted n-butane, contains secondary 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 feed gas stream containing n-butenes 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 dehydrogenated to form 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. set.
  • 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 more preferably 80% by volume or less. 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, i Ni 8 ZrCr 3 Ko, 20x and Moi2BiFeo, i Ni 8 AlCr 3 Ko, 20x), US 4,424,141
  • X Si, Mn and / or Al
  • 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).
  • 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 particularly preferred 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 a hearth furnace, in a fixed-bed or shell-and-tube reactor or in a 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 consist of pure catalyst or be diluted with a material that does not react with the reactant gas or components from 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, acrolein, 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 It can be kept at the desired level.
  • heat exchangers there can 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. Because, while the temperature of the product gas is adjusted to the desired temperature, a portion of the high-boiling by-products contained in the product gas may precipitate, therefore, 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, for example, toluene, xylenes, diethylbenzenes, trietylbenzenes, diisopropylbenzenes and triisopropylbenzenes. Particularly preferred is mesitylene.
  • aqueous solvents These can be made both acidic and alkaline, such as an aqueous solution of sodium hydroxide. Subsequently, a large part of the high-boiling secondary components and the water is separated from the product gas stream 2 by cooling and compression.
  • 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. Diethylbenzene, triethylbenzene, diisopropylbenzene and triisopropylbenzene can also be used.
  • 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, for example, additional nozzles, can be introduced into the quenching stage and pass through the product gas and the cooling medium together.
  • 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 Ca1) is cooled to 5 to 180 ° C, preferably to 30 to 130 ° C and even more preferably to 60 to 1 10 ° C.
  • the temperature of the coolant medium 3b at the inlet may generally be 25 to 200.degree. C., preferably 40 to 120.degree. C., particularly preferably 50 to 90.degree.
  • 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.
  • an aqueous phase can be obtained. This can be separated in a phase separator and the washing stage E) fed.
  • 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 purge stream 3a and the circulating amount can be kept constant by adding uncharged cooling medium 6.
  • the ratio of effluent amount and feed quantity depends on the vapor loading of the product gas and the product gas temperature at the end of the first quenching stage.
  • the stream 3a can be separated into an aqueous phase 3c and an organic phase 3d.
  • the cooled and possibly depleted in secondary components product gas stream 4 can now be a second quenching Ca2) are supplied. In this he can now be brought into contact again with an organic 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, to the gas exit of the second quench stage Ca2).
  • the coolant can be supplied in countercurrent to the product gas.
  • the temperature of the coolant medium 9b at the coolant inlet may be 5 to 100 ° C, preferably 15 to 85 ° C, particularly preferably 30 to 70 ° C.
  • 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 mass flow of butadiene in grams per hour, can generally be from 0.0001 to 5 l / g, preferably from 0.001 to 1 l / g and particularly preferably from 0.002 to 0.2 l / g amount.
  • 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 circuit as purge stream 9a, and the circulating amount can be kept constant by adding unladen cooling medium 10.
  • internals in the second quenching stage Ca2 may be present.
  • Such internals include, for example, bell, 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 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 removed 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, for example, 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). After each compression stage is followed by a cooling step, in which the gas stream is cooled to a temperature in the range of 15 to 60 ° C.
  • 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 13a of the loaded cooling medium can be withdrawn from circulation and the circulating amount of the cooling medium can be kept constant by adding uncharged 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 heat exchangers flushed with coolant or organic quench stages, which can be designed, 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.
  • the butadiene, n-butenes, oxygen, low-boiling hydrocarbons (methane, ethane, ethene, propane, propene, n-butane, isobutane), optionally water vapor, optionally carbon oxides and optionally inert gases and optionally traces of secondary components containing gas stream 12 is as Output current fed to the further treatment.
  • a step D) are non-condensable and low-boiling gas components comprising 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 the C4 hydrocarbons in a high-boiling absorbent (21 b and / or 26) and subsequent desorption of the C4 hydrocarbons separated.
  • oxygen 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 the C4 hydrocarbons in a high-boiling absorbent (21 b and / or 26) and subsequent desorption of the C4 hydrocarbons separated.
  • step D) comprises steps Da1), Da2) and Db): Da1) absorption of the C4 hydrocarbons comprising butadiene and n-butenes in a high-boiling absorbent (21b and / or 26), wherein an absorbent stream charged with C4 hydrocarbons and the gas stream 16 are obtained,
  • 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. It can be used in cocurrent, countercurrent or cross flow. 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. Rice and spray towers, graphite block absorbers, surface absorbers such as thick-film and thin-layer absorbers, as well as rotary columns, rags, cross-flow scrubbers and rotary scrubbers are also suitable.
  • an absorption column in the lower region of the butadiene, n-butenes and the low-boiling and non-condensable gas components containing gas stream 12 is supplied.
  • the high-boiling absorbent (21 b and / or 26) is abandoned.
  • 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 Ce 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-dimethylphthalate 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).
  • aromatic hydrocarbons more 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 is 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. This makes it possible, for example, to adjust the inlet flow of the ODH reactor to the desired C4 hydrocarbon content and oxygen 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 absorbent stream 21 b and / or 26 absorbable gases such as methane, through 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 piping the stripping column and by 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.
  • the stream 17 may optionally be cooled or heated and enters the desorber column as stream 19.
  • the entry point is generally 0 to 10 theoretical plates, preferably 2 to 8 theoretical plates, more preferably 3 to 5 theoretical plates below the top of the column.
  • the absorbent regenerated in the desorption stage is withdrawn as stream 20 together with the condensed water from the desorption column H.
  • This biphasic mixture can be cooled in a heat exchanger and separated as stream 21 in a decanter I into an aqueous stream 21 a and an absorbent stream 21 b.
  • a non-condensable gas 21 e preferably nitrogen, of minor components such as acetaldehyde, acrolein and methacrolein, as Electricity 21 d be discharged, can be exempted.
  • the purified water stream 21 c is evaporated in an evaporator K and fed as stripping steam stream 23 back into the desorption column H.
  • fresh water can be fed as stream 24 into the evaporator K.
  • a portion of the stream 21 c can be removed as stream 22 and fed to the wastewater treatment.
  • 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 cycle stream.
  • a purge stream 25 can be deducted.
  • 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 headspace of the desorption column is recycled as stream 30 in the column head to increase the separation efficiency of the column.
  • the desorption step 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.
  • the desorption stage can be heated by supplying a hot medium - such as water vapor - or by self-vapor, for example, by partial evaporation of the absorbent in the bottom of the desorber.
  • Suitable desorption columns are, for example, tray columns with bell, centrifugal and / or sieve bottom, 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.
  • the desorption column H is withdrawn from a side draw stream 31 containing methacrolein to prevent the accumulation of methacrolein in the absorbent recycle 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 taken off in the lower third of the desorption column.
  • the liquid side draw stream 31 generally contains 0.1 to 2
  • Wt .-% methacrolein 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 .-% C4 hydrocarbons and 30 to 60 wt .-% of the absorbent.
  • the liquid C4 product stream 28 leaving the condenser is then vaporized and preferably introduced into the scrubber L as stream 28a.
  • the gaseous C4 product stream 28a is scrubbed with an aqueous stream 38 which may contain at least portions of the aqueous condensate streams 3a and 8, respectively, from the quench stages B) and C) which are supplied as stream 38c.
  • the C4 product stream 28a may contain at least portions of the aqueous condensate streams 3a and 8, respectively, from the quench stages B) and C) which are supplied as stream 38c.
  • Water-soluble secondary components such as aldehydes washed out and discharged with the wash water stream 35 from the scrubber L.
  • the scrubber L may be carried out as any suitable column known to those skilled in the art. Suitable 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. However, there are also trickle and spray towers, graphite block absorbers, surface absorbers such as thick film and thin-layer absorbers and rotary columns, dishwashers, cross-flow scrubbers and rotary scrubbers into consideration.
  • the wash water stream 35 loaded with the secondary components is regenerated in the regeneration unit M by heating and stripping with a stripping gas, preferably nitrogen or steam, which is supplied as stripping gas stream 37.
  • the regenerated stream 38 is returned to the scrubber L.
  • the regeneration in the unit M can be carried out in any suitable column known to the person skilled in the art. Suitable columns are z. B. tray columns with bell, centrifugal and / or sieve plates, 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.
  • the stripping gas stream 36 leaving the regeneration unit M contains the secondary components received in the scrubber L.
  • a stream 38a is withdrawn as a purge stream and replaced by stream 38c and optionally a fresh water stream 38b.
  • the resulting in the quenching stages B and C aqueous condensate is fed into the water cycle of the (optional) washing step L.
  • aqueous quenching Condensates contain carboxylic acids, for example acetic acid, maleic acid and phthalic acid, which are formed as by-products in the oxidative dehydrogenation of n-butenes in step B) and are contained in the product gas stream b.
  • carboxylic acids chemically react with the minor components contained in the C4 product gas stream 28a, such as acrolein or methacrolein, and thus increase the washing efficiency in the washing stage L.
  • the stream 39 is separated by extractive distillation in step F) with an aqueous extractant which is selective for butadiene into a stream comprising butane and 2-butenes, a stream comprising butadiene 45 and a stream 50 containing the extractant and butadiene.
  • 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 contains trays, fillers or packings as internals. This generally has 30 to 70 theoretical plates, so that a sufficiently good release effect is achieved.
  • the washing column in the column head preferably has a backwashing zone. 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.
  • 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 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 of NMP and acetonitrile
  • mixtures of these extractants with cosolvents and / or tert-butyl ether for example methyl tert-butyl ether, ethyl tert-butyl ether, propyl tert .-Butyl ether, n- or iso-butyl tert-butyl ether
  • Particularly suitable is hydrous NMP, preferably with up to 20% by weight of water, more preferably with 7 to 10% by weight of water, in particular with 8.3% by weight of water, based on the mixture of water and extractant.
  • the overhead product stream 43 of the extractive distillation column N contains essentially butane and butenes and small amounts of butadiene and is withdrawn in gaseous or liquid form.
  • the stream 43 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.
  • One part is returned to the column as reflux 44.
  • the main uncondensed gases such as carbon dioxide and nitrogen-containing stream 41, which is separated from the top take-off stream 40, can be supplied to the exhaust gas treatment.
  • water can be discharged as stream 42 from the process.
  • the current 43 consisting essentially of n-butane and 2-butene can be supplied in whole or in part or else not in the C 4 feed of the ODH reactor.
  • this recycle stream can be catalytically isomerized prior to being fed to the ODH reactor.
  • the isomer distribution can be adjusted in accordance with the isomer distribution present in the thermodynamic equilibrium.
  • 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 extractive distillation column N is withdrawn from a side draw stream 45 consisting essentially of butadiene. Preferably, this is further purified in the distillation column O.
  • the stream 45 may contain as minor components water, the extractant and furan.
  • the butadiene content of stream 45 is generally> 98% by weight.
  • As top draw stream 47 or 49 of the distillation column O a butadiene with a purity of generally> 99 wt .-% is obtained as a value stream. A portion of this stream is recycled as stream 48 to the top of the column.
  • water, extractant and furan are enriched to stream 45.
  • the stream 46 is recycled as side feed stream into the extractive distillation column N.
  • the distillation column O generally has 1 to 20, preferably 3 to 10 theoretical plates and is generally at a bottom temperature in the range of 30 to 100 ° C, preferably from 50 to 80 ° C and a head temperature in the range of generally 10 to 70 ° C, preferably operated from 30 to 50 ° C.
  • the pressure in the distillation column is generally in the range of 1 to 8 bar, preferably from 2 to 6 bar.
  • the stream 50 obtained at the bottom of the extractive distillation column N generally contains the extractant, water, butadiene and small amounts of furan and is fed to a distillation column P.
  • a side draw stream 52 containing butadiene, water and extractant is recovered, which is highly enriched in furan.
  • the furan content of the side draw stream 52 is generally> 5% by weight and may be> 10% by weight.
  • an extractant and water-containing stream 59 which is added to the extractive distillation column N.
  • the gaseous top draw stream 51 has approximately the composition of the bottom draw stream 59 and is recycled to the bottom of the extractive distillation column N.
  • the distillation column N generally has 80 to 190, preferably 130 to 170 theoretical plates and is generally at a bottom temperature in the range of 40 to 150 ° C, preferably from 50 to 120 ° C and a head temperature in the range of generally 10 to 80 ° C, preferably operated from 30 to 60 ° C.
  • the pressure in the distillation column is generally in the range from 1 to 10 bar, preferably from 3 to 6 bar.
  • the distillation column P generally has 5 to 40, preferably 10 to 25 theoretical plates and is generally at a bottom temperature in the range of 60 to 230 ° C, preferably from 120 to 190 ° C and a head temperature in the range of generally 60 to 160 ° C, preferably operated from 80 to 130 ° C.
  • the pressure in the distillation column is generally in the range of 2 to 10 bar, preferably from 2.5 to 6 bar.
  • the side draw stream 52 generally contains 5 to 50 weight percent butadiene, 20 to 60
  • the stream 52 is separated into a material stream 57 containing furan and water and a stream 56 containing butadiene.
  • Stream 52 is fed to a wash column Q in which the extractant is backwashed with a stream of water 54.
  • the mass ratio of stream 52 to wash water stream 54 is generally 10: 1 to 0.1: 1.
  • a stream 55 of butadiene, water and furan is obtained.
  • a stream 53 of water and extractant is obtained, which is fed into the distillation column P.
  • the scrubbing column Q is preferably at a bottom temperature in the range of 100 to 180 ° C, in particular from 120 to 150 ° C, a top temperature in the range of 20 to 180 ° C, in particular from 100 to 150 ° C and a pressure in the range of 2 up to 10 bar, in particular operated from 2.5 to 6 bar.
  • the scrubbing column Q generally has 2 to 20, preferably 3 to 7 theoretical plates.
  • the stream 55 generally contains 10 to 50% by weight of butadiene, 30 to 80% by weight of water and 1 to 20% by weight of furan.
  • water and furan are condensed out of the stream 55 resulting in a liquid stream 57 consisting essentially of water and furan and a gaseous butadiene stream 56 which may still contain furan, higher boiling point (pentane) and water.
  • the stream 57 generally contains 10 to 25% by weight of furan and 75 to 90% by weight of water.
  • the stream 56 generally contains 90 to 98% by weight of butadiene, 0.5 to 5% by weight of furan, 0.5 to 5% by weight of high boilers and 0.1 to 2% by weight of water.
  • the gaseous stream 56 has a lower pressure than in the bottom of the column P due to pressure losses.
  • the stream 56 must either be condensed and conveyed by means of a pump into the column P or compressed with a compressor R and conveyed as a gas stream into the column P. According to FIG. 2, it is conveyed as condensed stream 56a into the column P.
  • the butadiene stream 56 can be recycled to the distillation column P.
  • the Butadien- Ström 56 can also be returned to the compressor E.
  • the process illustrated in FIG. 1 was numerically simulated.
  • the simulation program used corresponds to the commercially available program Aspen Plus ® for process simulation.

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Abstract

Procédé pour la préparation de butadiène à partir de n-butènes présentant les étapes : A) préparation d'un flux gazeux initial a contenant des n-butènes a ; B) injection du flux gazeux initial a contenant des n-butènes et d'un gaz contenant de l'oxygène dans au moins une zone de déshydrogénation par oxydation et déshydrogénation par oxydation des n-butènes en butadiène, un flux gazeux produit b contenant du butadiène étant obtenu ; Ca) refroidissement du flux gazeux produit b dans une ou plusieurs étapes de refroidissement par mise en contact avec un agent de refroidissement guidé en circulation, un condensat aqueux da étant obtenu ; Cb) compression du flux gazeux produit b résiduel dans au moins une étape de compression et le cas échéant dans au moins une étape de refroidissement, un condensat aqueux c1b et un flux gazeux c2 contenant du butadiène étant obtenus ; Da) séparation des constituants gazeux non condensables et de bas point d'ébullition en tant que flux gazeux d2 à partir du flux gazeux c2 par absorption des hydrocarbures en C4 comprenant du butadiène et des n-butènes dans un agent d'absorption, un flux d'agent d'absorption chargé d'hydrocarbures en C4 étant obtenu et Db) désorption consécutive des hydrocarbures en C4 à partir du flux d'agent d'absorption chargé dans une colonne de désorption, un flux gazeux produit en C4 d1 étant obtenu ; E) lavage facultatif du flux gazeux produit en C4 d1 avec un flux aqueux, un flux gazeux produit en C4 e1 appauvri en composants secondaires étant obtenu, F) séparation du flux produit en C4 d1 ou e1 par distillation extractive avec un agent d'extraction aqueux sélectif pour le butadiène en un flux de substances f1 contenant du butane et des 2-butènes, en un flux de substances f2 contenant du butadiène et en un flux de substances f3 contenant de l'agent d'extraction aqueux et du butadiène ; G) séparation d'un flux de substances g1 enrichi en furanne, contenant du butadiène, de l'eau et de l'agent d'extraction à partir du flux de substances f3, l'agent d'extraction aqueux étant récupéré ; H) séparation d'un flux de substances h1 contenant du furanne et de l'eau à partir du flux de substances g1, un flux de substances h2 contenant du butadiène étant obtenu.
PCT/EP2017/079718 2016-11-22 2017-11-20 Procédé pour la préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydante comprenant une séparation de furanne lors du traitement WO2018095840A1 (fr)

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CN113277586A (zh) * 2021-05-13 2021-08-20 温彦博 一种煤气化装置放空蒸汽回收系统
CN114163320A (zh) * 2021-12-17 2022-03-11 福建南平龙晟香精香料有限公司 一种龙涎酮中间体制备方法及其装置

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