EP3022169A1 - Procédé de production de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydative - Google Patents

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

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Publication number
EP3022169A1
EP3022169A1 EP14739155.1A EP14739155A EP3022169A1 EP 3022169 A1 EP3022169 A1 EP 3022169A1 EP 14739155 A EP14739155 A EP 14739155A EP 3022169 A1 EP3022169 A1 EP 3022169A1
Authority
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.)
Withdrawn
Application number
EP14739155.1A
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German (de)
English (en)
Inventor
Christian Walsdorff
Philipp Gruene
Christine Schmitt
Ragavendra Prasad BALEGEDDE RAMACHANDRAN
Jan Pablo JOSCH
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP14739155.1A priority Critical patent/EP3022169A1/fr
Publication of EP3022169A1 publication Critical patent/EP3022169A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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).
  • 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 converted to sulfolane, chloroprene and 1, 4-hexamethylenediamine (over 1, 4-dichlorobutene and adiponitrile). By 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).
  • any n-butenes containing mixture can be used.
  • a fraction may be used which as
  • n-butenes (1-butene and / or 2-butene) and was obtained from the C 4 fraction of a naphtha cracker by separating butadiene and isobutene.
  • 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 obtained by catalytic fluid cracking (FCC) can be used as the starting gas.
  • EP 2 177 266 A2 describes a catalyst based on Bi / Mo / Fe oxides and an associated process for the oxidative dehydrogenation of butenes to butadiene. However, the problem of the formation or the avoidance of explosive gas mixtures is not mentioned.
  • KR 2013036467 A describes a process for the oxidative dehydrogenation of butene
  • Butadiene in particular while avoiding fouling in the downstream area.
  • No. 8,003,840 B2 also describes a catalyst based on Bi / Mo / Fe oxides and a process for the oxidative dehydrogenation of butenes to butadiene.
  • the problem of the formation or avoidance of explosive mixtures is, however, excluded.
  • a disadvantage of the methods of the prior art is thus the passage through a range of explosive gas mixtures in the workup of the oxygen-containing
  • Product gas mixture if the composition of the oxygen-containing, C 4 - hydrocarbons containing product gas mixture in the absorption of C 4 - hydrocarbons from one (not explosive) "fat" to a (not explosive) "fat" to a (not explosive) "fat" to a (not explosive) "fat" to a (not explosive) "fat" to a (not explosive) "fat" to a (not explosive) "fat" to a (not explosive) "fat" to a (not
  • the present invention overcomes the aforementioned drawbacks by feeding a separate, methane-containing gas stream into the process at one or more points so that a non-explosive, hydrocarbon-rich "product mixture is always used in the work-up of the oxygen-containing C 4 -hydrocarbon-containing product gas mixture.
  • the nitrogen used as diluent gas or contained in air is partially or completely replaced by methane.
  • oxygen-containing gas in at least one oxidative dehydrogenation zone and oxidative
  • Compression stage wherein 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; Da) separation of 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 C 4 - hydrocarbons comprising butadiene and n-butenes in an absorbent, one with C4 Hydrocarbons laden absorbent stream and the gas stream d2 are obtained, and
  • steps E) and F) are subsequently carried out:
  • the methane-containing gas stream is fed in step B). In a further preferred variant, the methane-containing gas stream is fed in step Da). The methane-containing gas stream may also be fed between steps B) and Da). It can also be several methane-containing gas streams
  • Hydrocarbon-rich gas mixture is present in order to avoid the formation of an explosive gas mixture during the absorption step safely.
  • a distance of at least 2 vol .-% oxygen is maintained to the explosive area.
  • the explosive region is specific for the components present in the mixture and can be taken from databases or through experiments with the mixture different compositions are determined. These experimental methods are known to the person skilled in the art.
  • sufficient methane is fed in that the methane content of the gas stream d2 separated off in step Da) is at least 15% by volume.
  • sufficient methane is fed in that the methane content of the gas stream d2 obtained in step Da) is at least 20% by volume.
  • the methane-containing gas stream d2 separated off in step Da) is at least partially recycled to step B).
  • the proportion of the recycled part in the total flow is based on the proportion of nitrogen, which is replaced by methane.
  • 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 more preferably 80% by volume or less.
  • components other than nitrogen in the oxygen-containing gas it is generally 10% by volume or less, preferably 1% by volume or less. In a further embodiment, it is preferable to replace as much nitrogen as possible with methane and to return the stream d2 as completely as possible. It is then particularly preferred to use as pure oxygen as the oxygen-containing gas.
  • methane is used instead of nitrogen as a diluent gas. It is preferred, then as little nitrogen as possible in the process
  • the nitrogen content of the gas stream d2 obtained in step Da) is then preferably at most 10% by volume.
  • a gas stream which is as oxygen-rich as possible is then fed in step B) of the process.
  • an oxygen-containing gas having an oxygen content of at least 90 vol .-% is fed. Particularly preferred is technically pure oxygen is fed with a content of at least 95% oxygen.
  • the COx content in the gas stream d2 can be reduced by means of a wash before the gas stream d2 is returned to stage B).
  • a wash is particularly preferred when all of the nitrogen is substituted by methane and most of the gas stream is d2
  • the laundry is done in amine-powered scrubbers to remove CO2.
  • the gas stream d2 contained in step Da) is recycled to at least 80%, preferably at least 90%, in step B). This can be useful if only a small purge of electricity has to be removed from the gas stream d2.
  • an aqueous coolant or an organic solvent is used.
  • an organic solvent is used in the cooling stage Ca. These generally have a much higher solubility for the high-boiling ones
  • Preferred organic solvents used as coolants are aromatic ones
  • 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, at least a part of the
  • the stage Cb) generally comprises at least one compression stage Cba) and at least one cooling stage Cbb).
  • the compressed in the compression stage Cba) gas is brought into contact with a cooling agent.
  • 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 a part of this cooling agent is after
  • 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 one
  • step Da) desorption of the C 4 hydrocarbons from the loaded absorbent stream to obtain a C 4 product gas stream d1 consisting essentially of C 4 hydrocarbons and comprising less than 100 ppm oxygen.
  • the high-boiling absorbent used in step Da) is an aromatic hydrocarbon solvent, more preferably that used in step Ca)
  • aromatic hydrocarbon solvents in particular mesitylene. It is also possible to use diethylbenzenes, trietylbenzenes, diisopropylbenzenes and triisopropylbenzenes. Embodiments of the process according to the invention are shown in FIGS. 1 and 2 and are described in detail below.
  • n-butenes (1-butene and / or cis- / trans-2-butene), but also containing butene gas mixtures can be used.
  • 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 may also be used as starting gas comprising pure 1-butene, cis-2-butene, trans-2-butene or mixtures thereof obtained by dimerization of ethylene.
  • the starting gas mixture containing n-butenes is obtained by non-oxidative dehydrogenation of n-butane.
  • 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 those in the
  • the methane content of the gas mixture reacted in step B) is generally at least 10% by volume, preferably at least 20% by volume, when a methane-containing gas stream is fed to step B). It is generally not more than 90% by volume.
  • a methane-containing gas stream can be fed in as methane fresh gas stream and / or methane-containing recycle stream d2 in step B).
  • 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 1 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).
  • n-butenes ratio preference is given to a gas mixture which has a molar oxygen: n-butenes ratio of at least 0.5. Preference is given to operating at an oxygen: n-butenes ratio of 0.55 to 10.
  • the starting material gas with oxygen or an oxygen-containing gas and optionally additional inert gas, methane or
  • the reaction temperature of the oxydehydrogenation is generally by a
  • Heat exchange agent which is located around the reaction tubes, controlled. As such liquid heat exchange agents come z. B. melting salts or
  • Salt mixtures such as potassium nitrate, potassium nitrite, sodium nitrite and / or sodium nitrate and melting of metals such as sodium, mercury and alloys of various metals into consideration. But ionic liquids or heat transfer oils are used.
  • 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 reaction
  • Heat exchange agent and it forms a so-called hotspot.
  • the location and height of the hot spot 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 become.
  • Heat exchange agent is generally between 1 -150 ° C, preferably between 10-100 ° C and more preferably between 20-80 ° C. The temperature at the end of the
  • Catalyst bed is generally between 0-100 ° C, preferably between 0.1 -50 ° C, more preferably between 1 -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 in fixed bed tubular reactors or
  • 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 extends in
  • 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 is not compatible with the
  • 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. As secondary components, it also 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
  • oxygenates may be, for example, formaldehyde, furan, acetic acid, maleic anhydride, formic acid, methacrolein, methacrylic acid, crotonaldehyde, crotonic acid, propionic acid, acrylic acid,
  • 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 to a
  • Product gas can be kept at the desired level.
  • Product gas can be kept at the desired level.
  • Heat exchanger can be spiral heat exchangers, plate heat exchangers,
  • Double tube heat exchangers Double tube heat exchangers, multi-tube heat exchangers, boiler spiral heat exchangers, shell and 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. In this case, if two or more intended heat exchangers are arranged in parallel, thus allowing distributed cooling of the recovered product gas in the heat exchangers, the amount of high-boiling by-products deposited in the heat exchangers decreases and so their service life can be extended.
  • 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.
  • 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. Examples are aromatic hydrocarbon solvents, such as. B.
  • Toluene xylenes, diethylbenzenes, triethylbenzenes, diisopropylbenzenes and triisopropylbenzenes. Particularly preferred is mesitylene. It is also possible to use 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 ones
  • Hydrocarbons particularly preferably toluene, o-xylene, m-xylene, p-xylene or mesitylene, or mixtures thereof. It is also possible to use diethylbenzene, trietylbenzene,
  • 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 has 2, depending on the presence and temperature level of a
  • Heat exchanger before quench B a temperature of 100-440 ° 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 so that clogging by deposits in the area of the
  • Coolant inlet is minimized.
  • the product gas 2 in the first quenching stage B is cooled to 5-180 ° C, preferably to 30-130 ° C and even more preferably to 60-1 10 ° C.
  • the temperature of the product gas 2 in the first quenching stage B is cooled to 5-180 ° C, preferably to 30-130 ° C and even more preferably to 60-1 10 ° C.
  • Coolant medium 3b at the inlet may generally be 25-200 ° C, preferably 40-120 ° C, most preferably 50-90 ° C.
  • the pressure in the first quenching step 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). If larger amounts of high-boiling by-products are present in the product gas, it can easily be used to polymerize high-boiling
  • 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 stream of the cooling medium in liters per hour, based on the mass flow of butadiene in grams per hour, can generally be 0.0001 -5 l / g, preferably 0.001-1 l / g and particularly preferably 0.002-0.2 l / g be.
  • the temperature of the cooling medium 3 in the bottom can generally be 27-210 ° C., preferably 45-130 ° C., particularly preferably 55-95 ° C. Since the loading of the cooling medium 4 with secondary components increases over time, a portion of the loaded cooling medium can be withdrawn from the circulation as Purgestrom 3a and the circulating amount to 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 15-85 ° C and even more preferably 30-70 ° C, to the gas outlet of the second quenching stage C.
  • the coolant can be supplied in countercurrent to the product gas.
  • the temperature of the coolant medium 9b at the coolant inlet may be 5-100 ° C, preferably 15-85 ° C, particularly preferably 30-70 ° C.
  • the pressure in the second quenching stage C is not particularly limited, but is generally 0.01 -4 bar (ü), preferably 0.1 -2 bar (g) and more preferably 0.2-1 bar (g).
  • the second quenching stage 7 is preferably designed as a cooling tower.
  • the cooling medium 9b used in the cooling tower is frequently used in a circulating manner.
  • the recycle stream of the cooling medium 9b in liters per hour, based on the mass flow of butadiene in grams per hour, can generally be 0.0001 -5 l / g, preferably 0.3001-1 l / g and more preferably 0.002-0.2 l / g.
  • the temperature of the cooling medium 9 in the bottom can generally be 20-210.degree. C., preferably 35-120.degree. C., particularly preferably 45-85.degree. Since the loading of the cooling medium 9 with
  • 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 m2 / m3 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).
  • Solvent 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 by further structural measures, such as
  • Secondary components is depleted, 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 a cooling agent.
  • the product gas stream 5 from the solvent quench is in at least one
  • Compression stage E compressed and subsequently cooled further in the cooling apparatus F, wherein at least one condensate stream 14 is formed. There remains a 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 can
  • Product gas stream still contains 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 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 13b which is added as a cooling medium, may be an aqueous
  • Hydrocarbons particularly preferred are toluene, o-xylene, m-xylene, p-xylene, diethylbenzene, triethylbenzene, diisopropylbenzene, triisopropylbenzene, mesitylene or mixtures thereof.
  • the condensate stream 13a may be recycled to the recycle stream 3b and / or 9b of the quench. As a result, the C 4 components absorbed in the condensate stream 13 a 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.
  • 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.
  • Cooling water or heat transfer oils are used.
  • air cooling is preferably used using blowers.
  • Complementary gas stream containing 12 is the output current of the other
  • methane can be additionally added to the gas stream 12 to ensure that in the column G always a not
  • step D 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 C 4 Hydrocarbons in a high-boiling absorbent (20b and / or 23) and subsequent desorption of C 4 hydrocarbons separated.
  • step D as shown in FIG. 1, comprises the steps Da1), Da2) and Db):
  • the gas stream 12 is contacted with an inert absorbent and the C4 hydrocarbons are absorbed in the inert absorbent to obtain an absorbent laden with C4 hydrocarbons and an exhaust gas 16 containing the remaining gas constituents.
  • the C4 hydrocarbons are released from the high-boiling absorbent again.
  • Absorption column is always a non-explosive, hydrocarbon-rich rich gas mixture.
  • the oxygen content of the gas mixture during the absorption stage G is in the range of 3 to 10% by volume.
  • Absorbent is generally in the range of 15 to 97% by volume.
  • the absorption step may be in any suitable manner known to those skilled in the art
  • Absorption column can be performed. 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 packaging with a specific
  • 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 non-polar organic solvents, for example aliphatic C 1 to C 6 alkanes, or aromatic hydrocarbons, such as 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 d-Cs-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 .-%.
  • 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 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.
  • low-boiling hydrocarbons methane, ethane, ethene, propane, propene
  • C4 hydrocarbons butane, butenes, butadiene
  • inert gases optionally carbon oxides and optionally still contains water vapor.
  • Material flow can be partially fed to the ODH reactor.
  • the inlet flow of the ODH reactor can be adjusted to the desired C4 hydrocarbon content.
  • a large part of the methane can be recycled via this recycling. Then the methane used is not completely burned but is at least partially reused.
  • the methane content of stream 16 is generally at least 15% by volume, preferably at least 20% by volume. In general, the methane content is at most 95% by volume.
  • the stream 16 is divided and fed as stream 16b into the reactor A.
  • the remaining partial flow 16a can be used thermally or materially, for example in a synthesis gas plant.
  • 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 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 Absorbing solution done. 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 achieved by a piping of the
  • stripping is carried out in step Db) with a methane-containing gas stream.
  • this gas stream (stripping gas) contains> 90% by volume of methane.
  • the laden with C4 hydrocarbons absorbent stream 17 can in a
  • Heat exchangers are heated and then passed as stream 19 in a desorption column H.
  • the desorption step Db) by relaxing and stripping the loaded absorbent by a steam flow 23rd
  • the absorbent 20 regenerated in the desorption stage can be cooled in a heat exchanger.
  • the cooled stream 21 contains water in addition to the absorbent, which is separated in the phase separator I.
  • Phthalic anhydride can accumulate in the absorbent cycle stream.
  • a purge stream 25 can be deducted. This can be used alone or combined with the streams 3a and / or 9a and / or 13a in a distillation column T (FIG. 2) according to the prior art in low boilers 36, regenerated absorbent 26 and / or regenerated cooling medium 10 and / or 15 (FIG and 2) and high boilers 37 are separated. Preferably, it will be fed directly to the streams 15 and / or 10 and / or 6 to backwash the C 4 hydrocarbons still dissolved in the streams 25 and / or 3a and / or 9a and / or 13a into the process gas stream.
  • electricity is 25 in the
  • Distillation column T is separated, the streams 36 and 37, for example, burned and thus be used energetically.
  • the streams 13a and / or 9a and / or 3a can also be purified without the stream 25 in a distillation column T and returned to the process.
  • the circulation amount of the absorbent stream 21 b can be kept constant by adding unladen solvent 26.
  • the absorbent stream 21 b can be returned to the absorption stage G. Since the loading of the water flow 21 a with secondary components increases over time, this can be partially evaporated and the circulation rate of the water flow by adding unladen water 24 are kept constant.
  • 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, 0 to 50% by volume of 2-butenes and 0 to 10% by volume of methane, 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 25 in the column head to increase the separation efficiency of the column.
  • the liquid (stream 30) or gaseous (stream 29) C4 product streams leaving the condenser are then removed by extractive distillation in step E) with a butadiene-selective solvent into a butadiene and the material flow 31 containing the selective solvent and a butane and n-butane. Buteneene containing stream 32 separated.
  • 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 C4 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
  • the wash column has a backwash zone in the column head.
  • 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.
  • Mass ratio of extractant to C4 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 , in particular 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 each other e.g. NMP and acetonitrile, mixtures of these extractants with cosolvents and / or tert-butyl ether, e.g. 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 of the extractive distillation column contains essentially butane and butenes and in small amounts of butadiene and is withdrawn 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.
  • the stream consisting essentially of n-butane and 2-butene and, if appropriate, methane can be supplied in whole or in part or else 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 dehydrogenated oxidatively slower 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 stream comprising butadiene and the selective solvent is fractionated by distillation into a stream consisting essentially of the selective solvent and a stream comprising butadiene.
  • the stream obtained at the bottom of the extractive distillation column generally contains the extractant, water, butadiene and, in minor proportions, butenes and butane and is fed to a distillation column. In this can be obtained overhead or as a side take butadiene.
  • an extractant At the bottom of the distillation column falls an extractant and
  • Extractant and water-containing material stream of the composition corresponds to how it is added to the extraction.
  • the extractant and water-containing stream is preferably returned to the extractive distillation.
  • the desorption zone can be designed, for example, in the form of a wash column which contains from 2 to 30, preferably from 5 to 20, theoretical stages and, if appropriate, a backwashing zone with, for example, 4
  • 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.
  • a liquid hydrocarbon reflux to which the top fraction is condensed beforehand.
  • internals packings trays or packing are provided.
  • the distillation 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
  • Head temperature in the range of 0 to 70 ° C, in particular carried out 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, a reduced pressure and / or elevated temperature prevails in the desorption zone relative to the extraction zone.
  • the product stream 34 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.
  • Comparative Example describes the normal operating state with 6 vol.% Oxygen at the end of the ODH reactor without the addition of methane.
  • the example describes the use of methane in the gas stream in reactor, quench, compressor and absorber column, which ensures that the gas composition is always at least 2 vol .-% of the explosive limit. Part of the methane can be recycled from the exhaust stream of the absorber column in the reactor. Due to the distance of 2 Vol .-% to the explosion limit can be technically realized that fluctuations in the process, caused by faulty or failing valves or flow meters, leaving the operating state detected quickly enough and thus can be reacted quickly enough to enter the explosion area to prevent. Possible technical solutions are switching off the supply of oxygen when limit value is reached, intertizing, uncoupling the apparatus and switching the gas flow to a torch.
  • a process gas 2 having a temperature of 380 ° C., a pressure of 1.3 bar and the composition shown in Table 2 is provided.
  • This gas stream is cooled in Quenchteil B with a mesitylene circulation stream at a temperature of 35 ° C and to a temperature of 90 ° C.
  • Quenchteil B with a mesitylene circulation stream at a temperature of 35 ° C and to a temperature of 90 ° C.
  • Mass ratio of the circulation stream 3b to the process gas 2 and the purge current 3a is 1: 1 to 0.067.
  • the gas stream 4 is in the second quenching stage C with another mesitylene circulation stream 9b which enters the quench at 35 ° C at the head end, further cooled to 45 ° C.
  • the resulting gas stream 5 has the composition shown in Table 2, while the
  • Mass ratio between stream 4 and 9b 1 to 2.38 and a purge stream 6 is withdrawn with a share of 1% from the stream 9 and passed into the first quench.
  • the gas stream 5 is drawn in a 4-stage compressor as shown in Figure 1
  • Compression stage has a temperature of 40 ° C and that shown in Table 2
  • This stream is in the absorber column G by passing in countercurrent and entering the column with 10 bar absolute and 35 ° C at the top of the column
  • Absorbent stream 21 b separated into a gas stream 16 and a mainly charged with C 4 - hydrocarbons absorbent stream. The loaded one
  • Absorbent stream is passed through a stream 18 consisting of nitrogen with a
  • Total volume fraction of organic compounds in the gas stream in the absorber column a greater distance to the explosive range can be maintained.
  • the numbers represent the composition of the currents 2, 4, 5, 12 and 16 in the diagram.

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Abstract

L'invention concerne un procédé de production de butadiène à partir de n-butènes, comprenant les étapes consistant à : A) préparer un courant gazeux de départ a contenant des n-butènes ; B) injecter le courant gazeux de départ a contenant des n-butènes et un gaz contenant de l'oxygène dans au moins une zone de déshydrogénation oxydative et déshydrogéner les n-butènes par oxydation pour donner du butadiène en produisant un courant de gaz produit b qui contient 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 composants secondaires à haut point d'ébullition, le cas échéant des oxydes de carbone et le cas échéant des gaz inertes ; Ca) refroidir le courant de gaz produit b en le mettant en contact avec un agent réfrigérant et condenser une partie au moins des composants secondaires à haut point d'ébullition ; Cb) comprimer le courant de gaz produit b restant dans au moins un étage de compression pour donner au moins un courant de condensat aqueux c1 et un courant gazeux c2 contenant du butadiène, des n-butènes, de la vapeur d'eau, de l'oxygène, des hydrocarbures à bas point d'ébullition, le cas échéant des oxydes de carbone et le cas échéant des gaz inertes ; Da) séparer du courant gazeux c2 les constituants gazeux non condensables et à bas point d'ébullition comprenant de l'oxygène, des hydrocarbures à bas point d'ébullition, le cas échéant des oxydes de carbone et le cas échéant des gaz inertes sous la forme d'un courant gazeux d2 par absorption des hydrocarbures C4, comprenant le butadiène et les n-butènes, dans un agent absorbant pour donner un courant d'agent absorbant chargé en hydrocarbures C4 et le courant gazeux d2 ; et ensuite Db) désorber les hydrocarbures C4 du courant d'agent absorbant chargé pour donner un courant de gaz produit C4 d1. Le procédé est caractérisé en ce que, à un endroit au moins de la tranche du procédé comprenant les étapes B), Ca), Cb) et Da), on injecte en plus un courant gazeux contenant du méthane en des quantités propres à éviter la formation d'un mélange gazeux explosible à l'étape Da).
EP14739155.1A 2013-07-18 2014-07-15 Procédé de production de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydative Withdrawn EP3022169A1 (fr)

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PCT/EP2014/065068 WO2015007698A1 (fr) 2013-07-18 2014-07-15 Procédé de production de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydative

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ES2704140T3 (es) * 2012-09-20 2019-03-14 Lummus Technology Inc Preabsorbedor para la extracción de butadieno
EP3197851B1 (fr) 2014-09-26 2019-05-08 Basf Se Procédé de fabrication de 1,3-butadiène à partir de n-butènes par déshydratation oxydante
EP3215478B1 (fr) 2014-11-03 2018-08-29 Basf Se Procédé de fabrication de 1,3-butadiène à partir de n-butènes par déshydratation oxydante
WO2016075065A1 (fr) 2014-11-14 2016-05-19 Basf Se Procédé de production de 1,3-butadiène par déshydrogénation de n-butènes grâce à la préparation d'un flux de matières contenant du butane et du 2-butène
EP3047904A1 (fr) 2015-01-22 2016-07-27 Basf Se Système catalyseur pour oxydation d'o-xylène et/ou de naphtalène pour produire de l'anhydride phtalique
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
EA201792113A1 (ru) 2015-03-26 2018-04-30 Басф Се Способ получения 1,3-бутадиена из h-бутенов путем окислительного дегидрирования
EP3274086B1 (fr) 2015-03-27 2019-01-30 Basf Se Corp catalytique servant à l'oxydation catalytique du so2 en so3
EP3497073A1 (fr) * 2016-08-09 2019-06-19 Basf Se Procédé pour le démarrage d'un réacteur pour la déshydrogénation par oxydation de n-butènes
WO2018095776A1 (fr) * 2016-11-22 2018-05-31 Basf Se Procédé pour la préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation par oxydation comprenant un lavage aqueux du flux gazeux produit en c4
KR102064314B1 (ko) * 2016-12-29 2020-01-09 주식회사 엘지화학 부타디엔 제조방법
US10407363B2 (en) 2017-08-16 2019-09-10 Saudi Arabian Oil Company Steam-less process for converting butenes to 1,3-butadiene
WO2019168276A1 (fr) 2018-02-27 2019-09-06 주식회사 엘지화학 Procédé de préparation de 1,3-butadiène
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ITMI20112403A1 (it) * 2011-12-28 2013-06-29 Polimeri Europa Spa Composizione catalitica e procedimento per la deidrogenazione di buteni o miscele di butani e buteni a dare 1-3 butadiene

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