WO2016151033A1 - Procédé de préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydative - Google Patents

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

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WO2016151033A1
WO2016151033A1 PCT/EP2016/056427 EP2016056427W WO2016151033A1 WO 2016151033 A1 WO2016151033 A1 WO 2016151033A1 EP 2016056427 W EP2016056427 W EP 2016056427W WO 2016151033 A1 WO2016151033 A1 WO 2016151033A1
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gas stream
stream
butenes
butadiene
hydrocarbons
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PCT/EP2016/056427
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German (de)
English (en)
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Jan Pablo Josch
Ragavendra Prasad Balegedde Ramachandran
Stephan DEUBLEIN
Regina Benfer
Anton Wellenhofer
Ulrike Wenning
Heinz Boelt
Hendrik Reyneke
Christine TOEGEL
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Basf Se
Linde Aktiengesellschaft
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Publication of WO2016151033A1 publication Critical patent/WO2016151033A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/005—Processes comprising at least two steps in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/09—Purification; Separation; Use of additives by fractional condensation
    • 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).
  • Butadiene (1,3-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 ) used.
  • Butadiene is further converted to sulfolane, chloroprene and 1, 4-hexamethylenediamine (over 1, 4-dichlorobutene and adiponitrile). By dimerization of butadiene it is also possible to produce vinylcyclohexene, 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. At the
  • Butadiene can also be obtained by oxidative dehydrogenation of n-butenes (1-butene and / or 2-butene) in the presence of molecular oxygen.
  • oxidative dehydrogenation oxydehydrogenation, ODH
  • any n-butenes containing mixture can be used.
  • a fraction containing n-butenes (1-butene and / or 2-butene) as a main component and obtained from the C 4 fraction of a naphtha cracker by separating butadiene and isobutene can be used.
  • gas mixtures which comprise 1-butene, cis-2-butene, trans-2-butene or mixtures thereof and which have been obtained by dimerization of ethylene can also be used as the feed gas stream.
  • n-butenes containing gas mixtures obtained by catalytic fluid cracking (FCC) can be used as the feed gas stream.
  • the N2 / 02 ratio in the reaction gas mixture is adjusted to the desired value by diluting air as the oxygen-containing gas with nitrogen gas.
  • JP 201 1 -006381 A of Mitsubishi addresses the risk of peroxide formation in the working up part of a process for the preparation of conjugated alkadienes.
  • the solution describes the addition of polymerization inhibitors to the absorption solutions for the process gases and the adjustment of a maximum peroxide content of 100 ppm by weight by heating the absorption solutions.
  • JP 201 1 -001341 A a two-stage cooling is described for a process for the oxidative dehydrogenation of alkenes to conjugated alkadienes.
  • the product discharge gas of the oxidative dehydrogenation is first adjusted to a temperature between 300 and 221 ° C and then further cooled to a temperature between 99 and 21 ° C.
  • an occasional washing out of deposits from the heat exchangers with organic or aqueous solvents is described.
  • solvents for example, aromatic hydrocarbons such as toluene or xylene or an alkaline aqueous solvent such as the aqueous solution of sodium hydroxide are described.
  • JP 2010-90083 A describes a process for the oxidative dehydrogenation of n-butenes to butadiene, in which the product gas of the oxidative dehydrogenation is cooled and dehydrated. Butadiene and unreacted butenes and butane are then absorbed in a solvent from the gas stream containing C4 hydrocarbons. The residual gas not absorbed by the solvent is then disposed of by combustion.
  • JP 2012072086 it is described that as the oxygen-containing gas, a gas from which the hydrocarbons, such as butadiene, n-butene, n-butane and isobutane were separated from the product gas mixture, can be recycled to the oxydehydrogenation.
  • the hydrocarbons such as butadiene, n-butene, n-butane and isobutane were separated from the product gas mixture
  • n-butene fractions often come from different sources and have different compositions.
  • n-butene fractions used are n-butenes (1-butene, cis-2-butene and trans-2-butene) and isobutene-containing gas mixtures which are obtained by non-oxidative dehydrogenation of n-butane .
  • n-butenes 1,3-butene, cis-2-butene and trans-2-butene
  • isobutene-containing gas mixtures which are obtained by non-oxidative dehydrogenation of n-butane
  • fractions which are the main constituents part of n-butenes and which were obtained from the C 4 fraction of a naphtha cracker by separation of butadiene and isobutene.
  • n-butenes and isobutene-containing gas mixtures obtained by fluid catalytic cracking (FCC) can also be used.
  • the composition of the n-butenes-containing feed gas stream of the oxidative dehydrogenation may be subject to short-term fluctuations. This is especially true for the coupling of a non-oxidative catalytic dehydrogenation of n-butane to n-butenes with an oxidative dehydrogenation of n-butenes to butadiene.
  • the conversions and selectivities obtainable in the oxidative dehydrogenation stage depend on the reaction parameters pressure, temperature and space velocity, which have an optimum for a particular isomeric composition of the feed gas stream.
  • Fluctuations in the isomer composition can not adjust the reaction parameters fast enough to the altered composition to ensure stable operation of the entire production plant in terms of conversion and selectivity.
  • the object of the invention is to provide a process for the preparation of butadiene by oxidative dehydrogenation of n-butenes, in which the composition of the n-butene-containing feed gas mixtures used is subject to temporal variations, and which can still be operated stably in terms of conversion and selectivity.
  • the object is achieved by a process for the preparation of butadiene from n-butenes with the following steps: A) providing a feed gas stream a1 comprising n-butenes, 1-butenes, 2-butenes and isobutene,
  • the feed stream of a time-varying composition can be fed continuously or discontinuously into the buffer tank.
  • the feed gas stream a1 is generally withdrawn continuously.
  • the feed stream aO used are n-butenes (1-butene, cis-2-butene and trans-2-butene) and isobutene-containing gas mixtures. Such gas mixtures can be obtained, for example, by non-oxidative dehydrogenation of n-butane. Fractions which contain n-butenes as the main constituent and are obtained from the C 4 fraction of a naphtha crack by removal of butadiene and isobutene can also be used as feed stream aO. Further, as the feed stream aO n-butenes and isobutene-containing gas mixtures can be used, which were obtained by catalytic fluid cracking (FCC).
  • FCC catalytic fluid cracking
  • the starting stream aO 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-butenes and unreacted n-butane, contains minor constituents.
  • 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.
  • the feed stream aO contains from 10 to 30% by volume of 1-butene, from 50 to 80% by volume of 2-butenes and from 0 to 5% by volume of isobutene. In addition, it generally contains 10 to 30% by volume of butanes (n-butane, isobutanes), 0 to 5% by volume of C 1 -C 3 -hydrocarbons (methane, ethane, ethene, propane and propene), 0 Up to 5% by volume of C5 + hydrocarbons (pentanes and higher boiling hydrocarbons) and 0 to 5% by volume of inert gases (nitrogen, CO2).
  • the feed gas stream a1 preferably contains 15 to 25% by volume of 1-butene, 55 to 75% by volume of 2-butenes and 0 to 5% by volume of isobutene. In addition, it generally contains 15 to 25% by volume of butane (n-butane, isobutane), 0 to 5% by volume of C 1 -C 3 -hydrocarbons (methane, ethane, ethene, propane and propene), 0 to 5% by volume of C5 + hydrocarbons (pentanes and higher boiling hydrocarbons) and 0 to 5% by volume of inert gases (nitrogen, CO2).
  • butane n-butane, isobutane
  • C 1 -C 3 -hydrocarbons methane, ethane, ethene, propane and propene
  • C5 + hydrocarbons penentanes and higher boiling hydrocarbons
  • inert gases nitrogen, CO2
  • the buffer container has at least one size, which ensures a 12-hour buffering of the feed gas stream a1, d. H. the amount which can be taken up by the buffer container corresponds to the amount of feed gas stream a1 fed into the reactor over a period of 12 hours.
  • the buffer container has a buffer capacity that allows at least 24 hours buffering of the feed gas stream a1.
  • the storage of the feed stream is generally carried out under a pressure of 1, 2 to 6 bar, preferably 2 to 5 bar absolute.
  • the buffer tank has a volume in the range of 500 to 2000 m 3 .
  • the mass flow of the feed gas stream a1 into the oxydehydrogenation zone is 10 to 50 t h.
  • the buffer tank is generally spherical or cylindrical. It is generally made of commercially available metallic pressure vessel steels. Due to the buffer container according to the invention, the concentration of 1-butene, 2-
  • the process according to the invention preferably also comprises the following further process steps:
  • the stage Ca) can be preceded by at least one cooling stage in which the product gas stream b is cooled by indirect cooling in a heat exchanger.
  • the stage Ca) can be carried out in several stages in stages Ca1) to Can), preferably in two stages in two stages Ca1) and Ca2). In this case, particularly preferably at least part of the coolant is supplied after passing through the second stage Ca2) as cooling agent of the first stage Ca1).
  • 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 as the cooling agent in step Ca) when an organic solvent is used in the cooling step Ca).
  • at least part of this cooling agent is fed after passing through the at least one cooling stage Cbb) as cooling agent of stage Ca).
  • the cooling stage Cbb) may consist of heat exchangers.
  • 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).
  • an organic solvent is preferably used. These 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 plant components, as water or alkaline aqueous solutions.
  • Preferred organic solvents used as cooling agents are aromatic hydrocarbons, particular preference is given to toluene, o-xylene, m-xylene, p-xylene, mesitylene, all possible constitutional isomers of mono-, di- and triethylbenzene and all possible constitutional isomers of mono-, di-, and triisopropylbenzene or mixtures thereof. Preference is given to aromatic hydrocarbons having a boiling point at 1013.25 hPa of more than 120 ° C. or mixtures thereof. Especially preferred is mesitylene.
  • Step Da) preferably comprises the steps Daa) to Dac):
  • the absorbent used in the separation step Da) is an aromatic hydrocarbon solvent. Preference is given to toluene, o-xylene, m-xylene, p-xylene, mesitylene, all possible constitutional isomers of mono-, di- and triethylbenzene and all possible constitutional isomers of mono-, di- and triisopropylbenzene or mixtures thereof. Aromatic hydrocarbons having a boiling point at 1013.25 hPa of more than 120 ° C. are preferred. Particularly preferred is mesitylene. More specifically, in the separation step Da), the same aromatic hydrocarbon solvent is used as in the preceding cooling step Ca) when an organic solvent is used in the cooling step Ca). By absorption of C 4 hydrocarbons comprising butadiene and n-butenes from the
  • Gas stream c2 in the aromatic hydrocarbon solvent, non-condensable and low-boiling gas components comprising oxygen, low-boiling hydrocarbons, optionally carbon oxides and optionally inert gases are obtained as gas stream d2. At least part of this gas stream d2 is recycled as circulating gas stream a2 into the oxidative dehydrogenation (step B)).
  • the content of aromatic hydrocarbon solvent in the circulating gas stream a2 is preferably less than 1% by volume.
  • the content of aromatic hydrocarbon solvent in the circulating gas stream a2 is limited to less than 1% by volume in that the separation stage Da) at temperatures preferably below 50 ° C., more preferably below 40 ° C. and / or operated at a pressure higher than 5 bar absolute, more preferably at 10 bar absolute and higher.
  • the absorbent used in the separation stage Da) can be cooled to a low temperature before entering the separation stage Da).
  • step B) the reaction gas mixture containing the n-butenes and isobutene-containing feed gas stream a1, an oxygen-containing gas, an oxygen-containing cycle gas stream a2 and optionally further components in at least one dehydrogenation zone (the ODH reactor tor) is fed and in the gas mixture butenes dehydrogenated oxidatively to butadiene in the presence of an oxydehydrogenation catalyst.
  • 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 further 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 are also proposed as catalysts.
  • the multimetal oxide contains cobalt and / or nickel.
  • the multimetal oxide contains chromium.
  • 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 have the general formula (Ia): Moi2BiaFebCOcNidCr e X 1 fX 2 gOy (la), with
  • 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).
  • the molecular oxygen-containing gas generally contains more than 10% by volume, preferably more than 15% by volume, and more preferably more than 20% by volume of molecular oxygen. It is preferably air.
  • the upper limit of the content of molecular oxygen is 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 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, it is generally 10% by volume or less, preferably 1% by volume or less.
  • 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 input gas stream with oxygen or at least one oxygen-containing gas, such as air, and optionally additional inert gas or steam can be mixed.
  • the resulting oxygen-containing gas mixture is then fed to the oxydehydrogenation.
  • inert gases such as nitrogen and also water (as water vapor) may be contained together in the reaction gas mixture.
  • Nitrogen can be used to adjust the oxygen concentration and prevent the formation of an explosive gas mixture, the same applies to water vapor.
  • Steam also serves to control the coking of the catalyst and to dissipate the heat of reaction.
  • the reaction temperature of the oxydehydrogenation is generally controlled by a heat exchange medium located around the reaction tubes.
  • Suitable liquid heat exchangers include, for example, melts of salts such as potassium nitrate, potassium nitrite, sodium nitrite and / or sodium nitrate and melts of metals such as sodium, mercury and alloys of various metals. But ionic liquids or heat transfer oils are used.
  • the temperature of the heat exchange medium is between 220 to 490 ° C and preferably between 300 to 450 ° C and more preferably between 350 and 420 ° C.
  • the temperature in certain sections of the interior of the reactor during the reaction may be higher than that of the heat exchange medium and a so-called hotspot is formed.
  • the location and height of the hotspot is determined by the reaction conditions, but it may also be regulated by the dilution ratio of the catalyst layer or the flow rate of mixed gas.
  • the difference between hotspot temperature and the temperature of the heat exchange medium is generally between 1 to 150 ° C, preferably between 10 to 100 ° C and more preferably between 20 to 80 ° C.
  • the temperature at the end of the catalyst bed is generally between 0 to 100 ° C, preferably between 0.1 to 50 ° C, more preferably between 1 to 25 ° C above the temperature of the heat exchange medium.
  • the reactor pressure is generally 1 to 4 bar, preferably 2 to 3 bar.
  • 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 configured in the ODH reactor may consist of a single layer or of two or more layers. These layers may be pure catalyst or diluted with a material that does not react with the feed gas stream or components from the product gas of the reaction.
  • the catalyst layers may consist of solid material or supported shell catalysts.
  • the product gas stream leaving the oxidative dehydrogenation generally contains unreacted 1-butene and 2-butene, oxygen and water vapor.
  • the product gas stream leaving the oxidative dehydrogenation generally contains unreacted 1-butene and 2-butene, oxygen and water vapor.
  • it furthermore generally contains carbon monoxide, carbon dioxide, inert gases (mainly nitrogen), low-boiling hydrocarbons such as methane, ethane, ethene, propane and propene, butane and isobutane, optionally hydrogen and optionally oxygen-containing hydrocarbons, so-called oxygenates.
  • Oxygenates may be, for example, formaldehyde, furan, acetic acid, maleic anhydride, formic acid, methacrolein, methacrylic acid, crotonaldehyde, crotonic acid, propionic acid, acrylic acid, methyl vinyl ketone, benzaldehyde, benzoic acid, phthalic anhydride, fluorenone, anthraquinone and butyraldehyde.
  • the product gas stream 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 150 to 400 ° C, preferably 160 to 300 ° C, more preferably 170 to 250 ° C.
  • heat exchangers include spiral heat exchangers, plate 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.
  • the heat exchanger system should preferably have two or more heat exchangers.
  • the two or more heat exchangers provided 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 may be used so long as it is capable of dissolving the high-boiling by-products. Examples are aromatic hydrocarbon solvents such as toluene and xylenes, as well as alkaline aqueous solvents such as the aqueous solution of sodium hydroxide.
  • This stage is also referred to below as quench.
  • This quench can consist of only one stage or of several stages.
  • the cooling can be effected by contacting with a coolant, preferably an organic solvent.
  • the cooling medium used is organic solvents, preferably aromatic hydrocarbons, particularly preferably toluene, o-xylene, m-xylene, p-xylene, mesitylene, all possible constitutional isomers of mono-, di- and triethylbenzene and all possible constitutional isomers of mono- , Di- and triisopropylbenzene or mixtures thereof.
  • aromatic hydrocarbons having a boiling point at 1013.25 hPa of above 120 ° C or mixtures thereof.
  • the stage Ca comprises two cooling stages Ca1) and Ca2), in which the product gas stream b 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, a temperature of 100 to 440 ° C.
  • the product gas is brought into contact with the cooling medium in the 1st quench stage.
  • 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 in the first quenching stage 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 at the inlet may generally be 25 to 200 ° C, preferably 40 to 120 ° C, particularly preferably 50 to 90 ° C.
  • the pressure in the first quenching stage 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 is designed as a cooling tower.
  • the cooling medium used in the cooling tower is often used in a circulating manner.
  • the circulation flow of the cooling medium 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 0.0001 to 1 l / g and particularly preferably from 0.002 to 0.2 l / g be.
  • the temperature of the cooling medium 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 with secondary components increases over time, a portion of the loaded cooling medium can be withdrawn from the circulation as a purge stream and the circulation volume can be kept constant by adding unzula- denem cooling medium. The ratio of effluent quantity and amount added depends on the vapor loading of the product gas and the product gas temperature at the end of the first quenching stage.
  • condensation of water may occur in the first quench stage.
  • an additional aqueous phase may form, which may additionally contain water-soluble secondary components. This can then be subtracted in the bottom of the quenching stage. Preference is given to an operation in which no aqueous phase is formed in the first quench stage.
  • the cooled and possibly depleted in secondary components product gas stream can now be fed to a second quenching stage. In this he can now be brought into contact again with a cooling medium.
  • the choice of the coolant is not particularly limited.
  • the cooling medium used is preferably organic solvents, particularly preferably aromatic hydrocarbons, in particular toluene, o-xylene, m-xylene, p-xylene, mesitylene, all possible constitution isomers of mono-, di- and triethylbenzene and all possible constitution isomers of mono-, di- and Triisopro- pylbenzol or mixtures thereof, used.
  • aromatic hydrocarbons having a boiling point at 1013.25 hPa of above 120 ° C or mixtures thereof.
  • 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.
  • the coolant can be supplied in countercurrent to the product gas.
  • the temperature of the coolant medium 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 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 used in the cooling tower is often used in a circulating manner.
  • the circulation flow of the cooling medium in liters per hour can generally be from 0.0001 to 5 l / g, preferably from 0.0001 to 1 l / g and particularly preferably from 0.002 to 0, 2 l / g.
  • condensation of water may occur in the second quench stage.
  • an additional Liehe aqueous phase may form, which may additionally contain water-soluble secondary components. This can then be subtracted in the bottom of the quenching stage.
  • the temperature of the cooling medium 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 with secondary components increases over time, a portion of the loaded cooling medium can be withdrawn as purge stream from the circulation, and the circulating amount can be kept constant by adding unladen cooling medium.
  • internals may be present in the second quenching stage.
  • Such internals include, for example, bell, centrifugal and / or sieve trays, columns with structured packings, eg sheet metal packings having a specific surface area of 100 to 1000 m 2 / m 3 such as Mellapak® 250 Y, and packed columns.
  • the coolant circulations of the two quench stages can be both separated from each other and connected to each other.
  • the power can be supplied to the power 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, with the second-stage coolant Ca 2) loaded with secondary components being led into the first stage Ca1).
  • the coolant removed from the second stage Ca2) contains fewer secondary components than the coolant removed from the first stage Ca1).
  • suitable structural measures such as the installation of a demister, can be taken.
  • high-boiling substances which are not separated from the product gas in the quench, can be removed from the product gas by further structural measures, such as further gas scrubbing.
  • a gas stream which comprises n-butane, 1-butene, 2-butenes, butadiene, optionally oxygen, hydrogen, water vapor, in small quantities methane, ethane, ethene, propane and propene, isobutane, carbon oxides, inert gases and parts contains the coolant used in the quench. Furthermore, traces of high-boiling components can remain in this gas stream, which were not quantitatively separated in the quench.
  • high-boiling components examples include methyl vinyl ketone, methyl ethyl ketone, crotonaldehyde, acrylic acid, propionic acid, maleic anhydride, ethylbenzene, styrene, furanone, benzoic acid, benzaldehyde, fluorenone and anthraquinone.
  • this gas stream may contain formaldehyde, methacro- lein and / or furan.
  • the product gas stream from the quench is compressed in at least one compression stage and subsequently further cooled in the cooling apparatus, wherein at least one condensate stream containing water is formed. If a coolant other than water is used in the quench, the coolant used in the quench can continue to condense and optionally form a separate phase. There remains a gas stream 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 can take place 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 cooling is preferably carried out by contacting with an organic solvent as a cooling agent. Alternatively, heat exchangers can also be used.
  • the condensate stream can therefore also comprise a plurality of streams in the case of multistage compression.
  • the condensate stream largely consists of water (aqueous phase) and, if necessary, the coolant (organic phase) used in the quench.
  • Both streams may also contain minor components such as low boilers, C4 hydrocarbons, oxygenates and carbon oxides.
  • the condensed quench coolant can be cooled in a heat exchanger and recycled as coolant into the apparatus. Since the loading of this cooling medium with side components increases over time, a portion of the loaded cooling medium can be withdrawn from circulation and the circulation volume of the cooling medium can be kept constant by adding unladen coolant.
  • the coolant which is added as a cooling medium, thus also preferably consists of the aromatic hydrocarbon solvent used as quench coolant.
  • the condensate stream can be returned to the recycle stream of the quench.
  • Suitable compressors are, for example, tur bo-, rotary piston and reciprocating compressors.
  • the compressors can be driven, for example, with an electric motor, an expander or a gas or steam turbine.
  • Typical compression ratios (outlet pressure: inlet pressure) per compressor stage are between 1, 5 and 3.0, depending on the design.
  • the cooling of the compressed gas takes place in flushed with organic solvent heat exchangers or organic quench, which can be performed, for example, as a tube bundle, spiral or plate heat exchanger.
  • coolant cooling water or heat transfer oils are used 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 c2 is as Output current fed to the further treatment.
  • a step Da) are non-condensable and low-boiling gas constituents, oxygen, low-boiling hydrocarbons (methane, ethane, ethene, propane, propene), carbon oxides and inert gases in an absorption column from the process gas stream c2 by absorption of C4 hydrocarbons in an aromatic hydrocarbon solvent as a high-boiling absorbent and subsequent desorption of the C 4 hydrocarbons separated.
  • the step Da) comprises the steps Daa) to Dac):
  • the absorption stage of the gas stream c2 is brought into contact with the absorbent and the C4 hydrocarbons are absorbed in the absorbent, wherein a C4 hydrocarbons laden absorbent and the other gas constituents containing gas stream d2 is obtained, at least partially as a circulating gas stream in the oxidative dehydrogenation is recycled.
  • the C4 hydrocarbons are released from the absorbent again.
  • Suitable absorption agents are organic solvents, preferably aromatic hydrocarbons, particularly preferably toluene, o-xylene, m-xylene, p-xylene, mesitylene, all possible constitution isomers of mono-, di- and triethylbenzene as well as all possible constitutional isomers of mono-, di- and triisopropylbenzene or mixtures thereof. Also preferred are aromatic hydrocarbons having a boiling point at 1013.25 hPa of above 120 ° C or mixtures thereof. More specifically, in the separation step Da), the same aromatic hydrocarbon solvent is used as in the preceding cooling step Ca) when an organic solvent is used in the cooling step Ca).
  • Preferred absorbents are solvents which have a solubility for organic peroxides of at least 1000 ppm (mg active oxygen / kg solvent).
  • mesitylene is used as absorption absorbent.
  • 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, 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.
  • 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.
  • trickle and spray towers graphite block absorbers, surface absorbers such as thick-film and thin-layer absorbers, as well as rotary columns, dishwashers, 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 c2 is supplied. In the upper part of the absorption column, the absorbent is applied.
  • a gas stream d2 is withdrawn, which essentially comprises oxygen, low-boiling hydrocarbons (methane, ethane, ethene, propane, propene), the aromatic hydrocarbon solvent, optionally C4-hydrocarbons (butane, butane). ne, butadiene), optionally inert gases, optionally carbon oxides and optionally also water vapor.
  • This stream is at least partially supplied as a circulating gas stream a2 the ODH reactor. This makes it possible, for example, to adjust the inlet flow of the ODH reactor to the desired C4 hydrocarbon content.
  • at least 30% by volume, preferably at least 50% by volume, of the gas stream d2 are recycled as circulating gas stream a2 into the oxidative dehydrogenation zone.
  • the recycle stream is 10 to 70% by volume, preferably 30 to 60% by volume, based on the sum of all material streams fed into the oxidative dehydrogenation B).
  • the purge gas stream may be subjected to thermal or catalytic afterburning. In particular, it can be thermally utilized in a power plant.
  • residues in the absorbent dissolved oxygen can be discharged in a further column by flushing with a gas.
  • the remaining oxygen content is preferably so small that the stream d1 leaving the desorption column and containing butane, butene and butadiene only contains a maximum of 100 ppm of oxygen.
  • the stripping out of the oxygen in step Dab) 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 inert gases such as nitrogen, through the loaded absorption solution. With stripped C4 hydrocarbons are washed in the upper part of the absorption column back into the absorption solution by the gas stream is passed back into this absorption column. This can be done both by a piping of the stripping column and a direct assembly of the stripping column below the absorber column. Since the pressure in the stripping column part and the absorption column part is the same according to the invention, this direct coupling can take place.
  • Suitable stripping columns are, for example, bottom columns with bell-shaped, 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. But there are also trickle and spray towers and rotary columns, dishwashers, cross-flow scrubbers and rotary scrubbers into consideration. Suitable gases are for example nitrogen or methane.
  • the C4 hydrocarbon laden absorbent stream may include water. This can be separated as a stream from the absorbent in a decanter, so that a stream is obtained, which only contains the water dissolved in the absorbent.
  • the adsorbent stream d2 which has been freed from C4 hydrocarbons and freed as far as possible from water, can be heated in a heat exchanger and subsequently passed into a desorption column.
  • the desorption step De) is carried out by relaxation and / or heating of the loaded absorbent.
  • a preferred process variant is the use of a reboiler in the bottom of the desorption column.
  • the absorbent regenerated in the desorption stage can be cooled in a heat exchanger and returned to the absorption stage.
  • 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 circulation stream.
  • a purge can be deducted. This can be separated in a distillation column according to the prior art in low boilers, regenerated absorbent and high boiler.
  • the C4 product gas stream d1 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 head effluent of the desorption column, mainly containing C 4 hydrocarbons, is returned to the top of the column to increase the separation efficiency of the column.
  • the liquid or gaseous C4 product streams leaving the condenser can subsequently be separated by extractive distillation in step E) with a butadiene-selective solvent into a butadiene and the material stream containing the selective solvent and a stream containing n-butenes.
  • 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 designed in the form of a wash column which contains trays, fillers or packages as internals. This generally has 30 to 70 theoretical plates, so that a sufficiently good release effect is achieved.
  • the wash column has a backwash zone in the column head. This backwash zone 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 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 taken off in gaseous or liquid form.
  • the stream consisting essentially of n-butane and 2-butene contains up to 100% by volume of n-butane, 0 to 50% by volume of 2-butene and 0 to 3% by volume of further constituents, such as isobutane, isobutene , Propane, propene and Cs + hydrocarbons.
  • the stream consisting essentially of n-butane and 2-butenes can be fed wholly or partly to the C 4 feed of the ODH reactor.
  • this recycle stream can be catalytically isomerized prior to being fed to the ODH reactor. As a result, the isomer distribution can be adjusted in accordance with the isomer distribution present in the thermodynamic equilibrium.
  • 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 and optionally water-containing material flow is obtained, wherein the composition of the extractant and water-containing material stream corresponds to the composition as it is added to the extraction.
  • the extractant and water-containing stream is preferably returned to the extractive distillation.
  • the extraction solution thus withdrawn is transferred to a desorption zone, wherein the butadiene is desorbed again from the extraction solution and washed back.
  • the desorption zone can be embodied, for example, in the form of a wash column containing 2 to 30, preferably 5 to 20, theoretical stages and optionally, a backwashing zone having, for example, 4 theoretical stages. This backwash zone is used to recover the extractant contained in the gas phase by means of a liquid hydrocarbon reflux, to which the top fraction is condensed beforehand.
  • trays or packing are provided.
  • the distillation is preferably carried out at a bottom temperature in the range from 100 to 300 ° C., in particular in the range from 150 to 200 ° C.
  • the pressure in the distillation column is preferably in the range of 1 to 10 bar.
  • a reduced pressure and / or elevated temperature prevail over the extraction zone.
  • the product stream 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.
  • a butene stream of about 27 t / h is to be fed into the oxidative dehydrogenation zone.
  • An intermediate tank with a volume of approx. 1 100 m 3 is installed, which corresponds to a buffer capacity of approx. 24 hours.
  • the storage takes place under pressure at approx. 35 ° C.
  • the tank can be made either in the form of a spherical tank or in the form of a cylinder.
  • the butene fraction is conveyed from the intermediate tank with a pump to the oxidation reactor. From the pressure side of the pump, a line is returned to the intermediate tank, which causes an intensive mixing of the contents of the intermediate tank and additionally serves to ensure a minimum pump delivery.

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Abstract

L'invention concerne un procédé de préparation de butadiène à partir de n-butènes comprenant les étapes consistant à : A) mettre à disposition un flux de gaz de mise en oeuvre contenant des n-butènes a1 contenant du 1-butène, du 2-butène et de l'isobutène ; B) charger le flux de gaz de mise en œuvre contenant des n-butènes a1, un gaz contenant de l'oxygène et un flux de gaz de circuit contenant de l'oxygène a2 dans au moins une zone de déshydrogénation oxydative et procéder à la déshydrogénation oxydative des n-butènes en butadiène, ce qui permet d'obtenir un flux de gaz de produit b contenant du butadiène, des n-butènes n'ayant pas réagi, de la vapeur d'eau, de l'oxygène, des hydrocarbures à bas point d'ébullition, des composants secondaires à point d'ébullition élevé, le cas échéant des oxydes de carbone et le cas échéant des gaz inertes, Ca) refroidir le flux de gaz de produit b et le cas échéant séparer au moins partiellement les composants secondaires à point d'ébullition élevé et la vapeur d'eau, ce qui permet d'obtenir un flux de gaz de produit b', Cb) comprimer et refroidir le flux de gaz de produit b' en au moins une étape de compression et de refroidissement, ce qui permet d'obtenir au moins un flux de condensat aqueux c1 et un flux de gaz c2 contenant du butadiène, des n-butènes, de la vapeur d'eau, de l'oxygène, des hydrocarbrues à bas point d'ébullition, le cas échéant des oxydes de carbone et le cas échéant des gaz inertes, Da) absorber les hydrocarbures en C4 comprenant du butadiène et des n-butènes dans un dissolvant d'hydrocarbure aromatique comme agent d'absorption et séparer les composants 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, le dissolvant d'hydrocarbure aromatique et le cas échéant des gaz inertes comme flux de gaz d2 à partir du flux de gaz c2, ce qui permet d'obtenir un flux d'agent d'absorption chargé d'hydrocarbures en C4 et le flux de gaz d2, et procéder ensuite à la désorption des hydrocarbures en C4 à partir du flux d'agent d'absorption chargé, ce qui permet d'obtenir un flux de gaz de produit d1 en C4, Db) éventuellement renvoyer au moins partiellement le flux de gaz d2 sous forme de flux de gaz de circuit a2 dans la zone de déshydrogénation oxydative, caractérisé en ce que le flux de gaz de mise en œuvre a1 est prélevé dans un récipient tampon, qui est alimenté par un flux de mise en œuvre a0 contenant 15 à 30 % en volume de 1-butène, 50 à 80 % en volume de 2-butène et 0 à 5 % en volumed'isobutène, dont la composition se modifie dans le temps, ce qui permet de soumettre la composition du flux de gaz de mise en œuvre a1 à des fluctuations temporelles plus faibles que la composition du flux de mise en œuvre a0.
PCT/EP2016/056427 2015-03-26 2016-03-23 Procédé de préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydative WO2016151033A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10370310B2 (en) 2016-01-13 2019-08-06 Basf Se (Isenbruck Bösl Hörschler Llp) Method for preparing 1,3-butadiene from n-butenes by oxidative dehydrogenation
US10647639B2 (en) 2016-02-04 2020-05-12 Basf Se Method for preparing 1,3-butadiene from N-butenes by oxidative dehydrogeneation

Citations (4)

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US2377579A (en) * 1940-08-23 1945-06-05 Phillips Petroleum Co Process for dehydrogenation of hydrocarbons
US2381692A (en) * 1940-08-15 1945-08-07 Phillips Petroleum Co Process for the dehydrogenation of hydrocarbons
US3113164A (en) * 1955-06-20 1963-12-03 Phillips Petroleum Co Dehydrogenation process and recovery of the resulting dehydrogenated products
US4595788A (en) * 1983-11-25 1986-06-17 Nippon Zeon Co. Ltd. Process for producing butadiene

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
US2381692A (en) * 1940-08-15 1945-08-07 Phillips Petroleum Co Process for the dehydrogenation of hydrocarbons
US2377579A (en) * 1940-08-23 1945-06-05 Phillips Petroleum Co Process for dehydrogenation of hydrocarbons
US3113164A (en) * 1955-06-20 1963-12-03 Phillips Petroleum Co Dehydrogenation process and recovery of the resulting dehydrogenated products
US4595788A (en) * 1983-11-25 1986-06-17 Nippon Zeon Co. Ltd. Process for producing butadiene

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10370310B2 (en) 2016-01-13 2019-08-06 Basf Se (Isenbruck Bösl Hörschler Llp) Method for preparing 1,3-butadiene from n-butenes by oxidative dehydrogenation
US10647639B2 (en) 2016-02-04 2020-05-12 Basf Se Method for preparing 1,3-butadiene from N-butenes by oxidative dehydrogeneation

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