EP2945922A1 - Procédé de préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydative - Google Patents

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

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Publication number
EP2945922A1
EP2945922A1 EP14700500.3A EP14700500A EP2945922A1 EP 2945922 A1 EP2945922 A1 EP 2945922A1 EP 14700500 A EP14700500 A EP 14700500A EP 2945922 A1 EP2945922 A1 EP 2945922A1
Authority
EP
European Patent Office
Prior art keywords
stream
butadiene
butenes
hydrocarbons
stage
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Withdrawn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
EP14700500.3A
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German (de)
English (en)
Inventor
Jan Pablo Josch
Philipp GRÜNE
Christian Walsdorff
Oliver HAMMEN
Ragavendra Prasad Balegedde Ramachandran
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BASF SE
Original Assignee
BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP14700500.3A priority Critical patent/EP2945922A1/fr
Publication of EP2945922A1 publication Critical patent/EP2945922A1/fr
Withdrawn legal-status Critical Current

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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
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
    • C07C7/08—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds by extractive distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/11—Purification; Separation; Use of additives by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85—Chromium, molybdenum or tungsten
    • C07C2523/88—Molybdenum
    • C07C2523/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36

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).
  • ODH oxidative dehydrogenation
  • any n-butenes containing mixture can be used.
  • a fraction containing n-butenes (1-butene and / or 2-butene) as a main component and obtained from the C 4 fraction of a naphtha cracker by separating butadiene and isobutene can be used.
  • gas mixtures which comprise 1-butene, cis-2-butene, trans-2-butene or mixtures thereof and which have been obtained by dimerization of ethylene can also be used as starting gas.
  • n-butenes containing gas mixtures can be used as the starting gas, which were obtained by catalytic fluid catalytic cracking (FCC).
  • 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.
  • no information is given on the prevention or control of peroxides in upstream process steps.
  • the cooling step of the ODH reactor discharge with a water quench can be seen critically. Formed organic peroxides are hardly soluble in water, so that they can deposit and accumulate in solid or liquid form in the apparatus, rather than being discharged with the aqueous purge stream.
  • the temperature of the water quench is not so high that it can be assumed that the peroxides formed are sufficiently high and steady.
  • high-boiling minor components such as maleic anhydride, phthalic anhydride, benzaldehyde, benzoic acid, ethylbenzene, styrene, fluorenone, anthraquinone and others can be formed.
  • Such deposits can lead to blockages and a pressure drop increase in the reactor or behind the reactor in the field of workup and thus interfere with a regulated operation.
  • Deposits of said high-boiling secondary components can also impair the function of heat exchangers or damage moving apparatus such as compressors. Vapor-volatile compounds such as fluorenone can penetrate through a water-operated quench apparatus and precipitate in the gas discharge lines behind it. Thus, in principle there is also the risk that solid deposits in downstream equipment parts, such as compressors, get there and cause damage.
  • US 2012/0130137 A1 paragraph [0122] also refers to the problem of high-boiling by-products.
  • phthalic anhydride, anthraquinone and fluorenone are mentioned, which would typically be present in concentrations of 0.001-0.10 vol% in the product gas.
  • a cooling liquid quench tower
  • cooling liquids are called water or aqueous alkali solutions.
  • JP-A 201 1 -001341 describes a two-stage cooling process for the oxidative dehydrogenation of alkenes to give conjugated alkadienes.
  • the product discharge gas of the oxidative dehydrogenation is initially adjusted to a temperature between 300 and 221 ° C and then further cooled to a temperature between 99 and 21 ° C. It is described in paragraphs et seq. That heat exchangers are preferably used for adjusting the temperature between 300 and 221 ° C., although part of the high boilers from the product gas could also precipitate in these heat exchangers.
  • JP-A 201 1 -001341 therefore, an occasional washing out of deposits from the heat exchangers with organic or aqueous solvents is described.
  • the solvent for example, aromatic hydrocarbons such as toluene or xylene or an alkaline aqueous solvent such as the aqueous solution of sodium hydroxide are described.
  • aromatic hydrocarbons such as toluene or xylene or an alkaline aqueous solvent such as the aqueous solution of sodium hydroxide are described.
  • a B driving style a structure with two heat exchangers arranged in parallel is described in JP-A 201 1 -001341, which are each operated or purged alternately.
  • the object of the present invention is to provide a method which overcomes the above-mentioned disadvantages of known methods.
  • a method is to be provided in which deposits are avoided by high-boiling organic secondary constituents in the ODH downstream devices.
  • a method is to be provided in which the possible accumulation of organic peroxides is avoided. It is another object of the invention to reduce high loads of wastewater with organic compounds in dissolved, emulsified or suspended form, as well as the accumulation of polluted with organic compounds wastewater.
  • step F) Distillation of the butadiene and the material stream e1 containing the selective solvent into a stream f1 consisting essentially of the selective solvent and a stream f2 containing butadiene.
  • step A) a feed gas stream containing n-butenes is provided.
  • an organic solvent is used in the cooling stage Ca). These generally have a much higher solubility for the high-boiling by-products, which can lead to deposits and clogging in the plant parts downstream of the ODH reactor, than water or alkaline-aqueous solutions.
  • Preferred organic solvents used as cooling agents are aromatic hydrocarbons, more preferably toluene, o-xylene, m-xylene, p-xylene or mixtures thereof.
  • 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, particularly preferably at least part of the solvent is fed 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 in step Ca) as a cooling agent.
  • 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 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 steps Da) to De):
  • the high-boiling absorbent used in step Da) is preferably an aromatic hydrocarbon solvent, particularly preferably the aromatic hydrocarbon solvent used in step Ca), in particular toluene.
  • Embodiments of the method according to the invention are shown in FIGS. 1 to 3 and will be described in detail below.
  • feed gas stream pure 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.
  • 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.
  • n-butenes containing gas mixtures obtained by catalytic fluid cracking (FCC) can be used as the starting gas.
  • the starting gas mixture containing n-butenes is obtained by non-oxidative dehydrogenation of n-butane.
  • a non-oxidative catalytic dehydrogenation with the oxidative dehydrogenation of the n-butenes formed, a high yield of butadiene, based on n-butane used, can be obtained.
  • a gas mixture is obtained which, in addition to butadiene 1-butene, 2-butene and unreacted n-butane, contains minor constituents.
  • Common secondary constituents are hydrogen, water vapor, nitrogen, CO and CO2, methane, ethane, ethene, propane and propene.
  • the composition of the gas mixture leaving the first hydrogenation zone can vary greatly depending on the mode of operation of the dehydrogenation.
  • the product gas mixture has a comparatively high content of water vapor and carbon oxides.
  • the product gas mixture of the non-oxidative dehydrogenation has a comparatively high content of hydrogen.
  • step B the feed gas stream containing n-butenes and an oxygen-containing gas are fed into at least one dehydrogenation zone (the ODH reactor 1) and the butenes contained in the gas mixture are oxidatively dehydrogenated to form 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 other additional components, such as potassium, cesium, magnesium, zirconium, chromium, nickel, cobalt, cadmium, tin, lead, germanium, lanthanum, manganese, tungsten, phosphorus, cerium, aluminum or silicon.
  • Iron-containing ferrites have also been proposed as catalysts.
  • the multimetal oxide contains cobalt and / or nickel. In a further preferred embodiment, the multimetal oxide contains chromium. In a further preferred embodiment, the multimetal oxide contains manganese.
  • Mo-Bi-Fe-O-containing multimetal oxides are Mo-Bi-Fe-Cr-O or Mo-Bi-Fe-Zr-O-containing multimetal oxides.
  • Preferred systems are described for example in US 4,547,615 (Moi2BiFeo, i Ni 8 ZrCr 3 Ko, 20x and Moi2BiFeo, i Ni 8 AlCr 3 Ko, 20x), US 4,424,141 (Moi2BiFe Co4,5Ni2 3, 5 Po, 5KO, lox + Si0 2 ), DE-A 25 30 959 (3 Moi2BiFe Co4,5Ni2,5Cro, 5KO, iO x, Moi 3, 7 5 3 BiFe Co4,5Ni2,5Geo, 5KO, 80 x, Moi2BiFe 3 Co4,5Ni 2, 5Mno, 5KO , x and x
  • Suitable multimetal oxides and their preparation are further described in US 4,423,281 (Moi2BiNi 8 Pbo, 5 Cr 3 Ko, 20x and Moi2BibNi 7 Al 3 Cro, 5Ko, 50x), US 4,336,409 (Moi2BiNi 6 Cd2Cr 3 Po, 5 Ox), DE-A 26 00 128 (Moi2BiNi 0 , 5Cr 3 Po, 5 Mg7, 5 Ko, iOx + Si0 2 ) and DE-A 24 40 329 (Moi2BiCo4,5Ni 2 , 5Cr 3 Po, 5 Ko, iOx).
  • 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,
  • the molecular oxygen-containing gas generally contains more than 10% by volume, preferably more than 15% by volume and even 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.
  • the starting material gas can be mixed with oxygen or an oxygen-containing gas, for example air, and optionally additional inert gas or water vapor.
  • the resulting oxygen-containing gas mixture is then fed to the oxydehydrogenation.
  • the reaction temperature of the oxydehydrogenation is generally controlled by a heat exchange medium located around the reaction tubes.
  • liquid heat exchange agents come z. B. melting of salts 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.
  • the temperature of the heat exchange medium is between 220 to 490 ° C, 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 -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 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 reactor tubes accommodated in the tube bundle reactor is 15,000 to 30,000 or up to 40,000 or up to 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 1 may consist of a single layer or of 2 or more layers. These layers may be pure catalyst or diluted with a material that does not react with the source gas or components of the product gas of the reaction. Furthermore, the catalyst layers may consist of solid material 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.
  • водородн ⁇ онал ⁇ н ⁇ е как ⁇ онент As secondary components 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.
  • carbon monoxide carbon dioxide
  • inert gases mainly nitrogen
  • low-boiling hydrocarbons such as methane, ethane, ethene, propane and propene, butane and isobutane
  • hydrogen and optionally oxygen-containing hydrocarbons so-called oxygenates.
  • Oxygenates may be, for example, formaldehyde, furan, acetic acid, maleic anhydride, formic acid, methacrolein, methacrylic acid, crotonaldehyde, crotonic acid, propionic acid, acrylic acid, methyl vinyl ketone, styrene, benzaldehyde, benzoic acid, phthalic anhydride, fluorenone, anthraquinone and butyraldehyde.
  • the product gas stream 2 at the reactor exit is characterized by a temperature near the temperature at the end of the catalyst bed.
  • the product gas stream is then brought to a temperature of 150-400 ° C, preferably 160-300 ° C, more preferably 170-250 ° C. It is possible to isolate the line through which the product gas stream flows to keep the temperature in the desired range, or to use a heat exchanger. This heat exchanger system is arbitrary as long as the temperature of the product gas can be maintained at the desired level with this system.
  • heat exchangers As an example of a heat exchanger, spiral heat exchangers, plate heat exchangers, double-tube heat exchangers, multi-tube heat exchangers, boiler spiral heat exchangers, shell-shell heat exchangers, liquid-liquid Contact heat exchangers, air heat exchangers, direct contact heat exchangers and finned tube heat exchangers. Because, while the temperature of the product gas is adjusted to the desired temperature, a portion of the high-boiling by-products contained in the product gas may precipitate, therefore, the heat exchanger system should preferably have two or more heat exchangers.
  • the two or more 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.
  • aromatic hydrocarbon solvents such as. As toluene and xylenes, and alkaline aqueous solvents such.
  • alkaline aqueous solvents such as sodium hydroxide.
  • the cooling takes place according to the invention by contacting with an organic solvent.
  • This stage is also referred to below as quench.
  • This quench may consist of only one stage (3 in FIG. 1) or of several stages (for example 3, 7 in FIG. 1).
  • the product gas stream 2 is thus brought directly into contact with an organic solvent as the cooling medium 4 and thereby cooled.
  • the cooling medium used according to the invention are organic solvents, preferably aromatic hydrocarbons, particularly preferably toluene, o-xylene, m-xylene, p-xylene or mixtures thereof.
  • ie 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 2 depending on the presence and temperature level of a heat exchanger before the quench 3, a temperature of 100-440 ° C.
  • the product gas is in the 1.
  • Quench stage 3 brought into contact with the cooling medium of organic solvent.
  • the cooling medium can be introduced through a nozzle in order to achieve the most efficient possible mixing with the product gas.
  • internals such as, for example, additional nozzles, can be introduced into the quenching stage and pass through the product gas and the cooling medium together.
  • the coolant inlet into the quench is designed to minimize clogging due to deposits in the area of the coolant inlet.
  • the product gas 2 in the first quenching stage 3 is cooled to 5-180 ° C, preferably to 30-130 ° C and even more preferably to 60-1 10 ° C.
  • the temperature of the coolant telmediums 4 at the inlet may generally be 25-200 ° C, preferably 40-120 ° C, particularly preferably 50-90 ° C.
  • the pressure in the first quenching stage 3 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 3 is designed as a cooling tower.
  • the cooling medium 4 used in the cooling tower is often used circulating in a quench circulation.
  • 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 0.0001 -5 l / g, preferably 0.001-1 l / g and particularly preferably 0.002-0.2 l / g.
  • the temperature of the cooling medium 4 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, part of the loaded cooling medium can be withdrawn from the circulation as purge stream 4a and the circulating amount can be kept constant by adding unladen cooling medium 4b. 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.
  • an additional aqueous phase 5 may form, which may additionally contain water-soluble secondary components. This can then be withdrawn in the bottom of the quenching stage 3.
  • the aqueous phase can also be separated off in an additional phase separator. This can be, for example, within the quench circulation.
  • the aqueous phase may be withdrawn or at least partially recycled to the quench.
  • the cooling medium 4 can be withdrawn or at least partially returned to the quench.
  • the phase separator may be in the purge current 4a, for example.
  • the aqueous phase may be withdrawn or at least partially recycled to the quench.
  • the cooling medium 4 can be at least partially returned to the quench.
  • the aqueous fraction in the recirculation of the quench circulation can amount to several hundreds of vol. Ppm, possibly several vol.%, Or the quench circulation can to a large extent consist of the aqueous phase.
  • the cooled and possibly depleted in secondary components product gas stream 6 can now be fed to a second quenching stage 7.
  • a cooling medium 8 in contact.
  • organic solvents preferably aromatic hydrocarbon solvents, particularly preferably toluene, o-xylene, m-xylene, p-xylene and mixtures thereof, are used as the cooling medium 8.
  • the product gas is cooled to 5 to 100 ° C, preferably 15-85 ° C and even more preferably 30 to 70 ° C, to the gas outlet of the second quenching stage 7.
  • the coolant can be supplied in countercurrent to the product gas.
  • the temperature of the coolant medium 8 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 7 is not particularly limited, but is generally 0.01 to 4 bar (g), preferably 0.1 to 2 bar (g) and particularly preferably 0.2 to 1 bar (g).
  • the second quenching stage 7 is preferably designed as a cooling tower.
  • the cooling medium 8 used in the cooling tower is frequently used circulating in a quench circulation.
  • the recycle stream of the cooling medium 8 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 more preferably 0.002-0.2 l / g ,
  • condensation of water may occur in the second quenching stage 7.
  • an additional aqueous phase 9 may form, which may additionally contain water-soluble secondary components. This can then be withdrawn in the bottom of the quenching stage 7.
  • the aqueous phase can also be separated off in an additional phase separator. This can be, for example, within the quench circulation.
  • the aqueous phase may be withdrawn or at least partially recycled to the quench.
  • the cooling medium 8 can be at least partially returned to the quench. In this case, the aqueous content in the recirculation of the quench circulation is low.
  • the phase separator can be located, for example, in the purge stream 8a.
  • the aqueous phase may be withdrawn or at least partially recycled to the quench.
  • the cooling medium 8 can be at least partially returned to the quench.
  • the aqueous fraction in the recirculation of Quenchumlaufs several hundred vol.-ppm, possibly several vol .-% or the quench circulation can to a large extent from the
  • the temperature of the cooling medium 8 in the bottom can generally be 20-210 ° C., preferably 35-120 ° C., particularly preferably 45-85 ° C. Since the loading of the cooling medium 8 with secondary components increases over time, part of the loaded cooling medium can be withdrawn from the circulation as purge stream 8a, and the circulating amount can be kept constant by adding unladen cooling medium 8b.
  • internals in the second quenching stage 8 may be present.
  • Such internals include, for example bell, centrifugal and / or sieve plates, columns with structured packings, such as sheet metal Packages 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 8a can be supplied to the current 4b or replace it.
  • the desired temperature of the circulating streams can be adjusted by means of suitable heat exchangers.
  • the cooling stage Ca) is carried out in two stages, wherein the solvent of the second stage Ca2) loaded with secondary components is passed into the first stage Ca1).
  • the solvent removed from the second stage Ca2) contains less secondary components than the solvent removed from the first stage Ca1).
  • suitable structural measures such as the installation of a demister, can be taken.
  • high-boiling substances which are not separated from the product gas in the quench, can be removed from the product gas by further structural measures, such as further gas scrubbing.
  • a gas stream 10 is obtained in which 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 of the solvent used in the quench. Furthermore, 10 traces of high-boiling components can remain in this gas stream, which were not quantitatively separated in the quench.
  • the gas stream b from the cooling step Ca which is depleted in high-boiling secondary components, is cooled in step Cb) in at least one compression stage Cba) and preferably in at least one cooling stage Cbb) by contacting with an organic solvent as the cooling agent.
  • the product gas stream 10 from the solvent quench is compressed in at least one compression stage 11 and subsequently further cooled in the cooling apparatus 13, wherein at least one condensate stream 15 containing water is formed. Furthermore, the solvent used in the solvent quench condenses, forming a separate phase 14. There remains a Gasstrom16 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 10 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 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 (aqueous phase 15) and the solvent used in the quench (organic phase 14). 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 14 can be cooled in a heat exchanger and recycled as a coolant into the apparatus 13. Since the loading of this cooling medium 14 with secondary components increases over time, a portion of the loaded cooling medium can be withdrawn from the circulation (14a) and the circulating amount of the cooling medium by adding unladen solvent (14b) are kept constant.
  • the solvent 14b which is added as a cooling medium, thus also preferably consists of the aromatic hydrocarbon solvent used as quench solvent.
  • the condensate stream 14a can be returned to the circulating stream 4b and / or 8b of the quench. As a result, the C4 components absorbed in the condensate stream 14a 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 is carried out with organic solvent purged heat exchangers or organic quench, which may be designed, 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 minor components containing gas stream 16 is supplied as output stream of further treatment.
  • 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 17 as gas stream 19 from the process gas stream 16 by absorption of C4 Hydrocarbons in a high-boiling absorbent (28 and / or 30) and subsequent desorption of the C4 hydrocarbons separated.
  • step D as shown in FIG.
  • the gas stream 16 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 19 containing the remaining gas constituents.
  • the C4 hydrocarbons are released from the high-boiling absorbent again.
  • the absorption stage can be carried out in any suitable absorption column known to the person skilled in the art.
  • the absorption can be carried out 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 bottom, columns with structured packings, eg sheet metal packings with a specific surface area of 100 to 1000 m 2 / m 3 as Mellapak® 250 Y, and packed columns.
  • Suitable absorbents are relatively nonpolar organic solvents, for example aliphatic Cs to Cis alkanes, or aromatic hydrocarbons, such as the paraffin-derived middle oil fractions, toluene or bulky groups, or mixtures of these solvents, such as 1,2-dimethyl phthalate may be added.
  • Suitable absorbers 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 mixed from biphenyl and diphenyl ether, preferably in the azeotropic composition, for example the commercially available Diphyl ® . Often, this solvent mixture contains di-methyl phthalate in an amount of 0.1 to 25 wt .-%. In a preferred embodiment in the absorption stage Da), the same solvent as in the cooling stage Ca) is used.
  • Preferred absorbents are solvents which have a solubility for organic peroxides of at least 1000 ppm (mg active oxygen / kg solvent).
  • toluene is used as the absorption solvent
  • an offgas stream 19 is withdrawn which comprises essentially oxygen, low-boiling hydrocarbons (methane, ethane, ethene, propane, propene), optionally C 4 -hydrocarbons (butane, butenes, butadiene), optionally inert gases, if appropriate carbon oxides and optionally still contains water vapor.
  • This stream can be partially fed to the ODH reactor.
  • the inlet flow of the ODH reactor can be adjusted to the desired C4 hydrocarbon content.
  • step Db) can be carried out in any suitable column known to the person skilled in the art.
  • the stripping can be carried out by simply passing non-condensable gases, preferably inert gases such as nitrogen, through the loaded absorption solution. With stripped C4 hydrocarbons are washed in the upper part of the absorption column 17 back into the absorption solution by the gas stream is passed back into this absorption column.
  • Suitable Stippkolonnen are z. B. tray columns with bell, centrifugal and / or sieve tray, columns with structured packings, z. B. Sheet metal packings with a specific surface area of 100 to 1000 m 2 / m 3 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 20 contains water. This is separated in a decanter 21 as stream 22 from the absorbent, so that a stream 23 is obtained, which contains only the redeemed water in the absorbent.
  • the laden with C4 hydrocarbons, largely freed from water absorbent stream 23 can be heated in a heat exchanger and then passed as stream 24 in a desorption column 25.
  • 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 25.
  • the absorbent 27 regenerated in the desorption stage can be cooled in a heat exchanger and recycled as stream 28 into the absorption stage 17.
  • low boilers 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 stream 29 can be deducted. This can be used alone or combined with the streams 14a and / or 8b and / or 4b in a distillation column 35 (FIG.
  • the C4 product gas stream 31 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.
  • the liquid (stream 32) or gaseous (stream 33) C4 product streams leaving the condenser are then removed by extractive distillation in step E) with a solvent selective for butadiene into a butadiene and the material stream containing the selective solvent and an Buteneene containing stream 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 is contacted with an extractant, preferably an N-methylpyrrolidone (NMP) / water mixture, in an extraction zone.
  • NMP N-methylpyrrolidone
  • the extraction zone is generally carried out in the form of a wash column which contains soils, fillers or particles. contained as internals. This generally has 30 to 70 theoretical plates, so that a sufficiently good release effect is achieved.
  • the wash column has a backwash zone in the column head.
  • This backwash zone serves to recover the extractant contained in the gas phase by means of a liquid hydrocarbon recirculation, for which purpose the overhead fraction is condensed beforehand.
  • the mass ratio 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 of 100 to 250 ° C, in particular at a temperature in the range of 1 10 to 210 ° C, a head temperature in the range of 10 to 100 ° C, in particular in the range of 20 to 70 ° C and a pressure in the range of 1 to 15 bar, in particular operated in the range of 3 to 8 bar.
  • the extractive distillation column preferably has from 5 to 70 theoretical plates.
  • Suitable extractants are butyrolactone, nitriles such as acetonitrile, propionitrile, methoxypropionitrile, ketones such as acetone, furfural, N-alkyl-substituted lower aliphatic acid amides such as dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, N-formylmorpholine, N-alkyl-substituted cyclic acid amides (lactams) such as N Alkylpyrrolidones, especially N-methylpyrrolidone (NMP).
  • NMP N-methylpyrrolidone
  • alkyl-substituted lower aliphatic acid amides or N-alkyl substituted cyclic acid amides are used.
  • Particularly advantageous are dimethylformamide, acetonitrile, furfural and in particular NMP.
  • mixtures of these extractants with 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-butene can be supplied 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.
  • 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 extracted is transferred to a desorption zone, wherein the butadiene is desorbed again from the extraction solution and backwashed.
  • the desorption zone can be embodied, for example, in the form of a wash column which has 2 to 30, preferably 5 to 20 theoretical stages and optionally a backwashing zone with, for example, 4 theoretical stages.
  • This backwash zone serves to recover the extractant contained in the gas phase by means of a liquid hydrocarbon reflux, for which purpose 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 top temperature in the range of 0 to 70 ° C, in particular in the range of 10 to 50 ° C.
  • the pressure in the distillation column is preferably in the range of 1 to 10 bar. In general, a reduced pressure and / or elevated temperature prevails in the desorption zone relative to 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.
  • the example describes the use of toluene phases in both the quench and compression steps as well as in the C4 absorption.
  • an excellent redemption of a number of high-boiling secondary components is already effected in the quench and deposits are prevented behind the quench.
  • the recycle of the purge streams of the second quench, the intercooler of the compressor, and the C4 absorption / desorption into the recycle streams upstream of the process minimizes the loss of C4 hydrocarbons dissolved in the discharged toluene.
  • a process gas 2 with a temperature of 210 ° C, a pressure of 1, 3 bar and the composition shown in Table 1 is provided.
  • This gas stream is cooled in the quench part 3 with a toluene circulation stream having a temperature of 35 ° C and a composition as shown in Table 1 in stream 4 to a temperature of 60 ° C.
  • a number of secondary components are dissolved out of the gas stream, and the composition of the process gas stream changes to the concentrations shown for stream 6.
  • the mass ratio of the cycle stream 4 to the process gas 2 and the purge stream 4a is 1 to 0.2 to 0.0033.
  • the stream 4b consists, on the one hand, of the purge streams 8a (2nd quench stage) and, on the other hand, of a make-up stream of fresh toluene.
  • the gas stream 6 is further cooled in the second quenching stage 7 with a further toluene circulation stream 8, which enters the quench at 35 ° C at the head end, further to 40 ° C.
  • the resulting gas stream 10 has the composition shown in Table 1, while the mass ratio between stream 6 and 8 is 1 to 5.6 and a purge stream 8a is withdrawn from stream 8 at a rate of 2% and passed into the first quench section.
  • the stream 8b consists of 0.2% of the purge stream 29 of the C4 absorption to 51, 6% from the streams 14a, 14a ', 14a "and 14a'" (purge of the heat exchanger behind the compressor stages 1 to 4) and to 48.2% from fresh toluene.
  • the gas stream 10 is compressed to 10 bar absolute in a 4-stage compressor with drawn as in Figure 1 intercoolers.
  • the purge streams 14a, 14a ', 14a "and 14a'" are all fed to stream 8b.
  • the resulting gas flow 16 "' (output flow of the heat exchanger 13"' behind the 4th compression stage) has a temperature of 35 ° C and the composition shown in Table 1.
  • This stream is separated in the absorber column 17 by the countercurrent and the column with 10 bar absolute and 35 ° C at the top of the column entering absorbent stream 28 into a gas stream 19 and a mainly loaded with C4 hydrocarbons absorbent stream.
  • the laden absorbent stream is freed from oxygen by a stream 18 consisting of nitrogen at a temperature of 35 ° C so far that the gas stream 33 leaving the desorber column has only 10 ppm oxygen.
  • the mass ratio between stream 16 "'and 28 is 1 to 2.48, and the mass ratio between 28 and 18 is 1 to 0.006.
  • a stream 22, mainly water, is withdrawn, accounting for 0.002% of the stream 20 and the exact composition of which is shown in Table 2.
  • the resulting stream 23 is heated to 120 ° C and passed as stream 24 to the desorber column 25 at a top pressure of 5.5 bar absolute
  • the mass flow ratio between stream 26 at a temperature of 175 ° C and stream 27 is 1 to 100.
  • the mass flow ratio between the overhead streams 31 and 34 is 1 to 0.56 and the product stream 33 has the composition shown in Table 2 and is passed on to the above-described extractive distillation.
  • the current 32 does not occur in this example.
  • Acetic acid 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
  • the example describes the use of mesitylene in the quenching step.
  • mesitylene in the quenching step.
  • a process gas 2 having a temperature of 190 ° C., a pressure of 1.3 bar and the composition shown in Table 3 is provided.
  • This gas stream is cooled down in the quench part 3 with a mesitylene / water circulation stream 4 having a phase ratio of 8: 1 (mesitylene: water) at a temperature of 35 ° C. to a temperature of 71 ° C.
  • a number of secondary components are dissolved out of the gas stream and the composition of the process gas stream changes to the concentrations shown for stream 6.
  • the mass ratio of the circulation stream 4 to the process gas 2 and the purge current 4a is 1 to 0.1 to 0.01.
  • the current 4b consists on the one hand of the purge current 8a (2nd quenching stage) and on the other hand of a make-up stream of fresh mesitylene / water with a phase ratio of 5: 2 (mesitylene: water).
  • the gas stream 6 is in the second quenching stage 7 with a further mesitylene circulation stream 8 which enters the quench at 35 ° C at the head end, further cooled to 54 ° C.
  • the resulting gas stream 10 shows the depletion of minor components shown in Table 4, while the mass ratio between stream 6 and 8 is 1 to 3.8, and a purge stream 8a at 4.25% is withdrawn from stream 8 and passed into the first quench section becomes.
  • the stream 8b consists of 100% fresh mesitylene.

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Abstract

L'invention concerne un procédé de préparation de butadiène à partir de n-butènes, comportant les étapes suivantes : A) obtention d'un courant de gaz de réaction a contenant des n-butènes ; B) amenée du courant de gaz de réaction a contenant les n-butènes et d'un gaz contenant de l'oxygène dans au moins une zone de déshydrogénation oxydative, et déshydrogénation oxydative des n-butènes en butadiène, un courant de gaz 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 auxiliaires à haut point d'ébullition, le cas échéant des oxydes de carbone et le cas échéant des gaz inertes étant obtenu ; Ca) refroidissement du courant de gaz produit b par mise en contact avec un solvant organique comme moyen de refroidissement, Cb) compression du courant de gaz produit b dans au moins un étage de compression, au moins un flux de condensat aqueux c1 et un courant de gaz 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 étant obtenus ; D) séparation de composants gazeux non condensables et à bas point d'ébullition, comprenant l'oxygène, les hydrocarbures à bas point d'ébullition, le cas échéant les oxydes de carbone et le cas échéant les gaz inertes, comme courant de gaz d2 depuis le courant de gaz c2 par absorption des hydrocarbures en C4, comprenant le butadiène et les n-butènes, dans un moyen d'absorption, un flux de moyen d'absorption chargé d'hydrocarbures en C4 et le courant de gaz d2 étant obtenus, suivie de la désorption des hydrocarbures en C4 depuis le flux de moyen d'absorption chargé, un courant de gaz produit en C4 d1 étant obtenu ; E) séparation du courant de produit en C4 d1 par distillation extractive avec un solvant sélectif pour le butadiène en un flux de matière e1 contenant le butadiène et le solvant sélectif et un flux de matière e2 contenant les n-butènes ; F) distillation du flux de matière e1 contenant le butadiène et le solvant sélectif en un flux de matière f1 consistant essentiellement en le solvant sélectif et en un flux de matière f2 contenant le butadiène.
EP14700500.3A 2013-01-15 2014-01-15 Procédé de préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydative Withdrawn EP2945922A1 (fr)

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PCT/EP2014/050675 WO2014111409A1 (fr) 2013-01-15 2014-01-15 Procédé de préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydative

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EP2945921B1 (fr) * 2013-01-16 2017-03-22 Basf Se Procédé de préparation de butadiène par déshydrogénation oxydative de n-butènes, avec surveillance de la teneur en peroxyde lors de l'élaboration du produit
JP2017524011A (ja) * 2014-08-12 2017-08-24 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 酸化的脱水素反応によりｎ−ブテン類から１，３−ブタジエンを製造するための方法
JP6608916B2 (ja) * 2014-09-26 2019-11-20 ビーエーエスエフ ソシエタス・ヨーロピア 酸化的脱水素化によりｎ−ブテン類から１，３−ブタジエンを製造するための方法
WO2016071268A1 (fr) * 2014-11-03 2016-05-12 Basf Se Procédé de préparation de 1,3-butadiène à partir de n-butènes par déshydrogénation oxydative
CN107667084A (zh) * 2015-03-26 2018-02-06 巴斯夫欧洲公司 由正丁烯通过氧化脱氢生产1,3‑丁二烯
EA201792147A1 (ru) * 2015-03-26 2018-05-31 Басф Се Способ получения 1,3-бутадиена из н-бутенов путем окислительного дегидрирования
KR102061238B1 (ko) 2015-11-11 2019-12-31 주식회사 엘지화학 공액디엔 제조장치 및 제조방법
KR102070309B1 (ko) * 2015-11-13 2020-01-28 주식회사 엘지화학 공액디엔 제조장치 및 제조방법
KR102061237B1 (ko) 2015-11-30 2019-12-31 주식회사 엘지화학 공액디엔 제조장치 및 제조방법
EP3402769B1 (fr) * 2016-01-13 2020-03-25 Basf Se Procede de fabrication de 1,3-butadiene a partir de n-butenes par deshydratation oxydante
CN108884003A (zh) * 2016-02-04 2018-11-23 巴斯夫欧洲公司 通过氧化脱氢由n-丁烯制备1,3-丁二烯的方法
KR102200814B1 (ko) * 2016-12-29 2021-01-11 주식회사 엘지화학 부타디엔 제조방법
KR102064316B1 (ko) * 2016-12-29 2020-01-09 주식회사 엘지화학 부타디엔 제조방법
KR102246175B1 (ko) * 2016-12-29 2021-04-29 주식회사 엘지화학 부타디엔 제조방법
KR102246184B1 (ko) * 2016-12-29 2021-04-29 주식회사 엘지화학 부타디엔 제조방법
KR102061242B1 (ko) * 2016-12-29 2019-12-31 주식회사 엘지화학 부타디엔 제조방법
KR102246185B1 (ko) * 2016-12-29 2021-04-29 주식회사 엘지화학 부타디엔 제조방법
JP7196155B2 (ja) * 2018-03-06 2022-12-26 株式会社Ｅｎｅｏｓマテリアル １，３－ブタジエンの製造方法

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