EP3083529A1 - Production de butadiène par déshydrogénation oxydative de n-butène après isomérisation préalable - Google Patents

Production de butadiène par déshydrogénation oxydative de n-butène après isomérisation préalable

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Publication number
EP3083529A1
EP3083529A1 EP14806313.4A EP14806313A EP3083529A1 EP 3083529 A1 EP3083529 A1 EP 3083529A1 EP 14806313 A EP14806313 A EP 14806313A EP 3083529 A1 EP3083529 A1 EP 3083529A1
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European Patent Office
Prior art keywords
butene
isomerization
mixture
catalyst
zone
Prior art date
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EP14806313.4A
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German (de)
English (en)
Inventor
Felix GÄRTNER
Guido Stochniol
Jörg SCHALLENBERG
Horst-Werner Zanthoff
Oliver Markus Busch
Stephan Peitz
Frank GEILEN
Arne Reinsdorf
Natalya Prodan
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Evonik Operations GmbH
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Evonik Degussa GmbH
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Publication of EP3083529A1 publication Critical patent/EP3083529A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8876—Arsenic, antimony or bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/08—Alkenes with four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/12—Alkadienes
    • C07C11/16—Alkadienes with four carbon atoms
    • C07C11/167—1, 3-Butadiene
    • 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
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
    • C07C5/25—Migration of carbon-to-carbon double bonds
    • C07C5/2506—Catalytic processes
    • C07C5/2512—Catalytic processes with metal oxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/10—Magnesium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/12—Silica and alumina
    • 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
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/18—Arsenic, antimony or bismuth
    • 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
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/28—Molybdenum
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention relates to a process for the preparation of 1,3-butadiene by heterogeneously catalyzed oxidative dehydrogenation of n-butene, in which a butene mixture containing at least 2-butene is provided.
  • 1,3-butadiene (CAS No. 106-99-0) is an important basic chemical of the chemical industry. It represents the starting component in important polymers with a variety of applications, including in the automotive industry.
  • 1,3-butadiene In addition to the 1,3-butadiene still exists the 1,2-butadiene, which, however, due to its low industrial importance hardly considered. As far as “butadiene” or “BD” is mentioned here, 1,3-butadiene is always meant.
  • C 4 streams are mixtures of different hydrocarbons with four carbon atoms which are produced in petroleum crackers as co-product in the production of ethylene and propylene.
  • the butenes include the four isomeric substances 1-butene, cis-2-butene, trans-2-butene and isobutene.
  • 1-Butene and the two 2-butenes belong to the group of linear butenes, while isobutene is a branched olefin.
  • the linear C 4 olefins 1-butene, cis-2-butene and trans-2-butene are also summarized as "n-butene”.
  • FCC fluid catalytic cracker
  • the butenes are not obtained pure but as a so-called "C 4 cut .”
  • alkanes saturated C 4 -hydrocarbons
  • Hydrocarbons containing more or less than four carbon atoms for example, but not limited to propane and / or pentenes
  • An alternative source of butenes are, for example, chemical processes such as the dehydrogenation of butane, ethylene dimerization, metathesis, the methanol to olefin technology, Fischer Tropsch, as well as the fermentative or pyrolytic conversion of renewable resources.
  • butadiene-containing C 4 streams are scarce, the production of butadiene by oxidative dehydrogenation from butenes is currently being investigated more intensively.
  • WO2006075025 or WO2004007408A1 describes a process which couples an autothermally catalyzed, nonoxidative dehydrogenation of butane to butene with an oxidative dehydrogenation of the butenes produced to give butadiene.
  • This opens a direct route for the production of butadiene from butane, which is technically except for the production of Maleic anhydride is little used in chemical transformations.
  • Disadvantages of this method are large recycling streams through the recycling of butane, which increase the equipment and operating costs.
  • butadiene from n-butene mixtures, which in addition to 1-butene also contain a high proportion of 2-butene.
  • a disadvantage of this process is that the two 2-butenes are less reactive than the 1-butene and therefore the residence time of the n-butenes in the double fixed bed is unnecessarily long: Here, the slower reaction determines the duration of the process. The higher the proportion of 2-butene compared to 1-butene, the more negative this effect has. Therefore, the process is set to a limited 1-butene to 2-butene ratio to achieve sufficiently high n-butene conversions. Insofar as variable sources of raw materials supply butene mixtures with a variable ratio of 1-butene to 2-butene, losses in the yield of butadiene must be accepted according to this method.
  • the invention is based on the object of specifying a process for the economic production of 1,3-butadiene on a large industrial scale, which is provided as a raw material, a butene mixture whose content of 1-butene compared to its 2- Butene content is rather low, in which the ratio of 1-butene to 2-butene is subject to fluctuations and in which the absolute contents of 1-butene and 2-butene change over time.
  • a difficult raw material butadiene is to be produced in high yield.
  • This object is achieved by a two-stage process in which in a first stage the butene mixture is subjected to a heterogeneously catalyzed isomerization to obtain an at least partially isomerized butene mixture, and then in a second stage, the at least partially isomerized obtained in the first stage Butene mixture is subjected to oxidative dehydrogenation.
  • the invention therefore provides a process for the preparation of 1,3-butadiene by heterogeneously catalyzed oxidative dehydrogenation of n-butene, in which a butene mixture containing at least 2-butene is provided, in which the butene mixture provided to obtain an at least partially isomerized butene mixture subjected to heterogeneously catalyzed isomerization, and in which then the at least partially isomerized butene mixture is subjected to oxidative dehydrogenation.
  • a basic idea of the present invention consists first of all in improving the overall process of butadiene production by replacing the comparatively less reactive 2-butenes with significantly more reactive 1-butene.
  • thermodynamic equilibrium of 1-butene and 2-butene It can be enough, too
  • An embodiment of the invention accordingly provides that the isomerization takes place in such a way that 2-butene containing butene mixture is isomerized to 1-butene in the butene mixture provided, so that the content of 1-butene in the at least partially isomerized butene mixture is increased compared to the butene mixture provided.
  • the isomerization takes place in such a way that the butene mixture containing 1-butene is isomerized to 2-butene, so that the content of 1-butene in the at least partially isomerized butene mixture is lowered compared to the provided butene mixture.
  • the at least partially isomerized butene mixture obtained from the isomerization becomes
  • the higher butadiene yield is also realized by the choice of a catalyst optimized for the respective reaction stage. Accordingly, an isomerization catalyst is provided for the first reaction stage (isomerization) during which oxidative dehydrogenation (second stage) occurs in the presence of a specific dehydrogenation catalyst.
  • Catalysts will usually result in non-identical catalysts being used for isomerization and for oxidative dehydrogenation. Accordingly, a preferred embodiment of the invention provides that the isomerization catalyst and the dehydrogenation catalyst are not identical. As isomerization catalysts are in principle all catalysts in question, which the
  • Double bond isomerization of 2-butene to 1-butene catalyze In general, the mixed oxide compositions containing aluminum oxides, silicon oxides, and mixtures and
  • the said catalytically active materials may additionally be modified by oxides of the elements Mg, Ca, Sr, Na, Li, K, Ba, La, Zr, Sc and also oxides of the manganese, iron and cobalt group.
  • the content of the metal oxide based on the total catalyst is 0.1 to 40 wt .-%, preferably 0.5 to 25 wt .-%.
  • Suitable isomerization catalysts are disclosed inter alia in DE3319171, DE3319099, US4289919, US3479415, EP234498, EP129899, US3475511, US4749819, US4992613, US4499326, US4217244, WO03076371 and WO02096843.
  • the isomerization catalyst comprises at least two different components, wherein the two components are mixed together or wherein the first component is applied to the second component.
  • the first component is the substantially catalytically active substance, during which the second component acts as a carrier material.
  • the carrier of a classical supported catalyst is also catalytically active. For this reason, in this context, regardless of any catalytic activity of a first component and a second
  • Particularly suitable isomerization catalysts have proven to be two-component systems which contain an alkaline-earth metal oxide on an acidic alumina support or on a mixture of Al 2 O 3 and SiO 2 .
  • Total catalyst is 0.5 to 30 wt .-%, preferably 0.5 to 20 wt .-%.
  • the alkaline earth metal oxide used can be magnesium oxide and / or calcium oxide and / or strontium oxide and / or barium oxide.
  • alumina or silica or a mixture of alumina and silica or aluminosilicate is used as a second component (that is, as "carrier").
  • a catalyst suitable for isomerization based on MgO and aluminosilicate is described in EP1894621B1.
  • Catalyst weight Alternatively, a heterogeneous catalyst can be used in which
  • Magnesium oxide is mixed as the first component with an aluminosilicate as a second component.
  • Such catalysts are disclosed in EP1894621A1.
  • catalysts which are suitable for the oxidative dehydrogenation of n-butene to butadiene can be used as catalysts for the oxidative dehydrogenation.
  • two catalyst classes come into consideration, namely mixed metal oxides from the group of (modified) bismuth Molybdate, and mixed metal oxides from the group of (modified) ferrites.
  • Very particular preference is given to using catalysts from the group of the bismuth molybdates, since these 1-butene react faster in the oxidative dehydrogenation to butadiene than 2-butene. In this way, comes by a previously carried out isomerization of 2-butene to 1-butene
  • Bismuth molybdates are catalysts according to formula (I),
  • D at least one of the elements from W, P,
  • E at least one of Li, K, Na, b, Cs, Mg, Ca, Ba, Sr,
  • F at least one of the elements of Cr, Ce, Mn, V,
  • G at least one of Nb, Se, Te, Sm, Gd, La, Y, Pd, Pt, Ru, Ag, Au
  • H at least one of Si, Al, Ti, Zr and the coefficients a to i represent rational numbers, those from the following, the
  • i 0 to 800 and x represents a number determined by the valence and frequency of elements other than oxygen.
  • Such catalysts are obtained, for example, by the production steps of co-precipitation, spray-drying, and calcination.
  • the powder thus obtained may be subjected to shaping, for example by tabletting, extrusion or coating of a carrier.
  • Such catalysts are described in US8003840, US8008227, US2011034326 and US7579501.
  • traces of coke deposits, isobutene, isobutane and butadiene may be formed during isomerization.
  • traces of saturated and unsaturated Ci- to C 3 -products, as well as higher-boiling saturated and unsaturated compounds, in particular Cg compounds, as well as coke and coke-like compounds can also be formed.
  • the deposition of coke on the isomerization catalyst causes its continuous deactivation.
  • the activity of the isomerization catalyst can be largely restored by regeneration, for example by burning the
  • Dehydration catalyst is possible by oxidation with an oxygen-containing gas.
  • the oxygen-containing gas can be air, technical oxygen, pure oxygen or oxygen-enriched air.
  • dehydrogenation catalysts deactivate much slower than isomerization catalysts.
  • isomerization catalysts have to be reactivated quite frequently.
  • the isomerization in an isomerization arrangement can be carried out continuously as follows: a) the isomerization arrangement comprises a reaction zone and a regeneration zone; b) the isomerization takes place within the reaction zone of the isomerization arrangement in FIG
  • Requires reaction zone which must be accomplished with a suitable funding. This increases the susceptibility of the system.
  • the isomerization arrangement comprises two universal zones, each optionally as
  • Reaction zone or can be used as a regeneration zone; b) one of the two universal zones is used as a reaction zone for isomerization,
  • both universal zones are used in parallel as reaction zones. Then one of the two universal zones is used as a regeneration zone, while the other universal zone continues to be used as a reaction zone. When the catalyst is fully reactivated in the regeneration zone, the other universal zone is placed in regeneration mode. Then both zones are used again as reaction zones. With this concept, regeneration is naturally started with a lower degree of deactivation than with the concept of cyclic exchange. Advantage of this method is the cost-saving continuous use of the entire space of both
  • the process is operated practically in one stage, the regeneration takes place in the single universal zone of the isomerization arrangement. Due to the isomerization during regeneration, losses in the yield of butadiene are to be accepted.
  • the regeneration is carried out in times in which the fluctuating with respect to its composition butene mixture has a favorable ODH for the 1-butene / 2-butene ratio.
  • the dehydrogenation catalyst can be reactivated in the same manner as described above for the isomerization catalyst. However, this will not be necessary since
  • Dehydrogenation catalysts are much slower to deactivate than isomerization catalysts. For this reason, after deactivation of the dehydrogenation catalyst, the system is simply shut down and the dehydrogenation catalyst regenerated or replaced in situ.
  • the butadiene to be produced is in a product mixture which consists of the oxidative
  • the product mixture contains in addition to the target product butadiene unreacted components of the butene mixture and unwanted by-products of oxidative dehydrogenation.
  • the product mixture contains butane, nitrogen, residues of oxygen, carbon monoxide, carbon dioxide, water (steam) and unreacted butene.
  • the product mixture may contain traces of saturated and unsaturated hydrocarbons, aldehydes and acids.
  • the product mixture is subjected to a butadiene separation, in the course of which 1,3-butadiene is separated from the other constituents of the product mixture.
  • the product mixture is preferably first cooled and with water in a
  • the butadiene separation is not limited to the process variant described here. Alternative isolation methods are described in Ullmann in the article cited above.
  • a preferred embodiment of the invention then provides that a portion of the product mixture is recycled and mixed with the provided butene mixture and / or the at least partially isomerized butene mixture. In this way, previously unreacted recyclables can again be subjected to isomerization and / or ODH.
  • a C 4 hydrocarbon stream obtained from the butadiene separation is recycled prior to isomerization and / or oxidative dehydrogenation to convert the butene unreacted in the first pass to butadiene.
  • the reaction conditions for the isomerization and / or the oxidative dehydrogenation are preferably at the following values:
  • temperature in this context is meant the temperature which is set at the reactor apparatus.
  • the actual reaction temperature may differ.
  • the reaction temperature ie the temperature measured on the catalyst, will also move within the ranges indicated.
  • both reactions take place at similar temperatures and pressures, because in this way energy-intensive intermediate compression or expansion or heating or cooling of the at least partially isomerized butene mixture can be dispensed with.
  • An energy-intensive purification between the two stages is also not required.
  • the use of a strontium-containing alumina-based catalyst for isomerization and a bismuth-molybdate-containing catalyst as a dehydrogenation catalyst allows the energy-saving implementation of both reaction steps under similar operating conditions.
  • the oxidative dehydrogenation is preferably carried out in the presence of an inert gas such as nitrogen and / or water vapor.
  • an inert gas such as nitrogen and / or water vapor.
  • a preferred embodiment of the invention provides that Water vapor and also the oxygen required for the oxidative dehydrogenation are metered after the isomerization and, accordingly, the material stream is fed downstream after the isomerization. In this way, the material flow through the isomerization becomes smaller, which reduces the associated with the reactor volume equipment costs.
  • the proportion of the water vapor in the mixture fed to the dehydrogenation is preferably from 1 to 30 molar equivalents, based on the sum of 1-butene and 2-butene, preferably from 1 to 10 molar equivalents, based on the sum of 1-butene and 2-butene.
  • the oxygen content in the mixture fed to the dehydrogenation is preferably 0.5 to 3 molar equivalents, based on the sum of 1-butene and 2-butene, preferably 0.8 to 2 molar equivalents, based on the sum of 1-butene and 2-butene.
  • the sum of all proportions of the various substances in% by volume results in a total proportion of 100% by volume.
  • the process according to the invention is particularly suitable for processing feed mixtures which contain a small proportion of 1-butene. Any streams containing 2-butene as the recoverable substrate can be used.
  • the butene mixture is preferably provided in gaseous form.
  • C 4 hydrocarbon streams of any type which contain no hydrocarbons having more or fewer than four carbon atoms in proportions of more than 10% by weight are suitable as feed mixtures.
  • butene-containing streams are provided as feed mixture in which the 1-butene concentration is below the thermodynamically given at the temperature in the isomerization equilibrium concentration of 1-butene based on n-butene.
  • the butene mixture provided has a content of butane between 0 and 90 wt .-%, while the content of n-butene is between 5 and 100 wt .-%. It is particularly preferred to use material streams in which the concentration of 2-butene is between 5 and 100% by weight.
  • alkanes and alkenes may be included. This applies in particular to isobutene, isobutane, propane, propene, neopentane, neopentene and butadiene.
  • the provided butene mixture may also contain other minor components, such as oxygen-containing components such as steam, water, acids or aldehydes and sulfur-containing components, such as.
  • oxygen-containing components such as steam, water, acids or aldehydes
  • sulfur-containing components such as.
  • nitrogen-containing components such as nitriles or amines.
  • the butene mixture provided has the following specification: a) the weight fraction of hydrocarbons having four carbon atoms is at least 90% relative to the total butene mixture provided; b) the proportion by weight of n-butane and isobutane in the sum based on the total supplied butene mixture 0 to 90%; c) the proportion by weight of isobutene, 1-butene, cis-2-butene and trans-2-butene is in the
  • the butene content of the butene mixture provided is 5 to 100%.
  • the percentages described here always complement each other to 100%.
  • butene blends are provided as a raw material having a varying content of 1-butene and 2-butene over time.
  • Such butene blends are quite inexpensive due to their problematic usability. Since the process according to the invention achieves a high butadiene yield even with a variable 1-butene / 2-butene ratio, its added value is such
  • Raw material sources especially large. It is also possible to use mixtures in which not only the isomer ratio, but also the absolute content of 1-butene and 2-butene fluctuates.
  • Raffinate III in this context means a C 4 -hydrocarbon stream which originates from a naphtha cracker and from which butadiene, isobutene and 1-butene have already been separated off III contains as olefinic value product almost exclusively 2-butene, which can be converted by means of the present method into higher-value 1,3-butadiene.
  • feed stream butene mixtures which are oxidative or
  • butane mixtures for example, Liquefied Petroleum Gas (LPG) is considered.
  • LPG Liquefied Petroleum Gas
  • butene-containing streams can be used as feed mixture, which are produced by fluid catalytic cracking (FCC) of petroleum fractions.
  • FCC fluid catalytic cracking
  • Such streams increasingly displace cracker C4 derived from naphtha crackers but hardly contain 1,3-butadiene.
  • the present process is therefore suitable for producing butadiene from FCC C4.
  • the butene mixtures used can also originate from C 2 dimerization reactions such as ethylene dimerization.
  • such butene-containing streams can be used, which are prepared by dehydration of 1-butanol or 2-butanol.
  • the provided butene mixture may also be a mixture of the above-described C 4 sources.
  • the supplied butene mixture can also be fed with a ezyclate from downstream process steps, in particular a part of butadiene-free product mixture. But it can also material flows immediately behind the
  • Depletion may be absorptive, adsorptive or via membrane separation.
  • An example of absorptive separation is butadiene extraction, whose C 4 -containing effluent is called "raffinate I.”
  • Another adsorbent process whose effluent can be used as an input mixture is the BUTENEX process
  • the OLE-SIV method can be used as input current.
  • FIG. 1a Method in double fixed bed
  • FIG. 1b Method in double fixed bed with intermediate inert bed
  • FIG. 1c Process in a simple fixed bed consisting of a physical
  • FIG. 1 d method in a single fixed bed consisting of a universal catalyst
  • FIG. 2 simplified process flow diagram
  • FIGS. 3a and b operating states of an isomerization arrangement comprising two
  • FIGS. 4a to 4c operating states of an isomerization arrangement comprising two
  • FIG. 5 isomerization arrangement in the form of a fluidized bed reactor
  • FIG. 6 isomerization arrangement comprising two fluidized-bed reactors
  • FIG. 7 Representation of the thermodynamic equilibrium concentration at 1-
  • the inventive method comprises two essential steps, namely the first
  • Both catalysts are heterogeneous fixed-bed catalysts that together form a double-fixed bed.
  • a spatial separation of the two beds by, for example, an inert bed 3 or a sieve bottom (FIG.
  • a single fixed bed is used, which consists of a physical mixture 4 of isomerization catalyst and dehydrogenation catalyst.
  • the 1-butene component is preferably reacted and thereby the
  • Figure 2 shows the schematic structure of a possible embodiment of the system for carrying out the method based on a simplified process flow diagram.
  • a butene mixture 6 is provided and transferred to an isomerization arrangement 7, in which the supplied butene mixture 6 is subjected to isomerization.
  • the supplied butene mixture 6 contained 2-butene to 1-butene such that at least partially isomerized that the content of 1-butene in the withdrawn from the isomerization 7, isomerized butene mixture 8 is increased.
  • the isomerization takes place until the thermodynamic equilibrium prevails in the isomerization arrangement
  • the isomerization is then not fully in the thermodynamic equilibrium, but more balanced than before the isomerization. If the isomer distribution of the butene mixture provided is shifted in the direction of 1-butene, ie it contains too little 2-butene, the isomerization leads to an increase in the 2-butene content in the at least partially isomerized butene mixture 8.
  • the partially or completely isomerized butene mixture 8 becomes into a dehydrogenation 9, in which the 1-butene and 2-butene contained in the isomerized butene mixture 8 is oxidatively dehydrated.
  • a product mixture 10 is withdrawn, which in addition to the desired butadiene also unreacted starting materials and other impurities of the may contain provided butene mixture 6.
  • the product mixture may contain 10 by-products formed in the isomerization 7 and the dehydrogenation 9.
  • the product mixture 10 is converted into a butadiene 12 separation.
  • the target product butadiene 11 is separated, so that a depleted in butadiene residue 13 of the product mixture 10 is obtained.
  • This radical 13 can be recycled to one of the preceding steps, for example by mixing with the at least partially isomerized butene mixture 8 and / or by mixing with the butene mixture 6 provided.
  • by-products can leave the process in the course of Butadienabtrennung 12 via a discharge stream 14.
  • an oxygen-containing stream 15 which is preferably added to the isomerized butene mixture 8, is required as further starting material.
  • water vapor can also be added to the isomerized butene mixture 8.
  • the acid-containing stream 15 and water vapor may also be added to the butene mixture 6 provided.
  • the oxygen can be in the form of pure oxygen, as an air mixture or with
  • FIGS. 3a and 3b schematically show the concept of an isomerization arrangement 7 provided with two universal zones 16a and 16b. Both universal zones 16a, 16b are with
  • the two universal zones 16a, 16b can each be used both as reaction zone 17 and as regeneration zone 18.
  • the first universal zone 16 a is used as a reaction zone such that supplied butene mixture 6 is subjected therein to isomerization, so that out of the
  • Reaction zone 17 an isomerized butene mixture 8 is withdrawn.
  • oxygen-containing gas 19 is applied to deposits such as in particular coke of the Burn down isomerization catalyst 1.
  • the resulting exhaust gases 20 are disposed of.
  • the regeneration of the isomerization catalyst 1 carried out in the regeneration zone 18 proceeds faster than the deactivation of that in the first universal zone 16a
  • Isomerization catalyst which is used according to its purpose for isomerization. For this reason, after completion of the regeneration, the flow with the oxygen-containing gas 19 is turned off, during which the isomerization in the reaction zone 17 continues. This operating state is not shown in the drawings.
  • the operating state shown in FIG. 3b is set.
  • the first universal zone 16a is used as the regeneration zone 18, during which the isomerization takes place in the second universal zone 16b.
  • Isomerization catalyst is not exchanged between the two universal zones 16a and 16b.
  • the switching between the two operating states 3a and 3b is carried out in operational practice according to fixed cycles whose duration is measured by experience.
  • FIGS. 3a and 3b show:
  • both universal zones 16a, 16b are operated in parallel as reaction zone 17 (FIG. 4a). Once deactivation has progressed so far that regeneration is worthwhile, only one universal zone 16b is switched to regeneration mode (FIG. 4b). The other universal zone 16a is further operated as reaction zone 17. Due to the now larger feed, the
  • Isomerization catalyst 1 in the second universal zone 16b can now be used for isomerization, while now being regenerated in the other universal zone 16a (FIG. 4c). After completion of this regeneration, both universal zones 16a, 16b are again operated in parallel as reaction zones 17 (FIG. 4a).
  • An alternative to using two universal zones is shown in FIG.
  • the isomerization arrangement 7 shown there is technically designed by a so-called fluidized bed reactor 21.
  • the fluidized bed reactor 21 is set up vertically and divided into a reaction zone 17 and into a
  • Regeneration zone 18 The regeneration zone 18 is arranged below the reaction zone 17.
  • the fluidized-bed reactor 21 is completely filled with isomerization catalyst 1 over both zones 17, 18.
  • the supplied butene mixture 6 is injected at the foot of the reaction zone 17, rises, is subjected to the isomerization and leaves as the isomerized butene mixture 8 the head of the fluidized bed reactor.
  • the regeneration zone 18 At its foot, oxygen-containing gas 19 is injected, rises and thereby regenerates the in the
  • Regeneration zone 18 located isomerization catalyst 1.
  • the resulting exhaust gas 20 leaves the fluidized bed reactor together with the isomerized butene mixture.
  • the isomerization catalyst 1 then slips from top to bottom through the reaction zone 17 and then through the regeneration zone 18. In this way, a continuous circulation of regeneration catalyst 1 is formed in countercurrent to the supplied butene mixture 6 or the oxygen-containing gas 19.
  • the circulation speed is the same as the Volumes of the reaction zone 17 and the regeneration zone 18 so dimensioned that the residence times of the isomerization catalyst 1 in the respective zones 17, 18 of their deactivation or
  • FIG. 6 Another alternative to the continuous, parallel operation of regeneration and reaction is shown schematically in Figure 6 isomerization 7.
  • This includes a reaction zone 17 and a regeneration zone 18, which are spatially separated from each other. Both zones 17 and 18 are executable either as fluidized bed reactors or as fluidized bed reactors and with
  • Isomerization catalyst 1 filled.
  • a fluidized bed reactor any technically known type is possible, for example, bubbling fluidized beds, risers, downers, etc. There may also be such
  • Fluidized beds are used in which steadily used catalyst by fresh
  • Catalyst is replaced from the outside. This is necessary for particularly strong abrasion.
  • the isomerization of supplied butene mixture 6 to at least partially isomerized butene mixture 8 takes place continuously. The regeneration of the consumed
  • Isomerization catalyst 1 is carried out in the regeneration zone 18 by charging the deactivated isomerization catalyst 1 with oxygen-containing gas 19, which is withdrawn after passing through the regeneration zone 18 as the exhaust gas 20. If the regeneration zone 18 as
  • Fluidized bed regenerator is carried out, the oxygen-containing gas 19 may be used as Fluidmaschinesmedium.
  • the provided butene mixture 6 can be used as fluidizing medium, provided that the reaction zone 17 is designed as a fluidized bed reactor.
  • a continuous exchange of used and freshly regenerated isomerization catalyst 1 between the two zones 17, 18 takes place via a continuously operated conveyor 22.
  • Catalyst stream and feed stream may be in both zones 17 and 18 in countercurrent or direct current; In all embodiments, zones 17 and 18 may be operated at different temperatures.
  • Dehydration arrangement can be performed. However, the regeneration of the ODH catalyst is not necessarily required because the dehydration catalyst in reality has a lifetime of about 3 years and therefore does not need to be regenerated periodically. Should it need to be regenerated, it changes at irregular intervals from a reaction mode to a regeneration mode. The dehydration arrangement therefore manages with a single universal zone.
  • the butene mixture 6 provided has a content of 1-butene, which is below the thermodynamically given
  • thermodynamic equilibrium concentration of 1-butene which results from the prevailing in the isomerization and / or in the oxidative dehydrogenation temperature. From Figure 7, the thermodynamic equilibrium concentration of 1-butene can be read in a mixture of 1-butene with 2-butene: In the particularly preferred interval of temperature for isomerization and dehydrogenation between 300 and 420 ° C is the equilibrium concentration of 1-butene between 21 vol.% And 25.5 vol.%. The proportion of 1-butene within the n-butene fraction in the butene mixture 6 provided is lower in the most preferred embodiment. Particularly demanding is the processing of butene mixtures whose composition fluctuates constantly. The fluctuations are compensated by the isomerization, so that the inventive method is ideal for the production of valuable butadiene from inferior streams.
  • composition of the butene mixture provided: n-butane: 69.4 vol%
  • the two-stage isomerization / ODH experiments were carried out in a laboratory apparatus comprising two tube reactors in series.
  • the first reactor (ISO zone) was filled with isomerization catalyst
  • the second reactor (ODH zone) with BiMo mixed oxide catalyst.
  • the C 4 mixture introduced into the first reaction zone was subjected to isomerization of the 2-butenes present in the C 4 mixture provided to 1-butene without further dilution at a reactor temperature of 380 ° C.
  • the concentration of 1-butene was determined during the examples by GC analysis after the ISO zone.
  • the isomerized C 4 mixture leaving the ISO zone at 380 ° C. contained 20.0% by volume + 0.4% by volume (based on the n-butene mixture of trans-2-cis-2 and 1) in all the examples described here.
  • Butene which is significantly above the 1-butene concentration which the C4 mixture provided has (5.2% by volume of 1-butene based on the n-butene mixture of trans-2-cis-2-and 1-butene).
  • the isomerized C4 mixture formed in the ISO zone was then mixed with steam and air and then introduced into the second tubular reactor (ODH zone).
  • the temperature of the second tubular reactor was varied in the range of 360-390 ° C in steps of 10 ° C.
  • Catalyst load 0.8 g n- butene / g catalyzer / h
  • Catalyst load 0.8 g n - B uten / g Kataiysator / h
  • the comparative experiments were carried out in a similar experimental apparatus in which no ISO zone was present.
  • the provided C 4 mixture was not subjected to isomerization, mixed directly with steam and air and fed to the ODH zone.
  • the molar ratios 0 2 (from air) / n-butene / steam in the feed introduced into the ODH zone were 1/1/4.
  • Catalyst load 0.8 g n - B skinning / g Kataiysator / h Feed: the provided C4 mixture was mixed with steam and air and the ODH zone supplied.
  • the molar ratios 0 2 (from air) / n-butene / steam in the feed introduced into the ODH zone were 1/1/4.

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Abstract

L'invention concerne un procédé de production de 1,3-butadiène par déshydrogénation oxydative de n-butène sous catalyse hétérogène, dans lequel on prépare au moins un mélange de butènes contenant du 2-butène. Le but de l'invention est de proposer un procédé de production économique de 1,3-butadiène à l'échelle industrielle dans lequel on prépare comme matière première un mélange de butènes dont la teneur en 1-butène par rapport à sa teneur en 2-butène est plutôt faible et dans lequel le rapport du 1-butène sur le 2-butène est soumis à des fluctuations. Ce but est atteint par un procédé en deux étapes dans lequel, dans une première étape, le mélange de butènes préparé est soumis à une isomérisation sous catalyse hétérogène pour obtenir un mélange de butènes au moins partiellement isomérisés et dans lequel ensuite, dans une seconde étape, le mélange de butènes au moins partiellement isomérisés, qui a été obtenu dans la première étape, est soumis à la déshydrogénation oxydative. Le procédé en deux étapes a un rendement en butadiène plus élevé que le procédé en une étape.
EP14806313.4A 2013-12-18 2014-12-04 Production de butadiène par déshydrogénation oxydative de n-butène après isomérisation préalable Withdrawn EP3083529A1 (fr)

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DE102013226370.8A DE102013226370A1 (de) 2013-12-18 2013-12-18 Herstellung von Butadien durch oxidative Dehydrierung von n-Buten nach vorhergehender Isomerisierung
PCT/EP2014/076569 WO2015090998A1 (fr) 2013-12-18 2014-12-04 Production de butadiène par déshydrogénation oxydative de n-butène après isomérisation préalable

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