WO2013013856A1 - Traitement final de mélanges d'hydrocarbures en c4 contenant des oléfines - Google Patents

Traitement final de mélanges d'hydrocarbures en c4 contenant des oléfines Download PDF

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Publication number
WO2013013856A1
WO2013013856A1 PCT/EP2012/059524 EP2012059524W WO2013013856A1 WO 2013013856 A1 WO2013013856 A1 WO 2013013856A1 EP 2012059524 W EP2012059524 W EP 2012059524W WO 2013013856 A1 WO2013013856 A1 WO 2013013856A1
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Prior art keywords
butene
butanol
fraction
optionally
weight
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PCT/EP2012/059524
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German (de)
English (en)
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Burkard Kreidler
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Evonik Oxeno Gmbh
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Priority to EP12723858.2A priority Critical patent/EP2734489A1/fr
Publication of WO2013013856A1 publication Critical patent/WO2013013856A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • 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
    • 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
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04—Alkali metals

Definitions

  • the present invention relates to a process for the workup of C 4 - hydrocarbon mixtures containing at least 2-butene in which the 2-butene is derivatized, separated in derivatized form and at least partially converted to 1-butene.
  • olefins are among the most important building blocks in organic chemistry. They form as
  • copolymers such as butyl rubber or ethylene-1 - butene copolymers.
  • Ethylene and propylene are obtained industrially by catalytic or thermal cracking of mixtures of saturated hydrocarbons from the refining of petroleum, such as liquefied petroleum gas (LPG), natural gas liquid (NGL), naphtha, or gas oil, especially steam cracking of naphtha.
  • LPG liquefied petroleum gas
  • NNL natural gas liquid
  • naphtha or gas oil, especially steam cracking of naphtha.
  • C 4 olefins (1,3-butadiene, isobutene, 1-butene, 2-butenes) and to a lesser extent C 5 and higher olefins are obtained.
  • the proportions of the individual fractions and their composition are determined by the type of
  • C 4 and higher olefins may further be promoted by synthesis reaction, ie
  • Oligomerization and cooligomerization of lower olefins for example, by oligomerization of ethylene using Ziegler catalysts or combined ethylene oligomerization and olefin metathesis can be obtained in the SHOP process developed by Shell and its variants, as well as by dehydrogenation of
  • Paraffins or be obtained from alcohols by dehydration.
  • the C2 fraction from the cracking of a mixture of saturated hydrocarbons contains ethane and acetylene in addition to ethylene, the C3 fraction in addition to propylene propene and Allen shares and propane.
  • Dimethylformamide or N-methylpyrrolidone and subsequent distillative separation of the olefin from the corresponding saturated hydrocarbon can be obtained from the C2 or C3 fraction of ethylene and propylene in a purity of at least 99.9%, as required for polymerization purposes.
  • the C 4 fraction from the cracking of a mixture of saturated hydrocarbons as essential components contains the butenisomers isobutene (bp .: -6.9 ° C), 1-butene (bp .: -6.3 ° C), cis-2 Butene (bp .: 3.7 ° C) and trans-2-butene (bp.: 0.9 ° C) and the alkanes n-butane (bp.: - 0.5 ° C) and isobutane (bp. : -1 1, 7 ° C) and polyunsaturated C 4 compounds, in particular 1, 3-butadiene (bp .: -4.4 ° C). From these mixtures 1-butene can not be separated economically by fractional distillation because of the low boiling point difference between isobutene and 1-butene and the very low separation factor.
  • the workup of the C 4 fraction is carried out by first removing the polyunsaturated hydrocarbons, mainly 1,3-butadiene, by extraction (-sdistillation) and / or converted by selective hydrogenation to linear butenes.
  • polyunsaturated hydrocarbons mainly 1,3-butadiene
  • extraction mainly 1,3-butadiene
  • / or converted by selective hydrogenation to linear butenes.
  • raffinate I is generally used in relation to its isomers higher reactivity of isobutene by isobutene is usually reacted with alcohol or water to form a derivative which can be easily separated from the rest of the hydrocarbon mixture.
  • isobutene is formed from methyl tert-butyl ether (MTBE), when using ethanol ethyl tert-butyl ether (ETBE) and when using water tert-butanol (TBA).
  • MTBE methyl tert-butyl ether
  • ETBE ethanol ethyl tert-butyl ether
  • TSA water tert-butanol
  • MTBE is preferably added as such to increase knocking resistance.
  • the olefins can be separated, for example by extraction distillation.
  • 1-Butene may then be distilled off from the olefin mixture by means of a column of sufficient separation efficiency and capacity, i. separated from the 2-butenes.
  • an olefin-containing C 4 -hydrocarbon mixture with a mass fraction of less than 1% by weight of butadiene raffinate I, C 4 stream of fluid catalytic cracking
  • Processes or selectively hydrogenated C 4 fraction from a cracking process are simultaneously hydrogenated and isomerized.
  • remaining residual butadiene is selectively hydrogenated until its mass fraction is less than 5 ppm and at the same time isomerizes 1-butene to the thermodynamically more stable 2-butenes.
  • the equilibrium position between 1-butene and the isomeric 2-butenes is for example at 80 ° C at a ratio of 1:17. If the isomerization is carried out in a reactive distillation, a virtually 1-butene-free top stream can be separated in this way, from which pure isobutene can be obtained by further work-up.
  • the distillation residue is an isobutene-free mixture which consists essentially of 2-butenes.
  • the isobutene has a lower purity compared with the separation based on a derivatization by hydration or etherification and secondly that 1-butene is converted into the reaction-bearing as well as economically less attractive 2-butenes.
  • WO 2008/065171 describes a process for the hydroformylation of olefins in which, in order to increase the yield of linear hydroformylation products, a large part of the olefins contained in the feed used with internals Double bond to 1-olefins isomehsiert.
  • Alumina, silica and / or aluminosilicate supports which are at least partially coated with alkali metal or alkaline earth metal oxides, lanthanides, elements of the iron group, manganese oxide and / or zirconium oxide and in the fixed bed, fluidized bed or moving bed are particularly suitable as catalysts which facilitate double bond isomerization be used.
  • the reaction is advantageously carried out at a pressure of 3-20 bar and a
  • Temperature is carried out in the range of 200 to 500 ° C, with a
  • Double bond isomerization is ensured, side reactions such as cleavage, skeletal isomerization, dehydrogenation and oligomerization, however
  • the double bond isomerization is limited by the thermodynamic equilibrium between the individual isomers, so that the maximum achievable proportion of the respective 1-olefin is fixed at a given temperature.
  • raffinate II for example, the maximum obtainable by isomerization of 2-butenes yield of 1-butene at a temperature of 250 ° C would be only 16%. Accordingly, higher conversions can only be achieved if unreacted olefins with an internal double bond have been separated off and, if appropriate, repeatedly fed to the isomerization stage.
  • the object of the present invention was thus to provide an efficient process comprising a few process steps for the processing of technical olefin-containing C 4 -hydrocarbon mixtures, in particular from cracking processes, with which the predominant fraction of 2-butenes can be isomerized to 1-butane as well as isobutene or isobutene derivatives on the one hand and 1-butene on the other hand can be separated in high purity.
  • the basis of the invention is, on the one hand, that the butenes present in an olefin-containing C 4 -hydrocarbon mixture can be reacted by reaction with water according to the rule of Markovnikov essentially to secondary and tertiary alcohols, which can be separated by distillation.
  • formed from isobutene tert-butanol can be separated in particular from 2-butanol formed from 1-butene and 2-butene material.
  • 2-butanol can then pass through catalytic elimination reaction are reacted under non isomerizing conditions to 1 - butene.
  • 2-butanol can be reacted by kinetically controlled dehydration under non-isomerizing conditions on a mixed oxide catalyst described in WO 2005/058485 A1 with surprisingly high selectivity of up to 98.5% to 1-butene.
  • the present invention therefore provides a process for working up C 4 -hydrocarbon mixtures containing at least 2-butene, the process comprising the following steps:
  • the method of the invention is the workup of
  • olefin-containing C 4 -hydrocarbon mixtures which are obtained in the cracking of mixtures of saturated hydrocarbons, for example in the context of the processing of crude oil or natural gas on an industrial scale. It is preferable that in the C 4 - hydrocarbon mixture in the present process is a C 4 fraction of a hydrocarbon mixture from a cracking process in petroleum processing.
  • the process of the present invention has the advantage that it allows in a simple and efficient manner at the same time an efficient separation of isomeric butenes as well as a substantial isomerization of 2-butenes to economically more significant 1-butene.
  • a process is described with which from a C 4 fraction advantageously both isobutene, tert-butyl alcohol (TBA) on the one hand and on the other highly highly enriched 1-butene with isomerization of
  • a particular procedural advantage of the invention is that the fraction separated in step b) does not have to be separated further into 2-butanol and 1-butanol, since in the course of the catalytic elimination both substances are finally converted to 1-butene. It is therefore sufficient to subject the separated fraction containing 2-butanol and optionally also 1-butanol as a whole to the elimination step. Apparative overhead for the isolation of 1-butanol is therefore eliminated.
  • the separated fraction can also further further
  • Another object of the present invention is directed to the use of 1-butene obtained by the method according to the invention as a monomer or comonomer for the production of polyolefins, wherein the 1-butene may optionally be purified by distillation additionally before use.
  • 1-butene obtained by the method according to the invention as a monomer or comonomer for the production of polyolefins, wherein the 1-butene may optionally be purified by distillation additionally before use.
  • all hydrocarbon mixtures which contain at least 2-butene and essentially hydrocarbons having 4 carbon atoms, in
  • the hydrocarbon mixture may typically contain further linear and / or branched olefins, preferably having 4 carbon atoms.
  • the C 4 -hydrocarbon mixture used in the process according to the invention comprises, for example, in addition to 2-butene, at least one or more components selected from 1-butene, isobutene and saturated hydrocarbons.
  • the C 4 -hydrocarbon mixture comprises, in addition to 2-butene, at least 1-butene, isobutene and saturated hydrocarbons.
  • the proportion of butenes is typically at least 95% by weight, preferably at least 99% by weight, particularly preferably at least 99.5% by weight, in each case based on the total weight of the monoethylenically unsaturated compounds present in the hydrocarbon mixture.
  • that used in the process according to the invention that used in the process according to the invention
  • Hydrocarbon mixture saturated and / or polyethylenically unsaturated hydrocarbons, preferably having 4 carbon atoms. Particular preference is given to those mixtures in which the proportion of saturated and mono- and polyethylenically unsaturated hydrocarbons with 4
  • the proportion of saturated hydrocarbons in the total weight of the hydrocarbon mixture is preferably at most 60% by weight, particularly preferably at most 40% by weight and very particularly preferably at most 20% by weight.
  • the hydrocarbon mixture used in the process according to the invention is preferably a large-scale olefin-containing C 4 - Hydrocarbon mixture. Suitable industrially available olefin-containing C 4 -hydrocarbon mixtures result primarily from the cracking of mixtures of saturated hydrocarbons in petroleum processing,
  • catalytic cracking for example in fluid catalytic cracking (FCC) or hydrocracking with subsequent dehydrogenation, but especially by thermal cracking processes, especially in the presence of water vapor
  • the use mixtures used in these processes are primarily liquefied petroleum gas (LPG), natural gas liquid (NGL), naphtha or gas oil.
  • LPG liquefied petroleum gas
  • NNL natural gas liquid
  • the hydrocarbon mixture used is a C 4 fraction from a hydrocarbon mixture from a cracking process in the
  • C 4 fractions are obtainable, for example, by fluid catalytic cracking or steam cracking of gas oil or by steam cracking of naphtha.
  • C 4 -hydrocarbon mixtures which can be used in the process of the present invention can furthermore also be carried, for example, by
  • a C 4 fraction from naphtha steam cracking suitable for use in the process according to the invention has, for example, a composition containing several or all of the following components:
  • a C 4 -hydrocarbon mixture from a fluid catalytic cracking (FCC) process can preferably also be used in the process according to the invention, which typically has a composition which contains several or all of the following components:
  • the content of oxygen-containing, sulfur-containing, nitrogen-containing and / or halogen-containing compounds in the C 4 -hydrocarbon mixture used is preferably not more than 500 ppm by weight, preferably not more than 100 ppm by weight, particularly preferably not more than 10% by weight. ppm, and more preferably not more than 1 ppm by weight, based in each case on the total weight of the mixture.
  • such compounds can be substantially removed by treating the C 4 -hydrocarbon mixture with a suitable adsorbent, such as with a molecular sieve in an upstream step.
  • Sulfur-containing impurities such as mercaptans can be removed, in particular by extraction with alkaline aqueous solution, optionally under catalytic oxidation. Suitable, known in the art such
  • the Merox processes of UOP and the fiber film processes of Merichem are desulfurization processes.
  • the C 4 -hydrocarbon mixture contains polyunsaturated hydrocarbons, such as 1,3-butadiene, vinylacetylene, ethylacetylene and 1,2-butadiene, these can preferably be present in one or more of these several of the processing according to the invention upstream process steps are removed by extraction and / or extraction distillation and / or by selective hydrogenation in monounsaturated
  • Hydrocarbons are transferred.
  • the extraction solvent is usually passed in countercurrent to the fully vaporized C 4 -hydrocarbon mixture in an extraction column from below, whereby the solvent is charged with the more soluble polyunsaturated compounds.
  • Components of dissolved monounsaturated compounds can be driven off by feeding polyunsaturated compounds at the lower end of the extraction column. At the top of the extraction column is obtained in this way a hydrocarbon mixture which is substantially free of polyunsaturated compounds.
  • Total of compounds is at most 1% by weight, preferably less than 0.2% by weight, based on the total weight of the butadiene-poor C 4 obtained .
  • Hydrocarbon mixture By selective hydrogenation, for example, according to the procedure described in EP 81 041 or DE 15 68 542, the proportion of polyunsaturated compounds can further to a residual content of less than 10 ppm by weight, preferably not more than 5 ppm by weight and completely more preferably not more than 1 ppm by weight, based on the total weight of the C 4 -
  • Residual content of at most 0.5% by weight, preferably less than 0.2% by weight, more preferably less than 0.1% by weight, very particularly preferably less than 10 ppm of 1,3-butadiene is particularly preferred in the process according to the invention .
  • a C 4 - fraction from a hydrocarbon mixture from a cracking process in petroleum processing, which has largely been freed, for example in the above-described manner of polyunsaturated compounds, in particular 1, 3-butadiene is particularly preferred in the process according to the invention .
  • a raffinate I which preferably as C 4 hydrocarbon mixture in
  • composition containing several or all of the following components:
  • hydrocarbon mixture Refer hydrocarbon mixture.
  • the subject matter of the present invention is thus directed to a process for working up C 4 -hydrocarbon mixtures containing at least 2-butene, the process comprising the following steps:
  • reaction with water in step a) of the process according to the invention can be carried out in particular by acid catalysis.
  • acidic catalysts are suitable
  • mineral acids e.g. Sulfuric acid, hydrochloric acid or
  • Nitric acid as well as acidic ion exchangers.
  • Lewis acids such as e.g.
  • Aluminum halides, BF 3 or SnCl 4 can be used as catalysts in process step a) of the process according to the invention.
  • reaction in process step a) is formed in accordance with the rule of Markovnikov from linear butenes, ie 2-butene and optionally present 1-butene, by addition reaction with water, essentially 2-butanol while isobutene contained in any of the C 4 - hydrocarbon mixture analogously tert tert.
  • Butanol results.
  • the proportion of 1-butanol formed in the reaction is low, typically ⁇ 10% by weight with respect to the total amount of butanol formed.
  • the reaction of the butenisomers with water over acidic catalysts is well known to those skilled in the art. As early as 1926, Benjamin T. Brooks in Chem. Rev., 1926, 2, 369-394 summarized that the isomeric butenes under identical
  • the C 4 -hydrocarbon mixture used in the process according to the invention comprises at least one or more
  • step a) optionally present 1-butene is at least partially reacted to 2-butanol and optionally also to 1-butanol and optionally to at least partially tert isobutene . Butanol reacted.
  • the C 4 -hydrocarbon mixture comprises, in addition to 2-butene, at least 1-butene, isobutene and saturated hydrocarbons, to which water is added in step a) for reaction, at least part of the 2-butene being added to 2 Butanol, 1-butene at least in part to 2-butanol and optionally also to 1-butanol and isobutene is at least partially reacted to tert-butanol.
  • the mixture obtained from process step a) is subsequently separated by material.
  • all physical / chemical separation processes with which an effective separation of the 2-butanol formed in step a) from any tert-butanol formed, on the one hand, and from the unreacted hydrocarbons, on the other hand can be regarded as suitable for use in the context of the present invention , Suitable embodiments usable
  • the separation in process step b) is carried out by distillation, preferably by means of fractional distillation.
  • the fraction to be subjected to the catalytic elimination, containing 2-butanol and optionally also 1-butanol is preferably withdrawn from the stripping section of the distillation column.
  • the distillation column may in this case be any distillation column known to the person skilled in the art, e.g. a bubble tray column, packed column, packed column or
  • Dividing wall column can be used.
  • the distillation can at a pressure of 1 to 50 bar absolute, preferably from 2 to 40 bar absolute and more preferably from 5 to 20 bar absolute setting a temperature in the bottom of the distillation column in the range of 40 to 250 ° C, in particular in the range 50 to 200 ° C and especially in the range of 60 to 140 ° C are performed.
  • the mixture obtained from process step a) can be separated into at least two fractions, namely a fraction comprising 2-butanol, at least partly formed by reaction of 2-butene with water, and a low-boiling fraction.
  • the term low-boiling fraction is to be understood as meaning a fraction of chemical compounds which have boiling points which are at least 30 K, preferably at least 50 K and particularly preferably at least 70 K lower than the boiling point of 2-butanol it is mainly hydrocarbons unconverted in process step a), ie saturated hydrocarbons, e.g. n-butane, isobutane, propane or pentenes or unreacted unsaturated hydrocarbons, i. especially butenes act. All within the scope of the present invention
  • the boiling point data used here refer to atmospheric pressure, as long as no deviating information is given.
  • Hydrocarbon mixture in addition to 2-butene at least one or more
  • step a) optionally present 1-butene at least in part to 2-butanol and optionally also to 1-butanol and optionally present isobutene at least in part to tert.- Butanol is reacted, the resulting mixture in process step b) can thus be separated by distillation
  • At least part of the low-boiling fraction is recycled to process step a).
  • This measure can serve to increase the total turnover of the butenes, provided that they are reacted only in part during a single reactor pass of the reaction with water.
  • Process step b) e.g. separated by a subsequent fractional distillation and the remaining portion containing the unsaturated compounds, then
  • process step b) optionally separated tert-butanol is converted in a particular embodiment of the method according to the invention at least in part by reversing the respective formation reaction, ie elimination of water, to isobutene.
  • the tert-butanol-containing fraction optionally after further purification, usually in the gas or liquid phase of heterogeneous acidic oxide catalysts such as SiO 2 -modified Al 2 O 3 catalysts in a
  • the fraction comprising 2-butanol and optionally 1-butanol is used after any further purification in step c) of the process according to the invention, in which a catalytic elimination of at least part of the separated 2-butanol to 1-butene takes place.
  • 1-butanol optionally present in a mixture with the 2-butanol can likewise be reacted to give 1-butanol.
  • catalytic elimination is to be understood as meaning a catalytic elimination of water (dehydration).
  • Process step c) is preferably carried out on a mixed oxide catalyst comprising zirconium dioxide, yttrium oxide (Y 2 O 3) and at least one alkali and / or Erdalkalinnetalloxid.
  • the catalyst comprises, in particular, a proportion of zirconium dioxide of 80 to 99 parts by mass, preferably of 93 to 96 parts by mass, a proportion of yttrium oxide (Y.sub.2O.sub.3) of 0.5 to 10, preferably 3.5 to 6 parts by mass, and a proportion of alkali metal oxide. and / or alkaline earth metal oxide of 0.1 to 3, preferably from 0.5 to 2, particularly preferably from 0.5 to 1 parts by mass. It may contain one or more oxide (s) from the group of alkali or alkaline earth metals, in particular a
  • Alkali metal oxide selected from potassium oxide and sodium oxide.
  • the preparation of the catalyst can be carried out as described in WO 2005/058485, page 6, line 21 to page 8, line 16 and examples 1 and 2.
  • the elimination mainly with the above-mentioned mixed oxide catalyst, is preferably carried out at a temperature in the range of 200 to 450 ° C, especially 280 to 380 ° C. It is preferably carried out in the gas phase.
  • the catalyst may in this case be suspended in the reactor or arranged in lumps in the fixed bed and the catalyst loading in grams of starting material per gram of catalyst per hour, 0.01 to 15 h "1 , preferably 0.5 to 5 h " 1 .
  • the pressure under which the elimination of water is carried out is in a range of 0.1 to 25 bar absolute, preferably from 0.2 to 10 bar absolute and more preferably between 1 and 5 bar absolute.
  • 1-butene Hofmann product
  • 2-butene Saytzev product
  • 2-butene is thermodynamically more stable than the isomeric 1-butene and therefore predominates in the product mixture under equilibrium conditions.
  • the mixed oxide catalyst preferably used in the process according to the invention comprising zirconium dioxide, yttrium oxide (Y 2 O 3) and at least one alkali metal and / or alkaline earth metal oxide permits selective kinetically controlled elimination to 1-butene as the desired product, especially when 2-butanol is used. Under the selected reaction conditions is also a subsequent
  • the total conversion can advantageously be increased by separating off at least part of the 1-butene by distillation after process step c) and, preferably, at least part of the 2-butanol unreacted in process step c), optionally mixed with 1-butanol, again the
  • Elimination according to step c) is supplied. Is also formed as a by-product in the elimination step formed butanone by distillation from the resulting
  • the process according to the invention therefore makes it possible to obtain 2-butenes contained in the originally used C 4 -hydrocarbon mixture overall
  • the proportion of the economically significant 1-butene which can be obtained from the olefin-containing C 4 hydrocarbon mixture used, can thus be significantly increased.
  • the present invention advantageously in a process comprising a few steps at the same time isobutene and 1-butene as important (co) monomers in high purity, wherein the proportion of 1-butene is significantly increased by the isomerization of 2-butene.
  • the 1-butene and 2-butene can be obtained.
  • the 1-butene is preferably obtained in a purity of at least 95% by weight, preferably at least 97% by weight. From a Roh-1-Butt of such quality can be by distillation with relatively few separation stages in comparison to the distillation of polymer grade raffinate II 1 -buten, ie a purity of at least 99.0
  • % By weight, preferably of at least 99.5% by weight.
  • the 1-butene obtained by means of the process according to the invention can be used as monomer or comonomer for the preparation of polyolefins, it being possible for the 1-butene optionally to have been additionally purified by distillation before use.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de traitement final de mélanges d'hydrocarbures en C4- contenant au moins du 2-butène, selon lequel le 2-butène est formé en dérivé, séparé sous forme de dérivé et au moins partiellement converti en 1-butène.
PCT/EP2012/059524 2011-07-22 2012-05-23 Traitement final de mélanges d'hydrocarbures en c4 contenant des oléfines WO2013013856A1 (fr)

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EP12723858.2A EP2734489A1 (fr) 2011-07-22 2012-05-23 Traitement final de mélanges d'hydrocarbures en c4 contenant des oléfines

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DE102011079674.6 2011-07-22
DE201110079674 DE102011079674A1 (de) 2011-07-22 2011-07-22 Aufarbeitung olefinhaltiger C4-Kohlenwasserstoffgemische

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113501742A (zh) * 2021-05-28 2021-10-15 中国石油化工股份有限公司 一种乙烯裂解c4的利用方法

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WO2017093858A1 (fr) * 2015-11-30 2017-06-08 Sabic Global Technologies B.V. Procédés de production d'oléfines

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1568542A1 (de) 1966-06-15 1970-05-06 Bayer Ag Verfahren zur hydrierenden Behandlung von budadien- und n-Buten-1-haltigen C4-Kohlenwasserstoffen
EP0081041A1 (fr) 1981-11-04 1983-06-15 Hüls Aktiengesellschaft Procédé d'hydrogénation sélective des hydrocarbures polyunsaturés en mixtures d'hydrocarbures
EP0497018A1 (fr) * 1989-04-28 1992-08-05 Mobil Oil Corporation Procédé d'oligomérisation d'oléfines en C2 à C5 à l'aide de catalyseurs à chrome réduit
US5382705A (en) * 1989-03-20 1995-01-17 Mobil Oil Corporation Production of tertiary alkyl ethers and tertiary alkyl alcohols
WO2005058485A1 (fr) 2003-12-18 2005-06-30 Oxeno Olefinchemie Gmbh Catalyseur et procede de preparation de 1-olefines a partir de 2-hydroxyalcanes
WO2008065171A1 (fr) 2006-11-30 2008-06-05 Basf Se Procédé pour l'hydroformulation d'oléfines

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1568542A1 (de) 1966-06-15 1970-05-06 Bayer Ag Verfahren zur hydrierenden Behandlung von budadien- und n-Buten-1-haltigen C4-Kohlenwasserstoffen
EP0081041A1 (fr) 1981-11-04 1983-06-15 Hüls Aktiengesellschaft Procédé d'hydrogénation sélective des hydrocarbures polyunsaturés en mixtures d'hydrocarbures
US5382705A (en) * 1989-03-20 1995-01-17 Mobil Oil Corporation Production of tertiary alkyl ethers and tertiary alkyl alcohols
EP0497018A1 (fr) * 1989-04-28 1992-08-05 Mobil Oil Corporation Procédé d'oligomérisation d'oléfines en C2 à C5 à l'aide de catalyseurs à chrome réduit
WO2005058485A1 (fr) 2003-12-18 2005-06-30 Oxeno Olefinchemie Gmbh Catalyseur et procede de preparation de 1-olefines a partir de 2-hydroxyalcanes
WO2008065171A1 (fr) 2006-11-30 2008-06-05 Basf Se Procédé pour l'hydroformulation d'oléfines

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
"Ullmanns Enzyklopädie der technischen Chemie", vol. 2, VERLAG CHEMIE, pages: 489 FF
ALLAN J. LUNDEEN ET AL, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 85, no. 14, 20 July 1963 (1963-07-20), pages 2180 - 2181, XP055034366, ISSN: 0002-7863, DOI: 10.1021/ja00897a041 *
BENJAMIN T. BROOKS, CHEM. REV., vol. 2, 1926, pages 369 - 394
K. WEISSERMEHL; J. ARPE: "Industrielle Organische Chemie", 1994, VCH VERLAG
L. F. MAREK ET AL: "Catalytic Vapor-Phase Hydration of 2-Butene under High Pressures", INDUSTRIAL & ENGINEERING CHEMISTRY, vol. 24, no. 12, 1 December 1932 (1932-12-01), pages 1428 - 1431, XP055034364, ISSN: 0019-7866, DOI: 10.1021/ie50276a021 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113501742A (zh) * 2021-05-28 2021-10-15 中国石油化工股份有限公司 一种乙烯裂解c4的利用方法

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