Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C11/00—Aliphatic unsaturated hydrocarbons
  • C07C11/02—Alkenes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
  • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
  • C07C2/88—Growth and elimination reactions
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
  • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
  • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
• • 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
• • 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
• • 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
  • C07C2523/16—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
  • C07C2523/16—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
  • C07C2523/30—Tungsten
• • 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
  • C07C2523/32—Manganese, technetium or rhenium
  • C07C2523/36—Rhenium

Definitions

• the present invention relates to a process for the preparation of higher ⁇ -olefins by a combination of isomerizing transalkylation with metathesis reactions.
• Higher ⁇ -olefins are of less technical importance than the short-chain olefins ethylene and propylene. Nevertheless, there are specific possible uses for the olefins belonging to this class, but so far there have only been general processes for the production of these higher olefins; targeted syntheses are not possible. For example, the dehydrogenation of higher paraffins leads to a mixture of olefins which mainly contain internal double bonds. Higher carbon number olefins with terminal double bonds can be produced by oligomerizing ethylene with transition metal catalysts, for example using the Ziegler process, the SHOP process from Shell or the ethyl process.
• ethylene is a high-priced raw material because it is a raw material for a large number of chemical products. This naturally also results in a high price for the ⁇ -olefins obtained therefrom by oligomerization.
• 1-octene can be produced specifically starting from butadiene by telomerization and subsequent pyrolysis of the C8 telomerization product. Disadvantages of the process are the low yields and in particular the problem of recycling the catalyst.
• the metathesis of butene-containing streams is known, but only for the construction of olefins with a carbon number up to C6.
• DE-A 100 13 253J describes the conversion of a mixture of 1-butene and 2-butene (raffinate II) to propene and 3-hexene, but it is not possible to build up carbon chains higher than C6 in this way.
• step a) Metathesis of 1-butene to a mixture of 3-hexene and ethene; b) separating the 3-hexene from the product mixture obtained in step a); c) reaction of the 3-hexene with an electrophile preferably containing water or a carboxylic acid and containing reactive hydrogen under acidic conditions which allows the addition of the electrophilic components to the olefinic double bond; d) cracking the product from step c), for example by dehydration, to produce a mixture of n-hexenes which contains 1-hexene in economically acceptable amounts.
• an electrophile preferably containing water or a carboxylic acid and containing reactive hydrogen under acidic conditions which allows the addition of the electrophilic components to the olefinic double bond
• This process does not allow selective extraction of 1-hexes, since the cracking process only leads to a mixture of the hexene isomers.
• EP-A 505 834 and EP-A 525 760 both disclose a process for the production of linear higher ⁇ -olefins by transalkylation reactions connected in series.
• a linear internal olefin having 4 to 30 carbon atoms or a mixture thereof is reacted with trialkylaluminum in the presence of an isomerization catalyst.
• a trialkylaluminum compound is formed in which at least one of the alkyl radicals is derived from the olefin used; this is in the form of a linear alkyl radical which is derived from the ⁇ -olefin which is formed by isomerization.
• the trialkylaluminum compound is then reacted with an ⁇ -olefin in a displacement reaction in which the linear ⁇ -olefin which was bound to the aluminum is released.
• the object of the present invention is to provide a process for the targeted production of certain longer-chain ⁇ -olefins.
• the process should make it possible to use educt sources other than the frequently used, high-priced lower olefins ethylene or propylene.
• This object is achieved by a process for the targeted production of linear ⁇ -olefins with a carbon number in the range from 6 to 20 from linear internal olefins with a lower carbon number, which comprises the following steps:
• Trialkylaluminum compound under isomerizing conditions whereby an olefin corresponding to the alkyl radical is released and the linear olefin used attaches to the aluminum with isomerization and formation of a corresponding linear alkylaluminum compound
• transalkylation is understood to mean the reaction of an internal olefin with a trialkylaluminum compound under isomerizing conditions.
• the internal olefin rearranges to a mixture of internal and terminal olefins with double bond isomerization, with only the terminal olefins reacting to form a linear aluminum alkyl. Then an olefin is released which corresponds to the alkyl radical which was previously bound to the aluminum.
• the olefin which is released in the reaction of the trialkylaluminum compound with the linear internal olefin is isolated and reacted again with the trialkylaluminum compound formed.
• the linear internal olefins with the carbon number (n / 2) + 1 and the linear internal olefins with the carbon number n are reacted together with the trialkylaluminum compound.
• steps a) and d) are carried out together in one reaction space.
• the subsequent release of the ⁇ -olefins with the carbon number (n / 2) + 1 and n (steps b) and e)) takes place together.
• the mixture of linear ⁇ -olefins obtained after the release by reaction with an olefin and having a carbon number of (n 2) + 1 and a carbon number n is then separated, the olefin having the carbon number (n 2) + 1 is fed to the self-metathesis reaction and the Isolated olefin with the carbon number n.
• a mixture of linear internal with linear terminal olefins can also be used as starting material. Since the corresponding terminal olefins are often valuable chemical feedstocks, they are frequently removed from the mixture subsequently used in the process according to the invention.
• a terminal olefin can also be used as starting material.
• the transalkylation a that is to say the isomerization of the internal starting olefin into a terminal olefin, becomes superfluous.
• the first step of the process according to the invention is then the self-metathesis reaction of the olefin with the Carbon number (n / 2) + 1, i.e. process step c).
• the subsequent process steps d) to f) are carried out unchanged.
• a preferred product that can be produced by the process according to the invention is 1-decene.
• Any hexene can be used in the reaction.
• 1-hexene is used as the starting olefin in the preparation of 1-decene. This is then converted into 5-decene in a self-metathesis reaction, from which 1-decene is then obtained.
• the hexene is obtained by metathesis of 1-butene; this creates 3 witches.
• Olefin mixtures containing 1-butene and 2-butene and optionally isobutene and butanes can be used as the source of 1-butene. These are among others obtained as a C4 fraction in various cracking processes such as steam cracking or FCC cracking.
• butene mixtures such as those obtained in the dehydrogenation of butanes or by dimerization of ethene, can be used.
• Butanes contained in the C4 fraction are inert. Dienes, alkynes or enynes that are present in the mixture used are removed using common methods such as extraction or selective hydrogenation.
• the butene content of the C4 fraction used in the process is 1 to 100% by weight, preferably 60 to 90% by weight.
• the butene content relates to 1-butene, 2-butene and isobutene.
• a C4 fraction is preferably used which is obtained in steam or FCC cracking or in the dehydrogenation of butane.
• Raffinate II is particularly preferably used as the C4 fraction, with the C4 stream being freed from disturbing impurities, in particular oxigenates, by appropriate treatment on adsorber protective beds, preferably on high-surface area aluminum oxides and / or molecular sieves.
• Raffinate II is obtained from the C4 fraction by first extracting butadiene and / or subjecting it to selective hydrogenation. After separation of isobutene, the raffinate II is then obtained.
• the mixtures mentioned above also contain internal olefins in addition to 1-butene, these must be converted into the terminal olefin before the metathesis reaction. This is done by a transalkylation, in which the olefin mixture is reacted with a trialkylaluminium compound under isomerizing conditions. The 1-butene is then liberated from the aluminum alkyl obtained by reaction with an olefin. It is preferred if the olefin liberated in the transalkylation of the butene is used after the isolation to liberate the 1-butene.
• Tripropylaiumium is used as the aluminum alkyl (see Appendix Figure 1).
• raffinate II is converted with tripropylaiumium to tri-n-butylaluminum and propene. Propene and the excess of C4 are separated off (2), C4 is returned to the transalkylation.
• the tri-n-butylaluminum is reacted with the previously isolated propene to give tripropylaiumium and 1-butene. Excess propene is isolated and reduced.
• the tripropylaiumium obtained is used in the transalkylation (1).
• the 1-butene is converted to 3-hexene and ethylene in a self-metathesis reaction (5). The valuable product ethylene is separated and used for other purposes.
• the 3-hexene formed is then subjected to transalkylation with tripropylaiumium (6), 5-decene, which is a successor product (see below), also being fed into the reactor.
• Mixed C3 / C6 / C10 aluminum alkyls are formed.
• the excesses of 3-hexene and 5-decene are separated off and recycled, the mixed aluminum alkyls formed are reacted in the reaction stage (8) with propene to tripropylaiumiumium and a mixture of 1-hexene and 1-decene. Excess propene is returned.
• Tripropylaiuminium is used again in the transalkylation stage (6).
• 1-Decen is removed as a product (9).
• 1-Hexen is used in this variant of the process for the construction of 5-decene in a self-metathesis reaction (10).
• the ethylene that is formed is product ejected and used for other purposes.
• the 5-decene obtained is used in the transalkylation (6).
• both butenes and also 3-hexene and 5-decene are used together as starting material in the transalkylation. This is shown in FIG. 2, in which the reference symbols have the meaning defined in FIG. 1 (see Appendix in FIG. 2).
• the mixture of trialkylaluminum, butene, hexene and decene and propene obtained after the transalkylation reaction (6) with tripropylaiumium is separated (7).
• the C4, C6 and ClO olefins are fed back into the reaction, propene and aluminum alkyl are fed to a further transalkylation (8), in which 1-butene, 1-hexene and 1 -decene are formed (9). These are separated, 1-decene isolated and 1-butene and 1-hexene used in a self-metathesis reaction (5 and 10).
• the C3 current is circulated.
• the products 3-hexene and 5-decene emerging from the metathesis reactor are used in the transalkylation (6).
• the resulting ethylene is separated off and used for other purposes.
• the 3-hexene is obtained from a C4-01efin mixture, in particular from raffinate II, by carrying out a metathesis reaction as described in DE 100 13 253.7 (applicant: BASF AG).
• This response involves the following steps:
• the raffinate II output stream which preferably has a high content of 1-butene by suitable selection of the parameters in the previous selective hydrogenation of butadiene, is in the presence of a metathesis catalyst which contains at least one compound of a metal from groups VI b, Vllb or VIII of the Periodic Table of the Elements, optionally with the addition of ethene, to a metathesis reaction in the course of which butenes contained in the starting stream to give an ethene, propene, butenes, 2-pentene, 3 - Hexen and butanes contained mixture are reacted, optionally based on the butenes 0.05 to
• the low boiler fraction a) obtained from b) is then separated by distillation into a fraction containing ethene and a fraction containing propene, the fraction containing ethene being returned to process step a) and the fraction containing propene being discharged as a product.
• the high boiler fraction obtained from b) is then separated by distillation into a low boiler fraction b) containing butenes and butanes, a middle boiler fraction c) containing pentene and a high boiler fraction d) containing hexene.
• fraction D is discharged as a product.
• the raffinate II output stream is obtained from the C4 fraction using the customary processes known to those skilled in the art, with disruptive isobutene and butadiene being removed. Suitable methods are disclosed in the application DE 100 13 253.7.
• the external mass balance of the process can be influenced in a targeted manner by variable use of ethene and by shifting the equilibrium by recycling certain partial flows.
• the 3-hexene yield is increased by suppressing the cross-metathesis of 1-butene with 2-butene by recycling 2-pentene to the metathesis step, so that no or as little as possible 1-butene is consumed here.
• ethylene is additionally formed, which reacts in a subsequent reaction with 2-butene to give the valuable product propene.
• the 3-hexene is then reacted with aluminum alkyl in a transalkylation. Otherwise, the process is carried out in the same way as is done when the hexene is obtained from raffinate II by transalkylation and subsequent metathesis.
• a preferred embodiment consists in carrying out the transalkylation of the olefin with the carbon number (n / 2) + 1 and the olefin with the carbon number n together in one reactor.
• This preferred embodiment is shown in FIG. 3.
• (5) denotes the reactor in which the process according to DE 100 13 253 J is operated.
• the remaining reference numerals have the meaning defined in FIG. 1 (see Appendix FIG. 3).
• Another preferred product that can be produced by the process according to the invention is 1-octene, which is used to an increasing extent as a comonomer in LLDPE.
• Linear pentene or a mixture of different linear pentenes is used as the starting material.
• FIG. 4 shows a preferred embodiment. 4
• the transalkylation of 2-pentene and 2-octene is carried out together, which is preferred according to the invention.
• the transalkylation reaction can be carried out separately for each of these two olefins (see Appendix Figure 4).
• Linear, internal pentene preferably 2-pentene, serves as the starting olefin.
• This is subjected to a transalkylation (6) with tripropylaiumium, 4-octene, which is a successor product (see below), also being fed into the reactor.
• tripropylaiumium, 4-octene which is a successor product (see below)
• Mixed C3 / C5 / C8 aluminum alkyls are formed.
• the excesses of 2-pentene and 4-octene are separated off and recycled; the mixed aluminum alkyls formed are reacted in the reaction stage (8) with propene to give tripropylaiumiumium and a mixture of 1-pentene and 1-octene. Excess propene is returned.
• Tripropylaiuminium is used again in the transalkylation stage (6).
• 1 octene is removed as a product (9).
• 1-pentene is used in this variant of the process for the construction of 4-octene in a self-metathesis reaction (10).
• the ethylene formed is removed as a valuable product and used for other purposes.
• the 4-octene obtained is used in the transalkylation (6). 5
• terminal olefin that is to say 1-pentene
• steps a) and b) according to the invention being omitted.
• a C4-containing olefin stream in particular raffinate II, is used to produce pentene.
• the starting olefin mixture is then converted into 2-pentene and propene using the 15 process described in DE 199 32 060.8, as shown in FIG. 4. The process includes the following steps:
• propene-containing fraction is discharged as a product.
• the high boiler fraction obtained from b) is then separated by distillation into a low boiler fraction B containing butenes and butanes, a middle boiler fraction C containing pentene and a high boiler fraction D containing hexene.
• Fractions B and D are completely or partially returned to process step a), fraction C is discharged as a product.
• the raffinate II starting stream used preferably has a high content of 2-butene, at least a ratio of 2-butene / l-butene of 1.
• the raffinate II output stream is obtained from the C4 fraction using the customary processes known to those skilled in the art, with disruptive isobutene and butadiene being removed. Suitable methods are disclosed in the application DE 199 32 060.8.
• the external mass balance of the process can be influenced in a targeted manner by variable use of ethene and by shifting the equilibrium by recycling certain partial flows.
• the 2-pentene yield can be increased by completely returning the C4 fraction obtained in step d) and the C5 fraction obtained in step d) to the metathesis reaction.
• the catalysts used in self-metathesis contain a compound of a metal from groups VI b, VII b or VIII of the periodic table of the elements.
• the catalysts can be applied to inorganic supports.
• the metathesis catalyst preferably contains an oxide of a metal from group VIb or VIIIb of the periodic table of the elements.
• the metathesis catalyst is selected from the group consisting of Re 2 0 7 , W0 3 and Mo0.
• the most preferred catalyst is Re 2 0, which is applied to ⁇ -Al 2 0 3 or Al 2 0 3 / B 2 0 / Si0 2 mixed carriers.
• the metathesis reaction can be carried out both in the gas phase and in the liquid phase.
• the temperatures are 0 to 200 ° C, preferably 40 to 150 ° C, the pressures 20 to 80 bar, preferably 30 to 50 bar.
• a linear, internal olefin which has 4 to 30 carbon atoms, or a mixture of such olefins with internal double bonds is reacted with a trialkylaluminum compound, the molar ratio of the linear olefins with internal double bonds to the trialkylaluminum being 1 to a maximum of 50/1.
• the reaction takes place in the presence of a catalytic amount of a nickel-containing isomerization catalyst which effects the isomerization of the internal olefinic double bond, whereby at least a small amount of linear ⁇ -olefin is produced.
• the alkyl groups are then displaced from the trialkylaluminum and a new alkylaluminum compound is formed in which at least one of the alkyl groups bonded to the aluminum is a linear alkyl derived from the corresponding linear ⁇ -olefin.
• the alkyl aluminum compound is then reacted with a 1-olefin in the presence of a displacement catalyst in order to displace the linear alkyl from the alkyl aluminum compound and to produce a free, linear ⁇ -olefin.
• the isomerization catalyst is selected from nickel (I ⁇ ) salts, nickel (II) carboxylates, nickel (II) acetonates and nickel (O) complexes, which can be stabilized with a trivalent phosphorus ligand.
• the isomerization catalyst is selected from the group consisting of nickel bis-1,5-cyclooctadiene, nickel acetate, nickel naphthenate, nickel octanoate, nickel 2-ethylhexanoate and nickel chloride.
• the transalkylation reaction can also be carried out according to other variants which are familiar or accessible to the person skilled in the art.
• isomerization catalysts which contain no Ni or no Ni compound can be used.
• the aluminum alkyls used in the transalkylation are known to the person skilled in the art. They will be available according to availability or for example aspects of the Reaction management selected. Examples of these compounds include triethyl aluminum, tripropylaium aluminum, tri-n-butyl aluminum and triisobutyl aluminum. Tripropylaium aluminum or triethyl aluminum is preferably used.
• Raffinate II with the respective composition is mixed in the respective ratio with freshly added ethene and the respective C4 and C5 recycling stream and metathetized in a 500 ml tubular reactor using a 10% Re 2 O catalyst.
• the discharge is separated into a C2 / 3, C4, C5 and C6 stream by means of three columns and the individual streams are analyzed by GC analysis.
• the C4 stream is split and divided into C4 purge (withdrawal) and C4 recycle.
• composition of raffinate II Composition of raffinate II:
• composition of raffinate II Composition of raffinate II:
• composition of raffinate II Composition of raffinate II:
• 3-Hexene and tripropylaiumium (hydride content less than 1000 ppm) are mixed in a molar ratio of 10: 1. After the mixture has been heated to boiling, a defined amount of nickel salt in toluene is added and the propene formed is allowed to escape. The amount of trihexylaluminum formed is calculated by taking samples at different times, hydrolyzing them with aqueous HCl and analyzing the organic phase by gas chromatography. The amount of trihexylaluminum originally formed results from the amount of n-hexane found.
• Trihexyl aluminum is placed in an autoclave and the same mass of propene is injected.
• the reaction is started by adding a defined amount of nickel salt in toluene to this solution at room temperature.
• samples are taken which are hydrolyzed with aqueous HCl.
• the organic phase is analyzed by gas chromatography and the amount of hexenes formed is determined.
• the catalyst (10% Re 2 0 7 to A1 2 0 3 ) is initially introduced into the reaction vessel under protective gas and 1-hexene is then added.
• the reaction starts spontaneously with strong gas evolution (ethene).
• the mixture is stirred at room temperature and the liquid phase is analyzed by gas chromatography after a defined time.
• the conversion is 80% after 24 h, the selectivity is 99%.
• 5-Decene and tripropylaiumium (hydride content less than 1000 ppm) are mixed in a molar ratio of 10: 1. After the mixture has been heated to boiling, add
• the amount of tridecylaluminum formed is calculated by adding samples are taken at different times, these are hydrolyzed with aqueous HCl and the organic phase is analyzed by gas chromatography. The amount of n-decane found gives the amount of tridecylaluminum originally formed.
• Tridecylaluminum is placed in an autoclave and the same mass of propene is injected.
• the reaction is started by adding 40 ppm of nickel as nickel naphthenate in toluene to this solution at room temperature.
• samples are taken which are hydrolyzed with aqueous HCl.
• the organic phase is analyzed by gas chromatography and the amounts of decene formed are determined.

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