EP1235767A1 - Kohlenwasserstoff-umwandlungsverfahren - Google Patents

Kohlenwasserstoff-umwandlungsverfahren

Info

Publication number
EP1235767A1
EP1235767A1 EP00986843A EP00986843A EP1235767A1 EP 1235767 A1 EP1235767 A1 EP 1235767A1 EP 00986843 A EP00986843 A EP 00986843A EP 00986843 A EP00986843 A EP 00986843A EP 1235767 A1 EP1235767 A1 EP 1235767A1
Authority
EP
European Patent Office
Prior art keywords
trimerisation
aluminium
chromium
alkyl
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00986843A
Other languages
English (en)
French (fr)
Inventor
John Thomas Dixon
Jacobus Johannes Cronje Grove
Alta Ranwell
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sasol Technology Pty Ltd
Original Assignee
Sasol Technology Pty Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sasol Technology Pty Ltd filed Critical Sasol Technology Pty Ltd
Publication of EP1235767A1 publication Critical patent/EP1235767A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes

Definitions

  • This invention relates to a hydrocarbon conversion process. More particularly, this invention relates to a hydrocarbon conversion process for the oligomerisation of olefins and derivatives thereof.
  • trimerisation of ethylene to 1-hexene is significant since, in addition to its use as a specific chemical, 1-hexene is extensively used in polymerisation processes either as a monomer or co monomer.
  • trime c products derived from longer chain olefins could be well utilized as synthetic lubricants (e.g. polyalphaolefins / PAO's), as well as various other applications such as drilling muds, and as feedstock to prepare detergents and plasticizers.
  • chromium-based processes for the trimerisation of ethylene to 1- hexene include:
  • European Patent No. 0 416 304 discloses the trimerisation of olefins by chromium-containing compounds, such as, for example, chromium pyrrolides that are prepared by forming a mixture of a chromium salt, a metal amide and an electron pair donor solvent, such as, for example, an ether. These chromium catalysts can be used either unsupported or supported on an inorganic oxide;
  • European Patent No. 0 668 105 discloses a process to trimerise ethylene to 1-hexene comprising contacting ethylene with a stabilized catalyst system comprising a chromium source, a pyrrole- containing compound, a metal alkyl and an aromatic compound;
  • European Patent No. 0 706 983 discloses a process for preparing an ⁇ -olefin oligomer which comprises oligomerising an ⁇ -olefin in a saturated hydrocarbon solvent in the presence of a chromium-based catalyst system comprising a combination of at least a chromium compound, an amine or metal amide, an alkylaluminium compound and a non-coordinating
  • Lewis acid-containing compound based on an element selected from groups NIB, IVB, VB and VIB of the periodic table;
  • European Patent No. 0 699 648 discloses a process for producing 1-hexene which comprises trimerising ethylene in a 1-hexene solvent in the presence of a catalyst system obtainable by contacting in a 1- hexene solvent a chromium-containing compound, trialkylaluminium or dialkylaluminium hydride, a pyrrole compound or derivative thereof and a group 13 (III B) or group 14 (IV B) halogen compound; and
  • US Patent No. 5,81 1 ,618 discloses a process for the trimerisation of ethylene, said process comprising reacting ethylene, using a catalyst comprising an aluminoxane and a polydentate phosphine, arsenic and/or stibine coordination complex of a chromium salt, such that 1-hexene is formed.
  • WO 98/47616 discloses that ionic liquids may be used as solvent and/or activator during the oligomerisation of olefins with a nickel complex as catalyst.
  • Heterogeneous catalysts systems are often selected over homogeneous catalyst systems due to relative ease of recovering and recycling such catalyst systems.
  • the process of trimerisation of ethylene using chromium catalysts supported on an inorganic oxide has problems of insufficient activity, poor selectivity towards the intended trimeric product and leads to unsatisfactory levels of polyethylene by-product.
  • Trimerisation processes using unsupported chromium catalyst systems involve the use of unsaturated hydrocarbon and/or saturated hydrocarbon and/or aromatic solvents. Consequently, recovery of chromium compounds from the reactor effluent stream requires several sequential steps.
  • Non-aqueous room-temperature ionic liquids are generally composed of large organic cations associated with inorganic or organic anions. They can be described as mixtures of salts that are liquid at temperatures below the individual melting points of the components.
  • Ionic liquids are either organic salts or mixtures consisting of at least one organic component, the most common organic salts used being alkylammonium, alkylphosphonium, N-alkylpyridinium, and N,N -dialkylimidazolium as cations, associated with inorganic or organic anions.
  • a hydrocarbon conversion process using a catalyst system including a non-nickel transition metal derived catalyst and one or more ionic liquids.
  • an oligomerisation process using a catalyst system including a non-nickel transition metal derived catalyst and one or more ionic liquids.
  • the ionic liquids may be liquid at room temperature, i.e. at below 50°C, typically at below 30°C. Usually the ionic liquids are liquid at between 15°C and 25°C.
  • the ionic liquids may be non-aqueous ionic liquids.
  • the ionic liquids may be used as a solvent / co-solvent or activator for the catalyst system of the invention.
  • the anions are essentially responsible for the chemical properties of ionic liquids, the most important of which, for coordination chemists, is the coordinating ability and/or reactivity of anions toward the metal centre of a complex. These properties are believed to depend on the nature of the anions themselves, such as the size and charge and also on the hardness of the metal centre, its oxidation state, and its surrounding ligands.
  • the ionic liquids of the process of the invention may include as cation an organic halide salt such as a quaternary ammonium salt, an imidazoiine or alkyl- substituted imidazoiine salt, a pyhdinium or alkyl-substituted pyridinium salt, a sulfonium or alkylsulfonium salt, or a phosphonium or alkyl-substituted phosphonium salt, or other suitable anion leading to ionic liquids having the desired properties.
  • an organic halide salt such as a quaternary ammonium salt, an imidazoiine or alkyl- substituted imidazoiine salt, a pyhdinium or alkyl-substituted pyridinium salt, a sulfonium or alkylsulfonium salt, or a phosphonium or alkyl-substituted phosphonium salt, or other suitable anion
  • the ionic liquids of the process of the invention may include as anion compounds of the formula R n MX 3 . n , or R m M 2 X 6 . m wherein
  • R is a Ci - CC-6 alkyl (or iso-alkyl) radical
  • M is aluminium, gallium, boron or iron (III);
  • X is a halogen atom
  • n is O, 1 , 2 or 3
  • m is 1 , 2 or 3.
  • the metal component of the anion compounds, M is typically aluminium and m and/or n is typically three; therefore, the anion is typically an alkyialuminium compound.
  • One such alkyialuminium useful as an anion for the process of the invention is triethyaluminium.
  • the anion is an alkylaluminoxane such as methylaluminoxane, or a borate anion such as B(C 6 F 5 ) 4 ⁇
  • the ionic liquids of the process of the invention may include as anion an alkylaluminoxane or iso-alkylaluminoxane.
  • the alkylaluminoxane may be methylaluminoxane, also known as MAO.
  • the ionic liquids of the process of the invention may include as anion tin and germanium halides, BF 4 " , SbF 6 “ , PF 6 “ , FSO 3 “ , CF 3 SO 3 “ , (CF 3 SO 2 ) 2 N ⁇ CF 3 CO 2 " ,copper, ammonium or phosphonium chlorides.
  • the ionic liquids of the process of the invention may include as anion large, weakly coordinating anions such as tetraphenylborate (BPh 4 " ) and related anions such as fluorinated derivatives of BPh " .
  • anion large, weakly coordinating anions such as tetraphenylborate (BPh 4 " ) and related anions such as fluorinated derivatives of BPh " .
  • the ionic liquids of the process of the invention may include B(p-C 6 H 4 F) 4 " ; B(C 6 F 5 ) 4 " , B(3,5-C 6 H 3 (CF 3 ) 2 ) 4 -), and PH 3 BCNBPIV.
  • CBnH 12 1-carba-c/oso-dodecacarborate (CBnH 12 " ) and related anions, 12-CBnHnCI “ , 12-CBnHnBr “ , 12-CBnHnl “ , ⁇ -CBnHnfCeFs) ' , 7,12- CBnH 10 , 7,12-CB 11 H 10 Br 2 , 7,12-CB 11 H 10 I 2 , 7, 8, 9, 10, 12-CBnH 7 C 15 , and 7, 8, 9, 10, 11 , 12-CBnH 6 C 16 ), as well as pentafluorooxotellurate (OTeF 5 ) and related anions.
  • anions of the formula M(OTeF 5 ) n m" wherein M is selected from Ni, Cu, Zn and Pd; n is either 4 or 6; and m is either 1 or 2.
  • Yet further useful anions include PW 12 O 40 3' and related anions, and HC(SO 2 CF 3 ) 2 " together with related anions.
  • Even further useful anions include the fulleride ion C 60 " , the relatively stable borate anion B(o-C 6 H 4 O 2 ) 2 " and the diborane anion H(1 ,8-(BMe 2 ) 2 c 10 H 6 ) ' .
  • the non-nickel transition metal derived catalyst of the catalyst system may be a chromium derived catalyst.
  • the catalyst system of the process of the invention may be a trimerisation catalyst system.
  • the trimerisation catalyst system may include the ionic liquids as solvent or co-solvent and/or activator together with at least one of a chromium source and a pyrrole-containing compound. Typically the chromium source and pyrrole-containing compound are used in combination.
  • the catalyst system may optionally include one or more of a metal alkyl, a halogen source, and an unsaturated hydrocarbon compound.
  • the chromium source of said catalyst system may consist of one or more organic and/or inorganic chromium compounds, with the chromium oxidation state ranging from 0 to 6.
  • chromium compounds are suitably expressed by the general formula CrX transit , wherein X may be the same or different and represents an organic or inorganic radical, group or compound; and n is an integer from 0 to 6.
  • the organic radical may have from about 1 to 20 carbon atoms per radical.
  • such radical is selected from the group consisting of alkyl, alkoxy, ester, ketone and/or amido radicals.
  • the X's include an organic compound
  • such organic compound may be selected from the group consisting of an amine compound, a phosphine compound, a phosphine oxide compound, a nitrosyl group, and an ether compound.
  • such inorganic radical may be selected from the group consisting of halides, nitrates, and sulphates
  • the chromium source may include one or more of chrom ⁇ um(lll)acetylacetonate, chromium (III) acetate, chromium (III) pyrrolide, chromium (III) 2,2,6,6,tetramethylheptad ⁇ onate, chromium (III) t ⁇ s(2-ethylhexanoate), b ⁇ s(N,N'-b ⁇ s(tr ⁇ methyls ⁇ lyl)benzam ⁇ d ⁇ nato) chromium (III) chloride, tr ⁇ chlorotr ⁇ s(4- ⁇ sopropyipy ⁇ d ⁇ ne) chromium (III), tnchloro (N,N,N',N',N"-pentamethyld ⁇ ethylenetr ⁇ am ⁇ ne) chromium (III) chloride, b ⁇ s-(2- d ⁇ methylphosph ⁇ no-ethyl)e
  • the pyrrole-containing compound of the trimerisation catalyst system includes pyrrole and derivatives thereof
  • pyrrole refers to hydrogen pyrrolide, i e C 4 H 5 N
  • a “pyrrolide”, for purposes of this specification, is defined as a compound containing a 5-membered, nitrogen containing heterocycle
  • the derivatives of pyrrole in the trimerisation catalyst system may include substituted pyrrolides, heteroleptic or homoleptic metal pyrrolide complexes, salts, and isotopes thereof
  • the pyrrole-containing compounds of the trimerisation catalyst system may have from about 4 to about 20 carbon atoms per molecule

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP00986843A 1999-11-26 2000-11-24 Kohlenwasserstoff-umwandlungsverfahren Withdrawn EP1235767A1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US16761699P 1999-11-26 1999-11-26
ZA9907340 1999-11-26
ZA997340 1999-11-26
US167616P 1999-11-26
PCT/ZA2000/000233 WO2001038270A1 (en) 1999-11-26 2000-11-24 Hydrocarbon conversion process

Publications (1)

Publication Number Publication Date
EP1235767A1 true EP1235767A1 (de) 2002-09-04

Family

ID=26863328

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00986843A Withdrawn EP1235767A1 (de) 1999-11-26 2000-11-24 Kohlenwasserstoff-umwandlungsverfahren

Country Status (5)

Country Link
EP (1) EP1235767A1 (de)
CN (1) CN1409694A (de)
AU (1) AU2302001A (de)
BR (1) BR0015901A (de)
WO (1) WO2001038270A1 (de)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001083447A2 (en) * 2000-05-04 2001-11-08 Sasol Technology (Pty) Ltd A halopyrrole ligand for use in a catalyst system
US6703338B2 (en) 2002-06-28 2004-03-09 Univation Technologies, Llc Polymerization catalyst activators, method of preparing, and their use in polymerization processes
US20050187418A1 (en) 2004-02-19 2005-08-25 Small Brooke L. Olefin oligomerization
US20070043181A1 (en) 2005-08-19 2007-02-22 Knudsen Ronald D Methods of preparation of an olefin oligomerization catalyst
US9550841B2 (en) 2004-02-20 2017-01-24 Chevron Phillips Chemical Company Lp Methods of preparation of an olefin oligomerization catalyst
US7384886B2 (en) 2004-02-20 2008-06-10 Chevron Phillips Chemical Company Lp Methods of preparation of an olefin oligomerization catalyst
US20050187098A1 (en) 2004-02-20 2005-08-25 Knudsen Ronald D. Methods of preparation of an olefin oligomerization catalyst
CN100457268C (zh) * 2006-09-08 2009-02-04 浙江大学 离子液体支载的乙酰丙酮金属的催化剂及制备方法
KR101057576B1 (ko) 2007-08-16 2011-08-17 에스케이종합화학 주식회사 선택적 에틸렌 올리머고화 촉매계
US7902415B2 (en) 2007-12-21 2011-03-08 Chevron Phillips Chemical Company Lp Processes for dimerizing or isomerizing olefins
US9586872B2 (en) 2011-12-30 2017-03-07 Chevron Phillips Chemical Company Lp Olefin oligomerization methods
CN103242118A (zh) * 2012-02-08 2013-08-14 西安艾姆高分子材料有限公司 一种合成新型乙烯齐聚物的方法
CN117884182A (zh) * 2023-12-18 2024-04-16 天津科技大学 极少聚合物生成的乙烯三聚、四聚的催化剂体系及其制备方法和应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0558187B1 (de) * 1992-02-19 1996-04-10 BP Chemicals Limited Butenpolymere
CN1123031A (zh) * 1994-02-10 1996-05-22 英国石油化学品有限公司 离子液体
US5543375A (en) * 1994-02-18 1996-08-06 Phillips Petroleum Company Olefin production
GB9707842D0 (en) * 1997-04-18 1997-06-04 Bp Chem Int Ltd Oligomerisation process
US20020010291A1 (en) * 1998-12-04 2002-01-24 Vince Murphy Ionic liquids and processes for production of high molecular weight polyisoolefins

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0138270A1 *

Also Published As

Publication number Publication date
WO2001038270A1 (en) 2001-05-31
AU2302001A (en) 2001-06-04
BR0015901A (pt) 2002-10-22
CN1409694A (zh) 2003-04-09

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