CN1112459A - Resolvable catalyst for preparation linear 2-olefin through low polymerisation of ethylene - Google Patents

Resolvable catalyst for preparation linear 2-olefin through low polymerisation of ethylene Download PDF

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Publication number
CN1112459A
CN1112459A CN94118706A CN94118706A CN1112459A CN 1112459 A CN1112459 A CN 1112459A CN 94118706 A CN94118706 A CN 94118706A CN 94118706 A CN94118706 A CN 94118706A CN 1112459 A CN1112459 A CN 1112459A
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CN
China
Prior art keywords
catalyst
catalyzer
olefin
ethylene
resolvable
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CN94118706A
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Chinese (zh)
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CN1072033C (en
Inventor
海因茨·博尔特
彼得·马塞厄斯·弗里茨
乔治·穆萨里
彼得·埃弗吉纳维奇·麦特科弗斯基
佩弗尔·西蒙诺维奇·切克瑞
瓦莱里·尼古拉维奇·梅尔尼克夫
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Linde GmbH
Saudi Basic Industries Corp
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Linde GmbH
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Publication of CN1112459A publication Critical patent/CN1112459A/en
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    • 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
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—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
    • B01J31/143—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 of aluminium
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • 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
    • C07C2531/025—Sulfonic acids
    • 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
    • C07C2531/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The catalyst is a derivative of the known catalysts comprising a zirconium salt of organic acids and an organoaluminium compound. The catalyst conforms to the formulation ZrCl(2-n)X(2+n) where 1.4 </= n </= 1.7, X = OCOR or OSO3R, and R and R' are alkyl, alkenyl or phenyl.

Description

Resolvable catalyst for preparation linear 2-olefin through low polymerisation of ethylene
The present invention relates to a kind of soluble catalyst that is used for preparing by ethylene oligomerization linear alpha-alkene, it contains a kind of organic acid zirconates and a kind of organo-aluminium compound.
Linear alpha-alkene for example contains the linear alpha-alkene of 4 to 8 carbon atoms, be widely used as for example polyolefin modified with comonomer or preparation softening agent, the raw material that surfactant and analogue are used and the compound that is used in enormous quantities.
Known by IT-A-24498A/79, ethene is at the oligomeric linear alpha-olefin of liquid phase.This is reflected under the temperature and pressure of raising and carries out in organic solvent (for example toluene, benzene or heptane).A kind of by two components, the catalyzer that promptly a kind of organic acid zirconates and a kind of organo-aluminium compound are formed is dissolved in this solvent.This known catalysts contains formula Zr(OCOR) 4Or Zr(OSO 3R ') 4The organic acid zirconates as zirconium compounds, R and R ' are alkyl, thiazolinyl or phenyl in the formula.As prior art, the document is quoted a kind of similar catalyzer, and it consists of Zr(OR) m(NR 2) nX p, R=hydrocarbon and X=halogen, condition is m+n+p=4.In two kinds of catalyzer, second component all is an organo-aluminium compound, and formerly under the situation of the zirconium compounds of Ti Chuing, second component is an alkyl sesquialter aluminum chloride.
US-PS 4434312 discloses a kind of hydrocarbon soluble catalyst that is used to prepare alpha-olefin wax, and it also contains a kind of zirconium compounds except a kind of dialkylaluminum halides and a kind of alkyl dihalide aluminium.The design of this patent documentation is the high-load paraffin that has greater than 20 carbon atoms of preparation under the specific molar ratio of aluminium and zirconium component in catalyzer.This patent documentation suggestion uses the organic acid zirconates as zirconium component, for example ZrCl 2(OOCR) 2Or ZrCl(OOCR) 3, R is an alkyl or phenyl in the formula.
Therefore, this known catalysts is accurately to have regulated stoichiometric compound, must be noted that accurate quantity ratio when it prepares.Yet this is a shortcoming for big plant-scale method.
Task of the present invention is, improve known catalyzer, make that under the situation of not losing catalyst effectiveness can produce on the one hand the product of same quality and needn't accurately note the metering of catalyst component when the preparation catalyzer, component on the other hand can also economize in raw materials.
According to the present invention, the solution of this task is to adopt the zirconates shown in the following formula: ZrCl (2-n)X (2+n), condition is 1.4≤n≤1.7, X=OCOR or OSO in the formula 3R ', R and R ' are alkyl, thiazolinyl or phenyl.
Therefore, catalyzer of the present invention can for example have
Composition.
The present invention is definite, with common ZrCl 4Needn't accurately react when preparing catalyzer by stoichiometric ratio with a kind of corresponding organic compound.Simplified the synthetic of catalyzer significantly.
Proved that specially suitable lipid acid is the lipid acid that 4 to 8 C atoms are arranged.Sulfonic acid also proves and can be used for catalyzer of the present invention.
In preparation during known catalysts, all tetravalences of zirconium entirely will be with for example carboxylate radical be saturated, thereby usually with the excess fatty acids operation, so that reaction can be finished fully.Consequently, in oligomerization process after this, also there is free lipid acid in the reaction mixture.Yet the present invention determines, hinders the oligomeric of ethyl with zirconium bonded lipid acid, thereby the quality of the prepared alpha-olefin of meeting deterioration.(because catalyzer of the present invention does not contain excess fats acid, so when oligomeric, can receive productive rate preferably).
Prepare catalyzer by the present invention and also have other advantage.
At first, owing to use a small amount of organic constituent, saved chemical.
Usually pressing formula ZrCl 4+ 4HOCOR → Zr(OCOR) 4When+4HCl prepared catalyzer, every mole of zirconium discharged 4 moles of HCl.As implied above, in catalyzer of the present invention, owing to do not have complete reaction, thereby the HCl that produces when the preparation catalyzer is less, this has just reduced the etching problem when catalyzer is synthetic.
The foam also definite in addition, that the foam during synthetic catalyzer of the present invention in the reaction mixture rises when being less than synthetic known catalysts, thereby the catalyzer building-up process is accelerated significantly.
Catalyzer of the present invention is synthetic not necessarily non-to carry out in pressurized vessel, and reason is that raw catalyst just forms under normal pressure and low temperature.
The present invention has determined that already for example the tetravalence with the complete saturated zirconium of fatty acid radical is unnecessary and disadvantageous, and this in the present invention thereby be invalid.Unique condition is, catalyzer dissolves in reaction medium, and reaction medium is a toluene in common ethylene oligomerization.In the whole processing condition of catalyzer of the present invention, all satisfy this point.
Further specify the present invention by means of a numerical value embodiment below.
Under the condition of room temperature and excluding air and moisture with 233gZrCl 4Be suspended in the 800ml toluene.Then add the 326g isopropylformic acid, and under refluxad be heated to boiling.At ZrCl 4Behind the pass into solution, slowly be heated to boiling, till no longer producing HCl fully.After reaction finishes, in limpid brown toluene solution, no longer include isopropylformic acid and exist.It is oligomeric that this solution does not need further processing promptly to can be used for.Steam solvent and after the dried residue, obtain a kind of light brown powder under vacuum under high vacuum, its analytical value is:
The calculated value trial value
C 41.9 42.1 weight %
H 6.1 6.3 weight %
Cl 2.5 2.4 weight %
Zr 21.5 21.6 weight %
Cl/Zr????????0.3????????0.28????????mol/mol

Claims (1)

1, be used for preparing by ethylene oligomerization the soluble catalyst of linear alpha-alkene, this catalyzer contains a kind of organic acid zirconates and a kind of organo-aluminium compound, it is characterized in that, adopts the zirconates of following formula:
Condition is 1.4≤n≤1.7, X=OCOR or OSO in the formula 3R ', R and R ' are alkyl, thiazolinyl or phenyl.
CN94118706A 1993-11-10 1994-11-08 Resolvable catalyst for preparation linear 2-olefin through low polymerisation of ethylene Expired - Fee Related CN1072033C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4338416.1 1993-11-10
DE4338416A DE4338416C1 (en) 1993-11-10 1993-11-10 Soluble catalyst for the preparation of linear alpha -olefins by oligomerisation of ethylene

Publications (2)

Publication Number Publication Date
CN1112459A true CN1112459A (en) 1995-11-29
CN1072033C CN1072033C (en) 2001-10-03

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CN94118706A Expired - Fee Related CN1072033C (en) 1993-11-10 1994-11-08 Resolvable catalyst for preparation linear 2-olefin through low polymerisation of ethylene

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DE (1) DE4338416C1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101888902B (en) * 2007-12-12 2013-11-13 沙特基础工业公司 Catalyst composition for oligomerization of ethylene oligomerization process and method for preparation thereof

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Publication number Priority date Publication date Assignee Title
DE102004043271A1 (en) * 2004-09-07 2006-03-09 Linde Ag Process for the synthesis of zirconium carboxylates
EP1911515A1 (en) * 2006-10-02 2008-04-16 Saudi Basic Industries Corporation Inc. Method for preparing a transition metal ester compound
US9133079B2 (en) 2012-01-13 2015-09-15 Siluria Technologies, Inc. Process for separating hydrocarbon compounds
CA2874526C (en) 2012-05-24 2022-01-18 Siluria Technologies, Inc. Oxidative coupling of methane systems and methods
US9969660B2 (en) 2012-07-09 2018-05-15 Siluria Technologies, Inc. Natural gas processing and systems
US9598328B2 (en) 2012-12-07 2017-03-21 Siluria Technologies, Inc. Integrated processes and systems for conversion of methane to multiple higher hydrocarbon products
EP3074119B1 (en) 2013-11-27 2019-01-09 Siluria Technologies, Inc. Reactors and systems for oxidative coupling of methane
CA3123783A1 (en) 2014-01-08 2015-07-16 Lummus Technology Llc Ethylene-to-liquids systems and methods
EP3097068A4 (en) 2014-01-09 2017-08-16 Siluria Technologies, Inc. Oxidative coupling of methane implementations for olefin production
US10377682B2 (en) 2014-01-09 2019-08-13 Siluria Technologies, Inc. Reactors and systems for oxidative coupling of methane
EP3169435B1 (en) 2014-07-18 2022-04-06 SABIC Global Technologies B.V. Catalyst composition and process for preparing linear alpha olefins
US10793490B2 (en) 2015-03-17 2020-10-06 Lummus Technology Llc Oxidative coupling of methane methods and systems
US9334204B1 (en) 2015-03-17 2016-05-10 Siluria Technologies, Inc. Efficient oxidative coupling of methane processes and systems
US20160289143A1 (en) 2015-04-01 2016-10-06 Siluria Technologies, Inc. Advanced oxidative coupling of methane
US9328297B1 (en) 2015-06-16 2016-05-03 Siluria Technologies, Inc. Ethylene-to-liquids systems and methods
WO2016205411A2 (en) 2015-06-16 2016-12-22 Siluria Technologies, Inc. Ethylene-to-liquids systems and methods
US20170107162A1 (en) 2015-10-16 2017-04-20 Siluria Technologies, Inc. Separation methods and systems for oxidative coupling of methane
CA3019396A1 (en) 2016-04-13 2017-10-19 Siluria Technologies, Inc. Oxidative coupling of methane for olefin production
WO2018118105A1 (en) 2016-12-19 2018-06-28 Siluria Technologies, Inc. Methods and systems for performing chemical separations
ES2960342T3 (en) 2017-05-23 2024-03-04 Lummus Technology Inc Integration of oxidative methane coupling procedures
WO2019010498A1 (en) 2017-07-07 2019-01-10 Siluria Technologies, Inc. Systems and methods for the oxidative coupling of methane

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4486615A (en) * 1960-09-14 1984-12-04 Exxon Research & Engineering Co. Preparation of linear olefin products
US4434312A (en) * 1978-03-02 1984-02-28 Exxon Research And Engineering Co. Preparation of linear olefin products
US4434313A (en) * 1981-12-14 1984-02-28 Exxon Research And Engineering Co. Preparation of linear olefin products
US4410750A (en) * 1981-12-14 1983-10-18 Exxon Research And Engineering Co. Preparation of linear olefin products

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101888902B (en) * 2007-12-12 2013-11-13 沙特基础工业公司 Catalyst composition for oligomerization of ethylene oligomerization process and method for preparation thereof

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CN1072033C (en) 2001-10-03

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