CN1108153A - Method for inactivating catalyst in preparation of linear 2-olefin by oligomerizing ethene with catalyst - Google Patents

Method for inactivating catalyst in preparation of linear 2-olefin by oligomerizing ethene with catalyst Download PDF

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CN1108153A
CN1108153A CN 94118707 CN94118707A CN1108153A CN 1108153 A CN1108153 A CN 1108153A CN 94118707 CN94118707 CN 94118707 CN 94118707 A CN94118707 A CN 94118707A CN 1108153 A CN1108153 A CN 1108153A
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catalyst
zirconium
lipid acid
water
preparation
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CN1061021C (en
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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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Saudi Basic Industries Corp
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Linde GmbH
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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
    • C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
    • 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
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

Process for catalyst deactivation in the catalytically accelerated preparation of linear alpha-olefins by oligomerisation of ethylene. The catalyst comprises a zirconium carboxylate and an organometallic compound. In order to terminate its oligomerisation ability, the catalyst must be deactivated immediately after conversion of the ethylene into the alpha-olefins. This is achieved by adding fatty acids obtained on removal of the catalyst from the reaction mixture by adsorption on aluminium oxide gel, followed by washing out with water and extraction.

Description

Method for inactivating catalyst in preparation of linear 2-olefin by oligomerizing ethene with catalyst
The present invention relates to a kind ofly quicken the method for ethylene oligomerization catalyst deactivation when preparing linear alpha-alkene in catalysis, wherein by in reaction mixture, adding the liquid catalyst that a kind of organic oxygen compound passivation is made up of a kind of carboxylic acid zirconium and a kind of organometallic compound, subsequently by it being separated from mixture with reproducible alumina gel absorption.
Linear alpha-alkene for example contains the linear alpha-alkene of 4 to 8 carbon atoms, for example is widely used as polyolefin modified with comonomer or as the raw material of preparation softening agent, surfactant and analogue and the compound that is used in a large number.
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 that improves a little and carries out in organic solvent (for example toluene, benzene or heptane).In solvent, dissolve in 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.This known catalysts contains formula Zr(OCOR) 4Or Zr(OSO 3R 9) 4The organic acid zirconates as zirconium compounds, R and R in the formula 9Be alkyl, thiazolinyl or phenyl.Second component is made up of alkyl sesquialter aluminum chloride.
Problem when using this catalyzer in liquid phase on the Technology is, be in the desirable moment, and for example reaction mixture flows out soon from reactor, and the oligomerization of interruption ethene is not so that undesirable side reaction that causes useless by product occurs.
In UdSSR inventor's certificate 1118038 and 1573785, this problem tentatively is resolved.Basic identical with the description of IT-A-24498A/79, in the method for this inventor's certificate, destroy catalyzer by adding stoichiometric alcohol.Thereafter reaction mixture is delivered on the sorbent material of high surface area, so that from reaction mixture, separate aluminium, zirconium and chromium complex thereof.As sorbent material, propose with particulate matter (silica gel, clay, zeolite), sawdust and other material.Yet, having proved that the shortcoming of this currently known methods is, must very modestly alcohol be separated with other component, because continuing to stay in the oligomeric solvent, alcohol may have destruction.In currently known methods with the steam reproducing adsorbent and reuse this sorbent material.
The another kind of approach that finishes catalyst activity is as described in the method for US-A-4486615.The there stops activity of such catalysts by adding carboxylic acid.This need add in the technology usually from the outside, thereby is again a kind of spending of can not ignore.
The objective of the invention is, propose a kind of in the oligomerization process of preparation alpha-olefin the method for catalyst deactivation, this method extremely effectively and not needs to add in addition chemical.
According to the present invention, the solution of this purpose is, washes the regenerating oxidation alumina gel by water, from the lipid acid that the carboxylate radical of water extracting catalyst zirconium component generates, uses it for catalyst deactivation with a kind of organic solvent subsequently.
Method of the present invention has series of advantages.
Because water flushing sorbent material, thereby be a kind of technology mode that is dirt cheap.The lipid acid that forms during flushing can be described as a kind of side effect of adsorbent reactivation, and the present invention destroys activity of such catalysts with it.Produce required lipid acid by technology itself by this way and recycle.Can realize going out lipid acid with the appropriate organic solvent extraction simply from the aqueous phase separation of flushing.Consider economic cause, the solvent identical with oligomerization used in suggestion here, promptly in most cases uses toluene.
In addition, two kinds of element zirconium and aluminium have also been separated during absorption.Zirconium is with ZrO 2Form is deposited on the sorbent material, and alkyl sesquialter aluminum chloride is filtered into oxychlorination aluminium, it can be separated with water.
Following process has taken place in concrete hypothesis:
The structure of active oligomerisation catalyst may be M-C 2H 5(M=metal).Chainpropagation is estimated at M-C 2H 5Carry out on the unit.
During with the lipid acid catalyst deactivation, M-C 2H 5The unit may be destroyed like this:
Further reaction such as figure below of zirconium compounds and water:
As mentioned above, ZrO 2Be deposited on the sorbent material, and lipid acid is used for catalyst deactivation.
Following reaction (chemisorption) takes place in Al component and alumina gel during catalyst separating:
Figure 941187071_IMG1
Then, be attached to the hydroxylation of the ethyl sesquialter aluminum chloride on the sorbent material by figure below:
Figure 941187071_IMG2
As mentioned above, the oxychlorination thing that forms here is in aqueous phase dissolved.This solution only contains aluminium as metal component, that is to say not contain heavy metal, so can send into water drain without other treatment step after the neutralization.Also back metallurgy method recovery aluminium can concentrated when needing.
With ZrO 2Form is stayed zirconium on the sorbent material and is not hindered after this catalyst separating, because ZrO 2Itself has good adsorption property.When changing exhausted alumina gel material, available metallurgical method reclaims zirconium.Such technology has surpassed 3%(weight when the Zr concentration on the alumina gel) time be economical.
During with the alumina gel separating catalyst, method of the present invention is very flexibly aspect technological operation: pressure and temperature is to the in fact not influence of efficient of catalyst separating.
The ester that has proved the lipid acid that contains 4 to 8 C carbon atoms is especially suitable for use as carboxylate radical.Sulphonate also can be used for catalyzer of the present invention.
Further specify the present invention by means of an embodiment below.
Discharging total amount by an oligomerization reactor under 31 bar pressures and 80 ℃ of temperature is 20,429kg/h Zr(OCOR) 4With 24kg/h Al 2Cl 3(C 2H 5) 3Be close to reactor exit and add the 36kg/h lipid acid dissolve in the 192kg/h toluene with catalyst deactivation.
The oligopolymer that then will contain decaying catalyst is sent in the adsorber, in about 31 crust and 75 ℃ of adsorptive catalyst components.
Adsorber is equipped with 50m 3Alumina gel estimates that adsorption time is 170 hours (operation).
After adsorption time finished, with 28,000kg/h water washed adsorber one hour, regenerated 2 crust and 75 ℃, and at this moment the organic ligand by catalyzer zirconium component forms lipid acid.From water, extract this lipid acid and be used for catalyst deactivation with 192kg/h toluene.

Claims (2)

1, the method for catalyst deactivation when catalysis acceleration ethylene oligomerization prepares linear alpha-alkene, wherein by add the liquid catalyst that a kind of organic oxygen compound comes passivation to be made up of a kind of carboxylic acid zirconium and a kind of organometallic compound to reaction mixture, after this by adsorbing separating catalyst from mixture with reproducible alumina gel, it is characterized in that, wash the regenerating oxidation alumina gel by water, from the lipid acid of water extraction, then this lipid acid is used for catalyst deactivation with a kind of organic solvent by the carboxylate radical generation of catalyzer zirconium component.
2, by the described method of claim 1, it is characterized in that, make organic solvent with toluene.
CN94118707A 1993-11-10 1994-11-08 Method for inactivating catalyst in preparation of linear 2-olefin by oligomerizing ethene with catalyst Expired - Fee Related CN1061021C (en)

Applications Claiming Priority (2)

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DE4338415A DE4338415C1 (en) 1993-11-10 1993-11-10 Process for catalyst deactivation in the catalytically accelerated preparation of linear alpha-olefins by oligomerisation of ethylene
DEP4338415.3 1993-11-10

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103649022A (en) * 2011-06-22 2014-03-19 开放型股份公司"希布尔控股" Method for the isolation of olefin oligomerization products and the decomposition of oligomerization catalyst residues
CN107207382A (en) * 2014-12-23 2017-09-26 公共型股份公司希布尔控股 The method for precipitating polymer and the organo-metallic catalyst of deactivation in olefin oligomerization

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1752433B1 (en) * 2005-08-10 2012-10-03 Linde AG Improved drying process for linear alpha-olefins
EP1754694A1 (en) * 2005-08-10 2007-02-21 Linde AG Method for deactivation and removal of catalytic components in the oligomerisation of ethylene
EP1777210B1 (en) * 2005-10-19 2009-05-27 Saudi Basic Industries Corporation Method for oligomerization and/or polymerization of ethylene with flushing of equipment and piping
EP2354113A1 (en) * 2010-02-04 2011-08-10 Linde AG Method for deactivation of a catalyst

Family Cites Families (6)

* 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
SU1118038A1 (en) * 1983-04-16 1999-03-27 В.Н. Мельников METHOD OF PURIFICATION OF OLIGOMERIZATION PRODUCTS AND DIMERIZATION OF ETHYLENE FROM RESIDUES OF A PROCESSED CATALYST
JPS62430A (en) * 1985-06-26 1987-01-06 Idemitsu Petrochem Co Ltd Production of linear alpha-olefin
SU1573785A1 (en) * 1988-04-28 1999-03-27 В.Н. Мельников METHOD FOR CLEANING PRODUCTS OF DI- AND OLIGOMERIZATION OF OLEFINS FROM RESIDUES OF A PROCESSED CATALYTIC COMPLEX
JP2761544B2 (en) * 1989-09-14 1998-06-04 出光石油化学株式会社 Method for producing linear α-olefin

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103649022A (en) * 2011-06-22 2014-03-19 开放型股份公司"希布尔控股" Method for the isolation of olefin oligomerization products and the decomposition of oligomerization catalyst residues
CN103649022B (en) * 2011-06-22 2015-11-25 公共型股份公司"希布尔控股" For separating of olefin oligomerization product and the method for decomposing oligomerisation catalyst resistates
CN107207382A (en) * 2014-12-23 2017-09-26 公共型股份公司希布尔控股 The method for precipitating polymer and the organo-metallic catalyst of deactivation in olefin oligomerization
CN107207382B (en) * 2014-12-23 2021-06-18 公共型股份公司希布尔控股 Method for precipitating polymer and deactivated organometallic catalyst in olefin oligomerization reactions

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