CN1048976C - Preparation of linear olefin - Google Patents

Preparation of linear olefin Download PDF

Info

Publication number
CN1048976C
CN1048976C CN94118705A CN94118705A CN1048976C CN 1048976 C CN1048976 C CN 1048976C CN 94118705 A CN94118705 A CN 94118705A CN 94118705 A CN94118705 A CN 94118705A CN 1048976 C CN1048976 C CN 1048976C
Authority
CN
China
Prior art keywords
reactor
oligomerization
solvent
ethene
catalyzer
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.)
Expired - Fee Related
Application number
CN94118705A
Other languages
Chinese (zh)
Other versions
CN1107828A (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
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.)
Saudi Basic Industries Corp
Original Assignee
Linde GmbH
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 Linde GmbH filed Critical Linde GmbH
Publication of CN1107828A publication Critical patent/CN1107828A/en
Application granted granted Critical
Publication of CN1048976C publication Critical patent/CN1048976C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • 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
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/04—Pressure vessels, e.g. autoclaves
    • 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
    • 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

Landscapes

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

Abstract

A process for the preparation of linear- alpha -olefins by oligomerisation of ethylene. The oligomerisation is carried out in the presence of an organic solvent and in the presence of a homogeneous liquid catalyst in an empty-tube oligomerisation reactor which is equipped in its upper part with a separator. The oligomerisation is carried out at a pressure of 31-50 bar and temperature of 80 DEG C.

Description

The preparation method of linear alpha-olefin and equipment
The present invention relates to prepare a kind of method and a kind of equipment of linear alpha-alkene by oligomerisation of ethylene in the presence of a kind of organic solvent and a kind of homogeneous liquid catalyst of forming by zirconium compounds and organometallic compound.
Linear alpha-alkene for example contains the linear alpha-alkene of 4 to 8 carbon atoms, be widely used as polyolefin modified with comonomer or preparation softening agent, surfactant and analogue with raw material and the compound that 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 60 to 100 ℃ of temperature and 5 to 30 atmospheric pressures and carries out in organic solvent (for example toluene, benzene or heptane).Liquid catalyst is dissolved in the solvent, and this catalyzer is made up of two components, promptly is made up of a kind of zirconium thing and a kind of organometallic compound.Zirconium compounds is formula Zr (OCOR) 4The organic acid zirconates, R is alkyl, alkene or phenyl in the formula.Second component is made up of a kind of organo-aluminium compound, wherein proves alkyl sesquialter aluminum chloride the most effectively.In this currently known methods, ethene is sent into the stirred reactor that the solvent that contains catalyzer is housed.The composition of oligomerization product can be controlled in the narrow scope by attemperation, zirconium component concentrations and mol ratio Al/Zr.
Yet currently known methods uses the suggestion of stirred reactor but to be proved to be disadvantageous.Reason is, owing to require bearing airtight, thereby the whipping appts of operation under high pressure is very expensive, thereby determine, must close stirred reactor continually, so that remove sedimentary polymkeric substance on reactor wall, because they are easy to separate coalescence thereby reduce product purity.
Therefore, task of the present invention is to improve known method and it is carried out in a simple reactor, and this reactor does not need whipping appts, thereby quite cheap, and is not easy to be disturbed.
According to the present invention, the solution of this task is, at 31 to 50 crust, under preferred 31 to 40 bar pressures, under about 80 ℃ of temperature, carry out this oligomerization in a kind of blank pipe reactor that solvent-catalyst mixture is housed, ethene is sent into from reactor bottom, and oligomerization product is discharged from reactor lower part with solvent and catalyzer.
Method of the present invention is carried out being higher than under the pressure of currently known methods.Owing to replaced known stirred reactor with blank pipe reactor of the present invention, it is possible to make that such work becomes, because there is not bearing here, thereby does not have sealing problem.Higher pressure also has an important advantage, promptly can obtain higher product purity.Proved the pressure of available 31 to 50 crust, and 31 to 40 crust are specially suitable.
Oligomericly in the liquid phase of oligomerization reactor bottom, carry out.Because reaction is heat release, the too high meeting of temperature of reaction causes product quality to reduce, thereby must derive reaction heat.In the method for the invention, this is finished by the ethene by reactor cycles.Ethene in the ethylene recycle is dissolved in liquid phase, to keep the required ethylene concentration of oligomerization.With excessive ethene control reaction temperature.This temperature on purpose remains on about 80 ℃.Proved already, in fact ethene was sent into oligomerization with 50 ℃ temperature.
Compare with known stirred reactor, blank pipe reactor of the present invention also has an advantage, and can pass through to regulate the exchange area between input airshed control gaseous ethylene and the fluidised form catalyzer, and make it satisfy various requirement, at first be the requirement that material changes.Usually, compare, need not can obviously improve exchange area by many consumed energies with stirred reactor.Even now, the foam of observing formation in blank pipe reactor of the present invention is lower than known stirred reactor.
According to the present invention, it is cylindric that oligomerization reactor is essentially, and there is a cross section convergent part upper end, and it has separates and washing function.Determine that in known agitator, under the main service temperature of ethene and light-weight oligopolymer, the steam of solvent upwards steams.This is undesirable in afterwards the equipment unit not only, and must discharge again and dispose.Therefore, in blank pipe reactor of the present invention,, be provided with the multi-wash column plate in it in order to isolate steam at the top contraction section.
The overhead vapor of blank pipe reactor of the present invention is cooled off outside reactor, comes liquefaction solvent steam and light oligopolymer with it.After isolating gas phase, make liquid phase part be back to the contraction section top, and on wash plate, distribute.Reduce high boiling component contained in the steam that from oligomerization reactor, rises thus in large quantities, make its downtake flow back to reaction zone again through plate.
The cross section of shell of reactor is the storage height of liquid layer that improves on the washing column plate in the effect of separator scope convergent, and this can cause better washing and condensation recovering effect.
Related to the present invention and catalyzer that on purpose use is made up of two components, one of them is a kind of zirconium compounds ZrCl mCarboxylate radical n, m+n=4 in the formula, m=0 to 2, carboxylate radical is by C 4To C 8Fatty acid derived obtains, and another is a kind of organometallic compound that has the organo-aluminium compound form of an ethyl ligand at least, for example as Al (C 2H 5) 3, Al 2Cl 3(C 2H 5) 3Or AlCl (C 2H 5) 2
Further specify the present invention by means of an embodiment shown in the drawings below.
In devices illustrated, the liquid catalyst that dissolves in toluene flows into oligomerization reactor 2 by pipeline 1.This liquid is made up of toluene and 35kg/h catalyzer that 11085kg/h contains small amounts of oligomer, and this catalyzer is made up of 7.5kg four isopropylformic acid zirconiums and 27.5kg/h ethyl sesquialter aluminum chloride again.This liquid is sent into reactor 2 under 31 bar pressures and 40 ℃ of temperature.
Is 15000kg/h by pipeline 3 to the equipment supply flow rate, and pressure is that 30.5 crust and temperature are 30 ℃ ethene.The ethene of this quantity is that normal running is necessary.Before device start, must at first add ethene in this way with the equipment volume respective numbers.Ethene circulates through reactor, two water coolers, two separators, a compressor and well heaters, so that derive reaction heat from reactor.In compressor 4, be forced into the pressure of 32.0 crust, in well heater 5, be heated to 50 ℃ temperature, and by the following oligomerization reactor 2 of sending into.In reactor 2, in solvent-catalyst mixture, carry out the oligomeric of ethene under with the situation that is blown into raising at ethene.Oligomerization product remains dissolved in the solvent.
The mixture of being made up of ethene and light alpha olefins leaves reactor by pipe 6, and according to the relation of the thermodynamic(al)equilibrium in the reactor, this mixture also contains some toluene.This mixture is cooled to 35 ℃ in water cooler 7, and is collected in the separator 8.The liquid of the time telling in cooling of being made up of toluene and alpha-olefin is distributed on the washing column plate of segregation section, and is used for reducing as much as possible the toluene that rises by on reactor 2 bottoms by the segregation section of managing 9 refluxing reactors 2.The gas part of being left in the separator 8 is carried out and is cooled to temperature in water cooler 10 is 5 ℃, and sends in the separator 11.Regulate the cooling in the water cooler 10, make the alkene heavier liquefy as much as possible than ethene.Supply with a kind of recirculation C by pipeline 12 to separator 11 from unshowned hydrocarbon separating device 2Fraction.This C 2The amount of fraction is 5137kg/h.Extract pure basically cyclic ethylene out by pipeline 13, after the fresh ethylene that pipe 3 is supplied with are mixed, through manage 3, compressor 4 and heating unit 5 be sent to reactor 2 again.The product liquid of separator 11 is sent to a unshowned alkene decomposition process by pipe 14, with currently known methods oligosaccharide mixture rectifying is become single fraction there.
By pipe 15 a kind of liquid mixture of forming by toluene, catalyzer, dissolved ethene and linear alpha-alkene of extraction from reactor 2.The oligomeric activity of reacting can be to cause not wishing in order not allowing have in the catalyzer equipment unit afterwards, catalyzer must be to destroy at short notice.This can realize by adding water or alcohol.Proved that best is to add lipid acid to finish this task.Therefore, at a mixing section 16 that is arranged on reactor 2 rear lines 15 nearby, in mixture, add lipid acid.To this, 3-6kg/h is just enough.This mixture arrives a bottom that the adsorber 17 of aluminum oxide for example is housed thereafter.Remove metallic compound in the liquid mixture, i.e. catalyzer in this absorption.This mixture enters pipe 14 by adsorber 17 tops subsequently, and in the fractionation fraction that carries out thus proposing previously.
Generally, contain the following substances of following amount by equipment through managing 14 the materials flow of leaving: ethene 4922.9kg/hC 2-C 4Alkane and alkene 2338.8kg/hC 6-C 8Alkene 4509.7kg/hC 10-C 12Alkene 3788.2kg/hC 14-C 16Alkene 2724.3kg/hC 18-C 20Alkene 1504.5kg/hC 22-C 24Alkene 579.9kg/hC 26-C 28Alkene 193.2kg/h toluene 10661.0kg/h
31222.5kg/h
Before resolving into single fraction in the alkene resolving device that these hydrocarbon are proposing, isolate toluene by currently known methods, and be sent to reactor 2 again by pipe 1.

Claims (8)

1, the method that in the presence of a kind of organic solvent and a kind of homogeneous liquid catalyst of forming by a kind of zirconium compounds and a kind of organometallic compound, prepares linear alpha-alkene by ethylene oligomerization, it is characterized in that, oligomericly in a blank pipe oligomerization reactor that solvent-catalyst mixture is housed, carrying out under 31 to 50 bar pressures, ethene is sent into reactor bottom, and oligomerization product is discharged from reactor lower part with solvent and catalyzer; Zirconium compounds in the described catalyzer is ZrCl mX nThe zirconium compounds of form, in the formula, m+n=4; M=0 to 2, X are the ligands of carboxylate radical form; Organometallic compound in the described catalyzer is the organo-aluminium compound that has an ethyl ligand at least.
2, in accordance with the method for claim 1, it is characterized in that, make solvent with toluene.
3, in accordance with the method for claim 1, it is characterized in that described carboxylate radical is by C 4-C 8Lipid acid obtains.
4, in accordance with the method for claim 1, it is characterized in that the organometallic compound in the catalyzer is Al (C 2H 5) 3, Al 2Cl 3(C 2H 5) 3Or AlCl (C 2H 5) 2
According to the described method of one of claim 1 to 4, it is characterized in that 5, pressure is 31 to 40 crust.
6, implement the oligomerization reactor of the described method of claim 1, have ethene and oligomerization product are used and solvent-catalyst mixture is used charging and discharge nozzle, it is characterized in that, vertically disposed, be in oligomerization reactor cylindraceous section convergence at an upper portion thereof and its separator is housed.
According to the described oligomerization reactor of claim 6, it is characterized in that 7, separator is provided with the multi-wash column plate.
According to the described oligomerization reactor of claim 7, it is characterized in that 8, the outlet pipe of ethene and rudimentary oligomerization product is connected with a separator with a water cooler, the separator bottom is connected with the segregation section of oligomerization reactor.
CN94118705A 1993-11-10 1994-11-08 Preparation of linear olefin Expired - Fee Related CN1048976C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19934338414 DE4338414C1 (en) 1993-11-10 1993-11-10 Process for the preparation of linear olefins
DEP4338414.5 1993-11-10

Publications (2)

Publication Number Publication Date
CN1107828A CN1107828A (en) 1995-09-06
CN1048976C true CN1048976C (en) 2000-02-02

Family

ID=6502282

Family Applications (1)

Application Number Title Priority Date Filing Date
CN94118705A Expired - Fee Related CN1048976C (en) 1993-11-10 1994-11-08 Preparation of linear olefin

Country Status (2)

Country Link
CN (1) CN1048976C (en)
DE (1) DE4338414C1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101253135B (en) * 2005-07-29 2012-05-23 林德股份公司 Process for the preparation of linear alpha-olefins with improved heat removal

Families Citing this family (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2759922B1 (en) * 1997-02-25 1999-05-07 Inst Francais Du Petrole IMPROVED CATALYTIC COMPOSITION FOR THE CONVERSION OF ETHYLENE TO LIGHT ALPHA OLEFINS
EP1748038A1 (en) * 2005-07-29 2007-01-31 Linde AG Method for preparing linear alpha-olefins
EP1749807A1 (en) * 2005-08-02 2007-02-07 Linde AG Method for producing linear alpha-olefins with improved product distribution
EP1752434A1 (en) * 2005-08-10 2007-02-14 Linde AG Improved method for preparation of linear alpha-olefins and reactor system therefore
EP1752433B1 (en) * 2005-08-10 2012-10-03 Linde AG Improved drying process for linear alpha-olefins
DE602005014647D1 (en) * 2005-10-19 2009-07-09 Linde Ag Process for the oligomerization and / or polymerization of ethylene by rinsing the plant and the pipes
EP1780189B1 (en) * 2005-10-19 2008-05-07 Saudi Basic Industries Corporation Oligomerization of ethylene
DE602005019239D1 (en) * 2005-10-20 2010-03-25 Linde Ag Process for the oligomerization of ethylene and reactor system therefor with cooling device
DE602006004961D1 (en) * 2006-03-21 2009-03-12 Linde Ag Process for the preparation of linear alpha-olefins with removal of aromatic by-products
DE602007010413D1 (en) * 2007-01-19 2010-12-23 Linde Ag Production process for linear alpha-olefins and reactor system therefor
EP2070593B1 (en) 2007-12-06 2010-08-04 Saudi Basic Industries Corporation Catalyst composition and process for preparing linear alpha-olefins
JP5450439B2 (en) 2007-12-12 2014-03-26 サウディ ベーシック インダストリーズ コーポレイション Catalyst composition for oligomerization of ethylene, oligomerization process and preparation method thereof
JP5539229B2 (en) * 2008-01-30 2014-07-02 リンデ アーゲー Process for preparing linear alpha olefins
EP2287142B1 (en) 2009-07-24 2013-11-06 Linde AG Method for preparing linear alpha-olefins
EP2311554A1 (en) * 2009-10-07 2011-04-20 Linde Aktiengesellschaft Method for reaction control of exothermic reaction and apparatus therefore
DE102010006589A1 (en) 2010-02-02 2011-08-04 Linde Aktiengesellschaft, 80331 Process for the preparation of linear α-olefins
CA2723515C (en) 2010-12-01 2018-05-15 Nova Chemicals Corporation Heat management in ethylene oligomerization
AU2013207783B2 (en) 2012-01-13 2017-07-13 Lummus Technology Llc Process for providing C2 hydrocarbons via oxidative coupling of methane and for separating hydrocarbon compounds
EP2855005A2 (en) 2012-05-24 2015-04-08 Siluria Technologies, Inc. Oxidative coupling of methane systems and methods
US9670113B2 (en) 2012-07-09 2017-06-06 Siluria Technologies, Inc. Natural gas processing and systems
WO2014089479A1 (en) 2012-12-07 2014-06-12 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
CN110655437B (en) 2014-01-08 2022-09-09 鲁玛斯技术有限责任公司 System and method for ethylene to liquids
US10377682B2 (en) 2014-01-09 2019-08-13 Siluria Technologies, Inc. Reactors and systems for oxidative coupling of methane
CA3225180A1 (en) 2014-01-09 2015-07-16 Lummus Technology Llc Oxidative coupling of methane implementations for olefin production
BR112016029706A2 (en) * 2014-06-19 2017-08-22 Sabic Global Technologies Bv reactor to perform processes for a product line; and method to perform a process
SG11201700034WA (en) 2014-07-18 2017-02-27 Sabic Global Technologies Bv Catalyst composition and process for preparing linear alpha olefins
WO2016047560A1 (en) * 2014-09-22 2016-03-31 三菱化学株式会社 Method for producing α-olefin oligomer
KR102385968B1 (en) 2014-09-22 2022-04-12 미쯔비시 케미컬 주식회사 Method and apparatus for producing α-olefin oligomer
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
CN118767993A (en) 2015-09-16 2024-10-15 沙特基础工业全球技术有限公司 Process for deactivation of olefin oligomerization catalysts
EP3362425B1 (en) 2015-10-16 2020-10-28 Lummus Technology LLC Separation methods and systems for oxidative coupling of methane
EP3442934A4 (en) 2016-04-13 2019-12-11 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
JP2020521811A (en) 2017-05-23 2020-07-27 ラマス テクノロジー リミテッド ライアビリティ カンパニー Integration of methane oxidation coupling process
AU2018298234B2 (en) 2017-07-07 2022-11-17 Lummus Technology Llc Systems and methods for the oxidative coupling of methane
FR3105019B1 (en) * 2019-12-18 2022-07-22 Ifp Energies Now GAS/LIQUID OLIGOMERIZATION REACTOR WITH SUCCESSIVE ZONES OF VARIABLE DIAMETER
FR3105018B1 (en) * 2019-12-18 2021-12-10 Ifp Energies Now OLIGOMERIZATION GAS / LIQUID REACTOR INCLUDING TRANSVERSAL INTERNALS
FR3123354B1 (en) * 2021-05-28 2023-05-26 Ifp Energies Now PROCESS FOR OLIGOMERIZATION IN A REACTOR WITH ZONES OF VARIABLE DIAMETERS COMPRISING A STEP FOR RECYCLING A PRECOOLED SOLVENT

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0328728A1 (en) * 1988-02-15 1989-08-23 Idemitsu Petrochemical Co. Ltd. The production of linear alpha-olefins
EP0481443A1 (en) * 1990-10-17 1992-04-22 Vectorpharma International S.P.A. Transdermal therapeutic compositions
EP2959960A1 (en) * 2014-06-24 2015-12-30 Alstom Technology Ltd High rotational momentum disperser and use

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3726938A (en) * 1971-11-16 1973-04-10 A Berger Olefin production

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0328728A1 (en) * 1988-02-15 1989-08-23 Idemitsu Petrochemical Co. Ltd. The production of linear alpha-olefins
EP0481443A1 (en) * 1990-10-17 1992-04-22 Vectorpharma International S.P.A. Transdermal therapeutic compositions
EP2959960A1 (en) * 2014-06-24 2015-12-30 Alstom Technology Ltd High rotational momentum disperser and use

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101253135B (en) * 2005-07-29 2012-05-23 林德股份公司 Process for the preparation of linear alpha-olefins with improved heat removal

Also Published As

Publication number Publication date
CN1107828A (en) 1995-09-06
DE4338414C1 (en) 1995-03-16

Similar Documents

Publication Publication Date Title
CN1048976C (en) Preparation of linear olefin
EP3551598B1 (en) Process for selective ethylene oligomerization with antifouling components
KR100780226B1 (en) Manufacturing process for ?-olefins
RU2616602C2 (en) Ethylene oligomerisation method
US4615998A (en) Catalyst suitable for synthesizing 1-butene by dimerization of ethylene
JP4857269B2 (en) Process for the preparation of linear alpha olefins
US4538018A (en) Surface conditioning in olefin dimerization reactors
EP2794537B1 (en) A hydroformylation process
WO2007016996A1 (en) Method for preparing linear alpha-olefins with improved heat removal
EP1694439B1 (en) Catalyst recovery process
AU695881B2 (en) Method for removing catalyst from an oligomer product
KR101928766B1 (en) Method of separating for recovering ethylene and process system
PL126648B1 (en) Method of obtaining an aldehyde
MX2007000398A (en) Process for improved yields of higher molecular weight olefins from lower molecular weight olefins.
EP0288295B1 (en) Process for the production of 2,3-dimethylbutene-1 from propene
US2360699A (en) Catalytic conversion process
JPH0457651B2 (en)
US3631121A (en) Dimerization of c2 to c10 olefins with deposited catalyst
US2418146A (en) Catalytic hydrocarbon conversion
US2527824A (en) Manufacture of xylene isomers
US3179712A (en) Extractive condensation process using a multistage column
JP3344594B2 (en) Reaction method
CN1064475A (en) New aromatic alkylation process
CN114100541A (en) Method for synthesizing isononanal by microchannel reaction device
CA1090830A (en) Method of obtaining primary alcohols with straight chains from c.sub.4hydrocarbon cuts

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C53 Correction of patent for invention or patent application
COR Change of bibliographic data

Free format text: CORRECT: CO-PATENTEE TO: SHATE FOUNDATION INDUSTRY CORPORATION

CP01 Change in the name or title of a patent holder

Co-patentee after: Saudi Basic Industries Corp.

C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20000202

Termination date: 20111108