WO2014008964A1 - Method for oligomerization of ethylene - Google Patents

Method for oligomerization of ethylene Download PDF

Info

Publication number
WO2014008964A1
WO2014008964A1 PCT/EP2013/001658 EP2013001658W WO2014008964A1 WO 2014008964 A1 WO2014008964 A1 WO 2014008964A1 EP 2013001658 W EP2013001658 W EP 2013001658W WO 2014008964 A1 WO2014008964 A1 WO 2014008964A1
Authority
WO
WIPO (PCT)
Prior art keywords
reactor
ethylene
butene
catalyst
oligomerization
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.)
Ceased
Application number
PCT/EP2013/001658
Other languages
English (en)
French (fr)
Other versions
WO2014008964A8 (en
Inventor
Anina Wöhl
Wolfgang Müller
Heinz BÖLT
Andreas Meiswinkel
Marco Harff
Anton Wellenhofer
Karl-Heinz Hofmann
Hans-Jörg ZANDER
Abduljelil ILIYAS
Shahid KHURRAM
Shahid Azam
Abdullah Al-Qahtani
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.)
Linde GmbH
Saudi Basic Industries Corp
Original Assignee
Linde GmbH
Saudi Basic Industries Corp
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
Priority to CN201380035491.7A priority Critical patent/CN104661989B/zh
Priority to ES13727521.0T priority patent/ES2651154T3/es
Priority to IN10972DEN2014 priority patent/IN2014DN10972A/en
Priority to EP13727521.0A priority patent/EP2872468B1/en
Priority to JP2015520830A priority patent/JP6081590B2/ja
Priority to BR112015000387-7A priority patent/BR112015000387B1/pt
Priority to US14/414,403 priority patent/US9896392B2/en
Priority to RU2015104130A priority patent/RU2616602C2/ru
Priority to KR1020157003434A priority patent/KR101719221B1/ko
Priority to MX2015000216A priority patent/MX362715B/es
Application filed by Linde GmbH, Saudi Basic Industries Corp filed Critical Linde GmbH
Priority to SG11201408518WA priority patent/SG11201408518WA/en
Priority to CA2878634A priority patent/CA2878634C/en
Publication of WO2014008964A1 publication Critical patent/WO2014008964A1/en
Anticipated expiration legal-status Critical
Publication of WO2014008964A8 publication Critical patent/WO2014008964A8/en
Ceased 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
    • 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
    • C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1865—Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
    • B01J31/187—Amide derivatives thereof
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1885—Ligands comprising two different formal oxidation states of phosphorus in one at least bidentate ligand, e.g. phosphite/phosphinite
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/107—Alkenes with six carbon atoms
    • 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
    • C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
    • C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
    • C07C2/22—Metal halides; Complexes thereof with organic compounds
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • 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
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • 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
    • C07C2531/24—Phosphines

Definitions

  • the present invention relates to a method for the oligomerization of ethylene.
  • catalyst compositions for the oligomerization of ethylene using various catalyst compositions are well known in the art. Typically, if very unspecific catalysts are used, a broad product distribution is obtained from C 4 to higher olefins and even polymeric materials. Higher linear alpha-olefins and polymeric materials may cause plugging and fouling of the oligomerization reactor and pipings connected therewith. Recently, catalyst compositions for the oligomerization of ethylene have been developed which are more specific to, for example, trimerization or tetramerization, thus resulting in a narrower product distribution, but still also producing higher linear alpha-olefins and polymeric materials.
  • WO 2009/006979 A2 describes a process and a corresponding catalyst system for the di-, tri- and/or tetramerization of ethylene, based on a chromium complex with a heteroatomic ligand, typically featuring a PNPNH-backbone and activated by an organoaluminum compound such as, e.g., trialkylaluminum or methylaluminoxane.
  • an organoaluminum compound such as, e.g., trialkylaluminum or methylaluminoxane.
  • Plug-flow reactor the reaction heat can be removed via the reactor wall.
  • reaction heat from the exothermic reaction has to be removed from the reactor. Due to the fact that the catalyst is very sensitive against high temperatures, a reaction temperature preferably between 30 and 70°C has to be maintained and controlled very precisely. Through the fact that small amounts of polyethylene are formed during the reaction, internal heat exchange surfaces show a tendency towards fouling. This leads inevitably to an unstable and/or unsafe operation of the reactor at only very limited times-on-stream. Therefore, such internal heat exchange surfaces should be avoided.
  • oligomerizing ethylene in the reactor c) discharging a reactor effluent comprising linear alpha-olefins including 1- butene, solvent, unconsumed ethylene dissolved in the reactor effluent, and catalyst composition from the reactor,
  • a steady state of the oligomerization is achieved in that equal amounts of 1-butene are removed from the reactor with the reactor effluent and are recycled into the reactor in step e).
  • step d) is carried out at a pressure below reaction pressure of step b).
  • the product stream (reactor effluent) is depressurized before it is sent to a separation section.
  • This has the advantage that the separation step can be enhanced.
  • the investment and operational costs are reduced when the separation section (distillation column) is operated at a lower pressure.
  • the C 2 + C 4 product which is recycled back to the reactor has to be either recompressed to reaction pressure or it can be liquefied and pumped back to the reactor.
  • deactivation agent is added in molar stoichiometric rates with respect to the catalyst and the co- catalyst, i.e. for example Cr-catalyst and aluminum alkyl activator, i.e. [Cat]+[Cocat]. This ensures a complete deactivation of the catalyst. Otherwise side-reactions in separation columns, for example olefin isomerization, are possible.
  • the most preferred deactivation agent is a long-chain alcohol, especially 1-decanol, which after separation does not end up in the desired product 1- hexene fraction or the solvent.
  • the purge stream may consist preferably of between 10 and 90 wt.-% 1 -butene while the rest of the stream is mainly ethylene.
  • the purge stream can be sent back, for example, to a steam cracker where ethylene and 1 -butene can be recovered. For the case that no cracker is available, this stream can be sold separately or used energetically. Depending on the situation, the purge stream can be used as fuel for boilers.
  • the loss of ethylene via the purge is comparably low.
  • the high 1-butene content in the reactor has a significant benefit for the removal of the reaction heat.
  • gaseous ethylene and evaporated 1-butene is condensed and recycled back to the reactor. Therefore, the enthalpy of evaporation of 1-butene is used for the heat removal. Consequently, the gaseous ethylene stream, which also serves as cooling medium, can be reduced.
  • the reactor cooling capacity can be enhanced significantly.
  • the enthalpy of evaporation of 1-butene can be used for cooling. Consequently, the gaseous ethylene stream, which also serves as cooling medium, can be reduced. This is beneficial since lower recompression and cooling requirements are necessary.
  • Reactor run times can be extended. Due to the better mobilization of the by-product polymer, the reactor fouling is reduced. Consequently, the interval before the reactor has to be cleaned again is extended.
  • Fig. 2 is a scheme for an ethylene oligomerization technology according to the present invention.
  • Fig. 1 illustrating a conventional process scheme for the oligomerization of ethylene, catalyst, solvent and ethylene are fed to a reactor where oligomerization, for example tri- merization takes place.
  • a liquid reactor effluent comprising solvent, unreacted ethylene, linear alpha-olefins and catalyst, is transferred to a first separation section where ethylene is separated.
  • This ethylene can be recycled back to the reactor, the recycling cycle may comprise ethylene polishing.
  • the heavier fractions are routed to a second and further separation sections where separation into different fractions, such as C 4 , C 6 , solvent, C 8 , Ci 0 , > C 12 , is effected.
  • catalyst 10, solvent 11 and ethylene 12 are also fed to a reactor 13 for oligomerization, for example trimerization, of ethylene.
  • the reactor effluent is directly sent to a C 4 /C 6 separation section 14 wherein both ethylene and C 4 are separated from the remainder.
  • Ethylene and C 4 (at least partly) are recycled into the reactor via line 16.
  • the recycle step may include a purge stream 17 and polishing 18 of ethylene.
  • the heavier fractions can be transferred to further separation sections 15.
  • a 300 ml pressure reactor equipped with dip tube, thermowell, gas entrainment stirrer, cooling coil, control units for temperature, pressure, and stirrer speed (all hooked up to a data acquisition system) was inertized with dry argon.
  • the isobaric ethene supply was maintained by an aluminum pressurized gas cylinder on a balance to monitor the ethene consumption over time by means of a computerized data acquisition system.
  • the reactor was heated to 100 C at reduced pressure for several hours to eliminate traces of water, oxygen and oxygenated impurities. Before the reaction the reactor was cooled down to the reaction temperature of 50°C.
  • the chosen volumes and masses correspond to a chromium concentration of 0.3 / 0.6 mmol/1 at a molar ligand to chromium ratio of 1.2 mol/mol, an Al / Cr - ratio of 24 mol/mol and a CI / Cr - ratio of 8 mol/mol.
  • the weight content of 1 -butene in the liquid phase was calculated using the process simulation tool UniSim. Following this procedure, a series of trimerization reactions was conducted with different amounts of 1-butene and different volumes of toluene to adjust different ratios of toluene/ 1- butene mixtures.
  • the initial 1-C4 weight ratio was determined by UniSim (50 / 100 ml toluene with additional mass of 1-butene, saturated with ethylene at 30 bar, 50°C)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
PCT/EP2013/001658 2012-07-10 2013-06-05 Method for oligomerization of ethylene Ceased WO2014008964A1 (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
KR1020157003434A KR101719221B1 (ko) 2012-07-10 2013-06-05 에틸렌의 올리고머화 방법
IN10972DEN2014 IN2014DN10972A (cg-RX-API-DMAC7.html) 2012-07-10 2013-06-05
EP13727521.0A EP2872468B1 (en) 2012-07-10 2013-06-05 Method for oligomerization of ethylene
JP2015520830A JP6081590B2 (ja) 2012-07-10 2013-06-05 エチレンのオリゴマー化のための方法
BR112015000387-7A BR112015000387B1 (pt) 2012-07-10 2013-06-05 método para oligomerização de etileno
US14/414,403 US9896392B2 (en) 2012-07-10 2013-06-05 Method for oligomerization of ethylene
RU2015104130A RU2616602C2 (ru) 2012-07-10 2013-06-05 Способ олигомеризации этилена
CN201380035491.7A CN104661989B (zh) 2012-07-10 2013-06-05 用于低聚乙烯的方法
ES13727521.0T ES2651154T3 (es) 2012-07-10 2013-06-05 Método para la oligomerización de etileno
MX2015000216A MX362715B (es) 2012-07-10 2013-06-05 Procedimiento para oligomerización de etileno.
SG11201408518WA SG11201408518WA (en) 2012-07-10 2013-06-05 Method for oligomerization of ethylene
CA2878634A CA2878634C (en) 2012-07-10 2013-06-05 Method for oligomerization of ethylene

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP12175732.2A EP2684857A1 (en) 2012-07-10 2012-07-10 Method for oligomerization of ethylene
EP12175732.2 2012-07-10

Publications (2)

Publication Number Publication Date
WO2014008964A1 true WO2014008964A1 (en) 2014-01-16
WO2014008964A8 WO2014008964A8 (en) 2015-02-19

Family

ID=48577680

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2013/001658 Ceased WO2014008964A1 (en) 2012-07-10 2013-06-05 Method for oligomerization of ethylene

Country Status (14)

Country Link
US (1) US9896392B2 (cg-RX-API-DMAC7.html)
EP (2) EP2684857A1 (cg-RX-API-DMAC7.html)
JP (1) JP6081590B2 (cg-RX-API-DMAC7.html)
KR (1) KR101719221B1 (cg-RX-API-DMAC7.html)
CN (1) CN104661989B (cg-RX-API-DMAC7.html)
BR (1) BR112015000387B1 (cg-RX-API-DMAC7.html)
CA (1) CA2878634C (cg-RX-API-DMAC7.html)
ES (1) ES2651154T3 (cg-RX-API-DMAC7.html)
IN (1) IN2014DN10972A (cg-RX-API-DMAC7.html)
MX (1) MX362715B (cg-RX-API-DMAC7.html)
RU (1) RU2616602C2 (cg-RX-API-DMAC7.html)
SG (1) SG11201408518WA (cg-RX-API-DMAC7.html)
TW (1) TWI582063B (cg-RX-API-DMAC7.html)
WO (1) WO2014008964A1 (cg-RX-API-DMAC7.html)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105085132A (zh) * 2014-05-08 2015-11-25 中国石油化工股份有限公司 一种优化乙烯齐聚工艺的方法及装置
US9707549B1 (en) 2016-05-26 2017-07-18 Chevron Phillips Chemical Company Lp Ethylene oligomerization catalyst systems using chemically-treated solid oxides
US9896392B2 (en) 2012-07-10 2018-02-20 Saudi Basic Industries Corporation Method for oligomerization of ethylene
WO2018116176A1 (en) * 2016-12-22 2018-06-28 Sabic Global Technologies B.V. Methods of producing linear alpha olefins

Families Citing this family (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2738151B8 (en) 2012-11-28 2014-12-17 Saudi Basic Industries Corporation Process for oligomerization of ethylene
EP2764914A1 (en) * 2013-02-11 2014-08-13 Linde AG Metalated PNPNH ligand, catalyst composition and use thereof in the oligomerization of ethylene
MX369759B (es) 2015-01-19 2019-11-20 Evonik Operations Gmbh Preparación combinada de buteno y octeno a partir de eteno.
US9505675B2 (en) * 2015-02-09 2016-11-29 Chevron Phillips Chemical Company Lp Deactivation of a process by-product
ES2987757T3 (es) * 2015-09-16 2024-11-18 Sabic Global Technologies Bv Procedimiento para la desactivación de un catalizador de oligomerización de olefinas
US10781147B2 (en) * 2015-12-22 2020-09-22 Sabic Global Technologies B.V. Methods for toluene recovery from linear alpha olefin production
TWI641590B (zh) * 2015-12-30 2018-11-21 薩比克全球科技公司 生產己烯之方法
WO2017187289A1 (en) * 2016-04-25 2017-11-02 Sabic Global Technologies B.V. Process for removing heat from an oligomerization reaction
US10414699B2 (en) 2016-05-27 2019-09-17 Chevron Phillips Chemical Company Lp Process improvements in selective ethylene oligomerizations
US10414698B2 (en) * 2016-05-27 2019-09-17 Chevron Phillips Chemical Company Lp Reduced polymer formation for selective ethylene oligomerizations
US10329212B2 (en) 2016-05-27 2019-06-25 Chevron Phillips Chemical Company Lp Reduced polymer formation for selective ethylene oligomerizations
US10280125B2 (en) * 2016-12-07 2019-05-07 Sumitomo Chemical Company, Limited Process for selective ethylene oligomerization with antifouling components
CN110072832B (zh) * 2016-12-20 2023-03-14 沙特基础工业全球技术有限公司 塔控制的方法
WO2018122704A1 (en) * 2016-12-30 2018-07-05 Sabic Global Technologies B.V. Method for temperature control in a bubble column reactor for selective 1-hexene production
WO2018122779A1 (en) * 2016-12-30 2018-07-05 Sabic Global Technologies B.V. Methods of producing linear alpha olefins
WO2018170054A1 (en) * 2017-03-14 2018-09-20 Saudi Arabian Oil Company Process for ethylene oligomerization to produce alpha-olefins
US10295685B2 (en) 2017-04-06 2019-05-21 Saudi Arabian Oil Company Generating common image gather using wave-field separation
US11016212B2 (en) 2017-04-11 2021-05-25 Saudi Arabian Oil Company Compressing seismic wavefields in three-dimensional reverse time migration
US10232339B2 (en) 2017-06-06 2019-03-19 Chevron Phillips Chemical Company Lp Fouling protection for an oligomerization reactor inlet
CN107746365A (zh) * 2017-08-30 2018-03-02 中国石油化工股份有限公司 一种选择性乙烯齐聚生产α‑烯烃的工艺方法及系统
US10183960B1 (en) 2017-09-22 2019-01-22 Chevron Phillips Chemical Company Lp Perfluorohydrocarbyl-N2-phosphinyl amidine compounds, chromium salt complexes, catalyst systems, and their use to oligomerize ethylene
US10493442B2 (en) 2017-09-22 2019-12-03 Chevron Phillips Chemical Company Lp Fluorinated N2-phosphinyl amidine compounds, chromium salt complexes, catalyst systems, and their use to oligomerize ethylene
US10294171B2 (en) 2017-09-22 2019-05-21 Chevron Phillips Chemical Company Lp Carbonyl-containing perfluorohydrocarbyl-N2-phosphinyl amidine compounds, chromium salt complexes and their use to oligomerize ethylene
US10464862B2 (en) 2017-09-28 2019-11-05 Chevron Phillips Chemical Company Lp Oligomerization reactions using aluminoxanes
KR102334373B1 (ko) * 2017-11-30 2021-12-02 에스케이이노베이션 주식회사 올레핀의 올리고머화 방법
US11275190B2 (en) 2018-05-16 2022-03-15 Saudi Arabian Oil Company Generating diffraction images based on wave equations
WO2020185426A1 (en) * 2019-03-13 2020-09-17 Tpc Group Llc Flexible manufacturing system for selectively producing different linear alpha olefins
KR102721498B1 (ko) 2019-07-24 2024-10-25 에스케이이노베이션 주식회사 에틸렌 올리고머화 공정의 미반응 에틸렌 회수 방법
FR3099476B1 (fr) * 2019-07-31 2021-07-30 Ifp Energies Now Procede d’oligomerisation mettant en œuvre un recycle du ciel gazeux
KR102592638B1 (ko) 2019-08-21 2023-10-23 주식회사 엘지화학 알파 올레핀 제조 방법 및 알파 올레핀 제조 장치
KR102577661B1 (ko) 2019-08-21 2023-09-11 주식회사 엘지화학 올리고머 제조 방법 및 올리고머 제조 장치
US11681043B2 (en) * 2019-09-03 2023-06-20 Saudi Arabian Oil Company Diffraction imaging using pseudo dip-angle gather
CN112745179A (zh) * 2019-10-30 2021-05-04 中国石油化工股份有限公司 乙烯齐聚生产α-烯烃的方法
CN112745185A (zh) * 2019-10-30 2021-05-04 中国石油化工股份有限公司 乙烯齐聚连续生产α-烯烃的方法
US11313988B2 (en) 2019-12-13 2022-04-26 Saudi Arabian Oil Company Identifying geologic features in a subterranean formation using seismic diffraction imaging
US11098140B2 (en) 2020-01-03 2021-08-24 Saudi Arabian Oil Company Production of 1-butene and ultra-high-molecular-weight polyethylene
US11402529B2 (en) 2020-01-09 2022-08-02 Saudi Arabian Oil Company Identifying geologic features in a subterranean formation using seismic diffraction and refraction imaging
US11467303B2 (en) 2020-03-09 2022-10-11 Saudi Arabian Oil Company Identifying geologic features in a subterranean formation using a post-stack seismic diffraction imaging condition
US11320557B2 (en) 2020-03-30 2022-05-03 Saudi Arabian Oil Company Post-stack time domain image with broadened spectrum
US11656378B2 (en) 2020-06-08 2023-05-23 Saudi Arabian Oil Company Seismic imaging by visco-acoustic reverse time migration
FR3112969B1 (fr) * 2020-07-30 2022-08-05 Ifp Energies Now Nouvelle composition catalytique a base de chrome et procede associe pour la trimerisation de l’ethylene en hexene-1
JP7366486B2 (ja) * 2020-09-07 2023-10-23 エルジー・ケム・リミテッド オリゴマーの製造方法
JP7265571B2 (ja) * 2021-03-05 2023-04-26 本田技研工業株式会社 炭素化合物の製造装置及び炭素化合物の製造方法
JP7176027B2 (ja) * 2021-03-11 2022-11-21 本田技研工業株式会社 二酸化炭素処理装置及び炭素化合物の製造方法
US11230514B1 (en) 2021-05-25 2022-01-25 Chevron Phillips Chemical Company, Lp Methods for recycling ethylene in an ethylene oligomerization reactor system
US11492305B1 (en) 2021-11-08 2022-11-08 Chevron Phillips Chemical Company, Lp Chromium phosphinyl hydroisoindole amidine complexes for tetramerization of ethylene
US11583843B1 (en) 2021-11-08 2023-02-21 Chevron Phillips Chemical Company, Lp Chromium phosphinyl isoindole amidine complexes for tetramerization of ethylene
US11505513B1 (en) 2021-11-08 2022-11-22 Chevron Phillips Chemical Company, Lp Chromium bicyclic phosphinyl amidine complexes for tetramerization of ethylene
CN116328839B (zh) * 2021-12-24 2025-02-28 中国石油化工股份有限公司 一种负载型乙烯齐聚主催化剂及乙烯齐聚催化剂组合物及应用
CN116328838A (zh) * 2021-12-24 2023-06-27 中国石油化工股份有限公司 一种金属有机骨架负载型乙烯齐聚催化剂组合物及应用
CN116328837B (zh) * 2021-12-24 2025-02-28 中国石油化工股份有限公司 一种乙烯齐聚催化剂组合物及应用
CN115028508B (zh) * 2022-06-30 2023-05-26 万华化学集团股份有限公司 一种pe生成量降低的乙烯四聚工艺
KR20240077879A (ko) * 2022-11-25 2024-06-03 롯데케미칼 주식회사 올레핀 올리고머화의 부산물 저감 방법

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4370456A (en) * 1981-11-23 1983-01-25 Union Carbide Corporation Catalyst composition for copolymerizing ethylene
US4721762A (en) * 1984-06-08 1988-01-26 Institut Francais Du Petrole Process for manufacturing an ethylene-1-butene copolymer from ethylene
US4777315A (en) * 1987-06-01 1988-10-11 Union Carbide Corporation Process for trimerization
US5856610A (en) * 1995-11-22 1999-01-05 Sumitomo Chemical Company, Limited Process for producing ethylene-α-olefin copolymers
EP1777208A1 (en) * 2005-10-20 2007-04-25 Saudi Basic Industries Corporation Method for oligomerization of ethylene and reactor system therefore with cooling device
WO2009006979A2 (en) * 2007-07-11 2009-01-15 Linde Ag Catalyst composition and process for di-, tri- and/or tetramerization of ethylene
WO2009068157A1 (en) * 2007-11-28 2009-06-04 Linde Ag Catalyst composition and process for oligomerization of ethylene
EP2106854A1 (en) * 2008-04-04 2009-10-07 Saudi Basic Industries Corporation Catalyst for oligomerization of ethylene, method for preparation thereof and process for oligomerization using it
EP2239056A1 (en) * 2009-04-09 2010-10-13 Saudi Basic Industries Corporation Catalyst composition and process for oligomerization of ethylene
US8076524B2 (en) 2006-02-03 2011-12-13 Exxonmobil Chemical Patents Inc. Process for generating alpha olefin comonomers

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4020121A (en) * 1975-12-15 1977-04-26 Shell Oil Company Oligomerization reaction system
EP2075242A1 (en) * 2001-12-20 2009-07-01 Sasol Technology (Proprietary) Limited Trimerisation and oligomerisation of olefins using a chromium based catalyst
BRPI0215088B1 (pt) 2001-12-20 2015-12-22 Sasol Tech Pty Ltd sistema catalisador de trimerização, e, processo para a oligomerização de olefinas
US8003839B2 (en) * 2006-02-03 2011-08-23 Exxonmobil Chemical Patents Inc. Process for generating linear apha olefin comonomers
US20070196005A1 (en) 2006-02-23 2007-08-23 White Christopher A Feature Tracing Process for M-mode Images
EP2684857A1 (en) 2012-07-10 2014-01-15 Saudi Basic Industries Corporation Method for oligomerization of ethylene
EP2738151B8 (en) * 2012-11-28 2014-12-17 Saudi Basic Industries Corporation Process for oligomerization of ethylene

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4370456A (en) * 1981-11-23 1983-01-25 Union Carbide Corporation Catalyst composition for copolymerizing ethylene
US4721762A (en) * 1984-06-08 1988-01-26 Institut Francais Du Petrole Process for manufacturing an ethylene-1-butene copolymer from ethylene
US4777315A (en) * 1987-06-01 1988-10-11 Union Carbide Corporation Process for trimerization
US5856610A (en) * 1995-11-22 1999-01-05 Sumitomo Chemical Company, Limited Process for producing ethylene-α-olefin copolymers
EP1777208A1 (en) * 2005-10-20 2007-04-25 Saudi Basic Industries Corporation Method for oligomerization of ethylene and reactor system therefore with cooling device
US8076524B2 (en) 2006-02-03 2011-12-13 Exxonmobil Chemical Patents Inc. Process for generating alpha olefin comonomers
WO2009006979A2 (en) * 2007-07-11 2009-01-15 Linde Ag Catalyst composition and process for di-, tri- and/or tetramerization of ethylene
WO2009068157A1 (en) * 2007-11-28 2009-06-04 Linde Ag Catalyst composition and process for oligomerization of ethylene
EP2106854A1 (en) * 2008-04-04 2009-10-07 Saudi Basic Industries Corporation Catalyst for oligomerization of ethylene, method for preparation thereof and process for oligomerization using it
KR20110000559A (ko) 2008-04-04 2011-01-03 린데 악티엔게젤샤프트 에틸렌의 올리고머화를 위한 촉매, 그것을 제조하기 위한 방법 및 그것을 사용하는 올리고머화를 위한 공정
EP2239056A1 (en) * 2009-04-09 2010-10-13 Saudi Basic Industries Corporation Catalyst composition and process for oligomerization of ethylene

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9896392B2 (en) 2012-07-10 2018-02-20 Saudi Basic Industries Corporation Method for oligomerization of ethylene
CN105085132A (zh) * 2014-05-08 2015-11-25 中国石油化工股份有限公司 一种优化乙烯齐聚工艺的方法及装置
US9707549B1 (en) 2016-05-26 2017-07-18 Chevron Phillips Chemical Company Lp Ethylene oligomerization catalyst systems using chemically-treated solid oxides
US9968921B2 (en) 2016-05-26 2018-05-15 Chevron Phillips Chemical Company Lp Ethylene oligomerization catalyst systems using chemically-treated solid oxides
WO2018116176A1 (en) * 2016-12-22 2018-06-28 Sabic Global Technologies B.V. Methods of producing linear alpha olefins

Also Published As

Publication number Publication date
TW201406704A (zh) 2014-02-16
EP2684857A1 (en) 2014-01-15
BR112015000387A8 (pt) 2019-02-19
ES2651154T3 (es) 2018-01-24
KR101719221B1 (ko) 2017-03-23
WO2014008964A8 (en) 2015-02-19
US9896392B2 (en) 2018-02-20
SG11201408518WA (en) 2015-02-27
BR112015000387B1 (pt) 2020-11-10
KR20150043313A (ko) 2015-04-22
MX362715B (es) 2019-01-25
RU2015104130A (ru) 2016-08-27
JP2015527311A (ja) 2015-09-17
CN104661989B (zh) 2018-05-22
RU2616602C2 (ru) 2017-04-18
EP2872468A1 (en) 2015-05-20
BR112015000387A2 (pt) 2017-06-27
MX2015000216A (es) 2015-04-10
CA2878634C (en) 2019-07-16
TWI582063B (zh) 2017-05-11
US20150203418A1 (en) 2015-07-23
CN104661989A (zh) 2015-05-27
CA2878634A1 (en) 2014-01-16
JP6081590B2 (ja) 2017-02-15
IN2014DN10972A (cg-RX-API-DMAC7.html) 2015-09-18
EP2872468B1 (en) 2017-11-15

Similar Documents

Publication Publication Date Title
US9896392B2 (en) Method for oligomerization of ethylene
RU2467796C2 (ru) Катализатор олигомеризации этилена, способ его получения и способ олигомеризации с его использованием
EP2646401B2 (en) Heat management in ethylene oligomerization
JP5158726B2 (ja) エチレンの二、三および／または四量体化のための触媒組成物およびプロセス
EP2630105B1 (en) Ethylene oligomerization
CA2747501C (en) "bulk" ethylene oligomerization
WO2011140629A1 (en) Oligomenzation of alpha olefins
WO2010034102A1 (en) Ethylene tetramerization catalysts comprising p-n-p ligands
WO2012142693A1 (en) Activation for oligomerization
EP2807173B1 (en) P-n-p ligand
WO2012045147A1 (en) Tetramerization ligands
US12157712B2 (en) Oligomerization process implementing the recycling of the gas headspace
CN104144936B (zh) P‑n‑p配体
KR20180012228A (ko) 올레핀 올리고머화, 이를 위한 촉매 조성물, 및 촉매 조성물의 제조 방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13727521

Country of ref document: EP

Kind code of ref document: A1

REEP Request for entry into the european phase

Ref document number: 2013727521

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2013727521

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: MX/A/2015/000216

Country of ref document: MX

ENP Entry into the national phase

Ref document number: 2878634

Country of ref document: CA

ENP Entry into the national phase

Ref document number: 2015520830

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 14414403

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 1020157003434

Country of ref document: KR

ENP Entry into the national phase

Ref document number: 2015104130

Country of ref document: RU

Kind code of ref document: A

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112015000387

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112015000387

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20150108