CN115028509B - Ethylene oligomerization process with enhanced reactivity and reduced polymer formation - Google Patents

Ethylene oligomerization process with enhanced reactivity and reduced polymer formation Download PDF

Info

Publication number
CN115028509B
CN115028509B CN202210779080.XA CN202210779080A CN115028509B CN 115028509 B CN115028509 B CN 115028509B CN 202210779080 A CN202210779080 A CN 202210779080A CN 115028509 B CN115028509 B CN 115028509B
Authority
CN
China
Prior art keywords
chromium
salt
pnp
compound
pentafluorophenyl
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.)
Active
Application number
CN202210779080.XA
Other languages
Chinese (zh)
Other versions
CN115028509A (en
Inventor
丁明强
张彦雨
陈冠良
车传亮
王大林
王磊
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.)
Wanhua Chemical Group Co Ltd
Original Assignee
Wanhua Chemical Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wanhua Chemical Group Co Ltd filed Critical Wanhua Chemical Group Co Ltd
Priority to CN202210779080.XA priority Critical patent/CN115028509B/en
Publication of CN115028509A publication Critical patent/CN115028509A/en
Application granted granted Critical
Publication of CN115028509B publication Critical patent/CN115028509B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • 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
    • B01J31/189—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 containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
    • B01J35/19—
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to a control process for ethylene oligomerization, in particular to a method for maintaining activity and byproduct polymer in a control range on the premise of limiting impurity types and content. The oligomerization process with ideal activity and by-product polymer content is realized mainly by limiting the amount of hydroxyl and/or amino compounds in the system within a specific range under the condition of not changing the main formula and process of oligomerization reaction.

Description

Ethylene oligomerization process with enhanced reactivity and reduced polymer formation
Technical Field
The invention belongs to the field of olefin polymerization, and in particular relates to a method for reducing PE (polyethylene) as a byproduct of ethylene oligomerization reaction on the basis of not sacrificing the selectivity and polymerization activity of a product.
Background
The linear alpha-olefin has wide industrial application, and the oligomer thereof can be used in various fields such as plasticizers, fatty acids, lubricating oil additives and the like; the copolymer can be used for producing polyolefin elastomer, and is used in various fields of shoe materials, polymer modification, automobiles and the like.
Since 2003, sasol corporation adopts chromium compounds with nitrogen-phosphorus coordination skeletons as catalysts to catalyze ethylene tetramerization at 45 ℃ and 4.5MPa to generate 16.6-32.7% of 1-hexene and 44-67% of 1-octene, researches on the aspects are made at home and abroad, and the structural design of catalyst ligands and the optimization of reaction equipment/process are concentrated. Because of the special nature of chromium catalysts, ethylene tetramerization inevitably produces partial polymers, and long-time accumulation of the polymers can cause blockage of a reaction kettle, a stirrer, a valve and a pipeline, and influence heat transfer and mass transfer; furthermore, the reaction uses a large amount of alkyl aluminum compound as a cocatalyst, so that the source is limited and the price is high, and how to reduce the dosage and improve the reaction activity is very necessary to reduce the production cost.
Patent (publication number CN 104271537B) reports a process for oligomerization of ethylene with reduced polymer formation, by deliberately introducing a non-metallic oxygen-containing additive into the reaction system to increase the reactivity and reduce the production of the polymer, preferably a gaseous oxygen-containing additive, to achieve better results. However, the content of gaseous impurities is difficult to control and affects the purity of the product, so that there is a need for developing an ethylene oligomerization process that is more simple and efficient in enhancing the reactivity and reducing the polymer content.
Disclosure of Invention
The invention aims to provide a method for improving the ethylene oligomerization activity, which can increase the reaction activity on the basis of not sacrificing the selectivity of a product and the byproduct PE.
Although hydroxyl and amine compounds are generally regarded as poisoning agents for ethylene oligomerization, the more so, the reaction is terminated. However, the inventors have surprisingly found that in existing catalytic systems, by controlling the amount of hydroxyl or amine compounds in the system within a specific range, an oligomerization process having both high reactivity and low by-product polymer content can be achieved without changing the main formulation and process of the oligomerization reaction.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a process for oligomerization of ethylene, characterized in that ethylene is oligomerized in a system comprising a chromium salt/PNP ligand, an aluminum alkyl compound, a boron salt, and an organic solvent at a reaction temperature and pressure to form an α -olefin, wherein the content of hydroxyl compounds and/or amine compounds in the system relative to the amount of organic solvent satisfies the following relationship: m is more than or equal to 0.4ppm (OH) +m (NH2) ≤4ppm。
In the invention, the reaction temperature is 45-50 ℃, and the reaction pressure is 4.0-5.0 MPaG.
In the present invention, the alkyl aluminum compound is selected from one or more of triethylaluminum, triisobutylaluminum, trioctylaluminum, methylaluminoxane (MAO) and Modified Methylaluminoxane (MMAO).
In the invention, the chromium-containing salt is a complex of metallic chromium, and is specifically selected from one or more of chromium tetrahydrofuran trichloride, chromium acetylacetonate, chromium 2-ethylhexanoate and chromium hexacarbonyl.
In the invention, the PNP ligand is a compound with a skeleton of a phosphine-nitrogen-phosphine structure, and is selected from one or more of N, N-bis (diphenylphosphino) -isopropylamine (iPr-PNP), N-bis (diphenylphosphino) -tert-butylamine (tBu-PNP), N-bis (diphenylphosphino) -1, 2-dimethylpropylamine (1, 2-DMP-PNP) and N, N-bis (diphenylphosphino) -cyclohexylamine (Cy-PNP).
In the invention, the boron salt is one or more boron-containing organic compounds selected from tris (pentafluorophenyl) boron, triphenylcarbon tetra (pentafluorophenyl) borate, N-dimethylanilinium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) boric acid-methyldi- (hexadecyl) ammonium salt and tetra (pentafluorophenyl) boric acid-methyldi- (octadecyl) ammonium salt.
In the present invention, the molar ratio of the chromium-containing salt to PNP ligand is 0.5 to 5, preferably 1 to 2.
In the present invention, the molar ratio of the alkyl aluminum compound to the chromium-containing salt is 10 to 1000, preferably 200 to 500.
In the present invention, the molar ratio of the boron salt to the chromium-containing salt is 0.5 to 3, preferably 1 to 2.
In the present invention, the mass ratio of the hydroxyl and amine based compounds to aluminum alkoxide is 0.05-5:100, preferably 0.3-3:100.
In the invention, the organic solvent is selected from one or more of n-hexane, n-heptane, cyclohexane, methylcyclohexane, tetrahydrofuran, toluene or xylene.
In the present invention, the hydroxyl/amine group containing compound is derived from ethylene or solvent entrainment or deliberate introduction: the hydroxyl compound is selected from one or more of deionized water, 1-hexanol, 1-octanol, 1-decanol or 2-ethyl-hexanol; the amino compound is one or more of tert-butylamine, 1-hexylamine, 1-octylamine, 1-decylamine, dodecylamine or 2-ethyl-hexylamine.
In the invention, the selectivity of 1-hexene and 1-octene in the alpha-olefin reaches 90-92%, the reaction activity reaches more than 800Kg/g Cr, and the polymer content is less than 0.3%.
Compared with the prior art, the invention has the beneficial effects that:
(1) On the one hand, the invention simplifies the purification process of the solvent or the raw material, enables the raw material to react under the condition of containing a certain amount of polar compounds such as hydroxyl or amino, simplifies the operation difficulty, improves the efficiency and reduces the operation cost.
(2) On the other hand, the hydroxyl or amino compound can generate certain on-line hydrolysis reaction with the alkyl aluminum compound in the system to generate partial other types of cocatalysts in situ, thereby reducing the consumption of the alkyl aluminum or forming more other types of active centers, improving the reaction activity and reducing the raw material cost.
Detailed Description
The following examples further illustrate the technical solutions provided by the present invention, but the present invention is not limited to the listed examples, but includes any other known modifications within the scope of the claims.
1. The raw material information related to the invention is as follows:
TABLE 1 sources of raw materials and specifications thereof
2. The test method of the sample in the invention is as follows:
the liquid phase products are characterized by gas chromatography, so that the quality of each liquid phase product is obtained, and the solid products are separated, dried and weighed;
analysis conditions for gas chromatography: the temperature of the sample injection product is 250 ℃; the temperature of the column box is 35 ℃;
heating program: firstly, keeping at 35 ℃ for 10 minutes, then raising the temperature to 250 ℃ at the speed of 10 ℃/min, then keeping at 250 ℃ for 10 minutes, and then starting to cool until the temperature reaches the room temperature;
detector temperature: 250 ℃; and (3) a carrier: 1.0Mpa; air: 0.03Mpa; hydrogen gas: 0.03Mpa;
characterization of the product with n-nonane as an internal standard, the calculation method is as follows:
wherein m1 represents the mass of a certain substance, m is the mass of nonane, a1 is the peak area of the substance measured in GC, and a is the peak area of n-nonane measured in GC. k is a correction coefficient.
Example 1
500mL of a high-pressure stainless steel reaction vessel was heated to 120℃and evacuated for 3 hours, during which nitrogen was replaced three times, and then evacuated and replaced three times with hydrogen. After cooling to room temperature, the mixture was introduced under a hydrogen pressure of 0.5MPa, and a methylcyclohexane solution containing 195mL of dehydrated and deoxidized methylcyclohexane (containing 0.4ppm of 2-ethyl-1-hexanol), 0.4mL of Modified Methylaluminoxane (MMAO), 2mL of a pre-prepared phosphine ligand (N, N-bis (diphenylphosphino) -tert-butylamine/chromium salt (chromium acetylacetonate) catalyst solution having a molar concentration of 1.0umol/L, and 2mL of a pre-prepared tetrakis (pentafluorophenyl) borate-methyldioctadecyl) ammonium salt were added thereto, and the reaction was carried out at a reaction temperature of 48℃and a rotation speed of 600rpm for 45 minutes while maintaining an ethylene pressure of 4.5 MPa.
After the reaction was completed, the reaction solution was suction-filtered, and the supernatant was GC-analyzed, and the solid product was dried in a vacuum oven at 80℃for 12 hours and weighed, thereby calculating the activity and selectivity of the product.
Example 2
The remaining operation of example 1 was repeated except that the addition amount of 2-ethyl-1-hexanol was changed to 1 ppm.
Example 3
The remaining operation of example 1 was repeated except that the addition amount of 2-ethyl-1-hexanol was changed to 2 ppm.
Example 4
The remaining operation of example 1 was repeated except that the addition amount of 2-ethyl-1-hexanol was changed to 4 ppm.
Example 5
500mL of a high-pressure stainless steel reaction vessel was heated to 120℃and evacuated for 3 hours, during which nitrogen was replaced three times, and then evacuated and replaced three times with hydrogen. After cooling to room temperature, the mixture was introduced under a hydrogen pressure of 0.5MPa, and a solution of methyl cyclohexane containing 197mL of dehydrated and deoxidized methylcyclohexane (containing 1.5ppm of 1-decanol), 0.24mL of Modified Methylaluminoxane (MMAO), 2mL of a pre-prepared phosphine ligand (N, N-bis (diphenylphosphino) -1, 2-dimethylpropylamine/chromium salt (chromium acetylacetonate) catalyst solution having a molar concentration of 0.5umol/L, and 1mL of a pre-prepared methyl cyclohexane solution of tetrakis (pentafluorophenyl) borate-methyldi- (hexadecyl) ammonium salt having a molar concentration of 1.0umol/L was added thereto, and the reaction was carried out at a reaction temperature of 45℃and a rotation speed of 600rpm for 30 minutes while maintaining an ethylene pressure of 4.5 MPa.
Example 6
500mL of a high-pressure stainless steel reaction vessel was heated to 120℃and evacuated for 3 hours, during which nitrogen was replaced three times, and then evacuated and replaced three times with hydrogen. After cooling to room temperature, a hydrogen pressure of 0.5MPa was introduced, and a toluene solution containing 195mL of dehydrated and deoxidized methylcyclohexane solution (containing 1ppm of deionized water), 0.3mL of Triethylaluminum (TEA), 2mL of a pre-prepared phosphine ligand (N, N-bis (diphenylphosphino) -isopropylamine/chromium salt (tetrahydrofuran-chromium trichloride) catalyst solution having a molar concentration of 0.3umol/L, and 2mL of a pre-prepared triphenylcarbon tetrakis (pentafluorophenyl) borate having a molar concentration of 0.3umol/L was added thereto, and the reaction was carried out at a reaction temperature of 48℃and a rotation speed of 600rpm for 60 minutes while maintaining an ethylene pressure of 4.5 MPa.
Example 7
500mL of a high-pressure stainless steel reaction vessel was heated to 120℃and evacuated for 3 hours, during which nitrogen was replaced three times, and then evacuated and replaced three times with hydrogen. After cooling to room temperature, the mixture was introduced under a hydrogen pressure of 0.5MPa, and a toluene solution containing 193mL of dehydrated and deoxidized methylcyclohexane solution (containing 4ppm of dodecylamine), 0.9mL of Triisobutylaluminum (TIBA), 3mL of a pre-prepared phosphine ligand (N, N-bis (diphenylphosphino) -cyclohexylamine/chromium salt (chromium trichloride tetrahydrofuran) catalyst solution having a molar concentration of 1.0 mol/L and 3mL of a pre-prepared triphenylcarbon tetrakis (pentafluorophenyl) borate were added thereto, and the mixture was reacted for 30 minutes at a reaction temperature of 48℃and a rotation speed of 600rpm while maintaining an ethylene pressure of 4.5 MPa.
Comparative example 1
The remaining operation of example 1 was repeated except that the addition amount of 2-ethyl-1-hexanol was changed to 0 ppm.
Comparative example 2
The remaining operation of example 1 was repeated except that the addition amount of 2-ethyl-1-hexanol was changed to 6 ppm.
Comparative example 3
The remaining operation of example 1 was repeated except that the addition amount of 2-ethyl-1-hexanol was changed to 8 ppm.
The composition of the oligomerization reaction obtained by each of the methods shown above is shown in the following table:
operational examples External additive Addition amount/ppm reactivity/Kg/g Cr 1-C6/％ 1-C8/％ PE/％
Example 1 2-ethyl-1-hexanol 0.4 800 43.7％ 47.9％ 0.3
Example 2 2-ethyl-1-hexanol 1 900 43.3％ 47.5％ 0.2
Example 3 2-ethyl-1-hexanol 2 880 43.2％ 47.8％ 0.2
Example 4 2-ethyl-1-hexanol 4 830 43.0％ 47.3％ 0.2
Example 5 1-decyl alcohol 1.5 870 32.3％ 57.7％ 0.3
Example 6 H 2 O 1 960 25.7％ 65.6％ 0.2
Example 7 Dodecyl amine 4 850 40.5％ 50.3％ 0.2
Comparative example 1 Without any means for 0 680 44.2％ 47.3％ 0.5
Comparative example 2 2-ethyl-1-hexanol 6 500 43.1％ 45.7％ 1.7
Comparative example 3 2-ethyl-1-hexanol 8 100 42.8％ 45.4％ 2.8
As can be seen from examples and comparative examples: and a certain amount of compound containing hydroxyl or amino is added into the oligomerization system, so that the polymerization activity is improved and the generation of byproduct polymer PE is reduced under the condition of keeping the selectivity basically unchanged. Without these additives in the system, the activity is slightly lower and PE is more; if the additives in the system are too much, the system can act as a quencher, resulting in reduced activity and even deactivation.
In summary, the foregoing is merely representative examples of the present invention and is merely illustrative of the present invention and not intended to limit the present invention, and any modifications of the present invention, including equivalent substitutions and additions of various materials, conversion of continuous or batch processes, etc., are included in the scope of the present invention, as will be appreciated by those skilled in the art. The scope of the invention is defined by the claims.

Claims (9)

1. A process for oligomerization of ethylene, characterized in that ethylene is oligomerized in a system comprising a chromium salt/PNP ligand, an aluminum alkyl compound, a boron salt, and an organic solvent at a reaction temperature and pressure to form an α -olefin, wherein the content of hydroxyl compounds and/or amine compounds in the system relative to the amount of organic solvent satisfies the following relationship: m is more than or equal to 0.4ppm (OH) + m (NH2) Less than or equal to 4ppm, the hydroxyl compound is selected from one or more of deionized water, 1-hexanol, 1-octanol, 1-decanol or 2-ethyl-hexanol; the amino compound is selected from one or more of tert-butylamine, 1-hexylamine, 1-octylamine, 1-decylamine, dodecylamine or 2-ethyl-hexylamine.
2. The method of claim 1, wherein the reaction temperature is 45-50 ℃ and the reaction pressure is 4.0-5.0 mpa g.
3. The method of claim 1, wherein the alkyl aluminum compound is selected from one or more of triethylaluminum, triisobutylaluminum, trioctylaluminum.
4. A method according to any one of claims 1-3, wherein the chromium salt is a complex of metallic chromium, in particular selected from one or more of chromium tetrahydrofuran trichloride, chromium acetylacetonate, chromium 2-ethylhexanoate and chromium hexacarbonyl.
5. A method according to any one of claims 1 to 3, wherein the PNP ligand is a compound having a phosphazene structure as a backbone and is selected from one or more of N, N-bis (diphenylphosphino) -isopropylamine (iPr-PNP), N-bis (diphenylphosphino) -tert-butylamine (tBu-PNP), N-bis (diphenylphosphino) -1, 2-dimethylpropylamine (1, 2-DMP-PNP), N-bis (diphenylphosphino) -cyclohexylamine (Cy-PNP).
6. A method according to any one of claims 1 to 3, wherein the boron salt is a boron-containing organic compound selected from one or more of tris (pentafluorophenyl) boron, triphenylcarbon tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate-methyldi- (hexadecyl) ammonium salt, tetrakis (pentafluorophenyl) borate-methyldi- (octadecyl) ammonium salt.
7. A method according to any of claims 1-3, wherein the mass ratio of hydroxyl and amine based compounds to alkyl aluminium is 0.05-5:100.
8. A process according to any one of claims 1 to 3, characterized in that the molar ratio of chromium-containing salt to PNP ligand is 0.5 to 5; and/or the molar ratio of the alkyl aluminum compound to the chromium-containing salt is 10 to 1000; and/or the molar ratio of the boron salt to the chromium-containing salt is 0.5-3.
9. A method according to any one of claims 1 to 3, wherein the organic solvent is selected from one or more of n-hexane, n-heptane, cyclohexane, methylcyclohexane, tetrahydrofuran, toluene or xylene.
CN202210779080.XA 2022-07-01 2022-07-01 Ethylene oligomerization process with enhanced reactivity and reduced polymer formation Active CN115028509B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210779080.XA CN115028509B (en) 2022-07-01 2022-07-01 Ethylene oligomerization process with enhanced reactivity and reduced polymer formation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210779080.XA CN115028509B (en) 2022-07-01 2022-07-01 Ethylene oligomerization process with enhanced reactivity and reduced polymer formation

Publications (2)

Publication Number Publication Date
CN115028509A CN115028509A (en) 2022-09-09
CN115028509B true CN115028509B (en) 2024-02-02

Family

ID=83128934

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210779080.XA Active CN115028509B (en) 2022-07-01 2022-07-01 Ethylene oligomerization process with enhanced reactivity and reduced polymer formation

Country Status (1)

Country Link
CN (1) CN115028509B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116251728B (en) * 2023-01-03 2023-09-19 万华化学集团股份有限公司 Method for reducing polymer adhesion in ethylene oligomerization reactor

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003004158A2 (en) * 2001-07-02 2003-01-16 Sasol Technology (Proprietary) Limited Catalyst comprising chromium and a ligand comprising a substituted cyclopentadiene and its use for trimerising olefins
CN104447161A (en) * 2013-09-16 2015-03-25 中国石油化工股份有限公司 Ethylene oligomerization method
CN104628503A (en) * 2013-11-08 2015-05-20 中国石油化工股份有限公司 Ethylene oligomerization method
CN113441185A (en) * 2020-03-26 2021-09-28 万华化学集团股份有限公司 Ethylene oligomerization catalyst and method for continuously producing 1-hexene and 1-octene
CN113773430A (en) * 2021-09-13 2021-12-10 万华化学集团股份有限公司 Preparation method of alpha-olefin copolymer
KR20220036234A (en) * 2020-09-15 2022-03-22 주식회사 엘지화학 Ligand compound organic chromium compound and catalyst composition comprising same
WO2022060108A1 (en) * 2020-09-15 2022-03-24 주식회사 엘지화학 Ligand compound, organic chromium compound, and catalyst system comprising same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9447202B2 (en) * 2012-05-09 2016-09-20 Sasol Technology (Proprietary) Limited Oligomerisation of olefinic compounds with reduced polymer formation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003004158A2 (en) * 2001-07-02 2003-01-16 Sasol Technology (Proprietary) Limited Catalyst comprising chromium and a ligand comprising a substituted cyclopentadiene and its use for trimerising olefins
CN104447161A (en) * 2013-09-16 2015-03-25 中国石油化工股份有限公司 Ethylene oligomerization method
CN104628503A (en) * 2013-11-08 2015-05-20 中国石油化工股份有限公司 Ethylene oligomerization method
CN113441185A (en) * 2020-03-26 2021-09-28 万华化学集团股份有限公司 Ethylene oligomerization catalyst and method for continuously producing 1-hexene and 1-octene
KR20220036234A (en) * 2020-09-15 2022-03-22 주식회사 엘지화학 Ligand compound organic chromium compound and catalyst composition comprising same
WO2022060108A1 (en) * 2020-09-15 2022-03-24 주식회사 엘지화학 Ligand compound, organic chromium compound, and catalyst system comprising same
CN113773430A (en) * 2021-09-13 2021-12-10 万华化学集团股份有限公司 Preparation method of alpha-olefin copolymer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"乙烯四聚新型助催化剂和配体的研究";丁万友;《中国优秀硕士学位论文全文数据库》(第06期);B016-131 *

Also Published As

Publication number Publication date
CN115028509A (en) 2022-09-09

Similar Documents

Publication Publication Date Title
CN107282126B (en) Ethylene tetramerization catalyst composition and application thereof
CN115028509B (en) Ethylene oligomerization process with enhanced reactivity and reduced polymer formation
KR20190063840A (en) Process for preparing oligomer using olefin
CN109476779B (en) Oligomerization of ethylene
CN114988980B (en) Method for producing 1-octene by high-activity oligomerization of ethylene
US20220001368A1 (en) Ligands for production of 1-hexene in chromium assisted ethylene oligomerization process
US11021418B2 (en) Method of olefin oligomerization
CN115028508B (en) Ethylene tetramerization process with reduced PE (polyethylene) production
CN114054095B (en) Ethylene oligomerization catalyst composition and application thereof
CN110801864B (en) Ethylene tetramerization catalyst composition and application thereof
CN114956939B (en) Ethylene oligomerization regulation and control method
CN112473739A (en) Ethylene oligomerization catalyst system, preparation method and application
CN109201119B (en) Ethylene oligomerization catalyst system, preparation method and application thereof
CN107282112B (en) Ethylene oligomerization catalyst composition and application thereof
CN107282131B (en) Catalyst composition and application thereof in ethylene tetramerization
CN107282133B (en) Ethylene tetramerization catalyst composition and application
CN105566038A (en) Ethene oligomerization continuous reaction method
CN105566025A (en) Ethene oligomerization continuous reaction method
CN116037207A (en) Catalyst composition for olefin oligomerization and preparation method and application thereof
CN105566039A (en) Ethene oligomerization continuous reaction method
CN107282122B (en) Ethylene tetramerization catalyst composition and application thereof
CN107282124B (en) Ethylene tetramerization catalyst composition and tetramerization method
CN107282108B (en) Ethylene oligomerization catalyst composition and application thereof
CN107282125B (en) Ethylene tetramerization catalyst composition and application thereof
CN105566040A (en) Ethene oligomerization continuous reaction method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant