Nothing Special   »   [go: up one dir, main page]

CN114988980A - Method for producing 1-octene by ethylene high-activity oligomerization - Google Patents

Method for producing 1-octene by ethylene high-activity oligomerization Download PDF

Info

Publication number
CN114988980A
CN114988980A CN202210678627.7A CN202210678627A CN114988980A CN 114988980 A CN114988980 A CN 114988980A CN 202210678627 A CN202210678627 A CN 202210678627A CN 114988980 A CN114988980 A CN 114988980A
Authority
CN
China
Prior art keywords
octene
ethylene
reaction
cocatalyst
material flow
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.)
Granted
Application number
CN202210678627.7A
Other languages
Chinese (zh)
Other versions
CN114988980B (en
Inventor
陈冠良
张彦雨
丁明强
车传亮
张鹏坤
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 CN202210678627.7A priority Critical patent/CN114988980B/en
Publication of CN114988980A publication Critical patent/CN114988980A/en
Application granted granted Critical
Publication of CN114988980B publication Critical patent/CN114988980B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04Preparation 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
    • C07C2/06Preparation 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
    • C07C2/08Catalytic processes
    • C07C2/26Catalytic processes with hydrides or organic compounds
    • C07C2/36Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143Catalysts 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/19Catalysts containing parts with different compositions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20Olefin oligomerisation or telomerisation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62Chromium
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The invention discloses a method for producing 1-octene by ethylene high-activity oligomerization, which comprises the following steps: a. forming a first material flow at least consisting of a main catalyst and an aluminoxane cocatalyst; b. forming a second stream consisting at least of an alkylaluminum-based cocatalyst; c. separately supplying the first and second streams to at least one reaction zone comprising ethylene monomer dissolved in a process solvent; d. polymerizing ethylene monomer in at least one reaction zone in the presence of the main catalyst, the aluminoxane cocatalyst and the alkylaluminum cocatalyst to produce 1-octene. The invention can ensure higher polymerization activity under the condition of reducing the dosage of the aluminoxane by a unique feeding mode, and can really realize the reduction of the cost.

Description

Method for producing 1-octene by ethylene high-activity oligomerization
Technical Field
The invention relates to an ethylene oligomerization method, in particular to a method for producing 1-octene by ethylene high-activity oligomerization.
Background
α -olefins (e.g., 1-hexene, 1-octene) are used in large amounts as comonomers for polyolefin polymerization as products of ethylene oligomerization, and in recent years, the market demand for α -olefins has been sharply increased with the development of high-end polyolefins such as POE, POP, and m-LLDPE.
At present, the production of 1-hexene in industry mainly depends on an ethylene selective trimerization process, the selectivity of 1-hexene is up to more than 96 percent, and for example, Phillips, medium petroleum and medium petrochemical industries have ethylene selective trimerization devices. However, 1-octene is mainly prepared by ethylene non-selective oligomerization, alpha-olefin produced by the traditional process is a mixture of C4-C20, the product conforms to Schulz-Flory distribution, the selectivity of 1-octene is generally 20-30%, continuous rectification and separation are needed for obtaining pure 1-octene, and the energy consumption is high. Sasol in south Africa developed a selective tetramerization process for ethylene in the presence of trivalent chromium compounds and i PrN(PPh 2 ) 2 the 1-octene is produced by selective tetramerisation of ethylene in the presence of a catalytic system comprising Methylaluminoxane (MAO) as co-catalyst, with 1-octene selectivity being up to over 70% (Journal of the American Chemical Society,126(2004) 14712). Sasol builds a first set of ethylene selective tetramerization device in 2014, and the production scale is 10 ten thousand tons per year.
However, the catalytic system developed by Sasol has a disadvantage in that the catalytic performance can be achieved only when an excessive amount of the expensive cocatalyst Methylaluminoxane (MAO) is used, that is, the Al/Cr molar ratio is 300-.
In order to reduce the production cost, it is currently common to use a combination of aluminoxane and aluminum alkyl to reduce the amount of MAO cocatalyst, for example, in the ethylene oligomerization process provided in CN109476779A, a cocatalyst mixture containing at least two different aluminum compounds (aluminoxane and aluminum alkyl) is used. CN106061607A combines the use of modified methylaluminoxane (MMAO-3a) and Triethylaluminum (TEA), which is believed to provide a cost effective cocatalyst system using MMAO-3a and TEA in combination. However, the above-mentioned method can not achieve a true economical efficiency because it can reduce the production cost and also cause a decrease in polymerization activity and product selectivity.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for producing 1-octene by ethylene high-activity oligomerization, which can ensure higher polymerization activity under the condition of reducing the dosage of aluminoxane by a unique feeding mode and can really realize the reduction of cost.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for producing 1-octene by ethylene high-activity oligomerization comprises the following steps:
a. forming a first material flow at least consisting of a main catalyst and an aluminoxane cocatalyst;
b. forming a second stream consisting at least of an alkylaluminum-based cocatalyst;
c. separately supplying the first and second streams to at least one reaction zone comprising ethylene monomer dissolved in a process solvent;
d. polymerizing ethylene monomers in at least one reaction zone in the presence of the main catalyst, the aluminoxane cocatalyst and the alkylaluminum cocatalyst to prepare a reaction solution containing 1-octene.
In the continuous research, the invention discovers that the activation effect of the alkyl aluminum cocatalyst on metal in the ethylene oligomerization reaction is far lower than that of the aluminoxane cocatalyst, so that the reduction of the dosage of the aluminoxane by directly mixing the alkyl aluminum and the aluminoxane can be at the expense of the reaction activity, and the cost reduction effect cannot be really achieved. Surprisingly, the invention can remarkably improve the polymerization activity under the condition of keeping lower dosage of the aluminoxane, is more beneficial to improving the yield of the 1-octene and further improves the economical efficiency of the device by mixing the main catalyst and the aluminoxane cocatalyst to form a first material flow and then respectively feeding the first material flow and a second material flow consisting of the alkylaluminum cocatalyst into the reaction zone.
In a preferred embodiment of the present invention, the first stream and the second stream each independently comprise a portion of the process solvent with or without ethylene monomer present.
In a preferred embodiment of the present invention, no ethylene monomer or only a low concentration of ethylene monomer, for example a mass concentration of 10% or less, is present in the first stream and in the second stream.
In a preferred embodiment of the present invention, the mixing time of the procatalyst and the aluminoxane based cocatalyst in the first stream before entering the reaction zone is from 30s to 30min, preferably from 5 to 10 min.
In a preferred embodiment of the present invention, the first stream comprises from 20 to 99% by weight of the total mass of the process solvent; the content of the process solvent in the second material flow accounts for 30-98% of the total mass of the second material flow.
In a preferred embodiment of the present invention, the process solvent is a non-coordinating inert liquid and/or a liquid olefin such as ethylene, 1-hexene, 1-octene serving as a monomer or reaction product, wherein the non-coordinating inert liquid is preferably a mixture of any one or more of isoparaffin, linear and branched aliphatic hydrocarbon, alkyl substituted or unsubstituted alicyclic hydrocarbon, halogenated hydrocarbon, aromatic hydrocarbon, nitrile, more preferably isoparaffin, isobutane, n-butane, n-pentane, isopentane, n-hexane, isohexane, n-heptane, n-octane, n-nonane, dodecane, cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, perfluorinated C-containing hydrocarbon 4-10 Any one or more of alkane, chlorobenzene, dichloromethane, benzene, toluene, mesitylene, xylene and acetonitrile.
In a preferable scheme provided by the invention, the polymerization reaction temperature in the reaction zone is 40-60 ℃, the reaction pressure is 3.0-6.0MPa, and the reaction time is 1-120min, preferably 30-60 min.
The reaction zone may be one or more reaction zones present in one reactor or one or more reactors combined with each other to form one or more reaction zones, and the definition of the reaction zone in the present invention is merely to provide a place for carrying out the ethylene polymerization reaction, and there is no particular limitation on the type and number of reactors involved.
The reactor type may be any one or a combination of more of a continuous stirred tank reactor, a tubular reactor, and a tower reactor.
In a preferred embodiment of the present invention, the main catalyst is a complex of chromium metal and a ligand;
the procatalyst may be one or more chromium metal complex catalysts and suitable ligands may be represented by the following formula I:
Figure BDA0003695620130000041
in formula I, A represents one or more of elements C, N, B, Si; r represents hydrogen, an alkyl group, a silyl group, or the like, which is bonded to A via a single bond or a double bond. Or, in the formula I, A-R represents a bridging group containing a skeleton structure such as-N-Si-, C-C-, C-C-, etc., wherein, the symbol only refers to a connecting position, and no specific meaning is provided.
As a preferred specific example, the main catalyst may be selected from:
(phenyl group) 2 PN (isopropyl) P (phenyl) 2
(phenyl group) 2 PN (tert-butyl) P (phenyl) 2
(phenyl group) 2 PN (1, 2-dimethylpropyl) P (phenyl) 2
(phenyl group) 2 P (tert-butyl) C ═ CHP (phenyl) 2
(phenyl group) 2 P (isopropyl) C ═ CHP (phenyl) 2
(phenyl group) 2 P (n-butyl) C ═ CHP (phenyl) 2
(phenyl group) 2 P (N-butyl) N-Si (methyl) 2 P (phenyl) 2
(phenyl group) 2 P (isopropyl) N-Si (methyl) 2 P (phenyl) 2
(phenyl group) 2 P (tert-butyl) N-Si (methyl) 2 P (phenyl) 2
In the first material flow, the dosage of the main catalyst and the aluminoxane cocatalyst is 1 (100) -300 in terms of the molar ratio of Cr/Al;
the feeding ratio of the first material flow and the second material flow is 1 (0.3-3) in terms of molar ratio of the aluminoxane cocatalyst to the alkylaluminum cocatalyst.
In a preferred embodiment provided by the present invention, the aluminoxane based cocatalyst is selected from C 1-5 The alkylaluminoxane or modified aluminoxane is preferably at least one of methylaluminoxane, ethylaluminoxane, propylaluminoxane, isobutylaluminoxane, isopropylaluminoxane, t-butylaluminoxane, modified methylaluminoxane, modified ethylaluminoxane and modified propylaluminoxane.
In a preferred embodiment of the present invention, the aluminum alkyl cocatalyst is C 1-30 Aluminum alkyls or C 1-30 The halogenated species of the alkyl aluminum is preferably at least one selected from the group consisting of trimethyl aluminum, triethyl aluminum, tri-n-hexyl aluminum, triisobutyl aluminum, tri-n-octyl aluminum, diethyl aluminum chloride, diisobutyl aluminum chloride and ethyl aluminum dichloride.
The invention can ensure higher polymerization activity under the condition of reducing the dosage of the aluminoxane by a unique feeding mode, and can really realize the reduction of the cost.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The source information of the main raw materials in the following examples:
(phenyl group) 2 PN (isopropyl) P (phenyl) 2 : synthesized according to the Journal of the American Chemical Society (2004),126(45), 14712-;
(phenyl group) 2 PN (tert-butyl) P (phenyl) 2 : synthesized according to the Journal of the American Chemical Society (2004),126(45), 14712-;
(phenyl group) 2 PN (1, 2-dimethylpropyl) P (phenyl) 2 : synthesized according to the Journal of the American Chemical Society (2004),126(45), 14712-;
(phenyl group) 2 P (tert-butyl) C ═ CHP (phenyl) 2 : synthesized according to the literature Catalysis Communications (2019),121, 15-18;
(phenyl group) 2 P (isopropyl) C ═ CHP (phenyl) 2 : synthesized according to the literature Catalysis Communications (2019),121, 15-18;
(phenyl group) 2 P (n-butyl) C ═ CHP (phenyl) 2 : synthesized according to the literature Catalysis Communications (2019),121, 15-18;
(phenyl group) 2 P (isopropyl) N-Si (methyl) 2 P (phenyl) 2 : according to the Catalysis Science&Technology (2017),7(21), 5011-5018;
(phenyl group) 2 P (2, 6-diisopropylphenyl) N-Si (methyl) 2 P (phenyl) 2 : according to the Catalysis Science&Technology (2017),7(21), 5011-5018;
(phenyl group) 2 P (cyclopentyl) N-Si (methyl) 2 P (phenyl) 2 : according to the Catalysis Science&Technology (2017),7(21), 5011-5018;
modified methylaluminoxane (MMAO-3 a): 7 wt% Al in n-heptane, Nomoon Chemicals International Inc.;
methylaluminoxane (MAO): 10.0 wt% Al in toluene, Nomoon Chemicals International Inc.;
ethyl Aluminoxane (EAO): 25 wt% Al in hexane, Beijing YinoKay science Co., Ltd;
isobutylaluminoxane (IBAO): 10 wt% Al in toluene, Beijing YinoKai science and technology Co., Ltd;
triethyl aluminum (TEA): 16.9 wt% Al in n-hexane, Beijing Yinokay science and technology Co., Ltd;
triisobutylaluminum (TIBA): 25.0 wt% Al in toluene, Beijing YinuoKai science and technology Co., Ltd;
trimethylaluminum (TMA): 16.5 wt% Al in toluene, Ikonyka technologies, Beijing;
chromium acetylacetonate: 98%, Beijing Yinaoka science and technology Co., Ltd;
toluene: 99%, kyo illinois technologies ltd;
secondly, the following test method is adopted in each example of the invention:
the liquid phase products are characterized by gas chromatography, so that the mass of each liquid phase product is obtained, and the solid products are separated, dried and weighed;
analysis conditions for gas chromatography: sample injection temperature: 250 ℃; the temperature of the column box is 35 ℃;
temperature rising procedure: firstly keeping the temperature at 35 ℃ for 10 minutes, then increasing the temperature to 250 ℃ at the speed of 10 ℃/min, then keeping the temperature at 250 ℃ for 10 minutes, and then beginning to cool until the room temperature;
detector temperature: 250 ℃; carrier: 1.0 Mpa; air: 0.03 MPa; hydrogen gas: 0.03 MPa;
the product was characterized by nonane as an internal standard and calculated as follows:
Figure BDA0003695620130000071
wherein m1 represents the mass of a certain substance in the product, m is the mass of nonane, a1 is the peak area of the substance measured in GC, a is the peak area of nonane measured in GC, and k is the correction coefficient.
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
Preparing a main catalyst a-1:
873.3mg (2.50mmol) of chromium acetylacetonate and 1602mg (3.75mmol) (phenyl) are weighed out 2 PN (isopropyl) P (phenyl) 2 Dissolved in 500ml of a toluene solution to prepare a toluene solution having a concentration of 5.0. mu. mol/ml (in terms of chromium).
The main catalyst a-2 is configured:
873.3mg (2.50mmol) of chromium acetylacetonate and 1655mg (3.75mmol) (phenyl) 2 PN (tert-butyl) P (phenyl) 2 Dissolved in 500ml of a toluene solution to prepare a toluene solution having a concentration of 5.0. mu. mol/ml (in terms of chromium).
Preparing a main catalyst a-3:
873.3mg (2.50mmol) of chromium acetylacetonate and 1708mg (3.75mmol) (phenyl) are weighed out 2 PN (1, 2-dimethylpropyl) P (phenyl) 2 Dissolving in 500ml toluene solution, and preparingIn the form of a toluene solution with a concentration of 5.0. mu. mol/ml (calculated as chromium).
Configuring a main catalyst a-4:
873.3mg (2.50mmol) of chromium acetylacetonate and 1644mg (3.75mmol) (phenyl) are weighed out 2 P (isopropyl) C ═ CHP (phenyl) 2 Dissolved in 500ml of a toluene solution to prepare a toluene solution having a concentration of 5.0. mu. mol/ml (in terms of chromium).
Configuring a main catalyst a-5:
873.3mg (2.50mmol) of chromium acetylacetonate and 1696mg (3.75mmol) (phenyl) are weighed out 2 P (tert-butyl) C ═ CHP (phenyl) 2 Dissolved in 500ml of a toluene solution to prepare a toluene solution having a concentration of 5.0. mu. mol/ml (in terms of chromium).
Configuring a main catalyst a-6:
873.3mg (2.50mmol) of chromium acetylacetonate and 1794mg (3.75mmol) (phenyl) are weighed out 2 P (n-butyl) C ═ CHP (phenyl) 2 Dissolved in 500ml of a toluene solution to prepare a toluene solution having a concentration of 5.0. mu. mol/ml (in terms of chromium).
Configuring a main catalyst a-7:
873.3mg (2.50mmol) of chromium acetylacetonate and 1821mg (3.75mmol) (phenyl) are weighed out 2 P (isopropyl) N-Si (methyl) 2 P (phenyl) 2 Dissolved in 500ml of a toluene solution to prepare a toluene solution having a concentration of 5.0. mu. mol/ml (in terms of chromium).
Configuring a main catalyst a-8:
873.3mg (2.50mmol) of chromium acetylacetonate and 2264mg (3.75mmol) (phenyl) are weighed out 2 P (2, 6-diisopropylphenyl) N-Si (methyl) 2 P (phenyl) 2 Dissolved in 500ml of a toluene solution to prepare a toluene solution having a concentration of 5.0. mu. mol/ml (in terms of chromium).
The main catalyst a-9 is configured:
873.3mg (2.50mmol) of chromium acetylacetonate and 1918mg (3.75mmol) (phenyl) are weighed out 2 P (cyclopentyl) N-Si (methyl) 2 P (phenyl) 2 Dissolved in 500ml of a toluene solution to prepare a toluene solution having a concentration of 5.0. mu. mol/ml (in terms of chromium).
[ example 1 ]
Before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours, replaced by nitrogen, replaced by ethylene for 3 times after being cooled to normal temperature, and 100ml toluene is added into the reaction kettle. 1ml of procatalyst a-1 and 0.23ml of MMAO-3a (Al/Cr ═ 100) were mixed for 5min to form a first stream, 0.75ml of TMA as a second stream; adding the first material flow and the second material flow into a reaction kettle respectively, adding 100ml of toluene into the reaction kettle, raising the temperature in the reaction kettle to 40 ℃, and introducing 4.0MPa of ethylene to start reaction. After the reaction for 20min, 10mL of ethanol containing 10 vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
The molar ratio of the alumoxane in the first stream to the aluminum alkyl in the second stream is designated as Ali/aiii, where Ali/aiii is 1:3 in this example.
[ examples 2 to 27 ]
Ethylene polymerization was carried out by referring to substantially the same method as in example 1 except for the difference in reaction conditions shown in Table 1.
The following comparative examples 1 to 4 were compared with example 1:
comparative example 1
Before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours, replaced by nitrogen, replaced by ethylene for 3 times after being cooled to normal temperature, and added with 100ml toluene. 1ml of main catalyst a-1, 0.23ml of MMAO-3a (Al/Cr ═ 100) and 0.75ml of TMA are added into a reaction kettle in sequence, 100ml of toluene is added into the reaction kettle, then the temperature in the reaction kettle is raised to 40 ℃, and 4.0MPa of ethylene is introduced to start the reaction. After the reaction for 20min, 10mL of ethanol containing 10 vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
Comparative example 2
Before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours, replaced by nitrogen, replaced by ethylene for 3 times after being cooled to normal temperature, and 100ml toluene is added into the reaction kettle. 1ml of procatalyst a-1 and 0.75ml of TMA were mixed for 5min to form a first stream, 0.23ml of MMAO-3a was used as a second stream; adding the first material flow and the second material flow into a reaction kettle respectively, adding 100ml of toluene into the reaction kettle, raising the temperature in the reaction kettle to 40 ℃, and introducing 4.0MPa of ethylene to start reaction. After the reaction for 20min, 10mL of ethanol containing 10 vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
Comparative example 3
Before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours, replaced by nitrogen, replaced by ethylene for 3 times after being cooled to normal temperature, and 100ml toluene is added into the reaction kettle. Mixing 0.23ml MMAO-3a and 0.75ml TMA for 5min to form a first stream, and using 1ml main catalyst a-1 as a second stream; and respectively adding the first material flow and the second material flow into a reaction kettle, adding 100ml of methylbenzene into the reaction kettle, raising the temperature in the reaction kettle to 40 ℃, and introducing 4.0MPa of ethylene to start reaction. After the reaction for 20min, 10mL of ethanol containing 10 vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
Comparative example 4
Before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours, replaced by nitrogen, replaced by ethylene for 3 times after being cooled to normal temperature, and added with 100ml toluene. Premixing 1ml of main catalyst a-1, 0.23ml of MMAO-3a (Al/Cr is 100) and 0.75ml of TMA for 5min, adding the premixed materials into a reaction kettle at one time, supplementing 100ml of toluene to the reaction kettle, raising the temperature in the reaction kettle to 40 ℃, and introducing 4.0MPa of ethylene to start reaction. After the reaction for 20min, 10mL of ethanol containing 10 vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
The following comparative examples 5-8 were compared with example 6:
comparative example 5
Before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours, replaced by nitrogen, replaced by ethylene for 3 times after being cooled to normal temperature, and 100ml toluene is added into the reaction kettle. 1ml of main catalyst a-2, 0.69ml of MMAO-3a (Al/Cr is 300) and 0.75ml of TEA are added into a reaction kettle in sequence, 100ml of toluene is added into the reaction kettle, then the temperature in the reaction kettle is raised to 50 ℃, and 4.0MPa of ethylene is introduced to start the reaction. After the reaction for 20min, 10mL of ethanol containing 10 vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
Comparative example 6
Before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours, replaced by nitrogen, replaced by ethylene for 3 times after being cooled to normal temperature, and 100ml toluene is added into the reaction kettle. 1ml of procatalyst a-2 and 0.75ml of TEA were mixed for 7min to form a first stream, 0.69ml of MMAO-3a was used as the second stream; adding the first material flow and the second material flow into a reaction kettle respectively, adding 100ml of toluene into the reaction kettle, raising the temperature in the reaction kettle to 50 ℃, and introducing 4.0MPa of ethylene to start reaction. After the reaction for 20min, 10mL of ethanol containing 10 vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
Comparative example 7
Before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours, replaced by nitrogen, replaced by ethylene for 3 times after being cooled to normal temperature, and 100ml toluene is added into the reaction kettle. 0.69ml of MMAO-3a and 0.75ml of TEA were mixed for 7min to form a first stream, and 1ml of procatalyst a-2 was used as the second stream; adding the first material flow and the second material flow into a reaction kettle respectively, adding 100ml of toluene into the reaction kettle, raising the temperature in the reaction kettle to 50 ℃, and introducing 4.0MPa of ethylene to start reaction. After the reaction for 20min, 10mL of ethanol containing 10 vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
Comparative example 8
Before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours, replaced by nitrogen, replaced by ethylene for 3 times after being cooled to normal temperature, and 100ml toluene is added into the reaction kettle. Premixing 1ml of main catalyst a-2, 0.69ml of MMAO-3a and 0.75ml of TEA for 7min, adding the premixed catalyst into a reaction kettle at one time, adding 100ml of toluene into the reaction kettle, raising the temperature in the reaction kettle to 50 ℃, and introducing 4.0MPa of ethylene to start reaction. After the reaction for 20min, 10mL of ethanol containing 10 vol% aqueous hydrochloric acid was added to the reaction solution to terminate the reaction.
The reactivity and the product selectivity in each example and comparative example were measured, and the results are shown in table 1. The experimental result shows that the feeding mode of the invention can ensure higher catalytic activity under the condition of lower dosage of aluminoxane, thereby really realizing the reduction of production cost.
Reaction conditions in Table 1, examples and comparative examples
Figure BDA0003695620130000121
Figure BDA0003695620130000131

Claims (10)

1. A method for producing 1-octene by ethylene high-activity oligomerization is characterized by comprising the following steps:
a. forming a first material flow at least consisting of a main catalyst and an aluminoxane cocatalyst;
b. forming a second stream consisting at least of an alkylaluminum-based cocatalyst;
c. separately supplying the first and second streams to at least one reaction zone comprising ethylene monomer dissolved in a process solvent;
d. polymerizing ethylene monomers in at least one reaction zone in the presence of the main catalyst, the aluminoxane cocatalyst and the alkylaluminum cocatalyst to prepare a reaction solution containing 1-octene.
2. The method for producing 1-octene according to claim 1, wherein the first material flow and the second material flow each independently comprise a portion of the process solvent and with or without ethylene monomer.
3. The method for producing 1-octene according to claim 2, wherein no ethylene monomer or only a low concentration of ethylene monomer, such as mass concentration less than or equal to 10%, is present in the first and second streams.
4. A process for the high-activity oligomerization of ethylene to 1-octene according to any one of claims 1-3, characterized in that the mixing time of the procatalyst and the aluminoxane cocatalyst in the first stream before entering the reaction zone is 30s-30min, preferably 5-10 min.
5. The method for producing 1-octene according to claim 2, wherein the content of process solvent in the first material flow is 20-99% of the total mass; the content of the process solvent in the second material flow accounts for 30-98% of the total mass of the second material flow.
6. The method for producing 1-octene by oligomerization of ethylene with high activity according to claim 2, wherein the process solvent is a non-coordinated inert liquid and/or liquid olefin serving as monomer or reaction product, such as ethylene, 1-hexene, 1-octene, wherein the non-coordinated inert liquid is preferably a mixture of any one or more of isoparaffin, linear and branched aliphatic hydrocarbon, alkyl substituted or unsubstituted alicyclic hydrocarbon, halogenated hydrocarbon, aromatic hydrocarbon, nitrile, more preferably isoparaffin, isobutane, n-butane, n-pentane, isopentane, n-hexane, isohexane, n-heptane, n-octane, n-nonane, dodecane, cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, perfluorinated C-olefin 4-10 Any one or more of alkane, chlorobenzene, dichloromethane, benzene, toluene, mesitylene, xylene and acetonitrile.
7. The method for producing 1-octene according to any one of claims 1-6, wherein the polymerization temperature in the reaction zone is 40-60 ℃, the reaction pressure is 3.0-6.0MPa, and the reaction time is 1-120min, preferably 30-60 min.
8. The method for producing 1-octene according to any one of claims 1-7, wherein the main catalyst is a complex of chromium metal and ligand;
in the first material flow, the dosage of the main catalyst and the aluminoxane cocatalyst is 1 (100) -300 in terms of the molar ratio of Cr/Al;
the feeding ratio of the first material flow and the second material flow is 1 (0.3-3) in terms of molar ratio of the aluminoxane cocatalyst to the alkylaluminum cocatalyst.
9. The method for producing 1-octene according to claim 8, wherein said aluminoxane based cocatalyst is selected from C 1-5 The alkylaluminoxane or modified aluminoxane is preferably at least one of methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isopropylaluminoxane, t-butylaluminoxane, modified methylaluminoxane, modified ethylaluminoxane and modified propylaluminoxane.
10. The method for producing 1-octene according to claim 8, wherein said alkylaluminium cocatalyst is C 1-30 Alkyl aluminium or C 1-30 The halogenated species of the alkyl aluminum is preferably at least one selected from the group consisting of trimethyl aluminum, triethyl aluminum, tri-n-hexyl aluminum, triisobutyl aluminum, tri-n-octyl aluminum, diethyl aluminum chloride, diisobutyl aluminum chloride and ethyl aluminum dichloride.
CN202210678627.7A 2022-06-15 2022-06-15 Method for producing 1-octene by high-activity oligomerization of ethylene Active CN114988980B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210678627.7A CN114988980B (en) 2022-06-15 2022-06-15 Method for producing 1-octene by high-activity oligomerization of ethylene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210678627.7A CN114988980B (en) 2022-06-15 2022-06-15 Method for producing 1-octene by high-activity oligomerization of ethylene

Publications (2)

Publication Number Publication Date
CN114988980A true CN114988980A (en) 2022-09-02
CN114988980B CN114988980B (en) 2023-05-30

Family

ID=83035294

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210678627.7A Active CN114988980B (en) 2022-06-15 2022-06-15 Method for producing 1-octene by high-activity oligomerization of ethylene

Country Status (1)

Country Link
CN (1) CN114988980B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3140775A1 (en) * 2022-10-17 2024-04-19 IFP Energies Nouvelles New catalytic composition based on supported chromium or titanium
CN118290214A (en) * 2024-04-07 2024-07-05 广东众和工程设计有限公司 Method for preparing linear alpha-olefin by ethylene high-selectivity oligomerization

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060223960A1 (en) * 2005-04-01 2006-10-05 Nova Chemicals (International) S.A. Modified (MAO + aluminum alkyl) activator
WO2018012793A1 (en) * 2016-07-14 2018-01-18 Sk Innovation Co., Ltd. Oligomerization of ethylene
CN111774098A (en) * 2020-07-21 2020-10-16 万华化学集团股份有限公司 Ethylene oligomerization catalyst system, preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060223960A1 (en) * 2005-04-01 2006-10-05 Nova Chemicals (International) S.A. Modified (MAO + aluminum alkyl) activator
WO2018012793A1 (en) * 2016-07-14 2018-01-18 Sk Innovation Co., Ltd. Oligomerization of ethylene
CN111774098A (en) * 2020-07-21 2020-10-16 万华化学集团股份有限公司 Ethylene oligomerization catalyst system, preparation method and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3140775A1 (en) * 2022-10-17 2024-04-19 IFP Energies Nouvelles New catalytic composition based on supported chromium or titanium
WO2024083616A1 (en) * 2022-10-17 2024-04-25 IFP Energies Nouvelles Novel chromium- or titanium-based supported catalytic composition
CN118290214A (en) * 2024-04-07 2024-07-05 广东众和工程设计有限公司 Method for preparing linear alpha-olefin by ethylene high-selectivity oligomerization

Also Published As

Publication number Publication date
CN114988980B (en) 2023-05-30

Similar Documents

Publication Publication Date Title
EP1100761B1 (en) Process for dimerizing olefins
RU2467796C2 (en) Ethylene oligomerisation catalyst, method of producing said catalyst and oligomerisation method using said catalyst
CA2708011C (en) Integrated chemicals complex containing olefins
NL2023317B1 (en) Method and catalyst for selective oligomerization of ethylene
CN114988980A (en) Method for producing 1-octene by ethylene high-activity oligomerization
CA2500069A1 (en) Selective isomerization and linear dimerization of alpha-olefins using cobalt catalysts
CN112473740A (en) Ethylene oligomerization catalyst system, preparation method and application
CN109174191B (en) Catalyst for ethylene selective oligomerization reaction
CN112570026B (en) Catalyst system for ethylene oligomerization and oligomerization method
CN112473738B (en) Ethylene oligomerization catalyst system and preparation method and application thereof
CN112742483B (en) Catalyst system for ethylene selective oligomerization and preparation and application thereof
CN109476779B (en) Oligomerization of ethylene
CN112387311A (en) Ethylene oligomerization catalyst system, preparation method and application thereof
CN110449186B (en) Reaction method for selective oligomerization of ethylene, catalyst system and application thereof
CN109701642B (en) Catalyst composition and application thereof
CN114054095B (en) Ethylene oligomerization catalyst composition and application thereof
CN107597191B (en) Catalyst for preparing 1-hexene by ethylene trimerization
CN114618588A (en) Catalyst system for ethylene oligomerization and oligomerization method
CN112473739A (en) Ethylene oligomerization catalyst system, preparation method and application
CN112473741B (en) Ethylene oligomerization catalyst system and preparation method and application thereof
CN107282112B (en) Ethylene oligomerization catalyst composition and application thereof
CN105566026A (en) Ethylene tripolymerization method
CN113600241B (en) Catalyst system for selective trimerization of ethylene and preparation and application thereof
CN114409494B (en) Method for improving yield of alpha-olefin in ethylene oligomerization reaction
CN114797970B (en) Ethylene oligomerization modification auxiliary agent and homogeneous catalysis system thereof

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