CN107282131B - Catalyst composition and application thereof in ethylene tetramerization - Google Patents
Catalyst composition and application thereof in ethylene tetramerization Download PDFInfo
- Publication number
- CN107282131B CN107282131B CN201610197151.XA CN201610197151A CN107282131B CN 107282131 B CN107282131 B CN 107282131B CN 201610197151 A CN201610197151 A CN 201610197151A CN 107282131 B CN107282131 B CN 107282131B
- Authority
- CN
- China
- Prior art keywords
- composition
- aluminum
- transition metal
- metal compound
- group
- 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
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, 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
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic 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
-
- 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
- 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
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/24—Phosphines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst composition for ethylene tetramerization, which comprises a diphosphine ligand shown as a formula I, a transition metal compound, an aluminum-containing cocatalyst and tert-butyl hydroperoxide;
in the formula R1And R2Each independently selected from alkyl, cycloalkyl or aryl; r3、R4、R5And R6Each independently selected from aryl or cycloalkyl. The invention also discloses a method for ethylene tetramerization by using the composition. According to the catalyst composition of the present invention, ethylene tetramerization activity and 1-octene selectivity can be improved.
Description
Technical Field
The invention relates to the field of ethylene oligomerization, in particular to a catalyst composition for ethylene tetramerization. The invention also relates to the application of the catalyst composition in ethylene tetramerization reaction.
Background
1-octene is used as an important organic raw material and a chemical intermediate, and is mainly used for producing high-quality Polyethylene (PE). Linear Low Density Polyethylene (LLDPE) produced by copolymerizing 1-octene and ethylene can obviously improve various properties of PE, especially mechanical property, optical property, tear strength and impact strength of polyethylene, and is very suitable for packaging films, agricultural covering films for greenhouses, sheds and the like, and simultaneously 1-octene is also used as an intermediate of plasticizer, fatty acid, detergent alcohol and lubricating oil additive.
The conventional 1-octene production method is an ethylene oligomerization method, the ethylene oligomerization technology is distributed according to Schulz-Flory, not only 1-octene products are obtained, but also other α -olefin and a small amount of solid high polymer are obtained, and the selectivity of the target product 1-octene is very low and is not more than 30 percent, for example, the SHOP method adopted by Shell (US3676523) uses a nickel metal catalyst system to carry out ethylene oligomerization reaction, 11 percent of 1-octene can be obtained, U.S. Pat. No. 6 (US6184428) reports that a nickel compound is used as the catalyst to catalyze ethylene oligomerization, the yield of 1-octene is 19 percent, Japanese patent JP2002121157 reports that zirconium metal catalyst is used to carry out ethylene oligomerization reaction, wherein the content of 1-865 is about 15 percent, recently reported that ethylene tetrameric ternary catalyst system can synthesize 1-octene with high selectivity, such as patent application CN1741850A (WO2004/056478A1), CN1741849A (WO2004/056479A1), CN 4, CN101351424A, CN 4624, CN101291734A and 1, which are all the problems of the prior art of aluminum tetralkoxide, such as the prior art that the prior art is seriously-aluminoxane is seriously used for the severe when the ethylene oligomerization reaction is used as a high-aluminium cocatalyst is used for the conventional aluminium cocatalyst is used, the conventional aluminium catalyst, the problem of aluminium-cocatalyst is used in the process which is considered to cause the serious environmental pollution of the severe reaction, and the high-aluminium.
Disclosure of Invention
In view of the application of phosphine-containing ligands in ethylene tetramerization, the inventors of the present application have conducted extensive and intensive studies in the field of catalysts for ethylene tetramerization, and surprisingly found that ethylene tetramerization reaction under the action of a catalyst composition comprising a bisphosphine ligand represented by formula I, a transition metal compound, an aluminum-containing cocatalyst and tert-butyl hydroperoxide has higher reaction activity, and the reaction initiation is rapid, the operation is stable, the repeatability is good, and the selectivity of 1-octene in the product is also greatly improved; the tert-butyl hydroperoxide is used as organic peroxide to promote the reaction, thereby overcoming the technical bias of the technical personnel in the field and achieving unexpected technical effect.
According to a first aspect of the present invention, there is provided a catalyst composition for ethylene tetramerization, comprising a bisphosphine ligand of formula I, a transition metal compound, an aluminum-containing cocatalyst, and tert-butyl hydroperoxide;
in the formula R1And R2Each independently is an alkyl, cycloalkyl or aryl group; r3、R4、R5And R6Each independently is aryl or cycloalkyl.
According to the invention, the introduction of tert-butyl hydroperoxide into the catalyst composition improves the catalytic activity and the selectivity of 1-octene.
In a preferred embodiment of the present invention, the alkyl group means C1-C20Straight-chain or branched saturated alkyl, preferably C1-C10Straight or branched saturated alkyl, more preferably C1-C6Straight or branched chain saturated alkyl. Specifically, the alkyl group may be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, n-hexyl, sec-hexyl, isohexyl, n-heptyl, isomers thereof, and the like; preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl.
In a preferred embodiment of the present invention, said cycloalkyl means C3-C10Cycloalkyl, preferably C3-C6A cycloalkyl group. In particular, the alkyl group may be selected from cyclopropylAlkyl, cyclopentyl and cyclohexyl.
In a preferred embodiment of the present invention, said substitution means that one or more carbon atoms of said alkyl, cycloalkyl or aryl group are substituted by a heteroatom selected from oxygen, nitrogen and sulfur. Optionally said aryl wherein one or more ring carbon atoms are substituted with a heteroatom selected from oxygen, nitrogen and sulfur. Preferably, the aryl group is substituted by halogen or C1-C20Alkyl substitution.
In a preferred embodiment of the present invention, said aryl group means C5-C20Monocyclic or polycyclic aromatic groups, in particular, the aryl groups may be selected from phenyl, naphthyl and pyridyl. Substituted aryl groups such as substituted phenyl and the like.
In some preferred embodiments of the present invention, the transition metal compound may be a transition metal compound commonly used in the art, such as a compound of chromium, molybdenum, iron, titanium, zirconium or nickel, preferably at least one of chromium chloride, chromium acetylacetonate, chromium isooctanoate, chromium tris (tetrahydrofuran) trichloride, or the like.
In some preferred embodiments of the invention, the molar ratio of aluminum in the cocatalyst of the invention to the metal in the transition metal compound is from 30:1 to 1000:1, preferably from 100:1 to 800:1, more preferably from 200:1 to 500:1, such as from 200:1 to 300:1, or from 300:1 to 500: 1. The molar ratio of the ligand to the transition metal compound is 0.5:1-2: 1. Within this range, the composition has higher activity and selectivity.
In some preferred embodiments of the present invention, the composition further comprises an organic solvent. The weight content of the tert-butyl hydroperoxide contained in the catalyst composition is 25-1000ppm by taking the weight of the organic solvent as a reference; more preferably 150-750ppm, most preferably 250-500 ppm.
In a preferred embodiment of the invention, the organic solvent is selected from the group consisting of methylcyclohexane, heptane, cyclohexane, diethyl ether, tetrahydrofuran, benzene, toluene, xylene and dichloromethane, preferably methylcyclohexane or heptane.
In some embodiments of the invention, the aluminum-containing cocatalyst is selected from the group consisting of alkyl aluminum compounds and alkoxy aluminum compounds, preferably alkyl aluminum compounds.
In some preferred embodiments of the invention, the aluminum alkoxide is C1-C4Alkylaluminoxane of which C1-C4The alkyl is a straight chain or branched chain alkyl; preferably, the aluminoxane is selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane and isobutylaluminoxane; more preferably methylaluminoxane. The alkyl aluminum compound has a general formula of AlWnYmWherein n is an integer of 1 to 3, m is an integer of 0 to 2, and m + n is equal to 3, and when a plurality of W are present, they may be the same or different, and are each independently a straight chain or branched C1-C8An alkyl group; when a plurality of Y's are present, they may be the same or different, each being independently selected from halogen, preferably chlorine and/or bromine; further preferably, the alkyl aluminum compound is selected from at least one of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, diethyl aluminum chloride and ethyl aluminum dichloride, more preferably trimethyl aluminum, triethyl aluminum and/or triisobutyl aluminum.
In some preferred embodiments of the invention, the amount of the ligand, transition metal compound, and co-catalyst in the catalyst composition is a catalytic amount. In a particular embodiment, the bisphosphine ligand is present in an amount of 2 to 500. mu. mol/L, preferably 5 to 50. mu. mol/L, based on the volume of the composition; the content of the transition metal compound is 2-500 mu mol/L, preferably 5-50 mu mol/L; .
A second embodiment of the present invention relates to a process for the tetramerisation of ethylene comprising carrying out the tetramerisation of ethylene in the presence of the catalyst composition described above.
In a preferred embodiment of the present invention, the reaction temperature of the ethylene tetramerization reaction is 0 to 200 ℃, preferably 10 to 100 ℃, more preferably 30 to 60 ℃; the reaction pressure is 0.1-20 MPa. In general, the activity increases with increasing ethylene pressure.
In the ethylene tetramerization reaction of the present invention, any two or three of the bisphosphine ligand, the transition metal compound, the cocatalyst and the tert-butyl hydroperoxide in the catalyst composition may be mixed in advance, and then added to the reaction system together with the other one or two; or directly adding the four components of diphosphine ligand, transition metal compound, cocatalyst and tert-butyl hydroperoxide into the reaction system; or after premixing the four components of the diphosphine ligand, the transition metal compound, the cocatalyst and the tert-butyl hydroperoxide, directly adding the components into the reaction system in the form of a mixture. The organic solvent may be added during the mixing process in any of the above mixing methods.
Ethylene tetramerization was performed using the catalyst composition of the present invention, and after the reaction was completed, gas chromatography and mass spectrometry were performed. The product obtained mainly comprises C6And C8With a small amount of C4、C10、C12The selectivity of 1-octene in α -olefin tetramerization product can reach over 70%, and the result shows that the catalyst activity can exceed 1X 10 to the maximum8g·mol(Cr)-1·h-1The above. The high molecular weight polymer is very small.
In the invention, especially in the pilot plant and industrial production process of ethylene tetramerization, the catalyst composition can effectively catalyze the ethylene tetramerization reaction, and has ultrahigh reaction activity, rapid reaction initiation, stable operation and good repeatability.
The invention adopts the catalyst composition containing diphosphine ligand, transition metal compound, aluminum-containing cocatalyst and tert-butyl hydroperoxide to carry out ethylene tetramerization reaction, and tert-butyl hydroperoxide is used as organic peroxide in the reaction, thus accelerating the reaction speed, and especially in the pilot plant and industrial production processes of ethylene tetramerization, the catalyst composition can effectively catalyze the ethylene tetramerization reaction, has ultrahigh reaction activity, greatly improves the selectivity of 1-octene in the product, and has the advantages of rapid reaction initiation, stable operation and good repeatability. The reported ethylene tetramerization or oligomerization catalyst system has reaction conditions which are always required to be carried out under anhydrous and anaerobic conditions, but the catalyst of the invention has higher reaction activity in the presence of organic peroxide, namely tert-butyl hydroperoxide, and has the advantages of rapid reaction initiation, stable operation, good repeatability and beneficial effect.
Detailed Description
The following examples are merely illustrative of the present invention in detail, but it should be understood that the scope of the present invention is not limited to these examples.
In an embodiment of the invention: the ligand is prepared by reacting substituted alkyne with diphenyl phosphine chloride and further under the action of a titanium catalyst.
The nuclear magnetic resonance was detected by an AV400MHz nuclear magnetic resonance spectrometer of Bruker, Switzerland.
The gas chromatography was performed using a Hewlett packard 5890 chromatograph.
The mass spectrum was detected by a Trace DSQ type gas chromatograph-mass spectrometer (Philippine corporation, USA).
Example 1
A300 mL stainless steel polymerizer was used. Heating the autoclave to 80 ℃, vacuumizing, replacing with nitrogen for a plurality of times, filling ethylene for replacing once, and reducing to the set temperature. Mu. mol of bisphosphine ligand (where R is1Is methyl, R2Is ethyl, R3、R4、R5And R6All of phenyl), 1 mu mol of chromium trichloride, a cocatalyst of triethylaluminum, tert-butyl hydroperoxide and an organic solvent of methylcyclohexane, wherein the total volume of the mixed solution is 100mL, the weight content of the tert-butyl hydroperoxide is 25ppm based on the weight of the organic solvent, and the molar ratio of aluminum to chromium is 300. Controlling the reaction pressure to be 4.0MPa, and introducing ethylene to carry out ethylene tetramerization reaction. After the reaction is carried out for 0.5 hour, the temperature of the system is reduced to room temperature, the gas phase product is collected in a gas metering tank, the liquid phase product is collected in a conical flask, and the gas chromatography analysis is carried out after the metering. The data are shown in Table 1.
Example 2
The same as in example 1, except that the content of t-butyl hydroperoxide was 150ppm by weight. The data are shown in Table 1.
Example 3
The same as in example 1, except that the content of t-butyl hydroperoxide was 250ppm by weight. The data are shown in Table 1.
Example 4
The same as in example 1, except that the content of t-butyl hydroperoxide was 500ppm by weight. The data are shown in Table 1.
Example 5
The same as in example 1, except that the content by weight of t-butyl hydroperoxide was 750 ppm. The data are shown in Table 1.
Example 6
The same as in example 1, except that the content by weight of t-butyl hydroperoxide was 1000 ppm. The data are shown in Table 1.
Example 7
The same as example 1, except that the t-butyl hydroperoxide was contained in an amount of 500ppm by weight and the molar ratio of aluminum to chromium was 200. The data are shown in Table 1.
Example 8
The same as example 1, except that the t-butyl hydroperoxide was contained in an amount of 500ppm by weight and the molar ratio of aluminum to chromium was 500. The data are shown in Table 1.
Example 9
The same as in example 1, except that the t-butyl hydroperoxide content was 500ppm by weight and the reaction temperature was 30 ℃. The data are shown in Table 1.
Example 10
The same as in example 1, except that the t-butyl hydroperoxide content was 500ppm by weight and the reaction temperature was 60 ℃. The data are shown in Table 1.
Example 11
The same as in example 1, except that the t-butyl hydroperoxide content by weight was 500ppm and R1Is n-butyl, R2Is cyclohexyl, R3、R4、R5And R6Are all phenyl groups. The data are shown in Table 1.
Example 12
The same as in example 1, except that the t-butyl hydroperoxide content by weight was 500ppm and R1Is tert-butyl, R2Is cyclopentyl, R3、R4、R5And R6Are all phenyl groups. The data are shown in Table 1.
Example 13
The same as in example 1, except that the t-butyl hydroperoxide content by weight was 500ppm and R1、R2、R3、R4、R5And R6Are all phenyl groups. The data are shown in Table 1.
Example 14
The same as in example 1, except that the t-butyl hydroperoxide content by weight was 500ppm and R1Is cyclopropyl, R2Is phenyl, R3、R4、R5And R6Are all phenyl groups. The data are shown in Table 1.
Example 15
The same as in example 1, except that the t-butyl hydroperoxide was present in an amount of 500ppm R1Is methyl, R2Is ethyl, R3、R4、R5And R6Are all cyclohexyl. The data are shown in Table 1.
Comparative example 1
The same as in example 1, except that the content of t-butyl hydroperoxide was 0ppm by weight. The data are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the catalyst composition of the present invention has an increased catalytic activity in the presence of t-butyl hydroperoxide, and exhibits a good catalytic activity and selectivity to 1-octene. In the obtained product, the selectivity of the 1-octene can reach more than 70 percent.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (19)
1. A catalyst composition for ethylene tetramerization comprises a diphosphine ligand shown as a formula I, a transition metal compound, an aluminum-containing cocatalyst and tert-butyl hydroperoxide;
in the formula R1And R2Each independently is an alkyl, cycloalkyl or aryl group; r3、R4、R5And R6Each independently is an aryl or cycloalkyl group, the composition further comprising an organic solvent;
the weight content of the tert-butyl hydroperoxide is 25-1000ppm by taking the weight of the organic solvent as a reference;
the molar ratio of the aluminum in the cocatalyst to the metal in the transition metal compound is 30:1-1000: 1;
the molar ratio of the ligand to the transition metal compound is 0.5:1-2: 1.
2. The composition of claim 1, wherein the alkyl group is C1-C20A linear or branched saturated alkyl group; and/or said cycloalkyl is C3-C10A cycloalkyl group; and/or said aryl is C5-C20Monocyclic or polycyclic aryl; and/or one or more of the carbon atoms of the alkyl, cycloalkyl or aryl group is substituted or unsubstituted with a heteroatom selected from oxygen, nitrogen and sulfur.
3. The composition of claim 2, wherein the alkyl group is C1-C10A linear or branched saturated alkyl group, and/or said cycloalkyl group is C3-C6A cycloalkyl group; and/or said aryl is substituted by halogenOr C1-C20Alkyl groups are substituted or unsubstituted.
4. The composition of claim 2, wherein the alkyl group is C1-C6A straight or branched chain saturated alkyl group.
5. The composition of any one of claims 1 to 4, wherein the alkyl group is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, n-hexyl, sec-hexyl, isohexyl, n-heptyl, and isomers thereof; and/or, said cycloalkyl is selected from cyclopropyl, cyclopentyl and cyclohexyl; and/or said aryl is selected from phenyl, naphthyl and pyridyl.
6. The composition according to claim 5, wherein the alkyl group is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl.
7. The composition as set forth in any one of claims 1 to 4, wherein the t-butyl hydroperoxide is present in an amount of 150-750ppm by weight based on the weight of the organic solvent.
8. The composition as set forth in any one of claims 1 to 4, wherein the t-butyl hydroperoxide is present in an amount of 250-500ppm by weight based on the weight of the organic solvent.
9. The composition of any one of claims 1 to 4, wherein the molar ratio of aluminum in the cocatalyst to the metal in the transition metal compound is from 100:1 to 800: 1.
10. The composition of any one of claims 1 to 4, wherein the molar ratio of aluminum in the cocatalyst to the metal in the transition metal compound is from 200:1 to 500: 1.
11. Composition according to any one of claims 1 to 4, characterized in that the transition metal compound can be chosen from at least one of the compounds of chromium, molybdenum, iron, titanium, zirconium or nickel.
12. The composition of claim 11, wherein the transition metal compound is at least one of chromium chloride, chromium acetylacetonate, chromium isooctanoate, and chromium tris (tetrahydrofuran) trichloride.
13. The composition of any one of claims 1-4, wherein the aluminum-containing co-catalyst is selected from at least one of an alkyl aluminum compound and an alkoxy aluminum compound.
14. The composition of claim 13, wherein the aluminum-containing cocatalyst is selected from at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylalumoxane, ethylalumoxane, and modified methylalumoxane.
15. The composition according to any one of claims 1 to 4, wherein the organic solvent is at least one selected from the group consisting of methylcyclohexane, heptane, cyclohexane, diethyl ether, tetrahydrofuran, benzene, toluene, xylene, and methylene chloride.
16. A process for the tetramerisation of ethylene, comprising performing an ethylene tetramerisation reaction in the presence of the catalyst composition for the tetramerisation of ethylene according to any one of claims 1 to 15.
17. The method of claim 16, wherein the reaction temperature of the ethylene tetramerization reaction is 0 to 200 ℃; the reaction pressure is 0.1-20 MPa; and/or, the content of the diphosphine ligand is 2-500 mu mol/L by taking the volume of the composition as a calculation reference; the content of the transition metal compound is 2-500 mu mol/L.
18. The method of claim 17, wherein the reaction temperature of the ethylene tetramerization reaction is 10 to 100 ℃; and/or, the content of the diphosphine ligand is 25-50 mu mol/L by taking the volume of the composition as a calculation reference; the content of the transition metal compound is 5-50 mu mol/L.
19. The process according to claim 17, wherein the reaction temperature of the ethylene tetramerization reaction is 30-60 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610197151.XA CN107282131B (en) | 2016-03-31 | 2016-03-31 | Catalyst composition and application thereof in ethylene tetramerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610197151.XA CN107282131B (en) | 2016-03-31 | 2016-03-31 | Catalyst composition and application thereof in ethylene tetramerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107282131A CN107282131A (en) | 2017-10-24 |
| CN107282131B true CN107282131B (en) | 2020-04-07 |
Family
ID=60087733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610197151.XA Active CN107282131B (en) | 2016-03-31 | 2016-03-31 | Catalyst composition and application thereof in ethylene tetramerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107282131B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113600244A (en) * | 2021-08-06 | 2021-11-05 | 山东京博石油化工有限公司 | Catalyst for synthesizing 1-octene and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101605605A (en) * | 2007-01-18 | 2009-12-16 | Sk能源株式会社 | Ethene four gathers catalyst systems and uses this catalyst system to prepare the method for 1-octene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5450439B2 (en) * | 2007-12-12 | 2014-03-26 | サウディ ベーシック インダストリーズ コーポレイション | Catalyst composition for oligomerization of ethylene, oligomerization process and preparation method thereof |
-
2016
- 2016-03-31 CN CN201610197151.XA patent/CN107282131B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101605605A (en) * | 2007-01-18 | 2009-12-16 | Sk能源株式会社 | Ethene four gathers catalyst systems and uses this catalyst system to prepare the method for 1-octene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107282131A (en) | 2017-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107282126B (en) | Ethylene tetramerization catalyst composition and application thereof | |
| JP6621472B2 (en) | Deactivator and method for reducing by-products of olefin oligomerization using the same | |
| CN107282129B (en) | Ethylene trimerization and tetramerization catalyst composition and application thereof | |
| JP2020001035A (en) | Method of making selective oligomer of ethylene and catalyst thereof | |
| CN107207545B (en) | Ligand compound, oligomerization catalyst system and olefin oligomerization method using the same | |
| CN105562099A (en) | Ethylene tetrapolymerization catalyst composition and ethylene tetrapolymerization method | |
| TWI434733B (en) | Catalyst composition and process for preparing linear alpha-olefins | |
| CN105562095A (en) | Ethylene tetrapolymerization catalyst composition and ethylene tetrapolymerization method | |
| CN103100420A (en) | Catalyst composition for ethylene tetramerization and preparation method of ligand thereof | |
| CN111282596B (en) | Ethylene oligomerization high-selectivity catalyst system and application thereof | |
| EP3484929B1 (en) | Oligomerization of ethylene | |
| CN107282131B (en) | Catalyst composition and application thereof in ethylene tetramerization | |
| US11021418B2 (en) | Method of olefin oligomerization | |
| CN107282133B (en) | Ethylene tetramerization catalyst composition and application | |
| CN105562097B (en) | A kind of catalyst for ethylene tetramerization composition and ethylene tetramerization method | |
| CN114054095B (en) | Ethylene oligomerization catalyst composition and application thereof | |
| CN107282128B (en) | Ethylene tetramerization catalyst composition and ethylene tetramerization method | |
| CN107282112B (en) | Ethylene oligomerization catalyst composition and application thereof | |
| CN107282125B (en) | Ethylene tetramerization catalyst composition and application thereof | |
| CN107282122B (en) | Ethylene tetramerization catalyst composition and application thereof | |
| CN107282127B (en) | Catalyst composition for ethylene trimerization and tetramerization and application thereof | |
| CN107580600B (en) | Ligand compound, catalyst system for olefin oligomerization, and method for olefin oligomerization using the catalyst system | |
| CN107282132B (en) | Ethylene tetramerization catalyst composition and application thereof | |
| CN105562096A (en) | Ethylene tetrapolymerization catalyst composition and ethylene tetrapolymerization method | |
| CN107282124B (en) | Ethylene tetramerization catalyst composition and tetramerization 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 |