CN109201119B - Ethylene oligomerization catalyst system, preparation method and application thereof - Google Patents
Ethylene oligomerization catalyst system, preparation method and application thereof Download PDFInfo
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- CN109201119B CN109201119B CN201710547537.3A CN201710547537A CN109201119B CN 109201119 B CN109201119 B CN 109201119B CN 201710547537 A CN201710547537 A CN 201710547537A CN 109201119 B CN109201119 B CN 109201119B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 125
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 110
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000005977 Ethylene Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000004711 α-olefin Substances 0.000 claims abstract description 27
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 12
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical group C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 claims description 13
- 239000012442 inert solvent Substances 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 12
- 239000012018 catalyst precursor Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 7
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 claims description 4
- YIWTXSVNRCWBAC-UHFFFAOYSA-N 3-phenylpentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)C1=CC=CC=C1 YIWTXSVNRCWBAC-UHFFFAOYSA-N 0.000 claims description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000005049 silicon tetrachloride Substances 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical group CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 24
- 238000006555 catalytic reaction Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 9
- 239000012263 liquid product Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical group 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 229910007932 ZrCl4 Inorganic materials 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- -1 alkoxy zirconium chloride Chemical compound 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
- C07C2/22—Metal halides; Complexes thereof with organic compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
- C07C2531/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of titanium, zirconium or hafnium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to an ethylene oligomerization catalyst system, a preparation method and application thereof, wherein the catalyst system comprises: from ZrX4Alcohols and SiClnR4‑nThe silicon compound is reacted to prepare the main catalyst, beta-diketone and alkyl aluminum cocatalyst. The catalyst system of the present invention can improve the product distribution of the oligomerization product and increase the yield of alpha-olefin.
Description
Technical Field
The invention relates to an ethylene oligomerization catalyst system, a preparation method and application thereof. In particular to a homogeneous zirconium catalyst system for preparing linear alpha-olefin by ethylene oligomerization and a preparation method and application thereof.
Background
It is customary in industry to refer to terminal olefins of C4 or greater (double bonds at the ends of the molecular chain) as alpha-olefins. Alpha-olefins, which are industrial products, have a wide distribution of carbon numbers (C4-C40), and are widely used as linear alpha-olefins having carbon numbers in the range of C6-C20.
The olefin oligomerization is a main way for producing alpha-olefin, the current mature processes include a Gulf method, an Ethyl method and an SHOP method, catalysts used in the three processes are alkyl aluminum or nickel compounds, the reaction conditions are severe, and the pressure can reach dozens of MPa generally. Compared with the three processes, when the zirconium compound is used as the catalyst, the reaction conditions are relatively mild, the pressure is generally between 2MPa and 3MPa, but the low-carbon part in the oligomerization product is more.
CN101745422A discloses an olefin oligomerization catalyst, a preparation method and an application thereof, wherein the catalyst is alkoxy zirconium chloride, and the obtained oligomerization product contains less low carbon part but more C20 +. CN101816951A discloses an ethylene oligomerization catalyst and a preparation method thereof, which reduces the content of C20+ in oligomerization products to a certain extent by carrying out silicon modification on zirconium oxychloride. Although the foregoing documents have made improvements to zirconium-based ethylene oligomerization catalysts, there is still room for improvement in the yields of fractions C6 to C20 and in the yields of alpha-olefins.
In addition, zirconium-based ethylene oligomerization catalysts generally lead to the formation of high polymers, which block the lines during the oligomerization process and seriously impair the industrial production, and the aforementioned documents do not mention this.
Disclosure of Invention
The invention provides an ethylene oligomerization catalyst system, a preparation method and application thereof, the catalyst can improve the product distribution of oligomerization products and improve the yield of alpha-olefin; the polymerization under specific conditions can also avoid the generation of high polymers.
The present invention mainly includes the following matters.
1. An ethylene oligomerization catalyst system comprising:
(1) from ZrX4Alcohols and SiClnR4-nA main catalyst obtained by reacting the silicon compound; wherein X is Cl, Br or I, n is 0, 1, 2, 3 or 4, and R is a hydrocarbyl group;
(2) a beta-diketone of the structure;
wherein R1 and R2 are both hydrocarbyl groups, R3 is hydrogen or hydrocarbyl groups, and at least one of R1, R2 and R3 is a substituted or unsubstituted phenyl group; and
(3) an alkylaluminum cocatalyst.
2. The catalyst system according to 1, wherein in the beta-diketone, both R1 and R2 are methyl groups, and R3 is a substituted or unsubstituted phenyl group; alternatively, R3 is hydrogen, R1, R2 are each independently substituted or unsubstituted phenyl; alternatively, R3 is hydrogen, R1 is methyl, and R2 is substituted or unsubstituted phenyl.
3. Catalyst system according to any of the preceding claims, characterized in that the beta-diketone is dibenzoylmethane, 1-benzoylacetone or 3-phenyl-2, 4-pentanedione.
4. A catalyst system according to any one of the preceding claims, characterized in that the preparation process of the procatalyst comprises:
(1) in an inert solvent, ZrX4Reacting with alcohol to obtain solutionA step of liquid; and
(2) mixing the solution obtained in the step (1) with SiClnR4-nThereby producing the main catalyst;
wherein, X is Cl, Br or I, n is 0, 1, 2, 3 or 4, and R is alkyl.
5. The catalyst system according to 4, characterized in that, in the preparation method of the main catalyst, the inert solvent in the step (1) is benzene, toluene, xylene, trimethylbenzene, n-hexane or cyclohexane, and any mixture thereof.
6. The catalyst system according to 4 or 5, characterized in that in the preparation method of the main catalyst, alcohol and ZrX are used4The molar ratio of (a) to (b) is 3:1 to 9:1, preferably 3:1 to 6: 1.
7. The catalyst system according to any one of 4 to 6, wherein in the preparation method of the main catalyst, SiCl is usednR4-nAnd ZrX4The molar ratio of (a) to (b) is 0.5:1 to 20:1, preferably 2:1 to 10: 1.
8. The catalyst system according to any one of 4 to 7, wherein the general formula of the main catalyst in the preparation method is SiClnR4-nThe silicon compound of (a) is trimethylchlorosilane, silicon tetrachloride or diphenyldichlorosilane.
9. The catalyst system according to any one of 4 to 8, wherein in the preparation method of the main catalyst, the reaction temperature in the step (1) is 60 to 120 ℃, preferably 60 to 80 ℃.
10. The catalyst system according to any one of 4 to 9, wherein in the preparation method of the main catalyst, the reaction temperature in the step (2) is-5 ℃ to 10 ℃, preferably 0 ℃ to 10 ℃, and more preferably 0 ℃ to 5 ℃.
11. The catalyst system according to any of the preceding claims, characterized in that the alcohol is n-butanol.
12. The catalyst system according to any one of the preceding claims, characterized in that the molar ratio of beta-diketone to zirconium is 0.1:1 to 5: 1.
13. A catalyst system according to any one of the preceding claims characterised in that the alkylaluminium cocatalyst is diethylaluminium monochloride, triethyldialuminium trichloride, monoethylaluminium dichloride or triethylaluminium.
14. The catalyst system according to any of the preceding claims, characterized in that the molar ratio of aluminium to zirconium in the catalyst system is 5:1 to 100:1, preferably 5:1 to 20: 1;
15. a method for preparing a catalyst precursor liquid for preparing alpha-olefin by ethylene oligomerization comprises the following steps:
(1) in an inert solvent, ZrX4Reacting with alcohol to prepare a solution; x is Cl, Br, or I;
(2) mixing the solution obtained in the step (1) with SiClnR4-nN is 0, 1, 2, 3 or 4, R is a hydrocarbyl group; and
(3) adding a beta-diketone of the formula to the solution obtained in step (2) to thereby obtain said catalyst precursor solution;
wherein R1 and R2 are both hydrocarbyl groups, R3 is hydrogen or hydrocarbyl groups, and at least one of R1, R2 and R3 is a substituted or unsubstituted phenyl group.
16. A catalyst system for the oligomerization of ethylene to alpha-olefins, said catalyst system being prepared by adding an alkylaluminum cocatalyst to said catalyst precursor liquid at 15.
17. A process for oligomerization of ethylene to linear alpha-olefins, characterized in that the oligomerization of ethylene to linear alpha-olefins is carried out in an inert solvent in the presence of a catalyst system as described in 1 or 13.
18. The ethylene oligomerization method according to 17, characterized in that the oligomerization temperature is 30 ℃ to 120 ℃, preferably 60 ℃ to 80 ℃; the ethylene pressure is 0.1MPa to 20 MPa.
19. The ethylene oligomerization method according to 17 or 18, characterized in that the ethylene pressure is 8MPa to 20 MPa.
Compared with the prior art, the oligomerization product is more reasonably distributed, the yield of the alpha-olefin is higher, and the generation of high polymer can be avoided.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Technical terms in the present invention are defined according to the definitions given herein, and terms not defined are understood according to the ordinary meanings in the art.
In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are considered part of the original disclosure or original description of the present invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such combination to be clearly unreasonable.
All features disclosed in this invention may be combined in any combination and such combinations are understood to be disclosed or described herein unless a person skilled in the art would consider such combinations to be clearly unreasonable. The numerical points disclosed in the specification include not only the numerical points specifically disclosed but also the endpoints of each numerical range, and any combination of these numerical points should be considered as the range disclosed or described in the present invention, regardless of whether the numerical pairs are disclosed herein.
Catalyst system for oligomerization of ethylene
The invention firstly provides an ethylene oligomerization catalyst system, which comprises:
(1) from ZrX4Alcohols and SiClnR4-nA main catalyst obtained by reacting the silicon compound; wherein X is Cl, Br or I, n is 0, 1, 2, 3 or 4, and R is a hydrocarbyl group;
(2) a beta-diketone of the structure;
wherein R1 and R2 are both hydrocarbyl groups, R3 is hydrogen or hydrocarbyl groups, and at least one of R1, R2 and R3 is a substituted or unsubstituted phenyl group; and
(3) an alkylaluminum cocatalyst.
In the present invention, ZrX4Preferably ZrCl4。
In the present invention, there is no particular limitation on the alcohol, and those skilled in the art can select an appropriate alcohol based on the disclosure of the prior art or by simple experiment. Generally, alkanols of C3 to C8 are selected.
In the present invention, the alcohol is preferably n-butanol, propanol or hexanol.
In the present invention, the p-type compound is SiClnR4-nThe silicon compound of (a) is not particularly limited, and those skilled in the art can select a suitable silicon compound based on the disclosure of the prior art or by simple experiment. Generally, R is alkyl with 1-4 carbon atoms or aryl with 6-8 carbon atoms; n is 1, 2, 3 or 4.
In the present invention, the general formula is SiClnR4-nThe silicon compound of (a) is preferably silicon tetrachloride, trimethylchlorosilane or diphenyldichlorosilane.
In the present invention, for ZrX4Alcohols and SiClnR4-nThe reaction mode between the silicon compounds of (a) is not particularly limited, and those skilled in the art can select a suitable mode known in the art.
Said "ZrX4Alcohols and SiClnR4-nIn the reaction between silicon compounds of (1), "alcohol and ZrX4The molar ratio of (a) to (b) is 3:1 to 9:1, preferably 3:1 to 6: 1.
Said "ZrX4Alcohols and SiClnR4-nIn the reaction between silicon compounds of (2), "SiClnR4-nAnd ZrX4The molar ratio of (a) to (b) is 0.5:1 to 20:1, preferably 2:1 to 10:1, and more preferably 2:1 to 5: 1.
In the beta-diketone, preferably, both R1 and R2 are methyl groups, and R3 is a substituted or unsubstituted phenyl group.
In another preferred aspect, in the beta-diketone, R3 is hydrogen, and R1 and R2 are each independently substituted or unsubstituted phenyl.
In still another preferred aspect, in the β -diketone, R3 is hydrogen, R1 is methyl, and R2 is substituted or unsubstituted phenyl.
In the present invention, the beta-diketone is preferably dibenzoylmethane, 1-benzoylacetone or 3-phenyl-2, 4-pentanedione.
In the catalyst system, the mol ratio of the beta-diketone to the zirconium is 0.1: 1-5: 1, preferably 0.2: 1-2: 1.
The aluminum alkyl cocatalysts are known in the art. Typically, the aluminum alkyl cocatalyst is of the formula AlRnX3-nAnd (c) a compound, wherein n is 1 to 3.
In the present invention, the alkylaluminum cocatalyst is preferably diethylaluminum monochloride, triethyldialuminum trichloride, monoethylaluminum dichloride or triethylaluminum.
The molar ratio of aluminium to zirconium in the catalyst system for ethylene oligomerization is known in the art. Generally, the molar ratio of aluminum to zirconium is from 5:1 to 100: 1.
In the present invention, the molar ratio of aluminum to zirconium is preferably 5:1 to 80:1, and more preferably 5:1 to 50: 1.
The invention provides a preferable preparation method of the main catalyst, which comprises the following steps:
(1) in an inert solvent, ZrX4Reacting with alcohol to prepare a solution; and
(2) mixing the solution obtained in the step (1) with SiClnR4-nThereby producing the main catalyst;
wherein, X is Cl, Br or I, n is 0, 1, 2, 3 or 4, and R is alkyl.
In the invention, the inert solvent is a solvent which is harmless to the catalytic performance of the ethylene oligomerization catalyst and the ethylene oligomerization reaction.
In the present invention, the inert solvent is preferably benzene, toluene, xylene, trimethylbenzene, n-hexane or cyclohexane, and any mixture thereof.
In the preparation method of the main catalyst, the reaction temperature in the step (1) is 60-120 ℃, and preferably 60-80 ℃.
In the preparation method of the main catalyst, the reaction temperature in the step (2) is-5-10 ℃, preferably 0-10 ℃, and more preferably 0-5 ℃.
(II) preparation method of catalyst precursor liquid for preparing alpha-olefin by ethylene oligomerization
The invention provides a preparation method of a catalyst precursor liquid for preparing alpha-olefin by ethylene oligomerization, which comprises the following steps:
(1) in an inert solvent, ZrX4Reacting with alcohol to prepare a solution; x is Cl, Br, or I;
(2) mixing the solution obtained in the step (1) with SiClnR4-nN is 0, 1, 2, 3 or 4, R is a hydrocarbyl group; and
(3) adding a beta-diketone of the formula to the solution obtained in step (2) to thereby obtain said catalyst precursor solution;
wherein R1 and R2 are both hydrocarbyl groups, R3 is hydrogen or hydrocarbyl groups, and at least one of R1, R2 and R3 is a substituted or unsubstituted phenyl group.
In the preparation method of the catalyst precursor liquid, the raw materials and the proportions thereof are the same as those of the corresponding parts, and the details are not repeated herein.
The invention also provides a catalyst system for preparing alpha-olefin by ethylene oligomerization, which is prepared by adding an alkyl aluminum cocatalyst into the catalyst precursor liquid.
Ethylene oligomerization method for preparing linear alpha-olefin
The invention provides a method for preparing linear alpha-olefin by ethylene oligomerization, which comprises the step of carrying out oligomerization on ethylene in an inert solvent in the presence of the catalyst system to generate the linear alpha-olefin.
The reaction temperature for the oligomerization of ethylene is known. In general, the oligomerization temperature is from 30 ℃ to 120 ℃.
In the invention, the oligomerization temperature is preferably 60-100 ℃, and more preferably 60-80 ℃.
In the invention, the ethylene oligomerization method for preparing linear alpha-olefin can be implemented in a wider ethylene pressure range, such as 0.1MPa to 20 MPa. The oligomerization pressure of the existing zirconium catalyst is generally between 2MPa and 3MPa, and the method can be implemented in the range, so that a better oligomerization effect is obtained. However, the process of the invention is carried out at higher ethylene pressures, for example from 8MPa to 20MPa, and the formation of high polymers can be avoided. In the invention, the preferable ethylene oligomerization pressure is 8MPa to 10 MPa.
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way.
In the examples and comparative examples, the difference in mass of the oligomerization system before and after the reaction was the mass of the reaction product, and the catalyst activity was calculated from this mass.
In the examples and comparative examples, the liquid product and the solid product were separated by filtration. Adding sodium hydroxide-ethanol solution into the liquid product to terminate the reaction, washing with water, and performing gas chromatography quantitative analysis on the liquid product distribution (gas chromatograph is Agilent 7890A, SE-52 type chromatographic column, temperature rising procedure of the chromatogram is that the initial temperature is 45 deg.C, staying for 4 min, then rising to 270 deg.C at 25 deg.C/min, gasifying, and detecting temperature is 300 deg.C). The solid product was washed with ethanol, placed in an evaporation dish, dried and weighed.
In the examples and comparative examples, the liquid product distribution was calculated as the mass fraction of each liquid product component on the basis of the mass of the liquid product.
The calculation formulas for the polymer content and the α -olefin yield in table 1 are respectively:
the polymer content (mass of solid product/mass of reaction product) x 100%
α -olefin yield ═ mass of α -olefin/mass of liquid product x 100%
Example 1
This example illustrates the preparation of the ethylene oligomerization catalyst system of the present invention.
2.33g (10mmol) of ZrCl4Placing the mixture into a three-neck flask, adding 30mL of toluene, heating to 70 ℃, stirring for 1 hour, adding 30mmol of n-butanol, refluxing at 85 ℃ for reaction for 4 hours, cooling to 0 ℃, adding 3.82mL (30mmol) of trimethylchlorosilane for reaction for 4 hours, adding 5mmol of dibenzoylmethane, and then adding toluene until the solution is 50mL to obtain an oligomerization catalyst solution A with the zirconium concentration of 0.2 mol/L.
Example 2
This example illustrates the preparation of the ethylene oligomerization catalyst system of the present invention.
The same procedure as in example 1 was followed, except that: the amount of dibenzoylmethane was 2mmol to prepare catalyst solution B.
Example 3
This example illustrates the preparation of the ethylene oligomerization catalyst system of the present invention.
The same procedure as in example 1 was followed, except that: the amount of dibenzoylmethane used was 20mmol, and catalyst solution C was prepared.
Example 4
This example illustrates the preparation of the ethylene oligomerization catalyst system of the present invention.
The same procedure as in example 1 was followed, except that: 5mmol of dibenzoylmethane was replaced with 5mmol of 3-phenyl-2, 4-pentanedione to prepare a catalyst solution D.
Example 5
This example illustrates the preparation of the ethylene oligomerization catalyst system of the present invention.
The same procedure as in example 1 was followed, except that: 5mmol of dibenzoylmethane was replaced with 5mmol of 1-benzoylacetone to prepare a catalyst solution E.
Example 6
This example illustrates the preparation of the ethylene oligomerization catalyst system of the present invention.
The same procedure as in example 1 was followed, except that: 30mmol of trimethylchlorosilane is replaced by 100mmol of silicon tetrachloride to prepare a catalyst solution F.
Example 7
This example illustrates the preparation of the ethylene oligomerization catalyst system of the present invention.
The same procedure as in example 1 was followed, except that: 30mmol of trimethylchlorosilane was replaced with 30mmol of diphenyldichlorosilane, to prepare a catalyst solution G.
Comparative example 1
This comparative example illustrates the preparation of a comparative ethylene oligomerization catalyst system.
The same procedure as in example 1 was followed, except that: 5mmol of dibenzoylmethane was replaced with 5mmol of acetylacetone to prepare a catalyst solution H.
Comparative example 2
This comparative example illustrates the preparation of a comparative ethylene oligomerization catalyst system.
The same procedure as in example 1 was followed, except that: catalyst solution I was prepared without the addition of dibenzoylmethane.
Comparative example 3
This comparative example illustrates the preparation of a comparative ethylene oligomerization catalyst system.
The same procedure as in example 6 was followed, except that: catalyst solution J was prepared without the addition of dibenzoylmethane.
Example 8
This example illustrates the catalytic reaction effectiveness of the ethylene oligomerization catalyst system of the present invention.
200ml of toluene, 1.75ml of triethylaluminum (TRIETHYL) having a concentration of 2.0 mol/liter and 1.15ml of triethylaluminum (TETA) having a concentration of 1.0 mol/liter were sequentially charged into a reaction vessel in the absence of water and oxygen to give a solution of the oligomerization catalyst A prepared in example 1 in an Al/Zr molar ratio of 23.25. Ethylene was charged into the reactor to 3.0MPa, and reacted at 80 ℃ for 1 hour. After the reaction is finished, cooling to 25 ℃, discharging the gas product, collecting the liquid product, adding a small amount of sodium hydroxide ethanol solution with the concentration of 0.5 mol/L to terminate the reaction, and washing and drying to obtain the oligomerization product. The results of the oligomerization reaction are shown in Table 1.
Example 9
This example illustrates the catalytic reaction effectiveness of the ethylene oligomerization catalyst system of the present invention.
The ethylene oligomerization was carried out as in example 8, except that: the catalyst B solution prepared in example 2 was used. The results of the oligomerization reaction are shown in Table 1.
Example 10
This example illustrates the catalytic reaction effectiveness of the ethylene oligomerization catalyst system of the present invention.
The ethylene oligomerization was carried out as in example 8, except that: the catalyst C solution prepared in example 3 was used. The results of the oligomerization reaction are shown in Table 1.
Example 11
This example illustrates the catalytic reaction effectiveness of the ethylene oligomerization catalyst system of the present invention.
The ethylene oligomerization was carried out as in example 8, except that: the catalyst D solution prepared in example 4 was used. The results of the oligomerization reaction are shown in Table 1.
Example 12
This example illustrates the catalytic reaction effectiveness of the ethylene oligomerization catalyst system of the present invention.
The ethylene oligomerization was carried out as in example 8, except that: the catalyst E solution prepared in example 5 was used. The results of the oligomerization reaction are shown in Table 1.
Example 13
This example illustrates the catalytic reaction effectiveness of the ethylene oligomerization catalyst system of the present invention.
The ethylene oligomerization was carried out as in example 8, except that: the catalyst F solution prepared in example 6 was used. The results of the oligomerization reaction are shown in Table 1.
Example 14
This example illustrates the catalytic reaction effectiveness of the ethylene oligomerization catalyst system of the present invention.
The ethylene oligomerization was carried out as in example 8, except that: the catalyst G solution prepared in example 7 was used. The results of the oligomerization reaction are shown in Table 1.
Example 15
This example illustrates the catalytic reaction effectiveness of the ethylene oligomerization catalyst system of the present invention.
The ethylene oligomerization was carried out as in example 8, except that: the reaction was carried out at 60 ℃ for 1 hour. The results of the oligomerization reaction are shown in Table 1.
Example 16
This example illustrates the catalytic reaction effectiveness of the ethylene oligomerization catalyst system of the present invention.
The ethylene oligomerization was carried out as in example 8, except that: the reaction was carried out under an ethylene pressure of 8MPa for 1 hour. The results of the oligomerization reaction are shown in Table 1.
Example 17
This example illustrates the catalytic reaction effectiveness of the ethylene oligomerization catalyst system of the present invention.
The ethylene oligomerization was carried out as in example 8, except that: the reaction was carried out under an ethylene pressure of 12MPa for 1 hour. The results of the oligomerization reaction are shown in Table 1.
Example 18
This example illustrates the catalytic reaction effectiveness of the ethylene oligomerization catalyst system of the present invention.
The ethylene oligomerization was carried out as in example 8, except that: the catalyst I solution prepared in comparative example 2 was used and dibenzoylmethane was added so that the molar ratio of dibenzoylmethane to zirconium was 1: 1. The results of the oligomerization reaction are shown in Table 1.
Comparative example 4
This comparative example illustrates the catalytic reaction effect of the ethylene oligomerization catalyst system used for comparison.
The ethylene oligomerization was carried out as in example 8, except that: the catalyst was the catalyst H solution prepared in comparative example 1. The results of the oligomerization reaction are shown in Table 1.
Comparative example 5
This comparative example illustrates the catalytic reaction effect of the ethylene oligomerization catalyst system used for comparison.
The ethylene oligomerization was carried out as in example 8, except that: the catalyst was the catalyst I solution prepared in comparative example 2. The results of the oligomerization reaction are shown in Table 1.
Comparative example 6
This comparative example illustrates the catalytic reaction effect of the ethylene oligomerization catalyst system used for comparison.
The ethylene oligomerization was carried out as in example 8, except that: the catalyst was the catalyst J solution prepared in comparative example 3. The results of the oligomerization reaction are shown in Table 1.
Comparative example 7
This comparative example illustrates the catalytic reaction effect of the ethylene oligomerization catalyst used for comparison.
The ethylene oligomerization was carried out as in example 4, except that: the catalyst is zirconium tetrachloride. The results of the oligomerization reaction are shown in Table 1.
Claims (16)
1. An ethylene oligomerization catalyst system comprising:
(1) from ZrX4Alcohols and SiClnR4-nA main catalyst obtained by reacting the silicon compound; wherein X is Cl, Br or I, n is 0, 1, 2, 3 or 4, and R is a hydrocarbyl group; in the preparation method of the main catalyst, alcohol and ZrX4The molar ratio of (a) to (b) is 3:1 to 9: 1;
(2) a beta-diketone of the structure;
wherein R1 and R2 are both hydrocarbyl groups, R3 is hydrogen or hydrocarbyl groups, and at least one of R1, R2 and R3 is a substituted or unsubstituted phenyl group; and
(3) an alkylaluminum cocatalyst.
2. The catalyst system of claim 1 wherein the beta-diketone is dibenzoylmethane, 1-benzoylacetone, or 3-phenyl-2, 4-pentanedione.
3. The catalyst system of claim 1, wherein the procatalyst is prepared by a process comprising:
(1) in an inert solvent, ZrX4Reacting with alcohol to prepare a solution; and
(2) mixing the solution obtained in the step (1) with SiClnR4-nThereby producing the main catalyst;
wherein, X is Cl, Br or I, n is 0, 1, 2, 3 or 4, and R is alkyl.
4. The catalyst system according to claim 3, wherein the main catalyst is prepared by a method wherein the inert solvent of step (1) is benzene, toluene, xylene, trimethylbenzene, n-hexane or cyclohexane, and any mixture thereof.
5. The catalyst system of claim 3 wherein the procatalyst is prepared by a process in which SiCl is addednR4-nAnd ZrX4The molar ratio of (a) to (b) is 0.5:1 to 20: 1.
6. The catalyst system of claim 3 wherein the procatalyst is prepared by a process which comprises the step of preparing a procatalyst having the formula SiClnR4-nThe silicon compound of (a) is trimethylchlorosilane, silicon tetrachloride or diphenyldichlorosilane.
7. The catalyst system according to claim 3, wherein in the preparation method of the main catalyst, the reaction temperature of the step (1) is 60 ℃ to 120 ℃; the reaction temperature of the step (2) is-5 ℃ to 10 ℃.
8. The catalyst system of claim 1 wherein the alcohol is n-butanol.
9. The catalyst system of claim 1, wherein the molar ratio of beta-diketone to zirconium is 0.1:1 to 5: 1.
10. The catalyst system of claim 1 wherein the alkylaluminum cocatalyst is diethylaluminum monochloride, triethyldialuminum trichloride, ethylaluminum dichloride or triethylaluminum.
11. The catalyst system of claim 1, wherein the molar ratio of aluminum to zirconium is from 5:1 to 100: 1.
12. A method for preparing a catalyst precursor liquid for preparing alpha-olefin by ethylene oligomerization comprises the following steps:
(1) in an inert solvent, ZrX4Reacting with alcohol to prepare a solution; x is Cl, Br, or I; alcohol and ZrX4The molar ratio of (a) to (b) is 3:1 to 9: 1;
(2) mixing the solution obtained in the step (1) with SiClnR4-nN is 0, 1, 2, 3 or 4, R is a hydrocarbyl group; and
(3) adding a beta-diketone of the formula to the solution obtained in step (2) to thereby obtain said catalyst precursor solution;
wherein R1 and R2 are both hydrocarbyl groups, R3 is hydrogen or hydrocarbyl groups, and at least one of R1, R2 and R3 is a substituted or unsubstituted phenyl group.
13. A catalyst system for the oligomerization of ethylene to alpha-olefins, said catalyst system being prepared by adding an aluminum alkyl cocatalyst to the procatalyst liquid of claim 12.
14. A process for oligomerization of ethylene to linear alpha-olefins, characterized in that the oligomerization of ethylene to linear alpha-olefins is carried out in an inert solvent in the presence of a catalyst system according to claim 1 or 13.
15. The ethylene oligomerization method according to claim 14, wherein the oligomerization temperature is 30 ℃ to 120 ℃ and the ethylene pressure is 0.1MPa to 20 MPa.
16. A process for oligomerization of ethylene according to claim 14 or 15, characterized in that the ethylene pressure is between 8MPa and 20 MPa.
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