CN117920354A - Catalyst for synthesizing alpha-olefin by oligomerization of ethylene and preparation method thereof - Google Patents
Catalyst for synthesizing alpha-olefin by oligomerization of ethylene and preparation method thereof Download PDFInfo
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- CN117920354A CN117920354A CN202410086552.2A CN202410086552A CN117920354A CN 117920354 A CN117920354 A CN 117920354A CN 202410086552 A CN202410086552 A CN 202410086552A CN 117920354 A CN117920354 A CN 117920354A
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- 239000004711 α-olefin Substances 0.000 title claims abstract description 39
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000005977 Ethylene Substances 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 29
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 8
- -1 methylaluminoxane compound Chemical class 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- KGWXYUFIQHXOIL-UHFFFAOYSA-K CC(C)C1=CC=CC(C(C)C)=C1O[Ti](Cl)(Cl)C1(C)C(C)=C(C)C(C)=C1C Chemical compound CC(C)C1=CC=CC(C(C)C)=C1O[Ti](Cl)(Cl)C1(C)C(C)=C(C)C(C)=C1C KGWXYUFIQHXOIL-UHFFFAOYSA-K 0.000 claims abstract description 9
- GDBLZKMJBVGZTR-UHFFFAOYSA-K Cl[Ti](OC1=C(C=CC=C1)C1=CC=CC=C1)(C1(C(=C(C(=C1C)C)C)C)C)Cl Chemical compound Cl[Ti](OC1=C(C=CC=C1)C1=CC=CC=C1)(C1(C(=C(C(=C1C)C)C)C)C)Cl GDBLZKMJBVGZTR-UHFFFAOYSA-K 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 30
- 239000002244 precipitate Substances 0.000 claims description 27
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 claims description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 18
- 239000002071 nanotube Substances 0.000 claims description 18
- 238000000967 suction filtration Methods 0.000 claims description 18
- 238000009210 therapy by ultrasound Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000001291 vacuum drying Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 16
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 14
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 229940069096 dodecene Drugs 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000010689 synthetic lubricating oil Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical class C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for synthesizing alpha-olefin by ethylene oligomerization and a preparation method thereof, comprising the following raw materials in parts by weight: pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride 40-60 parts; 20-30 parts of pentamethylcyclopentadienyl- (2, 6-diisopropyl phenoxy) -titanium dichloride; 0-2 parts of methylaluminoxane compound; 2-10 parts of modified carbon nano tube. The catalyst of the invention has high activity, can be used for catalyzing and synthesizing alpha-olefin, can synthesize alpha-olefin with high activity and high selectivity, reduces ethylene unit consumption, and has obvious economic benefit.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a catalyst for synthesizing alpha-olefin by ethylene oligomerization and a preparation method thereof.
Background
Alpha-olefin is a high-added value chemical raw material, can be used as a comonomer to produce high-end polyethylene, and can be used as a raw material to produce base oil for high-grade synthetic lubricating oil. Alpha-olefins are also basic raw materials for the production of fine chemicals such as additives, adhesives, sealants, high-grade plasticizers, and detergents. Among the alpha-olefin products, 1-hexene, 1-octene and 1-decene have the highest added value and the greatest demand. Wherein 1-hexene and 1-octene are main comonomers for synthesizing PE-RT, POE and other high-end polyethylene products, and 1-octene and 1-decene are basic raw materials of base oil-PAO of high-grade synthetic lubricating oil.
Currently, the world technology for producing alpha-olefins is mainly ethylene oligomerization technology. Ethylene oligomerization techniques are mainly divided into two categories: firstly, the technology for producing wide-distribution alpha-olefin by ethylene oligomerization is that alpha-olefin (C4-C20) with even-numbered carbon is obtained by ethylene oligomerization, and then single alpha-olefin (such as 1-hexene, 1-octene and 1-decene) or multicomponent alpha-olefin composition is obtained by separating the alpha-olefin; secondly, a high-selectivity ethylene oligomerization technology which takes single alpha-olefin as a target product, such as a technology of synthesizing 1-hexene by ethylene trimerization and a technology of synthesizing 1-octene by ethylene tetramerization, is adopted to obtain 1-hexene and 1-octene.
However, the prior art still has some defects, such as poor selectivity, low yield and the like.
Disclosure of Invention
The invention aims to provide a catalyst for synthesizing alpha-olefin by ethylene oligomerization and a preparation method thereof.
A catalyst for oligomerization of ethylene to alpha-olefins, comprising the following raw materials in parts by weight:
the preferable technical scheme comprises the following raw materials in parts by weight:
As a preferable technical scheme, the diameter of the modified carbon nano-tube is 20-100 micrometers.
As a preferable embodiment, the particle size of the methylaluminoxane compound is 20 to 60 μm.
The invention also discloses a preparation method of the catalyst for synthesizing alpha-olefin by ethylene oligomerization, which comprises the following steps:
1) Adding the carbon nano tube into a mixed acid solution for ultrasonic treatment to obtain black viscous liquid; adding deionized water into the black viscous liquid, standing at room temperature for 24 hours, and pouring out supernatant; adding deionized water again for secondary sedimentation, and repeating the steps until the pH value of the supernatant is neutral; then carrying out suction filtration and separation on the precipitate, and washing the precipitate with ultrapure water until the obtained black precipitate is neutral; drying and grinding the black precipitate to obtain carbon oxide nanotubes with openings at two ends and diameters of 100-200 mu m; adding the obtained carbon oxide nano tube into a dimethylsilyl bisindene zirconium dichloride solution for 24 hours of ultrasonic treatment, pouring into a sand filter funnel for suction filtration, and then performing suction filtration washing with anhydrous diethyl ether until the filtrate is transparent; then carrying out vacuum drying on the black precipitate in the sand core funnel to obtain a modified carbon nano tube; adding 1-10 g of carbon oxide nano tube into every 100ml of dimethylsilyl bisindene zirconium dichloride solution, wherein the temperature of ultrasonic treatment is 20-40 ℃, the temperature of vacuum drying is 30-50 ℃, and the time of vacuum drying is 2-4 h;
2) 2 to 10 weight parts of modified carbon nano tube, 40 to 60 weight parts of pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride, 20 to 30 weight parts of pentamethylcyclopentadienyl- (2, 6-diisopropylphenoxy) -titanium dichloride and 0 to 2 weight parts of methylaluminoxane compound are mixed to obtain the catalyst for synthesizing alpha-olefin by ethylene oligomerization.
As a preferable technical scheme, the mixed acid solution in the 1) is a mixed solution of 70% concentrated sulfuric acid and 68% concentrated nitric acid; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1.
As a preferable technical scheme, the dimethylsilyl bisindene zirconium dichloride solution contains 0.5-1 g of dimethylsilyl bisindene zirconium dichloride in every 100ml of water.
The preparation method of the catalyst for synthesizing alpha-olefin by ethylene oligomerization adopts the technical scheme, and comprises the following steps: 1) Adding the carbon nano tube into a mixed acid solution for ultrasonic treatment to obtain black viscous liquid; adding deionized water into the black viscous liquid, standing at room temperature for 24 hours, and pouring out supernatant; adding deionized water again for secondary sedimentation, and repeating the steps until the pH value of the supernatant is neutral; then carrying out suction filtration and separation on the precipitate, and washing the precipitate with ultrapure water until the obtained black precipitate is neutral; drying and grinding the black precipitate to obtain carbon oxide nanotubes with openings at two ends and diameters of 100-200 mu m; adding the obtained carbon oxide nano tube into a dimethylsilyl bisindene zirconium dichloride solution for 24 hours of ultrasonic treatment, pouring into a sand filter funnel for suction filtration, and then performing suction filtration washing with anhydrous diethyl ether until the filtrate is transparent; then carrying out vacuum drying on the black precipitate in the sand core funnel to obtain a modified carbon nano tube; adding 1-10 g of carbon oxide nano tube into every 100ml of dimethylsilyl bisindene zirconium dichloride solution, wherein the temperature of ultrasonic treatment is 20-40 ℃, the temperature of vacuum drying is 30-50 ℃, and the time of vacuum drying is 2-4 h; 2) 2 to 10 weight parts of modified carbon nano tube, 40 to 60 weight parts of pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride, 20 to 30 weight parts of pentamethylcyclopentadienyl- (2, 6-diisopropylphenoxy) -titanium dichloride and 0 to 2 weight parts of methylaluminoxane compound are mixed to obtain the catalyst for synthesizing alpha-olefin by ethylene oligomerization.
The invention has the beneficial effects that:
The catalyst of the invention has high activity, can be used for catalyzing and synthesizing alpha-olefin, and can synthesize alpha-olefin with high activity and high selectivity, so that the ethylene unit consumption is reduced.
Detailed Description
The invention provides a catalyst for synthesizing alpha-olefin by ethylene oligomerization and a preparation method thereof.
The invention is further described in connection with the following embodiments in order to make the technical means, the creation features, the achievement of the purpose and the effect of the invention easy to understand.
Example 1:
1) Adding the carbon nano tube into a mixed acid solution for ultrasonic treatment to obtain black viscous liquid; adding deionized water into the black viscous liquid, standing at room temperature for 24 hours, and pouring out supernatant; adding deionized water again for secondary sedimentation, and repeating the steps until the pH value of the supernatant is neutral; then carrying out suction filtration and separation on the precipitate, and washing the precipitate with ultrapure water until the obtained black precipitate is neutral; drying and grinding the black precipitate to obtain carbon oxide nanotubes with openings at two ends and diameters of 100-200 mu m; adding the obtained carbon oxide nano tube into a dimethylsilyl bisindene zirconium dichloride solution for 24 hours of ultrasonic treatment, pouring into a sand filter funnel for suction filtration, and then performing suction filtration washing with anhydrous diethyl ether until the filtrate is transparent; then, the black sediment in the sand core funnel is dried in vacuum to obtain the modified carbon nano tube; adding 1g of carbon oxide nano tube into every 100ml of dimethylsilyl bisindene zirconium dichloride solution, wherein the temperature of ultrasonic treatment is 20-40 ℃, the temperature of vacuum drying is 30-50 ℃, and the time of vacuum drying is 2-4 hours;
2) 6 parts by weight of modified carbon nano tube, 50 parts by weight of pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride, 36 parts by weight of pentamethylcyclopentadienyl- (2, 6-diisopropylphenoxy) -titanium dichloride and 1 part by weight of methylaluminoxane compound are mixed to obtain the ethylene oligomerization alpha-olefin catalyst.
The mixed acid solution in the step 1) is a mixed solution of 70% concentrated sulfuric acid and 68% concentrated nitric acid; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1.
The dimethylsilyl bisindene zirconium dichloride solution contains 1g of dimethylsilyl bisindene zirconium dichloride in 100ml of water.
Example 2:
1) Adding the carbon nano tube into a mixed acid solution for ultrasonic treatment to obtain black viscous liquid; adding deionized water into the black viscous liquid, standing at room temperature for 24 hours, and pouring out supernatant; adding deionized water again for secondary sedimentation, and repeating the steps until the pH value of the supernatant is neutral; then carrying out suction filtration and separation on the precipitate, and washing the precipitate with ultrapure water until the obtained black precipitate is neutral; drying and grinding the black precipitate to obtain carbon oxide nanotubes with openings at two ends and diameters of 100-200 mu m; adding the obtained carbon oxide nano tube into a dimethylsilyl bisindene zirconium dichloride solution for 24 hours of ultrasonic treatment, pouring into a sand filter funnel for suction filtration, and then performing suction filtration washing with anhydrous diethyl ether until the filtrate is transparent; then, the black sediment in the sand core funnel is dried in vacuum to obtain the modified carbon nano tube; adding 10g of carbon oxide nano tube into every 100ml of dimethylsilyl bisindene zirconium dichloride solution, wherein the temperature of ultrasonic treatment is 20-40 ℃, the temperature of vacuum drying is 30-50 ℃, and the time of vacuum drying is 2-4 hours;
2) Mixing 2 parts by weight of modified carbon nano tube, 40 parts by weight of pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride and 20 parts by weight of pentamethylcyclopentadienyl- (2, 6-diisopropylphenoxy) -titanium dichloride to obtain the catalyst for synthesizing alpha-olefin by ethylene oligomerization.
The mixed acid solution in the step 1) is a mixed solution of 70% concentrated sulfuric acid and 68% concentrated nitric acid; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1.
The dimethylsilyl bisindene zirconium dichloride solution contains 0.5g of dimethylsilyl bisindene zirconium dichloride in every 100ml of water.
Example 3:
1) Adding the carbon nano tube into a mixed acid solution for ultrasonic treatment to obtain black viscous liquid; adding deionized water into the black viscous liquid, standing at room temperature for 24 hours, and pouring out supernatant; adding deionized water again for secondary sedimentation, and repeating the steps until the pH value of the supernatant is neutral; then carrying out suction filtration and separation on the precipitate, and washing the precipitate with ultrapure water until the obtained black precipitate is neutral; drying and grinding the black precipitate to obtain carbon oxide nanotubes with openings at two ends and diameters of 100-200 mu m; adding the obtained carbon oxide nano tube into a dimethylsilyl bisindene zirconium dichloride solution for 24 hours of ultrasonic treatment, pouring into a sand filter funnel for suction filtration, and then performing suction filtration washing with anhydrous diethyl ether until the filtrate is transparent; then, the black sediment in the sand core funnel is dried in vacuum to obtain the modified carbon nano tube; adding 5g of carbon oxide nano tube into every 100ml of dimethylsilyl bisindene zirconium dichloride solution, wherein the temperature of ultrasonic treatment is 20-40 ℃, the temperature of vacuum drying is 30-50 ℃, and the time of vacuum drying is 2-4 hours;
2) 10 parts by weight of modified carbon nano tube, 60 parts by weight of pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride, 30 parts by weight of pentamethylcyclopentadienyl- (2, 6-diisopropylphenoxy) -titanium dichloride and 2 parts by weight of methylaluminoxane compound are mixed to obtain the ethylene oligomerization alpha-olefin catalyst.
The mixed acid solution in the step 1) is a mixed solution of 70% concentrated sulfuric acid and 68% concentrated nitric acid; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1.
The dimethylsilyl bisindene zirconium dichloride solution contains 0.8g of dimethylsilyl bisindene zirconium dichloride in 100ml of water.
The catalyst for oligomerization of ethylene to alpha-olefins of example 1 was used as a main catalyst
The polymerization reaction is carried out in a 500mL stainless steel high-pressure reaction kettle, the polymerization kettle with mechanical stirring is heated to 150 ℃, vacuum pumping is carried out for 1h, a system is adjusted to a temperature condition required by polymerization, ethylene gas with the pressure of 0.1MPa is filled into the polymerization kettle, methylcyclohexane solution (the total volume of the final solution is 330 mL) containing a certain amount of alkyl aluminum and Modified Methylaluminoxane (MMAO) is added into the polymerization kettle, the temperature is kept constant for a period of time, stirring is started, hydrogen with the pressure of 0.15MPa is filled into the kettle to an equilibrium state, ethylene gas is filled into the kettle, the total pressure in the kettle reaches 4.5MPa, the reaction kettle waits for 10min, the ethylene reaches dissolution equilibrium, and then a main catalyst is added into the reaction kettle for a period of time. Adding 10mL of ethanol into the reactor to quench the reaction, stopping the polymerization process, cooling the reactor to room temperature, discharging the gas in the residual reactor, collecting the gas in a gas metering tank, filtering the liquid phase product, collecting the liquid phase product in a silk bottle, and drying the insoluble polymer obtained by filtering in a vacuum oven to obtain the mass of the insoluble polymer. And measuring the collected gas and liquid phase products and then carrying out gas chromatographic analysis.
The amount of the main catalyst is 2.0 mu mol;
the polymerization temperature is 55 ℃, the partial pressure of hydrogen in the polymerization kettle is 0.15MPa, the total polymerization pressure is 4.5MPa, and the polymerization time is 30min.
Experimental analysis results show that the catalyst provided by the invention is used for catalyzing ethylene oligomerization, and the obtained alpha-olefin products mainly comprise high-carbon alpha-olefins of 1-octene, 1-decene and 1-dodecene, wherein the selectivity of the 1-octene is more than 26%, the highest selectivity of the 1-decene is 29.84%, the highest selectivity of the 1-decene is more than 43%, the highest selectivity of the 1-decene is 49.21%, and the highest selectivity of the 1-dodecene is more than 16%, and the highest selectivity of the 1-dodecene is 20.07%.
The foregoing has shown and described the basic principles, main features and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A catalyst for oligomerization of ethylene to alpha-olefins, characterized by comprising the following raw materials in parts by weight:
pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride 40-60 parts;
20-30 parts of pentamethylcyclopentadienyl- (2, 6-diisopropyl phenoxy) -titanium dichloride;
0-2 parts of methylaluminoxane compound;
2-10 parts of modified carbon nano tube.
2. A catalyst for the oligomerization of ethylene to α -olefins according to claim 1, comprising the following raw materials in parts by weight:
50 parts of pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride;
26 parts of pentamethylcyclopentadienyl- (2, 6-diisopropylphenoxy) -titanium dichloride;
1 part of methylaluminoxane compound;
6 parts of modified carbon nano tube.
3. A catalyst for the oligomerization of ethylene to α -olefins according to any of the claims 1 to 2, characterized in that: the diameter of the modified carbon nano-tube is 20-100 micrometers.
4. A catalyst for the oligomerization of ethylene to α -olefins according to any of the claims 1 to 2, characterized in that: the particle size of the methylaluminoxane compound is 20 to 60 micrometers.
5. A process for preparing a catalyst for the oligomerization of ethylene to α -olefins according to any of claims 1 to 2, comprising the steps of:
1) Adding the carbon nano tube into a mixed acid solution for ultrasonic treatment to obtain black viscous liquid; adding deionized water into the black viscous liquid, standing at room temperature for 24 hours, and pouring out supernatant; adding deionized water again for secondary sedimentation, and repeating the steps until the pH value of the supernatant is neutral; then carrying out suction filtration and separation on the precipitate, and washing the precipitate with ultrapure water until the obtained black precipitate is neutral; drying and grinding the black precipitate to obtain carbon oxide nanotubes with openings at two ends and diameters of 100-200 mu m; adding the obtained carbon oxide nano tube into a dimethylsilyl bisindene zirconium dichloride solution for 24 hours of ultrasonic treatment, pouring into a sand filter funnel for suction filtration, and then performing suction filtration washing with anhydrous diethyl ether until the filtrate is transparent; then carrying out vacuum drying on the black precipitate in the sand core funnel to obtain a modified carbon nano tube; adding 1-10 g of carbon oxide nano tube into every 100ml of dimethylsilyl bisindene zirconium dichloride solution, wherein the temperature of ultrasonic treatment is 20-40 ℃, the temperature of vacuum drying is 30-50 ℃, and the time of vacuum drying is 2-4 h;
2) 2 to 10 weight parts of modified carbon nano tube, 40 to 60 weight parts of pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride, 20 to 30 weight parts of pentamethylcyclopentadienyl- (2, 6-diisopropylphenoxy) -titanium dichloride and 0 to 2 weight parts of methylaluminoxane compound are mixed to obtain the catalyst for synthesizing alpha-olefin by ethylene oligomerization.
6. The method for preparing the catalyst for oligomerization of ethylene to alpha-olefins according to claim 5, wherein: the mixed acid solution in the step 1) is a mixed solution of 70% concentrated sulfuric acid and 68% concentrated nitric acid; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3:1.
7. The method for preparing the catalyst for oligomerization of ethylene to alpha-olefins according to claim 5, wherein: the dimethylsilyl bisindene zirconium dichloride solution contains 0.5-1 g of dimethylsilyl bisindene zirconium dichloride in 100ml of water.
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| CN202410086552.2A CN117920354A (en) | 2024-01-22 | 2024-01-22 | Catalyst for synthesizing alpha-olefin by oligomerization of ethylene and preparation method thereof |
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