CN111019027A - Catalyst for oligomerization of 1-decene and preparation method and application thereof - Google Patents
Catalyst for oligomerization of 1-decene and preparation method and application thereof Download PDFInfo
- Publication number
- CN111019027A CN111019027A CN201811173546.1A CN201811173546A CN111019027A CN 111019027 A CN111019027 A CN 111019027A CN 201811173546 A CN201811173546 A CN 201811173546A CN 111019027 A CN111019027 A CN 111019027A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- decene
- oligomerization
- reaction
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 title claims abstract description 215
- 239000003054 catalyst Substances 0.000 title claims abstract description 124
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 97
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 239000011651 chromium Substances 0.000 claims abstract description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 10
- 125000000547 substituted alkyl group Chemical group 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 35
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 28
- 239000002199 base oil Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 7
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 6
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 23
- OEOUWMSQXZQDIP-UHFFFAOYSA-N CC[Al](CC)CC.CC1=CC=CC=C1 Chemical compound CC[Al](CC)CC.CC1=CC=CC=C1 OEOUWMSQXZQDIP-UHFFFAOYSA-N 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000000539 dimer Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- 229910017318 Mo—Ni Inorganic materials 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- -1 chloroaluminum toluene Chemical compound 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- IOVPULPCISZBEU-UHFFFAOYSA-H CC1=CC=CC=C1.C([O-])([O-])=O.[Al+3].C([O-])([O-])=O.C([O-])([O-])=O.[Al+3].CC1=CC=CC=C1 Chemical compound CC1=CC=CC=C1.C([O-])([O-])=O.[Al+3].C([O-])([O-])=O.C([O-])([O-])=O.[Al+3].CC1=CC=CC=C1 IOVPULPCISZBEU-UHFFFAOYSA-H 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000010689 synthetic lubricating oil Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- OAFMYIADTCIEFV-UHFFFAOYSA-N hexane;triethylalumane Chemical compound CCCCCC.CC[Al](CC)CC OAFMYIADTCIEFV-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010688 mineral lubricating oil Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/14—Monomers containing five or more carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for oligomerization of 1-decene, a preparation method and application thereof, wherein the preparation method comprises the following steps: step 1, dissolving trivalent chromium acetate in a solvent, then soaking a gamma-alumina carrier in the trivalent chromium acetate for 2-4 hours, and then removing the solvent to prepare a catalyst precursor; step 2, placing the catalyst precursor in a reaction bottle, heating up in sections under the protection of inert gas, keeping the temperature constant at 150-240 ℃ for 0.3-2h, then heating up to 400-600 ℃ for roasting time for 3-6 h, and then cooling down; step 3, dripping an alkyl aluminum or substituted alkyl aluminum compound into a reaction bottle at the temperature of 60-80 ℃, and stirring at constant temperature for reaction for 5-10 hours; filtering and washing to obtain the catalyst with the chromium content of 1.05-3.36 wt%.
Description
Technical Field
The invention relates to a catalyst suitable for α -alkene oligomerization, a preparation method and application thereof, in particular to a catalyst for 1-decene oligomerization, a preparation method and application thereof.
Background
Compared with the traditional mineral oil, the synthetic lubricating oil has excellent performance, such as dynamic viscosity (Kv), Viscosity Index (VI), Pour Point (PP), volatility and the like, and the thermal performance, the oxygen resistance, the sensitivity to additives, the ignition point and the like of the synthetic lubricating oil are superior to those of the mineral lubricating oil.
The traditional Lewis acid catalyst has corrosivity on equipment in the process of preparing synthetic oil, is easy to generate three wastes, has high environmental hazard, and has high branching rate and low viscosity index. And the PAO branching ratio prepared by adopting the chromium-based catalyst is lower than 0.19.
US 4827064 discloses a synthetic process for preparing lubricant base oils using heterogeneous chromium based catalysts by loading chromium acetate as a catalyst precursor onto the surface of silica followed by reduction with carbon monoxide. Although the active site is not defined, it is believed that divalent chromium reacts with the carbonyl ligand. The influence of the branching ratio of the oligomer, the calcination temperature and the reaction conditions on VI is introduced.
CN 1948243 a discloses a preparation method of a catalyst using silica gel to load trivalent chromium acetate, and discusses the process conditions for preparing the catalyst and oligomerization conditions.
However, the preparation conditions of the catalysts are harsh, the flow is long, the prepared catalysts have low content of active components, the chromium content is less than 1 percent, the 1-decene oligomerization reaction is difficult to effectively initiate, the oligomerization reaction time is long, and the yield of the PAO base oil is low.
Disclosure of Invention
The invention aims to provide a preparation method of a catalyst for oligomerization of 1-decene, which aims to overcome the defects that the catalyst in the prior art has harsh preparation conditions, long flow and difficult effective initiation of oligomerization of 1-decene.
Another object of the present invention is to provide a catalyst for oligomerization of 1-decene.
Another object of the present invention is to provide a use of the catalyst for oligomerization of 1-decene.
In order to achieve the above object, the present invention provides a method for preparing a catalyst for oligomerization of 1-decene, comprising the steps of:
step 1, dissolving trivalent chromium acetate in a solvent, then soaking a gamma-alumina carrier in the trivalent chromium acetate for 2-4 hours, and then removing the solvent to prepare a catalyst precursor;
step 2, placing the catalyst precursor in a reaction bottle, heating up in sections under the protection of inert gas, keeping the temperature constant at 150-240 ℃ for 0.3-2h, then heating up to 400-600 ℃ for roasting time for 3-6 h, and then cooling down; and
step 3, dripping an alkyl aluminum or substituted alkyl aluminum compound into a reaction bottle at the temperature of 60-80 ℃, and stirring at constant temperature for reaction for 5-10 hours; filtering and drying to obtain the catalyst with the chromium content of 1.05-3.36 wt%.
The invention relates to a preparation method of a catalyst for oligomerization of 1-decene, wherein a gamma-alumina carrier is a spherical or strip-shaped alumina carrier.
The preparation method of the catalyst for oligomerization of 1-decene comprises the steps of preparing a spherical gamma-alumina carrier with the diameter of 1.3-2.3 mm, preferably 1.5-2.0 mm, and the specific surface area of 100-180 m2Per g, preferably 120 to 160m2The total pore volume is more than or equal to 1.25 mL/g. Compared with the gamma-alumina carrier with the total pore volume of about 1.0mL/g, the gamma-alumina carrier with the large pore diameter is selected, so that the conversion rate of oligomerization reaction can be improved, the carrier blocking phenomenon is reduced, the recycling times of the carrier catalyst are increased, and the mass ratio of the trivalent chromium acetate to the spherical gamma-alumina is 1: 6-9.
The invention relates to a preparation method of a catalyst for oligomerization of 1-decene, wherein, when trivalent chromium acetate is dissolved by a solvent in the step 1, the mass percentage concentration of the chromium acetate is between 2 and 5 percent.
The invention relates to a preparation method of a catalyst for oligomerization of 1-decene, wherein the solvent is absolute ethyl alcohol or acetic acid.
The preparation method of the catalyst for oligomerization of 1-decene, disclosed by the invention, comprises the step 1 of dipping for 3-4 hours.
The invention relates to a preparation method of a catalyst for oligomerization of 1-decene, wherein in the step 3, the alkyl aluminum or substituted alkyl aluminum is triethyl aluminum, triisobutyl aluminum, diethyl aluminum monochloride or sesqui aluminum, and the molar ratio of the alkyl aluminum or substituted alkyl aluminum to trivalent chromium acetate is 1-2: 1.
the preparation method of the catalyst for oligomerization of 1-decene is characterized in that all reaction processes are carried out under the protection of inert gas, and the inert gas is nitrogen or argon.
In order to achieve the aim, the invention also provides a catalyst for oligomerization of 1-decene prepared by the preparation method.
In order to achieve the purpose, the invention also provides an application of the catalyst in 1-decene oligomerization, wherein the mass ratio of 1-decene to the catalyst is 80-100: 1, the 1-decene oligomer is obtained by reacting at 90-150 ℃ and 0.8-1.2 MPa for 4-10 h in the presence of a cocatalyst.
The catalyst is applied to oligomerization of 1-decene, wherein the cocatalyst is trimethyl aluminum, triethyl aluminum or methylaluminoxane, and the molar ratio of Al to Cr is 30-50.
The catalyst is applied to 1-decene oligomerization, wherein the reaction temperature is 100 ℃ and 120 ℃ and the reaction time is 8-10 h in the 1-decene oligomerization process.
The catalyst is applied to oligomerization of 1-decene, wherein the oligomerization of 1-decene is hydrogenated to obtain a kinematic viscosity of 15-40 mm at 100 DEG C2(ii) a PAO base oil with a viscosity index of 157-177.
The specific method for hydrogenating the 1-decene oligomer comprises the following steps of filtering a catalyst after the 1-decene oligomerization reaction is finished, distilling under normal pressure to remove a solvent, and distilling under reduced pressure to remove unreacted monomers and partial dimers to obtain the 1-decene oligomer; then Mo-Ni/gamma-Al2O3The catalyst is used for a period of time of 0.5 to 1.0h at a temperature of 200 to 230 ℃, a pressure of 2.0 to 3.0MPa and a space velocity of 0.5 to 1.0-1Hydrogenating the 1-decene oligomer under the condition that the hydrogen-oil ratio is 500-750: 1 to finally obtain the product with the kinematic viscosity of 15-40 mm at 100 DEG C2(ii) a PAO base oil with a viscosity index of 157-177.
The invention has the beneficial effects that:
the invention reduces the environmental pollution by heterogeneous polymerization system, easy separation of catalyst and product, and recycling of catalyst. The oligomerization product is distilled to separate the dimer, and the viscosity of the obtained product is 40.0mm2The viscosity of the product of the PAO base oil/s can be increased or decreased by adjusting the catalyst proportion or the polymerization reaction process parameters so as to meet the requirements of producing PAO products with different viscosity grades.
Drawings
FIG. 1 is a process flow diagram of a process for preparing a catalyst for oligomerization of 1-decene as described herein.
FIG. 2 is a process flow diagram for the hydrogenation of 1-decene oligomers as described herein.
Detailed Description
The following describes specific embodiments of the present invention. The present invention is not limited to the following embodiments. These examples are provided only for the purpose of further illustration to facilitate the understanding of the present invention and do not limit the scope of the present invention.
A preparation method of a catalyst for oligomerization of 1-decene comprises the following steps:
step 1, dissolving trivalent chromium acetate in a solvent, then soaking a gamma-alumina carrier in the trivalent chromium acetate for 2-4 hours, and then removing the solvent to prepare a catalyst precursor;
step 2, placing the catalyst precursor in a reaction bottle, heating up in sections under the protection of inert gas, keeping the temperature constant at 150-240 ℃ for 0.3-2h, then heating up to 400-600 ℃ for roasting time for 3-6 h, and then cooling down; and
step 3, dripping an alkyl aluminum or substituted alkyl aluminum compound into a reaction bottle at the temperature of 60-80 ℃, and stirring at constant temperature for reaction for 5-10 hours; filtering and drying to obtain the catalyst with the chromium content of 1.05-3.36 wt%.
The invention relates to a preparation method of a catalyst for oligomerization of 1-decene, wherein a gamma-alumina carrier is a spherical or strip-shaped alumina carrier.
The preparation method of the catalyst for oligomerization of 1-decene comprises the steps of preparing a spherical gamma-alumina carrier with the diameter of 1.3-2.3 mm, preferably 1.5-2.0 mm, and the specific surface area of 100-180 m2Per g, preferably 120 to 160m2The total pore volume is more than or equal to 1.25 mL/g. Compared with the gamma-alumina carrier with the total pore volume of about 1.0mL/g, the gamma-alumina carrier with the large pore diameter is selected, so that the conversion rate of oligomerization reaction can be improved, the carrier blocking phenomenon is reduced, the recycling times of the carrier catalyst are increased, and the mass ratio of the trivalent chromium acetate to the spherical gamma-alumina is 1: 6-9.
The invention relates to a preparation method of a catalyst for oligomerization of 1-decene, wherein, when trivalent chromium acetate is dissolved by a solvent in the step 1, the mass percentage concentration of the chromium acetate is between 2 and 5 percent.
The invention relates to a preparation method of a catalyst for oligomerization of 1-decene, wherein the solvent is absolute ethyl alcohol or acetic acid.
The preparation method of the catalyst for oligomerization of 1-decene, disclosed by the invention, comprises the step 1 of dipping for 3-4 hours.
The invention relates to a preparation method of a catalyst for oligomerization of 1-decene, wherein in the step 3, the alkyl aluminum or substituted alkyl aluminum is triethyl aluminum, triisobutyl aluminum, diethyl aluminum monochloride or sesqui aluminum, and the molar ratio of the alkyl aluminum or substituted alkyl aluminum to trivalent chromium acetate is 1-2: 1.
the preparation method of the catalyst for oligomerization of 1-decene is characterized in that all reaction processes are carried out under the protection of inert gas, and the inert gas is nitrogen or argon.
The invention also provides a catalyst for oligomerization of 1-decene prepared by the preparation method.
The invention also provides an application of the catalyst in 1-decene oligomerization, wherein the mass ratio of 1-decene to the catalyst is 80-100: 1, the reaction temperature is 90-150 ℃, the reaction pressure is 0.8-1.2 MPa, and the 1-decene oligomer is obtained after reaction for 4-10 hours in the presence of a cocatalyst.
The catalyst is applied to oligomerization of 1-decene, wherein the cocatalyst is trimethyl aluminum, triethyl aluminum or methylaluminoxane, and the molar ratio of Al to Cr is 30-50.
The catalyst is applied to 1-decene oligomerization, wherein the reaction temperature is 100 ℃ and 120 ℃ and the reaction time is 8-10 h in the 1-decene oligomerization process.
The catalyst is applied to oligomerization of 1-decene, wherein the oligomerization of 1-decene is hydrogenated to obtain a kinematic viscosity of 15-40 mm at 100 DEG C2(ii) a PAO base oil with a viscosity index of 157-177.
Example 1
Preparation of chromium oligomerization catalyst of 1-deceneThe method comprises the following steps:
(1) preparation of the catalyst precursor
200g of gamma-alumina carrier is added into 0.5L of 2 percent by mass of acetic acid solution of chromium acetate, the solution is soaked for 4 hours at normal temperature, and the solvent is drained.
(2) Catalyst activation
And (3) placing the catalyst precursor into a reaction bottle and a tubular furnace, heating to 200 ℃ for 0.5h, then continuing heating to 400 ℃ for 6h, cooling under the atmosphere of argon, and storing in a glove box for later use.
(3) Catalyst reduction
Placing the activated supported catalyst precursor into a reaction bottle, adding 0.5L of toluene, dropwise adding 50mL of 1M triethyl aluminum toluene solution at 80 ℃ under the stirring condition, and stirring at constant temperature for reaction for 8 hours; after the reaction is finished, cooling, filtering and drying are carried out, so as to obtain the supported catalyst with the chromium content of 1.05 omega percent; and sealed and stored in a glove box.
The application of the catalyst for oligomerization of 1-decene includes the following steps:
(1) 50mL of n-hexane, 1 g of the supported catalyst, 108mL of 1-decene, and 4.5mL of a 10% MAO toluene solution (n (Al/Cr) ═ 30) were charged into a 250mL autoclave, and an oligomerization reaction was carried out at a reaction temperature of 100 ℃ and a reaction pressure of 1.0MPa for 10 hours. Stopping the reaction, filtering the catalyst, washing the product compound with water, distilling under normal pressure to remove the solvent, the monomer and the dimer, and drying to obtain the final 1-decene oligomer; the 1-decene conversion was 47.6 ω%.
(2) With Mo-Ni/gamma-Al2O3The catalyst is at the temperature of 230 ℃, the pressure of 3.0MPa and the space velocity of 0.5h-1And hydrogenating the 1-decene oligomer under the condition of hydrogen-oil ratio of 500:1 to finally obtain the PAO base oil.
The kinematic viscosity of PAO base oil at 100 ℃ is 16.86mm2(s) viscosity index 162.
Example 2
Example 2 differs from example 1 in that:
(1) preparation of the catalyst precursor
Soaking for 3 hours by adopting an ethanol solution of 5% chromium acetate in percentage by mass;
the method specifically comprises the following steps: 200g of gamma-alumina carrier is added into 0.5L of ethanol solution with 5 percent of chromium acetate by mass fraction, the mixture is soaked for 3 hours at normal temperature, and the solvent is drained.
(2) Catalyst activation
Roasting at 500 deg.c for 5 hr;
the method specifically comprises the following steps: and (3) placing the catalyst precursor into a reaction bottle and a tubular furnace, heating to 200 ℃ for 0.5h, then continuing heating to 500 ℃ for 5h, cooling under the atmosphere of argon, and storing in a glove box for later use.
(3) Catalyst reduction
150mL of 1M triisobutylaluminum hexane solution is dropwise added at 60 ℃ under the stirring condition, and the mixture is stirred at constant temperature for reaction for 8 hours;
the method specifically comprises the following steps: placing the activated supported catalyst precursor into a reaction bottle, adding 0.5L of toluene, dropwise adding 150mL of 1M triethyl aluminum hexane solution at 60 ℃ under the stirring condition, and stirring at constant temperature for reaction for 8 hours; after the reaction is finished, cooling, filtering and drying are carried out, so as to obtain the supported catalyst with the chromium content of 1.76 omega%; and sealed and stored in a glove box.
The application of the 1-decene oligomerization catalyst is characterized in that:
(1) oligomerization was carried out for 10 hours at a reaction temperature of 150 ℃ using 6.5mL of 2M triethylaluminum toluene solution.
The method specifically comprises the following steps: (1) 50mL of n-hexane, 108mL of the above supported catalyst, and 6.5mL of a 2M triethylaluminum toluene solution (n (Al/Cr) ═ 30) were charged into a 250mL autoclave, and an oligomerization reaction was carried out at a reaction temperature of 150 ℃ and a reaction pressure of 1.0MPa for 10 hours. Stopping the reaction, filtering the catalyst, washing the product compound with water, distilling under normal pressure to remove the solvent, the monomer and the dimer, and drying to obtain the final 1-decene oligomer; the 1-decene conversion was 51.7 ω%.
(2) With Mo-Ni/gamma-Al2O3The catalyst is at the temperature of 230 ℃, the pressure of 3.0MPa and the space velocity of 0.5h-1Oligomerization of 1-decene under the condition of hydrogen-oil ratio of 500:1Hydrogenating the product to finally obtain the PAO base oil.
The kinematic viscosity of PAO base oil at 100 ℃ is 15.16mm2(s) viscosity index 157.
Example 3
Example 3 differs from example 2 in that:
(1) preparation of the catalyst precursor
Adopting an acetic acid solution with 5% of chromium acetate by mass, and soaking for 2 hours;
the method specifically comprises the following steps: 200g of gamma-alumina carrier is added into 0.5L of acetic acid solution with 5 percent of chromium acetate by mass fraction, the solution is immersed for 2 hours at normal temperature, and the solvent is drained.
(2) Catalyst activation
Roasting for 6 hours at 600 ℃;
the method specifically comprises the following steps: and (3) placing the catalyst precursor into a reaction bottle and a tubular furnace, heating to 200 ℃ for 0.5h, then continuing heating to 600 ℃ for 6h, cooling under the atmosphere of argon, and storing in a glove box for later use.
(3) Catalyst reduction
Dropwise adding 200mL of 1M chloroaluminum toluene solution at 60 ℃ under the stirring condition, and stirring at constant temperature for reaction for 5 hours;
the method specifically comprises the following steps: placing the activated supported catalyst precursor into a reaction bottle, adding 0.5L of toluene, dropwise adding 200mL of 1M toluene solution of diethyl aluminum monochloride at 60 ℃ under the stirring condition, and stirring at constant temperature for reaction for 5 hours; after the reaction is finished, cooling, filtering and drying are carried out, so as to obtain the supported catalyst with the chromium content of 3.36 omega percent; and sealed and stored in a glove box.
The application of the 1-decene oligomerization catalyst is characterized in that:
(1) oligomerization is carried out for 10 hours at the reaction temperature of 120 ℃ by adopting 10mL of 2M triethyl aluminum toluene solution.
The method specifically comprises the following steps: (1) 50mL of n-hexane, 1 g of the supported catalyst, 108mL of 1-decene, and 10mL of a 2M triethylaluminum toluene solution (n (Al/Cr) ═ 30) were charged into a 250mL high-pressure polymerization vessel, and oligomerization was carried out at a reaction temperature of 120 ℃ and a reaction pressure of 1.0MPa for 10 hours. Stopping the reaction, filtering the catalyst, washing the product compound with water, distilling under normal pressure to remove the solvent, the monomer and the dimer, and drying to obtain the final 1-decene oligomer; the 1-decene conversion was 62.0 ω%.
(2) With Mo-Ni/gamma-Al2O3The catalyst is at the temperature of 230 ℃, the pressure of 3.0MPa and the space velocity of 0.5h-1And hydrogenating the 1-decene oligomer under the condition of hydrogen-oil ratio of 500:1 to finally obtain the PAO base oil.
The kinematic viscosity of PAO base oil at 100 ℃ is 28.26mm2(s) viscosity index 172.
Example 4
Example 4 differs from example 3 in that:
(1) preparation of the catalyst precursor
Soaking for 4 hours by adopting an acetic acid solution of chromium acetate with the mass fraction of 4%;
the method specifically comprises the following steps: 200g of gamma-alumina carrier is added into 0.5L of acetic acid solution with 4 percent of chromium acetate by mass fraction, the solution is immersed for 2 hours at normal temperature, and the solvent is drained.
(3) Catalyst reduction
Dropwise adding 200mL of 1M aluminum sesquicarbonate toluene solution at 70 ℃ under the stirring condition, and stirring at constant temperature for reaction for 10 hours;
the method specifically comprises the following steps: placing the activated supported catalyst precursor into a reaction bottle, adding 0.5L of toluene, dropwise adding 200mL of 1M aluminum sesqui-toluene solution at 70 ℃ under the stirring condition, and stirring at constant temperature for reaction for 10 hours; after the reaction is finished, cooling, filtering and drying are carried out, so as to obtain the supported catalyst with the chromium content of 3.12 omega percent; and sealed and stored in a glove box.
The application of the 1-decene oligomerization catalyst is characterized in that:
(1) oligomerization is carried out for 10 hours at the reaction temperature of 100 ℃ by adopting 10mL of 2M triethyl aluminum toluene solution.
The method specifically comprises the following steps: (1) 50mL of n-hexane, 1 g of the supported catalyst, 108mL of 1-decene, and 10mL of a 2M triethylaluminum toluene solution (n (Al/Cr) ═ 30) were charged into a 250mL high-pressure polymerization vessel, and oligomerization was carried out at a reaction temperature of 100 ℃ and a reaction pressure of 1.0MPa for 10 hours. Stopping the reaction, filtering the catalyst, washing the product compound with water, distilling under normal pressure to remove the solvent, the monomer and the dimer, and drying to obtain the final 1-decene oligomer; the 1-decene conversion was 55.7 ω%.
(2) With Mo-Ni/gamma-Al2O3The catalyst is at the temperature of 230 ℃, the pressure of 3.0MPa and the space velocity of 0.5h-1And hydrogenating the 1-decene oligomer under the condition of hydrogen-oil ratio of 500:1 to finally obtain the PAO base oil.
The kinematic viscosity of PAO base oil at 100 ℃ is 26.74mm2(s), viscosity index 171.
Example 5
Example 5 differs from example 3 in that:
(1) preparation of the catalyst precursor
Adopting an acetic acid solution with 3% of chromium acetate by mass, and soaking for 4 hours;
the method specifically comprises the following steps: 200g of gamma-alumina carrier is added into 0.5L of acetic acid solution with 3 percent of chromium acetate by mass fraction, the solution is soaked for 4 hours at normal temperature, and the solvent is drained.
The rest steps are the same as those in the embodiment 3, and specifically comprise the following steps:
(2) catalyst activation
And (3) placing the catalyst precursor into a reaction bottle and a tubular furnace, heating to 200 ℃ for 0.5h, then continuing heating to 600 ℃ for 6h, cooling under the atmosphere of argon, and storing in a glove box for later use.
(3) Catalyst reduction
Placing the activated supported catalyst precursor into a reaction bottle, adding 0.5L of toluene, dropwise adding 200mL of 1M toluene solution of diethyl aluminum monochloride at 60 ℃ under the stirring condition, and stirring at constant temperature for reaction for 5 hours; after the reaction is finished, cooling, filtering and drying are carried out, so as to obtain the supported catalyst with the chromium content of 2.68 omega percent; and sealed and stored in a glove box.
The application of the 1-decene oligomerization catalyst is characterized in that:
(1) 50mL of n-hexane, 1 g of the supported catalyst, 108mL of 1-decene, and 10mL of a 2M triethylaluminum toluene solution (n (Al/Cr) ═ 30) were charged into a 250mL high-pressure polymerization vessel, and oligomerization was carried out at a reaction temperature of 120 ℃ and a reaction pressure of 1.0MPa for 10 hours. Stopping the reaction, filtering the catalyst, washing the product compound with water, distilling under normal pressure to remove the solvent, the monomer and the dimer, and drying to obtain the final 1-decene oligomer; the 1-decene conversion was 52.3 ω%.
(2) With Mo-Ni/gamma-Al2O3The catalyst is at the temperature of 230 ℃, the pressure of 3.0MPa and the space velocity of 0.5h-1And hydrogenating the 1-decene oligomer under the condition of hydrogen-oil ratio of 500:1 to finally obtain the PAO base oil.
The kinematic viscosity of PAO base oil at 100 ℃ is 26.74mm2(s), viscosity index 167.
Example 6
Example 6 differs from example 3 in that:
(1) preparation of the catalyst precursor
Soaking for 4 hours by adopting an ethanol solution of chromium acetate with the mass fraction of 4%;
the method specifically comprises the following steps: 200g of gamma-alumina carrier is added into 0.5L of ethanol solution with 4 percent of chromium acetate by mass fraction, the mixture is soaked for 4 hours at normal temperature, and the solvent is drained.
(3) Catalyst reduction
Dropwise adding 150mL of 1M aluminum sesquicarbonate toluene solution at 80 ℃ under the stirring condition, and stirring at constant temperature for reaction for 10 hours;
the method specifically comprises the following steps: placing the activated supported catalyst precursor into a reaction bottle, adding 0.5L of toluene, dropwise adding 150mL of 1M aluminum sesqui-toluene solution at 80 ℃ under the stirring condition, and stirring at constant temperature for reaction for 10 hours; after the reaction is finished, cooling, filtering and drying are carried out, so as to obtain the supported catalyst with the chromium content of 3.30 omega percent; and sealed and stored in a glove box.
α -olefin oligomerization catalyst, characterized by:
(1) oligomerization was carried out for 10 hours at a reaction temperature of 90 ℃ using 15mL of 2M triethylaluminum toluene solution.
The method specifically comprises the following steps: (1) 50mL of n-hexane, 1 g of the supported catalyst, 108mL of 1-decene, and 15mL of a 2M triethylaluminum toluene solution (n (Al/Cr) ═ 30) were charged into a 250mL high-pressure polymerization vessel, and oligomerization was carried out at a reaction temperature of 90 ℃ and a reaction pressure of 1.0MPa for 10 hours. Stopping the reaction, filtering the catalyst, washing the product compound with water, distilling under normal pressure to remove the solvent, the monomer and the dimer, and drying to obtain the final 1-decene oligomer; the 1-decene conversion was 68.0 ω%.
(2) With Mo-Ni/gamma-Al2O3The catalyst is at the temperature of 230 ℃, the pressure of 3.0MPa and the space velocity of 0.5h-1And hydrogenating the 1-decene oligomer under the condition of hydrogen-oil ratio of 500:1 to finally obtain the PAO base oil.
The kinematic viscosity of PAO base oil at 100 ℃ is 28.05mm2(s), viscosity index 177.
Example 7
Example 7 the same example 3, α -olefin oligomerization catalyst was used, except that:
(1) oligomerization was carried out for 10 hours at a reaction temperature of 90 ℃ using 15mL of 2M triethylaluminum toluene solution.
The method specifically comprises the following steps: (1) 50mL of n-hexane, 1 g of the supported catalyst, 108mL of 1-decene, and 15mL of a 2M triethylaluminum toluene solution (n (Al/Cr) ═ 40) were charged into a 250mL high-pressure polymerization vessel, and oligomerization was carried out at a reaction temperature of 90 ℃ and a reaction pressure of 1.0MPa for 10 hours. Stopping the reaction, filtering the catalyst, washing the product compound with water, distilling under normal pressure to remove the solvent, the monomer and the dimer, and drying to obtain the final 1-decene oligomer; the 1-decene conversion was 70.0 ω%.
(2) With Mo-Ni/gamma-Al2O3The catalyst is at the temperature of 230 ℃, the pressure of 3.0MPa and the space velocity of 0.5h-1And hydrogenating the 1-decene oligomer under the condition of hydrogen-oil ratio of 500:1 to finally obtain the PAO base oil.
The kinematic viscosity of PAO base oil at 100 ℃ is 31.17mm2(s) viscosity index 175.
Example 8
Example 8 the same example 3, α -olefin oligomerization catalyst was used, except that:
(1) oligomerization was carried out for 10 hours at a reaction temperature of 90 ℃ using 15mL of 2M triethylaluminum toluene solution.
The method specifically comprises the following steps: (1) 50mL of n-hexane, 108mL of the above supported catalyst, and 15mL of a 2M triethylaluminum toluene solution (n (Al/Cr) ═ 50) were charged into a 250mL autoclave, and then an oligomerization reaction was carried out at a reaction temperature of 90 ℃ and a reaction pressure of 1.0MPa for 10 hours. Stopping the reaction, filtering the catalyst, washing the product compound with water, distilling under normal pressure to remove the solvent, the monomer and the dimer, and drying to obtain the final 1-decene oligomer; the 1-decene conversion was 68.3 ω%.
(2) With Mo-Ni/gamma-Al2O3The catalyst is at the temperature of 230 ℃, the pressure of 3.0MPa and the space velocity of 0.5h-1And hydrogenating the 1-decene oligomer under the condition of hydrogen-oil ratio of 500:1 to finally obtain the PAO base oil.
The kinematic viscosity of PAO base oil at 100 ℃ is 35.45mm2(s), viscosity index 177.
Example 9
Example 9 the same example 3, α -olefin oligomerization catalyst was used, except that:
(1) oligomerization was carried out for 10 hours at a reaction temperature of 90 ℃ using 15mL of 2M triethylaluminum toluene solution.
The method specifically comprises the following steps: (1) 50mL of n-hexane, 1 g of the supported catalyst, 125mL of 1-decene, and 15mL of a 2M triethylaluminum toluene solution (n (Al/Cr) ═ 30) were charged into a 250mL high-pressure polymerization vessel, and oligomerization was carried out at a reaction temperature of 90 ℃ and a reaction pressure of 1.0MPa for 10 hours. Stopping the reaction, filtering the catalyst, washing the product compound with water, distilling under normal pressure to remove the solvent, the monomer and the dimer, and drying to obtain the final 1-decene oligomer; the 1-decene conversion was 60.7 ω%.
(2) With Mo-Ni/gamma-Al2O3The catalyst is at the temperature of 230 ℃, the pressure of 3.0MPa and the space velocity of 0.5h-1And hydrogenating the 1-decene oligomer under the condition of hydrogen-oil ratio of 500:1 to finally obtain the PAO base oil.
The kinematic viscosity of PAO base oil at 100 ℃ is 28.58mm2(s) viscosity index 173.
Example 10
Example 10 the same example 3, α -olefin oligomerization catalyst was used, except that:
(1) oligomerization was carried out for 10 hours at a reaction temperature of 90 ℃ using 15mL of 2M triethylaluminum toluene solution.
The method specifically comprises the following steps: (1) 50mL of n-hexane, 1 g of the supported catalyst, 139mL of 1-decene, and 15mL of a 2M triethylaluminum toluene solution (n (Al/Cr) ═ 30) were charged into a 250mL high-pressure polymerization vessel, and oligomerization was carried out at a reaction temperature of 90 ℃ and a reaction pressure of 1.0MPa for 10 hours. Stopping the reaction, filtering the catalyst, washing the product compound with water, distilling under normal pressure to remove the solvent, the monomer and the dimer, and drying to obtain the final 1-decene oligomer; the 1-decene conversion was 61.7 ω%.
(2) With Mo-Ni/gamma-Al2O3The catalyst is at the temperature of 230 ℃, the pressure of 3.0MPa and the space velocity of 0.5h-1And hydrogenating the 1-decene oligomer under the condition of hydrogen-oil ratio of 500:1 to finally obtain the PAO base oil.
The kinematic viscosity of PAO base oil at 100 ℃ is 27.33mm2(s) viscosity index 165.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (11)
1. A preparation method of a catalyst for oligomerization of 1-decene is characterized by comprising the following steps:
step 1, dissolving trivalent chromium acetate in a solvent, then soaking a gamma-alumina carrier in the trivalent chromium acetate for 2-4 hours, and then removing the solvent to prepare a catalyst precursor;
step 2, placing the catalyst precursor in a reaction bottle, heating up in sections under the protection of inert gas, keeping the temperature constant at 150-240 ℃ for 0.3-2h, then heating up to 400-600 ℃ for roasting time for 3-6 h, and then cooling down; and
step 3, dripping an alkyl aluminum or substituted alkyl aluminum compound into a reaction bottle at the temperature of 60-80 ℃, and stirring at constant temperature for reaction for 5-10 hours; filtering and drying to obtain the catalyst with the chromium content of 1.05-3.36 wt%.
2. The method for preparing the catalyst for oligomerization of 1-decene according to claim 1, wherein the γ -alumina support is a spherical or bar-shaped alumina support.
3. The method for preparing the catalyst for oligomerization of 1-decene according to claim 2, wherein the spherical γ -alumina support has a diameter of 1.3-2.3 mm and a specific surface area of 100-180 m2The total pore volume is not less than 1.25mL/g, and the mass ratio of the trivalent chromium acetate to the spherical gamma-alumina is 1: 6-9.
4. The method for preparing the catalyst for oligomerization of 1-decene according to claim 1, wherein the mass percentage concentration of the chromium acetate is between 2% and 5% when the trivalent chromium acetate is dissolved by the solvent in the step 1.
5. The method for preparing a catalyst for oligomerization of 1-decene according to claim 1, wherein the solvent is absolute ethanol or acetic acid.
6. The method for preparing the catalyst for oligomerization of 1-decene according to claim 1, wherein the alkyl aluminum or substituted alkyl aluminum in step 3 is triethyl aluminum, triisobutyl aluminum, diethyl aluminum monochloride or sesqui aluminum, and the molar ratio of the alkyl aluminum or substituted alkyl aluminum to the trivalent chromium acetate is 1-2: 1.
7. the catalyst for oligomerization of 1-decene prepared by the method according to any one of claims 1 to 6.
8. The application of the catalyst in oligomerization of 1-decene as described in claim 7, wherein the mass ratio of 1-decene to the catalyst is 80-100: 1, and the 1-decene oligomer is obtained by reacting at 90-150 ℃ and 0.8-1.2 MPa in the presence of a cocatalyst for 4-10 h.
9. The use of the catalyst of claim 8 in oligomerization of 1-decene, wherein the cocatalyst is trimethylaluminum, triethylaluminum or methylaluminoxane, and the molar ratio of Al to Cr is 30 to 50.
10. The application of the catalyst in oligomerization of 1-decene as claimed in claim 8, wherein the reaction temperature is 100 ℃ and the reaction time is 8-10 h in the oligomerization of 1-decene.
11. The application of the catalyst in oligomerization of 1-decene according to claim 8, wherein the oligomerization of 1-decene is hydrogenated to obtain a kinematic viscosity of 15-40 mm at 100 ℃2(ii) a PAO base oil with a viscosity index of 157-177.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811173546.1A CN111019027B (en) | 2018-10-09 | 2018-10-09 | Catalyst for oligomerization of 1-decene and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811173546.1A CN111019027B (en) | 2018-10-09 | 2018-10-09 | Catalyst for oligomerization of 1-decene and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111019027A true CN111019027A (en) | 2020-04-17 |
CN111019027B CN111019027B (en) | 2022-03-01 |
Family
ID=70190958
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811173546.1A Active CN111019027B (en) | 2018-10-09 | 2018-10-09 | Catalyst for oligomerization of 1-decene and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111019027B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113337311A (en) * | 2021-04-16 | 2021-09-03 | 华东理工大学 | Ultra-high viscosity index poly-alpha-olefin base oil and preparation method and application thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030023126A1 (en) * | 2000-01-24 | 2003-01-30 | Kostantinos Kourtakis | Gel catalysts and methods for their use in catalytic dehydrogenation processes |
CN1948243A (en) * | 2005-10-14 | 2007-04-18 | 中国人民解放军空军油料研究所 | Preparation method of high viscosity index poly alpha olefine synthetic oil |
CN103159875A (en) * | 2011-12-09 | 2013-06-19 | 中国石油化工股份有限公司 | Chromium-polyethylene catalyst |
CN103666552A (en) * | 2012-09-04 | 2014-03-26 | 中国石油天然气股份有限公司 | Preparation method of medium-viscosity poly-alpha-olefin base oil |
CN106881119A (en) * | 2015-12-16 | 2017-06-23 | 中国石油天然气股份有限公司 | Poly alpha-olefin synthetic oil catalyst and its preparation method |
-
2018
- 2018-10-09 CN CN201811173546.1A patent/CN111019027B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030023126A1 (en) * | 2000-01-24 | 2003-01-30 | Kostantinos Kourtakis | Gel catalysts and methods for their use in catalytic dehydrogenation processes |
CN1948243A (en) * | 2005-10-14 | 2007-04-18 | 中国人民解放军空军油料研究所 | Preparation method of high viscosity index poly alpha olefine synthetic oil |
CN103159875A (en) * | 2011-12-09 | 2013-06-19 | 中国石油化工股份有限公司 | Chromium-polyethylene catalyst |
CN103666552A (en) * | 2012-09-04 | 2014-03-26 | 中国石油天然气股份有限公司 | Preparation method of medium-viscosity poly-alpha-olefin base oil |
CN106881119A (en) * | 2015-12-16 | 2017-06-23 | 中国石油天然气股份有限公司 | Poly alpha-olefin synthetic oil catalyst and its preparation method |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113337311A (en) * | 2021-04-16 | 2021-09-03 | 华东理工大学 | Ultra-high viscosity index poly-alpha-olefin base oil and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN111019027B (en) | 2022-03-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5068487A (en) | Olefin oligomerization with BF3 alcohol alkoxylate co-catalysts | |
CN103666552B (en) | Preparation method of medium-viscosity poly-alpha-olefin base oil | |
CN111019734B (en) | Poly alpha-olefin base oil and preparation method thereof | |
WO2015087303A2 (en) | Catalyst compositions for selective dimerization of ethylene | |
CN102060646B (en) | Method for synthesizing 1-decene oligomer | |
JP2013512328A (en) | Production of oligomers from nonene | |
EP0477673A1 (en) | Process for producing olefin oligomer | |
CN111019027B (en) | Catalyst for oligomerization of 1-decene and preparation method and application thereof | |
CN106881119A (en) | Poly alpha-olefin synthetic oil catalyst and its preparation method | |
WO2002051777A1 (en) | Process for producing low polymer of ethylene | |
US4048109A (en) | Oligomerization process and catalysts therefor | |
CN106883899B (en) | Preparation method of poly alpha-olefin synthetic oil with high viscosity index | |
CN111013611B (en) | Preparation method of olefin polymerization catalyst and preparation method of poly alpha-olefin base oil | |
CN113637103B (en) | Preparation method of ultra-high viscosity poly alpha-olefin synthetic base oil | |
CN109369836A (en) | A kind of cyclopentadienyl rare-earth metal carbon monoxide-olefin polymeric and its application containing heterocycle structure | |
EP0139343B1 (en) | Method for the oligomerization of alpha-olefins | |
CN113150826B (en) | Low-viscosity and high-viscosity index poly alpha-olefin base oil and preparation method thereof | |
CN103305263A (en) | Preparation method of poly alpha-olefin base oil with high viscosity index | |
CN111013610A (en) | Immobilized Lewis acid catalyst, preparation method thereof and α -olefin oligomerization reaction using catalyst | |
US2980744A (en) | Preparation of viscous polymers | |
CN110041457B (en) | Alpha-olefin polymerization catalyst, preparation method thereof and alpha-olefin polymerization method | |
CN114618588A (en) | Catalyst system for ethylene oligomerization and oligomerization method | |
JPS6126561B2 (en) | ||
US3810952A (en) | Liquid copolymers of 1,3-butadiene and 1-monoolefins,their preparation and uses | |
RU2666736C1 (en) | Method for producing synthetic high viscosity polyalphaolefin base oils |
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 |