CN111019027B - 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
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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 alpha-olefin oligomerization, a preparation method and application thereof, in particular to a catalyst for 1-decene oligomerization, a preparation method and application thereof.
Background
With the development of the times, the demand for lubricating oils in the market is increasing more and more, and therefore the demand for high quality lubricating oils is significantly increasing. Synthetic lubricating oils have superior properties compared to conventional mineral oils, such as: kinetic viscosity (Kv), Viscosity Index (VI), Pour Point (PP), volatility, etc. The synthetic lubricating oil has better thermal performance and oxidation resistance, and better sensitivity and ignition point performance than mineral lubricating oil. Compared with mineral oil with the same viscosity, the synthetic oil has the advantages of superior viscosity-temperature performance, pour point, condensation point, VI, high-temperature thermal oxidation stability, evaporation loss and sensitivity to additives to the mineral oil, less coking, no toxicity, skin infiltration and the like. Polyalphaolefins in synthetic oils have been developed as one of the fastest growing types, and catalysts for synthesizing polyalphaolefins are mainly of Lewis acid type, Ziegler-Natta type, metallocene type, ionic liquid type. Different catalytic systems and different product properties.
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 large pore diameter can improve the conversion rate of oligomerization reaction, reduce the carrier blocking phenomenon and increase the carrierThe catalyst is recycled, 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 application of the catalyst in oligomerization of 1-decene and the application thereofIn the method, the 1-decene oligomer is hydrogenated to 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 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-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 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.
The application of alpha-olefin oligomerization catalyst is 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 as example 3, the application of the catalyst for oligomerization of alpha-olefins, 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 as example 3, the application of the catalyst for oligomerization of alpha-olefins, 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 as example 3, the application of the catalyst for oligomerization of alpha-olefins, 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 as example 3, the application of the catalyst for oligomerization of alpha-olefins, 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 (9)
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 a catalyst with the chromium content of 1.05-3.36 wt%;
the gamma-alumina carrier is a spherical or strip-shaped alumina carrier, the diameter of the spherical gamma-alumina carrier is 1.3-2.3 mm, and the specific surface area is 100-180 m2The total pore volume is more than or equal to 1.25mL/g, and the mass ratio of the trivalent chromium acetate to the spherical gamma-alumina is 1: 6-9;
the molar ratio of the alkyl aluminum or substituted alkyl aluminum to the trivalent chromium acetate is 1-2: 1.
2. 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.
3. The method of claim 1, wherein the solvent is acetic acid.
4. The method for preparing a 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.
5. The catalyst for oligomerization of 1-decene prepared by the method according to any one of claims 1 to 4.
6. The application of the catalyst in oligomerization of 1-decene as described in claim 5, 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 for 4-10 h in the presence of a cocatalyst.
7. The use of the catalyst of claim 6 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.
8. The application of the catalyst in oligomerization of 1-decene as claimed in claim 6, wherein the reaction temperature is 100 ℃ and the reaction time is 8-10 h in the oligomerization of 1-decene.
9. The application of the catalyst in oligomerization of 1-decene according to claim 6, 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.
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| 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 |
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| 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 |
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