CN113185998A - Narrow-distribution PAO base oil with C8-C10 alpha-olefin tetramer as main component and preparation method thereof - Google Patents
Narrow-distribution PAO base oil with C8-C10 alpha-olefin tetramer as main component and preparation method thereof Download PDFInfo
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
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- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
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Abstract
The invention relates to an alpha-olefin oligomer PAO with narrow distribution, low viscosity and high viscosity index and a preparation method thereof, wherein the alpha-olefin oligomer PAO takes C8-C10 alpha-olefin tetramer as a main component. Firstly, carrying out oligomerization on alpha-olefin of C8-C10 at the temperature of 50-120 ℃ and the aluminum-zirconium ratio of 100: 1-1000: 1 by using metallocene as a catalyst for catalyzing, wherein the reaction time is 2-10 hours, distilling at normal pressure to remove a solvent, distilling at reduced pressure to remove an alpha-olefin monomer, separating an alpha-olefin dimer, wherein the conversion rate of the reaction monomer is more than 60%, and the kinematic viscosity of the separated alpha-olefin dimer at 100 ℃ is 1.8-2.9 cSt; and catalyzing the alpha-olefin dimer by using an AlCl 3-supported catalyst at the temperature of 70-150 ℃, reacting for 3-12 hours, washing the alpha-olefin dimer to be neutral by using a NaO hour solution and distilled water after the reaction is finished, removing the solvent by normal pressure distillation, and removing unreacted monomers by reduced pressure distillation to finally obtain the PAO with narrow distribution, low viscosity and high viscosity index by using the alpha-olefin tetramer as a main component.
Description
Technical Field
The invention relates to a method for synthesizing alpha-olefin (PAO) with narrow distribution, low viscosity and high viscosity index by using an alpha-olefin tetramer as a main component through a two-step method, which mainly comprises the following steps: in the first step, metallocene is used to catalyze alpha-olefin to synthesize low-viscosity oligomer, and high-purity alpha-olefin dimer is obtained through separation, and in the second step, Lewis acid is used to catalyze the alpha-olefin dimer obtained through separation in the first step.
Background
In recent years, petroleum plants are all dedicated to synthesizing oligomeric hydrocarbons to improve the performance of natural mineral base oil, and high-grade base oil is developed towards low viscosity and high viscosity index. The industry's search for synthetic lubricating oils has focused primarily on increasing the viscosity of the fluids available over a wide temperature range, having higher viscosity index, better lubricating ability, thermal stability, oxidation stability and low pour point compared to mineral oils, and having low coefficients of friction and therefore higher mechanical efficiency than mineral oils when applied under a range of operating conditions and loads.
The viscosity-temperature relationship of lubricating oils is considered to be a key index, and the viscosity of mineral oils used as single-phase, multi-phase lubricating oils varies greatly with ambient temperature, with a low viscosity index. Lubricating oils with high viscosity index are desirable, and still have a higher viscosity at high temperatures, allowing for better lubrication and protection in machine applications. VI is calculated according to ASTM method D2270.
PAOs are synthetic hydrocarbons which may be used as lubricating base oils and are synthesized from alpha olefin monomers, typically 1-octene to 1-dodecene, 1-decene being most desirable, although copolymers of ethylene and propylene, or ethylene and high molecular weight olefins as described in U.S. Pat. No. 4,956,122, are also known. The PAOs have good flowing property at low temperature, relatively high thermal stability and oxidation stability, small steam loss at high temperature, high viscosity index, good friction property, good hydraulic stability and good wear resistance. PAOs are non-toxic and miscible with mineral oils or greases, and are therefore suitable for use as engine oils, compressor oils, hydraulic oils, gear oils or greases. PAOs contain tertiary hydrogens that are easily oxidized and have reduced stability, so the amount of tertiary hydrogens should be minimized to improve the oxidative stability of synthesized hydrocarbons.
Metallocene catalysts are pioneering new catalysts that have been commercialized in the early 90 s and are causing a revolution in the polyolefin industry. The metallocene catalyst has the advantages of high catalytic activity, narrow relative molecular weight distribution of the generated polymer, controllable polymer structure, tailorable polymer molecules and the like. Schaerf et al, in patent US5,284,988, propose a process for preparing a wide range of synthetic lubricating oils to meet the varying viscosity needs of the market. The preparation process comprises two steps: (a) a part of olefin is catalyzed to generate isomerization, and an intermediate containing trisubstituent is generated; (b) then polymerizing the intermediates, and synthesizing the polymer in the presence of an oligomerization catalyst.
The company scofflon, in patent US8,536,391, proposes a process for the synthesis of PAOs from supported metallocene-catalyzed alpha-olefins, using a metallocene catalyst system comprising: metallocenes and solid oxides chemically treated with electron-withdrawing anions. The produced poly-alpha-olefin and PAOs have high viscosity index and low pour point, KV at 100 deg.C is 20-1200cSt, pour point is less than 20 deg.C, PAOs are mainly head-tail bonded, and have great application value in lubricating oil and viscosity correction. The products are mainly alpha-olefin homopolymers without olefin monomers, hydrogenated alpha-olefin homopolymers and alpha-olefin copolymers, and hydrogenated alpha-olefin copolymers. Experiments have found that in metallocene olefin polymerisation catalysts, long chain alpha olefins (C3 and above) are affected by the metallocene and related catalyst components, i.e. the metallocene and the solid oxide chemically treated with an electron withdrawing anion.
One difficulty in the synthesis of oligomeric oils from alpha olefins is the separation of the different components from the polymerization product mixture based on their different viscosities; another difficulty is that the chemical process has difficulty controlling the isomerization of alpha olefins; a third problem is that this process often produces large amounts of dimers that are not suitable for use as lubricating oils. The invention adopts a homogeneous metallocene catalyst system with a single active center, and adopts a two-step method to produce oligomer base oil which has narrow distribution, low viscosity and high viscosity index and meets the market demand.
Disclosure of Invention
The present invention has been made in view of the above facts, and an object thereof is to synthesize a polyalphaolefin PAO having a narrow distribution, a low viscosity and a high viscosity index by a two-step process.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
(1) alpha-olefin monomer treatment:
desirably, the alpha-olefin has one hydrogen atom on the second carbon atom, at least two hydrogen atoms on the third carbon atom, or at least one hydrogen atom on the fourth carbon atom. The alpha-olefins used in the PAO synthesis are typically C8 to C10 alpha-olefins. Before synthesizing PAO, the C8-C10 alpha-olefin needs to be subjected to necessary water removal treatment, and simultaneously needs to be introduced with argon for protection and sealed for standby.
(2) The metallocene catalyst is used for catalyzing alpha-olefin oligomerization and is characterized in that: adding a certain amount of C8-C10 alpha-olefin into a three-neck flask which is filled with argon and is used for removing water and oxygen, heating to a proper temperature of 50-120 ℃, adding a cocatalyst MAO, wherein the ratio of aluminum to zirconium is 100-1000, adding a metallocene catalyst dissolved in toluene, reacting for 2-10 hours, adding hydrochloric acid ethanol (29:1) to terminate the reaction after the reaction is finished, filtering, distilling under normal pressure to remove a terminator and a solvent, and distilling under reduced pressure to remove unreacted monomers to obtain the poly alpha-olefin PAO in the first step. The poly-alpha-olefin PAO obtained in the first step has the conversion rate of 60-90 w%, the KV at 100 ℃ of 2-3 cSt, the viscosity index VI of more than 150 and the dimer content of more than 60%.
(3) Metallocene catalysts suitable for use in catalyzing the oligomerization of alpha-olefins can be classified into non-bridged, and constrained geometry types. The non-bridged metallocene catalyst is a halogenated or alkylated transition metal compound with common cyclopentadienyl (such as cyclopentadienyl, indenyl, fluorenyl, etc.) as ligand. The non-bridged metallocenes which can be used in the invention have the formula [ (C6H5) C (CH3)2 (. eta.5-C5H 4) ]2ZrCl2, [ nBuC (CH3)2 (. eta.5-C5H 4) ]2ZrCl2, [ CH3O (CH2)2 (. eta.5-C5H 4) ]2ZrCl 2.
Constrained geometry metallocenes are ideal catalysts for PAO polymerization. The constrained geometry metallocene used in the present invention has the formula: tBuNC (CH) 2 (. eta.5-C5H) ZrCl, tBuNCCH (C6H) (. eta.5-C5H) ZrCl, tBuNCH (C6H) (. eta.5-C5H) ZrCl, tBuNC (CH) 2 (. eta.5-C5H) ZrCl, CH ═ CHCH2 (CH) 2 (. eta.5-C5H) ZrCl, tBuNSi (CH) 2 (. eta.5-C5H) ZrCl, tBuNC (CH) 2 (. eta.5-C5H) TiCl, tBuNC (C6H 4) 2 (. eta.5-C5H) TiCl, (C5H) NC (CH) 2 (. eta.5-C5H) ZrCl, the structural formula is:
(4) the cocatalyst may be an aluminum oxy compound (methyl aluminum compound), a trialkyl aluminum compound, an alkyl aluminum hydride compound, an alkyl halogen compound, an organozinc compound, an organomagnesium compound, an organoboron compound, an ionic compound, a borate compound, an aluminate compound, or a mixture thereof. The invention uses MAO (10 wt% toluene solution), and the main function of the catalyst promoter MAO in the olefin polymerization process is as follows: removing impurities in the reaction system; methylating the metallocene complex to promote the formation of alkylated cationic active sites; the methylated metallocene complex is eliminated by Cl-HCH 3-to form a metallocene alkyl cation with 14 electron system, and the dianion is a [ MAO-CH3- ] anion formed by MAO and CH3-, so that the metallocene alkyl cation can be stabilized, and the catalyst is prevented from being deactivated in a bimolecular reaction mode by forming a crown aluminoxane complex stabilizing cation with the cation in a similar mechanism of crown ether stabilizing cation, wherein the ratio of Al: the Zr ratio is between 100 and 1000.
(5) In addition, before synthesis, a catalyst needs to be prepared in advance, and the preparation method of the supported AlCl3 comprises the following steps: soaking Al2O3 in an equal volume of 1mol/L soaking solution for 6 hours; the impregnation solution can be hydrochloric acid, sodium carbonate, nickel sulfate, mixed solution of hydrochloric acid and nickel sulfate, and mixed solution of sodium carbonate and sodium sulfate; then the impregnated carrier is dried for 3 hours at 80 ℃, then roasted for 6 hours in a muffle furnace at 600 ℃, and placed in a glove box for standby. Then anhydrous A lCl3, the pretreated carrier and the solvent were added in proportion to a round-bottomed flask equipped with a magnetic stirrer, and a reflux reaction was performed under argon shield for 3 hours. After the reaction is finished, the immobilized catalyst particles are filtered and filtered, and are washed for 3 times by using a solvent, and then the immobilized catalyst particles are dried to remove the solvent, so that the whole process is free of water and oxygen. Finally, the immobilized alpha lCl3 catalyst is obtained and is stored in an anhydrous and anaerobic state for later use.
(6) The single-component lubricating oil PAO prepared by polymerizing dipolymer with solid-supported AlCl3 is characterized in that: adding the immobilized AlCl3 into a dimer, adding a small amount of cocatalyst (ethanol, distilled water, butanone, n-butyl ether and the like, wherein the molar ratio of the addition amount of the ethanol to AlCl3 is 0-1.5), maintaining the temperature at 70-150 ℃, reacting for 3-12 hours, washing for three times by using 8% NaOH after the reaction is finished, washing to be neutral by using deionized water, and removing residual water and unreacted dimer through reduced pressure distillation to obtain the narrow-distribution, low-viscosity and high-viscosity single-component alpha-olefin PAO. The conversion rate of the obtained PAO is 60-80 w%, the KV at 100 ℃ is 5.5-7 cSt, the viscosity index VI is 140-150, and the tetramer content is more than 77%.
(7) Fe in atomic weight ratio: ni: mo is 0.05-0.15: 0.25-0.28: the Mo-Ni-Fe/gamma-Al 2O3 catalyst of 1 is used for carrying out hydrogenation reaction on the poly alpha-olefin oligomer of C8-C10 obtained in the step (2) under the conditions of temperature of 160-220 ℃, pressure of 2.0-3.0 MPa, space velocity of 0.5-1.0 hour < -1 > and hydrogen-oil ratio of 500-750: 1 to obtain the final PAO base oil.
The specific implementation mode is as follows:
the following description relates to a specific embodiment of the method for synthesizing a narrow-distribution PAO containing an alpha-olefin tetramer as a main component. The present invention is not limited to the following embodiments.
EXAMPLE 1 preparation of Nickel doped AlCl 3/gamma-alumina Supported catalyst
The preparation of the nickel-doped AlCl 3/gamma-alumina supported catalyst comprises the following steps:
(1) dipping the gamma-alumina carrier
Dipping the gamma-alumina carrier in 0.5M (mol/L, i.e. mol/L) nickel sulfate solution for 2 hours at room temperature, then drying in vacuum, and roasting at high temperature of 800 ℃ for 2 hours; the high-temperature roasting in the step is carried out under the protection of inert gas;
(2) carrying out solution immobilization on aluminum trichloride
Under the protection of inert gas, 10g of anhydrous aluminum trichloride is prepared into a solution in 150ml of toluene solvent, then the solution is added into 15g of alumina carrier which is activated by dipping treatment, the solution is kept for 4 hours at the reflux temperature, the organic solvent is removed by filtration, the supported catalyst is washed by the organic solvent, and the alpha-olefin oligomerization supported catalyst is obtained after vacuum drying.
Elemental content determination was performed by verhardard titration on the aluminum trichloride supported catalyst prepared in example 1, and the chlorine content was 10.86 ω% and the nickel content was 0.35%.
Example 2
(1) Oligomerization of alpha-olefins:
the treated 100 ml of 1-decene monomer is injected into a dry, sealed and argon-filled three-neck flask, heated to a preset temperature of 65 ℃, added with 2.00 ml of 10 percent MAO solution, stirred evenly, added with a catalyst of tBuNC (CH3)2 (. eta.5-C5H 4) ZrCl21.85 mg, and reacted for 6 hours at a reaction temperature of 75 ℃. After the reaction, 10 ml of ethanol hydrochloride solution (1:29 vol.) was added to terminate the reaction. Distilling at 150 deg.C under normal pressure to remove solvent such as ethanol and toluene to obtain 1-decene oligomerization mixture; the monomer conversion was calculated to be 79.5%, the 1-decene dimer content in the 1-decene oligomerization mixture was 61.5%, the 1-decene trimer content was 28.1%, the 1-decene tetramer content was 8.6%, and the 1-decene pentamer content was 1.8% or higher. Carrying out reduced pressure distillation under the vacuum degree of 0.50-0.80 mm Hg, and collecting 105-126 ℃ fractions to obtain a 1-decene dimer product; the mass percentage of the separated alpha-olefin dimer is more than 96.79 percent.
(2) Alpha-olefin dimer re-reaction:
adding 150 g of 1-decene oligomer dimer into an anhydrous and oxygen-free argon-filled three-neck flask, heating to 70 ℃, adding 10g of the nickel-doped AlCl 3/gamma-alumina supported catalyst prepared in example 1, wherein the molar ratio of the tert-butyl alcohol cocatalyst to AlCl3 is 0.5, reacting for 10 hours, performing alkali washing and water washing on the product after the reaction is finished, performing reduced pressure distillation under the vacuum degree of 0.50-0.80 mm Hg to remove fractions below 130 ℃, and collecting fractions above 130 ℃ to obtain the C8-C10 poly alpha-olefin oligomer, wherein the yield of the oligomer is 66.4%.
(3) Hydrogenation of poly-alpha-olefin oligomers of C8-C10:
the poly alpha-olefin oligomer is hydrogenated by using a Mo-Ni-Fe/gamma-Al 2O3 catalyst under the conditions of 200 ℃ of temperature, 2.0MPa of pressure, 1.0 hour-1 of space velocity and 750:1 of hydrogen-oil ratio.
The final PAO base oil had a kinematic viscosity at 100 ℃ of 6.68cSt, a viscosity index of 145, a pour point of-53 ℃ and a bromine number of 0.029 bromine g/100g PAO.
The contents of all components in the oligomer are as follows according to the analysis of GC-Ms data of PAO base oil: the content of hydrocarbon (namely, decene dimer) with the average molecular weight of 282 g/mol is 5.4 percent, the content of hydrocarbon (namely, decene tetramer) with the average molecular weight of about 564 g/mol is 82.0 percent, and the content of oligomer with the average molecular weight distribution of more than 680 g/mol and more accounts for 12.6 percent.
Example 3:
(1) oligomerization of alpha-olefins:
the treated 100 ml of 1-decene monomer is injected into a dry, sealed and argon-filled three-neck flask, heated to a preset temperature of 65 ℃, added with 2.00 ml of 10 percent MAO solution, stirred evenly, added with the catalyst tBuNC (CH3)2 (. eta.5-C5H 4) ZrCl22.05 mg, and reacted for 2 hours at 120 ℃. After the reaction, 10 ml of ethanol hydrochloride solution (1:29 vol.) was added to terminate the reaction. Distilling at 150 deg.C under normal pressure to remove solvent such as ethanol and toluene to obtain 1-decene oligomerization mixture; the monomer conversion was calculated to be 72.4% and the 1-decene dimer content in the 1-decene oligomerization mixture was 68.2%. Carrying out reduced pressure distillation under the vacuum degree of 0.50-0.80 mm Hg to collect 105-126 ℃ fraction to obtain 1-decene dimer product; the mass percentage of the separated alpha-olefin dimer is more than 97.3 percent.
(2) Alpha-olefin dimer re-reaction:
adding 150 g of 1-decene oligomer dimer into an anhydrous and oxygen-free argon-filled three-neck flask, heating to 150 ℃, adding 10g of the nickel-doped AlCl 3/gamma-alumina supported catalyst prepared in example 1, wherein the molar ratio of the tert-butyl alcohol cocatalyst to AlCl3 is 0.5, reacting for 3 hours, performing alkali washing and water washing on the product after the reaction is finished, performing reduced pressure distillation under the vacuum degree of 0.50-0.80 mm Hg to remove fractions below 130 ℃, and collecting fractions above 130 ℃ to obtain the poly alpha-olefin oligomer with the yield of 60.5 percent of C8-C10.
(3) Hydrogenation of poly-alpha-olefin oligomers of C8-C10:
the poly alpha-olefin oligomer is hydrogenated by using a Mo-Ni-Fe/gamma-Al 2O3 catalyst under the conditions of 200 ℃ of temperature, 2.0MPa of pressure, 1.0 hour-1 of space velocity and 750:1 of hydrogen-oil ratio.
The final PAO base oil has a kinematic viscosity at 100 ℃ of 5.60cSt, a viscosity index of 150, a pour point of-55 ℃ and a bromine number of 0.032 bromine g/100g PAO.
The contents of all components in the oligomer are as follows according to the analysis of GC-Ms data of PAO base oil: the content of hydrocarbon (namely, decene dimer) with the average molecular weight of 282 g/mol is 7.7 percent, the content of hydrocarbon (namely, decene tetramer) with the average molecular weight of about 564 g/mol is 77.4 percent, and the content of oligomer with the average molecular weight distribution of more than 680 g/mol and more accounts for 14.9 percent.
Example 4:
(1) oligomerization of alpha-olefins:
100 ml of the treated 1-decene monomer was poured into a dry, sealed and argon-filled three-neck flask, heated to a preset temperature of 50 ℃, 2.00 ml of 10% MAO solution was added, and after stirring, the catalyst [ nBuC (CH3)2 (. eta.5-C5H 4) ]2 ZrCl22.0 mg was added, and the reaction temperature was maintained at 50 ℃ for 10 hours. After the reaction, 10 ml of ethanol hydrochloride solution (1:29 vol.) was added to terminate the reaction. Distilling at 150 deg.C under normal pressure to remove solvent such as ethanol and toluene to obtain 1-decene oligomerization mixture; the monomer conversion was calculated to be 82.0% and the 1-decene dimer content in the 1-decene oligomerization mixture was 60.5%. Carrying out reduced pressure distillation under the vacuum degree of 0.50-0.80 mm Hg to collect 105-126 ℃ fraction to obtain 1-decene dimer product; the mass percentage of the separated alpha-olefin dimer is more than 96.0 percent.
(2) Alpha-olefin dimer re-reaction:
adding 150 g of 1-decene oligomer dimer into an anhydrous and oxygen-free argon-filled three-neck flask, heating to 120 ℃, adding 10g of the nickel-doped AlCl 3/gamma-alumina supported catalyst prepared in example 1, wherein the molar ratio of an ethanol cocatalyst to AlCl3 is 0.5, reacting for 3 hours, performing alkali washing and water washing on a product after the reaction is finished, performing reduced pressure distillation under the vacuum degree of 0.50-0.80 mm Hg to remove fractions below 130 ℃, and collecting fractions above 130 ℃ to obtain the poly alpha-olefin oligomer with the yield of 75.1 percent of C8-C10.
(3) Hydrogenation of poly-alpha-olefin oligomers of C8-C10:
the poly alpha-olefin oligomer is hydrogenated by using a Mo-Ni-Fe/gamma-Al 2O3 catalyst under the conditions of 200 ℃ of temperature, 2.0MPa of pressure, 1.0 hour-1 of space velocity and 750:1 of hydrogen-oil ratio.
The final PAO base oil has a kinematic viscosity at 100 ℃ of 7.56cSt, a viscosity index of 140, a pour point of-52 ℃ and a bromine number of 0.036 bromine g/100g PAO.
The contents of all components in the oligomer are as follows according to the analysis of GC-Ms data of PAO base oil: the content of hydrocarbon (i.e. decene dimer) with the average molecular weight of 282 g/mol is 8.4%, the content of hydrocarbon (i.e. decene tetramer) with the average molecular weight of about 564 g/mol is 79.8%, and the content of oligomer with the average molecular weight distribution of more than 680 g/mol and above accounts for 11.8%.
Example 5:
(1) oligomerization of alpha-olefins:
the treated 100 ml of 1-decene monomer is injected into a dry, sealed and argon-filled three-neck flask, heated to a preset temperature of 65 ℃, added with 2.80 ml of 10% MAO solution, stirred evenly, added with the catalyst tBuNSi (CH3)2 (. eta.5-C5H 4) ZrCl22.2 mg, and reacted for 8 hours at 80 ℃. After the reaction, 10 ml of ethanol hydrochloride solution (1:29 vol.) was added to terminate the reaction. Distilling at 150 deg.C under normal pressure to remove solvent such as ethanol and toluene to obtain 1-decene oligomerization mixture; the monomer conversion was calculated to be 92.0% and the 1-decene dimer content in the 1-decene oligomerization mixture was 66.8%. Carrying out reduced pressure distillation under the vacuum degree of 0.50-0.80 mm Hg, and collecting 105-126 ℃ fractions to obtain a 1-decene dimer product; the mass percentage of the separated alpha-olefin dimer is more than 97.2 percent.
(2) Alpha-olefin dimer re-reaction:
adding 150 g of 1-decene oligomer dimer into an anhydrous and oxygen-free argon-filled three-neck flask, heating to 70 ℃, adding 10g of the nickel-doped AlCl 3/gamma-alumina supported catalyst prepared in example 1, wherein the molar ratio of an ethanol cocatalyst to AlCl3 is 0.5, reacting for 10 hours, performing alkali washing and water washing on a product after the reaction is finished, performing reduced pressure distillation under the vacuum degree of 0.50-0.80 mm Hg to remove fractions below 130 ℃, and collecting fractions above 130 ℃ to obtain the poly alpha-olefin oligomer with the purity of C8-C10, wherein the yield of the oligomer is 65.1%.
(3) Hydrogenation of poly-alpha-olefin oligomers of C8-C10:
the poly alpha-olefin oligomer is hydrogenated by using a Mo-Ni-Fe/gamma-Al 2O3 catalyst under the conditions of 200 ℃ of temperature, 2.0MPa of pressure, 1.0 hour-1 of space velocity and 750:1 of hydrogen-oil ratio.
The final PAO base oil had a kinematic viscosity at 100 ℃ of 6.35cSt, a viscosity index of 141, a pour point of-53 ℃ and a bromine number of 0.034 bromine g/100g PAO.
The contents of all components in the oligomer are as follows according to the analysis of GC-Ms data of PAO base oil: the content of hydrocarbon (i.e. decene dimer) with the average molecular weight of 282 g/mol is 9.0%, the content of hydrocarbon (i.e. decene tetramer) with the average molecular weight of about 564 g/mol is 77.8%, and the content of oligomer with the average molecular weight distribution of more than 680 g/mol and above accounts for 13.2%.
Example 6:
(1) oligomerization of alpha-olefins:
100 ml of the treated 1-decene monomer was poured into a dry, sealed and argon-filled three-neck flask, heated to a preset temperature of 65 ℃, 2.50 ml of 10% MAO solution was added, and after stirring, the catalyst [ nBuC (CH3)2 (. eta.5-C5H 4) ]2 ZrCl22.5 mg was added, and the reaction temperature was maintained at 100 ℃ for 5 hours. After the reaction, 10 ml of ethanol hydrochloride solution (1:29 vol.) was added to terminate the reaction. Distilling at 150 deg.C under normal pressure to remove solvent such as ethanol and toluene to obtain 1-decene oligomerization mixture; the monomer conversion was calculated to be 86.2% and the 1-decene dimer content in the 1-decene oligomerization mixture was 62.2%. Carrying out reduced pressure distillation under the vacuum degree of 0.50-0.80 mm Hg to collect 105-126 ℃ fraction to obtain 1-decene dimer product; the mass percentage of the separated alpha-olefin dimer is more than 94.2 percent.
(2) Alpha-olefin dimer re-reaction:
adding 150 g of 1-decene oligomer dimer into an anhydrous and oxygen-free argon-filled three-neck flask, heating to 100 ℃, adding 10g of the nickel-doped AlCl 3/gamma-alumina supported catalyst prepared in example 1, wherein the molar ratio of an ethanol cocatalyst to AlCl3 is 0.5, reacting for 6 hours, performing alkali washing and water washing on a product after the reaction is finished, performing reduced pressure distillation under the vacuum degree of 0.50-0.80 mm Hg to remove fractions below 130 ℃, and collecting fractions above 130 ℃ to obtain the poly alpha-olefin oligomer with the yield of 72.3 percent of C8-C10.
(3) Hydrogenation of poly-alpha-olefin oligomers of C8-C10:
the poly alpha-olefin oligomer is hydrogenated by using a Mo-Ni-Fe/gamma-Al 2O3 catalyst under the conditions of 200 ℃ of temperature, 2.0MPa of pressure, 1.0 hour-1 of space velocity and 750:1 of hydrogen-oil ratio.
The final PAO base oil had a kinematic viscosity at 100 ℃ of 5.38cSt, a viscosity index of 142, a pour point of-54 ℃ and a bromine number of 0.030 bromine g/100g PAO.
Example 7:
steps (1) to (3) were the same as in example 2 except that 1-decene was replaced by 1-octene.
The final PAO base oil had a kinematic viscosity at 100 ℃ of 5.36cSt, a viscosity index of 133, a pour point of-55 ℃ and a bromine number of 0.033 bromine g/100g PAO.
The contents of all components in the oligomer are as follows according to the analysis of GC-Ms data of PAO base oil: the content of hydrocarbon with average molecular weight of about 226 g/mol, namely octene dimer is 9.1%, the content of hydrocarbon with average molecular weight of about 452 g/mol, namely octene tetramer is 85.7%, and the content of oligomer with average molecular weight distribution of more than 660 g/mol and above accounts for 5.2%.
Example 8:
steps (1) to (3) were the same as in example 2 except that 1-decene was replaced by 1-dodecene.
The final PAO base oil had a kinematic viscosity at 100 ℃ of 6.90cSt, a viscosity index of 136, a pour point of-51 ℃ and a bromine number of 0.030 bromine g/100g PAO.
Example 9:
steps (1) to (3) were the same as in example 3, except that 1-decene was replaced with 1-dodecene in step (2).
The final PAO base oil has a kinematic viscosity at 100 ℃ of 6.60cSt, a viscosity index of 142, a pour point of-52 ℃ and a bromine number of 0.031 bromine g/100g PAO.
The above examples are only preferred embodiments of the present invention.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the method of the present invention, and these modifications and decorations should be regarded as being within the protection scope of the present invention.
Claims (4)
1. A narrow-distribution PAO base oil taking a C8-C10 alpha-olefin tetramer as a main component is characterized in that: in the PAO, the content of C8-C10 alpha-olefin dimer is less than 10%, the content of C8-C10 alpha-olefin tetramer is more than 77%, the content of pentamer and above components is less than 15%, Kv100 ℃ of base oil is 5.6-6.9 cSt, and the viscosity index is 133-150.
2. The method for preparing the PAO base oil with narrow distribution and the main component of which is the tetramer of the C8-C10 alpha-olefin, as claimed in claim 1, is characterized by comprising the following steps: (1) adding 100-200 g of treated C8-C10 alpha-olefin into a three-neck flask which is filled with argon and is used for removing water and oxygen, heating to 50-120 ℃, adding a proper amount of cocatalyst MAO (wherein the aluminum-zirconium ratio is 400-1000), adding 5 mg of metallocene catalyst, reacting for 2-10 hours, adding 10-30 ml of ethanol solution of hydrochloric acid with a molar ratio of 1:29 after the reaction is finished, filtering to obtain a polymer mixture filtrate, distilling at 175 ℃ under normal pressure to remove a solvent and unreacted monomers, and carrying out reduced pressure distillation at a vacuum degree of 0.50-0.80 mm Hg to collect 105-126 ℃ fractions to obtain a C8-C10 alpha-olefin dimer product; (2) adding 5-10 g of supported AlCl3 catalyst into 100-200 g of C8-C10 alpha-olefin dimer separated in the step (1), adding 0.01-0.10 g of cocatalyst (water, ethanol, tert-butyl alcohol or the like), heating to 70-150 ℃, reacting for 3-10 hours, washing with 8% NaOH after the reaction is finished, washing with deionized water to be neutral, and removing fractions below 135 ℃ by reduced pressure distillation under the vacuum degree of 0.60-0.80 mm Hg to obtain C8-C10 poly alpha-olefin oligomer; (3) fe in atomic weight ratio: ni: mo is 0.05-0.15: 0.25-0.28: the catalyst Mo-Ni-Fe/gamma-Al 2O3 of 1 is used for carrying out hydrogenation reaction on the poly alpha-olefin oligomer of C8-C10 obtained in the step (2) under the conditions of temperature of 160-220 ℃, pressure of 2.0-3.0 MPa, space velocity of 0.5-1.0 hour < -1 >, and hydrogen-oil ratio of 500-750: 1 to obtain the alpha-olefin oligomer PAO with narrow distribution, low viscosity and high viscosity index, which takes C8-1C 10 alpha-olefin tetramer as a main component.
3. The method for preparing PAO with narrow distribution by using tetramer of alpha-olefin as main component according to claim 2, wherein: the metallocene catalyst in the step (1) is [ nBuC (CH3)2 (eta 5-C5H4) ]2ZrCl2, tBuNC (CH3)2 (eta 5-C5H4) ZrCl2, tBuNSi (CH3)2 (eta 5-C5H4) ZrCl2 and the like.
4. The method for preparing PAO with narrow distribution by using tetramer of alpha-olefin as main component according to claim 2, wherein: the supported AlCl3 catalyst in the preparation step (2) is nickel-doped AlCl 3/gamma-alumina, wherein the content of nickel metal is 0.30-0.45%, and the content of chlorine is 10.2-15.50%; the cocatalyst is ethanol, tert-butyl alcohol and the like, and the molar ratio of the cocatalyst to AlCl3 is 0.5.
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