CN113185998B - Narrow-distribution PAO base oil taking C8-C10 alpha-olefin tetramer as main component and preparation method thereof - Google Patents

Narrow-distribution PAO base oil taking C8-C10 alpha-olefin tetramer as main component and preparation method thereof Download PDF

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CN113185998B
CN113185998B CN202110411029.9A CN202110411029A CN113185998B CN 113185998 B CN113185998 B CN 113185998B CN 202110411029 A CN202110411029 A CN 202110411029A CN 113185998 B CN113185998 B CN 113185998B
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pao
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米普科
江铃
卢攀峰
赵瑞达
高针针
虞惠艳
董素琴
尹萌
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East China University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • 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
    • C10G69/126—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 polymerisation, e.g. oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1088—Olefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/302—Viscosity
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/304—Pour point, cloud point, cold flow properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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 a C8-C10 alpha-olefin tetramer as a main component. The preparation method of the PAO comprises the following steps of firstly, catalyzing C8-C10 alpha-olefin to perform oligomerization at a temperature range of 50-120 ℃ under an aluminum-zirconium ratio of 1-1000; and then catalyzing alpha-olefin dimer by using an AlCl3 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

Narrow-distribution PAO base oil with C8-C10 alpha-olefin tetramer as main component and preparation method thereof
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, when used as single-phase, multi-phase lubricating oils, varies greatly with ambient temperature and is relatively low. 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 is minimized to improve the oxidative stability of synthetic 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. U.S. Pat. No. 5,284,988 to Schaerf et al teaches a process for preparing a wide range of synthetic lubricating oils to meet the different viscosity requirements 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 scoffllon, 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, 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 realize the 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 PAO is synthesized, the C8-C10 alpha-olefin needs to be subjected to necessary water removal treatment, and meanwhile, argon is introduced for protection, and the mixture is 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 filled with argon and filled with water and oxygen to remove, heating to a proper temperature of between 50 and 120 ℃, adding a cocatalyst MAO, wherein the aluminum-zirconium ratio is between 100 and 1000, adding a metallocene catalyst dissolved in toluene to react for 2 to 10 hours, stopping the reaction, adding ethanol hydrochloride (29. 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 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 present invention have the formula [ (C6H 5) C (CH 3) 2 (. Eta.5-C5H 4) ]2ZrCl2, [ nBuC (CH 3) 2 (. Eta.5-C5H 4) ]2ZrCl2, [ CH3O (CH 2) 2 (. Eta.5-C5H 4) ]2ZrCl2.
Constrained geometry metallocenes are ideal catalysts for PAO polymerization. The constrained geometry metallocene used in the present invention has the formula: tbucnc (CH 3) 2 (η 5-C5H 4) ZrCl2, tbucncch 3 (C6H 5) (η 5-C5H 4) ZrCl2, tbucch (C6H 5) (η 5-C5H 4) ZrCl2, tbucnc (C5H 10) (η 5-C5H 4) ZrCl2, nbucc (CH 3) 2 (η 5-C5H 4) ZrCl2, CH2= CHCH2NC (CH 3) 2 (η 5-C5H 4) ZrCl2, tbucnsi (CH 3) 2 (η 5-C5H 4) ZrCl2, tbucc (CH 3) 2 (η 5-C5H 4) TiCl2, (C5H 10) NC (CH 3) 2 (η 5-C5H 4) ZrCl2, and the structural formulae are:
Figure RE-GDA0003116942400000031
(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, the dianion is a [ MAO-CH3- ] anion formed by MAO and CH3-, the metallocene alkyl cation can be stabilized, and the metallocene alkyl cation can be stabilized by forming a crown aluminoxane complex with the cation to prevent the catalyst from being deactivated in a bimolecular reaction mode by a mechanism similar to that of stabilizing the cation by crown ether, 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 dipping 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; and drying the impregnated carrier at 80 ℃ for 3 hours, roasting the impregnated carrier in a muffle furnace at 600 ℃ for 6 hours, and putting the impregnated carrier in a glove box for later use. Then, anhydrous acll 3, 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 protection 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-lCl 3 catalyst is obtained and stored in a water-free and oxygen-free state for later use.
(6) The single-component lubricating oil PAO prepared from the solid-supported AlCl3 polymeric dimer is characterized in that: adding the immobilized AlCl3 into the dimer, adding a small amount of cocatalyst (ethanol, distilled water, butanone, n-butyl ether and the like, wherein the molar ratio of the added ethanol to AlCl3 is 0-1.5), maintaining the temperature between 70 and 150 ℃, reacting for 3 to 12 hours, finishing the reaction, washing with 8 percent NaOH for three times, washing with deionized water to be neutral, and distilling under reduced pressure to remove residual water and unreacted dimer, thereby obtaining 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 to 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 to C10 obtained in the step (2) under the conditions of temperature of 160 to 220 ℃, pressure of 2.0 to 3.0MPa, space velocity of 0.5 to 1.0 hour < -1 > and hydrogen-oil ratio of 500 to 750, so as 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) Impregnating a 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 verhart 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 21.85 mg of catalyst tBuNC (CH 3) 2 (. Eta.5-C5H 4) ZrClI, and reacted for 6 hours at a reaction temperature of 75 ℃. After the reaction was completed, 10 ml of ethanol hydrochloride solution (1. Distilling at 150 deg.C under normal pressure to remove solvents such as ethanol and toluene to obtain 1-decene oligomerization mixture; the monomer conversion was calculated to be 79.5%, with the 1-decene dimer content of the 1-decene oligomer mixture being 61.5%, the 1-decene trimer content being 28.1%, the 1-decene tetramer content being 8.6%, and the 1-decene pentamer content being 1.8% or more. 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 96.79 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 the example 1, wherein the molar ratio of the tert-butyl alcohol cocatalyst to the 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 ℃, 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 to C10:
the poly alpha-olefin oligomer is subjected to hydrogenation reaction by using a Mo-Ni-Fe/gamma-Al 2O3 catalyst under the conditions of the temperature of 200 ℃, the pressure of 2.0MPa, the space velocity of 1.0 hour-1 and the hydrogen-oil ratio of 750.
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 2.05 mg of catalyst tBuNC (CH 3) 2 (. Eta.5-C5H 4) ZrCl2, and reacted for 2 hours at a reaction temperature of 120 ℃. After the reaction was completed, 10 ml of ethanol hydrochloride solution (1. 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 the 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 ℃, collecting fractions above 130 ℃ to obtain the C8-C10 poly alpha-olefin oligomer, wherein the yield of the oligomer is 60.5%.
(3) Hydrogenation of poly-alpha-olefin oligomers of C8 to C10:
the poly alpha-olefin oligomer is subjected to hydrogenation reaction by using a Mo-Ni-Fe/gamma-Al 2O3 catalyst under the conditions of the temperature of 200 ℃, the pressure of 2.0MPa, the space velocity of 1.0 hour-1 and the hydrogen-oil ratio of 750.
The final PAO base oil has a kinematic viscosity of 5.60cSt at 100 ℃, 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 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 above accounts for 14.9 percent.
Example 4:
(1) Oligomerization reaction of alpha-olefin:
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 50 ℃, added with 2.00 ml of 10% MAO solution, stirred evenly, added with 2.0 mg of catalyst [ nBuC (CH 3) 2 (. Eta.5-C5H 4) ]2ZrCl2, and reacted for 10 hours at 50 ℃. After the reaction was completed, 10 ml of ethanol hydrochloride solution (1. 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 the example 1, wherein the molar ratio of the ethanol cocatalyst to the 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 ℃, collecting fractions above 130 ℃ to obtain the C8-C10 poly alpha-olefin oligomer, wherein the yield of the oligomer is 75.1%.
(3) Hydrogenation of poly-alpha-olefin oligomers of C8 to C10:
the poly alpha-olefin oligomer is subjected to hydrogenation reaction by using a Mo-Ni-Fe/gamma-Al 2O3 catalyst under the conditions of the temperature of 200 ℃, the pressure of 2.0MPa, the space velocity of 1.0 hour-1 and the hydrogen-oil ratio of 750.
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 GC-Ms data analysis of the PAO base oil can obtain that the contents of all the components in the oligomer are as follows: 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 2.2 mg of catalyst tBuNSi (CH 3) 2 (. Eta.5-C5H 4) ZrCl2, and reacted for 8 hours at 80 ℃. After the reaction was completed, 10 ml of ethanol hydrochloride solution (1. Distilling at 150 deg.C under normal pressure to remove solvents 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 to collect 105-126 ℃ fraction to obtain 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 the example 1, wherein the molar ratio of the ethanol cocatalyst to the 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 ℃, collecting fractions above 130 ℃ to obtain the C8-C10 poly alpha-olefin oligomer, wherein the yield of the oligomer is 65.1%.
(3) C8-C10 poly alpha-olefin oligomer hydrogenation:
the poly alpha-olefin oligomer is subjected to hydrogenation reaction by using a Mo-Ni-Fe/gamma-Al 2O3 catalyst under the conditions of the temperature of 200 ℃, the pressure of 2.0MPa, the space velocity of 1.0 hour-1 and the hydrogen-oil ratio of 750.
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:
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 2.50 ml of 10% MAO solution, stirred evenly, added with 2.5 mg of catalyst [ nBuC (CH 3) 2 (. Eta.5-C5H 4) ]2ZrCl2, and reacted for 5 hours at a reaction temperature of 100 ℃. After the reaction was completed, 10 ml of ethanol hydrochloride solution (1. 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 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 C8-C10 poly alpha-olefin oligomer, wherein the yield of the oligomer is 72.3%.
(3) Hydrogenation of poly-alpha-olefin oligomers of C8 to C10:
the poly alpha-olefin oligomer is subjected to hydrogenation reaction by using a Mo-Ni-Fe/gamma-Al 2O3 catalyst under the conditions of temperature of 200 ℃, pressure of 2.0MPa, space velocity of 1.0 hour-1 and hydrogen-oil ratio of 750.
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 has a kinematic viscosity of 5.36cSt at 100 ℃, 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 a hydrocarbon having an average molecular weight of about 226 g/mol, i.e., octene dimer, was 9.1%, the content of a hydrocarbon having an average molecular weight of about 452 g/mol, i.e., octene tetramer, was 85.7%, and the content of an oligomer having an average molecular weight distribution of greater than 660 g/mol or more was 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 merely 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 the protection scope of the present invention.

Claims (2)

1. A preparation method of narrow-distribution PAO base oil taking C8-C10 alpha-olefin tetramer as a main component 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, and controlling the ratio of aluminum to zirconium to be 400-105 mg of metallocene catalyst is added between 00 hours for reaction for 2 to 10 hours, after the reaction is finished, 10 to 30 ml of ethanol solution of hydrochloric acid with the molar ratio of 1; (2) The catalyst used for the alpha-olefin dimer re-reaction is solid-supported AlCl 3 Catalysts, in particular nickel-doped AlCl 3 The gamma-alumina contains 0.30 to 0.45 percent of nickel metal and 10.2 to 15.50 percent of chlorine; the cocatalyst is ethanol, tert-butyl alcohol, cocatalyst and AlCl 3 The molar ratio is 0.5; 5 to 10g of solid-carried AlCl 3 Adding 100-200 g of C8-C10 alpha-olefin dimer separated in the step (1) into a catalyst, adding 0.01-0.10 g of cocatalyst, heating to 70-150 ℃, reacting for 3-10 hours, washing with 8-percent NaOH after the reaction is finished, washing with deionized water to be neutral, and distilling under reduced pressure under the vacuum degree of 0.60-0.80 mm Hg to remove fractions below 135 ℃ to obtain C8-C10 poly alpha-olefin oligomer; (3) Fe in atomic weight ratio: ni: mo is 0.05-0.15: 0.25 to 0.28:1 of Mo-Ni-Fe/gamma-Al 2 O 3 The catalyst is prepared at the temperature of 160-220 ℃, the pressure of 2.0-3.0 MPa and the space velocity of 0.5-1.0 hour -1 And (3) carrying out hydrogenation reaction on the C8-C10 poly alpha-olefin oligomer obtained in the step (2) under the condition that the hydrogen-oil ratio is 500-750, so as to obtain the alpha-olefin oligomer PAO which takes the C8-C10 alpha-olefin tetramer as a main component and has narrow distribution, low viscosity and high viscosity index.
2. The method for preparing the narrow-distribution PAO base oil by using the tetramer of the alpha-olefin as the main component in the claim 1 is characterized in that: the metallocene catalyst in the step (1) is [ nBuC (CH) 3 ) 2 (η 5 -C 5 H 4 )] 2 ZrCl 2 、tBuNC(CH 3 ) 2 (η 5 -C 5 H 4 ) ZrCl 2 And tBuNSi (CH) 3 ) 2 (η 5 -C 5 H 4 ) ZrCl 2 。
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