CN116554920A - Preparation method of lubricating oil base oil - Google Patents
Preparation method of lubricating oil base oil Download PDFInfo
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- CN116554920A CN116554920A CN202210114227.3A CN202210114227A CN116554920A CN 116554920 A CN116554920 A CN 116554920A CN 202210114227 A CN202210114227 A CN 202210114227A CN 116554920 A CN116554920 A CN 116554920A
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- metallocene
- raw material
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- 239000002199 base oil Substances 0.000 title claims abstract description 54
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 77
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000002994 raw material Substances 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000012968 metallocene catalyst Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 230000001050 lubricating effect Effects 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000012190 activator Substances 0.000 claims description 8
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- VVNYDCGZZSTUBC-UHFFFAOYSA-N 5-amino-2-[(2-methylpropan-2-yl)oxycarbonylamino]-5-oxopentanoic acid Chemical compound CC(C)(C)OC(=O)NC(C(O)=O)CCC(N)=O VVNYDCGZZSTUBC-UHFFFAOYSA-N 0.000 claims description 5
- TUNXOQMJKRHUBH-UHFFFAOYSA-L [Cl-].[Cl-].[Zr++].CCCC1=CC=CC1.CCCC1=CC=CC1 Chemical compound [Cl-].[Cl-].[Zr++].CCCC1=CC=CC1.CCCC1=CC=CC1 TUNXOQMJKRHUBH-UHFFFAOYSA-L 0.000 claims description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003350 kerosene Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- LOKCKYUBKHNUCV-UHFFFAOYSA-L dichlorozirconium;methylcyclopentane Chemical group Cl[Zr]Cl.C[C]1[CH][CH][CH][CH]1.C[C]1[CH][CH][CH][CH]1 LOKCKYUBKHNUCV-UHFFFAOYSA-L 0.000 claims description 3
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims description 3
- AQYCWSHDYILNJO-UHFFFAOYSA-N methyl 6-methyl-3-oxo-4h-1,4-benzoxazine-8-carboxylate Chemical compound N1C(=O)COC2=C1C=C(C)C=C2C(=O)OC AQYCWSHDYILNJO-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims 2
- 239000004711 α-olefin Substances 0.000 abstract description 9
- 229920013639 polyalphaolefin Polymers 0.000 description 24
- 150000001336 alkenes Chemical class 0.000 description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 bis (ethylcyclopentadiene) zirconium dichloride Chemical compound 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011951 cationic catalyst Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000010722 industrial gear oil Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 1
- 239000010688 mineral lubricating oil Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/08—Butenes
-
- 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
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
- C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Lubricants (AREA)
Abstract
The invention provides a preparation method of lubricating oil base oil, which adopts a two-step polymerization method and comprises the following steps: taking 1-butene as a raw material, and catalyzing the 1-butene to polymerize by a metallocene catalyst system in the first step of polymerization; alCl is adopted in the second polymerization step 3 As a catalyst, the product obtained by the first polymerization step is used as a raw material for polymerization, so that the addition amount of long-chain alpha-olefin is reduced or the addition of long-chain alpha-olefin is avoided, the utilization value of 1-butene is improved, the cost is further reduced, the synthetic raw material source of PAO base oil is widened, and the product performance is improved.
Description
Technical Field
The invention relates to the technical field of lubricating base oil, in particular to a preparation method of lubricating base oil.
Background
The poly alpha-olefin (PAO) base oil is IV-type lubricating oil base oil, and compared with the traditional mineral lubricating oil base oil (I, II and III-type base oil), the poly alpha-olefin (PAO) base oil has the advantages of excellent viscosity and temperature performance, good low-temperature fluidity, excellent high-temperature oxidation resistance, good shear stability, small evaporation loss and the like, and is particularly suitable for extreme environments such as high load, high rotating speed, high vacuum, high-energy radiation, strong oxidation medium and the like. Viscosity is one of the most important physical parameters of PAO base oil, and the viscosity at 100 ℃ is customarily lower than 10mm 2 The product of/S is called low viscosity PAO base oil, and has viscosity of 10-40mm at 100deg.C 2 The product between/S is called medium viscosity PAO base oil, and the viscosity is higher than 40mm at 100 DEG C 2 The product of/S is referred to as a high viscosity PAO base oil. The PAO base oil with medium and high viscosity has irreplaceable outstanding excellent performance, and is mainly used for high-grade gear oil, industrial gear oil, lubricating grease and the like, and supports high-end manufacturing and quality upgrading of lubricating oil.
At present, the raw materials for synthesizing PAO base oil are mainly C 8 -C 12 The high-viscosity product prepared by polymerizing 1-decene as a raw material has the best performance, but the source and price of the raw material 1-decene limit the increase of the yield of PAO base oil, so that the search for a low-price raw material to replace the 1-decene for synthesizing PAO plays an important role in promoting the development of PAO.
Further, many researchers have developed the preparation of 1-butene into lubricating oil baseResearch on basic oil, research on copolymerization of 1-butene and long-chain olefin by university of Tianjin science and technology and other universities, and PAO preparation by copolymerization of 1-butene and long-chain alpha-olefin by using bis (tetramethyl cyclopentadienyl) zirconium dichloride as catalyst at northeast petroleum university, and synthesis of the catalyst with viscosity of 67.08mm at 100 DEG C 2 And/s, the polyolefin synthetic oil with the viscosity index of 121 and the pour point of-21 ℃ is obtained, so that PAO with excellent comprehensive performance is obtained, but the addition of long-chain olefin increases the cost of raw materials.
The prior art relates to a technology for synthesizing lubricating oil base oil by taking 1-butene as a raw material, comprising a one-step PAO preparation technology and a two-step PAO preparation technology by copolymerizing 1-butene and long-chain olefin, wherein the related catalysts are Ziegler-Natta and BF respectively 3 、AlCl 3 The catalyst, the addition of long-chain olefin in the process of synthesizing the lubricating oil base oil by adopting the method in the prior art, can increase the cost of raw materials, and the performance of the prepared product needs to be improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of lubricating oil base oil, which adds two steps of processes, further reacts by taking long-chain olefin generated by one step of process as a raw material, reduces the addition amount of long-chain alpha-olefin or avoids the addition of long-chain alpha-olefin, improves the utilization value of 1-butene, further reduces the cost and widens the synthetic raw material sources of PAO base oil.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a preparation method of lubricating oil base oil adopts a two-step polymerization method, and comprises the following steps:
taking 1-butene as a raw material, and catalyzing the 1-butene to polymerize by a metallocene catalyst system in the first step of polymerization; alCl is adopted in the second polymerization step 3 As a catalyst, the product obtained by the first polymerization step is used as a raw material for polymerization.
In some of these embodiments, the metallocene catalyst to 1-butene molar ratio is 1:1.5×
10 5 -4.5×10 5 。
In some of these embodiments, the metallocene catalyst system comprises a main catalyst selected from the group consisting of bis (methylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, kerosene fraction, bis (ethylcyclopentadienyl) zirconium dichloride, and bis (propylcyclopentadiene) zirconium dichloride.
In some of these embodiments, the activator in the metallocene catalyst system is a boron agent; the auxiliary agent in the metallocene catalyst system is an alkyl aluminum mixture.
In some of these embodiments, the boron agent is Ph 3 CB(C 6 F 5 ) 4 、B(C 6 F 5 ) 3 、Ph 3 CB[(CF 3 ) 2 C 6 H 3 ] 4 The method comprises the steps of carrying out a first treatment on the surface of the The alkyl aluminum is preferably one or any two of triisobutyl aluminum and diethyl aluminum dichloride.
In some of these embodiments, the molar ratio of boron in the activator to metallocene in the procatalyst in the metallocene system is from 2 to 10.
In some of these embodiments, the molar ratio of aluminum in the auxiliary agent to metallocene in the procatalyst in the metallocene system is 50 to 150.
In some of these embodiments, the conditions of the first polymerization step are: the reaction temperature is 50-100 ℃ and the reaction time is 0.5-3 h.
In some embodiments, the first-stage polymerization product is directly used as a second-stage raw material after catalyst separation, or the first-stage polymerization product is used as a second-stage raw material after catalyst separation and heavy components above 320 ℃ are distilled out.
In some of these embodiments, the second polymerization step is conducted at a temperature of 50 to 80 ℃.
A lubricating base oil is prepared by the method for preparing the lubricating base oil.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the preparation method of the lubricating oil base oil provided by the invention uses 1-butene as a raw material, adds two steps of processes on the prior art, controls the polymerization depth of the first metallocene catalyst to realize the purpose of controlling the composition and distribution of products, and the products are suitable for the second polymerization step and control the second polymerization process to further synthesize the products suitable for being used as the lubricating oil base oil, thereby reducing the addition amount of long-chain alpha-olefin or avoiding the addition of long-chain alpha-olefin, widening the raw material source of PAO base oil, improving the utilization value of 1-butene, improving the economy of the whole process and the product performance, and improving the economic benefit for enterprises.
2. The preparation method of the lubricating oil base oil provided by the invention takes the low-carbon olefin 1-butene as the raw material to realize the synthesis of the 1-butene into the lubricating oil base oil product, and the viscosity of the product is 15-25mm at 100 DEG C 2 The viscosity index is larger than 120, the pour point is lower than-39 ℃, and the product performance is improved.
Detailed Description
The following detailed description of the present invention is provided in connection with specific embodiments to further understand the objects, aspects and effects of the present invention, but is not intended to limit the scope of the invention as defined in the appended claims.
The prior art relates to a technology for synthesizing lubricating oil base oil by taking 1-butene as a raw material, comprising a one-step PAO preparation technology and a two-step PAO preparation technology by copolymerizing 1-butene and long-chain olefin, wherein the closest technology compared with the invention in the prior art adopts a two-step technology, and the catalysts involved in the prior art are respectively Ziegler-Natta and BF 3 、AlCl 3 Catalysts, not using metallocene catalysts with AlCl 3 Catalyst two-step method catalyst 1-butene synthesis of PAO base oil report.
In the embodiment, 1-butene is taken as a raw material, a metallocene catalyst with a specific structure is synthesized, the polymerization depth is controlled to obtain a product with a certain composition and distribution, and the product is taken as the raw material to carry out two-step polymerization to synthesize a product suitable for being used as PAO base oil.
The embodiment provides a preparation method of lubricating oil base oil, which adopts a two-step polymerization method and comprises the following steps: taking 1-butene as a raw material, and catalyzing the 1-butene to polymerize by a metallocene catalyst system in the first step of polymerization; alCl is adopted in the second polymerization step 3 As a catalyst, in a first polymerization stageAnd polymerizing the product obtained by the reaction as a raw material.
In the embodiment, a double-catalysis system and a two-step polymerization process are adopted, wherein the metallocene is adopted to catalyze the polymerization of 1-butene in the first step, the raw material 1-butene is dehydrated before being used, and the water content is lower than 10ppm; controlling the polymerization process conditions to obtain the product with the composition distribution of: 45-65% of gasoline fraction (IBP-180 ℃), 22-45% of kerosene fraction (140-240 ℃), 25-45% of diesel fraction (200-350 ℃) and less than 10% of distillate oil (350-500 ℃) without heavy oil component; alCl is adopted in the second step 3 The catalyst is polymerized by taking the product of the first step as a raw material, the catalyst is removed, and the hydrogenation fractionation is carried out to obtain the product with the viscosity of 15-25mm at 100 DEG C 2 And/s, the viscosity index is more than 120, and the pour point is lower than-39 ℃.
Wherein the molar ratio of the metallocene catalyst to the 1-butene is 1:1.5X10 5 -4.5×10 5 。
Wherein, the main catalyst metallocene in the metallocene catalyst system is bis (methylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, kerosene fraction, bis (ethylcyclopentadienyl) zirconium dichloride and bis (propylcyclopentadiene) zirconium dichloride; the activator in the metallocene catalyst system is a boron agent; the auxiliary agent in the metallocene catalyst system is an alkyl aluminum mixture.
Further, the boron agent is Ph 3 CB(C 6 F 5 ) 4 、B(C 6 F 5 ) 3 、Ph 3 CB[(CF 3 ) 2 C 6 H 3 ] 4 The method comprises the steps of carrying out a first treatment on the surface of the The alkyl aluminum is preferably one or any two of triisobutyl aluminum and diethyl aluminum dichloride.
Wherein the molar ratio of boron in the activator to metallocene in the main catalyst in the metallocene system is 2-10.
Wherein the molar ratio of the aluminum in the auxiliary agent and the metallocene in the main catalyst in the metallocene system is 50-150.
Wherein the conditions of the first polymerization step are as follows: the reaction temperature is 50-100 ℃ and the reaction time is 0.5-3 h.
Wherein the first polymerization product is directly used as a second-step raw material after catalyst separation, or the first polymerization product is used as a second-step raw material after catalyst separation, and then heavy components with the temperature of more than 320 ℃ are distilled out; the polymerization temperature of the second step is controlled between 50 and 80 ℃.
The first step adopts metallocene catalyst, and the high-carbon mixed olefin with controllable polymerization degree and regular structure and containing long-chain branches can be obtained by controlling polymerization conditions, and then the second step of cationic polymerization reaction is carried out by taking the high-carbon mixed olefin as a raw material, and the second step of process conditions are controlled by utilizing the heterogeneous catalysis function of the cationic catalyst, so that the polymerization degree and the isomerization degree of the polymer are controlled, the obtained polymer contains complex products with long chain branch lengths, and the viscosity-temperature performance is improved while the low-temperature fluidity is also considered.
To sum up, in an autoclave reactor, firstly adding a metallocene catalyst system, then respectively adding 1-butene (liquid phase feed), carrying out olefin polymerization reaction, controlling reaction conditions, cooling the obtained material to room temperature after the reaction is finished, emptying the reaction kettle, discharging the material, carrying out post-treatment, carrying out second-step polymerization, and adding AlCl during the polymerization 3 Controlling polymerization conditions, carrying out post-treatment on the product after reacting for a period of time, and carrying out reduced pressure distillation to remove the oligomer below 320 ℃ to obtain the target product for performance measurement. In the embodiment, 1-butene is used as a raw material, a two-step process is added on the prior art, the polymerization depth of the first-step metallocene catalyst is controlled to realize the purpose of controlling the composition and distribution of products, the products are suitable for the second-step polymerization, the second-step polymerization process is controlled to further synthesize the products suitable for being used as lubricating oil base oil, the addition amount of long-chain alpha-olefin is reduced or the addition of long-chain alpha-olefin is avoided, the raw material source of PAO base oil is widened, the utilization value of 1-butene is improved, the economy of the whole process is improved, the product performance is improved, and the economic benefit is improved for enterprises.
The preparation method of the lubricating oil base oil provided by the embodiment of the invention comprises the following steps:
and (3) a first polymerization step:
1) Before polymerization starts, 300ml of refined cyclohexane is used for cleaning a reaction kettle, the kettle cleaning temperature is 100 ℃, the kettle cleaning time is 0.5h to 1h, after the cyclohexane is discharged, the polymerization reaction kettle is purged by high-purity nitrogen, so that air and trace water in the polymerization reaction kettle are ensured to be removed;
2) Cooling to a preset reaction condition by using circulating water after nitrogen purging, adding quantitative raw material 1-butene (weight-reducing weighing method), a cocatalyst, an activator and a main catalyst, starting stirring, setting the reaction temperature, and controlling the reaction temperature by using a cooling system. After reacting for a certain time, discharging unreacted monomers, transferring the product into a 500mL round bottom flask, stopping with 10% acidified ethanol, filtering, alkaline washing, water washing, collecting and weighing for later use.
3) 10ml of the mixture was analyzed for composition, and the components below 320℃were distilled off to calculate the conversion.
4) The activator and the main catalyst in the first step 2) are premixed and stirred uniformly in 20ml of toluene.
And a second polymerization step:
1) Adding the materials obtained in the first step into a three-neck flask, placing the three-neck flask into an ice salt bath, adding AlCl3 and an acidulant, reacting for a certain time at a low temperature, heating, reacting for a certain time at a high temperature, and detecting the temperature of a reaction system by adopting a thermometer.
2) After the reaction is finished, adding clay into the product, carrying out suction filtration to obtain a colorless product, and distilling out an oligomerization component below 320 ℃ to obtain the product to be detected.
The invention provides another embodiment, a lubricating base oil, which is prepared by adopting the preparation method of the lubricating base oil, and the obtained product has the viscosity of 15-25mm at 100 DEG C 2 And/s, the viscosity index is more than 120, and the pour point is lower than-39 ℃.
Raw material or equipment source: comprises raw material names, specifications, manufacturers, etc
1-butene, polymerization grade.
Evaluation analysis method:
the viscosity at 40℃and 100℃was measured according to the method specified in GB/T265, and the viscosity index was calculated using the GB/T1995 method. (CAV 2200 fully automatic kinematic viscosity Analyzer by Cannon instruments, U.S. A.) according to GB/T1995; the pour point of the oil product is measured by an analysis method specified in GB/T3535 (DSY-006A petroleum product pour point/cloud point measuring instrument of glass instruments factory, tianjin); the composition distribution and fraction analysis (Agilent technologies Co., ltd. 7890A gas chromatograph) of the product were determined according to the method prescribed by ASTM 2887.
Specific examples:
example 1
The polymerization reaction is carried out by adopting the polymerization steps, firstly, the pretreatment of a reaction kettle is carried out, and then, the polymerization reaction is started: (1) 200g of 1-butene and 3.5ml of triisobutylaluminum (toluene concentration of triisobutylaluminum is 1.0 mmol/ml) were added to a polymerization reactor, the temperature was initially raised, the heating rate was controlled at 2℃per minute, the temperature was raised to 50℃and a catalyst containing 0.02mmol of bis (tetramethylcyclopentadienyl) zirconium dichloride and 0.05mmol of B (C) 6 F 5 ) 3 (prepared into toluene solution with concentration of 0.05mmol/ml in advance), reacting for 1.0h, stopping stirring, cooling to room temperature, flashing out unreacted monomers, filling nitrogen for replacement for 4 times, discharging the materials into 50ml of acidified ethanol (10%), stopping polymerization, and weighing and analyzing after impurity removal treatment to obtain the composition; (2) adding the materials into a three-mouth bottle, controlling the reaction temperature to be 50 ℃, and adding AlCl 3 2g, controlling the reaction for 3h, adding 25g-40g of clay into the product, stirring for 0.5h, carrying out suction filtration to obtain a colorless product, and finally distilling off the oligomeric component below 320 ℃ to obtain the product for measurement. The composition of the one-stage polymerization product and the analysis of the properties of the two-stage polymerization product are shown in Table 1.
Example 2
The same polymerization process as in example 1 was used, except that: (1) 2.8ml of monoethyl aluminum dichloride was added to a polymerization vessel, heated to 80℃and a solution containing 0.02mmol of bis (pentamethyl-or methylcyclopentadiene) zirconium dichloride and 0.025mol of B (C) 6 F 5 ) 3 The reaction temperature was controlled at 80℃and the reaction was carried out for 0.5h. (2) Adding the materials into a three-mouth bottle, controlling the reaction temperature to be 70 ℃, and adding AlCl 3 5g, and the reaction was controlled for 3h.
Example 3
The same polymerization process as in example 1 was used, except that: (1) 1.5ml of diethylaluminum chloride was added to the polymerization vessel, the temperature was raised to 75℃and a solution containing 0.037mmol of bis (propylcyclopentadiene) zirconium dichloride and 0.02mmol of Ph was added 3 CB(C 6 F 5 ) 4 The reaction temperature was controlled at 75℃and the reaction was carried out for 2 hours. (2) Adding the materials into a three-mouth bottle, controlling the reaction temperature to be 80 ℃, and adding AlCl 3 7g, and the reaction was controlled for 2h.
Example 4
The same polymerization process as in example 1 was used, except that: (1) 2.8ml of diethylaluminum chloride was added to the polymerization vessel, the temperature was raised to 70℃and a solution containing 0.044mmol of bis (ethylcyclopentadiene) zirconium dichloride and 0.15mmol of Ph was added 3 CB[(CF 3 ) 2 C 6 H 3 ] 4 The reaction temperature was controlled at 70℃and the reaction was carried out for 3 hours. (2) Adding the materials into a three-mouth bottle, controlling the reaction temperature to be 80 ℃, and adding AlCl 3 3g, the reaction was controlled for 3h.
Example 5
The same polymerization process as in example 1 was used, except that: (1) 2.8ml of diethylaluminum chloride was added to the polymerization vessel, the temperature was raised to 70℃and a solution containing 0.044mmol of bis (propylcyclopentadiene) zirconium dichloride and 0.15mmol of Ph was added 3 CB[(CF 3 ) 2 C 6 H 3 ] 4 The reaction temperature was controlled at 70℃and the reaction was carried out for 3 hours. (2) Adding the materials into a three-mouth bottle, controlling the reaction temperature to be 80 ℃, and adding AlCl 3 3g, the reaction was controlled for 3h.
Comparative example 1
The same polymerization method as in (1) of example 1 was employed, and only the polymerization of the step (1) was carried out in this example, and the obtained product was subjected to a impurity removal treatment, and finally, the oligomeric component at 320℃or lower was distilled off, and no lubricating oil base oil component was found in the component. Indicating that the target product was not obtained under this condition.
Comparative example 2
The same polymerization method as in (2) of example 1 was employed, and only the polymerization of the step (2) was carried out in this example, and the obtained product was subjected to impurity removal treatment, and finally the oligomeric component was distilled off at 320℃or lower, and the product was subjected to test analysis.
TABLE 1 one-step polymerization product composition and lubricating base oil Properties
As can be seen from the table data, the purpose of controlling the composition and distribution of the product is achieved by adjusting the one-step process catalyst and the process parameters, the fraction oil section content in the obtained polymerization product is lower than 10%, the fraction oil section content of the gas, coal and firewood is high, the yield of the light component below 320 ℃ is higher than 80% after vacuum distillation, and the viscosity of the obtained polymerization product at 100 ℃ is 15-25mm 2 A lubricating base oil product having a viscosity index greater than 120 and a pour point less than-39 ℃. The polymer obtained in the step (2) is measured to have a viscosity index lower than 90 and a pour point lower than 30 ℃ so as to show that the viscosity-temperature performance and the low-temperature fluidity of the obtained polymer are not ideal.
The present invention is not limited to the above-mentioned embodiments, and any equivalent embodiments which can be changed or modified by the technical content disclosed above can be applied to other fields, but any simple modification, equivalent changes and modification made to the above-mentioned embodiments according to the technical substance of the present invention without departing from the technical content of the present invention still belong to the protection scope of the technical solution of the present invention.
Claims (11)
1. A preparation method of lubricating oil base oil is characterized by comprising the following steps: the polymerization is carried out by adopting a two-step method, which comprises the following steps:
taking 1-butene as a raw material, and catalyzing the 1-butene to polymerize by a metallocene catalyst system in the first step of polymerization; alCl is adopted in the second polymerization step 3 As a catalyst, the product obtained by the first polymerization step is used as a raw material for polymerization.
2. The method for producing a lubricating base oil according to claim 1, characterized in that: the molar ratio of the metallocene catalyst to the 1-butene is 1:1.5X10 5 -4.5×10 5 。
3. The method for producing a lubricating base oil according to claim 1 or 2, characterized in that: the main catalyst metallocene in the metallocene catalyst system is bis (methylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, kerosene fraction, bis (ethylcyclopentadienyl) zirconium dichloride and bis (propylcyclopentadiene) zirconium dichloride.
4. A method of preparing a lubricant base oil according to claim 3, characterized in that: the activator in the metallocene catalyst system is a boron agent; the auxiliary agent in the metallocene catalyst system is an alkyl aluminum mixture.
5. The method for producing a lubricating base oil according to claim 4, wherein: the boron agent is Ph 3 CB(C 6 F 5 ) 4 、B(C 6 F 5 ) 3 、Ph 3 CB[(CF 3 ) 2 C 6 H 3 ] 4 The method comprises the steps of carrying out a first treatment on the surface of the The alkyl aluminum is preferably one or any two of triisobutyl aluminum and diethyl aluminum dichloride.
6. The method for producing a lubricating base oil according to claim 4, wherein: the molar ratio of boron in the activator to metallocene in the main catalyst in the metallocene system is 2-10.
7. The method for producing a lubricating base oil according to claim 4, wherein: the molar ratio of the aluminum in the auxiliary agent and the metallocene in the main catalyst in the metallocene system is 50-150.
8. The method for producing a lubricating base oil according to claim 1, characterized in that: the conditions of the first polymerization step are as follows: the reaction temperature is 50-100 ℃ and the reaction time is 0.5-3 h.
9. The method for producing a lubricating base oil according to claim 1 or 8, characterized in that: the catalyst of the first polymerization product is separated to be directly used as the raw material of the second step, or the heavy component with the temperature of more than 320 ℃ is distilled out to be used as the raw material of the second step after the catalyst of the first polymerization product is separated.
10. The method for producing a lubricating base oil according to claim 1, characterized in that: the polymerization temperature of the second step is controlled between 50 and 80 ℃.
11. A lubricating base oil, characterized in that: a lubricant base oil prepared by the process of any one of claims 1-10.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007011973A1 (en) * | 2005-07-19 | 2007-01-25 | Exxonmobil Chemical Patents Inc. | Process to produce low viscosity poly-alpha-olefins |
| CN105925340A (en) * | 2008-03-18 | 2016-09-07 | 埃克森美孚化学专利公司 | Process for synthetic lubricant production |
| CN108929186A (en) * | 2017-05-27 | 2018-12-04 | 中国石油天然气股份有限公司 | Method for preparing high viscosity index lubricating oil base oil |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007011973A1 (en) * | 2005-07-19 | 2007-01-25 | Exxonmobil Chemical Patents Inc. | Process to produce low viscosity poly-alpha-olefins |
| CN105925340A (en) * | 2008-03-18 | 2016-09-07 | 埃克森美孚化学专利公司 | Process for synthetic lubricant production |
| CN108929186A (en) * | 2017-05-27 | 2018-12-04 | 中国石油天然气股份有限公司 | Method for preparing high viscosity index lubricating oil base oil |
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