CN111286385B - Synthetic method of lubricating oil base oil - Google Patents
Synthetic method of lubricating oil base oil Download PDFInfo
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- CN111286385B CN111286385B CN201811492496.3A CN201811492496A CN111286385B CN 111286385 B CN111286385 B CN 111286385B CN 201811492496 A CN201811492496 A CN 201811492496A CN 111286385 B CN111286385 B CN 111286385B
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- 239000002199 base oil Substances 0.000 title claims abstract description 38
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 37
- 238000010189 synthetic method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 173
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 64
- 239000000463 material Substances 0.000 claims abstract description 58
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 42
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000005977 Ethylene Substances 0.000 claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims abstract description 20
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000003825 pressing Methods 0.000 claims abstract description 3
- 239000010959 steel Substances 0.000 claims abstract description 3
- 150000001336 alkenes Chemical class 0.000 claims description 44
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 23
- 238000005336 cracking Methods 0.000 claims description 20
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 15
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical group CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 5
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims 4
- 238000006653 Ziegler-Natta catalysis Methods 0.000 claims 1
- 230000001050 lubricating effect Effects 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 46
- 239000002994 raw material Substances 0.000 abstract description 44
- 238000004821 distillation Methods 0.000 abstract description 33
- 229920013639 polyalphaolefin Polymers 0.000 abstract description 25
- 239000003513 alkali Substances 0.000 abstract description 16
- -1 carbon olefin Chemical class 0.000 abstract description 5
- 239000012043 crude product Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 2
- 238000012512 characterization method Methods 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- 238000011056 performance test Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 58
- 239000000178 monomer Substances 0.000 description 25
- 238000010438 heat treatment Methods 0.000 description 23
- 239000001993 wax Substances 0.000 description 23
- 239000010936 titanium Substances 0.000 description 21
- 239000003921 oil Substances 0.000 description 19
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- 239000000539 dimer Substances 0.000 description 16
- 238000001914 filtration Methods 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 15
- 238000011049 filling Methods 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- 239000012535 impurity Substances 0.000 description 15
- 239000002699 waste material Substances 0.000 description 15
- 239000012467 final product Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000001308 synthesis method Methods 0.000 description 7
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 6
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 229910010066 TiC14 Inorganic materials 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers used as base material
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A synthetic method of lubricating oil base oil comprises the following steps: adding high carbon olefin and ethylene into a high pressure white steel polymerization reaction kettle simultaneously, adding a Ziegler-Natta catalyst, starting the reaction, controlling the conditions in the polymerization process, after the reaction is finished, pressing the materials into a second reaction kettle through nitrogen (or cooling to room temperature in the same reaction kettle), and simultaneously adding AlCl into the materials3The catalyst is added, the polymerization reaction condition is controlled, after the reaction is finished, the reaction kettle is vented and depressurized, the obtained crude product is subjected to an alkali washing process to remove residual catalyst, unreacted high-carbon olefin is removed through depressurization distillation, and the product obtained after hydrogenation is subjected to structural characterization to measure the branching degree and performance tests to measure the indexes of the product such as viscosity, viscosity index, pour point and the like. The invention adopts the complex raw material high-carbon olefin as the raw material, and the synthesized poly alpha-olefin lubricating oil base oil has excellent viscosity-temperature performance and low-temperature performance.
Description
Technical Field
The invention relates to a synthetic method of lubricating oil base oil, mainly aims to improve the viscosity-temperature performance and the low-temperature performance of the lubricating oil base oil, and belongs to the field of lubricating oil.
Background
The poly-alpha-olefin lubricating oil base oil (PAO) is lubricating oil base oil with excellent comprehensive performance, has the advantages of high viscosity index, low pour point, good hydrolytic stability and oxidation stability, wide liquid phase range, small evaporation loss, low pour point, high viscosity index, good thermal oxidation stability and the like compared with mineral base oil, can meet increasingly harsh OEM specifications, and meets the modern severe requirements on energy conservation and environmental protection.
PAO is a high carbon alpha-olefin (C) oligomerized with ethylene8-C12) The raw material composition, namely the carbon number of olefin directly influences the performance of the oil, the higher the carbon number, the higher the viscosity index and the higher the pour point; the carbon number becomes lower, and vice versa. The PAO prepared by using 1-decene as a raw material has the best comprehensive performance, has a high viscosity index and a low pour point, but because the price of the 1-decene is higher, the source of the 1-decene is limited, the supply is increasingly tense, and various synthetic oil production companies develop hydrocarbon PAO with different carbon numbers and broaden the source of the raw material, for example, when the PAO is prepared by cracking alpha-olefin by using wax, the synthetic PAO has the characteristics of low viscosity index and poor viscosity-temperature performance due to the complex structure of the adopted raw material, so that the use effect of the lubricating oil is seriously influenced. And the lubricating oil base oil which meets different use temperature requirements can be synthesized through catalyst and process improvement.
For example, in the aspect of cracking olefin by wax, patent CN201310260208.2 is developed to solve the problems of single raw material and coal liquefaction product of poly-alpha-olefin lubricating oil base oil in the prior artThe problem of low utilization rate of the coal wax is that the synthetic poly alpha-olefin lubricating oil base oil is prepared by using a material flow rich in alpha-olefin and obtained by cracking the coal wax as a raw material and using a mixture of aluminum halide and titanium halide as a catalyst, wherein the viscosity index of the synthetic poly alpha-olefin lubricating oil base oil is more than 135, and the viscosity is 8-13 mm at 100 DEG C2(s) a condensation point of less than-45 ℃. Literature comparison of quality of PAO products from olefin cracking by wax with production of 1-decene discloses the use of AlCl3As a catalyst, wax cracking olefin and 1-decene mixed olefin and 1-decene are respectively used as raw materials to prepare PAO base oil, and the properties of PAO synthesized by different raw materials are compared: the carbon number distribution of wax cracking olefin is wide, and the wax cracking olefin contains a small amount of non-ideal components, so that the number of byproducts is large, the quality of the product is reduced by side reaction, and the viscosity of the produced PAO product at 100 ℃ is 2-14 mm2s, viscosity index lower than 110; for 1-decene with quality superior to that of wax cracked olefin, the 1-decene and the wax cracked olefin are mixed according to a certain proportion, the carbon number distribution is adjusted, and the viscosity index of the produced PAO is improved to 133; 1-decene with higher purity is used, the molecular weight distribution is adjusted through a polymerization process, the molecular weight distribution of the product is concentrated, the viscosity index is 153, and the low-temperature performance is superior to that of a wax cracking raw material product. Literature "preparation of Low viscosity synthetic Hydrocarbon oils by cracking olefins with wax" BF3The method is characterized in that the catalyst is a soap cracking olefin as a raw material (distillation range is 150-250 ℃), and the quality level of the product obtained after blending is close to that of high-quality synthetic oil synthesized by foreign 1-decene.
In the aspect of preparing catalysts for poly-alpha-olefin lubricating oil base oil, the currently used catalysts mainly comprise aluminum chloride catalysts, Ziegler system catalysts and BF3In recent years, efficient ionic liquid-based catalytic systems and related processes have been developed. It is generally believed that: the Ziegler-Natta catalyst system is mainly used for producing medium and high viscosity lubricating oil (100 ℃, 40-100 mm)2Predominantly,/s), AlCl3Catalyst with viscosity in production as main component, BF3The catalyst is mainly used for producing low viscosity. Such as: in connection with Ziegler-Natta catalytic systems, patent US311316 discloses the synthesis of TiC14And A1(i-Bu) as a catalytic system, and the method for preparing the poly-alpha-olefin lubricating oil by catalyzing 1-decene and obtaining the productHas a viscosity index of greater than 135 and a pour point of less than-25 ℃. Patent US464241 discloses a mixture of Triethylaluminium (TEA), chloropropene or chlorotert-butane and TiC14The product is a catalytic system, hexane is used as a solvent, and the 1-decene is catalyzed to polymerize to obtain the product with the viscosity index of more than 140. Document (C)2H5)2AlCl/TiCl4The preparation of high viscosity index lubricating oil by catalyzing 1-decene polymerization is introduced in (C)2H5)2A1C1/TiC14The catalyst is used for catalyzing the polymerization of 1-decene to obtain a synthetic lubricating oil with the viscosity index of 173, and poly alpha-olefin with various viscosities can be prepared by adjusting A1/Ti. Patent CN107304237A adopts a two-step method with C8～C12Is prepared from Ziegler-Natta and BF3As a catalyst, the poly-alpha-olefin lubricating oil base oil is synthesized, and the viscosity of the produced PAO product at 100 ℃ is 40-53 mm2s, viscosity index 152-10A mixture of olefins.
The Ziegler system catalyst has the characteristic of controllable central structure, the obtained product has regular molecular structure and low branching rate, and the product has excellent viscosity-temperature performance, but the low-temperature performance, especially the low-temperature shear resistance, of the product is poor due to the regular long-chain molecules. AlCl3The catalyst is a carbonium ion oligomerization mechanism, has the characteristic of branching the product skeleton, is easy to control the reaction, has excellent low-temperature fluidity and low molecular polymerization degree, and is mainly suitable for producing medium-viscosity lubricating oil products.
Disclosure of Invention
The invention mainly aims to solve the problems of poor viscosity-temperature performance and low-temperature performance of the polyalphaolefin lubricating oil base oil synthesized by high-carbon olefin serving as a complex raw material in the prior art and solve the current situations that the polyalphaolefin lubricating oil base oil is single in raw material and the utilization rate of highly branched olefin is not high.
The invention aims to provide a method for improving the viscosity-temperature performance and the low-temperature performance of a product by taking high-carbon olefin as a raw material and adding ethylene copolymerization and a two-step polymerization process.
Hair brushThe preparation method is characterized by obviously utilizing high-branched olefins such as complex wax cracking raw materials, hexene-1 device by-products, decene, refinery butene and the like as raw materials to copolymerize with ethylene, and simultaneously adopting a two-step polymerization process, wherein in the first step of reaction process, ethylene and high-carbon olefin are added for copolymerization, so that the carbon number of a main chain is increased, the branching degree of a product is reduced, the catalyst dosage, the aluminum-titanium ratio and the reaction time are controlled, the polymerization degree of the reaction is controlled, the poly alpha-olefin with a relatively regular molecular structure is obtained theoretically, and the viscosity-temperature performance of the high-branched product is improved; then adding AlCl with isomerization performance in the second step3The product of the first step and unreacted monomers are polymerized by controlling the addition of a catalytic system, the addition ratio of two catalysts and the polymerization time to obtain a molecular structure with a regular molecular main chain structure, so that the product has good viscosity-temperature characteristics and the problem of poor low-temperature performance of the product is solved.
The invention provides a synthetic method of lubricating oil base oil, which comprises the following steps:
step (1): adding high-carbon olefin and ethylene into a high-pressure white steel polymerization reaction kettle simultaneously, adding a Ziegler-Natta catalyst, starting to react, controlling reaction conditions in the polymerization process, and cooling to room temperature in the same reaction kettle or pressing the materials into a second reaction kettle through nitrogen after the reaction is finished;
step (2): adding AlCl into the material obtained in the step (1)3And (3) controlling the addition amount of the catalyst and polymerization conditions, and performing post-treatment after the reaction to obtain the lubricating oil base oil.
The synthesis method of the lubricating oil base oil provided by the invention is characterized in that the high-carbon olefin is preferably one or more of wax cracking olefin, refinery mixed butene and hexene-1 device byproduct mixed decene.
The synthesis method of the lubricating oil base oil provided by the invention has the advantages that the mass usage amount of the ethylene is preferably 20-50%, more preferably 30-48%, and most preferably 30-40% based on the mass of the high-carbon olefin.
The invention provides a synthesis method of lubricant base oil, wherein the Ziegler-Natta catalyst system is preferably TiCl4Aluminum alkyl.
The invention provides a synthesis method of lubricating oil base oil, wherein TiCl is adopted in the Ziegler-Natta catalyst system based on the addition quality of high-carbon olefin4The mass usage is preferably 1% to 5%, more preferably 1% to 4%, and most preferably 2% to 4%.
The synthesis method of the lubricating oil base oil provided by the invention is characterized in that the molar ratio of Al to Ti in the Ziegler-Natta catalyst system is preferably 5-15: 1, and most preferably 5-10: 1.
The synthesis method of the lubricating oil base oil provided by the invention is characterized in that the Ziegler-Natta catalytic reaction time in the step (1) is preferably 10-60 min, and most preferably 30-40 min.
The invention provides a synthetic method of lubricating oil base oil, wherein AlCl is adopted3AlCl in catalyst3With TiCl in a Ziegler-Natta catalyst4The mass ratio of (A) to (B) is preferably 0.5-7: 1, more preferably 0.5-5: 1, and most preferably 2-5: 1.
The invention provides a synthetic method of lubricating oil base oil, wherein AlCl is adopted in the step (2)3The catalytic reaction time is preferably 30min to 120min, and most preferably 60min to 120 min.
The invention provides a synthetic method of lubricating oil base oil, wherein AlCl is adopted3The catalytic reaction temperature is preferably 80 ℃ to 180 ℃, more preferably 120 ℃ to 180 ℃, and most preferably 150 ℃ to 180 ℃.
The synthesis method provided by the invention can also be illustrated as follows:
step (1): carrying out single-site catalytic reaction on a complex olefin monomer or a branched olefin monomer and short-chain olefin under the action of a Ziegler-Natta catalyst system, and after the reaction is finished, taking heat through external circulation;
step (2): controlling the reaction temperature to be room temperature, and adding the immobilized AlCl3/γ-Al2O3Control ofPreparing polymerization conditions to obtain polyolefin oligomerization mixture. The two-step reaction can be carried out in the same reaction kettle or two reaction kettles connected in series.
Wherein the olefin monomer is highly branched olefin such as wax cracking olefin, mixed butene, and byproduct mixed decene of a hexene-1 device.
Wherein the short-chain olefin is ethylene.
Wherein the reaction pressure in the first step is 0-5.0 MPa.
Wherein the reaction time in the first step is controlled within 10 min-60 min, preferably 30 min-40 min.
In the step (1), the dosage of the short-chain olefin is 20-50% by mass of the branched olefin monomer, preferably 30-48% by mass of the branched olefin monomer, and most preferably 30-40% by mass of the branched olefin monomer.
Wherein the Ziegler-Natta catalyst system is TiCl4Aluminum alkyl.
In the Ziegler-Natta catalyst system, based on the adding quality of branched olefin monomer, TiCl4The mass consumption is 1-5%, preferably 1-4%, and most preferably 2-4%.
Wherein in the Ziegler-Natta catalyst system, the molar ratio of Al to Ti is 5-15: 1, and most preferably 5-10: 1.
Wherein in the step (2), AlCl is adopted3In the catalyst system, with TiCl in step (1)4Based on the mass of AlCl3/TiCl4The mass ratio of (A) to (B) is 0.5-7: 1, more preferably 0.5-5: 1, and most preferably 2-5: 1.
Wherein said AlCl3The catalytic reaction time is 30min to 120min, preferably 60min to 120 min.
Wherein said AlCl3The catalytic reaction temperature is 80-180 ℃, preferably 120-180 ℃ and the most preferably 150-180 ℃.
Specifically, the present invention can be further detailed as follows:
A1L autoclave reactor was initially charged with a mixture of highly branched olefins of complex composition, ethylene was passed throughThe raw materials are subjected to two-step reaction, firstly, a Ziegler-Natta catalyst system is utilized to carry out olefin polymerization reaction, the reaction conditions are controlled, and the obtained materials are cooled to room temperature after the reaction is finished. Then adding AlCl into the material obtained in the first step3And (3) a catalytic system, controlling polymerization conditions, emptying the reaction kettle, discharging materials, carrying out post-treatment, and analyzing and determining the obtained product.
The two-step polymerization process is carried out according to the following steps:
1) adding 300mL of refined cyclohexane into a high-pressure reaction kettle before polymerization begins, heating to 110 ℃, washing the kettle for 30min, discharging cyclohexane, and then blowing the polymerization reaction kettle with high-purity nitrogen to ensure that air and trace water in the polymerization reaction kettle are removed;
2) injecting high-carbon olefin raw material and TiCl serving as main catalyst into the polymerization reaction kettle in the step 1)4And a cocatalyst, wherein the addition amount of the high-carbon olefin is 100 g-150 g, the addition amount of the solvent is 0.5-1 time (50 g-150 g) of the mass addition amount of the liquid high-carbon olefin, and the catalyst TiCl41 g-7.5 g, wherein the addition amount of the auxiliary agent alkyl aluminum is 5-15 in terms of the molar ratio of the addition amount of the main catalyst: 1, opening an ethylene valve, and controlling the quality of ethylene in an inlet pipeline to be 20-75 g. The reaction kettle is started to stir, and simultaneously the temperature is increased, the temperature is controlled to be 80-100 ℃, and the polymerization time is 10-60 min. After the temperature has dropped to room temperature, a second polymerization stage (in the reactor of stage 1 or by forcing the batch into a second reactor connected in series with nitrogen) is carried out in accordance with AlCl3/TiCl4The mass ratio of (A) to (B) is 0.5-5: 1, controlling AlCl3The addition amount is 0.5g to 37.5g, the reaction temperature is 80 ℃ to 180 ℃, the reaction is carried out for 30min to 120min, and then the materials are discharged for post treatment.
The general formula of the alkyl aluminum compound is AlRnX(3-n)Wherein R is an alkyl group, an aralkyl group, an aryl group, etc., having 1 to 20 carbon atoms; x is halogen; n is an integer of 0 to 3; trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum monochloride, ethylaluminum dichloride and the like, among which triethylaluminum and diethylaluminum monochloride are preferred.
The product post-treatment comprises the following specific processes: putting the reaction materials into a 250mL flask filled with alkaline earth, heating and stirring, reacting for 1.5-2 h after the temperature reaches 170-180 ℃, then filtering to obtain a crude product, carrying out reduced pressure distillation on the crude product to remove unreacted monomers and dimers to obtain a final product, and analyzing and determining according to a conventional analysis method.
The invention has the beneficial effects that:
the invention provides a method for improving viscosity-temperature performance by using olefin with complex composition as a raw material and adding ethylene short chain molecules to improve the length of a molecular main chain, reduce branching degree and improve viscosity-temperature performance; secondly, two catalytic systems are added into the same reactor (or two reactors connected in series), the catalyst used in the first step is a single-center Zielgler-Natta catalyst which can improve the polymerization degree and the regularity, and the second AlCl catalyst3The catalyst improves isomerization, controls the proportion of the main catalysts of the two catalytic systems, achieves the synergistic effect of the main catalysts and the main catalysts, and improves the viscosity-temperature performance and the low-temperature performance of the lubricating oil base oil which is prepared by taking the highly branched olefin with complex composition as the raw material. Solves the problems of single raw material and low utilization rate of highly branched olefin of the polyalphaolefin lubricating oil base oil.
Detailed Description
The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and process are given, but the scope of the present invention is not limited to the following examples, which are illustrative and not limiting the scope of the present invention. The experimental methods in the following examples, which are not specified under specific conditions, are generally performed under conventional conditions.
The amount of ethylene monomer used:
in the present invention, the amount of ethylene used is not particularly limited, and the amount of ethylene used is preferably 20 to 50% by mass based on the amount of the higher olefin added. If the ethylene quality is less than 20% of the high-carbon olefin, the use amount is too low, so that the ethylene insertion rate in the product is low, the branching degree of the product is high, and the viscosity index is reduced; if the ethylene quality is more than 50% of the higher olefins, the amount is too high, resulting in that the reaction is dominated by ethylene polymerization, the conversion of the higher olefins is reduced, and low molecular waxes are present in the product.
Amount of cocatalyst used in the Ziegler-Natta catalyst system:
in the present invention, the amount of the co-catalyst used in the Ziegler-Natta catalyst system is not particularly limited, and it is generally preferable that the molar ratio of Al/Ti in the Ziegler-Natta catalyst system is 5 to 15: 1. If the molar ratio of Al to Ti in the catalyst system is lower than 5:1, the use amount of the cocatalyst is too small, the polymerization degree is low, and the product viscosity is low; if the molar ratio of Al to Ti in the catalyst system is higher than 15:1, the use amount of the cocatalyst is excessive, partial high polymerization reaction can be caused, and the product contains high molecular wax, so that the product performance is influenced.
The present invention is further illustrated by the following examples, which are not intended to limit the invention thereto.
Example 1
Adopting the two olefin raw materials and the two-step polymerization process to carry out polymerization reaction, firstly cleaning the reaction kettle for half an hour by cyclohexane, then purging the reaction kettle for three times by nitrogen, removing air and trace water in the polymerization reaction kettle, and starting to carry out the first-step polymerization reaction: 100g of wax cracking olefin raw material, 50g of cyclohexane solvent and TiCl are sequentially added into a polymerization reaction kettle41g of triethyl aluminium Al (Et) in an Al/Ti molar ratio of 5:13Introducing 20g of ethylene raw material, starting to heat and stir, controlling the reaction temperature to be 80-100 ℃, and stopping stirring after reacting for 10 min. And (3) when the temperature in the reaction kettle is reduced to room temperature, carrying out a second step of reaction: adding AlCl into a reaction kettle30.5g of catalyst, starting stirring, controlling the reaction temperature to be 150 ℃ through heat taking of external circulation, stopping stirring after reacting for 30min, emptying the reaction kettle, filling nitrogen for replacing for 4 times, introducing tail gas into alkali liquor for absorption, putting reaction materials into a three-neck flask filled with alkaline earth, putting the three-neck flask into an oil bath for heating reaction, filtering to remove the waste catalyst and impurities, transferring the materials into a distillation flask, performing reduced pressure distillation to remove the materials into reaction monomers and dimers, and performing viscosity, viscosity index and pour point measurement on the final product to obtain the product with the kinematic viscosity of 40mm at 100 DEG C2(ii) a viscosity index of 157 and a pour point of-48 ℃.
Example 2
The same polymerization as in example 1 was carried outThe process comprises the following steps: 100g of wax cracking olefin raw material, 50g of cyclohexane solvent and TiCl are sequentially added into a polymerization reaction kettle47.5g of Al (Et) was added in a molar ratio of Al to Ti of 10:1350g of ethylene raw material is introduced, the temperature is raised and the stirring is started, the reaction temperature is controlled to be 80 ℃, and the stirring is stopped after the reaction is carried out for 40 min. And (3) when the temperature in the reaction kettle is reduced to room temperature, carrying out a second step of reaction: adding AlCl into a reaction kettle315g of catalyst, starting stirring, controlling the reaction temperature to be 80 ℃ by taking heat through external circulation, stopping stirring after reacting for 30min, emptying the reaction kettle, filling nitrogen for replacing for 4 times, introducing tail gas into alkali liquor for absorption, putting reaction materials into a three-neck flask filled with alkaline earth, putting the three-neck flask into an oil bath for heating reaction, filtering to remove waste catalyst and impurities, transferring the materials into a distillation flask, performing reduced pressure distillation to remove the materials into reaction monomers and dimers, and measuring the viscosity, the viscosity index and the pour point of a final product to obtain the product with the kinematic viscosity of 35mm at 100 DEG C2The viscosity index was 150 in a/s ratio and the pour point was-45 ℃.
Example 3
The same polymerization process as in example 1 was used: 150g of wax cracking olefin raw material, 100g of cyclohexane solvent and TiCl are added into a polymerization reaction kettle in sequence47.5g of aluminum diethyl monochloride Al (Et) are added according to the Al/Ti molar ratio of 15:12And introducing 50g of ethylene raw material into the reactor, heating and stirring, controlling the reaction temperature to be 90 ℃, and stopping stirring after reacting for 60 min. And (3) when the temperature in the reaction kettle is reduced to room temperature, carrying out a second step of reaction: adding AlCl into a reaction kettle320g of catalyst, starting stirring, controlling the reaction temperature to be 180 ℃ by taking heat through external circulation, stopping stirring after reacting for 60min, emptying the reaction kettle, filling nitrogen for replacing for 4 times, introducing tail gas into alkali liquor for absorption, putting reaction materials into a three-neck flask filled with alkaline earth, putting the three-neck flask into an oil bath for heating reaction, filtering to remove waste catalyst and impurities, transferring the materials into a distillation flask, performing reduced pressure distillation to remove the materials into reaction monomers and dimers, and measuring the viscosity, the viscosity index and the pour point of a final product to obtain the product with the kinematic viscosity of 40mm at 100 DEG C2The viscosity index was 150 in a/s ratio and the pour point was-45 ℃.
Example 4
The same polymerization process as in example 1 was used: 125g of wax cracking olefin raw material, 100g of cyclohexane solvent and TiCl are added into a polymerization reaction kettle in sequence45g of Al/Ti molar ratio 10:1, diethyl aluminum monochloride Al (Et)2And introducing 50g of ethylene raw material Cl, starting heating and stirring, controlling the reaction temperature to be 100 ℃, and stopping stirring after reacting for 60 min. And (3) when the temperature in the reaction kettle is reduced to room temperature, carrying out a second step of reaction: adding AlCl into a reaction kettle335g of catalyst, starting stirring, controlling the reaction temperature to be 180 ℃ by taking heat through external circulation, stopping stirring after reacting for 120min, emptying the reaction kettle, filling nitrogen for replacing for 4 times, introducing tail gas into alkali liquor for absorption, putting reaction materials into a three-neck flask filled with alkaline earth, putting the three-neck flask into an oil bath for heating reaction, filtering to remove waste catalyst and impurities, transferring the materials into a distillation flask, performing reduced pressure distillation to remove the materials into reaction monomers and dimers, and measuring the viscosity, the viscosity index and the pour point of a final product to obtain the product with the kinematic viscosity of 36mm at 100 DEG C2The viscosity index was 147, the pour point-48 ℃.
Example 5
The same polymerization process as in example 1 was carried out except that decene as a byproduct from the hexene-1 apparatus was used as a raw material, and 100g of mixed decene, 50g of cyclohexane solvent, and TiCl were sequentially added to the polymerization reactor41g of triethyl aluminium Al (Et) in an Al/Ti molar ratio of 5:13Introducing 20g of ethylene raw material, starting to heat and stir, controlling the reaction temperature to be 80-100 ℃, and stopping stirring after reacting for 10 min. And (3) when the temperature in the reaction kettle is reduced to room temperature, carrying out a second step of reaction: adding AlCl into a reaction kettle30.5g of catalyst, starting stirring, controlling the reaction temperature to be 150 ℃ through heat taking of external circulation, stopping stirring after reacting for 30min, emptying the reaction kettle, filling nitrogen for replacing for 4 times, introducing tail gas into alkali liquor for absorption, putting reaction materials into a three-neck flask filled with alkaline earth, putting the three-neck flask into an oil bath for heating reaction, filtering to remove the waste catalyst and impurities, transferring the materials into a distillation flask, performing reduced pressure distillation to remove the materials into reaction monomers and dimers, and performing viscosity, viscosity index and pour point measurement on the final product to obtain a product with the temperature of 100 DEG CThe dynamic viscosity is 20mm2(ii) a viscosity index of 131 and a pour point of-48 ℃.
Example 6
The same polymerization procedure as in example 5 was used: 100g of mixed decene, 50g of cyclohexane solvent and TiCl are added into a polymerization reaction kettle in sequence47.5g of Al (Et) was added in a molar ratio of Al to Ti of 10:1350g of ethylene raw material is introduced, the temperature is raised and the stirring is started, the reaction temperature is controlled to be 80 ℃, and the stirring is stopped after the reaction is carried out for 40 min. And (3) when the temperature in the reaction kettle is reduced to room temperature, carrying out a second step of reaction: adding AlCl into a reaction kettle315g of catalyst, starting stirring, controlling the reaction temperature to be 180 ℃ by taking heat through external circulation, stopping stirring after reacting for 60min, emptying the reaction kettle, filling nitrogen for replacing for 4 times, introducing tail gas into alkali liquor for absorption, putting reaction materials into a three-neck flask filled with alkaline earth, putting the three-neck flask into an oil bath for heating reaction, filtering to remove waste catalyst and impurities, transferring the materials into a distillation flask, performing reduced pressure distillation to remove the materials into reaction monomers and dimers, and measuring the viscosity, the viscosity index and the pour point of a final product to obtain the product with the kinematic viscosity of 25mm at 100 DEG C2Viscosity index of 128 and pour point of-40 ℃.
Example 7
The same polymerization procedure as in example 5 was used: 150g of mixed decene, 100g of cyclohexane solvent and TiCl are added into a polymerization reaction kettle in sequence47.5g of aluminum diethyl monochloride Al (Et) are added according to the Al/Ti molar ratio of 15:12And introducing 75g of ethylene raw material Cl, starting heating and stirring, controlling the reaction temperature to be 100 ℃, and stopping stirring after reacting for 60 min. And (3) when the temperature in the reaction kettle is reduced to room temperature, carrying out a second step of reaction: adding AlCl into a reaction kettle325g of catalyst, starting stirring, controlling the reaction temperature to be 180 ℃ by taking heat through external circulation, stopping stirring after reacting for 60min, emptying the reaction kettle, filling nitrogen for replacing for 4 times, introducing tail gas into alkali liquor for absorption, putting reaction materials into a three-neck flask filled with alkaline earth, putting the three-neck flask into an oil bath for heating reaction, filtering to remove the waste catalyst and impurities, transferring the materials into a distillation flask, performing reduced pressure distillation to remove the materials into reaction monomers and dimers, and measuring the viscosity, the viscosity index and the pour point of a final productThe kinematic viscosity of the obtained product at 100 ℃ is 28mm2The viscosity index was 130 and the pour point was-42 ℃.
Example 8
The same polymerization procedure as in example 5 was used: adding 125g of mixed decene, 100g of cyclohexane solvent and TiCl into a polymerization reaction kettle in sequence45g of Al (Et) was added in a molar ratio of Al to Ti of 10:12And introducing 60g of ethylene raw material Cl, starting heating and stirring, controlling the reaction temperature to be 100 ℃, and stopping stirring after reacting for 60 min. And (3) when the temperature in the reaction kettle is reduced to room temperature, carrying out a second step of reaction: adding AlCl into a reaction kettle335g of catalyst, starting stirring, controlling the reaction temperature to be 180 ℃ by taking heat through external circulation, stopping stirring after reacting for 120min, emptying the reaction kettle, filling nitrogen for replacing for 4 times, introducing tail gas into alkali liquor for absorption, putting reaction materials into a three-neck flask filled with alkaline earth, putting the three-neck flask into an oil bath for heating reaction, filtering to remove waste catalyst and impurities, transferring the materials into a distillation flask, performing reduced pressure distillation to remove the materials into reaction monomers and dimers, and measuring the viscosity, the viscosity index and the pour point of a final product to obtain the product with the kinematic viscosity of 18mm at 100 DEG C2The viscosity index was 127 and the pour point was-45 ℃.
Example 9
The same polymerization process as in example 1 was used: 125g of cyclohexane solvent and TiCl are added into a polymerization reaction kettle in sequence45g of Al (Et) was added in a molar ratio of Al to Ti of 10:13125g of mixed C-Si material (liquid phase feeding), 20g of ethylene raw material is introduced, the temperature is raised and the stirring is started, the reaction temperature is controlled at 100 ℃, and the stirring is stopped after the reaction is carried out for 30 min. And (3) when the temperature in the reaction kettle is reduced to room temperature, carrying out a second step of reaction: adding AlCl into a reaction kettle310g of catalyst, starting stirring, controlling the reaction temperature to be 150 ℃ through heat taking of external circulation, stopping stirring after reacting for 30min, emptying the reaction kettle, filling nitrogen for replacing for 4 times, introducing tail gas into alkali liquor for absorption, putting reaction materials into a three-neck flask filled with alkaline earth, putting the three-neck flask into an oil bath for heating reaction, filtering to remove the waste catalyst and impurities, transferring the materials into a distillation flask, performing reduced pressure distillation to remove the materials into reaction monomers and dimers, and performing viscosity on final productsMeasuring the viscosity index and the pour point to obtain a product with the kinematic viscosity of 28mm at 100 DEG C2Viscosity index of 120/s and pour point of-35 ℃.
Example 10
The same polymerization procedure as in example 9 was used: 100g of cyclohexane solvent and TiCl are added into a polymerization reaction kettle in sequence47.5g of Al (Et) was added in a molar ratio of Al to Ti of 10:13Mixing 100g of carbon four material (liquid phase feeding), introducing 50g of ethylene raw material, starting to heat and stir, controlling the reaction temperature to be 100 ℃, and stopping stirring after reacting for 60 min. And (3) when the temperature in the reaction kettle is reduced to room temperature, carrying out a second step of reaction: adding AlCl into a reaction kettle335g of catalyst, starting stirring, controlling the reaction temperature to be 180 ℃ by taking heat through external circulation, stopping stirring after reacting for 120min, emptying the reaction kettle, filling nitrogen for replacing for 4 times, introducing tail gas into alkali liquor for absorption, putting reaction materials into a three-neck flask filled with alkaline earth, putting the three-neck flask into an oil bath for heating reaction, filtering to remove waste catalyst and impurities, transferring the materials into a distillation flask, performing reduced pressure distillation to remove the materials into reaction monomers and dimers, and measuring the viscosity, the viscosity index and the pour point of a final product to obtain the product with the kinematic viscosity of 24mm at 100 DEG C2Viscosity index of 120/s and pour point of-32 ℃.
Example 11
The same polymerization process as in example 1 was used: sequentially adding 100g of wax cracking olefin raw material into a polymerization reaction kettle, and respectively adding 20-50 g of mixed decene, 80g of cyclohexane solvent and TiCl47.5g of Al (Et) was added in a molar ratio of Al to Ti of 10:1350g of ethylene raw material is introduced, the temperature is raised and the stirring is started, the reaction temperature is controlled to be 80 ℃, and the stirring is stopped after the reaction is carried out for 40 min. And (3) when the temperature in the reaction kettle is reduced to room temperature, carrying out a second step of reaction: adding AlCl into a reaction kettle3Stirring 15g of catalyst, controlling the reaction temperature to be 120 ℃ by taking heat through external circulation, stopping stirring after reacting for 30min, emptying the reaction kettle, filling nitrogen for replacing for 4 times, introducing tail gas into alkali liquor for absorption, putting reaction materials into a three-neck flask filled with alkaline earth, putting the three-neck flask into an oil bath for heating reaction, filtering to remove the waste catalyst and impurities, transferring the materials into a distillation flask, and reducing the temperatureThe reaction monomer and the dimer are separated out by pressure distillation, and the final product is subjected to viscosity, viscosity index and pour point measurement to obtain the product with the kinematic viscosity of 25-35 mm at 100 DEG C2The viscosity index is 135-157 per second, and the pour point is-45 ℃.
Example 12
The same polymerization process as in example 1 was used: 100g of wax cracking olefin raw material, 20g of mixed decene, 20g of mixed butene (liquid phase feed), 80g of cyclohexane solvent and TiCl are sequentially added into a polymerization reaction kettle45g of Al (Et) was added in a molar ratio of Al to Ti of 10:1350g of ethylene raw material is introduced, the temperature is raised and the stirring is started, the reaction temperature is controlled to be 90 ℃, and the stirring is stopped after the reaction is carried out for 40 min. And (3) when the temperature in the reaction kettle is reduced to room temperature, carrying out a second step of reaction: adding AlCl into a reaction kettle325g of catalyst, starting stirring, controlling the reaction temperature to be 80 ℃ through heat taking of external circulation, stopping stirring after reacting for 60min, emptying the reaction kettle, filling nitrogen for replacing for 4 times, introducing tail gas into alkali liquor for absorption, putting reaction materials into a three-neck flask filled with alkaline earth, putting the three-neck flask into an oil bath for heating reaction, filtering to remove waste catalyst and impurities, transferring the materials into a distillation flask, performing reduced pressure distillation to remove the materials into reaction monomers and dimers, and measuring the viscosity, the viscosity index and the pour point of a final product to obtain the product with the kinematic viscosity of 15-25 mm at 100 DEG C2The viscosity index is 125-135 per second, and the pour point is-40 ℃.
Comparative example 1
The same polymerization procedure as in example 8 was used, except that no ethylene was added during the reaction: 125g of mixed decene material, 100g of cyclohexane solvent and TiCl are added into a polymerization reaction kettle in sequence45g of Al (Et) was added in a molar ratio of Al to Ti of 10:12And Cl, starting heating and stirring, controlling the reaction temperature to be 100 ℃, and stopping stirring after reacting for 60 min. And (3) when the temperature in the reaction kettle is reduced to room temperature, carrying out a second step of reaction: adding AlCl into a reaction kettle3Stirring 35g of catalyst, controlling the reaction temperature to be 180 ℃ by means of external circulation heat extraction, stopping stirring after reacting for 120min, emptying the reaction kettle, filling nitrogen for replacing for 4 times, introducing tail gas into alkali liquor for absorption, and putting reaction materials into the reaction kettle containing alkaline earthThe three-mouth flask is placed in an oil bath for heating reaction, the waste catalyst and impurities are removed by filtration, the materials are transferred into a distillation flask and are removed into reaction monomers and dimers by reduced pressure distillation, and the final product is subjected to viscosity, viscosity index and pour point measurement to obtain the product with the kinematic viscosity of 16mm at 100 DEG C2The viscosity index was 108 and the pour point was-42 ℃.
Comparative example 2
The same polymerization starting material as in example 8 was used, except that the reaction process was a one-step process: 125g of mixed decene serving as a raw material, 100g of cyclohexane solvent and TiCl are sequentially added into a polymerization reaction kettle45g of Al (Et) was added in a molar ratio of Al to Ti of 10:12Cl, starting heating and stirring, controlling the reaction temperature to be 100 ℃, stopping stirring after reacting for 60min, emptying the reaction kettle, filling nitrogen for replacing for 4 times, introducing alkali liquor into tail gas for absorption, putting reaction materials into a three-neck flask filled with alkaline earth, putting the three-neck flask into an oil bath for heating reaction, filtering to remove waste catalyst and impurities, transferring the materials into a distillation flask, performing reduced pressure distillation to remove the materials into reaction monomers and dimers, and performing viscosity, viscosity index and pour point measurement on the final product to obtain the product with the kinematic viscosity of 22mm at 100 DEG C2Viscosity index 102, pour point-30 ℃.
Comparative example 3
The same polymerization starting material as in example 8 was used, except that the reaction process was a one-step process: adding 125g of mixed decene serving as a raw material and 100g of cyclohexane solvent into a polymerization reaction kettle in sequence, and adding AlCl into the reaction kettle335g of catalyst, starting stirring, controlling the reaction temperature to be 180 ℃ by taking heat through external circulation, stopping stirring after reacting for 120min, emptying the reaction kettle, filling nitrogen for replacing for 4 times, introducing tail gas into alkali liquor for absorption, putting reaction materials into a three-neck flask filled with alkaline earth, putting the three-neck flask into an oil bath for heating reaction, filtering to remove waste catalyst and impurities, transferring the materials into a distillation flask, performing reduced pressure distillation to remove the materials into reaction monomers and dimers, and measuring the viscosity, the viscosity index and the pour point of a final product to obtain the product with the kinematic viscosity of 26mm at 100 DEG C2The viscosity index was 108 and the pour point was-42 ℃.
Claims (7)
1. A synthetic method of lubricating oil base oil is characterized by comprising the following steps:
(1) adding high-carbon olefin and ethylene into a high-pressure white steel polymerization reaction kettle simultaneously, adding a Ziegler-Natta catalyst, starting to react, controlling reaction conditions in the polymerization process, and cooling to room temperature in the same reaction kettle or pressing the materials into a second reaction kettle through nitrogen after the reaction is finished;
(2) adding AlCl into the material obtained in the step (1)3Catalyst, controlling the adding amount of the catalyst and polymerization conditions, and obtaining the lubricating oil base oil after the reaction is finished and post-treatment is carried out;
the Ziegler-Natta catalyst system is TiCl4Aluminum alkyl;
the molar ratio of Al to Ti in the Ziegler-Natta catalyst system is 5-15: 1;
the AlCl3AlCl in catalyst3With TiCl in a Ziegler-Natta catalyst4The mass ratio of (A) to (B) is 0.5-5: 1.
2. the method for synthesizing the lubricating oil base oil according to claim 1, wherein the high-carbon olefin is one or more of a wax cracking olefin, a refinery mixed butene and a hexene-1 unit byproduct mixed decene.
3. The method for synthesizing lubricant base oil according to claim 1, wherein the mass amount of the ethylene is 20-50% based on the mass of the high-carbon olefin.
4. The process of claim 1, wherein the Ziegler-Natta catalyst system comprises TiCl based on the higher olefin loading mass4The mass consumption is 1-5%.
5. The method for synthesizing lubricant base oil according to claim 1, wherein the Ziegler-Natta catalysis reaction time in the step (1) is 10min to 60 min.
6. The method for synthesizing lubricant base oil according to claim 1, wherein AlCl is adopted in the step (2)3The catalytic reaction time is 30-120 min.
7. The method of claim 1, wherein the AlCl is present in the lubricating base oil3The catalytic reaction temperature is 80-180 ℃.
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