CN108251155A - Preparation method of low-viscosity poly α -olefin synthetic oil - Google Patents
Preparation method of low-viscosity poly α -olefin synthetic oil Download PDFInfo
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- CN108251155A CN108251155A CN201611238965.XA CN201611238965A CN108251155A CN 108251155 A CN108251155 A CN 108251155A CN 201611238965 A CN201611238965 A CN 201611238965A CN 108251155 A CN108251155 A CN 108251155A
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- catalyst
- synthetic oil
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- low viscosity
- poly alpha
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- 238000002360 preparation method Methods 0.000 title claims description 30
- 229920013639 polyalphaolefin Polymers 0.000 title abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 70
- 238000004064 recycling Methods 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000000539 dimer Substances 0.000 claims abstract description 10
- 239000013067 intermediate product Substances 0.000 claims abstract description 9
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 6
- 150000007524 organic acids Chemical class 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 57
- 239000007789 gas Substances 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 26
- 239000004711 α-olefin Substances 0.000 claims description 23
- 239000003426 co-catalyst Substances 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 18
- 238000007701 flash-distillation Methods 0.000 claims description 15
- 238000005292 vacuum distillation Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 10
- 239000013589 supplement Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 2
- 239000003921 oil Substances 0.000 abstract description 58
- 239000000178 monomer Substances 0.000 abstract description 6
- 238000001704 evaporation Methods 0.000 abstract description 5
- 239000002199 base oil Substances 0.000 abstract description 4
- 230000000536 complexating effect Effects 0.000 abstract description 4
- 239000010687 lubricating oil Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000008020 evaporation Effects 0.000 abstract description 3
- 238000006384 oligomerization reaction Methods 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 229910015900 BF3 Inorganic materials 0.000 description 51
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 36
- 150000001875 compounds Chemical class 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 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
- 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
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/22—Higher olefins
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process for preparing low-viscosity poly α -olefine synthetic oil includes dewatering raw material, refining, and BF3Taking alcohol or organic acid complex as a catalyst, carrying out oligomerization under the conditions that the temperature is 0-100 ℃ and the pressure is 0-1.0 MPa, carrying out flash evaporation treatment on a reaction product after the reaction is finished, and separating gas phase BF3Catalyst, gas phase BF3Compressing and recycling the oil phase, precipitating or centrifuging the oil phase to separate the complexing catalyst and the poly α -olefin lubricating oil, recycling the complexing catalyst, washing the oil phase with alkaline water to obtain a clean intermediate product, distilling under reduced pressure to separate a monomer and a dimer, and then carrying out hydrotreating to obtain the saturated poly α -olefin lubricating oil base oil.
Description
Technical field
The invention belongs to petrochemical industries, are related to from a kind of preparation method of low viscosity poly alpha olefine synthetic oil.
Background technology
About low viscosity poly alpha olefine synthetic oil as lubricating oil and its catalyst recovery technology, disclose both at home and abroad big
Measure the relevant technologies and patent.
US3763244 is disclosed using BF3/ aqueous systems catalysis routine C6~C16 alpha-olefins prepare low pour point lubricating oil
Method;When US5191140A is using water and acetic anhydride as co-catalyst, 100 DEG C of kinematic viscosity are obtained as 3.58cSt and viscosity index (VI)
For 125 product, olefin conversion 76.8%;US3742082 discloses one kind with BF3For catalyst, phosphoric acid or water is help
The molar ratio of the method that catalyst C6~C10 alpha-olefins, especially 1- decene synthesize dimerizing olefins body, catalyst and alkene
It is 0.005:1~0.1:1, reaction temperature is 100~150 DEG C.Above-mentioned patent is using water or water and other materials as co-catalyst, drop
Low production cost, but easily bring etching problem, and material that corrosion class is improved, plant investment cost can be significantly increased,
Therefore to avoid equipment and pipeline corrosion, equipment investment is reduced, maintains device long-period stable operation, the water reduced in raw material contains
Amount reduces corrosion and is necessary.
US6939943 and CN1204152 C disclose a kind of side for being passivated and recycling boron trifluoride when preparing polyisobutene
Method adds in the BF in methanol, ethyl alcohol or the mixture of methanol and ethyl alcohol enrichment precipitated product in party's normal direction reaction product3Point
From then standing sedimentation separates and recovers alcohol phase, further by alcohols and BF3Separation, and recycle in the right way.
US4227027 is more containing 2 or more alkyl by being added in the reaction mixture containing boron trifluoride complex catalyst
First alcohol makes it that addition reaction only occur with the boron trifluoride in composition catalyst, forms precipitation so as to remove boron trifluoride, leads to
Cross the method that heat resolve recycling boron trifluoride is carried out to addition compound product.This method can bring impurity into, easily cause catalyst and tire out
Product.
Method disclosed in Unexamined Patent 2-45429 bulletins is by the use of boron trifluoride ether complex as catalyst, carries out alkene
The method of the alkylated reaction of hydro carbons and aromatic compound, in the method, before the reaction or reaction after several stages,
At room temperature, phosphoric acid, acetic acid, phenol of 0.05~2 mole etc. is added into reaction system relative to boron trifluoride ether complex
Weak acid, then the system after standing separation reaction, is layered catalyst member, the catalyst layer of separation is intactly used as
The method of the catalyst of next alkylated reaction.This method can bring catalyst impurities into.
Hironaka etc. has found that fluoroalkane hydro carbons can also dissolve BF3Complex compound, the molecular formula of fluoric ether are represented by
CnHmF2n-m+2.Extractant is added in the reaction solution of polymerisation, one layer is containing BF3And BF3The solvent layer of complex compound, it is another
Layer is reaction product layer, the BF that the solvent layer distillation containing catalyst is isolated3And BF3Complex compound Returning reacting system repeats profit
With.This method can bring impurity fluoroalkane hydro carbons into, while increase separation process and operating cost.
CN1217726A utilizes the BF after electroluminescent sedimentation separation and recovery olefinic polyreaction3Complex compound.This method -100
DEG C~+50 DEG C of temperature range, direct current and/or alternating voltage (in the range of 0.001~40kV/mm) are applied to reaction product
Afterwards, due in BF3It acts under electric field action and clears up there are electric polarization or electric deflection between ligand, complex molecule is mutual
Electricity repel disappear, complex molecule aggregation, relative density difference cause aggregation complex sedimentation.This method is easily implemented, and does not change
Become BF3With the molar ratio of polar compound, the composition catalyst of separation and recovery can be continuing with, and shortcoming is to be electrolysed for a long time
The side reaction of polymer may be caused.Apply voltage swing and electrolysis time length has a significant impact to separating effect.This method
It is novel ingenious, it is a kind of more promising separation and recovery method.Sedimentation is also needed to further for industrialized production
Deepen the effect of settling research under the conditions of the exploration and amplification of experiment condition.
US6410812B1 this method is using the BF in the flashed vapour of the alcohols Separation by Complexation such as butanol recycling flash drum overhead3,
Bottoms liquid enters the BF in parallel coalescer separation and recovery product3Complex compound.This method is preferable, but is very easy to cause BF3
The excessive buildup of complex compound.
US5811616 is using flash distillation/evaporation technology separation and recovery BF3, polymeric reaction product enters flash distillation/evaporating area,
Flash distillation/evaporating area release generates BF3, BF3It is transported by jet pump back to reactor and has continued catalytic action.The characteristics of this technique
It is the noble gas before polymerisation in removing alkene, so the gas discharged in flash distillation/evaporation only has BF3, BF3It can directly return
Return to polymer reactor.Disclosed in Unexamined Patent 6-287211 bulletins, in the system for using boron trifluoride complex catalyst
In, by heating reaction mixture, it is allowed to generate boron trifluoride gas, makes the boron trifluoride gas of generation and relative to boron trifluoride mistake
The ligand contact of surplus amount, forms new complex, the method for cycling and reutilization into reactive tank.The composite distillations such as Zhang Weijiang-phase
Butanol and BF in the advantages of vacuum distillation cracking is abundant in separating technology and flash distillation-complexing technique3Complexing is sufficiently separated recycling BF3
The advantages of gas, has designed and developed a kind of vacuum distillation -ol class complexing technique to separate and recover BF3Complex compound, the technique is first
To the BF of polymerizate in vacuum (distilling) column3Complex compound carries out vacuum cracking, cracks the BF of generation3Gas etc. enters BF3Network
It attaches together and puts and complexing agent counter current contacting, BF3It is recycled after being captured by complexing back to polymer reactor.Above method needs disappear
The problems such as consuming a large amount of energy consumption, and easily causing corrosion.
Invention content
The object of the present invention is to provide a kind of corrosion of equipment rate is low, low viscosity poly alpha olefin of device long-period stable operation
The preparation method of synthetic oil (PAO), and easy to operate, inexpensive, low energy consumption efficiently separate is provided and recycles boron trifluoride and network
The method of catalyst is closed, and is recycled utilization, so as to reduce production cost, while reduces disposal of pollutants.
For this purpose, the present invention provides a kind of preparation method of low viscosity poly alpha olefine synthetic oil, following steps are specifically included:
(1) feed purification:Dehydration refinement treatment is carried out to raw material alpha-olefin, makes its water content≤10ppm;
(2) polymerisation:Co-catalyst, water content≤10ppm are added in the feed, and are filled with major catalyst BF3Into
Row reaction, co-catalyst and BF3With reference to complex catalyst is obtained, reaction product is finally obtained;
(3) it flashes:Reaction product progress flash distillation process is obtained into the first oil phase and gas phase, gas phase is detached for complex catalyst
The BF being recycled3, recycle, while terminate polymerisation;
(4) it precipitates:First oil phase carries out precipitation process, obtains catalyst layer and the second oil phase, is returned by catalyst layer
The complex catalyst of receipts recycles, and the second oil phase carries out alkali cleaning, washing or direct washing process, obtain after gas-liquid separation
Clean intermediate products;
(5) vacuum distillation is with adding hydrogen:Intermediate products obtain light component and heavy constituent through vacuum distillation, and light component is recycling
Alpha-olefin and alpha-olefin dimer obtain poly alpha olefine synthetic oil after the hydrogenated saturated process of heavy constituent.
The preparation method of low viscosity poly alpha olefine synthetic oil of the present invention, in step (4), it is preferred that described
The gas that two oil phases go out through gas-liquid separation is the BF of recycling3。
The preparation method of low viscosity poly alpha olefine synthetic oil of the present invention, it is preferred that in step (1), the original
Material further includes the alpha-olefin of the recycling and alpha-olefin dimer;In step (2), include helping for supplement with the co-catalyst and urge
Agent and the complex catalyst of the recycling;The major catalyst further includes the BF of the recycling3。
The preparation method of low viscosity poly alpha olefine synthetic oil of the present invention, in step (2), the use of the co-catalyst
It measures to recycle complex catalyst and supplement in terms of the total amount of alcohol or acid in co-catalyst comes, total amount and the original of the alcohol or acid
The ratio between amount of substance of alpha-olefin is preferably 1 in material:50~1:1000, further preferably 1:100~1:500.
The preparation method of low viscosity poly alpha olefine synthetic oil of the present invention, wherein, the BF of the recycling3It is preferred that it pressurizes
Recycling after to 0.1~1.0MPa.
The preparation method of low viscosity poly alpha olefine synthetic oil of the present invention, wherein, the poly alpha olefine synthetic oil
100 DEG C of kinematic viscosity is preferably 2~10mm2/s。
The preparation method of low viscosity poly alpha olefine synthetic oil of the present invention, wherein, the raw material is preferably C8~C14
At least one of linear alpha-olefin.
The preparation method of low viscosity poly alpha olefine synthetic oil of the present invention, wherein, the co-catalyst is preferably C1
The monohydric alcohol of~C4 or the unitary organic acid of C1~C4.
The preparation method of low viscosity poly alpha olefine synthetic oil of the present invention, in step (2), it is preferred that reaction temperature
It is 0~100 DEG C to spend, and the reaction time is 0.1~2h, and reaction pressure is 0.01~1.0MPa.
The preparation method of low viscosity poly alpha olefine synthetic oil of the present invention, in step (3), it is preferred that flash distillation pressure
Power is -0.1~0MPa, and temperature is 0~100 DEG C.
The preparation method of low viscosity poly alpha olefine synthetic oil of the present invention, in step (4), it is preferred that place of settling
The residence time of reason is 1~20h, and temperature is 0~100 DEG C.
The preparation method of the low viscosity poly alpha olefine synthetic oil of the present invention, specifically includes following steps:
(1) dehydration refinement treatment is carried out by zeolite fixed-bed reactor to alpha-olefin raw material, makes raw material water content≤10ppm;
Usually contain minor amount of water in alpha-olefin raw material, and BF3The corrosivity of lewis acid catalyst is stronger, in order to as far as possible
Avoid the corrosion of equipment and pipeline, reply alpha-olefin raw material is carried out dehydrating, and is allowed to water content≤10ppm, and molecular sieve energy
It is enough cost-effectively to remove minor amount of water therein.
Molecular sieve adsorbing and dewatering is different and different with different raw materials and molecular sieve type, and the skill that the process is this field
Known to art personnel, therefore no longer it is described in detail.
(2) monomer and dimer (being obtained by following step (5)) of alpha-olefin raw material and recycling are squeezed into reactor
In, add in recycling complex catalyst (being obtained by following step (4)) and supplement supplement co-catalyst (water content≤
10ppm), it is filled with BF3It is reacted, co-catalyst and BF3With reference to obtaining complex catalyst.
The dosage of usual catalyst is according to the alcohol in the complex catalyst of recycling and the supplement co-catalyst of supplement or acid
Total amount is added to measure, and optimal proportion is alcohol or the ratio between acid and amount of substance of alpha-olefin raw material are 1:50~1:1000 ratio
The ratio between example addition, amount of optimisation substance are 1:100~1:500, and BF3Pressure then be usually 0~1MPa, optimum range 0.05
~0.2MPa, reaction temperature are then 0~100 DEG C, and reaction time is 0.1~2h, are most preferably then 0.5~1h.
(3) polymerizate flash distillation process:Reaction product progress flash distillation process is obtained into the first oil phase and gas phase, it is therefore an objective to point
From the BF being dissolved in polymerizate3Gas, while also decompose part complex catalyst, catalyst activity is terminated, and recycle
BF3, recycle.
Flashing pressure is -0.1~0MPa, and optimal pressure range is -0.98MPa~-0.5MPa;Flash temperature for 0~
100 DEG C, optimum temperature range is 20~60 DEG C, on this condition, the gaseous state BF dissolved in polymerizate3It can be kept completely separate,
And also decomposed is BF to complex compound therein3With alcohol or acid, BF3It can then be detached with product rapidly, and alcohol or acid are then dissolved in
In polymerizate, and generation inactive complexes are reacted with active catalyst, so as to fulfill the automatic termination of polymerisation.
The BF of vacuum flashing3Gas is then compressed to 0.1~1.0MPa by conduit pressurizer or compressor etc., direct or logical
It crosses storage tank to return in reactor, realizes BF3The reuse of gas.
(4) it precipitates:Recycle nonactive complex catalyst
After flash distillation process, the deactivated complex catalyst in oil is insoluble in polymerizate oil, and with gathering
Product oil phase ratio is closed, density is also larger, and under gravity, easily and oil-lamination, upper strata therein are more limpid
Oil be the second oil phase, lower floor is then catalyst layer (mainly BF3Complex compound), the complex catalyst so as to be recycled.
To further improve above-mentioned BF3Complex compound recovering effect, reduce disposal of pollutants, it is necessary into one for the second oil phase
Step carries out reduced pressure treatment, the BF generated due to complex compound decomposes convenient for recycling precipitation process3Gas or the BF being dissolved in oil3Gas
Body.
By flash distillation and precipitation process, the recycling of catalyst can be more fully realized, and remaining a small amount of catalyst leads to
Cross alkali cleaning, water-washing process thoroughly removes, obtain the process and be usually well known to those skilled in the art, therefore be no longer described in detail.
(5) vacuum distillation is with adding hydrogen
For the utilization rate and economic benefit of raising raw material, the clean intermediate products after alkali and/or washing are through vacuum distillation point
It from light components such as the monomers and dimer being recycled, and returns in reactor and is continuing with, remaining heavy constituent is not if
Saturation poly alpha olefine synthetic oil then carries out plus hydrogen saturated process, finally obtains qualified lube base oil, and further cut,
It can obtain the poly alpha olefin lube base oil product of different viscosities grade.
Vacuum distillation is also different and different with different raw materials and hydrogenation catalyst type from hydrogenation process conditions, and the mistake
Journey is well known to those skilled in the art, therefore is no longer described in detail.
Compared with prior art, the technology of the present invention solves the deficiencies in the prior art, has the advantages that following notable:
1. the present invention is reduced avoided equipment, pipeline rotten as much as possible using the water in molecular sieve dehydration technique removing raw material
Erosion, can reduce investment outlay cost.
2. the present invention can realize the self termination of polymerisation, and realize complex catalyst using vacuum flash technique
Recycling.
3. the shortcomings that energy consumption the invention avoids high-temperature cracking method is higher also avoids additional terminator or extractant etc.
Caused unnecessary impurity, simplifies subsequent treatment process.
4. present invention process is simple, easy to operate, process conditions are mild, and operating cost can significantly reduce.
Description of the drawings
Fig. 1 is the process flow chart of the preparation method of the low viscosity poly alpha olefine synthetic oil of the present invention;
Wherein, reference numeral:
1. molecular sieve water separation tower;2. reactor;3. flash vessel;4. booster;5. boron trifluoride storage tank;6. settling tank;7.
Catalyst recycling can;8. gas-liquid separator;9. alkali, water scrubber;10. vacuum distillation tower;11. hydrogenation reactor.
Specific embodiment
Following example is method in order to further illustrate the present invention, but be should not be limited thereto.
Following embodiment is being implemented down based on the technical solution of the present invention, gives detailed embodiment and mistake
Journey the technological parameter of actual conditions is not specified in the following example, usually according to normal condition.
Shown in Figure 1, the preparation method of low viscosity poly alpha olefine synthetic oil of the invention specifically includes following steps:
(1) dehydration refinement treatment is carried out by zeolite fixed-bed reactor (i.e. molecular sieve water separation tower 1) to alpha-olefin raw material, makes original
Expect water content≤10ppm;
(2) monomer and dimer (being obtained by following step (5)) of alpha-olefin raw material and recycling are squeezed into reactor 2
In, add in recycling complex catalyst (being obtained by following step (4)) and supplement supplement co-catalyst (water content≤
10ppm), it is filled with BF3It is reacted, co-catalyst and BF3With reference to obtaining complex catalyst.
(3) polymerizate flash distillation process:By flash vessel 3 reaction product is carried out flash distillation process, and to obtain the first oil phase gentle
Phase terminates catalyst activity, and recycles BF3, recycle.
The BF of vacuum flashing3Gas is then compressed to 0.1~1.0MPa by conduit pressurizer 4, passes through boron trifluoride storage tank 5
Back in reactor 2, BF is realized3The reuse of gas.
(4) it precipitates:Recycle nonactive complex catalyst
After flash distillation process, liquid material by flash vessel 3 enter settling tank 6, oil in deactivated complex catalysis
Agent is insoluble in polymerizate oil, and easily and oil-lamination, upper strata therein are that the second oil phase enters gas for more limpid oil
Liquid/gas separator 8, lower floor are then catalyst layer (mainly BF3Complex compound), complex catalyst so as to be recycled, which enters, urges
Agent recycling can 7.
(5) vacuum distillation is with adding hydrogen
Second oil phase continue by gas-liquid separator 8 enter alkali, water scrubber 9, alkali and/or washing after clean intermediate products by
The light components such as monomer and dimer of the vacuum distillation tower 10 through being evaporated under reduced pressure isolated recycling, and return in reactor 2
Be continuing with, remaining heavy constituent such as carried out by hydrogenation reactor 11 if unsaturated poly alpha olefine synthetic oil plus hydrogen saturated process,
Qualified lube base oil is finally obtained, and is further cut, can obtain the poly alpha olefin lubrication oil base of different viscosities grade
Plinth oil product.
Implement when going into operation of the method for the invention, can price alcohol or organic acid catalyst be added in reaction kettle, wait until
Complex catalyst accumulation to it is enough when implement catalyst and recycle, naturally it is also possible to set catalyst be complexed in advance after directly plus
Enter into reaction kettle.
Examples 1 to 6
It is Material synthesis low viscosity PAO to be dehydrated refined 1- decene (water content is 8ppm), with butanol (water content
It is 9ppm) co-catalyst, the amount ratio of butanol and 1- decene is 1:100 (amounts of substance), in 30 DEG C, BF3Pressure is 0.2MPa
Under the conditions of react, reaction time 1h, gained reaction product carry out flash distillation process, different flash conditions are respectively adopted and are dodged
Experiment (being shown in Table 1, obtain embodiment 1-6) is steamed, obtains the first oil phase and gas phase, gas phase, that is, flashed vapour Returning reactor after supercharging,
First oil phase then enters settling vessel and carries out precipitation process.
1 flash process of table is to BF3Removal effect
Embodiment 7~11:
(i.e. precipitated oil) is fed using the first oil phase of embodiment 3 as precipitation, different deposition conditions is respectively adopted and carries out
Precipitation test (is shown in Table 2, obtain embodiment 7-11), obtains second oil phase on upper strata and the catalyst layer of lower floor, the second oil phase is through gas
After liquid separation, gained gas merges compression processing with flashed vapour, and remaining oil phase (i.e. degassing oil) carries out alkali cleaning, washing process obtains water
Washing oil (i.e. clean intermediate products), measures the fluorine content of washing oil, and analyze the composition of the catalyst layer of lower floor, is listed in table 2.
2 sedimentation separation of table is to BF3Removal effect
Intermediate products obtain poly alpha olefin after continuing on through vacuum distillation separating monomer and dimer back end hydrogenation saturated process
Synthetic oil.
Embodiment 12~13:
By the complex catalyst (in terms of butanol therein) recycled by the catalyst layer of embodiment 9 and 1- decene by substance
The ratio between amount 1:120 ratio is added in reactor, while with the gas phase BF in recycling can3As supplement gas, control in reactor
Pressure for 0.2MPa, reaction temperature carries out PAO synthetic reactions under the conditions of being 30 DEG C, and under the same reaction conditions by fresh
Catalyst product composition obtained by the reaction is compared, and is as a result listed in table 3.
Table 3 recycles the reaction effect of catalyst
As shown in Table 3, the complex catalyst of this method recycling still has higher reactivity.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
It should all belong to the scope of protection of the present invention.
Claims (12)
1. a kind of preparation method of low viscosity poly alpha olefine synthetic oil, it is characterised in that:Specifically include following steps:
(1) feed purification:Dehydration refinement treatment is carried out to raw material alpha-olefin, makes its water content≤10ppm;
(2) polymerisation:Co-catalyst, water content≤10ppm are added in the feed, and are filled with major catalyst BF3It carries out anti-
Should, co-catalyst and BF3With reference to complex catalyst is obtained, reaction product is finally obtained;
(3) it flashes:Reaction product progress flash distillation process is obtained into the first oil phase and gas phase, gas phase is isolated for complex catalyst
The BF of recycling3, recycle, while terminate polymerisation;
(4) it precipitates:First oil phase carries out precipitation process, obtains catalyst layer and the second oil phase, is recycled by catalyst layer
Complex catalyst recycles, and the second oil phase carries out alkali cleaning, washing or direct washing process, obtain cleaning after gas-liquid separation
Intermediate products;
(5) vacuum distillation is with adding hydrogen:Intermediate products obtain light component and heavy constituent through vacuum distillation, and light component is α-alkene of recycling
Hydrocarbon and alpha-olefin dimer obtain poly alpha olefine synthetic oil after the hydrogenated saturated process of heavy constituent.
2. the preparation method of low viscosity poly alpha olefine synthetic oil according to claim 1, which is characterized in that in step (4),
The gas that second oil phase goes out through gas-liquid separation is the BF of recycling3。
3. the preparation method of low viscosity poly alpha olefine synthetic oil according to claim 1 or 2, which is characterized in that step (1)
In, the raw material further includes the alpha-olefin of the recycling and alpha-olefin dimer;In step (2), the co-catalyst includes mending
The co-catalyst and the complex catalyst of the recycling filled;The major catalyst further includes the BF of the recycling3。
4. the preparation method of low viscosity poly alpha olefine synthetic oil according to claim 3, which is characterized in that in step (2),
The dosage of the co-catalyst by recycle complex catalyst and supplement co-catalyst in alcohol or acid total amount come in terms of, the alcohol or
The ratio between the total amount of acid and the amount of substance of alpha-olefin in the raw material are 1:50~1:1000.
5. the preparation method of low viscosity poly alpha olefine synthetic oil according to claim 4, which is characterized in that the alcohol or acid
Total amount and the raw material in the ratio between the amount of substance of alpha-olefin be 1:100~1:500.
6. the preparation method of low viscosity poly alpha olefine synthetic oil according to claim 1 or 2, which is characterized in that described time
The BF of receipts3It is forced into recycling after 0.1~1.0MPa.
7. the preparation method of low viscosity poly alpha olefine synthetic oil according to claim 1, which is characterized in that the poly- α-alkene
100 DEG C of kinematic viscosity of hydrocarbon synthetic oil is 2~10mm2/s。
8. the preparation method of low viscosity poly alpha olefine synthetic oil according to claim 1, which is characterized in that the raw material is
At least one of C8~C14 linear alpha-olefins.
9. the preparation method of low viscosity poly alpha olefine synthetic oil according to claim 1, which is characterized in that the co-catalysis
Agent is the monohydric alcohol of C1~C4 or the unitary organic acid of C1~C4.
10. the preparation method of low viscosity poly alpha olefine synthetic oil according to claim 1, which is characterized in that step (2)
In, reaction temperature is 0~100 DEG C, and the reaction time is 0.1~2h, and reaction pressure is 0.01~1.0MPa.
11. the preparation method of low viscosity poly alpha olefine synthetic oil according to claim 1, which is characterized in that step (3)
In, flashing pressure is -0.1~0MPa, and temperature is 0~100 DEG C.
12. the preparation method of low viscosity poly alpha olefine synthetic oil according to claim 1, which is characterized in that step (4)
In, the residence time of precipitation process is 1~20h, and temperature is 0~100 DEG C.
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