CN106883899B - A kind of preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI) - Google Patents
A kind of preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI) Download PDFInfo
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/02—Well-defined hydrocarbons
- C10M105/04—Well-defined hydrocarbons aliphatic
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/862—Iron and chromium
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
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- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/86—Chromium
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- C—CHEMISTRY; METALLURGY
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/02—Well-defined aliphatic compounds
- C10M2203/0206—Well-defined aliphatic compounds used as base material
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- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
Abstract
The present invention relates to a kind of preparation methods of the poly alpha olefine synthetic oil of high viscosity index (HVI), method includes the following steps: oligomerisation catalyst is added in the feed, 30~120min is reacted under conditions of 20~50 DEG C；Separating catalyst, reaction product and unreacted 'alpha '-olefin monomers, the reaction product is distilled plus hydrogen, obtains kinematic viscosity > 40cSt at 100 DEG C, the poly alpha olefine synthetic oil of viscosity index (VI) > 150.For this method using cheap branched alpha-olefin as synthesis material, fictitious hosts valuableness 1- decene polymerization prepares the PAO of high viscosity index (HVI).Using the branched alpha-olefin as synthesis material, by-product not only can use, increase operation rate, and prepare the PAO of high viscosity index (HVI) using self-produced decene fictitious hosts valuableness 1- decene polymerization, reduce cost, increase economic benefit.
Description
Technical field
The present invention relates to a kind of preparation methods of poly alpha olefine synthetic oil, more particularly to one kind to be suitable for preparation lubrication oil base
The preparation method of the high viscosity index poly alpha olefine synthetic oil of plinth oil.
Background technique
Poly alpha olefin (PAO) synthetic oil is the optimal synthetic lubricant base oil of current performance, have high viscosity index,
Low volatility, low-flow, preferable cutting performance and excellent high temperature oxidation resistance；With traditional mineral lubricant oil base oil
(I, II, III class base oil) is compared, and PAO evaporation loss is small, stability is good, use temperature range is wide, with common material compatibility
It is the features such as good and nontoxic, not only extensive in the civilian industrial application such as automobile, industry, even more used in the industries such as Aeronautics and Astronautics, military project
The main source of top-grade lubricating oil base oil.
PAO is usually by C6-C20One kind of alpha-olefin catalytic oligomerization synthesis has the oligomer of branch saturation, wherein the 1- last of the ten Heavenly stems
Alkene is preferred material, and there are commonly BF for oligomerisation catalyst systems3System, Cr system, Al chemical combination objects system and Ziegler-
Natta etc..The catalytic polymerization of alpha-olefin is the known technology for preparing PAO synthetic lubricant fluid.For producing the method for PAO in many
It is disclosed in patent, such as US patent Nos.3149178；3382291；3742082；3780128；4172855 and 4956122；
Chinese patent Nos.1948243A；102015787A；102924208A etc..
In addition to use 1- decene for raw material other than, other raw materials are used to synthesize the patent of PAO and also have been reported that, such as US patent
No.4956122 can obtain 2~100cSt of viscosity wide range of viscosities at 100 DEG C using ethylene and more advanced olefin-copolymerization
PAO product.The alkene mixture of 1- octene, 1- decene and 1- dodecylene can also be used to preparation PAO, such as patent
CN1505643A and 101102982A.Chinese patent CN103100419A is using support type organo-aluminum compound and as promotor
Proton donor two components as catalyst system, carry out the oligomerisation reaction of mixing decene, the conversion ratio for mixing decene is greater than
50%, but properties of product are not described.In international publication WO2006/071135A1 patent, at catalyst system Al (O)
Make alpha-olefin isomerization under the action of HClTBCh and oligomeric for or mixtures thereof higher alkene.
Viscosity index (VI) (VI) indicates the degree that all fluid viscosities vary with temperature.Viscosity index (VI) is higher, indicates that fluid is viscous
Degree is influenced by temperature smaller.China begins to production synthetic hydrocarbon oil early in the seventies, but uses wax olefin cracking more, and product is viscous
Degree index is low, thermostability is poor.At the beginning of the nineties, Mobil Oil Corporation is to improve lubricating oil service performance, with C6-C20Linear α-alkene
Hydrocarbon is raw material, develops HVI-PAO technique, generates high-viscosity index lubricating oil under polymerization conditions.Viscosity index (VI) is lubricating oil
One important performance indexes of base oil provide in patent CN1948243A and a kind of prepare high viscosity index poly alpha olefine synthesis
Oil method contact α-decene raw material with active chromium catalyst in tank reactor, and 0.1-2.0MPa, 100~
2~20h is reacted at 250 DEG C；Wherein the catalyst is load chromium type, and product viscosity index is greater than 190, but requires in this method
Linear alpha-alkene weight percent in α-decene raw material should be not less than 95%, and moisture content should be lower than 100ug/g, peroxide
Content should be lower than 5ug/g.
The above-mentioned method for preparing PAO can be synthesized viscous using expensive 1- decene as raw material using suitable catalyst system
The higher PAO product of index is spent, but uses non-linear alkene (such as mixing decene or other branched alpha-olefins) for raw material, polymerization effect
Fruit is poor, and conversion ratio is low, and product viscosity index is not high.The above method simultaneously not applicable refers to using non-linear alkene as raw material for high viscosity
The synthesis of number PAO product.It is rarely reported at present for directlying adopt branched alpha-olefins polymerization and prepare the PAO of high viscosity index (HVI).
Summary of the invention
The object of the present invention is to provide one kind using cheap branched alpha-olefins as raw material, in support type double activity center catalyst
The method of high viscosity index poly alpha olefine synthetic oil is prepared under effect.Poly alpha olefine synthetic oil quality made from this method is good, receives
Rate is high, at low cost.
In order to achieve the above objectives, the present invention provides a kind of preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI), packet
It includes following steps: oligomerisation catalyst being added in the feed, 30~120min is reacted under conditions of 20~50 DEG C；Separation catalysis
Agent, reaction product and unreacted 'alpha '-olefin monomers, the reaction product is distilled plus hydrogen, obtains poly alpha olefine synthetic oil；
The raw material includes the branched alpha-olefins containing 4~14 carbon atoms, line style α-alkene containing 4~14 carbon atoms
Hydrocarbon and alkene with molecule internal double bond are in terms of 100% by the weight of raw material, and branched alpha-olefins account for 0.1-91.0%, line style α-
Alkene accounts for 0.5-4.0%, and surplus is the alkene of molecule internal double bond.
The preparation of the oligomerisation catalyst:
Using the method for step impregnation, one of selection active component corresponding metal salt of metal oxide first is in deionization
It dissolves in water, is immersed on carrier with resulting metal salt solution, 30~180min is stirred at 25~50 DEG C, it is dry, it takes above-mentioned
Carrier after drying places it in the roasting of Muffle furnace high temperature, and load can further be had to the load of metal oxide if necessary
Body is in reducing gas (H2Or CO) under atmosphere, higher valence metal oxide is reduced to metal suboxide.Then it is urged above-mentioned
Agent parent, is added in the organic solvent of another inorganic metal salt and is loaded, for example, toluene, acetone, chlorobenzene isopropanol
Support type double activity center catalyst can be obtained in equal solvent, then saves, is spare.In the preparation step of above-mentioned catalyst, institute
Stating the corresponding metal salt of metal oxide is the soluble vanadic salts such as nitric acid vanadium, vanadyl oxalate, vanadic sulfate；Chromic nitrate, chromic acetate,
The solubility chromic salts such as chromium sulfate.
The distillation of reaction product plus hydrogen:
In method provided by the present invention, distillation and hydrogenation process for reaction product do not have particular/special requirement, distillation
Process can use device and atmospheric and vacuum distillation commonly used in the art, as long as can be realized unconverted monomer and dimer, three
The difference product separation such as oligomer more than aggressiveness and the tetramer.Similarly, for the hydrogenation process also without spy
Different to require, as long as can reach hydrogenation of net product purpose, common hydrogenation catalyst, equipment, process conditions etc. be can be used.
The preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI) of the present invention, the branched alpha-olefins preferably account for
5-80%.
The preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI) of the present invention, the branched alpha-olefins are more preferable
Account for 15-60%.
The preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI) of the present invention, the branched alpha-olefins preferably select
Free 2- butyl-1- hexene, 3- propyl-1- heptene, 4- ethyl-1- octene, 5- methyl-1-nonene, 4- butyl-1- decene, 3-
At least one of butyl -1- decene, 2- ethyl -1- laurylene and the formed group of 6- ethyl -1- laurylene.
The preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI) of the present invention, the branched alpha-olefins are averaged
Carbon atom number is preferably 8.9-12.5.
The preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI) of the present invention, the oligomerisation catalyst preferably wrap
Carrier and double activated component are included, the double activated component preferably includes metal oxide and Lewis acid type metal salt.
The preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI) of the present invention, the Lewis acid type metal salt
It is preferably selected from by AlCl3、FeCl3、SnCl4、TiCl4And ZnCl2At least one of formed group.
The preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI) of the present invention, the metal oxide are preferably
V2O5And/or CrO.
The preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI) of the present invention, the carrier are preferably selected from by two
At least one of formed group of silica, aluminum oxide, chromatographic silica gel, molecular sieve.
The preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI) of the present invention, the molecular sieve are preferably MCM-
41, MCM-48 or SBA-15.
The preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI) of the present invention, the reaction temperature are preferably 25
~35 DEG C, the reaction time is preferably 60~100min.
Compared with prior art, the preparation method of poly alpha olefine synthetic oil provided by the present invention has the beneficial effect that
(1) using cheap branched alpha-olefin as synthesis material, fictitious hosts valuableness 1- decene polymerization prepares high viscosity index (HVI)
PAO, branched alpha-olefins used can be selected from preparing linear alpha-alkene, such as 1- hexene, 1- octene, 1- decene or high-carbon α-alkene
Hydrocarbon (C12~C20 +) in byproduct；Or from decene device, which is separated by filtration using column chromatography silica gel, removes useless
The impurity such as catalyst.Using the branched alpha-olefin as synthesis material, by-product not only can use, increase operation rate, and use
Self-produced decene fictitious hosts valuableness 1- decene polymerization prepares the PAO of high viscosity index (HVI), reduces cost, increases economic benefit.
(2) the resulting poly alpha olefin of the preparation method, viscosity index (VI) with higher (kinematic viscosity > at 100 DEG C
40cSt, viscosity index (VI) > 150), quality is good, and yield is higher；Simple operation of process improves process economy.
(3) preparation method uses support type double activity center catalyst, for active branched alpha-olefin, compared to normal
Traditional homogeneous catalyst is advised, activity is weaker, by modulation metal species and proportion, can reach the purpose of the control degree of polymerization, system
It is standby simple, strong operability.
Specific embodiment
The present invention is described in further detail by the following examples, but these embodiments are not considered as to limit of the invention
System.
The preparation of 1 oligomerisation catalyst of embodiment
By 8g silica (pore volume 0.50cm3/ g, average pore size is in 2.0nm, specific surface area 158m2/ g) it is immersed in
In nitric acid vanadium aqueous solution (vanadium load capacity is 0.20wt%), leaching 30min, filtering are continuously stirred in 25 DEG C of water-baths, 100 DEG C of vacuum are done
Dry 6h；The silica supports for being impregnated with nitric acid vanadium are placed in Muffle furnace and are roasted, are warming up to 120 DEG C, constant temperature 2h first,
It is warming up to 350 DEG C, constant temperature 1h later, is continuously heating to 450 DEG C, constant temperature 6h, finally Temperature fall is cooling under a nitrogen.It will obtain
Sample be immersed in the toluene solution of alchlor (Al load capacity be 12.00wt%) again, continuously stir dipping at room temperature
2h, 100 DEG C of vacuum drying 6h obtain oligomerisation catalyst and save for use.
The preparation of 2 oligomerisation catalyst of embodiment
By 8g silica (pore volume 0.58cm3/ g, average pore size is in 12.5nm, specific surface area 100m2/ g) it is immersed in
In vanadyl oxalate aqueous solution (vanadium load capacity is 0.58wt%), dipping 50min is continuously stirred in 45 DEG C of water-baths, filtering, 100 DEG C true
The dry 6h of sky；The silica supports for being impregnated with vanadyl oxalate are placed in Muffle furnace and are roasted, are warming up to 120 DEG C first,
Constant temperature 2h is warming up to 350 DEG C, constant temperature 1h later, is continuously heating to 450 DEG C, constant temperature 6h, finally Temperature fall is cold under a nitrogen
But.Obtained sample is immersed in the aqueous isopropanol of titanium tetrachloride (Ti load capacity is 10.68wt%) again, is connected at room temperature
Continuous stirring dipping 2h, 100 DEG C of vacuum drying 6h, obtain oligomerisation catalyst and save for use.
The preparation of 3 oligomerisation catalyst of embodiment
By 10g aluminum oxide (gama-alumina, pore volume 1.34cm3/ g, average pore size is in 20nm, specific surface area
220m2/ g) it is immersed in chromic acetate aqueous solution (chromium load capacity is 12.00wt%), dipping is continuously stirred in 25 DEG C of water-baths
60min, filtering, 100 DEG C of vacuum drying 6h；The alumina carrier for being impregnated with chromic acetate is placed in Muffle furnace and is roasted
It burns, is warming up to 120 DEG C, constant temperature 2h first, is warming up to 350 DEG C, constant temperature 1h later, be continuously heating to 550 DEG C, constant temperature 6h, finally
Temperature fall is cooled to 200-300 DEG C under a nitrogen, is passed through reducibility gas H2, continue 1-3h, also by the chromated oxide contained
It originally was the chromium oxide of low price.Obtained sample is immersed in the aqueous isopropanol of titanium tetrachloride to (Ti load capacity is again
0.10wt%), dipping 4h, 100 DEG C of vacuum drying 6h are continuously stirred at room temperature, are obtained oligomerisation catalyst and are saved for use.
The preparation of 4 oligomerisation catalyst of embodiment
By 10g aluminum oxide (gama-alumina, pore volume 1.34cm3/ g, average pore size 20nm, specific surface area
220m2/ g) it is immersed in chromium nitrate aqueous solution (chromium load capacity is 11.56wt%), dipping is continuously stirred in 25 DEG C of water-baths
70min, filtering, 100 DEG C of vacuum drying 6h；The alumina carrier for being impregnated with chromic nitrate is placed in Muffle furnace and is roasted
It burns, is warming up to 120 DEG C, constant temperature 2h first, is warming up to 350 DEG C, constant temperature 1h later, be continuously heating to 550 DEG C, constant temperature 6h, finally
Temperature fall is cooled to 200-300 DEG C under a nitrogen, is passed through reducibility gas CO, continues 1-3h, also by the chromated oxide contained
It originally was the chromium oxide of low price.Obtained sample is immersed in the isopropyl acetone solution of ferric trichloride to (Fe load capacity is again
0.24wt%), dipping 4h, 100 DEG C of vacuum drying 6h are continuously stirred at room temperature, are obtained oligomerisation catalyst and are saved for use.
The preparation of 5 oligomerisation catalyst of embodiment
By 10g SBA-15 molecular sieve (pore volume 5.2cm3/ g, average pore size 3.9nm, specific surface area 500m2/ g) dipping
In chromium sulfate aqueous solution (chromium load capacity is 4.20wt%), dipping 80min is continuously stirred in 25 DEG C of water-baths, filtering, 100 DEG C true
The dry 6h of sky；The SBA-15 molecular sieve carrier for being impregnated with chromium sulfate is placed in Muffle furnace and is roasted, is warming up to 120 first
DEG C, constant temperature 2h is warming up to 350 DEG C, constant temperature 1h later, is continuously heating to 550 DEG C, constant temperature 6h, finally Temperature fall under a nitrogen
It is cooled to 200-300 DEG C, is passed through reducibility gas CO, continues 1-3h, the chromated oxide contained is reduced to the chromium oxide of low price.
Obtained sample is immersed in the toluene solution of zinc chloride (load capacity of Zn is 11.20wt%) again, is continuously stirred at room temperature
Dipping 4h, 100 DEG C of vacuum drying 6h are mixed, oligomerisation catalyst is obtained and saves for use.
The preparation of 6 oligomerisation catalyst of embodiment
By 10g MCM-41 molecular sieve (pore volume 1.20cm3/ g, average pore size 3.20nm, specific surface area 1000m2/g)
It is immersed in vanadic sulfate aqueous solution (vanadium load capacity is 0.38wt%), continuously stirs dipping 3h in 45 DEG C of water-baths, filter, 100
DEG C vacuum drying 6h；The MCM-41 carrier for being impregnated with vanadic sulfate is placed in Muffle furnace and is roasted, is warming up to 120 first
DEG C, constant temperature 2h is warming up to 350 DEG C, constant temperature 1h later, is continuously heating to 450 DEG C, constant temperature 6h, finally Temperature fall under a nitrogen
It is cooling.Obtained sample is immersed in the toluene solution of tin tetrachloride (Sn load capacity is 0.86wt%) again, is connected at room temperature
Continuous stirring dipping 4h, 100 DEG C of vacuum drying 6h, obtain oligomerisation catalyst and save for use.
Embodiment 7
By catalyst 3.02g made from embodiment 1, under nitrogen protection, it is added to the dry three neck round bottom flask of 500mL
In, then 120mL raw material is added into flask, consisting of branched alpha-olefins 91% (3- propyl -1- heptene 22.2%, 4- ethyl -
1- octene 25.2%, 5- methyl-1-nonene 30.6%, 2- butyl-1- hexene 6.2%, 2- ethyl-1- laurylene 6.8%), line
Type alpha-olefin 4.0% (1- decene 4.0%), alkene, that is, "inner" alkene 5.0% (5- decene 2.3%, 3- with molecule internal double bond
Methyl -4- nonene 1.1%, 2- ethyl -3- octene 1.6%), under the conditions of 20 DEG C of water-bath, stir polymerization reaction 30min, reaction
After, catalyst is filtered to isolate, monomer and dimer is distilled off, obtains product after adding hydrogen, product is collected and carries out performance
Test, is shown in Table 1.
Embodiment 8
By catalyst 3.02g made from embodiment 1, under nitrogen protection, it is added to the dry three neck round bottom flask of 500mL
In, then 120mL raw material is added into flask, consisting of branched alpha-olefins 88% (3- propyl -1- heptene 20.7%, 4- ethyl -
1- octene 26.2%, 5- methyl-1 nonene 31.6%, 2- butyl -1- decene alkene 9.5%), (the 1- octene of linear alpha-olefins 3.4%
3.4%), with alkene, that is, "inner" alkene 8.6% (5- decene 5.6%, 3- methyl -4- nonene 3.0%) of molecule internal double bond, In
Under the conditions of 35 DEG C of water-bath, stirring polymerization reaction 30min filters to isolate catalyst after reaction, and monomer and two is distilled off
Aggressiveness obtains product after adding hydrogen, collects product and is tested for the property, is shown in Table 1.
Embodiment 9
By catalyst 3.02g made from embodiment 1, under nitrogen protection, it is added to the dry three neck round bottom flask of 500mL
In, then 120mL raw material is added into flask, consisting of branched alpha-olefins 86.9% (3- propyl -1- heptene 18.5%, 4- second
Base -1- octene 24.2%, 3- butyl -1- decene 27.6%, 2- ethyl -1- laurylene 16.6%), 0.5% (1- of linear alpha-olefins
Laurylene 0.5%), alkene, that is, "inner" alkene 12.6% (5- decene 8.3%, 3- methyl -6- laurylene with molecule internal double bond
4.3%), under the conditions of 50 DEG C of water-bath, stirring polymerization reaction 30min filters to isolate catalyst after reaction, and distillation removes
Monomer and dimer are removed, obtains product after adding hydrogen, product is collected and is tested for the property, be shown in Table 1.
Embodiment 10
By catalyst 3.02g made from embodiment 2, under nitrogen protection, it is added to the dry three neck round bottom flask of 500mL
In, then 120mL raw material is added into flask, consisting of branched alpha-olefins 90.2% (4- ethyl -1- octene 35.2%, 4- fourth
Base -1- decene 30.6%, 2- butyl -1- hexene 20.1%), linear alpha-olefins 3.8% (1- decene 3.8%) have intramolecular
The alkene of double bond, that is, "inner" alkene 6% (5- decene 4.3%, 4- octene 1.7%), under the conditions of 25 DEG C of water-bath, stirring polymerization is anti-
It answers 30min, after reaction, filter to isolate catalyst, monomer and dimer is distilled off, obtain product after adding hydrogen, collect
Product is tested for the property, and is shown in Table 1.
Embodiment 11
By catalyst 3.02g made from embodiment 2, under nitrogen protection, it is added to the dry three neck round bottom flask of 500mL
In, then 120mL raw material is added into flask, consisting of branched alpha-olefins 80% (3- propyl -1- heptene 32.5%, 4- ethyl -
1- octene 25.2%, 2- ethyl -1-tetradecylene 22.3%), linear alpha-olefins 3.6% (1- decene 3.6%) have intramolecular double
The alkene of key, that is, "inner" alkene 16.4 (5- decene 8.9%, 6- laurylene 3.2%, 3- methyl -4- nonene 4.3%), in water-bath 25
Under the conditions of DEG C, stirring polymerization reaction 60min filters to isolate catalyst after reaction, and monomer and dimer is distilled off,
Product is obtained after adding hydrogen, product is collected and is tested for the property, be shown in Table 1.
Embodiment 12
By catalyst 3.02g made from embodiment 2, under nitrogen protection, it is added to the dry three neck round bottom flask of 500mL
In, then 120mL raw material is added into flask, consisting of branched alpha-olefins 60% (3- propyl -1- heptene 30.2%, 4- ethyl -
1- octene 29.8%), linear alpha-olefins 3.9% (1- decene 3.4%, 1- octene 0.6%) are with the alkene of molecule internal double bond
"inner" alkene 36.1% (5- decene 30.3%, 3- methyl -4- nonene 5.8%) stirs polymerization reaction under the conditions of 25 DEG C of water-bath
120min filters to isolate catalyst after reaction, and monomer and dimer is distilled off, and obtains product after adding hydrogen, collects and produce
Product are tested for the property, and are shown in Table 1.
Embodiment 13
By catalyst 3.02g made from embodiment 3, under nitrogen protection, it is added to the dry three neck round bottom flask of 500mL
In, then 120mL raw material is added into flask, consisting of branched alpha-olefins 40% (3- propyl -1- heptene 40%), line style α-alkene
Hydrocarbon 4.0% (1- decene 4.0%), alkene, that is, "inner" alkene 56% (5- decene 40.6%, 2- methyl-with molecule internal double bond
4- decene 5.6%, 3- methyl -4- nonene 9.8%), under the conditions of 28 DEG C of water-bath, polymerization reaction 100min is stirred, reaction terminates
Afterwards, catalyst is filtered to isolate, monomer and dimer is distilled off, obtains product after adding hydrogen, product is collected and is tested for the property,
It is shown in Table 1.
Embodiment 14
By catalyst 3.02g made from embodiment 4, under nitrogen protection, it is added to the dry three neck round bottom flask of 500mL
In, then 120mL raw material is added into flask, consisting of branched alpha-olefins 35% (5- methyl-1 nonene 20.6%, 2- butyl-
1- hexene 6.2%, 2- ethyl -1- laurylene 8.2%), linear alpha-olefins 2.8% (1- laurylene 2.8%) have intramolecular double
The alkene of key, that is, "inner" alkene 62.2% (5- decene 42.3%, 3- methyl -4- nonene 3.1%, 2- ethyl -3- octene
16.8%), under the conditions of 25 DEG C of water-bath, stirring polymerization reaction 60min filters to isolate catalyst after reaction, and distillation removes
Monomer and dimer are removed, obtains product after adding hydrogen, product is collected and is tested for the property, be shown in Table 1.
Embodiment 15
By catalyst 3.02g made from embodiment 5, under nitrogen protection, it is added to the dry three neck round bottom flask of 500mL
In, then 120mL raw material is added into flask, consisting of branched alpha-olefins 15% (4- ethyl -1- octene 15%), line style α-alkene
Hydrocarbon 3.7% (1- octene 3.4%, 1- decene 0.3%), alkene, that is, (5- decene of "inner" alkene 81.3% with molecule internal double bond
45%, 3- methyl -4- nonene 34.6%, 2- ethyl -3- octene 1.7%), under the conditions of 25 DEG C of water-bath, stir polymerization reaction
80min filters to isolate catalyst after reaction, and monomer and dimer is distilled off, and obtains product after adding hydrogen, collects and produce
Product are tested for the property, and are shown in Table 1.
Embodiment 16
By catalyst 3.02g made from embodiment 6, under nitrogen protection, it is added to the dry three neck round bottom flask of 500mL
In, then 120mL raw material is added into flask, consisting of branched alpha-olefins 0.1% (6- ethyl -1- laurylene 0.1%), line style
Alpha-olefin 3.5% (1- decene 3.5%), alkene, that is, "inner" alkene 96.4% (5- decene 56.3%, 3- with molecule internal double bond
Methyl -4- nonene 23.1%, 2- ethyl -3- octene 5.2%, 2- methyl -5- decene 11.8%), under the conditions of 25 DEG C of water-bath, stir
Polymerization reaction 60min is mixed, after reaction, catalyst is filtered to isolate, monomer and dimer is distilled off, is produced after adding hydrogen
Product are collected product and are tested for the property, are shown in Table 1.
Comparative example 1
8g silica is immersed in the toluene solution of alchlor (aluminium load capacity is 0.4wt%), at room temperature continuously
Stirring dipping 4h, 100 DEG C of vacuum drying 6h.The catalyst 3.02g that will be obtained is added to 500mL drying under nitrogen protection
In three neck round bottom flask, then 120mL raw material is added into flask, consisting of (2- butyl -1- the hexene of branched alpha-olefins 5%
5%), linear alpha-olefins 3.4% (1- decene 3.4%), alkene, that is, (5- decene of "inner" alkene 91.6% with molecule internal double bond
79.2%, 3- methyl -4- nonene 12.4%), under the conditions of 25 DEG C of water-bath, stir polymerization reaction 60min, after reaction, mistake
Catalyst is isolated in filter, and monomer and dimer is distilled off, and obtains product after adding hydrogen, is collected product and is tested for the property, is shown in Table
1。
Comparative example 2
8g silica is immersed in vanadyl oxalate aqueous solution (vanadium load capacity is 0.36wt%), it is continuous in 45 DEG C of water-baths
Stirring dipping 3h, filtering, 100 DEG C of vacuum drying 6h；By the silica supports for being impregnated with vanadyl oxalate be placed in Muffle furnace into
Row roasting, is warming up to 120 DEG C, constant temperature 2h first, is warming up to 350 DEG C, constant temperature 1h later, be continuously heating to 450 DEG C, constant temperature 6h,
Finally Temperature fall is cooling under a nitrogen.The catalyst 3.02g that will be obtained is added to 500mL dry three under nitrogen protection
In mouth round-bottomed flask, then 120mL raw material is added into flask, consisting of (3- propyl -1- the heptene of branched alpha-olefins 90.5%
46.3%, 4- ethyl -1- octene 15.2%, 5- methyl-1 nonene 20.6%, 2- ethyl -1- laurylene 8.4%), line style α-alkene
Hydrocarbon 3.2% (1- decene 3.2%), alkene, that is, "inner" alkene 6.3% (5- decene 2.5%, 3- methyl-with molecule internal double bond
4- nonene 3.1%, 2- ethyl -3- octene 0.7%), under the conditions of 25 DEG C of water-bath, polymerization reaction 60min is stirred, reaction terminates
Afterwards, catalyst is filtered to isolate, monomer and dimer is distilled off, obtains product after adding hydrogen, product is collected and is tested for the property,
It is shown in Table 1.
The performance parameter of 1 product of table
It as shown in Table 1, is original with cheap branched alpha-olefins using poly alpha olefine synthetic oil preparation method provided by the invention
Expect, under support type double activity center catalyst action, poly alpha olefine synthetic oil viscosity index (VI) (100 with higher obtained
Kinematic viscosity > 40cSt at DEG C, viscosity index (VI) > 150), viscosity temperature characteristic is good, high conversion rate.
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 modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (8)
1. a kind of preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI), which comprises the following steps: in raw material
Middle addition oligomerisation catalyst reacts 30~120min under conditions of 20~50 DEG C；Separating catalyst, reaction product and unreacted
'alpha '-olefin monomers, the reaction product distilled plus hydrogen, obtains poly alpha olefine synthetic oil；
The raw material include the branched alpha-olefins containing 4~14 carbon atoms, the linear alpha-olefins containing 4~14 carbon atoms and
Alkene with molecule internal double bond is in terms of 100% by the weight of raw material, and branched alpha-olefins account for 0.1-91.0%, linear alpha-olefins
0.5-4.0% is accounted for, surplus is the alkene of molecule internal double bond；
The oligomerisation catalyst includes carrier and double activated component, and the double activated component includes metal oxide and Lewis acid
Type metal salt, the Lewis acid type metal salt are selected from by AlCl3、FeCl3、SnCl4、TiCl4And ZnCl2In formed group
At least one, the metal oxide are V2O5And/or CrO.
2. the preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI) according to claim 1, which is characterized in that described
Branched alpha-olefins account for 5-80%.
3. the preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI) according to claim 2, which is characterized in that described
Branched alpha-olefins account for 15-60%.
4. the preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI) according to claim 1, which is characterized in that described
Branched alpha-olefins are selected from by 2- butyl-1- hexene, 3- propyl-1- heptene, 4- ethyl-1- octene, 5- methyl-1-nonene, 4- fourth
At least one in base -1- decene, 3- butyl -1- decene, 2- ethyl -1- laurylene and the formed group of 6- ethyl -1- laurylene
Kind.
5. the preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI) according to claim 1 or 4, which is characterized in that
The average carbon atom number of the branched alpha-olefins is 8.9-12.5.
6. the preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI) according to claim 1, which is characterized in that described
Carrier is selected from by least one of silica, aluminum oxide, chromatographic silica gel, the formed group of molecular sieve.
7. the preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI) according to claim 6, which is characterized in that described
Molecular sieve is MCM-41, MCM-48 or SBA-15.
8. the preparation method of the poly alpha olefine synthetic oil of high viscosity index (HVI) according to claim 1, which is characterized in that described
Reaction temperature is 25~35 DEG C, and the reaction time is 60~100min.
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