CN105062555B - A kind of coal alpha-olefin is the method for Material synthesis metallocene poly alpha olefin - Google Patents
A kind of coal alpha-olefin is the method for Material synthesis metallocene poly alpha olefin Download PDFInfo
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Abstract
The invention discloses a kind of method that coal alhpa olefin is Material synthesis metallocene polyalphaolefin.This method is：Cut cutting is carried out to coal alhpa olefin, obtains 80 DEG C~240 DEG C fraction sections；The coal alhpa olefin of 80~240 DEG C of fraction sections of foregoing acquisition, removes oxygenatedchemicals therein；It is foregoing remove oxygenatedchemicals coal alhpa olefin it is preheated after, add metallocene catalysis agent solution and carry out polymerisation, obtain polymerizate；Reaction is quenched by adding quencher in polymerisation, adds catalyst kish and boride in solid absorbent removing polymerizate.The present invention has synthesized the excellent mPAO of viscosity temperature characteristic using the coal alhpa olefin of fischer-tropsch synthesis process production as polymer raw under the action of metallocene catalyst；Expensive pure alpha-olefin polymerization raw material is instead of, on the one hand reduces the production cost of PAO, on the other hand, improves the economy of fischer-tropsch synthesis process.
Description
Technical field
The present invention relates to the technical field that alpha-olefine polymerizing prepares poly alpha olefine synthetic oil, and in particular to a kind of coal α-alkene
Hydrocarbon is the process of Material synthesis low viscosity metallocene poly alpha olefin.
Background technology
Poly alpha olefin (PAO) is one kind of synthetic base oil, is that a kind of Synthin prepared by chemical synthesis process moistens
Lubricating oil, its composition are the long chain alkanes of comparison rule, are a kind of synthetic lubricant base oils of excellent performance, are current synthesis hairs
One of most widely used oil base stock in motivation oil, gear oil and other iundustrial oils, fat.Oil pole is synthesized by its modulation
The earth extends application range of the lubricant grease under low temperature, high temperature, high load capacity and other harsh conditions, there is provided excellent is viscous
Warm nature energy, thermal oxidation stability, lubrication and wear resistance and detergency, thus the oil draining period is greatly extended, it slow down and set
Standby corrosion and abrasion, reduces the maintenance cycle of equipment, improves the utilization rate and service life of equipment.
Poly alpha olefin is usually produced by the technology of olefin catalytic polymerization, and the raw material used is the alpha-olefin of C8-C12
In monomer or mixed olefins, polymerization catalyst is lewis acid catalyst or Ziegler-Natta catalyst.By changing
The performance of base oil is improved into polymerization technique and polymerization catalyst.By development for many years, the production skill of poly alpha olefin
Art has very big improve.The PAO of low viscosity is usually using boron trifluoride as catalyst, medium viscosity and high viscosity
Then use alchlor to be produced for catalyst.It is often adjoint during carrying out catalytic polymerization using both catalyst
There are the side reactions such as cracking skeletal isomerization, rearrangement, many shorter side chains produced in the molecular structure for the PAO for causing to produce,
The presence of these short-side chains can cause the evaporation loss of base oil to increase to be reduced with flash-point, influences its performance.And use cyclopentadienyl
PAO molecules synthesized by metallic catalyst possess prominent backbone, and side chain different in size is stretched out with disordered fashion from backbone, its
Unique geometry can obtain very homogeneous chemical products, so it possesses pectinate texture, there is no upright side chain.With it is normal
Rule PAO possesses improved rheological behavior and flow performance compared to this shape, so as to preferably provide shear stability, relatively low
Pour point and higher viscosity index (VI), especially because having less side chain and there is the shear stable more much higher than conventional PAO
Property.These characteristics determine that it uses the application that target is high severity, including power drive system and gear oil, compressor profit
Lubricating oil, transmission fluid and industrial lubricant, to be different from conventional PAO, this poly- α-alkene using synthesized by metallocene catalyst
Hydrocarbon is referred to as metallocene poly alpha olefin, i.e. mPAO (metallence PAO).
Metallocene catalysis synthesis technique has following feature：First, metallocene catalysis alpha-olefine polymerizing has very high
Catalytic activity, up to every gram of catalyst of dozens or even hundreds of kilogram of PAO, so the catalysis consumed in the synthesis process
The amount of agent and co-catalyst is very small；Secondly as metallocene catalyst is single site catalysts, its catalytic polymerization degree can
Effectively adjusted with the variation of technique, there is very big elasticity, can directly be produced according to the actual requirements using this feature
The PAO products of viscosity grade, simplify the technological process of production needed for going out；Furthermore since the catalyst system and catalyzing has very high catalysis
Activity, thus only have reaction time 2 it is small when or so, substantially reduce the production cycle, improve production efficiency；Finally, due to institute
The amount very little of catalyst and co-catalyst, aftertreatment technology is simple, and can effectively reduce the discharge of the three wastes.
The raw material for synthesizing PAO is the alpha-olefin of C8-C12, comes from ethylene oligomerization product mostly, especially using 1- decene as original
Expect that the viscosity temperature characteristic of the PAO of synthesis is the most excellent.The distribution for coming from the alpha-olefin in the raw material of fischer-tropsch synthesis process follows
Anderson-Schulz-Flory is distributed, and carbon number is continuous and there are about 40% same carbon number alkane.Choose suitable carbon number alpha-olefin group
Into coal-to-olefin can as production PAO raw material so that the added value of coal alpha-olefin and Fischer-tropsch process is improved.
Poly alpha olefine synthetic oil be typically using alpha-olefin as raw material, polymerize under the action of lewis acid catalyst and
Obtain.Its production process generally comprises four polymerization, catalyst separation, distillation and hydrogenation technical process.Since the country does not have
The process units of C8-C12 alpha-olefins, all relies on imports, adds the production cost of state cohesion α-alkene, and taken based on high temperature-
The alpha-olefin mixture that support method is produced mainly is made of linear paraffin and linear alpha-olefin, at the same time containing a small amount of isohydrocarbon
Class and oxygenatedchemicals are (such as：Long-chain alcohol, long-chain aldehyde and alkyl acid), its main feature is that the carbon number of the mixture is continuously distributed, alkane
It is difficult to be separated by modes such as traditional distillations with α-alkene, the content of alpha-olefin ordinarily be about 45% or so.Pass through steaming
The suitable fraction section of cutting is evaporated, and after removing oxygenatedchemicals, coal-to-olefin can be used as the raw material of the poly- α-alkene of production.With ethene
The alpha-olefin of oligomerisation method production is more for the patent and document of raw material production PAO, and is by catalyst, coal α-alkene of metallocene
Material synthesis PAO has no related patents and report.
The PAO generally uses boron trifluoride of low viscosity is as the catalyst to produce, and main component is alpha-olefin in product
Tripolymer, the tetramer, pentamer and six a small amount of aggressiveness.In the course of the polymerization process due to the presence of a variety of catalytic active centers,
In addition to polymerisation, also there are the reaction such as double-bond isomerism, cytoskeleton rearrangement, cause obtained polymer isomerisation degree compared with
Height, higher isomerisation degree can cause the evaporation loss of base oil and flash-point to be affected.Metallocene catalyst has in itself
Some single active center are it is possible to prevente effectively from the appearance of the above problem.
The metallocene compound of synthesis low viscosity PAO be by one or two cyclopentadienyl group (or fluorenyl, indenyl) or its
The compound that derivative is formed with transition metal atoms Direct Bonding, this kind of catalyst is with Cp2MCl2Most commonly seen (M Ti,
Zr, Hf), Cp is can have various substituents on cyclopentadienyl group, indenyl or fluorenyl.
Co-catalyst is the important component of metallocene catalysis system, is generally divided into two big species：Alkylaluminoxane class
And organic boride.Wherein, alkylaluminoxane has methylaluminoxane, ethylaluminoxane, butyla-luminoxane and its mixture, this kind of
Co-catalyst reaches certain proportion in catalyst system and catalyzing can just play catalytic action, and usual Al/Zr is than 500:1、1000:1 also may be used
To be 1500:1 and 2000:1.The property of alkylaluminoxane is extremely active, meet the moisture content in air and oxygen can occur it is violent anti-
Should be simultaneously with strongly exothermic.Therefore, big dosage and unstable property and the price limit of costliness such co-catalyst should
With.
Catalyst system and catalyzing of the organic boride co-catalyst with metallocene composition in the presence of alkyl aluminum can be urged effectively
Change polymerisation, common organic boride there are B (C6F5)3,[Me2PhNH][B(C6F5)4], [R3NH][B(C6F5)4],[R4N]
[B(C6F5)4],[Ph3C][B(C6F5)4],[Me2PhNH][B((C6H3-3,5-(C F3)2))4],[Ph3C][B((C6H3-3,5-
(CF3)2))4],[NH4][B(C6H5)4], wherein the alkyl of R=C1-C16, Ph are phenyl.B/Zr is than being usually 1:1, alkyl aluminum
Usually trimethyl aluminium, triethyl aluminum and triisobutyl aluminium.Catalysis can be effectively performed in alkyl aluminum under relatively low dosage
Reaction.The property of organic boride is very stable, stable in the air can exist, and alkyl aluminum is more steady with respect to alkylaluminoxane
Fixed, price is relatively low.
United States Patent (USP) US6548723 discloses one kind using metallocene or organic metal amine salt catalysis 1- decene and ethene
The method that oligomerisation prepares lube base oil PAO, catalyst are mainly the cyclopentadienyl metallocene of non-bridging, are in Al/Zr
Gained PAO is low viscosity base oil when 1000.
The Chinese patent of publication number CN1549852 discloses one kind and one kind is prepared in the presence of single site catalysts
Or the method for a variety of olefin oligomers.Preferred alkenes are alpha-olefins, and the oligomer is poly- α-alkene (PAO).Made of so
PAO does not contain the tertiary hydrogen produced due to isomerization completely or substantially.Therefore, which has improved biological degradability, changes
Kind inoxidizability and/or the viscosity index (VI) of opposite higher.The PAO has such as to be answered as many useful of lubricant composition
With.
The means of special bridged metallocene catalysts that United States Patent (USP) US6706828 is mainly substituted using double indenyls of meso silicon bridgings is facing
Using 1- decene as Material synthesis PAO under hydrogen state, the catalyst catalytic performance of different meso with rac structures is different, by varying
The configuration ratio and Hydrogen Vapor Pressure of catalyst all have the viscosity temperature characteristic of catalyst system and obtained PAO products larger
Influence.
The lubricant oil composite of the Chinese patent invention of publication number CN101617033 contain 100 DEG C of kinematic viscosity for 1~
5mm2The lubricant base of/s and 100 DEG C of kinematic viscosity are 20~2000mm2/ s's is selected from olefin copolymer (OCP) and poly- α alkene
At least one of hydrocarbon (PAO), 100 DEG C of kinematic viscosity is 8.0mm2/ below s and viscosity index (VI) are more than 155.
Above-mentioned patent all obtains 1- decene or 1- octenes as raw material to polymerize to obtain mPAO using ethylene oligomerization method, does not make
With or refer to by raw material of coal alpha-olefin and to synthesize mPAO.The correlation of the mPAO of related coal-to-olefin synthesis is glued in the prior art
Warm data are also opposite to be lacked.
The content of the invention
It is an object of the present invention to provide the technique side that a kind of coal alpha-olefin is Material synthesis metallocene poly alpha olefin
Method.
Present invention technical solution used to achieve the above object is as follows：
A kind of coal alpha-olefin is the method for Material synthesis metallocene poly alpha olefin, and this method comprises the following steps：
Step 1, cut cutting is carried out to coal alpha-olefin by the method for distillation, obtains 80 DEG C~240 DEG C fraction sections；
Step 2, for foregoing acquisition 80~240 DEG C of fraction sections coal alpha-olefin, remove oxygenatedchemicals therein；
Step 3, after the coal alpha-olefin of foregoing removal oxygenatedchemicals is preheated, adds metallocene catalysis agent solution and carry out
Polymerisation, obtains polymerizate.
Preferably, this method further includes：Reaction is quenched by adding quencher in the polymerisation of the step 3, adds
Catalyst kish and boride in solid absorbent removing polymerizate.The quencher is selected from water, CO2, methanol, second
Alcohol and isopropanol, hydrochloric acid solution, sulfuric acid solution.The solid absorbent is selected from silica gel, activated alumina, carclazyte, diatomite, recessed
Convex rod soil, cellulose filter aid, and molecular sieve solid absorbent.The molecular sieve solid absorbent can use 3A molecules
Sieve, 4A molecular sieves, 5A molecular sieves, 13X molecular sieves, Y type molecular sieve, ZSM-5 molecular sieve, ZSM-22 molecular sieves, MCM-41 molecules
Sieve, SAPO-11 molecular sieves, SAPO-34 molecular sieves, SAPO-5 molecular sieves.
Further, it is above-mentioned to be distilled off mixing by the reaction mixture of Removal of catalyst kish and boride process
Close alkane and unreacted monomer, redistillation cut out the dimer for being not suitable as lube base oil, redistillation goes out part
Final product after tripolymer obtains lube base oil ingredient after hydrogenation.
Step 1 in above-mentioned synthesis technique is very crucial to synthesis mPAO, and different fractional compositions glue temperature to final product
Performance and performance have a significant impact, and the low alpha-olefin for make it that carbon number is relatively low of vapo(u)rizing temperature enters in raw material, and then influences production
The evaporation loss and flash-point of product, and vapo(u)rizing temperature is improved, the alpha-olefin of higher carbon number can cause the pour point of product to raise.It can lead to
Distillation cutting temperature is crossed to control the composition of raw material.Under the conditions of air-distillation, vapo(u)rizing temperature section is chosen 80 DEG C~240 DEG C and is evaporated
Segmentation, preferably 140 DEG C~200 DEG C.
Contain alcohol, aldehyde and the alkyl acids oxygenatedchemicals of a variety of different chain lengths in coal alpha-olefin, due to these chemical combination
Contain active hydrogen atom in the functional group of thing, these active groups can be with the co-catalyst alkyl aluminum class in metallocene catalysis system
Compound reacts, so that partially polymerized catalyst poisoning inactivates, the dosage increase of catalyst, adds and be produced into
This.Furthermore the oxidation stability of lubricating oil product can greatly be influenced by being brought into oxygenatedchemicals in base oil.Therefore, poly-
These oxygenatedchemicals to the toxic effect of catalyst are first removed before conjunction.
Further, the method for oxygenatedchemicals is in removal coal alpha-olefin in the step 2：By to coal α-alkene
Hydrocarbon adds alkali or alkaline earth metal passivator, is filtered after reacting a period of time in a heated condition, removes therein containing oxidation
Compound.The one kind of the alkali or alkaline earth metal passivator in Li, Na, K, Mg, or any two kinds or three in them
The combination (such as KNa alloys, KLi alloys) of kind, preferably metal Na.The addition of the alkali or alkaline earth metal passivator
For 0.2%~5%, preferably 0.8%.
Removing degree of the reaction temperature to oxygenatedchemicals impurity is most important in the step 2, chooses appropriate reaction
Temperature can make alkaline-earth metal be molten into liquid, more fully be contacted with the oxygenatedchemicals in coal-to-olefin, accelerate containing oxidation
The removing speed of compound impurity；The reaction temperature is usually 50~160 DEG C, preferably 100~120 DEG C.Reaction time is usually 1~
8h, preferably 2~6h.The polymerizate stability in storage removed after oxygenatedchemicals is more stable, can be with long distance transportation and storage
Deposit.
Further, polymeric reaction temperature is 90~120 DEG C in the step 3.The metallocene catalyst use is double just
Butyl cyclopentadienyl zirconium dichloride is major catalyst, and N, four penta phenyl fluoride boron hydrochlorate of N- dimethyl and triisobutyl aluminium are used as to help and urge
Agent.Aluminium/zirconium molar ratio is 10~100 in the metallocene catalysis agent solution, is preferably 20~50.
The metallocene catalysis agent solution average out to several pieces, are then added portionwise at regular intervals, it is generally divided into 4~
8 times, preferably 2~4 batches add.
Compared with prior art, beneficial effects of the present invention are as follows：
1, the present invention is using the coal alpha-olefin of fischer-tropsch synthesis process production as polymer raw, in the effect of metallocene catalyst
Under synthesized mPAO；Expensive pure alpha-olefine polymerizing raw material is instead of, on the one hand reduces the production cost of PAO, separately
On the one hand, the economy of fischer-tropsch synthesis process is improved.
2, the Parameter Conditions of the invention by optimizing each step in mPAO synthesis techniques, by controlling the ginseng in synthesis technique
Said conditions, have synthesized the excellent mPAO of viscosity temperature characteristic.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.Experiment behaviour in all examples below
Make all using Schlenk technologies in N2Carried out under atmosphere protection.Used raw material can be by being commercially available.It is used solid
Body adsorbent dries 4h in 110 DEG C of air atmosphere before use, is used after being then sealed.Used metallocene is urged
The preparation of agent solution carries out in glove box.If other materials can be used directly without explanation without processing is further purified.
Unless otherwise noted, all numbers are parts by weight, all percentage is weight percentage.Used coal-to-olefin
Raw material is after cutting, after removing the oxygenatedchemicals in raw material, chooses appropriate fraction section and carries out polymerisation.
The removal methods of the oxygenatedchemicals in coal alpha-olefin after cutting：Churned mechanically flask connection will be equipped with
Onto double pipeline, vacuumize remove reaction bulb in air, with high pure nitrogen replace 3-4 times, weigh a certain amount of coal α-
Alkene, and alkali or alkaline earth metal passivator is added, under high pure nitrogen protection, start and stir and begin to warm up, will suspend
Liquid is heated to 90 DEG C and maintains 2h, stops heating and stirring, is cooled to room temperature, and centrifuges, pours out supernatant.That isolates is upper
The Emathlite through overactivation is added in clear liquid, 4h is stirred at room temperature, after filtering out Emathlite, obtains by polishing purification
Alpha-olefin.
The test method of every viscosity temperature characteristic of the PAO obtained after treatment is as follows：
Oil product kinematic viscosity determination method and dynamic viscosity calculating method：GB/T 265
Oil product viscosity index (VI) calculating method：GB/T 1995
Petroleum products pour point determination method：GB/T 3535
The assay method of lubricating oil flash point:GB/T 3536-2008
Oil product and lubricant acid number and base number determination method (color indicator method):GB/T4945
Waxcrackα-olefin composition measuring method：Q/SH018.0001
Cut the removing of oxygenatedchemicals in coal alpha-olefin after cut：The burning of churned mechanically 1000ml will be equipped with
Bottle is connected on double pipeline, vacuumizes the air removed in reaction bulb, is replaced 3-4 times with high pure nitrogen, weighs the coal of 390g
Alpha-olefin processed, and add 3.1g metal NaK alloys, under high pure nitrogen protection, starts and stirs and begin to warm up, by suspension plus
Heat is to 90 DEG C and maintains 2h, stops heating and stirring, is cooled to room temperature, and centrifugation pours out supernatant, obtains by refining pure
The alpha-olefin of change.It is 0.01mg respectively that detection has been carried out to the acid number of coal alpha-olefin and the content of oxygenatedchemicals purified
KOH/g and 8 μ g/g.
Embodiment 1
The preparation of metallocene catalyst：Weigh 70mg catalyst to be dissolved in 16ml toluene solutions, adding 4ml concentration is
The triisobutylaluminum toluene solution stirring 15min of 1.0M, weighs the N of 140mg, on four penta phenyl fluoride boron hydrochlorate of N- dimethyl adds
State and continue to stir 30min in solution, 20ml metallocene catalysis agent solutions are made, it is stand-by.
Cut cutting is carried out to coal alpha-olefin by the method for distillation, obtains 125~200 DEG C of fraction sections；Using above-mentioned
Method carries out the removing of oxygenatedchemicals.The flask for the 1000ml for being equipped with magnetic agitation is connected on double pipeline, is taken out true
Sky removes the air in reaction bulb, is replaced 3-4 times with high pure nitrogen, weighs coals of the 500g by purifying removing oxygenatedchemicals
Alpha-olefin processed, is warming up to 115 DEG C, after 15min, adds prepared metallocene catalysis agent solution 20ml in advance, contains in solution
The double n-butyl cyclopentadienyl zirconium dichlorides of 70mg, the N of 140mg, four penta phenyl fluoride boron hydrochlorate of N- dimethyl and 4ml concentration are
Start to react in the triisobutylaluminum toluene solution injection raw material of 1.0M.The 20ml metallocene catalysis agent solution is divided into twice
Add, be initially added into 10ml metallocene catalysis agent solutions, second part of 10ml metallocene catalysis agent solution is added after 30min.Reaction
After carrying out 2.5h, add water to continue to stir 30min, add a small amount of solid absorbent activated alumina and continue to stir 3h, it is filtered, subtract
Unreacted monomer is distilled off in pressure, by gas chromatographic analysis, the dimer content 47.8% in product, and the content of trimer
For 29.0%, four poly- above heavy constituents 23.2%, conversion ratio 98.3%.The hydrogenation of mPAO carries out in 100ml autoclaves,
Hydrogenation catalyst is Raney nickel, 130 DEG C, reaction pressure 4MPa, reaction time 4h of reaction temperature.
Embodiment 2
With embodiment 1 difference lies in feed coal alpha-olefin distillation cutting temperature section be 130 DEG C~195 DEG C, its
His experimental method and operating condition are the same as embodiment 1.Dimer content 52.8% in product, the content of trimer is 27.5%,
Four poly- above heavy constituents 19.7%, conversion ratio 97.6%.
Embodiment 3
With embodiment 1 difference lies in feed coal alpha-olefin distillation cutting temperature section be 140 DEG C~185 DEG C, its
His experimental method and operating condition are the same as embodiment 1.Dimer content 50.8% in product, the content of trimer is 28.9%,
Four poly- above heavy constituents 20.3%, conversion ratio 98.1%.
MPAO in above-described embodiment 1-3 synthesized by the coal alpha-olefin raw material in different distillation cutting temperature sections glues temperature
Data are referring to table 1.
MPAO synthesized by the different distillation cutting temperature section raw materials of table 1 glues warm data
From the data of table 1：The mPAO viscosity index (VI)s that above-described embodiment 1-3 synthesis obtains are larger, show viscosity temperature characteristic
It is excellent.
Embodiment 4
The flask for the 1000ml for being equipped with magnetic agitation is connected on double pipeline, vacuumizes the sky removed in reaction bulb
Gas, is replaced 3-4 times with high pure nitrogen, weighs coal alpha-olefins of the 500g by purifying removing oxygenatedchemicals, it distills cutting
Temperature range is 145 DEG C~210 DEG C, is warming up to 110 DEG C, after 15min, adds prepared metallocene catalysis agent solution in advance
20ml, the N containing the double n-butyl cyclopentadienyl zirconium dichlorides of 70mg, 140mg, four penta phenyl fluoride boron hydrochlorate of N- dimethyl in solution
With the triisobutylaluminum toluene solution that 4ml concentration is 1.0M, metallocene catalysis agent solution, which is disposably added in raw material, to be started to react.
After reaction, add water to continue to stir 30min, add a small amount of solid absorbent activated alumina and continue to stir 3h,
Filtered, vacuum distillation removes unreacted monomer and dimer, the poly alpha olefin not being hydrogenated with.The hydrogenation of mPAO is in 100ml
Carried out in autoclave, hydrogenation catalyst is Raney nickel, 130 DEG C, reaction pressure 4MPa, reaction time 4h of reaction temperature.
Embodiment 5
Difference lies in polymeric reaction temperature it is 105 DEG C with embodiment 4, other experimental methods and the same embodiment of operating condition
4。
Embodiment 6
Difference lies in polymeric reaction temperature it is 100 DEG C with embodiment 4, other experimental methods and the same embodiment of operating condition
4。
Embodiment 7
Difference lies in polymeric reaction temperature it is 95 DEG C with embodiment 4, other experimental methods and the same embodiment of operating condition
4。
100 DEG C of viscosity, composition datas of poly alpha olefin obtained by above-described embodiment 4-7 are measured, the results are shown in Table 2.
Polymerizate composition and Viscosity Analysis obtained by 2 embodiment 4-7 of table
It can be seen that by data in table 2：With the rise of polymerization temperature, the content of the dimer in product increases, and three
The changes of contents of polymers is little, at the same the content of the heavy constituent such as tetramer reduce so cause the viscosity of obtained mPAO with
The rise of temperature and reduce.
Embodiment 8
Difference lies in Al/Zr in catalyst solution it is 20 with embodiment 4, other experimental methods and operating condition are the same as implementing
Example 4.
Embodiment 9
Difference lies in Al/Zr in catalyst solution it is 60 with embodiment 4, other experimental methods and operating condition are the same as implementing
Example 4.
Embodiment 10
Difference lies in Al/Zr in catalyst solution it is 80 with embodiment 4, other experimental methods and operating condition are the same as implementing
Example 4.
Embodiment 11
Difference lies in Al/Zr in catalyst solution it is 150 with embodiment 4, other experimental methods and operating condition are the same as real
Apply example 3.The composition data of poly alpha olefin obtained by above-described embodiment 8-11 is measured, the results are shown in Table 3.
Polymerizate composition and analysis obtained by 3 embodiment 8-11 of table
It can be seen that by data in table 3：With the increase of Al/Zr molar ratios, the dimer content in product has a little increasing
Add, the changes of contents of trimer is little, and the content of tetramer increased, when Al/Zr exceedes the conversion ratio of coal-to-olefin after 80s
Decline obvious.
Embodiment 12
Disposably it is added in raw material and is polymerize difference lies in catalyst solution with embodiment 1, other experimental methods
With operating condition with embodiment 1, the dimer content 50.3% in product, the content of trimer is 26.9%, four it is poly- more than weight
Component 22.8%, conversion ratio 85.6%.
The part preferred embodiment of the present invention is above are only, the present invention is not limited in the content of embodiment.For ability
For technical staff in domain, can there are various change and change in the concept of technical solution of the present invention, that is made appoints
What changes and change, within the scope of the present invention.
Claims (9)
1. a kind of coal alpha-olefin is the method for Material synthesis metallocene poly alpha olefin, this method comprises the following steps：
Step 1, cut cutting is carried out to coal alpha-olefin, obtains 80 DEG C~240 DEG C fraction sections；
Step 2, for foregoing acquisition 80~240 DEG C of fraction sections coal alpha-olefin, remove oxygenatedchemicals therein；Pass through
Alkali or alkaline earth metal passivator is added to coal alpha-olefin, mistake after a period of time is reacted under 50-160 DEG C of heating condition
Filter, removes alcohol, aldehyde and the alkyl acids oxygenatedchemicals of a variety of different chain lengths wherein contained；The alkali or alkaline earth metal
One or more combinations of the passivator in Li, Na, K, Mg；
Step 3, after the coal alpha-olefin of foregoing removal oxygenatedchemicals is preheated, adds metallocene catalysis agent solution and polymerize
Reaction, obtains polymerizate.
2. coal alpha-olefin as claimed in claim 1 is the method for Material synthesis metallocene poly alpha olefin, it is characterised in that should
Method further includes：Reaction is quenched by adding quencher in the polymerisation of the step 3, adds solid absorbent removing polymerization
Catalyst kish and boride in product.
3. coal alpha-olefin as claimed in claim 2 is the method for Material synthesis metallocene poly alpha olefin, it is characterised in that：Institute
State quencher and be selected from water, CO2, methanol, ethanol and isopropanol, hydrochloric acid solution, sulfuric acid solution.
4. coal alpha-olefin as claimed in claim 1 is the method for Material synthesis metallocene poly alpha olefin, it is characterised in that：Institute
The addition for stating alkali or alkaline earth metal passivator is 0.2%~5%.
5. coal alpha-olefin as claimed in claim 1 is the method for Material synthesis metallocene poly alpha olefin, it is characterised in that：Institute
The reaction temperature for stating removal oxygenatedchemicals is 50~160 DEG C, 1~8h of reaction time.
6. coal alpha-olefin as claimed in claim 1 is the method for Material synthesis metallocene poly alpha olefin, it is characterised in that：Institute
It is 90~120 DEG C to state polymeric reaction temperature in step 3.
7. such as the method that claim 1-6 any one of them coals alpha-olefin is Material synthesis metallocene poly alpha olefin, it is special
Sign is：The metallocene catalysis agent solution uses double n-butyl cyclopentadienyl zirconium dichlorides as major catalyst, N, N- diformazans
Four penta phenyl fluoride boron hydrochlorate of base and triisobutyl aluminium are as co-catalyst.
8. coal alpha-olefin as claimed in claim 7 is the method for Material synthesis metallocene poly alpha olefin, it is characterised in that：Institute
Aluminium in metallocene catalysis agent solution/zirconium molar ratio is stated as 10~100.
9. coal alpha-olefin as claimed in claim 1 is the method for Material synthesis metallocene poly alpha olefin, it is characterised in that：Institute
State metallocene catalysis agent solution and be equally divided into 2~4 parts, add reaction solution in batches.
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| CN109126711A (en) * | 2018-09-20 | 2019-01-04 | 青岛大学 | A method of it prepares with photo-catalysis function decolorising agent |
| CN111925823A (en) * | 2020-08-03 | 2020-11-13 | 中国石油化工股份有限公司 | System and method for hydrogenation process in preparation of mPAO |
| CN112920874B (en) * | 2021-01-11 | 2023-01-10 | 亚培烯科技（杭州）有限公司 | Preparation method of polyolefin synthetic oil |
| CN113637103B (en) * | 2021-08-23 | 2023-04-28 | 上海道普化学有限公司 | Preparation method of ultra-high viscosity poly alpha-olefin synthetic base oil |
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| CN101490105A (en) * | 2006-07-19 | 2009-07-22 | 埃克森美孚化学专利公司 | Process to produce polyolefins using metallocene catalysts |
| CN104152176A (en) * | 2013-05-14 | 2014-11-19 | 中国石油天然气股份有限公司 | Method for preparing poly-alpha-alkene synthetic oil from coal-based raw materials |
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| CN101490105A (en) * | 2006-07-19 | 2009-07-22 | 埃克森美孚化学专利公司 | Process to produce polyolefins using metallocene catalysts |
| CN104152176A (en) * | 2013-05-14 | 2014-11-19 | 中国石油天然气股份有限公司 | Method for preparing poly-alpha-alkene synthetic oil from coal-based raw materials |
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