CN102240563A - Alpha-olefin oligomerization immobilized catalyst and preparation and application thereof - Google Patents
Alpha-olefin oligomerization immobilized catalyst and preparation and application thereof Download PDFInfo
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- CN102240563A CN102240563A CN201010174749XA CN201010174749A CN102240563A CN 102240563 A CN102240563 A CN 102240563A CN 201010174749X A CN201010174749X A CN 201010174749XA CN 201010174749 A CN201010174749 A CN 201010174749A CN 102240563 A CN102240563 A CN 102240563A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000004711 α-olefin Substances 0.000 title claims abstract description 8
- 238000006384 oligomerization reaction Methods 0.000 title abstract description 4
- 239000003622 immobilized catalyst Substances 0.000 title abstract 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000003054 catalyst Substances 0.000 claims abstract description 92
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 47
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 42
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 28
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 28
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 28
- 150000003624 transition metals Chemical class 0.000 claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- -1 transition metal salt Chemical class 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000460 chlorine Substances 0.000 claims abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000004411 aluminium Substances 0.000 claims description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 15
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000005470 impregnation Methods 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 3
- 239000000539 dimer Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 description 28
- 239000000243 solution Substances 0.000 description 25
- 238000004448 titration Methods 0.000 description 15
- 238000000862 absorption spectrum Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 238000009938 salting Methods 0.000 description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to an alpha-olefin oligomerization immobilized catalyst and preparation and application thereof; the catalyst takes gamma-alumina as a carrier, and is loaded with aluminum trichloride and VIII-family transition metal salt, and the catalyst comprises the following components in percentage by weight: aluminum: 2.5-6.0%, chlorine: 6.0 to 12.0%, a group VIII transition metal: 0.5-5.0% by weight of SO4 2-And/or NO3 -The rest is gamma-alumina; the group VIII transition metal is iron, cobalt, nickel or copper; the immobilized catalyst has high activity and high stability in catalyzing oligomerization of 1-decene or 1-octene, overcomes the strong corrosivity of aluminum trichloride catalyst, is easy to separate from the product, and avoids the problems of a large amount of sewage and environmental pollution generated by the aluminum trichloride catalyst.
Description
Technical field
The present invention relates to gama-alumina solid-carried catalyst of a kind of 1-of being applicable to decene or the oligomerisation of 1-octene and its production and application.
Background technology
AlCl
3Catalyst is a kind of lewis acid catalyst, has characteristics such as polymer yield height, narrow molecular weight distribution, selectivity be good in catalysis alpha-olefin oligomerisation reaction; But AlCl
3Catalyst has severe corrosive, easily devices such as reactor is damaged, and influences the service life of device, thereby has reduced utilization rate, simultaneously AlCl
3Catalyst can produce large amount of sewage, as untimely processing meeting serious environment pollution, and reacted AlCl
3Catalyst is difficult to reclaim, and needs through post processing, otherwise can produce a large amount of corrosivity waste materials.
In order to reach the requirement of Green Chemistry, replace AlCl at solid acid catalysts such as exploitation load metal oxides
3, BF
3Etc. the traditional catalyst time, also making great efforts research AlCl
3Solid-supported catalyst.Hope can keep AlCl
3Under the prerequisite of good characteristic, problems such as corrosion that solution exists and environmental protection make it change environment amenable catalyst into.Support type AlCl
3Catalyst is a kind of efficient, eco-friendly novel solid acid catalyst, owing to have advantages of high catalytic activity and gentle reaction condition, receives much concern in recent years, is widely used in the research of polymerization and alkylated reaction.
Patent US 2,927, and 087 proposes the earliest, can pass through AlCl
3Steam makes AlCl with refractory oxides reactions such as the aluminium oxide that has surface hydroxyl, silica
3Solid-supported catalyst is emphasized to react the back and is purged with carrier gas being higher than under 300 ℃ the temperature, removes unreacted AlCl
3Necessity.
USP 4,929, and 800 with CCl
4, CH
3Cl or CH
2Cl
2Deng being solvent, the alchlor dissolving wherein, add carriers such as silica or aluminium oxide, at 50~80 ℃ and N
2Protection, lucifuge condition flow a few hours next time to a few days, can make the very high catalyst of alkane isomerization or lytic activity.
Patent USP 6,002, and 060 points out, are catalyst with the support type alchlor, and organo-aluminum compound is an auxiliary agent, can make alpha-olefin generation oligomerisation or copolyreaction.
CN1156338 and CN1939590 utilize the gas phase solid support method under the N2 carrier band, fresh alchlor to be brought into to have mesoporous and reaction tube that the granularity macropore double-pore structure is 20~200 order aluminium oxide in react, prepare AlCl
3Solid-supported catalyst, wherein chlorinty is 6.0~9.0 ω %.This carried catalyst has good catalytic activity and selectivity in isobutene polymerisation, show good stable.But in the fixed bed reaction of filling finely grained catalyst, exist tangible pressure to fall problem.
Summary of the invention
The objective of the invention is gama-alumina solid-carried catalyst that discloses a kind of 1-of being applicable to decene or the oligomerisation of 1-octene and its production and application.Supported catalyst catalysis 1-decene of the present invention or 1-octene oligomerisation reaction are active high, and product separates easily, and the recyclable recycling of catalyst reduces environmental pollution; Avoided the corrosion of homogeneous catalyst, also avoided halid existence in the 1-decene oligomerization product simultaneously reactor.
Catalyst component is as follows by weight percentage:
Aluminium: 2.5~6.0%
Chlorine: 6.0~12.0%
VIII group 4 transition metal: 0.5~5.0%
Deduction SO
4 2-Or/and NO
3 -All the other are gama-alumina outward;
The VIII group 4 transition metal is iron, cobalt, nickel or copper.
The preparation method of supported catalyst of the present invention is as follows:
1) gamma-aluminium oxide carrier is carried out the acidifying impregnation process: actual conditions is: under the room temperature, gamma-aluminium oxide carrier was flooded 4~12 hours in hydrochloric acid, sulfuric acid, nitric acid or their mixture solution of 0.5~2.0M, then 80~100 ℃ of vacuum drying 2~12 hours;
2) gamma-aluminium oxide carrier with acidifying carries out VIII group 4 transition metal salt impregnation process: actual conditions is: under the room temperature, the gamma-aluminium oxide carrier of acidifying was soaked 6~12 hours in the sulfate of VIII group 4 transition metal iron, cobalt, nickel or the copper of 0.5-3.0M or nitrate solution, then 80~100 ℃ of vacuum drying 2~12 hours; Under 300~800 ℃, carry out high-temperature roasting 6~16 hours again;
3) it is immobilized alchlor to be carried out solution: will 5~10g aluminum trichloride (anhydrous) add in 100ml carbon tetrachloride, chloroform or the dichloromethane solvent and make solution, join in the gamma-aluminium oxide carrier after 10~20g activates, under reflux temperature, kept 6~24 hours, remove and desolvate, wash with n-hexane, obtaining after the vacuum drying with the gama-alumina is carrier, and load has the catalyst of alchlor and VIII group 4 transition metal salt.
In the preparation of supported catalyst of the present invention, gamma-aluminium oxide carrier is ball-aluminium oxide carrier or bar shaped alumina support; Spherical gamma-aluminium oxide carrier diameter is 1.3~2.3mm, preferred 1.5~2.0mm, specific area 100~180m
2/ g, preferred 120~160m
2/ g, total pore volume 〉=1.0ml/g, strip carrier diameter 3mm, length is 4~10mm, preferred 5~8mm, its specific area is 100~200m
2/ g, preferred 140~180m
2/ g, total pore volume 〉=0.6ml/g.
Optimum acid is hydrochloric acid during the gamma-aluminium oxide carrier acid treatment, and suitable concentration of hydrochloric acid is 0.5~1.5M, and suitable dip time is 4~8 hours; Optimum transition metal salt was nickel nitrate or nickelous sulfate when the gamma-aluminium oxide carrier of acidifying flooded the VIII group 4 transition metal, suitable nickel nitrate solution concentration is 0.5-3.0M, or nickel sulfate solution concentration is 0.25-1.5M, and suitable dip time is 6~12 hours.Then 80~100 ℃ of vacuum drying 2~12 hours; Under 300~800 ℃, carry out high-temperature roasting 6~16 hours again.400 ℃ of optimum calcination temperatures, roasting time 12 hours.
In the preparation of supported catalyst of the present invention, optimum solvent is that carbon tetrachloride or carbon tetrachloride and chloroform volume ratio are 1: 1 mixed solvent during the load aluminum trichloride (anhydrous), best return time 12 hours.
Utilize the preparation method of supported catalyst of the present invention, the chlorinity of the load aluminum trichloride catalyst that finally makes is 6.0~12 ω %, aluminium: 2.5~6.0 ω %, VIII group 4 transition metal (iron, cobalt, nickel, copper): 0.5~5.0 ω %, deduction SO
4 2-, NO
3 -All the other are gama-alumina outward.
In this Preparation of catalysts, all courses of reaction all are to carry out under the inert gas shielding condition, and inert gas is nitrogen or argon gas.
Supported catalyst of the present invention is applied to catalysis 1-decene or 1-octene oligomerisation reaction, makes 1-decene or 1-octene oligomer.Its principle is according to the cationic oligomer reaction principle, adopts Lewis acid catalyst and promoter to form the complex catalysis system.The present invention is used as 1-decene or 1-octene oligomerisation reaction catalyst; 1-decene or 1-octene oligomerisation reaction are solvent with the n-hexane, and 1-decene or 1-octene and n-hexane volume ratio (3: 8)~(4: 1) are to react under 0.8~1.4MPa condition 5~6 hours in 80 ℃~120 ℃ of temperature, reaction pressure; Stop reaction then, filtering catalyst, air-distillation removes the n-hexane that desolvates, and unreacted monomer 1-decene or 1-suffering and part dimer are removed in decompression distillation, obtain the oligomer of final 1-decene or 1-octene.
1-decene conversion ratio 〉=50 ω %, 100 ℃ of kinematic viscosity 〉=3.46mm
2/ s.
The 1-decylene oligomer that the present invention obtains meets the requirement of lube base oil viscosity, the quality height of oil product.
The present invention can reduce the chlorinity in the product by heterogeneousization of polymerization system, makes catalyst can separate, recycle and reuse with product, reduces environmental pollution.
The specific embodiment
Embodiment 1
Spherical gamma-aluminium oxide carrier carries out the acidifying impregnation process: at room temperature, (the carrier diameter is 1.3~2.3mm, specific area 100~180m with spherical gamma-aluminium oxide carrier
2/ g, total pore volume 〉=1.0ml/g) in the hydrochloric acid solution of 1.0M, flooded 6 hours, again 80~100 ℃ of vacuum drying 12 hours.
VIII group 4 transition metal salting liquid is immobilized: at room temperature, the spherical gamma-aluminium oxide carrier of acidifying impregnation process was flooded 6 hours in the 0.5M nickel nitrate solution, then 100 ℃ of vacuum drying 12 hours.Under 400 ℃, carry out high-temperature roasting 6 hours at last.
Aluminum trichloride solution is immobilized: under argon shield; the 5g aluminum trichloride (anhydrous) is made solution in the 100ml carbon tetrachloride; join in the alumina support after 10g activates; under reflux temperature, kept 24 hours; remove and desolvate; with the n-hexane washing, obtain the alchlor supported catalyst after the vacuum drying.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 6.73 ω %; Survey metallic nickel, aluminium content with atomic absorption spectrum, nickel content is 0.67 ω %, and load aluminium content is 3.46 ω %.
The oligomerisation of catalysis 1-decene: in the 250ml polymerization autoclave, add n-hexane 80ml, above-mentioned supported catalyst 8g, 1-decene 30ml, co-catalyst water 0.0936mol (co-catalyst/-AlCl
2Mol ratio=0.90), under 80 ℃ of reaction temperatures, reaction pressure 1.0MPa condition, carried out 1-decene oligomerisation reaction 5 hours.Stop reaction, filtering catalyst removes the n-hexane that desolvates through the normal pressure distillation, and unreacted monomer 1-decene and part dimer are removed in decompression distillation, obtain final oligomer.1-decene conversion ratio 43.6 ω %, 100 ℃ of kinematic viscosity 3.46mm of oligomer
2/ s.
Embodiment 2
Preparation of load aluminum trichloride catalyst and catalysis 1-decene oligomerisation step condition are with embodiment 1, and difference is that the vehicle treated condition is: spherical gamma-aluminium oxide carrier was flooded 4 hours in the hydrochloric acid solution of 1.5M, again 80~100 ℃ of vacuum drying 12 hours; VIII group 4 transition metal salting liquid is immobilized: the spherical gamma-aluminium oxide carrier of acidifying impregnation process was flooded 6 hours in the 2.0M nickel nitrate solution, then 100 ℃ of vacuum drying 12 hours.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 8.45 ω %; Survey metallic nickel, aluminium content with atomic absorption spectrum, nickel content is 4.27 ω %, and load aluminium content is 3.45 ω %.
The oligomerisation of catalysis 1-decene records 1-decene conversion ratio 58.3 ω %, 100 ℃ of kinematic viscosity 6.64mm of oligomer
2/ s.
Embodiment 3
Preparation of load aluminum trichloride catalyst and catalysis 1-decene oligomerisation step condition are with embodiment 1, and difference is that the vehicle treated condition is: spherical gamma-aluminium oxide carrier was flooded 6 hours in the hydrochloric acid solution of 1.0M, again 80~100 ℃ of vacuum drying 12 hours; VIII group 4 transition metal salting liquid is immobilized: the spherical gamma-aluminium oxide carrier of acidifying impregnation process was flooded 6 hours in the 1.0M nickel nitrate solution, then 100 ℃ of vacuum drying 12 hours.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 7.95 ω %; Survey metallic nickel, aluminium content with atomic absorption spectrum, nickel content is 1.53 ω %, and load aluminium content is 4.57 ω %.
The oligomerisation of catalysis 1-decene records 1-decene conversion ratio 52.7 ω %, 100 ℃ of kinematic viscosity 5.29mm of oligomer
2/ s.
Embodiment 4
Preparation of load aluminum trichloride catalyst and catalysis 1-decene oligomerisation step condition are with embodiment 3, and difference is that VIII group 4 transition metal salting liquid is immobilized: replace nickel nitrate solution with nickelous sulfate.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 8.28 ω %; Survey metallic nickel, aluminium content with atomic absorption spectrum, nickel content is 3.21 ω %, and load aluminium content is 4.31 ω %.
The oligomerisation of catalysis 1-decene records 1-decene conversion ratio 59.1 ω %, 100 ℃ of kinematic viscosity 6.13mm of oligomer
2/ s.
Embodiment 5
Preparation of load aluminum trichloride catalyst and catalysis 1-decene oligomerisation step condition are with embodiment 4, and difference is that VIII group 4 transition metal salting liquid is immobilized: replace nickel sulfate solution with copper sulphate.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 10.68 ω %; Survey metallic copper, aluminium content with atomic absorption spectrum, copper content is 2.57 ω %, and load aluminium content is 4.04 ω %.
The oligomerisation of catalysis 1-decene records 1-decene conversion ratio 57.7 ω %, 100 ℃ of kinematic viscosity 9.85mm of oligomer
2/ s.
Embodiment 6
Preparation of load aluminum trichloride catalyst and catalysis 1-decene oligomerisation step condition are with embodiment 4, and difference is that VIII group 4 transition metal salting liquid is immobilized: replace nickel sulfate solution with ferric sulfate.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 6.51 ω %; Survey metallic iron, aluminium content with atomic absorption spectrum, iron content is 0.59 ω %, and load aluminium content is 3.13 ω %.
The oligomerisation of catalysis 1-decene records 1-decene conversion ratio 58.6 ω %, 100 ℃ of kinematic viscosity 6.99mm of oligomer
2/ s.
Embodiment 7
Preparation of load aluminum trichloride catalyst and catalysis 1-decene oligomerisation step condition are with embodiment 3, and difference is that VIII group 4 transition metal salting liquid is immobilized: dipping is 12 hours in the 1.0M nickel nitrate solution.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 9.00 ω %; Survey metallic nickel, aluminium content with atomic absorption spectrum, nickel content is 2.25 ω %, and load aluminium content is 4.38 ω %.The oligomerisation of catalysis 1-decene records 1-decene conversion ratio 55.4 ω %, 100 ℃ of kinematic viscosity 5.25mm of oligomer
2/ s.
Embodiment 8
Preparation of load aluminum trichloride catalyst and catalysis 1-decene oligomerisation step condition are with embodiment 7, and difference is that VIII group 4 transition metal salting liquid is immobilized: transition metal salt solution is the mixture of 1: 1 1.0M nickel nitrate solution of volume ratio and 1.0M copper-bath.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 8.30 ω %; Survey metallic nickel, copper, aluminium content with atomic absorption spectrum, nickel content is 1.15 ω %, and copper content is 1.08 ω %, and load aluminium content is 4.54 ω %.The oligomerisation of catalysis 1-decene records 1-decene conversion ratio 56.0 ω %, 100 ℃ of kinematic viscosity 6.45mm of oligomer
2/ s.
Embodiment 9
Load aluminum trichloride catalyst preparation process condition is with embodiment 3; difference is that aluminum trichloride solution is immobilized: under argon shield; the 10g aluminum trichloride (anhydrous) is made solution in the 100ml carbon tetrachloride; join in the alumina support after 10g activates; under reflux temperature, kept 24 hours; remove and desolvate,, obtain the alchlor supported catalyst after the vacuum drying with the n-hexane washing.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 8.24 ω %; Survey metallic nickel, aluminium content with atomic absorption spectrum, nickel content is 1.75 ω %, and load aluminium content is 3.84 ω %.
The oligomerisation of catalysis 1-decene records 1-decene conversion ratio 58.6 ω %, 40 ℃ of kinematic viscosity 18.94mm of oligomer
2/ s, 100 ℃ of kinematic viscosity 5.97mm
2/ s.
Embodiment 10
Preparation of load aluminum trichloride catalyst and catalysis 1-decene oligomerisation step condition are with embodiment 9, and difference is that aluminum trichloride solution is immobilized: reflux temperature kept 12 hours down.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 8.74 ω %; Survey metallic nickel, aluminium content with atomic absorption spectrum, nickel content is 2.02 ω %, and load aluminium content is 4.12 ω %.
The oligomerisation of catalysis 1-decene records 1-decene conversion ratio 61.24 ω %, 100 ℃ of kinematic viscosity 5.23mm of oligomer
2/ s.
Embodiment 11
Preparation of load aluminum trichloride catalyst and catalysis 1-decene oligomerisation step condition are with embodiment 9, and difference is that aluminum trichloride solution is immobilized: reflux temperature kept 6 hours down.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 8.20 ω %; Survey metallic nickel, aluminium content with atomic absorption spectrum, nickel content is 1.85 ω %, and load aluminium content is 3.91 ω %.
The oligomerisation of catalysis 1-decene records 1-decene conversion ratio 57.14 ω %, 100 ℃ of kinematic viscosity 460mm of oligomer
2/ s.
Embodiment 12
Preparation of load aluminum trichloride catalyst and catalysis 1-decene oligomerisation step condition are with embodiment 3, and it is the 1-octene that difference is to urge the oligomerisation monomer.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 7.95 ω %; Survey metallic nickel, aluminium content with atomic absorption spectrum, nickel content is 1.53 ω %, and load aluminium content is 4.57 ω %.
The catalyzed 1-octylene oligomerisation records 1-octene conversion ratio 67.0 ω %, 100 ℃ of kinematic viscosity 3.12mm of oligomer
2/ s.
Comparative example 1
Spherical gamma-alumina load aluminum trichloride catalyst preparation and catalysis 1-decene oligomerisation step condition are with embodiment 3, and difference is that carrier carried out impregnation process 2 hours with 0.5M hydrochloric acid, did not have the immobilized step of VIII group 4 transition metal salting liquid.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 6.88 ω %.
Products obtained therefrom 1-decene conversion ratio 37.8 ω %, 100 ℃ of kinematic viscosity 2.46mm of oligomer
2/ s.
Comparative example 2
Spherical gamma-alumina load aluminum trichloride catalyst preparation and catalysis 1-decene oligomerisation step condition are with embodiment 3, difference is not carry out carrier acidifying impregnation process and the immobilized step of VIII group 4 transition metal salting liquid, and carrier directly carries out aluminum trichloride solution through 400 ℃ of roastings after 6 hours immobilized.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 6.93 ω %.
Products obtained therefrom 1-decene conversion ratio is 30.30 ω %, 100 ℃ of kinematic viscosity 2.45mm of oligomer
2/ s.
Comparative example 3
Load aluminum trichloride catalyst preparation and catalysis 1-decene oligomerisation step condition be with embodiment 3,, difference is 200 ℃ of supported catalyst sintering temperatures.
By the Fo Erhade titration above-mentioned alchlor supported catalyst is carried out chlorinity and measures, in the supported catalyst chlorinity be 9.47 ω %.
Products obtained therefrom 1-decene conversion ratio 43.0 ω %, 100 ℃ of kinematic viscosity 4.24mm of oligomer
2/ s.
Claims (3)
1. alpha-olefin oligomerisation solid-carried catalyst, it is characterized in that: this catalyst is carrier with the gama-alumina, and load has alchlor and VIII group 4 transition metal salt, and catalyst component is as follows by weight percentage:
Aluminium: 2.5~6.0%,
Chlorine: 6.0~12.0%,
VIII group 4 transition metal: 0.5~5.0%,
Deduction SO
4 2-And/or NO
3 -All the other are gama-alumina outward;
The VIII group 4 transition metal is iron, cobalt, nickel or copper.
2. the preparation method of the described alpha-olefin oligomerisation of claim 1 solid-carried catalyst is characterized in that:
1) gamma-aluminium oxide carrier is carried out the acidifying impregnation process: actual conditions is: under the room temperature, gamma-aluminium oxide carrier was flooded 4~12 hours in hydrochloric acid, sulfuric acid, nitric acid or their mixture solution of 0.5~2.0M, then 80~100 ℃ of vacuum drying 2~12 hours;
2) gamma-aluminium oxide carrier with acidifying carries out VIII group 4 transition metal salt impregnation process: actual conditions is: under the room temperature, the gamma-aluminium oxide carrier of acidifying was soaked 6~12 hours in the sulfate of VIII group 4 transition metal iron, cobalt, nickel or the copper of 0.5-3.0M or nitrate solution, then 80~100 ℃ of vacuum drying 2~12 hours; Under 300~800 ℃, carry out high-temperature roasting 6~16 hours again;
3) it is immobilized alchlor to be carried out solution: will 5~10g aluminum trichloride (anhydrous) add in 100ml carbon tetrachloride, chloroform or the dichloromethane solvent and make solution, join in the gamma-aluminium oxide carrier after 10~20g activates, under reflux temperature, kept 6~24 hours, remove and desolvate, wash with n-hexane, obtaining after the vacuum drying with the gama-alumina is carrier, and load has the catalyst of alchlor and VIII group 4 transition metal salt.
3. the application of the described alpha-olefin oligomerisation of claim 1 solid-carried catalyst is characterized in that: be used for 1-decene or 1-octene oligomerisation reaction catalyst; 1-decene or 1-octene oligomerisation reaction are solvent with the n-hexane, and 1-decene or 1-octene and n-hexane volume ratio (3: 8)~(4: 1) are to react under 0.8~1.4MPa condition 5~6 hours in 80 ℃~120 ℃ of temperature, reaction pressure; Stop reaction then, filtering catalyst, air-distillation removes the n-hexane that desolvates, and unreacted monomer 1-decene or 1-suffering and part dimer are removed in decompression distillation, obtain the oligomer of final 1-decene or 1-octene.
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CN102728396A (en) * | 2012-06-04 | 2012-10-17 | 华东理工大学 | Preparation method and application of gamma-alumina supported aluminum trichloride catalyst |
CN102921437A (en) * | 2012-11-02 | 2013-02-13 | 华东理工大学 | Alpha-olefin oligomerization immobilized catalyst, preparation method and application thereof |
CN103666552A (en) * | 2012-09-04 | 2014-03-26 | 中国石油天然气股份有限公司 | Preparation method of medium-viscosity poly-alpha-olefin base oil |
CN104324734A (en) * | 2014-09-26 | 2015-02-04 | 沈阳化工大学 | Preparation method of catalyst suitable for synthesizing C8 and C12 through oligomerization of 1-butene |
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CN102728396A (en) * | 2012-06-04 | 2012-10-17 | 华东理工大学 | Preparation method and application of gamma-alumina supported aluminum trichloride catalyst |
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CN104324734A (en) * | 2014-09-26 | 2015-02-04 | 沈阳化工大学 | Preparation method of catalyst suitable for synthesizing C8 and C12 through oligomerization of 1-butene |
CN108187697A (en) * | 2017-12-28 | 2018-06-22 | 之江(四川)高新材料应用技术研究院有限公司 | Synthesize the method and used catalyst of 2- morpholine ethanols |
CN108772099A (en) * | 2018-04-03 | 2018-11-09 | 山东大学 | A kind of preparation method and application of porous Teflon load aluminum trichloride catalyst |
CN116023561A (en) * | 2021-10-25 | 2023-04-28 | 中国石油化工股份有限公司 | Supported polyolefin catalyst and preparation method and application thereof |
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