CN101618343A - Load-type olefin oligomerization catalyst and preparation method thereof - Google Patents
Load-type olefin oligomerization catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a load-type olefin oligomerization catalyst, which comprises a complex and an organic aluminum compound loaded on a medium-pore aluminum silica material and having an expression shown as formula (I). The catalyst contains 0.5 to 5.0 mass percent of nickel and 20 to 30 mass percent of aluminum; in the formula (I), R is selected from hydrogen, alkyl of C1 to C2, alkoxy or nitryl of C1 to C6, X is halogen or acetate moiety, and n is 1 or 2; the medium-pore aluminum silica material has a pseudo-boehmite phase structure, and comprises the anhydrous chemical composition based on the mass of oxide of (0-0.3)Na2O.(40-90)Al2O3.(10-60)SiO2, the specific surface area of the anhydrous chemical composition is between 200 and 400m<2>/g, the pore volume is between 0.5 and 2.0 ml/g, the average aperture is between 8 and 20nm and the most probable aperture is between 5 and 15nm. The catalyst is matched with the alkyl aluminum for olefin oligomerization, and higher reaction activity.
Description
Technical field
The present invention is a kind of load-type olefin oligomerization catalyst and preparation method thereof, specifically, is that a kind of nickel complex that will contain Schiff base ligand is carried on loaded catalyst of making on the carrier and preparation method thereof.
Background technology
Olefin oligomerization is an important component part of olefinic polyreaction, along with the expansion of modern production life to the specific products demand, uses olefin oligomerization, particularly reacts the technology for preparing higher carbon number alkene with ethylene oligomerization and is developed rapidly.
The tradition and famous ethylene oligomerization technology, as Gulf, Ethyl, SHOP method have the operating condition harshness, problem such as the one way catalyst activity is low, the product carbon number distribution is wide, product and raw material separation difficulty and waste liquid are difficult, particularly operating pressure is too high, reach about 20MPa, limited the economy of its technology.So, seek the technical research of under lower pressure, carrying out oligomerisation reaction more economic, easily row and never stop.
In recent years, research for the ethylene oligomerization homogeneous catalyst both at home and abroad mainly concentrates on the late transition metal catalyst system and catalyzing, as CN1389433A, CN1156415C, CN1398835A, USP063,662, CN1142142C, USP195, the research focus of numerous patents such as 665 mainly concentrates on by on the central metal and coordination environment and reaction condition that change major catalyst, how to improve selection of catalysts, the ideal that realizes molecular weight is cut out and is prolonged life of catalyst.
The heterogeneous catalyst of olefin(e) oligomerization comprises the load and the molecular sieve catalyst of homogeneous catalyst.Molecular sieve concentrated on as the research of olefin oligomerization catalyst some metallic atom is introduced molecular sieve or directly used some shape-selective molecular sieve catalyzed alkene oligomerisation reaction.Because reaction is subjected to the strong influence of this body structure of molecular sieve and surface reaction, up to the present be difficult to control product and distribute, fail to set up corresponding principle simultaneously and explained, so limited its development.And the load of homogeneous catalyst in view of the successful Application of olefin polymerization catalysis industrialization to supported catalyst, has bigger possibility and development prospect.This research is carried out for many years, is generally silica gel, magnesium chloride and zeolite etc. in order to supported carrier.Studies show that in a large number after homogeneous catalyst was immobilized, its catalytic activity and selectivity all obviously reduced.Two [(N-2 have been reported as Carlo Carlini etc. at AppliedCatalysis A:General 231 (2002) 307-320, the 6-diisopropyl phenyl) salicylic alidehyde imine] Ni forms the western Buddhist alkali nickel complex of support type on silica gel, when this catalyst is co-catalyst with MAO (MAO), its ethylene oligomerization activity is low than the activity of homogeneous catalyst, and has polymer to generate.
USP4628139 discloses a kind of ethylene oligomerisation catalyst and preparation method thereof, and nickel [(COD) with two (1, the 5-cyclo-octadiene)
2Ni] be immersed in respectively on Ω-6 zeolite, Ω-5 zeolite or the Y-zeolite, directly obtain carrying the nickel amount and be about 1～5% loaded catalyst, carry out the ethylene oligomerization reaction, reactivity is medium, is about 1.12 * 10
5GOligomer (molNi)
-1H
-1
USP4000211 discloses a kind of method of carrying out the monoolefine dimerization with loaded catalyst, using pyridine derivate to close nickel or trialkyl hydrogen phosphide dichloro as the dichloro of part closes nickel and is active component, unformed silicon-aluminium is the preparing carriers loaded catalyst, carry out ethylene oligomerization with this catalyst, the selectivity of butylene is higher in the oligomer.
Summary of the invention
The object of the present invention is to provide a kind of minus olefin oligomerization catalyst and preparation method, this catalyst has higher oligomerisation reaction activity, and C in the oligomerization product
8The content of above hydrocarbon is more.
Load-type olefin oligomerization catalyst provided by the invention comprises complex and the organo-aluminum compound with formula (I) expression formula that are carried on the mesoporous silicon aluminum, and the nickel content of catalyst is that 0.5～5.0 quality %, aluminium content are 15～35 quality %,
In the formula (I), R is selected from hydrogen, C
1～C
12Alkyl, C
1～C
6Alkoxyl or nitro, X is halogen or acetate, n is 1 or 2;
Described mesoporous silicon aluminum has the phase structure of boehmite, in the anhydrous chemical composition of oxide mass is: (0～0.3) Na
2O (40～90) Al
2O
3(10～60) SiO
2, its specific area is 200～400m
2/ g, pore volume are that 0.5～2.0ml/g, average pore size are that 8～20nm, most probable aperture are 5～15nm.
It is carrier that the present invention selects the mesoporous silicon aluminum for use, and handle carrier with organo-aluminum compound, and then Buddhist alkali is that the nickel complex of part is an active component to the west of the load, the supported olefin polymerization catalyst that obtains has very high catalytic activity in the catalyzed ethylene polymerization reaction, and oligomerisation reaction product carbon number distribution broad.
Description of drawings
Fig. 1 is the XRD figure of used carrier of the present invention.
The specific embodiment
The mesoporous silicon aluminum aperture that the present invention selects for use is big, pore distribution concentration, has good hydrothermal stability.After it is carried out preliminary treatment as carrier with organo-aluminum compound, the nickel compound load that will contain Schiff base ligand thereon, the two has better matching property, the loaded catalyst that makes has higher oligomerisation reaction activity, C in the oligomerization product
8The content of above aromatic hydrocarbons is more, and does not have the high polymer generation.
Activity of such catalysts component of the present invention is for having the salicylic alidehyde imine west Buddhist alkali nickel complex of formula (I) expression formula.In the formula (I), R is the substituting group on the salicylide phenyl ring, and its replacement position can be any replacement position on the phenyl ring, and the substituting group number can be 1～4, the preferred hydrogen of R, C
1～C
4Alkyl or C
1～C
3Alkoxyl.X in the formula (I) can be chlorine, bromine or acetate, preferred chlorine.
Preferred 1.0～the 2.0ml/g of the pore volume of mesoporous silicon aluminum of the present invention, the preferred 10～20nm of average pore size, its detailed preparation method can be with reference to CN1565733A.
Described organo-aluminum compound preferred alkyl aikyiaiurnirsoxan beta, as the MAO of MAO or aluminium isobutyl modification, organo-aluminum compound is alkyl aluminum or haloalkyl aluminium more preferably, as aluminium diethyl monochloride or triethyl aluminum.
Preferred 1.0～4.0 quality % of nickel content, aluminium content are 20～30 quality % in the described catalyst.
Preparation of catalysts method of the present invention comprises the steps:
(1) with after the roasting of mesoporous silicon aluminum, add aromatic hydrocarbons, under stirring condition, add organo-aluminum compound and handle, washing, drying then,
(2) get dried mesoporous silicon aluminum of (1) step, the complex with formula (I) in the presence of aromatic hydrocarbons or halogenated alkane fully reacts, and is dry with saturated hydrocarbons washing back.
Described method (1) step is that carrier is handled, and is first with the carrier roasting, and then handles with organo-aluminum compound.The sintering temperature of described mesoporous silicon aluminum is 200～800 ℃, preferred 400～600 ℃, and preferred 5～8 hours of roasting time.MAO, aluminium diethyl monochloride or the triethyl aluminum of described organo-aluminum compound preferable methyl aikyiaiurnirsoxan beta, aluminium isobutyl modification.Preferred 15～40 ℃ of the temperature that the adding organo-aluminum compound is handled in the carrier after roasting, in preferred 2～6 hours of processing time, the amount of the organo-aluminum compound of adding is 3～50 times of mesoporous silicon aluminum quality, preferred 10～30 times.
Described method (1) is in the step, and the medium that uses in the process with organo-aluminum compound processing carrier is aromatic hydrocarbons, and preferred aromatic hydrocarbons is toluene, and in the processing procedure, the dosage of aromatic hydrocarbons is 10～30 times of mesoporous silicon aluminum quality.After (1) goes on foot with organo-aluminum compound processing carrier, gained solid aromatic hydrocarbons, dry after the preferred toluene wash.
The inventive method (2) step is the load of active component, and the reaction temperature of carrier and complex is 0～120 ℃, and preferred 20～60 ℃, the reaction time is 1～8 hour.(2) going on foot reaction medium is aromatic hydrocarbons or halogenated alkane, the preferred toluene of described aromatic hydrocarbons, and the preferred carrene of halogenated alkane, the aromatic hydrocarbons of adding or the amount of halogenated alkane are 10～50 times of carrier quality.Carrier behind the load active component, dry with saturated hydrocarbons washing back, the preferred hexane of described saturated hydrocarbons.
The preparation method of complex of the present invention is: salicylaldehyde derivatives and aniline such as are pressed at mol ratio fully reaction in pure medium, and reaction temperature is 60～100 ℃.After the reaction product is cooled to and separates out crystal, be recrystallized with alcohol, the crystal that obtains after the drying is a salicylidene aniline complex.Above-mentioned salicylidene aniline complex and nickel compound are pressed 2.0～4.0: 1 molar ratio reaction in the presence of pure medium, collect the solids of reaction gained, wash, be drying to obtain the complex shown in the formula (I).
In the above-mentioned method for preparing complex, described pure preferred alcohol, preferred nickel acetate of described nickel compound or nickel chloride.
With the method that catalyst of the present invention carries out olefin(e) oligomerization, comprise making alkene in the presence of catalyst of the present invention and aluminum alkyl catalyst, under 1.0～4.0MPa, 20～80 ℃ of conditions, carry out oligomerisation reaction.
The aluminium in the described co-catalyst and the mol ratio of the nickel in the catalyst are 25～1000, and be preferred 25～500, more preferably 50～200.The preferred aluminium diethyl monochloride of described alkyl aluminum, trichlorine triethyl group two aluminium, trichlorine trimethyl two aluminium, dichloro one aluminium ethide or triethyl aluminum.The used solvent of oligomerisation reaction is selected from toluene, hexane, cyclohexane or carrene.
Further specify the present invention below by example, but the present invention is not limited to this.
Example 1
Preparation mesoporous silicon aluminum.
Getting 100ml concentration is 90gAl
2O
3The Al of/L
2(SO
4)
3Solution places beaker, dropwise adds ammoniacal liquor under stirring condition, is 8 until system pH, and being neutralized into the glue temperature is 55 ℃.It is 60gSiO that stirring condition adds 50ml content down
2The waterglass of/L is warming up to 80 ℃ and wore out 4 hours; Use NH
4Cl solution is pressed sediment (butt): ammonium salt: H
2O=1: 0.8: 15 mass ratio, carry out ion-exchange to remove sodium ion wherein at 60 ℃ to the sial sediment.Exchange repeats twice, carries out 0.5 hour at every turn, all washes, filters after each exchange, 120 ℃ of dryings 15 hours, obtains the mesoporous silicon aluminum then, and its chemical composition is 0.035Na
2O75.5Al
2O
324.4SiO
2, specific area is 378m
2/ g, pore volume are that 1.21ml/g, average pore size are that 10.55nm, most probable aperture are 7.5nm, and XRD spectra is seen Fig. 1.
Example 2
Prepare complex of the present invention.
0.15 mole of salicylide and 0.15 mole of aniline are added in the reactor, and the absolute ethyl alcohol that adds 100 milliliters refluxed 4 hours for 80 ℃, was cooled to 0 ℃, separated out crystal.Filter, the gained solid is recrystallized with 100 milliliters of absolute ethyl alcohols, decompression time obtains yellow acicular crystal in 25 ℃ of dryings 2 hours, is salicylidene aniline.
Four water nickel acetates of 1 gram (0.004 mole) are joined in 120 milliliters of absolute ethyl alcohols, after stirring, treating that solid dissolves fully, the salicylidene aniline part that adds 1.58 grams (0.008 mole), stirred 12 hours, and had a large amount of green solid to separate out, filter, with 30 milliliters of hexane wash filter cakes 3 times, with filter cake under reduced pressure in 60 ℃ of dryings 6 hours, obtaining the grass green pressed powder, is two (salicylidene aniline) nickel, and yield is 83.15 quality %.
Example 3
Prepare load-type olefin oligomerization catalyst of the present invention.
(1) handles carrier with aluminium compound
With the roasting 6 hours in 400 ℃ of air of the mesoporous silicon aluminum of example 1 preparation, be cooled to 25 ℃ in the nitrogen.Mesoporous silicon aluminum 1 gram after under nitrogen protection, getting roasting; add 20 milliliters of toluene; stirred 0.5 hour; and under stirring state; the MAO (production of U.S. Aldrich company) that adds 5 milliliters of aluminium isobutyl modifications; 25 ℃ were stirred 4 hours, filtered, solid is with toluene wash 3 times, and decompression is down in 60 ℃ of dryings 12 hours.
(2) preparation loaded catalyst
Getting dried mesoporous silicon aluminum of 1 gram (1) step is carrier, adds 15 milliliters of carrene, stirs 0.5 hour, under stirring state, adds and to be dissolved with 0.13 5.8 milliliters of dichloromethane solutions that restrain two (salicylidene aniline) nickel, 25 ℃ of stirrings 6 hours.Filter, solid is with hexane wash 3 times, decompression is down in 60 ℃ of dryings 6 hours, load-type olefin oligomerization catalyst A, it is that 1.06 quality %, aluminium content are 23.12 quality % that plasma emission spectrometry is measured nickel content.
Example 4
Method by example 3 prepares loaded catalyst, different is in (1) step, the aluminium diethyl monochloride that adds 10 milliliters in the mesoporous silicon aluminum is handled it, and nickel content is that 1.25 quality %, aluminium content are 28.16 quality % among the load-type olefin oligomerization catalyst B that makes.
Example 5
Method by example 3 prepares loaded catalyst, different is in (1) step, the aluminium diethyl monochloride that adds 10 milliliters in the mesoporous silicon aluminum is handled it, (2) add 8 milliliters of dichloromethane solutions being dissolved with 0.18 gram two (salicylidene aniline) nickel in the step in carrier, nickel content is that 1.77 quality %, aluminium content are 27.45 quality % among the load-type olefin oligomerization catalyst C that makes.
Example 6
Method by example 3 prepares loaded catalyst, different is in (1) step, the aluminium diethyl monochloride that adds 15 milliliters in the mesoporous silicon aluminum is handled it, (2) add 20 milliliters of dichloromethane solutions being dissolved with 0.45 gram two (salicylidene aniline) nickel in the step in carrier, nickel content is that 3.24 quality %, aluminium content are 27.87 quality % among the load-type olefin oligomerization catalyst D that makes.
Example 7
Method by example 3 prepares loaded catalyst, different is in (1) step, the MAO that in the mesoporous silicon aluminum, adds the modification of 10ml iso-butane, (2) add 8 milliliters of dichloromethane solutions being dissolved with 0.18 gram two (salicylidene aniline) nickel in the step in carrier, nickel content is that 1.59 quality %, aluminium content are 28.01 quality % among the load-type olefin oligomerization catalyst E that makes.
Example 8
Method by example 2 prepares complex, different is 3-cresotinic acid aldehyde and the aniline reaction that adds 6.8 grams (0.05 mole), the 3-cresotinic acid aldehyde anil and the four water nickel acetates that obtain are reacted in absolute ethyl alcohol by 2.1: 1.0 mol ratio, obtain two (3-cresotinic acid aldehyde anil) nickel of 9.1 grams, yield is 79.8 quality %.
Method by example 3 prepares loaded catalyst, different is in (1) step, the MAO that in the mesoporous silicon aluminum, adds the modification of 10ml iso-butane, (2) add 9.6 milliliters of dichloromethane solutions being dissolved with 0.23 gram two (3-cresotinic acid aldehyde anil) nickel in the step in carrier, nickel content is that 1.49 quality %, aluminium content are 28.05 quality % among the load-type olefin oligomerization catalyst F that makes.
Comparative Examples 1
Silica gel (Grace company produce, the trade mark 955) 200 ℃ of constant temperature 2 hours, is warming up to 600 ℃ of roastings 6 hours then, in nitrogen, is cooled to 25 ℃.Under nitrogen protection, silica gel 1 gram of the roasting of learning from else's experience adds 20 milliliters of toluene and stirred 0.5 hour; under agitation, add the MAO of 10 milliliters of aluminium isobutyl modifications, 25 ℃ were stirred 4 hours; filter, solid is with toluene wash 3 times, decompression is down in 60 ℃ of dryings 12 hours.
Adding 15 milliliters of carrene in above-mentioned dried mesoporous silicon aluminum stirred 0.5 hour, stir down, add 8 milliliters of dichloromethane solutions being dissolved with 0.18 gram two (salicylidene aniline) nickel, 25 ℃ were stirred 6 hours, filtration, solid hexane wash 3 times, decompression down in 60 ℃ of dryings 6 hours, obtains load-type olefin oligomerization catalyst M, and wherein nickel content is that 1.47 quality %, aluminium content are 5.81 quality %.
Comparative Examples 2
Method by Comparative Examples 1 prepares loaded catalyst, and different is, and to replace silica gel with mesoporous molecular sieve SBA-15 be the carrier of load active component, makes load-type olefin oligomerization catalyst N, and wherein nickel content is that 1.51 quality %, aluminium content are 7.76 quality %.
Comparative Examples 3
Method by Comparative Examples 1 prepares loaded catalyst, different is with silica be 3.5 amorphous silicon aluminium to replace silica gel be the carrier of load active component, the nickel content of the load-type olefin oligomerization catalyst Q that makes is that 1.60 quality %, aluminium content are 8.23 quality %.
Example 9～17
Following example carries out the ethylene oligomerization reaction.
In reactor, add 200 milliliters of hexanes successively, 1 ml concn is the hexane solution of the aluminium diethyl monochloride of 2.0M, add load-type olefin oligomerization catalyst, making the Al/Ni mol ratio is 100, and adding ethene to pressure in reactor is 3.0MPa, and 40 ℃ were reacted 0.5 hour, temperature of reactor is reduced to 25 ℃, get rid of gas products, collect fluid product, and add the ethanolic solution cessation reaction of the NaOH of a little 0.5M, through three washings, drying, obtain oligomerization product.Each example catalyst system therefor and activity thereof and oligomerization product distribute and see Table 1.
By table 1 data as can be known, the loaded catalyst of the present invention's preparation than the comparative catalyst M and the Q of silica gel and amorphous silicon aluminium load, has higher oligomerisation reaction activity, and has more C in the oligomerization product
8Hydrocarbon, than mesoporous molecular sieve carried comparative catalyst N, catalyst activity of the present invention is slightly high, C in the oligomerization product
8Above product increases.
Table 1
Claims (13)
1, a kind of load-type olefin oligomerization catalyst comprises complex and the organo-aluminum compound with formula (I) expression formula that are carried on the mesoporous silicon aluminum, and the nickel content of catalyst is that 0.5～5.0 quality %, aluminium content are 15～35 quality %,
In the formula (I), R is selected from hydrogen, C
1～C
12Alkyl, C
1～C
6Alkoxyl or nitro, X is halogen or acetate, n is 1 or 2;
Described mesoporous silicon aluminum has the phase structure of boehmite, in the anhydrous chemical composition of oxide mass is: (0～0.3) Na
2O (40～90) Al
2O
3(10～60) SiO
2, its specific area is 200～400m
2/ g, pore volume are that 0.5～2.0ml/g, average pore size are that 8～20nm, most probable aperture are 5～15nm.
2,, it is characterized in that R is selected from hydrogen, C in the described formula (I) according to the described catalyst of claim 1
1～C
4Alkyl or C
1～C
3Alkoxyl.
3, according to the described catalyst of claim 1, the pore volume that it is characterized in that described mesoporous silicon aluminum is that 1.0～2.0ml/g, average pore size are 10～20nm.
4,, it is characterized in that described organo-aluminum compound is MAO, aluminium diethyl monochloride or the triethyl aluminum of MAO, aluminium isobutyl modification according to the described catalyst of claim 1.
5, the described Preparation of catalysts method of a kind of claim 1 comprises the steps:
(1) with after the roasting of mesoporous silicon aluminum, add aromatic hydrocarbons, under stirring condition, add organo-aluminum compound and handle, washing, drying then,
(2) get dried mesoporous silicon aluminum of (1) step, the complex with formula (I) in the presence of aromatic hydrocarbons or halogenated alkane fully reacts, and is dry with saturated hydrocarbons washing back.
6, in accordance with the method for claim 5, it is characterized in that the sintering temperature of mesoporous silicon aluminum is 200～800 ℃ in (1) step.
7, in accordance with the method for claim 5, it is characterized in that the temperature that the adding organo-aluminum compound is handled in (1) step is 15～40 ℃.
8, in accordance with the method for claim 5, it is characterized in that described organo-aluminum compound of (1) step is MAO, aluminium diethyl monochloride or the triethyl aluminum of MAO, aluminium isobutyl modification.
9, in accordance with the method for claim 5, it is characterized in that (2) step described reaction temperature be 0～120 ℃.
10, in accordance with the method for claim 5, it is characterized in that described aromatic hydrocarbons of (2) step is toluene, halogenated alkane is a carrene, and saturated hydrocarbons is a hexane.
11, a kind of process for oligomerization of olefine comprises making alkene in the presence of described catalyst of claim 1 and aluminum alkyl catalyst, carries out oligomerisation reaction under 1.0～4.0MPa, 20～80 ℃ of conditions.
12, in accordance with the method for claim 11, it is characterized in that the aluminium in the described co-catalyst and the mol ratio of the nickel in the catalyst are 25～500.
13, in accordance with the method for claim 11, it is characterized in that described alkyl aluminum is aluminium diethyl monochloride, trichlorine triethyl group two aluminium, trichlorine trimethyl two aluminium, dichloro one aluminium ethide or triethyl aluminum.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104001546A (en) * | 2014-06-09 | 2014-08-27 | 浙江科技学院 | Supported catalyst for preparing hexa-olefin by dimerization of propylene and preparation method of supported catalyst |
| CN104014373A (en) * | 2014-06-09 | 2014-09-03 | 浙江科技学院 | Supported catalyst for synthesizing 2, 3-dimethyl butene through propylene dimerization and preparation method of supported catalyst |
| CN104056650A (en) * | 2013-03-21 | 2014-09-24 | 中国科学院青岛生物能源与过程研究所 | Nickel group-supported catalyst and preparation method and application thereof |
| CN109384863A (en) * | 2017-08-07 | 2019-02-26 | 中国石油化工股份有限公司 | Polyolefin catalyst and polyolefin and their preparation method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4628139A (en) * | 1985-09-20 | 1986-12-09 | Ashland Oil, Inc. | Bis(1,5-cyclooctadiene)Ni(O) catalyst and process for oligomerization of ethylene |
| CN1389443A (en) * | 2001-05-31 | 2003-01-08 | 中国科学院化学研究所 | Nicket compound catalyst for olefine oligomerization and its prepn. and application |
| CN1332949C (en) * | 2003-07-31 | 2007-08-22 | 中国石油化工股份有限公司 | Olefine oligomerization catalyst, and its preparation method and use |
| CN1695807A (en) * | 2004-05-14 | 2005-11-16 | 中国石油化工股份有限公司 | Ethylene oligomerization catalyst, preparation method and application |
-
2008
- 2008-06-30 CN CN2008101158680A patent/CN101618343B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104056650A (en) * | 2013-03-21 | 2014-09-24 | 中国科学院青岛生物能源与过程研究所 | Nickel group-supported catalyst and preparation method and application thereof |
| CN104056650B (en) * | 2013-03-21 | 2016-06-29 | 中国科学院青岛生物能源与过程研究所 | A kind of Supported Nickel Catalyst and its preparation method and application |
| CN104001546A (en) * | 2014-06-09 | 2014-08-27 | 浙江科技学院 | Supported catalyst for preparing hexa-olefin by dimerization of propylene and preparation method of supported catalyst |
| CN104014373A (en) * | 2014-06-09 | 2014-09-03 | 浙江科技学院 | Supported catalyst for synthesizing 2, 3-dimethyl butene through propylene dimerization and preparation method of supported catalyst |
| CN109384863A (en) * | 2017-08-07 | 2019-02-26 | 中国石油化工股份有限公司 | Polyolefin catalyst and polyolefin and their preparation method |
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