CN1160280C - Catalyst system for ethylene oligomerization and its preparing process and application - Google Patents

Catalyst system for ethylene oligomerization and its preparing process and application Download PDF

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CN1160280C
CN1160280C CNB011000821A CN01100082A CN1160280C CN 1160280 C CN1160280 C CN 1160280C CN B011000821 A CNB011000821 A CN B011000821A CN 01100082 A CN01100082 A CN 01100082A CN 1160280 C CN1160280 C CN 1160280C
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ethylene oligomerization
carrier
catalyst system
tungsten
reaction
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CN1363540A (en
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柳忠阳
郭存悦
张书清
贺大为
胡友良
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Institute of Chemistry CAS
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    • 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
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Abstract

The present invention relates to an efficient catalyst for preparing hexylene by ethylene oligomerization. The system of the catalyst uses an inorganic material containing a laminated structure as a carrier, a W-series catalyst as a main catalyst, organic amine as a ligand and organic aluminium as a cocatalyst. The catalyst has the characteristics of high activity of ethylene trimerization, good selectivity and storage stability, less consumption of the cocatalyst, etc.

Description

A kind of catalyst system for ethylene oligomerization and its production and use
The present invention relates to a kind of ethylene oligomerization that is used for and prepare the hexene catalyzer, particularly adopting tungsten catalyst is body of catalyst, and the organic compound that contains amine is its ligand, and aluminum alkyls is a promotor, prepares hexene by ethene.
Development along with the recent two decades of metallocene, the multipolymer of ethene and alpha-olefin has occupied poly 50% the market share gradually with its superior performance, and alpha-olefin majority wherein adopts the ethylene oligomerization preparation to form, wherein widely used at present catalyzer be SHOP (ShellHigher Olefin Process) type contain Ni catalyst P euckert M; Keim W Orangometallics 1983,2,594.In recent years, Fe-series catalyst by the Brookehard invention is a kind of highly active ethylene oligomerization catalyst that has, but the relatively poor (J.Am.Chem.Soc.1998 of its selectivity, 120,7143), because China is that research falls behind at ethylene oligomerization catalyst, has had a strong impact on the research and development of China at ethylene copolymer.
In the research of ethylene oligomerization catalyst, the tungsten series catalysts is one of them research branch, at the tungsten series catalysts is in the research, mainly be divided into two classes, wherein a class be not supported catalyst (U.S.Pat.No 3,813,453, US.Pat.No 3,897, and 512, US.Pat.No 3903,193, US.Pat.No.5059739), adopt the halogeno salt and the alkyl benzene amine of tungsten to react, the result shows, this catalyzer has good ethylene polymerization activity under the effect of corresponding aluminum alkyls, its polymeric primary product is the dipolymer of ethene, i.e. 1-butylene and isomate thereof.
Another kind of catalyzer is the catalyzer of carrierization, mainly is with above-mentioned catalyst system and carrier such as SiO 2, Al 2O 3, TiO 2, MgO, the characteristics of this catalyzer of ZrO and their mixture (USPat.No 5,466,648) are the characteristics that has kept ethylene dimerization, and this activity of such catalysts is more than doubled.
The present invention is based on above-mentioned research background, the use of discovery in carrier do not dabbled if you would take off the solid support material that this class of soil has the layered silicate structure, and the product of its oligomerisation is the dimerization product of ethene, do not have to adopt to contain report or the patent application of tungsten series catalysts as catalyst of ethylene trimerization.It is carrier that the present invention adopts the layered silicate inorganic materials, is Primary Catalysts with the tungsten series catalysts, and aluminum alkyls is a promotor, is successfully used to prepare the trimerization product of ethene, 1-hexene and isomer.
The catalyst system for ethylene oligomerization that the present invention dabbled comprises Primary Catalysts and promotor, and wherein Primary Catalysts comprises layered silicate inorganic materials, tungsten compound, organic amine compound; Promotor is an organo-aluminium compound.
Layered inorganic material of the present invention refers to: lithium type fluoro hectorite, sodium type fluoro hectorite, Hydrogen fluoro hectorite, calcium type fluoro hectorite, magnesium type fluoro hectorite, sodium base hectorite, synthetic hectorite, sodium hexafluorisilicate, talcum powder, sodium base talcum powder, fluoro mica, fluoro mica, polynite (Na, Li, K, H, Li, Ca, the Mg type), kaolin, wilkinite etc.These inorganic salt have laminate structure, are example with polynite (MMT), and it is a kind of 2: 1 type layer mineral, SiO 4Tetrahedrallayer and MO 6Octahedral layer is formed sandwich structural unit layer with 2: 1 ratio.Because at SiO 4Al has replaced Si in the tetrahedrallayer, and cationic charge reduces in the layer; Also because at MO 6In the octahedron, Mg has replaced a part of Al, and cationic charge also reduces in the layer like this.The long and is that lamella has negative charge, and interlayer is adsorbed with tradable positively charged ion.The above-mentioned inorganic carrier with laminated structure has higher specific surface area and suitable aperture, and its specific surface area is 50-500m 2/ g.
Tungsten compound of the present invention is the halides of tungsten and the oxide compound of tungsten, refers to WCl 6, WE 6, WBr 6, WI 6, WCl 4, WE 4, WBr 4, WOI 4, WOCl 4, WOBr 4, WO 2
Organic amine of the present invention is the compound with following array structure:
Figure C0110008200051
Wherein: R 1, R 2, R 3Be H, contain the alkyl of 1-20 carbon atom, replace or unsubstituted cyclopentenes.Its exemplary compounds is an aniline, monomethylaniline, xylidine, triethyl aniline, 2,6-xylidine, dimethyl-ethyl-cyclopentadienyl amine, dimethyl-cyclopentadienyl amine, cyclopentadienyl amine etc.
Promotor organoaluminum of the present invention is one or more the mixture in the following structural:
R nAlX 3-nOr R 3Al 2X 3
N=1 or 2 wherein;
R=alkyl (1-6 carbon atom, wherein the 2-4 carbon atom is good),
X is a halogen
Comparatively Chang Yong promotor is AlEt 2Cl, AlEt 2Br, AlEtCl 2, AlEtBr 2, Al (iBu) 2Cl, Al (iBu) 2Br, Al (iBu) Cl 2, Al (iBu) Br 2, Al (iPr) 2Cl, Al (iPr) 2Br, Al (iPr) Cl 2, Al (iPr) Br 2, Al 2Et 2Cl 3, Al 2Et 2Br 3, Al (heyl) 2Cl, Al (Heyl) 2Br.
Tungsten owner catalyzer of the present invention follows these steps to carry out:
1. the processing of inorganic carrier material: owing to exist the water and the organism of many absorption in the inorganic carrier, exist the hydroxyl of many free hydroxyls and bonding in the surface of inorganic carrier, because the too much hydroxyl on surface can influence the usefulness of catalyzer in the entire treatment process, therefore the unnecessary hydroxyl in the surface being removed is a process must carrying out.These solid support materials must carry out necessary processing just can be used to prepare tungsten series catalysts material, its treating processes is as follows, under protection of inert gas, above-mentioned carrier is heated to 50-880 ℃, top condition is at 50-400 ℃, under the condition that vacuumizes, handled 0-36 hour, the best treatment time is 0.5-10 hour, to finish planar water and the hydroxyl of removing carrier surface, removes the unnecessary hydroxyl in surface; A kind of method in addition is that the method such as the United States Patent (USP) (US.Pat.4,530,913) that adopt patent to use use hexamethyldisilane to handle, and perhaps adopts the mixing of these two kinds of methods, the order of processing to the hydroxy radical content in the solid support material without any influence.
2. with the carrier stratiform montmorillonite material of handling; under nitrogen protection; add tungsten compound; organic amine compound; it is the preparation effect that the variation of its order of addition(of ingredients) does not influence catalyzer; its content that adds tungsten is the 0.00001-0.02molW/g carrier, and optimum proportion is the 0.001-0.009molW/g carrier, and the mol ratio of organic amine and tungsten is 2: 1.
3. adding solvent in above-mentioned system makes this system form slurries, the solvent that adds can be that alkane also can be polar solvent, solvent must pass through anhydrous and oxygen-free and handle before using, solvent wherein comparatively commonly used is a benzene, chlorobenzene, 1, the 2-dichlorobenzene, toluene, the content of solvent are 5ml-100ml solvent/g carrier.
4. these slurries stir 1-60min under 0-60 ℃ of condition, then 40-180 ℃ condition back flow reaction 0.5-8 hour.
5. wash behind the reaction terminating, it is the oligomerisation Primary Catalysts that drying prepares tungsten.
The ethylene oligomerization reaction follows these steps to carry out: be equipped with in the 250ml there-necked flask of stirring, vacuum nitrogen filling gas, add 100ml toluene then, feed ethene, add promotor recited above, under 0-100 ℃, carry out the ethylene oligomerization reaction, behind the reaction 1-30min, the acidic alcohol termination reaction with 10%.
Catalyzer of the present invention and polyreaction have following characteristics:
1. to adopt the inorganic materials with laminate structure be carrier to catalyzer, and carrier has bigger specific surface and suitable surface tissue, contains hydroxyl on the surface, and can carry out the content of the hydroxyl of control surface by heat-treating methods.
2. this Preparation of catalysts method is simple, the stability in storage height of catalyzer.
3. this catalyzer has high polymerization activity, and its activity can reach 10 6GC 2H 4/ molW.h.
4. this catalyzer has dimerization and trimerization activity to ethene, is to adopt such metal catalyst to prepare the preparation method that ethylene oligomer has catalytic activity first.
Can obtain the isomer that this reaction product is 1-butylene and a spot of 1-butylene and the isomer (1HNMR:CDCl of 1-hexene and 1-hexene from the spectrum analysis of 1H NMR 3δ 4.58 S2-alkly-alkene 2H; 3.82dm 1-alkene 2H; 4.89dm 1H, 5.7m 1-alkene H), what obtain is ethylene oligomer.Wherein the content of 1-butylene carries out along with the degree of depth of reaction and reduces gradually, the content of 1-hexene increases gradually, shows from Study on Kinetics, and 1-butylene is the intermediate product of entire reaction, the content of its hexene can reach 80% at most, does not find any 1-octene in the reaction.
Embodiment
Embodiment 1:
Get micron order Na-polynite 10g and place retort furnace to be heated to 400 ℃ of processing 0.50 hour, vacuumize and handle after 2 hours, place there-necked flask, add WCl successively 60.2mol, 2,6-xylidine 0.4mol adds 50mol toluene, under 0 ℃ condition, stirred 1 hour, back flow reaction is 8 hours under 130 ℃ of conditions, and reaction finishes back toluene wash three times, then with hexane wash once, at last once with washed with dichloromethane, till washing lotion is colourless, vacuumized then dry 10 hours, obtain the olive-green fine catalyst.
Embodiment 2:
Get micron order H-polynite 5g and place retort furnace to be heated to 200 ℃ of processing 10 hours, vacuumize and handle after 4 hours, place there-necked flask, add WI successively 60.00005mol, xylidine 0.0001mol, add the 50mol chlorobenzene, stirred 1 hour under 60 ℃ condition, back flow reaction is 4 hours under 150 ℃ of conditions, reaction finishes back toluene wash three times, then once with hexane wash, at last once with washed with dichloromethane, till washing lotion is colourless, vacuumized then dry 10 hours, and obtained shallow olive-green fine catalyst.
Embodiment 3:
Getting micron order kaolin 5g places there-necked flask to be heated to 200 ℃ to vacuumize and handled 10 hours, add WBr successively 60.0004mol, cyclopentadienyl aniline 0.0008mol, add the 50mol dichlorobenzene, stir 1min under 40 ℃ condition, back flow reaction is 0.5 hour under 180 ℃ of conditions, reaction finishes back toluene wash three times, then once with hexane wash, at last once with washed with dichloromethane, till washing lotion is colourless, vacuumized then dry 10 hours, and obtained shallow olive-green fine catalyst.
Embodiment 4:
Getting micron order mica 5g places there-necked flask to be heated to 200 ℃ to vacuumize and handled 10 hours, add WOCl successively 40.0004mol, triethyl aniline 0.0008mol, add 50mol toluene, stir 10min under 40 ℃ condition, back flow reaction is 16 hours under 60 ℃ of conditions, reaction finishes back toluene wash three times, then once with hexane wash, at last once with washed with dichloromethane, till washing lotion is colourless, vacuumized then dry 10 hours, and obtained shallow olive-green fine catalyst.
Embodiment 5:
Getting micron order talcum powder 5g places there-necked flask to be heated to 200 ℃ to vacuumize and handled 10 hours, add WOCl successively 40.0004mol aniline 0.0008mol adds 50mol toluene, stirs 10min under 40 ℃ condition, back flow reaction is 16 hours under 60 ℃ of conditions, and reaction finishes back toluene wash three times; Then once, at last once, till washing lotion is colourless, vacuumized then dry 10 hours, obtain shallow olive-green fine catalyst with washed with dichloromethane with hexane wash.
Embodiment 6:
Getting micron order Na-polynite 5g places there-necked flask to be heated to 200 ℃ to vacuumize and handled 10 hours, add the hexamethyldisilane toluene solution and handled 1 hour, use toluene wash, vacuumize the polynite that drying obtains handling.Polynite is placed there-necked flask, add WOCl then successively 40.0004mol, 2,6 xylidine 0.0008mol add 50mol toluene, under 40 ℃ condition, stir 10min, back flow reaction is 16 hours under 60 ℃ of conditions, and reaction finishes back toluene wash three times, then with hexane wash once, at last once with washed with dichloromethane, till washing lotion is colourless, vacuumized then dry 10 hours, obtain shallow olive-green fine catalyst.
Embodiment 7:
Get micron order Na-polynite 5g and place there-necked flask, add the hexamethyldisilane toluene solution and handled 1 hour, use toluene wash, vacuumize the polynite that drying obtains handling.Polynite is placed there-necked flask, add WCl then successively 60.0004mol, 2,6 xylidine 0.0008mol add 50mol toluene, under 40 ℃ condition, stir 10min, back flow reaction is 16 hours under 60 ℃ of conditions, and reaction finishes back toluene wash three times, then with hexane wash once, at last once with washed with dichloromethane, till washing lotion is colourless, vacuumized then dry 10 hours, obtain shallow olive-green fine catalyst.
Embodiment 8:
The described catalyzer of embodiment 1-7 is used for the ethylene oligomerization reaction, its process follows these steps to carry out: be equipped with in the 250ml there-necked flask of stirring, vacuum nitrogen filling gas, add 100ml toluene then, feed ethene, add promotor recited above, under 0-100 ℃, carry out the ethylene oligomerization reaction, behind the reaction 1-30min, with 10% acidic alcohol termination reaction, its result is as shown in table 1.
The ethylene oligomerization result of the catalyzer among table 1 embodiment
The active 1-butylene 1-of Al/W temperature hexene
The catalyzer promotor
(mol) (℃) (10 5gC 2H 4/molW.h) (wt％) (wt％)
Embodiment 1 AlEt 2Cl 20 0 1.9 96 3
Embodiment 1 AlEt 2Cl 20 30 7.3 96 3
Embodiment 1 AlEt 2Cl 20 70 5.5 19 70
Embodiment 1 AlEt 2Cl 20 100 0.2-50
Embodiment 1 Al (iBu) 2Cl 20 70 2.2 25 70
Embodiment 2 AlEt 2Cl 200 70 2.3 26 70
Embodiment 3 AlEtCl 2100 70 1.07 18 77
Embodiment 4 Al (iPr) 2Cl 50 70 1.3 21 73
Embodiment 5 AlEt 2Cl 70 70 5.6 15 75
Embodiment 6 AlEtCl 210 70 3.6 30 63
Embodiment 7 AlEt 2Cl 90 70 2.3 18 73

Claims (8)

1. catalyst system for ethylene oligomerization, it is characterized in that this catalyst system comprises Primary Catalysts and promotor, wherein Primary Catalysts comprises Na, Li, K, H, Ca or the polynite of Mg type, kaolin or talcum powder layered inorganic material support, the halides of tungsten or the oxide compound of tungsten refer to WCl 6, WF 6, WBr 6, WI 6, WCl 4, WF 4, WBr 4, WOI 4, WOCl 4, WOBr 4Or WO 2,
The organic amine compound that structural formula is following,
Figure C0110008200021
Or
Figure C0110008200022
R 1, R 2, R 3Be H, the alkyl that contains the 1-20 carbon atom, cyclopentadienyl;
Promotor is an organo-aluminium compound, and its structural formula is
R nAlX 3-nOr R 3Al 2X 3
N=1 or 2 wherein;
The R=1-6 carbon atom alkyl;
X is a halogen.
2. a kind of catalyst system for ethylene oligomerization as claimed in claim 1 is characterized in that the described organic amine in the described Primary Catalysts is aniline, monomethylaniline, xylidine, triethyl aniline, dimethyl-ethyl-cyclopentadienyl amine, dimethyl-cyclopentadienyl amine or cyclopentadienyl amine.
3. a kind of catalyst system for ethylene oligomerization as claimed in claim 1 is characterized in that described promotor organoaluminum is AlEt 2Cl, AlEt 2Br, AlEtCl 2, AlEtBr 2, Al (iBu) 2Cl, Al (iBu) 2Br, Al (iBu) Cl 2, Al (iBu) Br 2, Al (iPr) 2Cl, Al (iPr) 2Br, Al (iPr) Cl 2, Al (iPr) Br 2, Al 2Et 2Cl 3, Al 2Et 2Br 3, Al (heyl) 2Cl or Al (Heyl) 2Br.
4. the preparation method of a kind of catalyst system for ethylene oligomerization as claimed in claim 1 is characterized in that described Primary Catalysts follows these steps to carry out:
(1) processing of inorganic carrier material: under protection of inert gas with above-mentioned Na, Li, K, H, Ca or the polynite of Mg type carrier, kaolin or talcum powder are heated to 50-880 ℃, under the condition that vacuumizes, handled 0.5-10 hour, or use hexamethyldisilane to handle, or adopt the combination treatment of two kinds of methods, the carrier stratiform inorganic materials that obtains handling;
(2) with the carrier stratiform inorganic materials of handling, under nitrogen protection, add tungsten compound, organic amine compound, wherein W content is the 0.00001-0.02molW/g carrier, the mol ratio of organic amine and tungsten is 2: 1;
(3) adding solvent in above-mentioned system makes this system form slurries, the solvent that adds is for handling alkane or polar solvent through anhydrous and oxygen-free, and wherein, described solvent is benzene, chlorobenzene, 1,2-dichlorobenzene or toluene, the content of solvent are 5ml-100ml solvent/g carrier;
(4) these slurries stir 1-60min under 0-60 ℃ of condition, then 40-180 ℃ condition back flow reaction 0.5-8 hour;
(5) wash behind the reaction terminating, it is the oligomerisation Primary Catalysts that drying prepares tungsten.
5. the preparation method of a kind of catalyst system for ethylene oligomerization as claimed in claim 4 is characterized in that described above-mentioned Na, Li, K, H, Ca or the polynite of Mg type carrier, and kaolin or talcum powder are heated to 50-400 ℃ and handled 0.5-10 hour.
6. the preparation method of a kind of catalyst system for ethylene oligomerization as claimed in claim 4 is characterized in that described tungsten/carrier ratio is the 0.001-0.009molW/g carrier.
7. the purposes of a kind of catalyst system for ethylene oligomerization as claimed in claim 1 is characterized in that it is used for the non-pressure process ethylene oligomerization and prepares the 1-hexene.
8. the purposes of a kind of catalyst system for ethylene oligomerization as claimed in claim 7, the preparation method who it is characterized in that hexene is in the 250ml there-necked flask of stirring is housed, vacuum nitrogen filling gas, add 100ml toluene then, feed ethene, add promotor recited above and Primary Catalysts, under 0-100 ℃, carry out the ethylene oligomerization reaction, behind the reaction 1-30min, the acidic alcohol termination reaction with 10%.
CNB011000821A 2001-01-09 2001-01-09 Catalyst system for ethylene oligomerization and its preparing process and application Expired - Fee Related CN1160280C (en)

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