CN1256968A - Novel catalyst for ethylene trimerization, its preparation process and application - Google Patents
Novel catalyst for ethylene trimerization, its preparation process and application Download PDFInfo
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- CN1256968A CN1256968A CN99120585A CN99120585A CN1256968A CN 1256968 A CN1256968 A CN 1256968A CN 99120585 A CN99120585 A CN 99120585A CN 99120585 A CN99120585 A CN 99120585A CN 1256968 A CN1256968 A CN 1256968A
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Abstract
The present invention relates to a quaternary chrome series catalyst for ethylene trimerization to prepare 1-hexane. Said catalyst contains a chrome compound, a pyrrole derivative, a trialkylaluminium and an accelerant. Said accelerant is a kind of halogenated alkyl substituted aromatic or halogenated aromatic compound whose aromatic ring contains at least one C1-2-alkyl radical substituted by at least two halogen atoms at alpha-site. Said catalyst features high reaction activity and selectivity and less by-product. Said invention also provides its preparation method.
Description
The present invention relates to a kind of catalyst that is used for ethylene trimer, or rather, is a kind of chromium-based catalysts that is used for ethylene trimer, also relates to this Preparation of catalysts method and application thereof.
The 1-hexene is polyolefinic important comonomer, also can be used as the intermediate of industrial many important compound.John R.Briggs is at J.Chem.Soc., Chem.Commun., and 1989, in the 674-675 page or leaf, reported with homogeneous phase ternary chromium-based catalysts system and come catalyzed ethylene trimerization selectivity to prepare the approach of 1-hexene.But should work in early days resulting catalyst activity and selectivity are all lower.
Reported a kind of improved chromium-based catalysts among the EP 0608447A1, to be used for trimerization, oligomerisation and/or copolyalkenamer.Wherein used the composition of a kind of azole compounds first as chromium-based catalysts, adopted a kind of lewis' acid and/or metal alkyls non-aqueous solution as activator, used a kind of hydrocarbon compound as solvent, this solvent also has the effect of stabilisation activator.Point out also in the document that also can choose wantonly in the catalyst system and contain a kind of halogen source, this halogen source covers extensively, both can be the halogenic ingredient that contains in above several composition, can be the halogen compounds that external source provides again, both can be inorganic halides, also can be the organohalogen compounds of numerous types.With former chromium-based catalysts ratio, though the ethylene trimer reactivity and the selectivity of this catalyst all are greatly increased, but still can not meet the demands, people wish further to improve the performance of catalyst.
Used Sn (OSO among the JP 08325319
2CF
3)
2Compound replaces in EP0608447A1 as optional member and the main halogen source SnCl that uses
4, with as isooctyl acid chromium, 2, the promoter of three-way catalysts such as 5-dimethyl pyrrole and triethyl aluminum, halogen compounds is included in the carbon monoxide-olefin polymeric as a necessary component of catalyst here, has formed a kind of quaternary chromium-based catalysts system.The activity and the selectivity of this quaternary chromium-based catalysts are significantly improved.
Inquired into the effect of the organic alkane compound of a class halo among the JP 08134131 as the promoter in the chromium-based catalysts, wherein used with contain on adjacent two carbon atoms of end three above halogen atoms as the saturated halogenated alkane of feature as by isooctyl acid chromium, 2, the promoter of the catalyst that 5-dimethyl pyrrole and triethyl aluminum are formed, to be used for catalyzed ethylene trimerization system 1-hexene, its catalytic activity has more obviously raising, but as if still dislike not enough, and its catalyst life remains to be prolonged.
By as seen above-mentioned, keep under the geostationary situation in three main components of chromium-based catalysts, people are concentrating on to screen suitable promoter, to expect further to improve the performance of the chromium-based catalysts that is used for ethylene trimer system 1-hexene, both made catalyst that the selectivity of high catalytic activity and high purpose product 1-hexene is arranged, and made the poly growing amount of accessory substance few as far as possible again.
The purpose of this invention is to provide a kind of new quaternary chromium-based catalysts system that is used for ethylene trimer, a kind of method and a kind of method of using this catalyst to prepare the 1-hexene with catalyzed ethylene selectivity trimerization for preparing this catalyst also is provided.
Press one aspect of the present invention, in the quaternary chromium-based catalysts of the present invention except containing a kind of chromium compound, a kind of azole derivatives and a kind of trialkylaluminium, also contain a kind of novel promoter composition, it is characterized in that this promoter comprises a kind of C that at least two halogen atoms of a quilt replace at alpha-position that contains at least on aromatic ring
1-2The aromatic hydrocarbons that the haloalkyl of-alkyl replaces or-haloarene compounds.
By an embodiment preferred of the present invention, the aromatic hydrocarbons that said haloalkyl replaces or-haloarene compounds is one or more compounds shown in the following general formula (I):
In the formula
X is F, Cl or Br;
N is 2 or 3;
R is H, CH
3, F, Cl or Br;
Y and Z are respectively H, F, Cl or Br;
M and w are respectively 0 or 1.
O is the integer of 0-3;
R ' is H, halogen, C
1-2-alkyl, or when o＞1, R ' can be identical or different above-mentioned group, or two R ' groups form a benzo-fused loop section jointly.
By the more preferably following formula of promoter of the present invention (I) compound,
Wherein
O is 0,
M is 1,
X and Y are Cl,
W be 0 and
N is 3.
In addition, more preferably following as formula (I) compound by promoter of the present invention,
Wherein
O is 0,
M and w are 1,
X and Z are Cl,
Y be F and
N is 3.
Preferred concrete promoter of using includes but not limited to following compounds in the catalyst of the present invention:
Three fluoro methylbenzene
Three chloro methylbenzene
Three bromo methylbenzene
Ortho position three fluoro fluoromethane benzene
Ortho position three chloro fluoromethane benzene
Ortho position three bromo fluoromethane benzene
Ortho position two fluoro fluoromethane benzene
Ortho position dichloro-methyl fluorobenzene
Ortho position two bromo fluoromethane benzene
Ortho position three fluoro methyl chloride benzene
Ortho position three chloro methyl chloride benzene
Ortho position three bromo methyl chloride benzene
Ortho position two fluoro methyl chloride benzene
Ortho position dichloro-methyl chlorobenzene
Ortho position two bromo methyl chloride benzene
Ortho position three fluoro methyl bromide benzene
Ortho position three chloro methyl bromide benzene
Ortho position three bromo methyl bromide benzene
Ortho position two fluoro methyl bromide benzene
Ortho position dichloro-methyl bromobenzene
Ortho position two bromo methyl bromide benzene
2,6-dichloro three fluoro methylbenzene
2,6-dichloro three chloro methylbenzene
2,6-dichloro three bromo methylbenzene
2,6-dichloro two fluoro methylbenzene
2,6-dichloro benzal chloride
2,6-dichloro two bromo methylbenzene
2,6-difluoro two fluoro methylbenzene
2,6-difluoro three chloro methylbenzene
2,6-difluoro three bromo methylbenzene
2,6-difluoro two fluoro methylbenzene
2,6-difluoro benzal chloride
2,6-difluoro two bromo methylbenzene
2,6-dibromo three fluoro methylbenzene
2,6-dibromo three chloro methylbenzene
2,6-dibromo two fluoro methylbenzene
2,6-dibromo benzal chloride
2-fluoro-6-chloro-three fluoro methylbenzene
2-fluoro-6-chloro-three chloro methylbenzene
2-fluoro-6-chloro-benzal chloride
2-fluoro-6-chloro-two fluoro methylbenzene
2-fluoro-6-chloro-three bromo methylbenzene
2-fluoro-6-bromo-three fluoro methylbenzene
2-fluoro-6-bromo-three chloro methylbenzene
2-chloro-6-bromo-two fluoro methylbenzene
2-chloro-6-bromo-benzal chloride
2-chloro-6-bromo-three fluoro methylbenzene
2-chloro-6-bromo-three chloro methylbenzene
2-fluoro-6-bromo-two fluoro methylbenzene
2-fluoro-6-bromo-benzal chloride
Wherein more effective promoter is:
Ortho position three chloro fluoromethane benzene
Ortho position three fluoro methyl chloride benzene
Ortho position three chloro methyl chloride benzene
Ortho position three fluoro fluoromethane benzene
2,6-two chloro-trichlorines are for methylbenzene
2-fluoro-6-chloro-three chloro methylbenzene
Wherein most preferred promoter comprises:
Ortho position three chloro fluoromethane benzene
Ortho position three fluoro methyl chloride benzene
Ortho position three chloro methyl chloride benzene
Ortho position three fluoro fluoromethane benzene
2,6-two chloro-trichlorines are for methylbenzene
2-fluoro-6-chloro-three chloro methylbenzene
The chromium compound that uses in the catalyst of the present invention comprises general formula CrR
1 1Those shown compounds, R in the formula
1Be organic negative ion or neutral molecule, R
1In contain 1-10 carbon atom usually, l is the integer of 0-6, the valence state of chromium is the 0-6 valency.Concrete R ' group is for example for containing organic matter or its group of carboxyl, beta-diketon base and alkyl.Consider that from the angle that is easy to dissolve chromium compound preferably comprises that one or both are selected from the compound in next group with easy operating:
| Chromic acetate | (CH 3COO) 3Cr |
| Caprylic acid chromium | (C 7H 15COO) 3Cr |
| Isooctyl acid chromium | (C 4H 9CH(C 2H 5)COO) 3Cr |
| Chromium acetylacetonate | (CH 3COCH 2COCH 3) 3Cr |
| Diisoamyl diene chromium | (C 5H 6) 2Cr |
| Dibenzene-chromium | (C 6H 6) 2Cr |
Wherein preferably is isooctyl acid chromium, caprylic acid chromium.
The azole derivatives that uses in the catalyst of the present invention be any with pyrrole structure as main body, can form the azole derivatives of coordination with chromium, its concrete example includes but not limited to be selected from the mixture of one or more compounds in following a group:
Pyrroles, 2,4-dimethyl pyrrole, 3,4-dimethyl pyrrole, 2,5-dimethyl pyrrole, pyrrolones-(2), 2-methyl-5-N-ethyl pyrrole N-, 2,5-dimethyl pyrrole ketone, 2-methyl-pyrroles and 3-methylpyrrole.
The alkyl aluminum compound that the present invention uses includes but not limited to be selected from a kind of compound or its mixture in following a group:
Triethyl aluminum, triisobutyl aluminium, ethyoxyl diethyl aluminum, chloro diethyl aluminum, chloro diisobutyl aluminum, tri-n-hexyl aluminum etc.Wherein especially preferred triethyl aluminum.
The reaction dissolvent that the present invention uses be for making catalyst component even miscible saturated alkane or cycloalkane mutually arbitrarily, is preferably selected from one or more the mixture in following one group of compound:
Normal heptane, normal octane, n-decane, isooctane, n-dodecane, cyclohexane or hexahydrotoluene.
Chromium compound in the carbon monoxide-olefin polymeric of the present invention (a) is generally a with the mol ratio of azole derivatives (b) and trialkylaluminium (c) and said promoter (d): b: c: d=1: 0.5-500: 50-5000: 0.5-500.Preferred mol ratio is 1: 1-20: 50-500: 1-50, more preferably 1: 2-6: 50-200: 1-30.
By another aspect of the present invention, the preparation method of quaternary chromium-based catalysts of the present invention also is provided, it may further comprise the steps: at first make said promoter, promptly contain the C that at least two halogen atoms of a quilt replace at alpha-position at least on aromatic ring
1-2The aromatic hydrocarbons that the haloalkyl of-alkyl replaces or-haloarene compounds (d) is pre-mixed with metal chromium compounds (a) as coordination center, and make it to take place complexation reaction, under the trimerization condition that has ethene to exist, this mixture joined then and contain in azole compounds (b) and the solution of trialkylaluminium (c) in alkane solvent, and cause ethylene trimer immediately and react.Can give catalyst with catalytic performance preferably by method for preparing catalyst of the present invention, because promoter is mixed to make promoter preferentially to occupy three mutual rectangular coordinate bond positions with central metal chromium with chromium compound, this helps three ethylene molecules and activates synchronously, and optionally trimerization is to generate the 1-hexene.
By another aspect of the present invention, also provide a kind of ethylene trimer to prepare the method for 1-hexene.Wherein in the conventional equipment that carries out ethylene trimer, catalytically effective amount, by in the presence of the catalyst of the invention described above method for preparing catalyst in-situ preparing, feed ethene and make it and catalyst carry out solution-air and contact, cause ethylene trimer, optionally generate purpose product 1-hexene.Reaction temperature is generally 20-200 ℃, is preferably 40-150 ℃, more preferably 60-130 ℃.Reaction pressure is generally 0.5-20.0MPa, is preferably 1.0-15.0MPa, more preferably 2.0-10.0MPa.Reaction time is generally 0.1-10 hour, is preferably 0.2-7 hour.In the reactant liquor of ethylene trimer reaction, anyly can cause that significant ethylene trimer catalyst amount reaction, catalytically effective amount is all feasible.In reactant liquor, will make the concentration of chromium compound (a) usually is 0.01-10.0mmol/L, is preferably 0.01-0.5mmol/L, more preferably 0.02-0.1mmol/L; Make the concentration of azole derivatives (b) be generally 0.03-30mmol/L, be preferably 0.05-2.0mmol/L, more preferably 0.05-0.5mmol/L; Make the concentration of trialkylaluminium (c) be generally 0.05-500mmol/L, be preferably 0.1-50mmol/L, more preferably 0.5-8.0mmol/L; Concentration by promoter of the present invention (d) is generally 0.01-50.0mmol/L, is preferably 0.02-5.0mmol/L, more preferably 0.05-2.0mmol/L.
Preparing the method for 1-hexene according to ethylene trimer of the present invention, that use quaternary chromium-based catalysts of the present invention can batch (-type), semi continuous or continous way ground carry out.The required equipment of various reactive modes all is conventional and commercially available getting, and those of ordinary skills all know its concrete pattern.
By quaternary chromium-based catalysts of the present invention have that the selectivity of reactivity height, purpose product 1-hexene is good, the high polybutadiene reaction product of ethene seldom and advantage such as life of catalyst is long.The reason possibility description below that causes the good catalytic performance of catalyst of the present invention, but the applicant wishes not to be subjected to the constraint of this mechanism explain:
About the ethylene selectivity trimerization reaction, the mechanism (referring to the 9th national catalysis academic meeting paper collection, 1998, BeiJing, China) that three ethylene molecules activated, took place trimerization was simultaneously proposed once.By the general formula of above-mentioned promoter as seen, this aromatic rings has the ability of three mutual rectangular coordinate bonds of the crome metal of plying in the centre, and can form the aromatic ring quasi-molecule complex of chromium; In the general formula-CX
nR
3-n part, when n=3, also can ply in the centre three mutual rectangular coordinate bonds of crome metal of three wherein contained halogens form the molecular complex of chromium and halogenated alkane; In the general formula
In the structure of part Y (or Z) and X atom also can be with three of central metal chromium mutual rectangular coordinate bond form chromium and the replacement of said haloalkyl aromatic hydrocarbons or-molecular complex of halogenated aryl hydrocarbon.Promoter of using with prior art such as inorganic metal chloride salt (as EP 0608447A1 and JP08325319), the organic saturated alkane of many halos (as JP08134131) are compared, and the novel promoter that the present invention uses has two substantial improvement.One is, as mentioned above, this promoter and central metal chromium have the coordination possibility of various ways, and can provide the chance of orthogonal coordinate bond more, that make three ethylene molecules and central metal chromium coordination simultaneously, this helps three ethylene molecules trimerization takes place once, generates the 1-hexene.It two is, with on the halogen atom that aromatic rings is connected or-CX
nR
3-nElectron density on the group on the halogen atom because the effect of big π key on the aromatic ring, is strengthened than the electron density of halogen on the saturated hydrocarbons halide that uses in the prior art, and this is convenient to and central metal chromium forms coordinate bond.As mentioned above, the promoter that the present invention uses form and molecular structure aspect with the promoter difference in itself of prior art use, determined the chromium-based catalysts of ethylene trimer system 1-hexene of the present invention to possess high activity, high selectivity, the accessory substance polymerized ethylene content characteristics in few and long service life simultaneously.
Following examples are used for clearlyer describing the present invention particularly, only limit to these contents but should not be construed as the present invention.
Embodiment 1
With 2.0 ml concns is 12.5mmol/L 2, the n-heptane solution of 5-dimethyl pyrrole (b) and 1 ml concn be normal heptane solvent that the n-heptane solution (c) of the triethyl aluminum of 0.5mol/L is crossed with dehydration of 80 milliliters of dryings and deoxidation treatment join replace through finding time and drying 0.5 liter of autoclave good, with electronic stirring in.This autoclave is connected with a prefabricate, in addition be that the n-heptane solution of isooctyl acid chromium (a) of 4.17mmol/L and the n-heptane solution of the 2-fluoro-6-chloro-three chloro methylbenzene (d) that 1.5 ml concns are 0.05mmol/L are mixed to join in the prefabricate with 1.2 ml concns, find time to replace, charge into 0.1MPa ethene, contact is 10 minutes under 25-30 ℃ condition, after treating that the autoclave temperature reaches 70 ℃, with 5.0MPa ethene the reactant mixture in the prefabricate is displaced in the autoclave fast, causes exothermic reaction immediately.The control reaction temperature is 100 ℃, and reaction pressure is 5.0MPa, keeps reaction 1 hour under this reaction condition.Gas and the liquid in the still is measured in reaction after finishing respectively, and with the composition of gas chromatographic analysis liquid and gas, solid product is weighed after the drying after filtration and at room temperature, trimerization reaction the results are shown in table 1.
Definition: catalyst efficiency: the total amount of the ethylene tripolymer that every gram crome metal generates,
Kg product/g Cr.
Catalytic activity: the total amount of the ethylene tripolymer that every gram crome metal per hour generates,
G product/Cr hour.
Table 1
| The heptane solvent total amount | ml | 80+5.5 |
| Isooctyl acid chromium amount | mmol(a) | 0.005 |
| 2,5-dimethyl pyrrole amount | mmol(b) | 0.025 |
| The triethyl aluminum amount | mmol(c) | 0.500 |
| The promoter kind | 2-fluoro-6-chlorine three chloro methylbenzene | |
| Accelerator dosage | mmol(d) | 0.075 |
| Catalyst proportion | A: b: c: d (mole) | 1∶5∶100∶15 |
| Reaction temperature | ℃ | 100 |
| Reaction pressure | MPa | 5.0 |
| Reaction time | Hour | 1.0 |
| Catalyst efficiency | Kg product/gCr | 321.26 |
| Catalytic activity | G product/g.Cr. hour | 321269.20 |
| Product distributes | Wt％ | |
| C 4＝ C 6＝ C 8＝ C 10＝ C 12+＝ PE | 0.14 89.43 0.50 5.74 4.13 0.06 | |
| C 6Middle α-nC 6Alkene content | Wt％ | 98.6 |
Embodiment 2:
Press operation and the proportioning of embodiment 1, except that the reaction time changed into 2 hours, all the other every reaction conditions were all identical with embodiment 1.Ethylene trimer reaction the results are shown in table 2.
Table 2
| The heptane solvent total amount | ml | 80+5.5 |
| Isooctyl acid chromium amount | mmol(a) | 0.005 |
| 2,5-dimethyl pyrrole amount | mmol(b) | 0.025 |
| The triethyl aluminum amount | mmol(c) | 0.500 |
| The promoter kind | 2-fluoro-6-chlorine three chloro methylbenzene | |
| Accelerator dosage | mmol(d) | 0.075 |
| Catalyst proportion | A: b: c: d (mole) | 1∶5∶100∶15 |
| Reaction temperature | ℃ | 100 |
| Reaction pressure | MPa | ?5.0 |
| Reaction time | Hour | 2.0 |
| Catalyst efficiency | Kg product/gCr | 583.46 |
| Catalytic activity | G product/g.Cr. hour | 291730.70 |
| Product distributes | Wt％ | |
| C 4＝ C 6＝ C 8＝ C 10＝ PE | 0.35 92.00 0.27 7.27 0.11 | |
| C 6Middle α-nC 6Alkene content | Wt％ | 98.32 |
Embodiment 3
Press operation and the proportioning of embodiment 1, except that the reaction time changed into 3 hours, all the other every reaction conditions were all identical with embodiment 1.Ethylene trimer reaction the results are shown in table 3.
Table 3
| The heptane solvent total amount | ml | 80+5.5 |
| Isooctyl acid chromium amount | mmol(a) | 0.005 |
| 2,5-dimethyl pyrrole amount | mmol(b) | 0.025 |
| The triethyl aluminum amount | mmol(c) | 0.500 |
| The promoter kind | 2-fluoro-6-chlorine three chloro methylbenzene | |
| Accelerator dosage | mmol(d) | 0.075 |
| Catalyst proportion | A: b: c: d (mole) | 1∶5∶100∶15 |
| Reaction temperature | ℃ | 100 |
| Reaction pressure | MPa | 5.0 |
| Reaction time | Hour | 3.0 |
| Catalyst efficiency | Kg product/gCr | 710.52 |
| Catalytic activity | G product/g.Cr. hour | 236948.16 |
| Product distributes | Wt％ | |
| C 4＝ C 6＝ C 8＝ C 10＝ PE | 0.62 86.11 0.46 11.80 0.14 | |
| C 6Middle α-nC 6Alkene content | Wt％ | 98.70 |
Embodiment 4
Press operation and the proportioning of embodiment 1, use instead the n-heptane solution of 2-chloro-three chloro methylbenzene that 2-chloro-three chloro methylbenzene, its consumption are 0.05mmol/L for 1.5ml concentration except that promoting kind, all the other every reaction conditions and operation are all identical with example 1, and ethylene trimer reacts the results are shown in table 4.
Table 4
| The heptane solvent total amount | ml | 80+5.5 |
| Isooctyl acid chromium amount | mmol(a) | 0.005 |
| 2,5-dimethyl pyrrole amount | mmol(b) | 0.025 |
| The triethyl aluminum amount | mmol(c) | 0.500 |
| The promoter kind | 2-chlorine three chloro methylbenzene | |
| Accelerator dosage | mmol(d) | 0.075 |
| Catalyst proportion | A: b: c: d (mole) | 1∶5∶100∶15 |
| Reaction temperature | ℃ | 100 |
| Reaction pressure | MPa | 5.0 |
| Reaction time | Hour | 1.0 |
| Catalyst efficiency | Kg product/gCr | 194.69 |
| Catalytic activity | G product/g.Cr. hour | 194961.50 |
| Product distributes | wt％ | |
| C 4＝ C 6＝ C 8＝ C 10＝ C 12+＝ PE | 0.10 91.00 0.53 6.89 1.30 0.09 | |
| C 6Middle α-nC 6Alkene content | wt％ | 98.0 |
Embodiment 5
With 6 ml concns is 2 of 12.5mmol/L, the n-heptane solution of 5-dimethyl pyrrole (b) and 3 ml concns be normal heptane solvent that the n-heptane solution of the triethyl aluminum (c) of 0.5mol/L is crossed with dehydration of 380 milliliters of dryings and deoxidation treatment join replace through finding time and drying 2 liters of autoclave good, with electronic stirring in.This autoclave is connected with a prefabricate, is neighbour-chloro-benzenyl trichloride (o-ClC of 25.0mmol/L with 5 ml concns in addition
6H
4CCl
3) n-heptane solution (d) and the n-heptane solution of the 6 ml concns isooctyl acid chromium (a) that is 4.17mmol/L be mixed to join in the prefabricate; Find time to replace, charge into 0.1MPa ethene, contact is 30 minutes under 25-30 ℃ condition.After treating that the autoclave temperature reaches 70 ℃, with 4.0MPa ethene the reactant mixture in the prefabricate is moved on in the autoclave fast, cause exothermic reaction immediately, the control reaction temperature is 80 ℃.Reaction pressure is 4.0～4.5MPa, keeps under this reaction condition and reacts 1 hour.Measure gas and liquid in the still after reaction is finished respectively, with the composition of gas chromatographic analysis gas phase and liquid phase, solid product is through weighing after the drying under filtration and the room temperature.Trimerization reaction the results are shown in table 5.
Table 5
| The heptane solvent total amount | ml | 380±20 |
| Isooctyl acid chromium amount | mmol(a) | 0.025 |
| 2,5-dimethyl pyrrole amount | mmol(b) | 0.075 |
| The triethyl aluminum amount | mmol(c) | 1.50 |
| The promoter kind | Neighbour-chloro-benzenyl trichloride | |
| Accelerator dosage | mmol(d) | 0.125 |
| Catalyst proportion | A: b: c: d (mole) | 1∶3∶60∶5 |
| Reaction temperature | ℃ | 80 |
| Reaction pressure | MPa | 4.0-4.5 |
| Reaction time | Hour | 1.0 |
| Catalyst efficiency | Kg product/gCr | 163.85 |
| Catalytic activity | G product/g.Cr. hour | 163846 |
| Product distributes | Wt％ | |
| C 4＝ C 6＝ C 8＝ C 10＝ C 12+＝ PE | 1.60 88.50 0.40 8.80 0.40 0.30 | |
| C 6Middle α-nC 6Alkene content | Wt％ | 98.80 |
The comparative example 1
Remove and use the promoter kind instead 1,1,2, it is that 5 ml concns are 1,1,2 of 25.0mmol/L that the 2-tetrachloroethanes replaces neighbour-chloro-trichloromethyl chlorobenzene, its consumption, outside the solution of 2-tetrachloroethanes in heptane, all the other operations are all identical with example 5, and the reaction result of ethylene trimer is listed in table 6.
Table 6
| The heptane solvent total amount | ml | 380+20 |
| Isooctyl acid chromium amount | mmol(a) | 0.025 |
| 2,5-dimethyl pyrrole amount | mmol(b) | 0.075 |
| The triethyl aluminum amount | mmol(c) | 1.50 |
| The promoter kind | 1,1,2, the 2-tetrachloroethanes | |
| Accelerator dosage | mmol(d) | 0.125 |
| Catalyst proportion | A: b: c: d (mole) | 1∶3∶60∶5 |
| Reaction temperature | ℃ | 80 |
| Reaction pressure | MPa | 4.0-4.5 |
| Reaction time | Hour | 1 |
| Catalyst efficiency | Kg product/gCr | 164.54 |
| Catalytic activity | G α-alkene/g.Cr. hour | 164538 |
| Product distributes | wt％ | |
| C 4＝ C 6＝ C 8＝ C 10＝ C 12+＝ PE | 5.0 86.0 0.70 5.30 2.80 0.40 | |
| C 6Middle α-nC 6Alkene content | wt％ | 96.0 |
The comparative example 2
Except that not adding neighbour-chloro-trichloromethyl chlorobenzene, the proportioning of all the other each components of catalyst is all identical with embodiment 5 with operation, and the reaction result of ethylene trimer is listed in table 7.
Table 7
| The heptane solvent total amount | ml | 385+15 |
| Isooctyl acid chromium amount | mmol(a) | 0.025 |
| 2,5-dimethyl pyrrole amount | mmol(b) | 0.075 |
| The triethyl aluminum amount | mmol(c) | 1.50 |
| The promoter kind | Do not have | |
| Accelerator dosage | mmol(d) | Do not have |
| Catalyst proportion | A: b: c (mole) | 1∶3∶60 |
| Reaction temperature | ℃ | 80 |
| Reaction pressure | MPa | 4.0-4.5 |
| Reaction time | Hour | 1 |
| Catalyst efficiency | Kg product/gCr | 71.94 |
| Catalytic activity | G α-alkene/g.Cr. hour | 71935 |
| Product distributes | wt％ | |
| C 4＝ C 6＝ C 8＝ C 10＝ C 12+＝ PE | 48.5 34.7 3.0 10.0 2.0 1.8 | |
| C 6Middle α-nC 6Alkene content | wt％ | 86 |
Claims (9)
1. chromium-based catalysts that is used for ethylene trimer, it comprises a kind of chromium compound (a), a kind of azole derivatives (b), a kind of alkyl aluminum (c) and a kind of promoter (d), it is characterized in that said promoter comprises a kind of C that at least two halogen atoms of a quilt replace at alpha-position that contains at least on aromatic ring
1-2The aromatic hydrocarbons that the haloalkyl of-alkyl replaces or-haloarene compounds.
2. according to the chromium-based catalysts of claim 1, it is characterized in that, the aromatic hydrocarbons that said haloalkyl replaces or-haloarene compounds is the compound shown in the following general formula (I):
In the formula,
X is F, Cl or Br,
N is 2 or 3,
R is H, CH
3, F, Cl or Br,
Y and Z are respectively H, F, Cl or Br,
M and w are respectively 0 or 1,
O is 0 to 3 integer;
R ' is H, halogen, C
1-2-alkyl,
Or when o＞1, R ' can be identical or different above-mentioned group, or two R ' form a benzo-fused ring jointly.
3. according to the chromium-based catalysts of claim 2, it is characterized in that in formula (I), o is 0, m is 1, and X and Y are Cl, and w is 0, and n is 3.
4. according to the chromium-based catalysts of claim 2, it is characterized in that in formula (I), o is 0, m and w are 1, and X is Cl, and Y is F, and Z is Cl, and n is 3.
5. according to each catalyst among the claim 1-4, it is characterized in that the component (a) and (b) that comprise in the said chromium-based catalysts, (c) and mol ratio (d) are (a): (b): (c): (d)=1: 0.5-500: 50-5000: 0.5-500.
6. according to the catalyst of claim 5, it is characterized in that said mol ratio is (a): (b): (c): (d)=1: 1-20: 50-500: 1-50.
7. according to the catalyst of claim 6, it is characterized in that said mol ratio is (a): (b): (c): (d)=1: 2-6: 50-200: 1-30.
8. method for preparing according to each catalyst among the claim 1-7, it is characterized in that, described chromium compound (a) and promoter (d) are pre-mixed, under the reaction condition of ethylene trimer, this mixture is passed in the n-heptane solution that contains azole derivatives (b) and alkyl aluminum (c) then, makes it to mix contact.
9. one kind prepares the method for 1-hexene by ethylene trimer, it is characterized in that, use catalytically effective amount as each the catalyst or the catalyst of method as claimed in claim 8 preparation among the claim 1-7, ethene is contacted with this catalyst and trimerization reaction takes place.
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| CN99120585A CN1108193C (en) | 1998-12-15 | 1999-10-09 | Novel catalyst for ethylene trimerization, its preparation process and application |
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| CN98125382.2 | 1998-12-15 | ||
| CN98125382 | 1998-12-15 | ||
| CN99120585A CN1108193C (en) | 1998-12-15 | 1999-10-09 | Novel catalyst for ethylene trimerization, its preparation process and application |
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