CN1108193C - Novel catalyst for ethylene trimerization, its preparation process and application - Google Patents
Novel catalyst for ethylene trimerization, its preparation process and application Download PDFInfo
- Publication number
- CN1108193C CN1108193C CN99120585A CN99120585A CN1108193C CN 1108193 C CN1108193 C CN 1108193C CN 99120585 A CN99120585 A CN 99120585A CN 99120585 A CN99120585 A CN 99120585A CN 1108193 C CN1108193 C CN 1108193C
- Authority
- CN
- China
- Prior art keywords
- chromium
- reaction
- catalyzer
- promotor
- chloro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a quaternary chromium catalyst for preparing 1-hexene by ethene trimerization, which comprises a chromium compound, a pyrrole derivative, a kind of trialkyl aluminum and an accelerating agent, wherein the accelerating agent is a halogenated alkyl substituted aromatic hydrocarbon or a halogenated aryl hydrocarbons compound at least containing a kind of C1 to 2 alkyl substituted by two halogen atoms on an alpha-position on an aromaticring. The catalyst has the characteristics of high reactivity and selectivity and few by-products. The present invention also provides a preparation method of the catalyst.
Description
Technical field
The present invention relates to a kind of catalyzer that is used for ethylene trimerization, or rather, is a kind of chromium-based catalysts that is used for ethylene trimerization, also relates to this Preparation of catalysts method and application thereof.
Background technology
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 EP0608447A1, to be used for trimerization, oligomerisation and/or copolyolefine.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 stabilization 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 trimerization reactive behavior and the selectivity of this catalyzer all are greatly increased, but still can not meet the demands, people wish further to improve the performance of catalyzer.
Used Sn (OSO among the JP08325319
2CF
3)
2Compound replaces in EP 0608447A1 as optional member and the main halogen source SnCl that uses
4, with as isocaprylic acid chromium, 2, the promotor of three-way catalysts such as 5-dimethyl pyrrole and triethyl aluminum, halogen compounds is included in the catalyst composition as a necessary component of catalyzer 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 JP08134131 as the promotor 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 isocaprylic acid chromium, 2, the promotor of the catalyzer 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 promotor, to expect further to improve the performance of the chromium-based catalysts that is used for ethylene trimerization system 1-hexene, both made catalyzer that the selectivity of high catalytic activity and high purpose product 1-hexene is arranged, and made the poly growing amount of by product few as far as possible again.
Summary of the invention
The purpose of this invention is to provide a kind of new quaternary chromium-based catalysts system that is used for ethylene trimerization, a kind of method and a kind of method of using this catalyzer to prepare the 1-hexene with catalyzed ethylene selectivity trimerization for preparing this catalyzer 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 cpd, a kind of pyrrole derivative and a kind of trialkylaluminium, also contain a kind of novel promotor composition, it is characterized in that this promotor 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
1-2Aromatic hydrocarbons or haloarene compounds that the haloalkyl of-alkyl replaces.
By an embodiment preferred of the present invention, aromatic hydrocarbons or haloarene compounds that said haloalkyl replaces are one or more benzene series shown in the following general formula (I) or benzene halide based compound:
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;
O is the integer of 1-3;
R ' is for being selected from H, halogen, C
1-2The identical or different group of-alkyl.
By the more preferably following formula of promotor of the present invention (I) compound,
Wherein
R ' is H,
O is 1,
X and Y are Cl,
N is 3.
In addition, more preferably following as formula (I) compound by promotor of the present invention,
Wherein
R ' is H,
O is 1,
X and Z are Cl,
Y be F and
N is 3.
Preferred concrete promotor of using includes but not limited to following compounds in the catalyzer of the present invention:
Three fluoro methylbenzene
Three chloro methylbenzene
Three bromo methylbenzene
Ortho position three fluoro methyl fluoride benzene
Ortho position three chloro methyl fluoride benzene
Ortho position three bromo methyl fluoride benzene
Ortho position two fluoro methyl fluoride benzene
Ortho position dichloro-methyl fluorobenzene
Ortho position two bromo methyl fluoride 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 monobromomethane benzene
Ortho position three chloro monobromomethane benzene
Ortho position three bromo monobromomethane benzene
Ortho position two fluoro monobromomethane benzene
Ortho position dichloro-methyl bromobenzene
Ortho position two bromo monobromomethane 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 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 promotor is:
Ortho position three chloro methyl fluoride benzene
Ortho position three fluoro methyl chloride benzene
Ortho position three chloro methyl chloride benzene
Ortho position three fluoro methyl fluoride benzene
2,6-two chloro-trichlorines are for methylbenzene
2-fluoro-6-chloro-three chloro methylbenzene
The chromium cpd that uses in the catalyzer 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, 1 is the integer of 0-6, the valence state of chromium is the 0-6 valency.Concrete R
1Group is for example for containing organism or its group of carboxyl, beta-diketon base and alkyl.Consider that from the angle that is easy to dissolve chromium cpd preferably comprises that one or both are selected from the compound in next group with easy handling:
| Chromium acetate | (CH 3COO) 3Cr |
| N-caprylic acid chromium | (C 7H 15COO) 3Cr |
| Isocaprylic 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 isocaprylic acid chromium, n-caprylic acid chromium.
The pyrrole derivative that uses in the catalyzer of the present invention be any with pyrrole structure as main body, can form the coordinate pyrrole derivative 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, pyrrolidone-(2), 2-methyl-5-N-ethyl pyrrole N-, 2,5-dimethyl pyrrole ketone, 2-methyl-pyrroles and 3-methylpyrrole.
The alkylaluminium cpd 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, oxyethyl group diethyl aluminum, chloro diethyl aluminum, chloro diisobutyl aluminum, tri-n-hexyl aluminum etc.Wherein especially preferred triethyl aluminum.
The reaction solvent that the present invention uses be for making catalyst component even miscible saturated alkane or naphthenic hydrocarbon mutually arbitrarily, is preferably selected from one or more the mixture in following one group of compound:
Normal heptane, octane, n-decane, octane-iso, n-dodecane, hexanaphthene or methylcyclohexane.
Chromium cpd in the catalyst composition of the present invention (a) is generally a with the mol ratio of pyrrole derivative (b) and trialkylaluminium (c) and said promotor (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 promotor, promptly contain the C that at least two halogen atoms of a quilt replace at alpha-position at least on aromatic ring
1-2Aromatic hydrocarbons that the haloalkyl of-alkyl replaces or haloarene compounds (d) are pre-mixed with metal chromium compounds (a) as coordination center, and make it to take place coordination 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 trimerization immediately and react.Can compose the muonic catalysis agent with catalytic performance preferably by method for preparing catalyst of the present invention, because promotor is mixed to make promotor preferentially to occupy three mutual rectangular coordinate bond positions with central metal chromium with chromium cpd, 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 trimerization to prepare the method for 1-hexene.Wherein in the conventional equipment that carries out ethylene trimerization, catalytically effective amount, by in the presence of the catalyzer of the invention described above method for preparing catalyst in-situ preparing, feed ethene and make it and catalyzer carry out solution-air and contact, cause ethylene trimerization, optionally generate purpose product 1-hexene.Temperature of reaction 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 reaction solution of ethylene trimerization reaction, anyly can cause that significant ethylene trimerization catalyst levels reaction, catalytically effective amount is all feasible.In reaction solution, will make the concentration of chromium cpd (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 pyrrole derivative (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 promotor 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 trimerization of the present invention, that use quaternary chromium-based catalysts of the present invention can intermittent 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 reactive behavior 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 catalyzer 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, once proposed three ethylene molecules and activated, take place trimeric mechanism (referring to the 9th national catalysis academic meeting paper collection, 1998, BeiJing, China) simultaneously.By the general formula of above-mentioned promotor as seen, this aromatic nucleus has the ability of three mutual rectangular coordinate bonds of the chromium metal of plying in the centre, and can form the aromatic ring quasi-molecule title complex of chromium; In the general formula-CX
nR
3-nPart, when n=3, also can ply in the centre three mutual rectangular coordinate bonds of chromium metal of three wherein contained halogenss form the molecular complex of chromium and halogenated alkane; In the general formula
Y (or Z) also can mutual rectangular coordinate bond form chromium and the aromatic hydrocarbons of said haloalkyl replacement or the molecular complex of halogenated aryl hydrocarbon with three of central metal chromium with the X atom in the structure of part.Promotor of using with prior art such as inorganic metal muriate salt (as EP0608447A1 and JP08325319), the organic saturated alkane of many halos (as JP08134131) are compared, and the novel promotor that the present invention uses has two substantial improvement.One is, as mentioned above, this promotor and central metal chromium have the coordination possibility of various ways, and can provide orthogonal coordinate bond more, that make three ethylene molecules and central metal chromium coordinate chance simultaneously, this helps three ethylene molecules trimerization takes place once, generates the 1-hexene.It two is, with on the halogen atom that aromatic nucleus 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 stable hydrocarbon halogenide that uses in the prior art, and this is convenient to and central metal chromium forms coordinate bond.As mentioned above, the promotor that the present invention uses form and molecular structure aspect with the promotor difference in itself of prior art use, determined the chromium-based catalysts of ethylene trimerization system 1-hexene of the present invention to possess high reactivity, highly selective, the by product polymerized ethylene content characteristics in few and long work-ing life simultaneously.
Embodiment
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 isocaprylic 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 reaction mixture in the prefabricate is displaced in the autoclave fast, causes thermopositive reaction immediately.Control reaction temperature is 100 ℃, and reaction pressure is 5.0MPa, keeps reaction 1 hour under this reaction conditions.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 phase prod 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 chromium metal generates,
Kg product/gCr.
Catalytic activity: the total amount of the ethylene tripolymer that every gram chromium metal per hour generates,
G product/gCr hour
Table 1
| The heptane solvent total amount | ml | 80+5.5 |
| Isocaprylic 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 promotor kind | 2-fluoro-6-chloro-three chloro methylbenzene | |
| Accelerator level | mmol(d) | 0.075 |
| Catalyst proportion | A: b: c: d (mole) | 1∶5∶100∶15 |
| Temperature of reaction | ℃ | 100 |
| Reaction pressure | MPa | 5.0 |
| Reaction times | Hour | 1.0 |
| Catalyst efficiency | Kg product/gCr | 321.26 |
| Catalytic activity | G product/gCr. 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 times changed into 2 hours, all the other every reaction conditionss were all identical with embodiment 1.Ethylene trimerization reaction the results are shown in table 2.
Table 2
| The heptane solvent total amount | ml | 80+5.5 |
| Isocaprylic 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 promotor kind | 2-fluoro-6-chloro-three chloro methylbenzene | |
| Accelerator level | mmol(d) | 0.075 |
| Catalyst proportion | A: b: c: d (mole) | 1∶5∶100∶15 |
| Temperature of reaction | ℃ | 100 |
| Reaction pressure | MPa | 5.0 |
| Reaction times | Hour | 2.0 |
| Catalyst efficiency | Kg product/gCr | 583.46 |
| Catalytic activity | G product/gCr. 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 times changed into 3 hours, all the other every reaction conditionss were all identical with embodiment 1.Ethylene trimerization reaction the results are shown in table 3.
Table 3
Embodiment 4
| The heptane solvent total amount | ml | 80+5.5 |
| Isocaprylic 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 promotor kind | 2-fluoro-6-chloro-three chloro methylbenzene | |
| Accelerator level | mmol(d) | 0.075 |
| Catalyst proportion | A: b: c: d (mole) | 1∶5∶100∶15 |
| Temperature of reaction | ℃ | 100 |
| Reaction pressure | MPa | 5.0 |
| Reaction times | Hour | 3.0 |
| Catalyst efficiency | Kg product/gCr | 710.52 |
| Catalytic activity | G product/gCr. 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 |
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 conditionss and operation are all identical with example 1, and ethylene trimerization reacts the results are shown in table 4.
Table 4
| The heptane solvent total amount | ml | 80+5.5 |
| Isocaprylic 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 promotor kind | 2-chloro-three chloro methylbenzene | |
| Accelerator level | mmol(d) | 0.075 |
| Catalyst proportion | A: b: c: d (mole) | 1∶5∶100∶15 |
| Temperature of reaction | ℃ | 100 |
| Reaction pressure | MPa | 5.0 |
| Reaction times | Hour | 1.0 |
| Catalyst efficiency | Kg product/gCr | 194.69 |
| Catalytic activity | G product/gCr. 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 isocaprylic 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 reaction mixture in the prefabricate is moved on in the autoclave fast, cause thermopositive reaction immediately, control reaction temperature is 80 ℃.Reaction pressure is 4.0～4.5MPa, keeps under this reaction conditions 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 phase prod 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 |
| Isocaprylic 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 promotor kind | Neighbour-chloro-benzenyl trichloride | |
| Accelerator level | mmol(d) | 0.125 |
| Catalyst proportion | A: b: c: d (mole) | 1∶3∶60∶5 |
| Temperature of reaction | ℃ | 80 |
| Reaction pressure | MPa | 4.0-4.5 |
| Reaction times | Hour | 1.0 |
| Catalyst efficiency | Kg product/gCr | 163.85 |
| Catalytic activity | G product/gCr. 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 promotor kind instead 1,1,2, it is that 5 ml concns are 1,1,2 of 25.0mmol/L that the 2-tetrachloroethane replaces neighbour-chloro-benzenyl trichloride, its consumption, outside the solution of 2-tetrachloroethane in heptane, all the other operations are all identical with example 5, and the reaction result of ethylene trimerization is listed in table 6.
Table 6
| The heptane solvent total amount | ml | 380+20 |
| Isocaprylic 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 promotor kind | Sym.-tetrachloroethane | |
| Accelerator level | mmol(d) | 0.125 |
| Catalyst proportion | A: b: c: d (mole) | 1∶3∶60∶5 |
| Temperature of reaction | ℃ | 80 |
| Reaction pressure | MPa | 4.0-4.5 |
| Reaction times | Hour | 1 |
| Catalyst efficiency | Kg product/gCr | 164.54 |
| Catalytic activity | G α-alkene/gCr. 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-benzenyl trichloride, the proportioning of all the other each components of catalyzer is all identical with embodiment 5 with operation, and the reaction result of ethylene trimerization is listed in table 7.
Table 7
| The heptane solvent total amount | ml | 385+15 |
| Isocaprylic 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 promotor kind | Do not have | |
| Accelerator level | mmol(d) | Do not have |
| Catalyst proportion | A: b: c (mole) | 1∶3∶60 |
| Temperature of reaction | ℃ | 80 |
| Reaction pressure | MPa | 4.0-4.5 |
| Reaction times | Hour | 1 |
| Catalyst efficiency | Kg product/gCr | 71.94 |
| Catalytic activity | G α-alkene/gCr. 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 (7)
1. chromium-based catalysts that is used for ethylene trimerization, it comprises a kind of chromium cpd (a), a kind of pyrrole derivative (b), a kind of aluminum alkyls (c) and a kind of promotor (d), it is characterized in that said promotor comprises a kind of C that contains at least two halogen atoms of a quilt in the alpha-position replacement on phenyl ring shown in the following general formula (I)
1-2Benzene series or ortho position halogeno-benzene based compound that the haloalkyl of-alkyl replaces:
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,
O is 1 to 3 integer,
R ' is for being selected from H, halogen, C
1-2The identical or different group of-alkyl.
2. according to the chromium-based catalysts of claim 1, it is characterized in that in formula (I), R ' is H, o is 1, and X and Y are Cl, and n is 3.
3. according to the chromium-based catalysts of claim 1, it is characterized in that in formula (I), R ' is H, o is 1, and X is Cl, and Y is F, and Z is Cl, and n is 3.
4. according to each catalyzer of claim 1 to 3, it is characterized in that mol ratio is (a): (b): (c): (d)=1: 1-20: 50-500: 1-50.
5. according to the catalyzer of claim 4, it is characterized in that said mol ratio is (a): (b): (c): (d)=1: 2-6: 50-200: 1-30.
6. method for preparing each catalyzer among the claim 1-5, it is characterized in that, described chromium cpd (a) and promotor (d) are pre-mixed, under the reaction conditions of ethylene trimerization, this mixture is passed in the n-heptane solution that contains pyrrole derivative (b) and aluminum alkyls (c) then, makes it to mix contact.
7. one kind prepares the method for 1-hexene by ethylene trimerization, it is characterized in that, use catalytically effective amount as each catalyzer among the claim 1-5, ethene is contacted with this catalyzer and trimerization reaction takes place.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99120585A CN1108193C (en) | 1998-12-15 | 1999-10-09 | Novel catalyst for ethylene trimerization, its preparation process and application |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98125382 | 1998-12-15 | ||
| CN98125382.2 | 1998-12-15 | ||
| CN99120585A CN1108193C (en) | 1998-12-15 | 1999-10-09 | Novel catalyst for ethylene trimerization, its preparation process and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1256968A CN1256968A (en) | 2000-06-21 |
| CN1108193C true CN1108193C (en) | 2003-05-14 |
Family
ID=25744797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99120585A Expired - Lifetime CN1108193C (en) | 1998-12-15 | 1999-10-09 | Novel catalyst for ethylene trimerization, its preparation process and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1108193C (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200502038A (en) | 2003-03-14 | 2005-01-16 | Chevron Phillips Chemical Co | Process to decrease or eliminate corrosion from the decomposition of halide containing olefin catalysts |
| US20050187418A1 (en) | 2004-02-19 | 2005-08-25 | Small Brooke L. | Olefin oligomerization |
| US20070043181A1 (en) | 2005-08-19 | 2007-02-22 | Knudsen Ronald D | Methods of preparation of an olefin oligomerization catalyst |
| US9550841B2 (en) | 2004-02-20 | 2017-01-24 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
| US7384886B2 (en) | 2004-02-20 | 2008-06-10 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
| CN100386149C (en) * | 2006-06-26 | 2008-05-07 | 中国石油天然气股份有限公司 | Ethylene trimerization catalyst and application thereof |
| US7902415B2 (en) | 2007-12-21 | 2011-03-08 | Chevron Phillips Chemical Company Lp | Processes for dimerizing or isomerizing olefins |
| US8471085B2 (en) | 2008-10-31 | 2013-06-25 | Chevron Phillips Chemical Company Lp | Oligomerization catalyst system and process for oligomerizing olefins |
| KR101642164B1 (en) * | 2008-10-31 | 2016-07-22 | 셰브론 필립스 케미컬 컴퍼니 엘피 | Compositions and catalyst systems of metal precursors and olefinic diluents |
| WO2011118533A1 (en) * | 2010-03-26 | 2011-09-29 | 三菱化学株式会社 | METHOD FOR PRODUCING α-OLEFIN OLIGOMER |
| CN103044181A (en) * | 2011-10-17 | 2013-04-17 | 中国石油天然气股份有限公司 | Method for preparing octene-1 by ethylene tetramerization reaction |
| CN103100420A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Catalyst composition for ethylene tetramerization and preparation method of ligand thereof |
| US9586872B2 (en) | 2011-12-30 | 2017-03-07 | Chevron Phillips Chemical Company Lp | Olefin oligomerization methods |
| CN108456228B (en) * | 2017-02-22 | 2020-11-13 | 李达刚 | Small steric barrier organic phosphine ligand, preparation method thereof and application of ligand in preparation of 1-octene and 1-hexene from ethylene |
| FR3113054B1 (en) * | 2020-07-30 | 2022-11-04 | Ifp Energies Now | METHOD FOR THE OLIGOMERIZATION OF ETHYLENE COMPRISING THE IN SITU PREPARATION OF THE CATALYTIC COMPOSITION |
| CN114773139B (en) * | 2022-06-01 | 2024-06-11 | 海南贝欧亿科技有限公司 | Co-production method of 1-octene and 1-hexene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1108967A (en) * | 1994-02-18 | 1995-09-27 | 菲利浦石油公司 | Olefin production |
| CN1128745A (en) * | 1994-09-05 | 1996-08-14 | 住友化学工业株式会社 | Method for prepn. of 1-hexene |
| CN1155530A (en) * | 1995-12-18 | 1997-07-30 | 菲利浦石油公司 | Olefin production |
-
1999
- 1999-10-09 CN CN99120585A patent/CN1108193C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1108967A (en) * | 1994-02-18 | 1995-09-27 | 菲利浦石油公司 | Olefin production |
| CN1128745A (en) * | 1994-09-05 | 1996-08-14 | 住友化学工业株式会社 | Method for prepn. of 1-hexene |
| CN1155530A (en) * | 1995-12-18 | 1997-07-30 | 菲利浦石油公司 | Olefin production |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1256968A (en) | 2000-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1108193C (en) | Novel catalyst for ethylene trimerization, its preparation process and application | |
| CN1140349C (en) | Catalyst for conversion of ethylene into light alpha olefins | |
| CN1107545C (en) | Improved catalytic composition and process for converting ethylene to light alpha olefins | |
| CN1245362C (en) | Process for producing catalyst system using stabilizing olefin | |
| CN1209386C (en) | Catalyst | |
| TWI645900B (en) | Novel catalyst composition and method for oligomerizing ethylene into 1-hexene | |
| CN1184240C (en) | Olefin production | |
| CN1155530A (en) | Olefin production | |
| CN1266424A (en) | Method for producing mixtures of monoolefinic (5-mononitriles by catalytic hydrocyanation in the presence of a catalyst containing at least one metallocene phoshor (III)-nicel-(0) complex | |
| CN1107132A (en) | Olefin production | |
| CN1651142A (en) | Catalyst component used for ethylene oligomerization, preparing process and application thereof | |
| CN1079417A (en) | C 2-C 5Paraffin dehydrogenation is with catalyst precarsor method and the catalyst composition that activates with this method | |
| CN1069033A (en) | Many active sites olefin polymerization catalysis and preparation thereof | |
| CN1065261A (en) | The catalyst composition for preparing the method for a chlorotrifluoroethylene and trifluoro-ethylene and be used for this method | |
| CN1128776C (en) | Catalyst for preparing 1-hexene from ethene by oligomerization and its application | |
| CN1065413A (en) | Catalyst system and method with liquid-phase production of methanol from synthesis gas | |
| CN1031364A (en) | The preparation method of butene-1 | |
| CN1488616A (en) | Preparation for fluro-halogenated ether | |
| CN1409694A (en) | Hydrocarbon conversion process | |
| CN1872416A (en) | Ethylene trimerization catalyst and application thereof | |
| CN1408733A (en) | Olefine polymerization catalyst containing double schiff base ligand and preparing method and use | |
| CN1255144A (en) | Catalyst solution for polymerization of 'alpha'-olefines | |
| CN1033090C (en) | Catalysts for polymerization of olefins | |
| CN1279069C (en) | Polyethylene catalyst and its preparation method | |
| CN1079091C (en) | Process for the dimerization of lower olefins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170209 Address after: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Patentee after: China Petroleum Chemical Co Address before: 102550 Yanshan Phoenix Road, Fangshan District, No., No. nine Patentee before: Beijing Research Inst. of Yanshan Petrochemical Corp. |
|
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20030514 |