CN1128776C - Catalyst for preparing 1-hexene from ethene by oligomerization and its application - Google Patents
Catalyst for preparing 1-hexene from ethene by oligomerization and its application Download PDFInfo
- Publication number
- CN1128776C CN1128776C CN00107545A CN00107545A CN1128776C CN 1128776 C CN1128776 C CN 1128776C CN 00107545 A CN00107545 A CN 00107545A CN 00107545 A CN00107545 A CN 00107545A CN 1128776 C CN1128776 C CN 1128776C
- Authority
- CN
- China
- Prior art keywords
- ethene
- hexene
- oligomerization
- catalyst
- chromium
- 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 - Fee Related
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
Abstract
The present invention relates to a catalyst compound for preparing 1-hexene from ethene by oligomerization and an application thereof. The catalyst is composed of chromic compounds, pyrrole derivatives, aluminium alkyl compounds, and a quaternary chromium catalyst composition which is composed of a kind of modifying addition. The present invention is characterized in that the modifying addition is a compound of which the general formula is XmARn (wherein X is Cl or F; m is equal to 3 to 6, R is F or Cl or Br or CCl3 or H; n is equal to 0 to 2; A is single-alicyclic ring alkyl or phenyl). The catalyst is used for preparing the 1-hexene from the ethene by oligomerization; the present invention has the characteristics of high reactivity and selectivity, and less generated quantity of byproducts and polyethylene.
Description
The present invention relates to olefin oligomerization catalyst, a kind of chromium-based catalysts and application thereof that is used for preparing 1-hexene from ethene by oligomerization of more specifically saying so.
The 1--hexene is polyolefinic important comonomer, method by ethylene oligomerization selectively producing 1-hexene, at J.Chem.Soc, chem.commun. (1989, the 674-675 page or leaf) reported in that homogeneous phase ternary chromium-based catalysts composition catalyzed ethylene oligomerisation selectivity makes the method for 1-hexene, but the used catalyst of this method is active and selectivity is all lower.
Reported a kind of improved chromium-based catalysts composition among the EP 0608447A1, be used for ethylene oligomerization and/or copolymerization, wherein used a kind of compound that contains chromium as one of component of catalyst composition; Use a kind of azole compounds as two of the component of chromium-based catalysts composition; Having adopted a kind of is activator as three of the component of this catalyst composition with lewis' acid and/or metal alkyl compound; Also point out simultaneously, halogen source also can choose any one kind of them in the catalyst system as four of the component in this catalyst composition, this halogen source both can be inorganic halides, also can be the Organohalogen compounds of numerous types, with former chromium-based catalysts ratio, this catalyzer is greatly increased to the selectivity of 1-hexene, but its catalytic activity is not high.
Used Sn (OSO among the JP 0832519
2CF
3)
2Compound replaces the halogen source of the 4th component among the EP0608447A1, as isocaprylic acid chromium, 2, the improving agent of 5-dimethyl pyrrole and triethyl aluminum three-way catalyst has formed a kind of quaternary chromium-based catalysts composition, and 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 improving agent in the chromium-based catalysts composition, wherein used with contain on adjacent two carbon atoms of end three above halogen atoms as the saturated haloalkane of feature as by isocaprylic acid chromium, 2,5-dimethyl arsenic is coughed up and the improving agent of the three-way catalyst that triethyl aluminum is formed, and its catalytic activity increases.
USP5 has reported in 910,619 and has adopted 1,2,3,4,5, the conduct of 6-HEXACHLOROBUTADIENE is by isocaprylic acid chromium, 2, the improving agent of 5-dimethyl pyrrole and triethyl aluminum ternary system catalyzer is formed the four-way catalyst composition, though this activity of such catalysts increases, but still can not meet the demands, people wish further to improve the performance of catalyzer.
From the above, keep under the geostationary situation in three main components of chromium-based catalysts, people are concentrating on to screen suitable improving agent, to expect further to improve the performance of the chromium-based catalysts that is used for ethylene oligomerization selectively producing 1-hexene, make the selectivity of existing high catalytic activity of catalyzer and high purpose product 1-hexene, make the poly growing amount of by product few as far as possible again.
The purpose of this invention is to provide a kind of quaternary chromium-based catalysts composition and method of making the same of the preparing 1-hexene from ethene by oligomerization that is used for having simultaneously high reactivity and highly selective and use this catalyst ethylene oligomerization optionally to produce the method for 1-hexene.
Quaternary chromium-based catalysts composition of the present invention is made up of chromium compounds a, pyrrole derivative b, alkylaluminium cpd c and improving agent d, and their mol ratio is a: b: c: d=1: 3-6: 50-150: 5-20.
Chromium compounds in the catalyzer of the present invention, pyrrole derivative, alkylaluminium cpd all have introduction in known ethylene oligomerization is produced the method for 1-hexene, characteristics of the present invention are to propose four component of a kind of new improving agent as catalyzer, the general formula of described improving agent compound is: XmARn, and in the formula: X is Cl, F; M is the integer of 3-6; R is H, F, Cl, Br or CCl
3N is the integer of 0-3; A is monoester cycloalkyl or phenyl.
The preferred compound of improving agent of the present invention comprises:
1. X is that Cl, m=5, R are that Cl, n=1, A are the compound promptly 1,2,3,5 of cyclohexyl in the general formula, 6-HEXACHLOROBUTADIENE γ one;
2. X is Cl or F, m=4 in the general formula, and R is CCl
3, n=2, A be the compound of phenyl, comprises 1,4--two (three chloro methyl)-2,3,5,6-tetrachlorobenzene, 1,3--two (three chloro methyl)-2,4,5,6-tetrachlorobenzene, 1,2--two (three chloro methyl)-3,4,5,6-tetrachlorobenzene, 1,4--two (three chloro methyl)-2,3,5,6-tetra fluoro benzene, 1,4--two (three chloro methyl)-2,5-two fluoro-3,6-dichlorobenzene, 1,4--two (three chloro methyl)-2-fluoro-3,5,6-trichlorobenzene, with 1,4--two (three chloro methyl)-2,3,5,6-tetrachlorobenzene the best.
3. X is that Cl or F, m=3, R are CCl in the general formula
3, n=3, A is the compound promptly 1,3 of phenyl, 5--three (three chloro methyl)-2,4,6-trichlorobenzene.
Chromium compounds in the catalyst composition of the present invention, its general formula is: CrR
1 q, R in the formula
1Be organic negative ion or neutral molecule, R
1In contain 1-10 carbon atom usually, q is the integer of 0-6, the valence state of chromium is the 0-6 valency, concrete R
1Group comprises the organic group that contains carboxyl, beta-diketon base and alkyl, consider from being easy to dissolving and easy handling, chromium compounds preferably comprises one or both the mixture in chromium acetate/n-caprylic acid chromium/isocaprylic acid chromium/chromium acetylacetonate/Dicyclopentadiene (DCPD) chromium/dibenzene-chromium/chromium naphthenate, and the best is isocaprylic acid chromium/n-caprylic acid chromium/chromium naphthenate.
Pyrrole derivative described in the catalyst composition of the present invention, the mixture that comprises following one or more compounds: 2,4-dimethyl pyrrole/3,4-dimethyl pyrrole/2,5-dimethyl pyrrole/2,5-dimethyl-3-N-ethyl pyrrole N-/pyrrolidone-(2)/2-methyl-5-N-ethyl pyrrole N-/1,2,5-trimethylammonium-3-N-ethyl pyrrole N-/2,5-dimethyl pyrrole-ketone-(3)/1-methylpyrrole/2-methyl-pyrroles/3-methylpyrrole and 2-methyl-pyrrolidone-(4).
Alkylaluminium cpd in the catalyst composition of the present invention comprises one or both mixtures in the following compounds: triethyl aluminum/triisobutyl aluminium/three n-butylaluminum/oxyethyl group diethyl aluminum/chloro diethyl aluminum/chloro diisobutyl aluminum/tri-n-hexyl aluminum and dichloro-aluminium triethyl, preferred triethyl aluminum.
Reaction solvent used in the present invention is for making any alkane or the naphthenic hydrocarbon that catalyst component is evenly miscible mutually and ethene solubleness is high, can be from following compounds preferred one or more mixture: normal heptane, isoheptane, octane, octane-iso, n-decane, n-dodecane, hexanaphthene, methylcyclohexane, pentamethylene.□
At first with improving agent (d) solution with mix again after chromium compounds (a) as central metal is dissolved in the solvent respectively, under the oligomerisation condition that has ethene to exist, this mixture solution is joined in the alkane solution that contains azole compounds (b) and trialkylaluminium (c) then, and cause the ethylene oligomerization reaction immediately.Can give catalyzer with catalytic performance preferably by method for preparing catalyst of the present invention, because being mixed with chromium cpd, catalyzer will make improving agent preferentially occupy three mutual rectangular coordinate bond positions of central metal chromium, this helps three ethylene molecules and activates synchronously, and optionally oligomerisation generates the 1-hexene.
The concrete application of catalyzer of the present invention is the method that ethylene oligomerization prepares the 1-hexene, in the conventional equipment of ethylene oligomerization, press each component significant quantity of catalyzer, under ethylene pressure, carry out the preparation of catalyzer original position, not open closely go into ethene it is fully contacted with catalyzer, cause ethylene oligomerization, optionally generate purpose product 1-hexene.Temperature of reaction is generally 40-200 ℃, 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 preferably 1-2 hour.In the reaction soln of ethylene oligomerization, making 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; The concentration of pyrrole derivative (b) is generally 0.02-30mmol/L, is preferably 0.03-2.0mmol/L, more preferably 0.05-0.5mmol/L; The concentration of trialkylaluminium (c) is generally 0.05-500mmol/L, is preferably 0.1-300mmol/L, 0.01-50mmol/L more preferably, and the concentration of improving agent (d) is 0.05-200mmol/L.
The preparation method of described 1-hexene is intermittent type/semi continuous or continous way, and the required equipment of various reactive modes all is conventional and for commercially available.
Major advantage of the present invention and effect:
Selected improving agent in the chromium-based catalysts of the present invention, because structure and composition with three mutual rectangular coordinate bonds of the chromium metal of can preferentially plying in the centre, help ethene coordination on three coordinate bonds of mutual rectangular chromium of three molecules, thereby help the autohemagglutination of three molecule ethene and optionally generate the 1-hexene, therefore catalyzer has that the reactive behavior height/purpose product 1-hexene selectivity is good, and the few characteristics of the poly growing amount of by product.
More specifically describe the present invention with example below, only limit to these contents but should not be construed as the present invention.
Example 1
After the 0.5L autoclave cleaned pressure testing with heptane, under 100 ℃ of vacuum dry 1 hour, be cooled to room temperature, with the ethene displacement with to charge into ethene stand-by to 0.02Mpa.In glove box, with 2.0 ml concns is 2 of 12.5mmol/L, the n-heptane solution of 5-dimethyl pyrrole (b) and 1.2 ml concns are that the solution (C) of normal heptane of the triethyl aluminum of 0.5mol/L joins in the syringe that contains 80 milliliters of normal heptanes, and the sealing outlet is stand-by.
The n-heptane solution that in addition with 1.2 ml concns is the isocaprylic acid chromium (a) of 4.17mmol/L is 1,2,3 of 0.05mmlo/L with 1.5 ml concns as improving agent, 4,5, both all suck the n-heptane solution of 6-HEXACHLOROBUTADIENE γ-body (d) in the syringe of 5ml, and the sealing outlet is stand-by.
To contain (b) and syringe (c), be injected into reactor,, stir and charge into ethene to 2.5-3.0Mpa with the ethene displacement from charging opening; To contain (a) and mixing solutions (d) and be injected into and press in the bullet, with the ethene displacement with charge into ethene to 5.0Mpa.When autoclave is rapidly heated to 70 ℃, with the ethene of 5.0Mpa will press in the bullet (a) and (d) solution be pressed in the autoclave, be warming up to 110 ℃, pressure maintains 5.0 ± 0.5Mpa, the stirring revolution is 900-1000rpm.Reacted with this understanding 1.2 hours, question response is finished postcooling to room temperature, gas is put into caught the metering of gas device, and reaction solution is weighed, and filters out by product polyethylene solid, and is at room temperature dry, weighs.Composition with gas chromatographic analysis gas-liquid phase.The reaction result of preparing 1-hexene from ethene by oligomerization is listed in table 1.Find out that by table 1 the catalytic activity height of catalyzer of the present invention can reach 350012g product/gcr.h, and the employing of USP5910619 patent is blended 1,2,3,4,5,6-HEXACHLOROBUTADIENE improving agent, the catalytic activity of reacting 1 hour is 180866g/g.h, does not obviously have catalytic activity height of the present invention.
Example 2
Operation according to example 1, remove 2, it is 2 of 12.5mmol/L that the consumption of 5-dimethyl pyrrole changes 1.2 ml concns into, outside the n-heptane solution of 5-dimethyl pyrrole, all the other every reaction conditionss are all identical with embodiment 1 with proportioning, and the reaction result of ethene system 1-hexene is listed in table 2.
Comparative example 1
According to the operation and the proportioning of example 1, remove and to use 1,2,3,4,5 instead, 6-HEXACHLOROBUTADIENE α-body replaces in the example 11,2,3,4,5, and outside 6-HEXACHLOROBUTADIENE γ-body, all the other every reaction conditionss are all identical with example 1, and the reaction result of ethene system 1-hexene is listed in table 3.
Example 3
With 0.5L autoclave under 100 ℃ of vacuum dry 1 hour, be cooled to room temperature after, with the ethene displacement with to charge into ethene stand-by to 0.02Mpa.In glove box, with 2.0 ml concns is 2 of 12.5mmol/L, the n-heptane solution of 5-dimethyl pyrrole (b) and 0.6 ml concn are that the solution (c) of normal heptane of the triethyl aluminum of 0.5mol/L joins in the syringe that contains 80 milliliters of normal heptanes, and the sealing outlet is stand-by.
The n-heptane solution that in addition with 1.2 ml concns is the isocaprylic acid chromium (a) of 4.17mmol/L is 1,2,3 of 0.05mmol/L with 1.5 ml concns as improving agent, 4,5, both all suck the n-heptane solution of 6-HEXACHLOROBUTADIENE γ-body (d) in the syringe of 5ml, and the sealing outlet is stand-by.
To contain (b) and syringe (c), be injected into reactor,, stir and charge into ethene to 2.5-3.0Mpa with the ethene displacement from charging opening; To contain (a) and mixing solutions (d) and be injected into and press in the bullet, with the ethene displacement with charge into ethene to 5.0Mpa.When autoclave is rapidly heated to 70 ℃, will press (a) and solution (d) in the bullet to be pressed in the autoclave with the ethene of 5.0Mpa, and be warming up to 110 ℃, pressure maintains 5.0 ± 0.5Mpa, and the stirring revolution is 800rpm, reacts with this understanding 1 hour.Question response is finished postcooling to room temperature, gas is put into caught the metering of gas device, and reaction solution is weighed, and filters out by product polyethylene solid, and is at room temperature dry, weighs.Composition with gas chromatographic analysis gas-liquid phase.The reaction result of preparing 1-hexene from ethene by oligomerization is listed in table 4.
Comparative example 2
According to the operation of example 1, except that not adding improving agent (d), all the other every reaction conditionss are all identical with example 3, and the reaction result of ethene system 1-hexene is listed in table 5.
Example 4
According to operation and the proportioning of embodiment 1, remove and use 1 instead, 4--two (three chloro methyl)-2,3,5, the 6-tetrachlorobenzene replaces 1,2,3,4,5, and 6-HEXACHLOROBUTADIENE γ-body is as outside the improving agent, and all the other every reaction conditionss are all identical with example 1 with proportioning.Ethene system 1-hexene reaction result is listed in table 6.Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
| Normal heptane solvent total amount (ml) | 80+5.5 |
| Isocaprylic acid chromium amount (mmol) | 0.005 |
| 2,5-dimethyl pyrrole amount (mmol) | 0.025 |
| Triethyl aluminum amount (mmol) | 0.600 |
| The improving agent kind | 1,2,3,4,5,6-HEXACHLOROBUTADIENE γ-body |
| Improve dosage (mmol) | 0.075 |
| Catalyst proportion (mol) | a∶b∶c∶d＝1∶5∶120∶15 |
| Temperature of reaction (℃) | 110±5 |
| Reaction pressure (Mpa) | 5.0±0.5 |
| Reaction times (hr) | 1.2 |
| Catalytic activity (the g product/gCr.H) | 350012 |
| Product distribution (wt%) | |
| C 1 ＝ | 0.24 |
| C 6 ＝ | 90.01 |
| C 8 ＝ | 0.43 |
| C 10 ＝ | 9.00 |
| C 12 ＝ | 0.22 |
| PE | 0.10 |
| C 6Middle n-α-C 6Alkene content (wt%) | 97.5 |
| Normal heptane solvent total amount (ml) | 80+5.5 |
| Isocaprylic acid chromium amount (mmol) | 0.005 |
| 2,5-dimethyl pyrrole amount (mmol) | 0.015 |
| Triethyl aluminum amount (mmol) | 0.600 |
| The improving agent kind | 1,2,3,4,5,6-HEXACHLOROBUTADIENE γ-body |
| Improve dosage (mmol) | 0.075 |
| Catalyst proportion (mol) | a∶b∶c∶d＝1∶3∶120∶15 |
| Temperature of reaction (℃) | 110±5 |
| Reaction pressure (Mpa) | 5.0±0.5 |
| Reaction times (hr) | 1.2 |
| Catalytic activity (the g product/gCr.H) | 250588 |
| Product distribution (wt%) | |
| C 1 ＝ | 0.52 |
| C 6 ＝ | 93.00 |
| C 8 ＝ | 0.32 |
| C 10 ＝ | 5.63 |
| C 12 ＝ | 0.42 |
| PE | 0.11 |
| C 6Middle n-α-C 6Alkene content (wt%) | 98.0 |
| Normal heptane solvent total amount (ml) | 80+5.5 |
| Isocaprylic acid chromium amount (mmol) | 0.005 |
| 2,5-dimethyl pyrrole amount (mmol) | 0.025 |
| Triethyl aluminum amount (mmol) | 0.600 |
| The improving agent kind | 1,2,3,4,5,6-HEXACHLOROBUTADIENE α-body |
| Improve dosage (mmol) | 0.075 |
| Catalyst proportion (mol) | a∶b∶c∶d＝1∶5∶120∶15 |
| Temperature of reaction (℃) | 110±5 |
| Reaction pressure (Mpa) | 5.0±0.5 |
| Reaction times (hr) | 1.2 |
| Catalytic activity (the g product/gCr.H) | 170625 |
| Product distribution (wt%) | |
| C 1 ＝ | 1.30 |
| C 6 ＝ | 86.00 |
| C 8 ＝ | 0.30 |
| C 10 ＝ | 12.00 |
| C 12 ＝ | 0.20 |
| PE | 0.20 |
| C 6Middle n-α-C 6Alkene content (wt%) | 95.88 |
| Normal heptane solvent total amount (ml) | 80+5.5 |
| Isocaprylic acid chromium amount (mmol) | 0.005 |
| 2,5-dimethyl pyrrole amount (mmol) | 0.025 |
| Triethyl aluminum amount (mmol) | 0.300 |
| The improving agent kind | 1,2,3,4,5,6-HEXACHLOROBUTADIENE γ-body |
| Improve dosage (mmol) | 0.075 |
| Catalyst proportion (mol) | a∶b∶c∶d＝1∶5∶60∶15 |
| Temperature of reaction (℃) | 110±5 |
| Reaction pressure (Mpa) | 5.0±0.5 |
| Reaction times (hr) | 1.0 |
| Catalytic activity (the g product/gCr.H) | 260885 |
| Product distribution (wt%) | |
| C 1 ＝ | 1.80 |
| C 6 ＝ | 88.60 |
| C 8 ＝ | 0.57 |
| C 10 ＝ | 8.33 |
| C 12 ＝ | 0.30 |
| PE | 0.4 |
| C 6Middle n-α-C 6Alkene content (wt%) | 97.0 |
| Normal heptane solvent total amount (ml) | 80+5.5 |
| Isocaprylic acid chromium amount (mmol) | 0.005 |
| 2,5-dimethyl pyrrole amount (mmol) | 0.025 |
| Triethyl aluminum amount (mmol) | 0.300 |
| The improving agent kind | Do not have |
| Improve dosage (mmol) | Do not have |
| Catalyst proportion (mol) | a∶b∶c＝1∶5∶60 |
| Temperature of reaction (℃) | 100±5 |
| Reaction pressure (Mpa) | 5.0±0.5 |
| Reaction times (hr) | 1.0 |
| Catalytic activity (the g product/gCr.H) | 46769 |
| Product distribution (wt%) | |
| C 1 ＝ | 48.60 |
| C 6 ＝ | 38.80 |
| C 8 ＝ | 2.90 |
| C 10 ＝ | 5.20 |
| C 12 ＝ | 0.60 |
| PE | 3.90 |
| C 6Middle n-α-C 6Alkene content (wt%) | 92.00 |
| Normal heptane solvent total amount (ml) | 80+5.5 |
| Isocaprylic acid chromium amount (mmol) | 0.005 |
| 2,5-dimethyl pyrrole amount (mmol) | 0.025 |
| Triethyl aluminum amount (mmol) | 0.600 |
| The improving agent kind | 1,4-(two) three chloro methyl-2,3,5,6-tetrachlorobenzene |
| Improve dosage (mmol) | 0.075 |
| Catalyst proportion (mol) | a∶b∶c∶d＝1∶5∶120∶15 |
| Temperature of reaction (℃) | 100±5 |
| Reaction pressure (Mpa) | 5.0±0.5 |
| Reaction times (hr) | 1.0 |
| Catalytic activity (the g product/gCr.H) | 356775 |
| Product distribution (wt%) | |
| C 1 ＝ | 0.93 |
| C 6 ＝ | 93.77 |
| C 8 ＝ | 0.21 |
| C 10 ＝ | 4.07 |
| C 12 ＝ | 0.82 |
| PE | 0.20 |
| C 6Middle n-α-C 6Alkene content (wt%) | 98.0 |
Claims (3)
1. a preparing 1-hexene from ethene by oligomerization catalyzer comprises chromium compounds a, pyrrole derivative b, aluminum alkyls c, it is characterized in that introducing a kind of improving agent d and forms the four-way catalyst composition, the mol ratio of composition is a: b: c: d=1: 3-6: 50-150: 5-20, and described properties-correcting agent d is 1,2,3,4,5,6-HEXACHLOROBUTADIENE γ-body, 1,4-two (three chloro methyl)-2,3,5,6-tetrachlorobenzene, 1,3,5-three (three chloro methyl)-2,4, the 6-trichlorobenzene.
2. the described Preparation of catalysts method of claim 1, it is characterized in that preparation process may further comprise the steps: chromium compounds a and properties-correcting agent d are dissolved in the solvent respectively, mix again, under the oligomerisation condition that has ethene to exist this mixing solutions joined in the alkane solution that contains pyrrole derivative b and aluminum alkyls c then and mix, described solvent is chosen one or more mixtures in normal heptane, isoheptane, octane, octane-iso, n-decane, n-dodecane, hexanaphthene, methylcyclohexane, pentamethylene.
3. the described Application of Catalyst of claim 1, it is characterized in that being used for the method that ethylene oligomerization prepares the 1-hexene is: at the conventional equipment of ethylene oligomerization, press each component significant quantity of catalyzer, under ethylene pressure, carry out the preparation of catalyzer original position, and constantly feed ethene, it is fully contacted with catalyzer, ethylene oligomerization takes place, optionally produce the 1-hexene, described reaction conditions: temperature 40-200 ℃, pressure 0.5-20.0Mpa, time 1-2 hour, the concentration of chromium compounds a in the reaction soln of ethylene oligomerization is 0.01-10.0mmol/L, and pyrrole derivative b is 0.02-30mmol/L, aluminum alkyls c is 0.05-500mmol/L, properties-correcting agent d is 0.05-200mmol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00107545A CN1128776C (en) | 2000-05-18 | 2000-05-18 | Catalyst for preparing 1-hexene from ethene by oligomerization and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00107545A CN1128776C (en) | 2000-05-18 | 2000-05-18 | Catalyst for preparing 1-hexene from ethene by oligomerization and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1294109A CN1294109A (en) | 2001-05-09 |
| CN1128776C true CN1128776C (en) | 2003-11-26 |
Family
ID=4578771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00107545A Expired - Fee Related CN1128776C (en) | 2000-05-18 | 2000-05-18 | Catalyst for preparing 1-hexene from ethene by oligomerization and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1128776C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050187418A1 (en) | 2004-02-19 | 2005-08-25 | Small Brooke L. | Olefin oligomerization |
| AU2005217601B2 (en) * | 2004-02-20 | 2012-02-16 | Chevron Phillips Chemical Company Lp | 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 |
| US20070043181A1 (en) | 2005-08-19 | 2007-02-22 | Knudsen Ronald D | 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 |
| CN100443178C (en) * | 2006-03-10 | 2008-12-17 | 中国石油天然气股份有限公司 | Catalyst composition of ethylene oligomerization and the application |
| US7902415B2 (en) | 2007-12-21 | 2011-03-08 | Chevron Phillips Chemical Company Lp | Processes for dimerizing or isomerizing olefins |
| CN102107146B (en) | 2009-12-29 | 2013-10-16 | 中国石油天然气股份有限公司 | Catalyst for synthesizing hexane-1 from ethylene trimerization and application of catalyst |
| US9586872B2 (en) | 2011-12-30 | 2017-03-07 | Chevron Phillips Chemical Company Lp | Olefin oligomerization methods |
| CN106925348B (en) * | 2015-12-31 | 2019-10-11 | 中国石油天然气股份有限公司 | Catalyst and its application |
-
2000
- 2000-05-18 CN CN00107545A patent/CN1128776C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1294109A (en) | 2001-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1184240C (en) | Olefin production | |
| CN1128776C (en) | Catalyst for preparing 1-hexene from ethene by oligomerization and its application | |
| DE10303931B4 (en) | Catalytic composition for dimerization, co-dimerization, oligomerization and polymerization of olefins | |
| JP6484475B2 (en) | Novel catalyst composition and process for oligomerization of ethylene to 1-hexene | |
| ES470120A1 (en) | Catalyst components and catalysts for polymerizing olefins prepared from the catalysts | |
| CN101547944B (en) | Process for production of polyolefins, polyolefins, and 1-hexene to be used as raw material in producing linear low-density polyethylene | |
| JPH06239920A (en) | Production of catalyst system and method of trimerization, oligomerization and/or polymerization of olefin | |
| EP0548805A1 (en) | Process for the preparation of polymerisation catalysts | |
| CN107282129B (en) | Ethylene trimerization and tetramerization catalyst composition and application thereof | |
| CN1070162C (en) | Catalytic composition and a process of olefins | |
| CN1108193C (en) | Novel catalyst for ethylene trimerization, its preparation process and application | |
| CN101888901B (en) | Catalyst composition and process for preparing linear alpha-olefins | |
| CN111349115B (en) | PNNP structural ligand, preparation method thereof, ethylene oligomerization catalyst system and application thereof | |
| CN1203034C (en) | Method for preparing 1-ethene under ethene oligomerizating catalyst system | |
| CN112742483B (en) | Catalyst system for ethylene selective oligomerization and preparation and application thereof | |
| CN1163456C (en) | Ethylene oligomerizing catalyst coated with solid hydrocarbon compound and its prepn | |
| JPH08134131A (en) | Production of alpha-olefin low polymer | |
| CN103102237B (en) | Method for improving performance of ethylene trimerization catalyst | |
| US7612245B2 (en) | Method for selective hydrogenation of polyunsaturated compounds into monounsaturated compounds using a homogeneous catalyst | |
| CN102558107B (en) | Process for preparing tris (tetrahydrofuran)-trihalogenated chromium and application thereof for preparing olefin oligomerization catalyst | |
| CN114054095B (en) | Ethylene oligomerization catalyst composition and application thereof | |
| CN111408407B (en) | Catalyst composition, preparation method thereof and application thereof in reaction of synthesizing 1-butene by ethylene selective dimerization | |
| CN1176114C (en) | Metallocene catalyst for polymerizing olefine | |
| CN1324866A (en) | Magnesium chlorid-alcohol carrier and olefine polymerizing catalyst component prepared with it | |
| CN113600241B (en) | Catalyst system for selective trimerization of ethylene and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| BB1A | Publication of application | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: CHINA PETROLEUM CO., LTD. Free format text: FORMER NAME OR ADDRESS: RESEARCH INST OPF DAQING PETRO-CHEMICAL BRANCH, CHINESE PETROLEUM GROUP |
|
| CP03 | Change of name, title or address |
Address after: 100011 Beijing city Dongcheng District No. 16 Andrew intercontinental building Patentee after: China Petroleum & Natural Gas Co., Ltd. Address before: 163714 Tuen Mun, Daqing, Heilongjiang Patentee before: Research Inst opf Daqing Petro-Chemical Branch, Chinese Petroleum Group |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20031126 Termination date: 20160518 |