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
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- 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
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- ethene
- hexene
- oligomerization
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- chromium
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- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 title claims abstract description 58
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 150000003233 pyrroles Chemical class 0.000 claims abstract description 8
- -1 polyethylene Polymers 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 239000005977 Ethylene Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 150000001845 chromium compounds Chemical class 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 5
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 229940094933 n-dodecane Drugs 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 abstract description 38
- 239000011651 chromium Substances 0.000 abstract description 38
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 37
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 239000004698 Polyethylene Substances 0.000 abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 229920000573 polyethylene Polymers 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 229910052794 bromium Inorganic materials 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 239000004411 aluminium Substances 0.000 abstract 1
- ZBZJXHCVGLJWFG-UHFFFAOYSA-N trichloromethyl(.) Chemical compound Cl[C](Cl)Cl ZBZJXHCVGLJWFG-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- PAPNRQCYSFBWDI-UHFFFAOYSA-N DMP Natural products CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 15
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 13
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 13
- 230000035484 reaction time Effects 0.000 description 7
- 238000006073 displacement reaction Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000005234 alkyl aluminium group Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- AVSIMRGRHWKCAY-UHFFFAOYSA-N 1,2,3,4,5-pentachloro-6-methylbenzene Chemical compound CC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl AVSIMRGRHWKCAY-UHFFFAOYSA-N 0.000 description 1
- BJQTYCQGIXZSNM-UHFFFAOYSA-N 1,4-dichloro-2-fluorobenzene Chemical compound FC1=CC(Cl)=CC=C1Cl BJQTYCQGIXZSNM-UHFFFAOYSA-N 0.000 description 1
- BJACAJDVRSHGCF-UHFFFAOYSA-N 1-methylpyrrole Chemical compound CN1[C]=CC=C1 BJACAJDVRSHGCF-UHFFFAOYSA-N 0.000 description 1
- MFFMQGGZCLEMCI-UHFFFAOYSA-N 2,4-dimethyl-1h-pyrrole Chemical compound CC1=CNC(C)=C1 MFFMQGGZCLEMCI-UHFFFAOYSA-N 0.000 description 1
- OJFOWGWQOFZNNJ-UHFFFAOYSA-N 3,4-dimethyl-1h-pyrrole Chemical compound CC1=CNC=C1C OJFOWGWQOFZNNJ-UHFFFAOYSA-N 0.000 description 1
- FEKWWZCCJDUWLY-UHFFFAOYSA-N 3-methyl-1h-pyrrole Chemical compound CC=1C=CNC=1 FEKWWZCCJDUWLY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 101000643890 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 5 Proteins 0.000 description 1
- 102100021017 Ubiquitin carboxyl-terminal hydrolase 5 Human genes 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- HVURSIGIEONDKB-UHFFFAOYSA-N benzene;chromium Chemical compound [Cr].C1=CC=CC=C1.C1=CC=CC=C1 HVURSIGIEONDKB-UHFFFAOYSA-N 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- VPCAAUUIFCAFRZ-UHFFFAOYSA-N butylalumane Chemical group CCCC[AlH2] VPCAAUUIFCAFRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- WADSLQQIOJIXTB-UHFFFAOYSA-L dichloroalumane Chemical compound Cl[AlH]Cl WADSLQQIOJIXTB-UHFFFAOYSA-L 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
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)
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.
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| US20050187418A1 (en) | 2004-02-19 | 2005-08-25 | Small Brooke L. | Olefin oligomerization |
| 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 |
| EP2287143B1 (en) * | 2004-02-20 | 2018-04-11 | 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 for ethylene oligomerization and application thereof |
| 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 hexene-1 by ethylene trimerization and application thereof |
| 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 application thereof |
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