CN100486944C - Novel method for preparing 1-hexene in presence of ethylene oligomerization catalyst system - Google Patents
Novel method for preparing 1-hexene in presence of ethylene oligomerization catalyst system Download PDFInfo
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- CN100486944C CN100486944C CNB031573509A CN03157350A CN100486944C CN 100486944 C CN100486944 C CN 100486944C CN B031573509 A CNB031573509 A CN B031573509A CN 03157350 A CN03157350 A CN 03157350A CN 100486944 C CN100486944 C CN 100486944C
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- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000005977 Ethylene Substances 0.000 title claims abstract description 18
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 150000003233 pyrroles Chemical class 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract 2
- 229910052804 chromium Inorganic materials 0.000 claims description 18
- 239000011651 chromium Substances 0.000 claims description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 6
- 150000001845 chromium compounds Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 4
- PAPNRQCYSFBWDI-UHFFFAOYSA-N 2,5-Dimethyl-1H-pyrrole Chemical compound CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 2
- 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 claims description 2
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 21
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 4
- 241000501667 Etroplus Species 0.000 abstract 1
- 125000005234 alkyl aluminium group Chemical group 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- -1 alkyl compound Chemical class 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- BJQTYCQGIXZSNM-UHFFFAOYSA-N 1,4-dichloro-2-fluorobenzene Chemical compound FC1=CC(Cl)=CC=C1Cl BJQTYCQGIXZSNM-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
- IKWJKXMMTRXCDI-UHFFFAOYSA-N 2,5-dimethylpyrrole Chemical compound CC1=CC=C(C)[N]1 IKWJKXMMTRXCDI-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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IWCQVOVBDXJJDF-UHFFFAOYSA-N benzene;chromium;cyclohexane Chemical compound [Cr].[CH-]1[CH-][CH-][CH-][CH-][CH-]1.C1=CC=CC=C1 IWCQVOVBDXJJDF-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 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
- 239000007795 chemical reaction product 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
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 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
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 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
- 230000002779 inactivation Effects 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- OXUCOTSGWGNWGC-UHFFFAOYSA-N octane Chemical compound CCCCCCC[CH2-] OXUCOTSGWGNWGC-UHFFFAOYSA-N 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000003756 stirring Methods 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
- 238000001291 vacuum drying Methods 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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a new method for preparing 1-hexene in the presence of ethylene oligomerization catalyst system, which comprises the steps of mixing a solvent with chromide , pyrrole derivatives (b), alkyl aluminum (c) and an improver (d) of the catalyst system, then feeding the mixture into a reactor, mixing raw material ethylene gas with reaction circulating liquid, then feeding the mixture into the reactor from a feeding hole with a nozzle, enabling the reaction liquid of the reactor to flow out from the bottom, cooling one part of the reaction liquid by a cooler, then mixing the cooled part of the reaction liquid with ethylene, and feeding the other part of the reaction liquid into a separation device.
Description
Technical field
The present invention relates to a kind of novel method that in the presence of catalyst system for ethylene oligomerization, prepares the 1-hexene.
2. background technology
Reported a kind of chromium-based catalysts composition among the EP 0608447A1,, wherein used a kind of compound that contains chromium as one of component of catalyst composition as the catalyzer of ethylene oligomerization and/or copolymerization; Use 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, and this halogen source both can be inorganic halides, also can be the Organohalogen compounds of numerous types, this catalyzer is higher to the selectivity of 1-hexene, but its catalytic activity is not high.
Used Sn (OSO among the JP 0832519
2F
3)
2Compound replaces the halogen source of the 4th component among the EP 0608447A1, has formed a kind of new 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 JP 08134131 as the improving agent in the chromium-based catalysts composition, wherein used to contain the improving agent of three above halogen atoms as feature on adjacent two carbon atoms of end, its catalytic activity increases.
USP 5,910, reported in 619 and adopted 1,2,3,4,5, and the 6-HEXACHLOROBUTADIENE is formed the four-way catalyst composition as improving agent; Chinese patent " a kind of catalyzer of preparing 1-hexene from ethene by oligomerization and application thereof " (CN1294109A) has used novel catalyst, and catalytic activity all is significantly improved, and 1-hexene selectivity has also had raising.But still can not meet the demands, people wish further to improve the performance of catalyzer, to improve catalytic activity.
Above ethylene oligomerization method all lays particular emphasis on the research to catalyzer, although 99/19380 pair of ethylene oligomerization method of WO is studied, but similar to other patents, reaction is carried out in common autoclave basically, and has produced mass transfer thus and the unequal problem of conducting heat.Because this reaction is a strong exothermal reaction, and the initial reaction stage rate of heat release is faster, therefore often owing to rate of heat transfer causes local temperature too high slowly, cause the part catalyst deactivation, influenced the efficient of catalyzer, so conversion of ethylene low (50~70%); And because rate of mass transfer in this reactor is slow, make the catalytic effect of complex catalyst be affected, catalytic activity reduces, often the reaction times longer, cause energy consumption to increase.Be reaction under high pressure owing to this reaction in addition, and need to stir, so need additional transmission mechanism, also brought thus to seal and safe problem.
Summary of the invention
The method that the purpose of this invention is to provide a kind of preparing 1-hexene from ethene by oligomerization makes the 1-hexene product that makes high yield in the short reaction times, the catalyst activity height, and the entire method energy consumption is low.
In the method for the present invention, an effusive reaction solution part is cooled off through water cooler, and with after ethene mixes, be circulated to reactor by the opening for feed that has at least one nozzle (being installed in the top of reactor), just formed vacuum at the nozzle place like this, surrounding liquid is flowed to the nozzle place, and run into traverse baffle, produced the circulation effect by the opposite side that the gas-liquid mixture of nozzle ejection arrives reactor.The effect of traverse baffle is that material is from bottom to top flowed in reactor, prevents that material from directly forming short circuit from following discharge port discharge.Because the speed that nozzle sprays into is very fast, so good mixing effect in the reactor, gas-liquid two-phase can reach the microcosmic mixed effect.Another part of reaction solution enters tripping device and carries out the product separation.Hexene wherein can be directly as the comonomer of LLDPE, and solvent can be recycled, and remaining catalyst recovery is handled.Before entering tripping device, carry out sampling analysis.
Preparing 1-hexene from ethene by oligomerization catalyzer and solvent are seen Chinese patent " a kind of catalyzer of preparing 1-hexene from ethene by oligomerization and application thereof " (CN1294109A).
Chromium compounds described in the catalyst composition of the present invention (a)) general formula is CrR
1 q, R in the formula
1Be organic anion or neutral molecule, R
1In include 1~10 carbon atom usually, q is 0~6 integer, the valence state of chromium is 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, more the chromium compounds of matters comprises one or more 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 (b), 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-/3-methylpyrrole and 2-methyl-pyrrolidone-(4).
Aluminum alkyls described in the catalyst composition of the present invention (c), comprise one or more 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.
Improving agent described in the catalyst composition of the present invention (d) is the compound of being represented by following general formula X mARn, and X is Cl, F in the formula, m=3~6, and R is F, Cl, Br, H, CCl
3, n=0~3, A is monoester cycloalkyl or phenyl.
Comprise 1,2,3,4,5,6-HEXACHLOROBUTADIENE γ body,
The preferred compound of improving agent (d) is 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, 1,3,5-three (three chloro methyl)-2,4,6-trichlorobenzene.
The used solvent of the present invention is to make any alkane or the naphthenic hydrocarbon that the catalyzer composition is evenly miscible mutually and ethene solubleness is high, can be one or more mixtures in the following compounds: normal heptane, isoheptane, octane, octane-iso, n-decane, n-dodecane, hexanaphthene, methylcyclohexane, pentamethylene.
The used terminator of the present invention is any compound that can make the catalyst component inactivation, as water, alcohols, phenols, ester class etc., comparatively ideal is in the following compounds one or more: water, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, phenol, ethyl acetate.
In reactor, reaction pressure, temperature of reaction are seen Chinese patent " a kind of catalyzer of preparing 1-hexene from ethene by oligomerization and application thereof " (CN1294109A).
Reaction pressure is generally 0.5~20.0Mpa, is preferably 1.0~15.0Mpa, more preferably 2.0~10.0Mpa; Temperature of reaction is generally 40~200 ℃, is preferably 40~150 ℃, more preferably 60~130 ℃; The inlet amount of catalyzer and solvent is advisable at 2~10ppm to satisfy catalyst in reactor a component concentrations, and comparatively ideal is 3~7ppm.The mol ratio of catalyzer in still is a:b:c:d=1:1~5:1~120:1~20
The reaction solution internal circulating load is 3~20 times of inlet amount, and comparatively ideal is 5~15 times.
Beneficial effect of the present invention
A. reactant mixes, and mass transfer, heat-transfer effect are good.
B.1-the selectivity height of hexene is greater than 95% (1-hexene selectivity is meant that the 1-hexene accounts for the percentage composition of entire reaction product).
C. the catalytic activity height of catalyzer is greater than 9 * 10
5G product/gCrh (catalytic activity is meant the product total amount that every gram chromium can generate in the unit time).
D. conversion of ethylene height is greater than 95%.
E. the problem that does not have mechanical seal.
Description of drawings
Accompanying drawing is the method sketch that ethylene oligomerization prepares the 1-hexene.For simplicity, omitted some in the accompanying drawings for realizing the essential optional equipment of the inventive method, as pump, valve, pressure unit, temperature transmitter, flow transmitter etc.
Concrete enforcement is trans
Embodiment 1
In reactor head ethylene feed pipe (1) is installed, inner at least one nozzle (7) of feed-pipe reactor, solvent (2) and catalyzer (3) parallel feeding pipe are installed, are put a traverse baffle (6) at reactor inner outlet end, outlet links to each other with feed-pipe (4) with tripping device (5) respectively.After reactor cleaned with normal heptane, 100 ℃ of following vacuum-dryings 1 hour, be cooled to room temperature, replace with ethene, open the ethene intake valve, keep reactor pressure to maintain 5.0Mpa, feed solvent, catalyzer pyrrole derivative (b) and aluminum alkyls (c) and improving agent (d) component, chromium compounds (a) component by certain flow, open recycle pump and water cooler, make to produce in the reactor and spray the circulation effect, keep reactor temperature to maintain 115 ℃, open the reactor outlet valve, make reaction solution enter tripping device, and sampling analysis.The results are shown in Table 1.
Embodiment 2-7
Processing condition and the results are shown in Table 1.
Claims (4)
1. the novel method of a preparation 1-hexene in the presence of catalyst system for ethylene oligomerization is characterized in that:
(1) chromium compounds of solvent and catalyst system (a), pyrrole derivative (b), aluminum alkyls (c), improving agent (d) component is mixed, and enters reactor afterwards;
(2) enter reactor by the opening for feed that has nozzle after material ethylene gas mixes with reaction cycle liquid;
(3) reaction solution in the reactor is flowed out by the bottom, and a part is wherein cooled off through water cooler, after the ethene of (2) mixes, is circulated to reactor by the opening for feed that has nozzle, and another part enters tripping device;
Chromium compounds (a) is: n-caprylic acid chromium, isocaprylic acid chromium, chromium acetylacetonate or Dicyclopentadiene (DCPD) chromium;
Derivative (b) is: 2, and 4-dimethyl pyrrole, 2,5-dimethyl pyrrole, 2,5-dimethyl-3-N-ethyl pyrrole N-or 2-methyl-5-N-ethyl pyrrole N-;
Aluminum alkyls (c) is: triethyl aluminum, oxyethyl group diethyl aluminum or chloro diisobutyl aluminum; Improving agent (d) is: 1,2,3,4,5, and 6-HEXACHLOROBUTADIENE γ body or 1,4-two (three chloro methyl)-2,3,5,6-tetrachlorobenzene;
(a): (b): (c): (d) be: 1: 3: 60: 10,1: 3: 120: 5 or 1: 5: 120: 15.
2. a kind of novel method for preparing the 1-hexene in the presence of catalyst system for ethylene oligomerization according to claim 1 is characterized in that: the 3-20 that described reaction solution internal circulating load is the raw material inlet amount doubly.
3. a kind of used equipment of novel method for preparing the 1-hexene in the presence of catalyst system for ethylene oligomerization according to claim 1, it is characterized in that: the opening for feed that described reactor has nozzle has at least one nozzle.
4. a kind of used equipment of novel method for preparing the 1-hexene in the presence of catalyst system for ethylene oligomerization according to claim 1, it is characterized in that: described reactor has traverse baffle near the exit.
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CNB031573509A CN100486944C (en) | 2003-09-19 | 2003-09-19 | Novel method for preparing 1-hexene in presence of ethylene oligomerization catalyst system |
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CNB031573509A CN100486944C (en) | 2003-09-19 | 2003-09-19 | Novel method for preparing 1-hexene in presence of ethylene oligomerization catalyst system |
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CN1490290A CN1490290A (en) | 2004-04-21 |
CN100486944C true CN100486944C (en) | 2009-05-13 |
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ES2371218T3 (en) * | 2009-04-09 | 2011-12-28 | Saudi Basic Industries Corporation | COMPOSITION OF CATALYST AND PROCEDURE FOR THE OLIGOMERIZATION OF ETHYLENE. |
CN112898460B (en) * | 2021-01-21 | 2023-05-26 | 江苏奥克化学有限公司 | Novel ethylene polymerization process |
CN114225968A (en) * | 2022-01-13 | 2022-03-25 | 中化泉州石化有限公司 | Ethylene trimerization catalyst composition |
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2003
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