CN1490291A - Method for preparing 1-hexene in presence of ethylene oligomerization catalyst system - Google Patents
Method for preparing 1-hexene in presence of ethylene oligomerization catalyst system Download PDFInfo
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- CN1490291A CN1490291A CNA031573517A CN03157351A CN1490291A CN 1490291 A CN1490291 A CN 1490291A CN A031573517 A CNA031573517 A CN A031573517A CN 03157351 A CN03157351 A CN 03157351A CN 1490291 A CN1490291 A CN 1490291A
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- hexene
- preparing
- catalyst system
- ethene
- ethylene oligomerization
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- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 title claims abstract description 53
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 23
- 239000005977 Ethylene Substances 0.000 title claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 150000003233 pyrroles Chemical class 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 150000001845 chromium compounds Chemical class 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 230000004907 flux Effects 0.000 claims 3
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 2
- 241000501667 Etroplus Species 0.000 abstract 1
- 125000005234 alkyl aluminium group Chemical group 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 18
- 229910052804 chromium Inorganic materials 0.000 description 17
- 239000011651 chromium Substances 0.000 description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 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 4
- 239000007788 liquid Substances 0.000 description 4
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 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
- PAPNRQCYSFBWDI-UHFFFAOYSA-N DMP Natural products CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- -1 alkyl compound Chemical class 0.000 description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 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 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 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
- 238000012545 processing Methods 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
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-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
- 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
- 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- 238000004140 cleaning Methods 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
- 238000013461 design Methods 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
- 238000006073 displacement reaction Methods 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
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material 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
- 238000012856 packing Methods 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
- 238000011160 research 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
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Classifications
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for preparing 1-hexene in the presence of ethylene oligomerization catalyst system, which comprises premixing a part of raw material ethylene gas with solvent, mixing with chromide , pyrrole derivative (b), alkyl aluminum (c) and improver (d) of the catalyst system, and feeding into a reactor with a stirrer through a gas distributor; the other part of ethylene gas directly enters a reactor, the reaction liquid of the reactor flows out from the middle part to an overflow groove, a catalyst terminator is added into the overflow groove, and then the reaction liquid enters a separation device.
Description
Technical field
The present invention relates to a kind of method that in the presence of catalyst system for ethylene oligomerization, prepares the 1-hexene.
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.
USP 5,910, reported in 619 and adopted 1,2,3,4,5, and the 6-HEXACHLOROBUTADIENE is formed the four-way catalyst composition, though this activity of such catalysts increases 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 is significantly improved.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; 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.
Summary of the invention
The purpose of this invention is to provide a kind of raising catalyst activity and 1-hexene selectivity, reduce energy consumption, make the method that in the short reaction times, makes the preparing 1-hexene from ethene by oligomerization of 1-hexene product.
In the method for the present invention, before entering reactor, make a part and the solvent of raw material ethene carry out premix, premix can carry out in premixed device and/or pipeline, again respectively with chromium compounds a, the pyrrole derivative b of catalyzer, aluminum alkyls c, improving agent d component enters into the reactor that has agitator after mixing by gas distributor.The effect of premix is to make ethene and solvent carry out sufficient mass transfer, increases the solubleness of ethene in solvent, and another part ethylene gas directly enters reactor.The percentage ratio that the ethene flow (Wt) that enters premixed device accounts for total ethylene feed flow (Wt) is 1~95%, and comparatively ideal is 20~90%, and optimal is 60~80%.
In the method for the present invention, described premixed device can be to be at least a L/D ratio greater than 20 stainless steel tube or stainless steel pressure container, and the lipophilicity filler can be added in inside.
In the method for the present invention, described gas distributor is the steel pipe that has the uniform distribution aperture on the tube wall.The per-cent of the hole diameter of sparger and stainless steel tube diameter can be any satisfy ethene and solvent equally distributed per-cent in reactor, is generally 0.2%~90%, is generally 5%~70%, is preferably 20%~50%.
In the method for the present invention, reaction solution can enter tripping device by any position of reactor, and this patent recommends to adopt the mode from reactor middle part discharging.This is because reaction is the high pressure-temperature reaction, reaction raw materials is a gas-liquid mixture, but the volatility of solvent is very strong, add the effect of stirring, make the gas-liquid face be difficult to distinguish,, enter overflow groove and get material from the middle part with the uncontrollable reaction discharging of liquidometer, the gas-liquid face can be distinguished, and therefore can well control liquid level.The reaction solution that comes out from overflow groove enters tripping device, and 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).
The general formula of the chromium compounds described in the catalyst composition of the present invention (a) is CrR
1 a, 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, CC1
3, n=0~3, A is monoester cycloalkyl or phenyl.
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 mean residence time of reaction is 0.2~2 hour, and comparatively ideal is 0.5~1.5 hour.
The effect of using present method is as follows:
A. after adopting this method, reactant mixes, and mass transfer, heat-transfer effect are good.
B.1-the selectivity height of hexene, (it is whole anti-that 1-hexene selectivity is meant that the 1-hexene accounts for greater than 91%
Answer the percentage composition of product).
C. the catalytic activity height of catalyzer is greater than 9 * 10
5(catalytic activity is meant list to g product/gCrh
The product total amount that every gram chromium can generate in the bit time).
Description of drawings
Accompanying drawing is the method sketch that ethylene oligomerization prepares the 1-hexene.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.
Embodiment
In the reactor (6) that has the agitator (7) that drives by motor (5), adorning the sparger (8) that has the stainless steel tube of uniform distribution aperture on the wall below the agitator.The per-cent of the hole diameter of sparger and stainless steel tube diameter is 50%, and sparger links to each other with premixed device (4), and premixed device is made of two stainless steel tubes, and the stainless steel tube L/D ratio is 20, the inner wire packing that adds.The premixed device opening for feed links to each other with raw material ethene (1) jar with solvent (2), raw material ethene (1) jar directly links to each other with reactor head again, the overflow groove (9) that links to each other with tripping device (10) links to each other with reactor middle part discharge port, and catalyst inlet (3) is located between sparger and the premixed device.
The reactor that assembling is finished 100 ℃ of following vacuum-dryings 1 hour, is cooled to room temperature after cleaning with hexanaphthene, with the ethene displacement, open the ethene intake valve, the maintenance reactor pressure is a setting pressure, feed the solvent hexanaphthene by certain flow, respectively with chromium compounds a, the pyrrole derivative b of catalyzer, aluminum alkyls c, improving agent d component, keep reactor temperature at design temperature, open the overflow groove 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.
Table 1 embodiment 1-7 processing condition and result
Embodiment | Temperature of reaction (℃) | Reaction pressure (MPa) | ????a | ????b | ????c | ????d | Catalyst molar ratio a: b: c: d | Mean residence time h | The sparger hole diameter is the per-cent of its stainless steel tube diameter | The ethene that enters premixed device accounts for the ratio of total ethene | Catalytic activity (the g product/gCrh) | Hexene-1 selectivity (%) |
??1 | ??110 | ??5.0 | ????1 | ????1 | ????1 | ????1 | ????1∶5∶120∶15 | ??1 | ????0.2 | ????20 | ????906836 | ????92.8 |
??2 | ??120 | ??5.1 | ????3 | ????2 | ????2 | ????2 | ????1∶5∶120∶15 | ??1.5 | ????10 | ????80 | ????1017396 | ????91.7 |
??3 | ??115 | ??5.5 | ????1 | ????1 | ????3 | ????1 | ????1∶3∶120∶5 | ??2 | ????30 | ????90 | ????1168633 | ????99.3 |
??4 | ??110 | ??5.5 | ????4 | ????3 | ????1 | ????1 | ????1∶3∶60∶10 | ??0.5 | ????60 | ????60 | ????1153468 | ????97.4 |
??5 | ??130 | ??5.5 | ????1 | ????4 | ????1 | ????1 | ????1∶5∶120∶15 | ??1.5 | ????80 | ????80 | ????1114923 | ????95.7 |
??6 | ??110 | ??4.5 | ????2 | ????1 | ????2 | ????1 | ????1∶3∶60∶10 | ??1 | ????70 | ????0 | ????126879 | ????87.6 |
??7 | ??115 | ??5.0 | ????1 | ????2 | ????1 | ????2 | ????1∶5∶120∶15 | ??0.5 | ????50 | ????50 | ????1045232 | ????98.7 |
Annotate:
Catalyzer a | Catalyzer b | Catalyzer c | Catalyzer d | ||||||
??1 | | 2, the 4-dimethyl | Triethyl aluminum | 1,2,3,4,5,6-HEXACHLOROBUTADIENE γ body | |||||
??2 | N- | 2, the 5-dimethyl pyrrole | The oxyethyl | 1,4-two (three chloro methyl)-2,3,5,6-tetrachlorobenzene | |||||
??3 | Chromium acetylacetonate | 2-methyl-5-N-ethyl pyrrole N- | The chloro diisobutyl aluminum | ||||||
??4 | Dicyclopentadiene (DCPD) | 2,5-dimethyl-3-N-ethyl pyrrole N- |
Claims (9)
1. method for preparing the 1-hexene in the presence of catalyst system for ethylene oligomerization is characterized in that:
(1) a part of raw material ethene and solvent are in premixed device behind the premix, again respectively with chromium compounds (a), the pyrrole derivative (b) of preparing 1-hexene from ethene by oligomerization catalyzer, aluminum alkyls (c), improving agent (d) component is mixed, enter into the reactor that has agitator by gas distributor afterwards, the ratio that the ethene flow (wt) that enters premixed device accounts for the ethene total flux (wt) that enters reactor is 1~95%;
(2) another part ethylene gas directly enters reactor, and the mean residence time of reaction is 0.2~2 hour;
(3) reaction solution of reactor flows out to overflow groove by the middle part, adds the catalyzer terminator in overflow groove, and then reaction product enters tripping device.
2. a kind of method for preparing the 1-hexene in the presence of catalyst system for ethylene oligomerization according to claim 1 is characterized in that: the ratio that the ethene flow (wt) that enters premixed device accounts for the ethene total flux (wt) that enters reactor is 20~90%.
3. a kind of method for preparing the 1-hexene in the presence of catalyst system for ethylene oligomerization according to claim 1 is characterized in that: the ratio that the ethene flow (wt) that enters premixed device accounts for the ethene total flux (wt) that enters reactor is 60~80%.
4. a kind of method for preparing the 1-hexene in the presence of catalyst system for ethylene oligomerization according to claim 1 is characterized in that: the mean residence time of reaction is 0.5~1.5 hour.
5. a kind of used equipment of method that in the presence of catalyst system for ethylene oligomerization, prepares the 1-hexene according to claim 1, it is characterized in that: described premixed device is at least one L/D ratio greater than 20 stainless steel tube or stainless steel pressure container, the inner lipophilicity filler that adds.
6. a kind of used equipment of 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 gas distributor is the steel pipe that has a plurality of apertures on the tube wall.
7. a kind of used equipment of 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 hole diameter that has on the described gas distributor tube wall is 0.2%~90% of a gas distributor tube diameter.
8. a kind of used equipment of 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 hole diameter that has on the described gas distributor tube wall is 5%~70% of a gas distributor tube diameter.
9. a kind of used equipment of 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 hole diameter that has on the described gas distributor tube wall is 20%~50% of a gas distributor tube diameter.
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