CN1872416A - Ethylene trimerization catalyst and application thereof - Google Patents
Ethylene trimerization catalyst and application thereof Download PDFInfo
- Publication number
- CN1872416A CN1872416A CNA2006100900636A CN200610090063A CN1872416A CN 1872416 A CN1872416 A CN 1872416A CN A2006100900636 A CNA2006100900636 A CN A2006100900636A CN 200610090063 A CN200610090063 A CN 200610090063A CN 1872416 A CN1872416 A CN 1872416A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- ethylene
- chromium
- reaction
- diphenyl
- 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.)
- Granted
Links
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 239000005977 Ethylene Substances 0.000 title claims abstract description 29
- 238000005829 trimerization reaction Methods 0.000 title claims abstract description 12
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011651 chromium Substances 0.000 claims abstract description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 14
- -1 polyethylene Polymers 0.000 claims abstract description 11
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims abstract description 4
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 3
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 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 abstract description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims abstract description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 3
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 3
- JYLPOJPHFDVWCY-UHFFFAOYSA-K oxolane;trichlorochromium Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1 JYLPOJPHFDVWCY-UHFFFAOYSA-K 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 238000002360 preparation method Methods 0.000 claims description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000013638 trimer Substances 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000001845 chromium compounds Chemical class 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 239000004698 Polyethylene Substances 0.000 abstract description 5
- 229920000573 polyethylene Polymers 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
- 125000005234 alkyl aluminium group Chemical group 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 2
- 241000501667 Etroplus Species 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 abstract 1
- FRBFQWMZETVGKX-UHFFFAOYSA-K chromium(3+);6-methylheptanoate Chemical compound [Cr+3].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O FRBFQWMZETVGKX-UHFFFAOYSA-K 0.000 abstract 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 abstract 1
- 239000003446 ligand Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 19
- 125000006267 biphenyl group Chemical group 0.000 description 17
- 235000010290 biphenyl Nutrition 0.000 description 16
- 239000004305 biphenyl Substances 0.000 description 16
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000006073 displacement reaction Methods 0.000 description 12
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000006384 oligomerization reaction Methods 0.000 description 5
- IBUWSVDQGMTMLO-UHFFFAOYSA-N C(C)(C)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical compound C(C)(C)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 IBUWSVDQGMTMLO-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- FAVTXBAMLQPDID-UHFFFAOYSA-N C1(=CC=CC=2C3=CC=CC=C3CC12)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical compound C1(=CC=CC=2C3=CC=CC=C3CC12)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 FAVTXBAMLQPDID-UHFFFAOYSA-N 0.000 description 3
- RHLYKLPLFQNWFO-UHFFFAOYSA-N C1(CC1)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical compound C1(CC1)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 RHLYKLPLFQNWFO-UHFFFAOYSA-N 0.000 description 3
- LSRLLOZBJURIHL-UHFFFAOYSA-N C1(CCCCC1)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical compound C1(CCCCC1)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 LSRLLOZBJURIHL-UHFFFAOYSA-N 0.000 description 3
- LGECWBPIYVTLMF-UHFFFAOYSA-N [N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical compound [N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 LGECWBPIYVTLMF-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- QXSZNDIIPUOQMB-UHFFFAOYSA-N 1,1,2,2-tetrabromoethane Chemical class BrC(Br)C(Br)Br QXSZNDIIPUOQMB-UHFFFAOYSA-N 0.000 description 1
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 150000004822 1,4-dichlorobenzenes Chemical class 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 229940044174 4-phenylenediamine Drugs 0.000 description 1
- CYSPWCARDHRYJX-UHFFFAOYSA-N 9h-fluoren-1-amine Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2N CYSPWCARDHRYJX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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)
- Catalysts (AREA)
Abstract
The invention relates to an ethylene trimerization catalyst consisting of a chromide a, a ligand b containing P and/or N, an alkyl aluminum c and an accelerant d and application thereof, wherein the molar ratio is 1: 0.5-100: 50-5000: 0.5-100 in sequence; a: is chromium acetylacetonate, chromium chloride tetrahydrofuran and/or chromium isooctanoate; b: is a compound of the general formula. R1、R2、R3、R4Is phenyl, benzyl, fluorenyl or naphthyl; r5Is isopropyl, butyl, cyclopropyl, cyclopentyl, cyclohexyl; c: is trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum or/and triisobutylaluminum; d: general formula X1RX2，X1，X2Is F, Cl, Br, I and/or alkoxy, R is alkyl or aryl; the catalyst is favorable for three molecules of ethylene to coordinate on three coordinate bonds of chromium which form right angles with each other, thereby being favorable for the self-polymerization of the three molecules of ethylene to selectively generate 1-hexene, and the catalyst has the characteristics of high activity, good selectivity of the 1-hexene and less polyethylene byproduct.
Description
Technical field
The present invention relates to catalyst of ethylene trimerization and application thereof that a kind of employing chromium compounds a, the part b that contains P and/or N, alkyl aluminum c and promoter d that is used for ethylene trimer forms.
Technical background
As everyone knows, 1-linear alpha-alkene such as alkene is important chemical product and intermediate, is widely used in fields such as polyethylene comonomer, plasticizer alcohol, essence and flavoring agent, synthetic lubricant fluid and oil dope.1-alkene is used as comonomer and can obviously improves poly density, improves mechanical performances such as its tear-proof and hot strength.When being used as plasticizer alcohol, can make low-temperature pliability, processability, the outdoor weather resistance of polyethylene products better, be particularly useful for making cable and wire, auto parts machinery or decoration etc.
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 carbon monoxide-olefin polymeric as the catalyst 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 carbon monoxide-olefin polymeric 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 carbon monoxide-olefin polymeric, and this halogen source both can be inorganic halides, also can be the organohalogen compounds of numerous types, this catalyst 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-hexachlorocyclohexanes is formed the four-way catalyst composition, though this activity of such catalysts increases as improver; Chinese patent " a kind of catalyst 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 catalyst, to improve catalytic activity.
In the ethylene oligomerization technology of WO2004/05647, the content of 1-octene is the highest by 69.3%, and 1-hexene content is 10～20%.
Summary of the invention
The objective of the invention is to select to have active height, 1-hexene selectivity is good, and the chromium-based catalysts of the few characteristics of accessory substance polyethylene is used for the ethylene trimer reaction, make under the effect that is reflected at promoter, 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.
The present invention relates to a kind of chrome catalysts system that is used for ethylene trimer, is the composition that contains following component:
(1) chromium compounds a: be chromium acetylacetonate, oxolane chromium chloride and/or isooctyl acid chromium;
(2) contain the part b of P and N: be following general formula compound
R
1, R
2, R
3, R
4Be phenyl, benzyl, fluorenyl, naphthyl; R
5Be isopropyl, butyl, cyclopropyl, cyclopenta, cyclohexyl;
(3) activator c: be trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum is or/and triisobutyl aluminium;
(4) promoter d: general formula is X
1RX
2, X
1, X
2Be F, Cl, Br, I and/or alkoxyl, R are alkyl, aromatic radical.
The mol ratio of a, b, c and d is 1: 0.5～100: 50～5000: 0.5～100, be preferably 1: 0.5～10: 50～1000: 0.5～and 50, more preferably 1: 1～5: 100～500: 1～20.
Can with a, b, c and four kinds of components of d after mixing 10 minutes under the inert environments, add in the reactor, feed ethene and carry out trimerization reaction; Also a, b, c and four kinds of components of d directly can be added in the reactor, feed ethene and carry out trimerization reaction.Reaction temperature is generally 30～200 ℃, is preferably 20～90 ℃, more preferably 30～70 ℃; Reaction pressure is 0.5～20.0MPa, is preferably 1～10MPa, more preferably 2～6MPa; Time is 0.1～2 hour, is preferably 0.3～1 hour, more preferably 0.5～0.7 hour;
The ethylene trimer reaction is mainly carried out in atent solvent.Selectable solvent comprises alkane, aromatic hydrocarbons, halogenated hydrocarbons, alkene etc.Typical solvent includes, but are not limited to benzene,toluene,xylene, isopropylbenzene, normal heptane, n-hexane, hexahydrotoluene, cyclohexane, 1-hexene, 1-octene, ionic liquid etc.
Major advantage of the present invention and effect:
Chromium-based catalysts of the present invention, because the effect of promoter is arranged, 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 catalyst has active high, 1-hexene selectivity is good, and the few characteristics of accessory substance polyethylene.
The specific embodiment
Embodiment 1
1, preparation (diphenyl) phosphorus nitrogen (cyclopropyl) phosphorus (diphenyl) part
(1) preparation N, N-diisopropyl dichlor-phosphoryl amine
Through N
2Fully add toluene (100mL) in the 250mL reactor that the band of displacement stirs, add PCl through processed
3(21.87mL 0.25mol), and cools to-20 ℃.(70mL 0.5mol), stirs and rises to room temperature after 3 hours and continued to react 2 hours again, filters then, dry product 38.1g (0.19mol, 74%) to add diisopropylamine under the room temperature while stirring lentamente.
(2) preparation phenyl-magnesium-bromide lattice reagent
Through N
2Add through the THF of processed (100mL) in the 250mL reactor of the band stirring of fully replacing, and the magnesium powder (9.11g, 0.375mol), ice bath cooling and slow dropping bromobenzene (11.775g, 0.075mol).After 2 hours, add hot reflux continuation reaction and obtained lattice reagent in 2 hours.
(3) preparation diphenyl phosphorus chloride
Through N
2Fully add through the THF of processed (100mL) in the 250mL reactor that the band of displacement stirs, be cooled to 0 ℃, slowly add N, and N-diisopropyl phosphorus dichloride acid amides (6.64mL, 36mmol).Rose to room temperature reaction 12 hours.Reactant mixture dilutes with cyclohexane then, and with dry HCl gas bubbling 1 hour, filters, and drying obtains chlorinated diphenyl base phosphorus.
(4) preparation (diphenyl) phosphorus nitrogen (cyclopropyl) phosphorus (diphenyl)
Through N
2Fully add carrene (20mL) in the 100mL reactor that the band of displacement stirs through processed, triethylamine (3.75mL), (1.326mL 7.2mmol), is cooled to 0 ℃ to diphenyl phosphorus chloride, slowly adds cyclopropylamine (3.6mmol).Rise to room temperature behind the stirring reaction 30min and continue reaction 12 hours.Filtration, drying obtain product (0.87g, 56.6%).
2, Preparation of catalysts
Through N
2Fully add toluene (10mL) in the 100mL reactor that the band of displacement stirs through processed, triethyl aluminum (10mL), (diphenyl) phosphorus nitrogen (cyclopropyl) phosphorus (diphenyl) (29mg), isooctyl acid chromium (12mg), 1,1,2, the 2-tetrachloroethanes (7mL, 0.54mmol) standby behind the room temperature reaction 10min.
3, ethylene trimer
The autoclave of 500mL is heated to and vacuumizes 2 hours, charges into ethene through nitrogen replacement for several times, cools to predetermined temperature, adds toluene (200mL) and above-mentioned catalyst through processed.Carrying out oligomerisation reaction under 80 ℃, the pressure of 5.0MPa, with ice bath cooling, release, is 10% acidifying ethanol cessation reaction with mass fraction behind the reaction 30min.The results are shown in subordinate list 1.
Embodiment 2
1, preparation (diphenyl) phosphorus nitrogen (cyclopenta) phosphorus (diphenyl) part
(1) preparation N, N-diisopropyl dichlor-phosphoryl amine
With embodiment 1.
(2) preparation phenyl-magnesium-bromide lattice reagent
With embodiment 1.
(3) preparation diphenyl phosphorus chloride
With embodiment 1.
(4) preparation (diphenyl) phosphorus nitrogen (cyclopenta) phosphorus (diphenyl)
Through N
2Fully add carrene (20mL) in the 100mL reactor that the band of displacement stirs through processed, triethylamine (3.75mL), diphenyl phosphorus chloride (1.326mL 7.2mol), is cooled to 0 ℃, slowly add cyclopenta amine (0.415mL, 3.5mmol).Rise to room temperature behind the stirring reaction 30min and continue reaction 12 hours.Filtration, drying obtain product (0.55g, 32.68%).
2, Preparation of catalysts
Through N
2Fully add cyclohexane (10mL) in the 100mL reactor that the band of displacement stirs through processed, trimethyl aluminium (10mL), (diphenyl) phosphorus nitrogen (cyclopenta) phosphorus (diphenyl) (31mg), CrCl
3(THF)
3(12mg), and 1,1,2,2 tetrabromoethanes (0.02,0.069mmol) standby behind the room temperature reaction 5min.
3, ethylene trimer
The autoclave of 500mL is heated to and vacuumizes 2 hours, charges into ethene through nitrogen replacement for several times, cools to predetermined temperature, adds cyclohexane (200mL) and above-mentioned catalyst through processed.Carrying out oligomerisation reaction under 30 ℃, the pressure of 6.0MPa, with ice bath cooling, release, is 10% acidifying ethanol cessation reaction with mass fraction behind the reaction 20min.The results are shown in subordinate list 1.
Embodiment 3
1, preparation (diphenyl) phosphorus nitrogen (fluorenyl) phosphorus (diphenyl) part
(1) preparation N, N-diisopropyl dichlor-phosphoryl amine
With embodiment 1.
(2) preparation phenyl-magnesium-bromide lattice reagent
With embodiment 1.
(3) preparation diphenyl phosphorus chloride
With embodiment 1.
(4) preparation (diphenyl) phosphorus nitrogen (fluorenyl) phosphorus (diphenyl)
Through N
2Fully add carrene (20mL) in the 100mL reactor that the band of displacement stirs through processed, triethylamine (3.75mL), diphenyl phosphorus chloride (1.326mL 7.2mol), is cooled to 0 ℃, slowly add fluorenamine (0.652g, 3.6mmol).Rise to room temperature behind the stirring reaction 30min and continue reaction 12 hours.Filtration, drying obtain product (0.48g, 24.3%).
2, Preparation of catalysts
Through N
2Fully add cyclohexane (10mL) in the 100mL reactor that the band of displacement stirs through processed, tri-propyl aluminum (10mL), (diphenyl) phosphorus nitrogen (fluorenyl) phosphorus (diphenyl) (35mg), Cr (acac)
3(12mg), 1, the 2-dimethoxy-ethane (0.4mL, 0.03lmmol), standby behind the room temperature reaction 5min.
3, ethylene trimer
The autoclave of 500mL is heated to and vacuumizes 2 hours, charges into ethene through nitrogen replacement for several times, cools to predetermined temperature, adds benzene (200mL) and above-mentioned catalyst through processed.Carrying out oligomerisation reaction under 20 ℃, the pressure of 2.0MPa, with ice bath cooling, release, is 10% acidifying ethanol cessation reaction with mass fraction behind the reaction 40min.The results are shown in subordinate list 1.
Embodiment 4
1, preparation 1, the two (N (P (phenyl) of 4-
2)
2)-benzene part
(1) preparation N, N-diisopropyl dichlor-phosphoryl amine
With embodiment 1.
(2) preparation phenyl-magnesium-bromide lattice reagent
With embodiment 1.
(3) preparation diphenyl phosphorus chloride
With embodiment 1.
(4) preparation 1, the two (N (P (phenyl) of 4-
2)
2)-benzene
Through N
2Fully add carrene (20mL) in the 100mL reactor that the band of displacement stirs through processed, triethylamine (3.75mL), diphenyl phosphorus chloride (1.326mL 7.2mmol), is cooled to 0 ℃, slowly adds 1, and the 4-phenylenediamine (0.19g, 1.8mmol).Rise to room temperature behind the stirring reaction 30min and continue reaction 12 hours.Filtration, drying obtain product (0.8g, 52.3%).
2, Preparation of catalysts
Through N
2Fully add cyclohexane (10mL) in the 100mL reactor that the band of displacement stirs, tri-butyl aluminum solution (7mL), preparation 1, the two (N (P (phenyl) of 4-through processed
2)
2)-benzene (27mg), 2 ethyl hexanoic acid chromium (10mg), 1,2-dichloroethanes (0.13mmol), standby behind the room temperature reaction 10min.
3, ethylene trimer
The autoclave of 500mL is heated to and vacuumizes 2 hours, charges into ethene through nitrogen replacement for several times, cools to predetermined temperature, adds heptane ((200mL) and above-mentioned catalyst through processed.Carrying out oligomerisation reaction under 90 ℃, the pressure of 7.0MPa, with ice bath cooling, release, is 10% acidifying ethanol cessation reaction with mass fraction behind the reaction 20min.The results are shown in subordinate list 1.
Embodiment 5
1, preparation (diphenyl) phosphorus nitrogen (isopropyl) phosphorus (diphenyl) part
(1) preparation N, N-diisopropyl dichlor-phosphoryl amine
With embodiment 1.
(2) preparation phenyl-magnesium-bromide lattice reagent
With embodiment 1.
(3) preparation diphenyl phosphorus chloride
With embodiment 1.
(4) preparation (diphenyl) phosphorus nitrogen (isopropyl) phosphorus (diphenyl)
With embodiment 1.
2, Preparation of catalysts
Through N
2Fully add dimethylbenzene (10mL) in the 100mL reactor that the band of displacement stirs through processed, triisobutyl aluminium (10mL), (diphenyl) phosphorus nitrogen (cyclohexyl) phosphorus (diphenyl) (29mg), CrCl
3(THF)
3(12mg), 1, standby behind 4-dichloro-benzenes (0.069mmol) the room temperature reaction 5min.
3, ethylene oligomerization
The autoclave of 500mL is heated to and vacuumizes 2 hours, charges into ethene through nitrogen replacement for several times, cools to predetermined temperature, adds dimethylbenzene ((200mL) and above-mentioned catalyst through processed.Carrying out oligomerisation reaction under 30 ℃, the pressure of 5.0MPa, with ice bath cooling, release, is 10% acidifying ethanol cessation reaction with mass fraction behind the reaction 50min.The results are shown in subordinate list 1.
Embodiment 6
1, preparation (diphenyl) phosphorus nitrogen (isopropyl) phosphorus (diphenyl) part
(1) preparation N, N-diisopropyl dichlor-phosphoryl amine
With embodiment 1.
(2) preparation phenyl-magnesium-bromide lattice reagent
With embodiment 1.
(3) preparation diphenyl phosphorus chloride
With embodiment 1.
(4) preparation (diphenyl) phosphorus nitrogen (isopropyl) phosphorus (diphenyl)
With embodiment 1.
2, Preparation of catalysts
Through N
2Fully add dimethylbenzene (10mL) in the 100mL reactor that the band of displacement stirs through processed, triethyl aluminum (10mL), (diphenyl) phosphorus nitrogen (cyclohexyl) phosphorus (diphenyl) (29mg), CrCl
3(THF)
3(12mg), 1, standby behind 4-dichloro-benzenes (0.069mmol) the room temperature reaction 5min.
3, ethylene oligomerization
The autoclave of 500mL is heated to and vacuumizes 2 hours, charge into ethene through nitrogen replacement for several times, cool to predetermined temperature, the MAO toluene solution (7mL), (diphenyl) phosphorus nitrogen (cyclohexyl) phosphorus (diphenyl) that adds isopropylbenzene (200mL) through processed, 1.4mol/L (29mg), CrCl
3(THF)
3(12mg), 1,4-dichloro-benzenes (0.069mmol).Carrying out oligomerisation reaction under 50 ℃, the pressure of 7.0MPa, with ice bath cooling, release, is 10% acidifying ethanol cessation reaction with mass fraction behind the reaction 30min.The results are shown in subordinate list 1.
Subordinate list 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Catalyst activity (g oligomer/mol Cr.h) * 10 7 | 5.68 | 4.51 | 9.24 | 5.12 | 1.25 | 4.21 |
| 1-butylene selectivity (wt%) | 0.32 | 0.98 | 0.15 | 0.02 | 0.48 | 0.25 |
| 1-hexene selectivity (wt%) | 95.03 | 96.25 | 95.16 | 96.30 | 97.21 | 95.08 |
| 1-octene selectivity (wt%) | 1.02 | 1.01 | 1.35 | 0.92 | 0.88 | 1.64 |
| Polymer | 0.2％ | 0.1％ | 0.2％ | 0.1％ | 0.1％ | 0.02％ |
Claims (6)
1. catalyst of ethylene trimerization is characterized in that: comprising:
(1) chromium compounds a: be chromium acetylacetonate, oxolane chromium chloride and/or isooctyl acid chromium;
(2) contain the part b of P and N: be following general formula compound
R
1, R
2, R
3, R
4Be phenyl, benzyl, fluorenyl, naphthyl; R
5Be isopropyl, butyl, cyclopropyl, cyclopenta, cyclohexyl;
(3) activator c: be trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum is or/and triisobutyl aluminium;
(4) promoter d: general formula is X
1RX
2, X
1, X
2Be F, Cl, Br, I and/or alkoxyl, R are alkyl, aromatic radical.
The mol ratio of a, b, c and d is 1: 0.5～100: 50～5000: 0.5～100.
2. catalyst of ethylene trimerization according to claim 1 is characterized in that: the mol ratio of a, b, c and d is 1: 0.5～10: 50～1000: 0.5～50.
3. catalyst of ethylene trimerization according to claim 1 is characterized in that: the mol ratio of a, b, c and d is 1: 1～5: 100～500: 1～20.
4. the application of catalyst of ethylene trimerization according to claim 1, it is characterized in that: be used for the ethylene trimer reaction, the ethylene trimer reaction is mainly carried out in atent solvent, in the conventional equipment of ethylene trimer, press each component effective dose of catalyst, under ethylene pressure, carry out the preparation of catalyst original position, and constantly feed ethene, it is fully contacted with catalyst, ethylene trimer takes place, reaction condition: 30～200 ℃ of temperature, pressure 0.5～20.0MPa, 0.1～2 hour time.
5. the application of catalyst of ethylene trimerization according to claim 4 is characterized in that: solvent comprises alkane, aromatic hydrocarbons, halogenated hydrocarbons, alkene.
6. the application of catalyst of ethylene trimerization according to claim 4 is characterized in that: solvent comprises, benzene,toluene,xylene, isopropylbenzene, normal heptane, n-hexane, hexahydrotoluene, cyclohexane, 1-hexene, 1-octene, ionic liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100900636A CN100386149C (en) | 2006-06-26 | 2006-06-26 | Ethylene trimerization catalyst and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100900636A CN100386149C (en) | 2006-06-26 | 2006-06-26 | Ethylene trimerization catalyst and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1872416A true CN1872416A (en) | 2006-12-06 |
| CN100386149C CN100386149C (en) | 2008-05-07 |
Family
ID=37483114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100900636A Active CN100386149C (en) | 2006-06-26 | 2006-06-26 | Ethylene trimerization catalyst and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100386149C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008014139A3 (en) * | 2006-07-25 | 2008-04-03 | Chevron Phillips Chemical Co | Olefin oligomerization catalysts and methods of using same |
| CN102107146A (en) * | 2009-12-29 | 2011-06-29 | 中国石油天然气股份有限公司 | Catalyst for synthesizing hexene-1 by ethylene trimerization and application thereof |
| CN101720253B (en) * | 2007-07-11 | 2013-07-17 | 林德股份公司 | Catalyst composition and process for di-, tri- and/or tetramerization of ethylene |
| CN111905832A (en) * | 2020-07-23 | 2020-11-10 | 天津科技大学 | Catalyst system for selective oligomerization of ethylene, reaction method and application thereof |
| CN113600244A (en) * | 2021-08-06 | 2021-11-05 | 山东京博石油化工有限公司 | Catalyst for synthesizing 1-octene and application thereof |
| CN115501914A (en) * | 2022-09-22 | 2022-12-23 | 中化泉州石化有限公司 | Ethylene trimerization catalyst containing depolymerizing agent and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4668838A (en) * | 1986-03-14 | 1987-05-26 | Union Carbide Corporation | Process for trimerization |
| US5376612A (en) * | 1989-08-10 | 1994-12-27 | Phillips Petroleum Company | Chromium catalysts and process for making chromium catalysts |
| JP3613642B2 (en) * | 1994-09-05 | 2005-01-26 | 住友化学株式会社 | Method for producing 1-hexene |
| JP3823429B2 (en) * | 1996-06-28 | 2006-09-20 | 住友化学株式会社 | Catalyst system and olefin reaction method |
| US5856257A (en) * | 1997-05-16 | 1999-01-05 | Phillips Petroleum Company | Olefin production |
| CN1108193C (en) * | 1998-12-15 | 2003-05-14 | 北京燕山石油化工公司研究院 | Novel catalyst for ethylene trimerization, its preparation process and application |
| US6455648B1 (en) * | 1999-12-29 | 2002-09-24 | Chevron Phillips Chemical Company Lp | Olefin production |
-
2006
- 2006-06-26 CN CNB2006100900636A patent/CN100386149C/en active Active
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8334420B2 (en) | 2006-07-25 | 2012-12-18 | Chevron Phillips Chemical Company Lp | Olefin oligomerization catalysts and methods of using same |
| US7378537B2 (en) | 2006-07-25 | 2008-05-27 | Chevron Phillips Chemical Company Lp | Olefin oligomerization catalysts and methods of using same |
| WO2008014139A3 (en) * | 2006-07-25 | 2008-04-03 | Chevron Phillips Chemical Co | Olefin oligomerization catalysts and methods of using same |
| US9555404B2 (en) | 2007-07-11 | 2017-01-31 | Saudi Basic Industries Corporation | Catalyst composition and process for di-, tri- and/or tetramerization of ethylene |
| CN101720253B (en) * | 2007-07-11 | 2013-07-17 | 林德股份公司 | Catalyst composition and process for di-, tri- and/or tetramerization of ethylene |
| EP2520366A1 (en) * | 2009-12-29 | 2012-11-07 | Petrochina Company Limited | Catalyst for synthesizing 1-hexene from ethylene trimerization and application thereof |
| US20120310025A1 (en) * | 2009-12-29 | 2012-12-06 | Petrochina Company Limited | Catalyst for Synthesizing 1-Hexene from Ethylene Trimerization and Application Thereof |
| JP2013515601A (en) * | 2009-12-29 | 2013-05-09 | ペトロチャイナ カンパニー リミテッド | Catalyst for synthesis of 1-hexene by trimerization of ethylene and use thereof |
| EP2520366A4 (en) * | 2009-12-29 | 2013-07-03 | Petrochina Co Ltd | Catalyst for synthesizing 1-hexene from ethylene trimerization and application thereof |
| WO2011079493A1 (en) * | 2009-12-29 | 2011-07-07 | 中国石油天然气股份有限公司 | Catalyst for synthesizing 1-hexene from ethylene trimerization and application thereof |
| 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 |
| US9421533B2 (en) * | 2009-12-29 | 2016-08-23 | Petrochina Company Limited | Catalyst or synthesizing 1-hexene from ethylene trimerization and application thereof |
| CN102107146A (en) * | 2009-12-29 | 2011-06-29 | 中国石油天然气股份有限公司 | Catalyst for synthesizing hexene-1 by ethylene trimerization and application thereof |
| CN111905832A (en) * | 2020-07-23 | 2020-11-10 | 天津科技大学 | Catalyst system for selective oligomerization of ethylene, reaction method and application thereof |
| CN113600244A (en) * | 2021-08-06 | 2021-11-05 | 山东京博石油化工有限公司 | Catalyst for synthesizing 1-octene and application thereof |
| CN115501914A (en) * | 2022-09-22 | 2022-12-23 | 中化泉州石化有限公司 | Ethylene trimerization catalyst containing depolymerizing agent and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100386149C (en) | 2008-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102107146B (en) | Catalyst for synthesizing hexene-1 by ethylene trimerization and application thereof | |
| CN101032695A (en) | Catalyst composition for ethylene oligomerization and application thereof | |
| CN1651142A (en) | Catalyst component used for ethylene oligomerization, preparing process and application thereof | |
| CN1184240C (en) | Olefin production | |
| CN1872416A (en) | Ethylene trimerization catalyst and application thereof | |
| CN1606539A (en) | Trimerisation and oligomerisation of olefins using a chromium based catalyst | |
| CN1296466A (en) | Oligomerization of propylene | |
| CN1741850A (en) | Tetramerization of olefins | |
| CN1351615A (en) | Method of polymerization | |
| CN1414880A (en) | Organometal compound catalyst | |
| CN103285926A (en) | Catalyst composition for ethylene oligomerization and application thereof | |
| CN1239526C (en) | Catalyst composition for olefinic polymerization | |
| CN1555349A (en) | Method for alpha-olefin trimerization | |
| CN1108193C (en) | Novel catalyst for ethylene trimerization, its preparation process and application | |
| CN1759098A (en) | Method for hydrocyanating an olefinically unsaturated compound | |
| CN1231500C (en) | Catalyst for polymerization and copolymerization of ethylene | |
| CN1247621C (en) | High-temperature ZIEGLER NATTA solution catalyst | |
| US20230053092A1 (en) | Ligands for Production of 1-Octene in Chromium Assisted Ethylene Oligomerization Process | |
| CN1478095A (en) | Catalyst composition and method of polymerization | |
| CN1027374C (en) | Polymers of carbon monoxide with one or more mono-olefins | |
| CN1789271A (en) | Method for synthesizing mono-metallocene compound | |
| CN1215097C (en) | Method for preparing polyalphaolefin from 1-octene | |
| CN1108312C (en) | Olefin polymerization catalyst and method for preparing polyolefin using said catalyst | |
| CN101816951A (en) | Ethylene oligomerization catalyst and preparation method | |
| JP3517279B2 (en) | Dimerization of lower olefins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 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 |