CN115445666A - 一种乙烯齐聚制备1-己烯的催化剂组合物及其应用 - Google Patents
一种乙烯齐聚制备1-己烯的催化剂组合物及其应用 Download PDFInfo
- Publication number
- CN115445666A CN115445666A CN202211158235.4A CN202211158235A CN115445666A CN 115445666 A CN115445666 A CN 115445666A CN 202211158235 A CN202211158235 A CN 202211158235A CN 115445666 A CN115445666 A CN 115445666A
- Authority
- CN
- China
- Prior art keywords
- hexene
- ethylene
- catalyst composition
- preparing
- oligomerization
- 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.)
- Pending
Links
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 title claims abstract description 82
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000005977 Ethylene Substances 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- 238000005829 trimerization reaction Methods 0.000 claims abstract description 22
- -1 indole compound Chemical class 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- SIKJAQJRHWYJAI-UHFFFAOYSA-N benzopyrrole Natural products C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims abstract description 10
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims abstract description 10
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003446 ligand Substances 0.000 claims description 19
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 18
- 241000501667 Etroplus Species 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 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 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- LQIIEHBULBHJKX-UHFFFAOYSA-N 2-methylpropylalumane Chemical compound CC(C)C[AlH2] LQIIEHBULBHJKX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 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 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 2
- JYLPOJPHFDVWCY-UHFFFAOYSA-K oxolane;trichlorochromium Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1 JYLPOJPHFDVWCY-UHFFFAOYSA-K 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical class [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 10
- 150000004820 halides Chemical class 0.000 abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 7
- 239000011574 phosphorus Substances 0.000 abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 abstract description 6
- 239000004698 Polyethylene Substances 0.000 abstract description 5
- 229920000573 polyethylene Polymers 0.000 abstract description 5
- 239000012442 inert solvent Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 23
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- OGFAWKRXZLGJSK-UHFFFAOYSA-N 1-(2,4-dihydroxyphenyl)-2-(4-nitrophenyl)ethanone Chemical compound OC1=CC(O)=CC=C1C(=O)CC1=CC=C([N+]([O-])=O)C=C1 OGFAWKRXZLGJSK-UHFFFAOYSA-N 0.000 description 1
- ZFLFWZRPMDXJCW-UHFFFAOYSA-N 2,5-dimethyl-1h-indole Chemical compound CC1=CC=C2NC(C)=CC2=C1 ZFLFWZRPMDXJCW-UHFFFAOYSA-N 0.000 description 1
- FUEGFUSXEBMAGH-UHFFFAOYSA-N C1CCCC1.[Cr] Chemical compound C1CCCC1.[Cr] FUEGFUSXEBMAGH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000012822 chemical development Methods 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006464 oxidative addition reaction Methods 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006894 reductive elimination reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种乙烯齐聚制备1‑己烯的催化剂组合物，由铬金属盐、吲哚化合物、烷基铝和无机含磷卤化物解聚剂共同组成，本发明的催化剂组合物用于催化乙烯三聚反应的步骤为：将乙烯齐聚制备1‑己烯的催化剂组合物中各成分分别溶于惰性溶剂中，以均相催化剂形式依次注入或提前混合均匀注入乙烯三聚反应体系中，随后提高乙烯压力，与催化剂充分接触，进行乙烯三聚反应，得到1‑己烯；本发明的乙烯齐聚制备1‑己烯的催化剂组合物具有催化剂活性高、1‑己烯选择性高、产物中聚乙烯副产物少，且在产业化中能降低成本等优点。
Description
技术领域
本发明属于催化剂技术领域，具体涉及一种乙烯齐聚制备1-己烯的催化剂组合物及其应用。
背景技术
线性α-烯烃是重要的有机化工原料，其中以1-己烯的应用最为广泛。1-己烯作为重要的有机原料和化学中间体，主要用于生产高端聚乙烯（PE）。与1-丁烯共聚树脂相比，由1-己烯与乙烯共聚生产的线性低密度聚乙烯（LLDPE）及高密度聚乙烯(HDPE)在聚乙烯的机械加工、耐热性、柔韧性和透明性等方面具有明显优势。特别适合于生产包装膜和农用覆盖膜。用1-己烯代替1-丁烯生产高性能的LLDPE和HDPE已经成为今后发展的必然趋势。1-己烯也是被列为入到国家石油和化工发展指南的鼓励重点发展化工产品。乙烯齐聚是目前工业上制备α-烯烃的主要方法之一，其产品质量更高。乙烯选择性齐聚制备1-己烯可以更好的适应市场需求，也是近年研究的热点。
乙烯选择性三聚生产1-己烯反应机理普遍认同单金属环三聚机理，最先由Manyik等提出，后经Briggs修正。该机理可描述为两分子的乙烯配位到铬中心，通过氧化加成生成铬金属环戊烷，然后第三个乙烯分子配位到铬中心上，并插入到铬环戊烷中生成铬环庚烷，该七元环通过β-氢转移和还原消除释放一分子的1-己烯。
对于乙烯选择性齐聚催化剂体系的活性和目的产物的选择性是评价该技术先进性的关键，现有的乙烯三聚催化剂体系大多是含有配体的铬系配合物，在铬源相对固定的条件下，调节配体的结构成了改变主催化剂结构及调节催化剂性能的必然手段。且催化剂体系中配体的结构对乙烯齐聚产物碳数的调控具有重要的作用，对催化性能有很大的影响，因此新型配体的研究和开发是乙烯三聚领域研究的热点。目前已报道的高选择性齐聚催化剂能得到将近90%的共选择性，但这还不能满足工业化的需求，因此，仍需进一步开发设计新型配体催化剂。
在乙烯选择性三聚方面，已有大量的专利。
1999年，Phillips申请专利US5856257采用铬系催化剂催化乙烯发生选择性三聚反应生成选择性高达95%的1-己烯，该装置工艺是目前世界上最先进的1-己烯工艺技术。
中国石油化工股份有限公司在专利CN102558107A中通过微波辐射快速高效的制备CrCl3THF3，以此为基础制备的铬系催化剂生产1-己烯选择性高于92%，纯度高达99.2%，并且该工艺于2007年在北京燕山石化公司建成5万吨/年的1-己烯生产工艺。
CN107233919B保护了一种催化剂组合物，包含专利中提到的配体化合物、过渡金属化合物和含铝助催化剂，该组合物对乙烯三聚的催化活性高，产物分布优，C6选择性高，1-己烯的选择性有95.5%。
CN105566026A公开了一种包含双膦配体、过渡金属化合物、含铝主催化剂和作为有机溶剂的脂肪烃的催化体系，独特的溶剂效应使1-己烯收率非常高，达98.4%。现有技术中，普遍认为水对乙烯齐聚反应工艺非常不利，因此齐聚反应一般都严格控制无水无氧环境。
专利CN105566044B在对双膦配体进行研究中发现，链烷烃溶剂中含有一定量水分的乙烯在该专利中提到的金属主催化剂和含铝助催化剂作用下，反而具有更高的三聚活性，C6选择性70.1%，1-己烯的纯度高达98.4%。总体而言，目前已产业化的或者在研的乙烯三聚技术，绝大部分采用吡咯或吡咯衍生物作为金属铬的配体。
现有技术仍然存在催化剂活性低、原料成本高、1-己烯的选择性低、聚合过程中会生成少量聚合物，影响装置连续运行的问题。
发明内容
为解决上述技术问题，本发明公开了一种乙烯齐聚制备1-己烯的催化剂组合物，其采用铬化物、吲哚化合物、烷基铝助剂和无机含磷卤化物解聚剂。本发明要求保护的一种上述含磷卤化物作为解聚剂和吲哚化合物作为配体的乙烯三聚催化剂体系催化乙烯三聚反应时，具有催化剂活性高、1-己烯选择性高、产物中聚乙烯副产物少，且在产业化中能降低成本等优点。
为实现上述目的，本发明的技术方案为：
一种乙烯齐聚制备1-己烯的催化剂组合物，包括以下组分：铬化物、配体、烷基铝助剂和解聚试剂；其中配体为吲哚化合物，结构式为
，其中R1、R2、R3、R4、R5、R6和R7相同或不同，选自氢、烷基、烷氧基、环烷基或卤素；所述解聚试剂为PCl3、PCl5、PBr5或PBr3。
进一步地，所述铬化物、配体、烷基铝助剂和解聚剂的摩尔比为：1:0.1~100:1~1000:1~1000；优选为1:0.1~10:1~500:1~50；更优选为1: 1~8：1~100:1~10。
进一步地，所述铬化物为异辛酸铬、乙酰丙酮铬、四氢呋喃氯化铬中的一种或多种。
进一步地，所述烷基铝助剂为三乙基铝、甲基铝氧烷、三甲基铝或异丁基铝。
上述乙烯齐聚制备1-己烯的催化剂组合物在乙烯三聚中的应用：将乙烯齐聚制备1-己烯的催化剂组合物中各成分分别溶于惰性溶剂中，以均相催化剂形式依次注入或提前混合均匀注入乙烯三聚反应体系中，随后提高乙烯压力，与催化剂充分接触，进行乙烯三聚反应，得到1-己烯。
进一步地，乙烯三聚反应的条件为：温度为30~250℃，压力为0.5~20MPa，时间为0.1~2h；所述惰性溶剂包括苯、甲苯、环己烷、甲基环己烷、正庚烷或正己烷。
进一步地，本发明的乙烯齐聚制备1-己烯的催化剂组合物的应用具体包括以下步骤：
（1）乙烯齐聚制备1-己烯的催化剂组合物制备：将乙烯齐聚制备1-己烯的催化剂组合物中各成分分别溶于经除水处理的惰性溶剂中制备成铬化物溶液、配体溶液、烷基铝助剂溶液和解聚剂溶液备用；
（2）反应前先将反应釜釜体和内衬置于烘箱中120 ℃烘干过夜，安装到反应釜上后密封，抽真空条件下加热至105℃恒温1 h，除去残留的水、氧和含氧杂质，然后温度设置为反应温度，使其自然降温，同时氮气填充，随后抽真空，重复三次，确保空气被置换干净，然后用真空泵抽走氮气，用乙烯填充，重复三次，保证釜体充满乙烯；
（3）在搅拌条件下使用注射器注入步骤（1）制得的烷基铝助剂溶液，待温度稳定至反应温度后，用注射器依次注入铬化物溶液、配体溶液和解聚试剂溶液，关闭尾气阀，调节减压阀，待压力升至预定压力值后开始计时，并记录质量流量计数据，反应结束后关闭乙烯气体，反应停止，关闭进气口阀门，卸下反应釜体，浸泡至冰水浴中使反应釜冷却至10℃以下。
开启尾气阀泄压后在搅拌条件下注入一定量5 ml 10%HCl/乙醇溶液，使烷基铝助剂淬灭，随后称取重量记录。取少量液相产物使用GC-MS分析产物。将剩余样品过滤，滤纸提前称量记录质量，随后搅拌桨上的聚合物用勺子刮下来，用溶剂清洗至烧杯里，将所得的聚合物置于真空烘箱中60℃干燥过夜，分别称重，计算获得聚合物的质量。根据MS可标定组分种类，根据GC结果结合液相产物质量和聚合物质量，可计算获得各产物的选择性以及催化剂活性。
本发明与现有技术相比：当前乙烯三聚的主流技术是使用四元催化剂组合物，即铬金属盐、吡咯化合物、烷基铝和有机含卤素化合物，有机氯化物虽对催化剂的活性和选择性有较大提高，但有机卤的对环境污染严重，同时有机氯也是一种致癌物质，对操作人员身体有较大伤害。基于此，本发明在铬系催化剂和烷基铝助催化剂两种主要成分保持不变的情况下，首次采用了无机含磷卤化物作为解聚剂，同时使用吲哚化合物代替吡咯化合物作为配体，即本发明由铬金属盐、吲哚化合物、烷基铝和无机含磷卤化物解聚剂共同组成乙烯三聚组合物。该解聚剂具有适当的给电子能力，可与烷基铝试剂结合，阻止其聚集，但又不影响其还原能力，最终该催化剂组合物具有优异的乙烯三聚催化性能。不仅能保持有机氯化物的高选择性和活性，还能减少环境污染以及对操作人员的身体伤害，此外无机含磷卤化物作为路易斯酸与有机卤化物相比价格低廉，有利于工业化推广。此外，吲哚化合物中苯环和旁边的含氮五元环形成共轭，具有较强刚性，在配位过程中结构稳定，不易转动，可以较为稳定的和金属中心形成单一活性中心，可以和活性中心发生较好的作用。与金属铬、烷基铝以及无机含磷卤化物给电子体共同作用，可以更加灵活地调节给单子性能，高效的催化乙烯分子与金属形成七元环，经β脱氢后释放一个1-己烯分子，且与吡咯相比，吲哚化合物具有较大的空间位阻，可以有效降低聚合物的生成，有利于长周期运行。
具体实施方式
下面结合具体实施例对本发明进一步说明，但本发明不限于此。
实施例1
乙烯齐聚反应在高压不锈钢反应釜中进行。反应前先将反应釜釜体置于烘箱中120℃烘干过夜，连接到评价体系，密封，抽真空条件下加热至100℃恒温1 h（尾气阀关闭），除去残留的水、氧和含氧杂质。然后将温度设置为80℃，使其自然降温，同时氮气填充，随后抽真空，重复三次，确保空气已被置换干净。然后用真空泵抽走氮气，用乙烯填充，重复三次，保证釜体充满乙烯。随后依次向其中加入溶剂环己烷和催化剂，催化剂中乙酰丙酮铬：2-甲基吲哚：三乙基铝：三氯化磷=1: 1:90: 10。控制反应压力为3MPa，反应1h后后停止反应，关闭进气口阀门，卸下反应釜体，浸泡至冰水浴中使反应釜冷却至10℃以下。开启尾气阀泄压后在搅拌条件下注入5 mL 10% HCl/乙醇溶液，使烷基铝淬灭，随后称取重量记录。取少量液相产物使用GC-MS分析产物。将剩余样品过滤，滤纸提前称量记录质量，随后搅拌桨上的聚合物用勺子刮下来，用溶剂清洗至烧杯里，将所得的聚合物置于真空烘箱中60℃干燥过夜，分别称重，计算获得聚合物的质量。根据MS可标定组分种类，根据GC结果结合液相产物质量和聚合物质量，可计算获得各产物的选择性以及催化剂活性。数据结果见表1。
实施例2
同实施例1，不同之处在于将三氯化磷改为五氯化磷，数据结果见表1。
实施例3
同实施例1，不同之处在于将三氯化磷改为三溴化磷，数据结果见表1。
实施例4
同实施例1，不同之处在于将三氯化磷改为五溴化磷，数据结果见表1。
实施例5
同实施例1，不同之处在于将2-甲基吲哚改为2，5-二甲基吲哚，数据结果见表1。
对比例1
同实施例1，不同之处在于将2-甲基吲哚改为吡咯，数据结果见表1。
对比例2
同实施例1，不同之处在于将三氯化磷改为六氯乙烷，数据结果见表1。
对比例3
同实施例1，不同之处在于将2-甲基吲哚改为吡咯，将三氯化磷改为六氯乙烷数据结果见表1。
表1 本发明的实施例和对比例反应条件及反应性能汇总表
以上实施例仅为了清楚的说明本发明内容，本发明的实施方式并不限制于此。凡在本发明的精神与原则之内，所做的任何修改、替换、改进等均应包含在本发明的保护范围之内。
Claims (7)
1.一种乙烯齐聚制备1-己烯的催化剂组合物，其特征在于：包括以下组分：铬化物、配体、烷基铝助剂和解聚剂；其中配体为吲哚化合物，结构式为
，其中R1、R2、R3、R4、R5、R6和R7相同或不同，选自氢、烷基、烷氧基、环烷基或卤素；所述解聚剂为PCl3、PCl5、PBr5或PBr3。
2.根据权利要求1所述的乙烯齐聚制备1-己烯的催化剂组合物，其特征在于：所述铬化物、配体、烷基铝助剂和解聚剂的摩尔比为：1:0.1~100:1~1000:1~1000。
3.根据权利要求2所述的乙烯齐聚制备1-己烯的催化剂组合物，其特征在于：所述铬化物、吲哚化合物、烷基铝助剂和解聚剂的摩尔比为1:0.1~10:1~500:1~50。
4.根据权利要求3所述的乙烯齐聚制备1-己烯的催化剂组合物，其特征在于：所述铬化物、吲哚化合物、烷基铝助剂和解聚剂的摩尔比为1: 1~8：1~100:1~10。
5.根据权利要求1所述的乙烯齐聚制备1-己烯的催化剂组合物，其特征在于：所述铬化物为异辛酸铬、乙酰丙酮铬、四氢呋喃氯化铬中的一种或多种。
6.根据权利要求1所述的乙烯齐聚制备1-己烯的催化剂组合物，其特征在于：所述烷基铝助剂为三乙基铝、甲基铝氧烷、三甲基铝或异丁基铝。
7.一种如权利要求1-6任一项所述的乙烯齐聚制备1-己烯的催化剂组合物在乙烯三聚中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211158235.4A CN115445666A (zh) | 2022-09-22 | 2022-09-22 | 一种乙烯齐聚制备1-己烯的催化剂组合物及其应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211158235.4A CN115445666A (zh) | 2022-09-22 | 2022-09-22 | 一种乙烯齐聚制备1-己烯的催化剂组合物及其应用 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115445666A true CN115445666A (zh) | 2022-12-09 |
Family
ID=84307140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211158235.4A Pending CN115445666A (zh) | 2022-09-22 | 2022-09-22 | 一种乙烯齐聚制备1-己烯的催化剂组合物及其应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115445666A (zh) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH107594A (ja) * | 1996-06-17 | 1998-01-13 | Tosoh Corp | １−ヘキセンの製造方法 |
| US5731487A (en) * | 1993-03-12 | 1998-03-24 | Sumitomo Chemical Company, Limited | Process for producing olefin having a terminal double bond |
| KR20030029253A (ko) * | 2001-10-05 | 2003-04-14 | 한국화학연구원 | 에틸렌 삼량화 반응에서 1-헥센의 선택도를 증가시키는촉매계 |
| CN1433433A (zh) * | 1999-12-29 | 2003-07-30 | 菲利浦石油公司 | 烯烃的生产 |
| CN106800494A (zh) * | 2017-01-03 | 2017-06-06 | 中国石油大学(北京) | 一种液相乙烯齐聚的催化剂及催化液相乙烯齐聚的方法 |
| CN112742483A (zh) * | 2021-01-21 | 2021-05-04 | 华东理工大学 | 一种用于乙烯选择性齐聚的催化剂体系及其制备和应用 |
| CN113880881A (zh) * | 2021-10-20 | 2022-01-04 | 中化泉州石化有限公司 | 一种刚性有机膦配体的合成及其在乙烯齐聚中的应用 |
| CN114225968A (zh) * | 2022-01-13 | 2022-03-25 | 中化泉州石化有限公司 | 一种乙烯三聚催化剂组合物 |
| CN114789067A (zh) * | 2022-04-26 | 2022-07-26 | 中化泉州石化有限公司 | 一种乙烯选择性齐聚催化剂组合物及其制备方法 |
-
2022
- 2022-09-22 CN CN202211158235.4A patent/CN115445666A/zh active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5731487A (en) * | 1993-03-12 | 1998-03-24 | Sumitomo Chemical Company, Limited | Process for producing olefin having a terminal double bond |
| JPH107594A (ja) * | 1996-06-17 | 1998-01-13 | Tosoh Corp | １−ヘキセンの製造方法 |
| CN1433433A (zh) * | 1999-12-29 | 2003-07-30 | 菲利浦石油公司 | 烯烃的生产 |
| KR20030029253A (ko) * | 2001-10-05 | 2003-04-14 | 한국화학연구원 | 에틸렌 삼량화 반응에서 1-헥센의 선택도를 증가시키는촉매계 |
| CN106800494A (zh) * | 2017-01-03 | 2017-06-06 | 中国石油大学(北京) | 一种液相乙烯齐聚的催化剂及催化液相乙烯齐聚的方法 |
| CN112742483A (zh) * | 2021-01-21 | 2021-05-04 | 华东理工大学 | 一种用于乙烯选择性齐聚的催化剂体系及其制备和应用 |
| CN113880881A (zh) * | 2021-10-20 | 2022-01-04 | 中化泉州石化有限公司 | 一种刚性有机膦配体的合成及其在乙烯齐聚中的应用 |
| CN114225968A (zh) * | 2022-01-13 | 2022-03-25 | 中化泉州石化有限公司 | 一种乙烯三聚催化剂组合物 |
| CN114789067A (zh) * | 2022-04-26 | 2022-07-26 | 中化泉州石化有限公司 | 一种乙烯选择性齐聚催化剂组合物及其制备方法 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114225968A (zh) | 一种乙烯三聚催化剂组合物 | |
| KR20150043313A (ko) | 에틸렌의 올리고머화 방법 | |
| Appukuttan et al. | Stereospecific polymerizations of 1, 3-butadiene catalyzed by Co (II) complexes ligated by 2, 6-bis (benzimidazolyl) pyridines | |
| CN105289741B (zh) | 一种氮磷配位骨架的铬催化剂及其在催化乙烯齐聚中的应用 | |
| CN112916046B (zh) | 一种三元催化剂体系及其在乙烯齐聚反应的应用 | |
| Huang et al. | Synthesis, Characterization of Rare‐Earth Metal Chlorides Bearing Indolyl‐Based NCN Pincer Ligand and Their Catalytic Activity toward 1, 4‐cis Polymerization of Isoprene | |
| CN111349115B (zh) | 一种pnnp结构配体和制备方法、一种乙烯齐聚反应催化剂体系及其应用 | |
| CN114789067A (zh) | 一种乙烯选择性齐聚催化剂组合物及其制备方法 | |
| US6559326B1 (en) | Substituted phosphinophenoxide-metal complexes for the polymerization of olefins | |
| EP3190118B1 (en) | Ligand compound, organic chrome compound, catalyst system for olefin oligomerization, and method for oligomerizing olefin using same | |
| CN115445666A (zh) | 一种乙烯齐聚制备1-己烯的催化剂组合物及其应用 | |
| CN115555048A (zh) | 一种乙烯三聚催化剂及其应用 | |
| CN106800494A (zh) | 一种液相乙烯齐聚的催化剂及催化液相乙烯齐聚的方法 | |
| CN115400800B (zh) | 一种乙烯选择性三聚催化剂组合物及其应用 | |
| CN115445667B (zh) | 一种乙烯齐聚用催化剂及其应用 | |
| CN115400801A (zh) | 一种含无机含磷卤化物和刚性结构化合物的催化剂组合物及其应用 | |
| VATANKHAH et al. | High performance bulky α-diimine nickel (II) catalysts for ethylene polymerization | |
| CN115501916B (zh) | 一种用于乙烯三聚的催化剂组合物及其应用 | |
| CN115501914A (zh) | 一种含解聚剂的乙烯三聚催化剂及其应用 | |
| CN115501913A (zh) | 一种含刚性结构化合物的催化剂及其在乙烯齐聚中的应用 | |
| CN115463691B (zh) | 一种用于制备1-己烯的催化剂组合物及其应用 | |
| CN105504127B (zh) | 一种负载型双金属聚乙烯催化剂及其应用 | |
| CN101376679B (zh) | 负载型钒系非茂聚烯烃催化剂及制备方法与应用 | |
| CN115555049A (zh) | 一种用于乙烯三聚的催化剂组合物及其应用 | |
| CN114011469A (zh) | 一种用于乙烯齐聚的催化剂组合物 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20221209 |