CN115463691A - 一种用于制备1-己烯的催化剂组合物及其应用 - Google Patents
一种用于制备1-己烯的催化剂组合物及其应用 Download PDFInfo
- Publication number
- CN115463691A CN115463691A CN202211158225.0A CN202211158225A CN115463691A CN 115463691 A CN115463691 A CN 115463691A CN 202211158225 A CN202211158225 A CN 202211158225A CN 115463691 A CN115463691 A CN 115463691A
- Authority
- CN
- China
- Prior art keywords
- hexene
- catalyst composition
- catalyst
- production
- aluminum
- 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
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000005977 Ethylene Substances 0.000 claims abstract description 30
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 21
- 238000005829 trimerization reaction Methods 0.000 claims abstract description 21
- -1 pyridine compound Chemical class 0.000 claims abstract description 20
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 241000501667 Etroplus Species 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 239000012442 inert solvent Substances 0.000 claims description 5
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims 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 description 3
- LQIIEHBULBHJKX-UHFFFAOYSA-N 2-methylpropylalumane Chemical compound CC(C)C[AlH2] LQIIEHBULBHJKX-UHFFFAOYSA-N 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
- 239000002815 homogeneous catalyst Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-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
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 150000004820 halides Chemical class 0.000 abstract description 9
- 239000003446 ligand Substances 0.000 abstract description 8
- 239000000047 product Substances 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
- 239000004698 Polyethylene Substances 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 3
- 229920000573 polyethylene Polymers 0.000 abstract description 3
- 150000001845 chromium compounds Chemical class 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- PAPNRQCYSFBWDI-UHFFFAOYSA-N 2,5-Dimethyl-1H-pyrrole Chemical compound CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 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
- 229910006113 GeCl4 Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000009467 reduction Effects 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
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical compound ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 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
- 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
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- 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)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种用于制备1‑己烯的催化剂组合物及其应用，具体是用于乙烯三聚的采用铬化物、吡啶化合物、烷基铝助催化剂和无机含磷卤化物解聚剂组成的催化剂组合物及其应用。本发明要求保护的一种上述含磷卤化物作为解聚剂和吡啶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。
Description
技术领域
本发明属于催化剂技术领域，具体涉及一种用于制备1-己烯的催化剂组合物及其应用。
背景技术
线性α-烯烃（LAO）作为一种重要的有机化工原料，在聚烯烃、润滑油基础油、洗涤醇领域有着广泛的应用，特别是近些年来，随着聚乙烯产量地进一步提升，以1-己烯为代表的共聚单体的表观消费量得到了进一步的提升。在1-己烯的制备方法中，乙烯选择性三聚制备1-己烯因其1-己烯的高选择性而被广泛应用。
Phillips公司在文章William.K.Reagen,Ted M.Pettij john.Jettroyw.Freeman,Chomium Catalysts and process for making chromium Castalysts公布了在含异辛酸铬、2,5-二甲基吡咯和三乙基铝的催化体系中加入第4组分GeCl4后，催化剂的催化活性提高至66400g/gCr.h，1-己烯的选择性提高至92%-98%，副产物的选择性低于1%，使乙烯选择性三聚研究取得突破性进展。随后，Phillips公司在专利US5856257中将第4组分替换为一氯二乙基铝，催化产物中1-己烯的选择性可高达95%。Phillips公司因其在乙烯选择性三聚方面的技术积累，使其率先实现了乙烯选择性三聚制备1-己烯的工业化生产你。荒术良刚在Phillips公司的启发下，将第4组分替换为四氯乙烷，催化活性骤然提高至157309g/gCr.h，1-己烯的选择性可达90%，使乙烯选择性三聚提高到一个新的水平。随后，各大公司对乙烯选择性三聚催化体系的第4组分进行大量研究。中石化在专利CN 1108193C披露的技术中，将4元催化体系中的第4组分替换为一种含卤的芳烃化合物，使催化剂的活性和选择性大大提高，并以此技术成功实现50kt/a的1-己烯工业化生产。中国石油天然气股份有限公司申请的专利CN1490291中催化剂体系采用含1,2,3,4,5,6-六氯环己烷γ体的第4组分，1-己烯的选择性高达99.3%，利用该三聚技术中石油分别于2007年和2014年在大庆石化公司和独山子石化公司实现1-己烯的产业化。
由此可以看出，在乙烯选择性三聚制备1-己烯的催化体系中，第4组分对催化剂的活性和选择性起着至关重要的作用。
发明内容
为解决上述问题，本发明提供了一种用于制备1-己烯的催化剂组合物及其应用，在金属铬盐、烷基铝保持不变的基础上，使用吡啶化合物作为配体、无机含磷卤化物作为解聚剂组成催化剂体系，该催化剂活性高，1-己烯选择性高，且生成的聚合物极少，有利于长周期运行。
为实现上述目的，本发明的技术方案为：
一种用于制备1-己烯的催化剂组合物，包括以下组分：
（1）铬化物；
（2）吡啶化合物：结构式如下：
（3）烷基铝助剂；
（4）解聚剂：PCl3、PCl5、PBr5、PBr3。
进一步地，所述铬化物、吡啶化合物、烷基铝助剂、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；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。
上述用于制备1-己烯的催化剂组合物的应用：将用于制备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，本发明的用于制备1-己烯的催化剂组合物的应用具体包括以下步骤：
（1）用于制备1-己烯的催化剂组合物制备：将用于制备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制备成铬化物溶液、吡啶化合物溶液、烷基铝助剂溶液、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、吡啶化合物溶液、解聚剂溶液，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：
烷基铝在使用过程中不稳定，极易聚合，主要以二聚体的形式存在。据In SituEPR Monitoring of Chromium Species Formed during CrPyrrolyl EthyleneTrimerization Catalyst Formation文献报道，金属Cr在烷基铝的作用下还原成一价，随后与配体配位后形成一定空间构型的配合物，但是在该过程中烷基铝为缺电子结构，极容易聚集。
另一方面，除烷基铝外，卤代烃作为乙烯三聚催化剂的第四组份也起了非常重要的作用，其能显著提高催化剂的选择性，主要机理为：（1）卤代烃中的氯原子能与烷基铝中的Al原子形成配位键，从而将二聚体的烷基铝拆解为单分子结构，增加烷基铝单体的浓度。（2）由于卤素原子比氮原子具有更大的电负性，能打开含氮配体中的N-H键，使含氮配体能以单分子形式存在于催化体系中，利于其与中心原子Cr配位。
当前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、烷基铝助催化剂和含卤素化合物，含卤素化合物的使用显著提高了烷基铝的利用率，同时卤素原子的给电子性也使催化体系的活性和选择性提高，目前所使用的含卤素化合物大多为有机物，有机卤化物虽对催化剂的活性和选择性有较大提高，但有机氯的对环境污染严重，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。
基于上述基础，本发明由铬金属盐、吡啶化合物（配体）、烷基铝和无机含磷卤化物共同组成乙烯三聚组合物，反应产物中1-己烯选择性高，与已公开的催化剂相比（吡咯为配体），副产物聚乙烯含量极少，且具有更高的活性；在产业化中可通过原位聚合进行乙烯三聚反应，不需要预聚。首先，无机含磷卤化物不仅能将聚合的烷基铝拆解为单分子结构，能保持有卤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。其次，本发明中吡啶环上通过连接不同的基团，与金属铬、烷基铝以及无机含磷卤化物给电子体共同作用，可以灵活调节其给电子性能和空间结构，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，含有不同基团的吡啶化合物具有与之更大的空间构型，因此在乙烯三聚催化剂中与金属配位后具有合适的空间位阻，可以有效降低聚合物的生成。
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。反应前高压反应釜在抽真空条件下加热至100℃恒温1 h，然后将温度设置为95℃，使其自然降温，同时氮气置换数次，然后用乙烯置换数次，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，催化剂中中乙酰丙酮铬：吡啶化合物：三乙基铝：三氯化磷=1: 1:100: 10），其中吡啶化合物1中R1=R3=R5=Cl，R2=R4=H。控制反应压力为4MPa，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 mL10% 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，不同之处在于吡啶化合物2结构（其中R1= R5=CH3，R2=R3=R4=H））数据结果见表1。
对比例1
同实施例1，不同之处在于将吡啶化合物改为吡咯，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。
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 (9)
1.一种用于制备1-己烯的催化剂组合物，其特征在于：包括以下组分：
（1）铬化物；
（2）吡啶化合物：结构式如下：
（3）烷基铝助剂；
（4）解聚剂：PCl3、PCl5、PBr5、PBr3。
2.根据权利要求1所述的用于制备1-己烯的催化剂组合物，其特征在于：所述铬化物、吡啶化合物、烷基铝助剂、解聚剂的摩尔比为：1:0.1~100:1~1000:1~1000。
3.根据权利要求2所述的用于制备1-己烯的催化剂组合物，其特征在于：所述铬化物、吡啶化合物、烷基铝助剂、解聚剂的摩尔比为1:0.1~10:1~500:1~50。
4.根据权利要求3所述的用于制备1-己烯的催化剂组合物，其特征在于：所述铬化物、吡啶化合物、烷基铝助剂、解聚剂的摩尔比为1: 1~8：1~100:1~10。
5.根据权利要求1所述的用于制备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所述的用于制备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任一项所述用于制备1-己烯的催化剂组合物的应用，其特征在于：将用于制备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。
8.根据权利要求7所述的应用，其特征在于：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。
9.根据权利要求7所述的应用，其特征在于：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。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211158225.0A CN115463691B (zh) | 2022-09-22 | 2022-09-22 | 一种用于制备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 |
|---|---|---|---|
| CN202211158225.0A CN115463691B (zh) | 2022-09-22 | 2022-09-22 | 一种用于制备1-己烯的催化剂组合物及其应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115463691A true CN115463691A (zh) | 2022-12-13 |
| CN115463691B CN115463691B (zh) | 2023-12-26 |
Family
ID=84335012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211158225.0A Active CN115463691B (zh) | 2022-09-22 | 2022-09-22 | 一种用于制备1-己烯的催化剂组合物及其应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115463691B (zh) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08239331A (ja) * | 1995-03-02 | 1996-09-17 | Mitsubishi Chem Corp | α−オレフイン低重合体の製造方法 |
| JPH09188634A (ja) * | 1996-01-08 | 1997-07-22 | Mitsubishi Chem Corp | α−オレフィン低重合体の製造方法 |
| JPH107594A (ja) * | 1996-06-17 | 1998-01-13 | Tosoh Corp | １−ヘキセンの製造方法 |
| CN1182729A (zh) * | 1996-02-02 | 1998-05-27 | 三菱化学株式会社 | 制造α－烯烃低聚物的方法 |
| US5856257A (en) * | 1997-05-16 | 1999-01-05 | Phillips Petroleum Company | Olefin production |
| KR20030029253A (ko) * | 2001-10-05 | 2003-04-14 | 한국화학연구원 | 에틸렌 삼량화 반응에서 1-헥센의 선택도를 증가시키는촉매계 |
| US20050215792A1 (en) * | 2004-03-24 | 2005-09-29 | De Boer Eric Johannes M | Transition metal complexes |
| US20080200743A1 (en) * | 2007-01-08 | 2008-08-21 | Ackerman Lily J | Methods For Oligomerizing Olefins With Chromium Pyridine Ether Catalysts |
| CN103044181A (zh) * | 2011-10-17 | 2013-04-17 | 中国石油天然气股份有限公司 | 一种乙烯四聚反应制备辛烯-1的方法 |
| CN108686706A (zh) * | 2018-06-22 | 2018-10-23 | 中国石油天然气股份有限公司 | 一种乙烯选择性齐聚的方法及催化剂 |
-
2022
- 2022-09-22 CN CN202211158225.0A patent/CN115463691B/zh active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08239331A (ja) * | 1995-03-02 | 1996-09-17 | Mitsubishi Chem Corp | α−オレフイン低重合体の製造方法 |
| JPH09188634A (ja) * | 1996-01-08 | 1997-07-22 | Mitsubishi Chem Corp | α−オレフィン低重合体の製造方法 |
| CN1182729A (zh) * | 1996-02-02 | 1998-05-27 | 三菱化学株式会社 | 制造α－烯烃低聚物的方法 |
| US5856612A (en) * | 1996-02-02 | 1999-01-05 | Mitsubishi Chemical Corporation | Process for producing α-olefin oligomer |
| JPH107594A (ja) * | 1996-06-17 | 1998-01-13 | Tosoh Corp | １−ヘキセンの製造方法 |
| US5856257A (en) * | 1997-05-16 | 1999-01-05 | Phillips Petroleum Company | Olefin production |
| KR20030029253A (ko) * | 2001-10-05 | 2003-04-14 | 한국화학연구원 | 에틸렌 삼량화 반응에서 1-헥센의 선택도를 증가시키는촉매계 |
| US20050215792A1 (en) * | 2004-03-24 | 2005-09-29 | De Boer Eric Johannes M | Transition metal complexes |
| US20080200743A1 (en) * | 2007-01-08 | 2008-08-21 | Ackerman Lily J | Methods For Oligomerizing Olefins With Chromium Pyridine Ether Catalysts |
| CN103044181A (zh) * | 2011-10-17 | 2013-04-17 | 中国石油天然气股份有限公司 | 一种乙烯四聚反应制备辛烯-1的方法 |
| CN108686706A (zh) * | 2018-06-22 | 2018-10-23 | 中国石油天然气股份有限公司 | 一种乙烯选择性齐聚的方法及催化剂 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115463691B (zh) | 2023-12-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3257871B1 (en) | Method for reducing olefin oligomerization byproduct using a deactivating agent | |
| US5491272A (en) | Method for oligomerizing an alpha-olefin | |
| JP6228724B2 (ja) | チタンをベースとする錯体と、ヘテロ原子によって官能基化されたアルコキシリガンドとを含む組成物を用いる、エチレンのブタ−１−エンへの二量体化のための方法 | |
| KR102280005B1 (ko) | 리간드 기재 크롬 촉매 및 에틸렌 올리고머화를 촉매하는 데 있어서의 이의 용도 | |
| KR20040072651A (ko) | 촉매 조성물 및 이를 이용한 올레핀 중합화 방법 | |
| CA2499844A1 (en) | Catalyst systems for ethylene oligomerisation to linear alpha olefins | |
| WO2009074203A1 (en) | Catalyst composition for oligomerization of ethylene oligomerization process and method for its preparation | |
| JP2020001035A (ja) | エチレンの選択的オリゴマー化の方法及びその触媒 | |
| CN114789067B (zh) | 一种乙烯选择性齐聚催化剂组合物及其制备方法 | |
| CN112916046B (zh) | 一种三元催化剂体系及其在乙烯齐聚反应的应用 | |
| JP2018503509A (ja) | オレフィンオリゴマー化反応用触媒システムおよびこれを用いたオレフィンオリゴマー化方法 | |
| CN102850168A (zh) | 一种防止或减少在反应器内壁形成粘附物的乙烯齐聚反应工艺 | |
| US20190224658A1 (en) | Catalyst system for olefin oligomerization and method for preparing olefin oligomer using same | |
| CN115463691A (zh) | 一种用于制备1-己烯的催化剂组合物及其应用 | |
| CN105457679A (zh) | 一种乙烯齐聚用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 | |
| CN115400800B (zh) | 一种乙烯选择性三聚催化剂组合物及其应用 | |
| KR20150058048A (ko) | 리간드 화합물, 올레핀 올리고머화용 촉매계, 및 이를 이용한 올레핀 올리고머화 방법 | |
| EP2268651B1 (en) | Sterically emcumbered bidentate and tridentate naphthoxy-imine metallic complexes | |
| CN114011469A (zh) | 一种用于乙烯齐聚的催化剂组合物 | |
| 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 | |
| CN115501914A (zh) | 一种含解聚剂的乙烯三聚催化剂及其应用 | |
| 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 | |
| CN116174040A (zh) | 一种乙烯三聚催化剂组合物及其应用 | |
| CN115445666A (zh) | 一种乙烯齐聚制备1-己烯的催化剂组合物及其应用 |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |