CN1072187C - 能够催化烯烃低聚反应的粒状分子筛及其制法 - Google Patents
能够催化烯烃低聚反应的粒状分子筛及其制法 Download PDFInfo
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- CN1072187C CN1072187C CN96191820A CN96191820A CN1072187C CN 1072187 C CN1072187 C CN 1072187C CN 96191820 A CN96191820 A CN 96191820A CN 96191820 A CN96191820 A CN 96191820A CN 1072187 C CN1072187 C CN 1072187C
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- 150000002430 hydrocarbons Chemical class 0.000 title description 12
- 229930195733 hydrocarbon Natural products 0.000 title description 10
- 239000004215 Carbon black (E152) Substances 0.000 title description 8
- 239000003054 catalyst Substances 0.000 title description 5
- 239000002808 molecular sieve Substances 0.000 claims abstract description 33
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 150000001336 alkenes Chemical class 0.000 claims abstract description 31
- 239000010457 zeolite Substances 0.000 claims abstract description 31
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 30
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 16
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- 229910052733 gallium Inorganic materials 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
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- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000001767 cationic compounds Chemical class 0.000 claims description 2
- 229910001411 inorganic cation Inorganic materials 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 13
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- 230000002349 favourable effect Effects 0.000 description 16
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- 239000002253 acid Substances 0.000 description 12
- 238000001354 calcination Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
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- 230000000694 effects Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
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- 239000004411 aluminium Substances 0.000 description 3
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- 230000008901 benefit Effects 0.000 description 3
- 238000005810 carbonylation reaction Methods 0.000 description 3
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- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- SGVYKUFIHHTIFL-UHFFFAOYSA-N 2-methylnonane Chemical compound CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical group CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical group CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 2
- UCRIXEWTILHNCG-UHFFFAOYSA-N 1-ethyl-2h-pyridine Chemical compound CCN1CC=CC=C1 UCRIXEWTILHNCG-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- SPGHPHFQNQIZME-UHFFFAOYSA-N 2-n-ethylethane-1,1,2-triamine Chemical compound CCNCC(N)N SPGHPHFQNQIZME-UHFFFAOYSA-N 0.000 description 1
- TYSIILFJZXHVPU-UHFFFAOYSA-N 5-methylnonane Chemical compound CCCCC(C)CCCC TYSIILFJZXHVPU-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 230000022244 formylation Effects 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- PLZDDPSCZHRBOY-UHFFFAOYSA-N inaktives 3-Methyl-nonan Natural products CCCCCCC(C)CC PLZDDPSCZHRBOY-UHFFFAOYSA-N 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- -1 propylene, butylene Chemical group 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/19—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/80—Mixtures of different zeolites
Abstract
结晶的分子筛,特别是沸石,每一晶粒有相同结构的芯和外层,Si:Al(SiO2:Al2O3)摩尔比芯核的大于外层的,在烯烃低聚合反应中得到低支链的产品。
Description
本发明涉及烃类,特别是烯烃的处理,涉及实现低聚和涉及在这种处理中所使用的催化剂。
在甲酰化,或羰基化反应中,采用烯烃作为原料,用于最后制造许多有价值的产品,如醇类、由醇类衍生的酯类和醚类、醛类和酸类。在这些最终用途的许多中,直链烃或稍带支链的烃与更密集的支链烃相比有许多优点。
但是,对一定的支链度来说,在密集支链烯烃自身的羰基化反应中,比直链或稍带支链结构的烯烃的活性低,而且一些同分异构体比其他的活性也低。
烯烃原料,特别是C4-C20和更尤其是C6-C15范围的烯烃原料,常常是通过低分子量原料的低聚反应来生产,在反应期间由于发生分子重排作用,即使原料是直链的,也可能产生不希望高比率的多支链烯烃。而且,由低聚反应生成的在烃链相互靠近处,或在烃链中间区域,或在上述两者处的支链的位置进一步降低在羰基化反应中分子的活性。
在其它区域,支链相对少的烃类有利;这些优点包括在表面活性剂和聚烯烃稳定剂的制造中,通过与烯烃反应的芳烃的烷基化反应。
因此,需要提供一种生产降低烃类物料支链度的烯烃低聚物的方法。
美国专利5284989号(Apelian等,转让给Mobil Oil Corporation)公开了在烯烃的催化低聚反应中,使用一种中等孔径选择形状的酸性结晶沸石,并讨论了影响产品直链度或支链度的几种因素。在沸石颗粒表面的酸活性据说对支链产品的生产有益,并提到沸石表面的脱铝会降低表面酸性,或表面酸性与结晶内部酸位置活性之比。在该专利中提及的现有技术还评述了其它降低酸活性的方法包括在不活泼的酸位置使用大体积胺(bulky amines);那篇专利的发明是对不活泼的表面酸位置,使用二羧酸。
在美国专利5250484号中(Beck等人,同样转让给Mobil),公开了通过使催化剂与氨-硼烷溶液接触后进行煅烧,在表面上生成一不活泼的陶瓷层来降低表面酸性。在美国专利4788374号中(Chu等人,同样转让给Mobil),揭示了在氟化物存在下,通过在金属硅酸盐芯核的表面上结晶SiO2在其上生成SiO2壳层来降低表面酸性。
本发明提供了用于烯烃低聚的一种方法,该方法包括在低聚条件下,使包括至少一种烯烃的原料与烯烃低聚催化剂接触,所述的催化剂包括粒状分子筛,分子筛的每粒包括一芯核和在其上沉积了一表面层,所述的芯核包括含硅和选自Al、Ga和Fe的至少一种元素的沸石,所述的表面层包括含硅和选自Al、Ga和Fe的至少一种元素的沸石,表面层的沸石和芯核的沸石有相同的结晶结构,而表面层的沸石的硅与选择元素之比高于芯核的。
本发明还提供了能够催化烯烃低聚的粒状分子筛,分子筛的每粒包括一芯核和在其上沉积了一表面层,所述的芯核包括含硅和选自Al、Ga和Fe的至少一种元素的沸石,而所述的表面层包括含硅和选自Al、Ga和Fe的至少一种元素的沸石,表面层的沸石和芯核的沸石有相同的结晶结构,且表面层的沸石的硅与选择元素之比高于芯核的。
本发明还提供了粒状分子筛的用途,所述分子筛的每一粒包括一芯核和在其上沉积了一表面层,所述的芯核包括含硅和选自Al、Ga和Fe的至少一种元素的沸石,而所述的表面层包括含硅和选自Al、Ga和Fe的至少一种元素的沸石,表面层的沸石和芯核的沸石有相同结晶结构,且表面层沸石的硅与选择元素之比高于芯核的。用作烯烃低聚催化剂,降低了低聚物产品的支链度。
本发明也提供了粒状分子筛的制造方法,所述的方法包括加热合成混合物的水溶液,所述合成混合物的水溶液包括硅源、选自Al、Ga和Fe的元素源、一价无机阳离子源和如果希望或需要,结构有机定向剂,合成混合物有分散在其中的含硅和选自Al、Ga和Fe的一个元素的分子筛的晶体,在晶体中硅与选择元素之摩尔比低于合成混合物中硅与相应源中的选择元素之摩尔比,使在晶体的表面上产生来自合成混合物的分子筛层的结晶。
在本发明上述方面的每个方面,选择元素优选是铝。芯核和外层的选择元素优选相同,但不是必需。例如,含镓的外层围绕含铝的芯核。
得到的结晶产品优选用铵离子或质子进行离子交换后,煅烧得到酸式分子筛。
煅烧在最高600℃,优选最高5002温度下进行。
本发明分子筛的制造方法的某些特征是与本领域的通用的,或如文献中描述的已知方法共有的。
这些特征可以简述如下:
所要求的硅源,例如这可以是胶体二氧化硅悬浮物,例如商标名为Ludox的销售品,或是细分散的固体,例如商标名为Aerosil的销售品。
适当的铝源可以是引入合成混合物的氧化铝,例如预先将Al2O3·3H2O溶于碱或将铝盐如Al2(SO4)3·18H2O溶在碱溶液中。适当的镓源例如是Ga2O3,也溶于碱溶液中,而对铁来说,适当的铁源优选Fe(NO3)3。在下面的描述中,为了清楚起见,将只参考用铝来进行描述。
合成混合物含的一价阳离子源例如碱金属如钠、钾或铯、或铵离子。这可以氢氧化物的形式方便地提供,因此,在所提供的碱溶液中可以中入氧化铝。
如果存在有机结构定向剂,则通过所谓的模板效应直接的形成假定的分子筛。在分子筛的合成中有机分子的作用是众所周知的,例如在例如Lok等人Zeoliten 1983,Vol.3,p282-291和Moretti等人Chim.Ind.(Milan)67,No.1-2,21-34(1985)中讨论过的。有机结构定向剂的效果是在结晶骨架的产生中,有机化合物用作模板围绕结晶骨架生长,或有机化合物产生结晶,直接生成粒状的结晶骨架。制备ZSM-22分子筛的结构有机定向剂优选一和二氨基链烷,链烷部分有高达12个碳原子,特别是4、6、8、10或12个碳原子的,例如1,6-二氨基己烷(这是优选的)、二乙胺、1-氨基丁烷或2,2′-二氨基二乙胺;含高达8个碳原子的芳胺类、有机杂环化合物,例如N-乙基吡啶鎓、聚亚烷基多胺类,如三亚乙基四胺或四亚乙基五胺和链烷醇胺类如乙醇胺或二乙醇胺。
模板R的量,按1,6-二氨基己烷优选模板计,在合成混合物中R/SiO2的摩尔比优选0.025-0.4。
在合成混合物中的SiO2/Al2O3摩尔比一般为至少150∶1,优选至少为250∶1,而可以高达1500∶1那么高。300∶1和900∶1之间,特别是300∶1和600∶1之间是特别优选的。
在结晶后沸石层中的SiO2/Al2O3的摩尔比可以高达30%,比合成混合物中的低;这可以考虑合成混合物各组分的比率选择中减少,以保证芯核和外层比率间所要求的关系。分散在合成混合物中芯核晶体中的SiO2/Al2O3的摩尔比最多120∶1有利,在40∶1-120∶1的范围内更有利,而优选为60-100∶1。
合成混合物中反应物的比率通常低于正常合成混合物的,即除了低铝含量外,合成混合物应当非常稀,例如用水稀释。例如,包含芯核物料的合成混合物可含高达85%,优选50%-80%(wt)的稀释剂,尤其是水。
在120℃-180℃的温度下实现结晶有利,优选的结晶温度为140℃-170℃。结晶时间为10-72小时,一般为15-48小时。
结晶后,沸石可用脱离子水或酸化水洗涤,然后,可以在干燥或煅烧步骤后,进行离子交换得到酸式沸石。
沸石优选在用铵离子交换后,在进行铵离子分解的条件下,形成氨和质子,这样就产生了酸式沸石。
酸式沸石也可以通过用酸和氢氯酸进行酸交换来制得。
铵离子交换可以任何适宜的方法,例如用NH4Cl、NH4NO3或NH4OH的水溶液处理晶体来进行。质子交换是通过晶体与稀酸溶液例如HCl接触进行是有利的。
在铵离子或质子交换后,晶体可以煅烧,在120℃-600℃的温度下进行煅烧有利,优选的煅烧温度为150℃-500℃。适宜的煅烧时间是1小时-几天,指定温度范围的上限部分中的温度相应短的加热时间,而指定温度范围下限中的温度相应较长的加热时间。
因此,例如,晶体可以在400℃的温度煅烧1-20小时。在120℃温度时,至少2天的较长煅烧时间,而优选3-5天,对得到足够的孔隙,一般是必须的。
分子筛可以进行后处理,如用水蒸汽进行后处理,或通过在制备期间或通过随后的离子交换,使之引入其它的阳离子,适宜的其它阳离子的实例是Ni、Cd、Cu、Zn、Pd、Ca、B和Ti及稀土金属。
本发明的分子筛的精制收缩(如下文定义)系数大于2有利,大于10更有利。
精制收缩系数CI°定义为正癸烷的氢异构化现象中在转化率为5%时2-甲基壬烷与5-甲基壬烷的比(参见J.A.Martens,M.Tielen,P.A.Jacobs和J.A.Martens,Pure and Applied Chem.,1986,Vol.58,p.1329)。
分子筛的CI°在2-10间的实例包括ZSM-5、11、12、35、38、48和57、SAPO-11、MCM-22和毛沸石,目前CI°为5和10间的那些是优选的。CI°大于10的分子筛的实例包括ZSM-22、ZSM-23和某些碱镁沸石类,因此最优选。
采用两种或两种以上分子筛的混合物也在本发明的低聚方法的范围内。
分子筛或沸石催化剂有利的是美国专利455-6477号和WO 93/25475号中描述的ZSM-22、这两篇专利中公开的内容引入本文作参考。
所采用的分子筛的晶粒粒径为5μm有利,优选为0.05-5μm,更优选为0.05-2μm,最优选为0.1-1.0μm。
以本发明的分子筛的总重量计表示的表面层的比率(重量)例如可为5%-20%,在煅5烧后一般为8%-15%。
分子筛可以粒状、粉末或其它形状如挤出物的形式使用。挤出物含分子筛和粘合剂如Al2O3、SiO2、硅铝酸盐或粘土有利,分子筛与粘合剂的重量比为10∶90-90∶10有利,优选20∶80-80∶20。例如分子筛和粘合剂通过将它们与存在的水的充分地混合在一起来混合,然后挤出或成型,例如通过造粒成形。
原料烯烃含2-12个碳原子有利,优选含2-6个碳原子;更优选的原料烯烃含丙烯、丁烯和戊烯。
本发明低聚方法的反应条件可以按照用于相同烯烃的现有技术的低聚方法的操作条件,只是使用了本发明的新颖的催化剂。
例如,烯烃用惰性稀释剂,例如液态或气态饱和烃,优选气态饱和烯烃掺合后,加入催化剂。对包括丙烯的原料来说,适宜的稀释剂是丙烷,烯烃与饱和烃重量比为90∶10-10∶90有利,优选10∶90-60∶40,特别是在约50∶50(重量)。相应地,对丁烯原料,适宜的稀释剂是丁烷,烯烃与饱和烃重量比为90∶10-10∶90有利,优选75∶25-50∶50,特别是约2∶1。原料是水合的有利;优选原料含0.05%-2%的重量水,在适当的温度例如25-60℃,通过将原料饱和引入所需比率的水,或通过泵喷射所需量的水。
低聚反应在160℃-300℃的温度范围进行有利,优选为170℃-260℃,更优选为180℃-260℃的温度,低聚反应在5-10MPa的压力下进行有利,优选6-8MPa的压力,烯烃的时空速为0.1-20,优选为0.5-10,最优选0.75-3.5whsv(重量时空速度)。
在采用现有技术一般的催化剂例如ZSM-22的烯烃低聚反应中,人们发现,从丁烯到辛烯,由于转化速率降低,对二聚物的选择性确提高了,但是支链度也提高了。但是使用本发明的催化剂,人们惊奇地发现,在低转化速率下,保持了对二聚物的选择性,同时降低了支链度。因此,低聚反应可以在低转化速率下进行,从低聚物中分离未反应的单体并进行循环,得到了二聚物的高选择性而不损失产品的直链性。
另外,本发明的催化剂有一附加的优点,那就是用大体积胺处理过的现有技术的物料,易于再生,例如通过煅烧,而不要求随后的胺处理。而且,本发明的催化剂在再生后与初始制备的本发明的催化剂相比,在烯烃低聚成低高支链产品的能力方面并没有差别。
下面用实施例描述本发明,其中的份数和百分数都是用重量表示,除非另有说明。
实施例1-3
催化剂的制备
实施例1
合成混合物的制备:
溶液A:组分 | 份数 |
H2OAl2(SO4)3·18H2ONaOH(98.4%)1,6-二氨基己烷 | 229.640.65382.1112.85 |
按所示的秩序将各组分溶于水中。溶液B:
组分 | 份数 |
Ludox AS-40(胶体SiO2) | 54.81 |
在三分钟内将溶液A与B混合,产生光滑的带白色的凝胶(合成混合物)。混合物C:
组分 份数
ZSM-22(H2O含量1.18%) 50.00
SiO2/Al2O3摩尔比73∶1
H2O 50.09ZSM-22的粒径小于等于1μm。
在5分钟内将混合物C的各组分混合,得到很粘的糊状物。添加72.54份的合成混合物后,混合15分钟。得到易倾注和均匀的块状物。
最终合成混合物的摩尔组成(包括晶体)是:
26.4Na2O/112.6R/Al2O3/372 SiO2/26580 H2O其中R′是1,6-二氨基己烷。
混合物含28.7%预制的ZSM-22晶体。
将80.87份合成混合物转移到不锈钢压热器中,在2小时的期间内加热到160℃,并在该温度下保持48小时。
产物过滤后,用500份水洗涤三次达pH为9.4,接着125℃干燥;用收得25.88份干燥产物。干燥后,产物有强烈的淡黄色外观,表明芯柱晶体被SiO2 ZSM-22外层或壳层覆盖。壳层与芯核的重量比计算如下:合成混合物的份数X预制晶体的份数
(80.87×0.287) 23.21
干燥产物份数 25.88
增加 2.67
壳层/未煅烧芯核之比2.67/23.32即0.12
按照假设在煅烧后壳层重量损失约12%,煅烧后壳层与芯核的预期重量比为约0.10∶1。
对干燥产物的X-射线衍射(XRD)表明ZSM-22结构被白硅石很轻度地污染。
实施例2
实施例1的下述步骤,得到摩尔组成为
53.0Na2O/226 R/Al2O3/246 SiO2/61045 H2O的最终合成混合物,其中R是1,6-二氨基己烷,含29.32%的预制ZSM-22晶体。
将111.24份含晶粒的合成混合物转移到不锈钢压热器,将该压热器置于在室温下的炉内。该炉在二小时期间内加热到158℃,并在该温度下保持24小时。
得到的结晶产物用水重复洗涤后,在125℃下干燥40小时。用收得35.8份干燥产物。用实施例1所述的方法计算,未煅烧壳层与芯核的重量比发现是0.10∶1,煅烧壳层与芯核的预期重量比约为0.09∶1。XRO表明是纯结晶ZSM-22结构。
实施例3
合成混合物的制备溶液A:
组分 | 份数 |
Al2(SO4)3·18H2ONaOH(98.4%)1,6-二氨基己烷H2O | 0.21932.1012.87175.00 |
首先将三组分按所示的顺序溶于175份水中。将54.82份胶体SiO2(Ludox AS40)溶液B置入混合器内,在混合器的容量注入溶液A,制备溶液A的容器用54.67份水冲洗,然后将洗水注入混合器。混合器中的物料搅拌三分钟,得到混合物C。将44.13份混合物加到40.46份水中,然后稀释的物料35.02份ZSM-22晶体混合。在混合5分钟后得到粘而可倾注的块状物D,其摩尔组成为:
78.9Na2O/336 R/Al2O3/1112 SiO2/85320 H2O其中R是1,6-二氨基己烷;含29.0%的干重量的ZSM-22晶体。
将110.05份块状物D转移不锈钢压热器,并将压热器置于室温的炉内。该炉在3小时内加热到150℃,并在该温度下保持24小时。在结晶产物分离后,用水洗涤三次,使pH为9.4(最后一次洗水),在120℃干燥过夜,得到35.75份干燥产物。按实施例1描述的方法计算表明,未煅烧壳层与芯核的重量比为0.12∶1,和煅烧壳层与芯核的预期重量比为0.10∶1。
在实施例1-3的每一个中,产品用0.5N NH4Cl溶液进行离子交换,洗涤后,在400℃下煅烧16小时。
实施例4和5和对比例A、B和C
烯烃低聚合
进行下述的实施例是说明在烯烃低聚反应中本发明制备的催化剂的有效性。在每种情况下,原料是用丁烷稀释的混合丁烯原料,其比率为烯烃为约65%,而饱和烃为35%,用40℃时水蒸汽饱和。反应器温度维持在205℃-235℃的范围,在每种情况下按水蒸汽增加天数。反应器压力保持在约7Mpa。
所使用的现有技术催化剂是(a)在实施例1-3中用作芯核晶体的ZSM-22催化剂(在下面的表1和2中称为“母体”)和(b)可力丁处理的ZSM-22,催化剂(a)和(b)都成型成直径为5mm的挤出物;本发明的催化剂和催化剂(a)以粉末状使用。表1给出了在205℃,7MPa和重量时空速度为1.3g烯烃/g催化剂/时条件下丁烯转化方面的催化活性。
表1
实施例号 | 催化剂 | 转化率% |
对比例A对比例B对比例C45 | (a)母体粉末(a)母体挤出物(b)可力丁处理的挤出物实施例1,粉末实施例2,粉末 | 97.080.38.191.384.9 |
实施例6-13
和对比例D-H
在这些实施例中,在丁烯低聚合反应中使用实施例1和2,对比例B和C的催化剂,比较生成辛烯的支链度。如上所述,参考实施例4和5所使用的原料和条件,但是改变加料速率,因此空速也改变,得到不同的转化率。结果列于下表2。
表2
实施例号 | 催化剂实施例 | 丁烯转化率% | 直链 | 辛烯异构体(%) | 平均支链度 | 对二聚物的选择性 | ||
一支链 | 二支链 | 三支链 | ||||||
对比例D对比例E对比例F对比例G对比例H7891011121314 | 对比例B对比例B对比例B对比例B对比例C11112222 | 74.884.690.296.173.573.979.591.393.472.781.191.595.0 | 4.23.94.35.88.46.15.64.24.75.55.55.46.8 | 40.639.342.247.466.456.354.645.247.158.156.052.263.4 | 50.252.349.844.923.435.137.247.046.033.135.940.527.8 | 5.04.53.72.00.82.52.53.52.23.32.71.91.9 | 1.561.571.531.431.181.341.371.501.461.341.361.391.25 | 49.548.445.031.758.258.257.848.546.156.961.156.547.3 |
Claims (2)
1.能够催化烯烃低聚反应的粒状分子筛,分子筛的每粒包括-芯核和在其上沉积了一表面层,所述芯核包括含硅和选自Al、Ga和Fe的至少一种元素的沸石,而所述的表面层包括含硅和选自Al、Ga和Fe的至少一种元素的沸石,表面层的沸石与芯核的沸石是相同的结晶结构,且表面层的硅与选择元素之比高于芯核的。
2.一种粒状分子筛的制造方法,该方法包括加热合成混合物的水溶液,所述合成混合物的水溶液包括硅源、选择元素Al、Ga和Fe的一个元素源,一价无机阳离子源,以及如果需要或要求,有机结构定向剂,合成混合物有分散在其中的含Si和选自Al、Ga和Fe的一个元素的分子筛的晶体,晶体中硅与所选元素的摩尔比低于合成混合物中它们各自源中硅与所选元素的摩尔比,以便使来自合成混合物的分子筛向晶体的表面结晶。
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GB9502342.0 | 1995-02-07 | ||
GBGB9502342.0A GB9502342D0 (en) | 1995-02-07 | 1995-02-07 | Hydrocarbon treatment and catalyst therefor |
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EP (1) | EP0808298B1 (zh) |
JP (1) | JP3937241B2 (zh) |
KR (1) | KR100360734B1 (zh) |
CN (2) | CN1072187C (zh) |
AT (1) | ATE171155T1 (zh) |
AU (1) | AU697790B2 (zh) |
CA (1) | CA2211043C (zh) |
DE (1) | DE69600667T2 (zh) |
ES (1) | ES2122782T3 (zh) |
GB (1) | GB9502342D0 (zh) |
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EP0808298B1 (en) | 1998-09-16 |
CN1173858A (zh) | 1998-02-18 |
DE69600667T2 (de) | 1999-04-08 |
US6013851A (en) | 2000-01-11 |
ES2122782T3 (es) | 1998-12-16 |
CA2211043C (en) | 2001-03-20 |
EP0808298A1 (en) | 1997-11-26 |
KR19980701991A (ko) | 1998-06-25 |
ATE171155T1 (de) | 1998-10-15 |
GB9502342D0 (en) | 1995-03-29 |
JP3937241B2 (ja) | 2007-06-27 |
AU697790B2 (en) | 1998-10-15 |
US6300536B1 (en) | 2001-10-09 |
CN1277951A (zh) | 2000-12-27 |
ZA96891B (en) | 1996-07-16 |
JPH10513459A (ja) | 1998-12-22 |
CA2211043A1 (en) | 1996-08-15 |
DE69600667D1 (de) | 1998-10-22 |
WO1996024567A1 (en) | 1996-08-15 |
AU4539596A (en) | 1996-08-27 |
KR100360734B1 (ko) | 2003-02-07 |
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