CN101035618A - 具有沸石和高度中孔性的加氢处理催化剂 - Google Patents
具有沸石和高度中孔性的加氢处理催化剂 Download PDFInfo
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- CN101035618A CN101035618A CNA2005800341486A CN200580034148A CN101035618A CN 101035618 A CN101035618 A CN 101035618A CN A2005800341486 A CNA2005800341486 A CN A2005800341486A CN 200580034148 A CN200580034148 A CN 200580034148A CN 101035618 A CN101035618 A CN 101035618A
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- catalyst
- zeolite
- zsm
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- 239000010457 zeolite Substances 0.000 title claims abstract description 92
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 91
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000011148 porous material Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
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- 238000009835 boiling Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
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- 230000000737 periodic effect Effects 0.000 claims description 4
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- 230000001588 bifunctional effect Effects 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 2
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 claims description 2
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- 125000005842 heteroatom Chemical group 0.000 claims description 2
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- 239000000203 mixture Substances 0.000 description 30
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- 239000000463 material Substances 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 239000000499 gel Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 238000001354 calcination Methods 0.000 description 11
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
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- 229910000510 noble metal Inorganic materials 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical class CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
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- 206010013786 Dry skin Diseases 0.000 description 5
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- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- -1 diethyl glycol ester Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 239000010937 tungsten Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
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- 239000011651 chromium Substances 0.000 description 3
- 238000009415 formwork Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 2
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- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- QAEJQYZWUGANBZ-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;silicon Chemical class [Si].OCCN(CCO)CCO QAEJQYZWUGANBZ-UHFFFAOYSA-N 0.000 description 1
- IRMOUQGSNFXEJH-UHFFFAOYSA-N 4,6,11-trioxa-1-aza-5-aluminabicyclo[3.3.3]undecane Chemical compound [Al+3].[O-]CCN(CC[O-])CC[O-] IRMOUQGSNFXEJH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- FWXIVOMYGUEKGC-UHFFFAOYSA-N N.O(Cl)Cl.[Ru] Chemical compound N.O(Cl)Cl.[Ru] FWXIVOMYGUEKGC-UHFFFAOYSA-N 0.000 description 1
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- 229910004298 SiO 2 Inorganic materials 0.000 description 1
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- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
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- HHUIAYDQMNHELC-UHFFFAOYSA-N [O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O HHUIAYDQMNHELC-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
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- 229910021529 ammonia Inorganic materials 0.000 description 1
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- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
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- 150000005324 oxide salts Chemical class 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种用于烃类转化的催化剂,其包括至少以下三种组分:(1)具有加氢功能的至少一种元素,(2)至少一类微孔沸石,和(3)多孔的非晶态无机氧化物,其具有无规互连的中孔,且X射线反射的2θ角为0.5度至2.5度。
Description
相关申请的交叉参考
本申请要求在2004年9月7日提交的美国临时申请系列号60/607,607的优先权。本申请是2005年4月8日提交的共同未决美国申请系列号11/101,858的部分继续申请,后者是2002年12月6日提交的美国申请系列号10/313,720的分案申请,该美国申请系列号10/313,720是2001年11月27日提交的美国申请系列号09/995,227的部分继续申请,且现已被授权,其美国专利号为6,762,143,所述美国申请系列号09/995,227是1999年9月7日提交的美国申请系列号09/390,276的部分继续申请,且现已被授权,其美国专利号为6,358,486,本申请要求其优先权,所有前述申请和/或专利均被引入本文以供参考。
发明背景
1.发明领域
本发明涉及具有加氢功能和酸性功能的双功能催化剂。
2.相关领域的背景
目前,大多数烃加工技术基于沸石催化剂。沸石催化剂在本领域是公知的,它们具有以均匀的孔径大小规则排列的孔体系。但是,这些材料趋于仅具有微孔,或者仅具有中孔。微孔是指直径小于约2nm的孔。中孔是指直径范围为约2nm至约50nm的孔。
因为这些烃加工反应是受传质限制的,所以具有理想孔径大小的催化剂将促进把反应物传递到催化剂活性位点,并把产物传递出催化剂。
还需要在多孔构架内具有功能化位点的改良材料,用于涉及烃和其它有机化合物的催化转化和/或吸附的过程。
发明概述
本文提供了用于烃类转化的催化剂,所述催化剂包括如下至少三种组分:(1)具有加氢功能的至少一种元素,(2)至少一类微孔沸石,和(3)多孔的非晶态无机氧化物,其具有无规互连的中孔,X射线反射的2θ角为0.5度至2.5度。
附图简述
下面参考附图来描述本发明,其中:
图1描绘了如实施例1、2和3制备的纯沸石β和沸石β/TUD-1的X射线衍射(XRD)图案;
图2描绘了如实施例1、2和3制备的纯沸石β和沸石β/TUD-1的中孔性;
图3描绘了中孔材料、MCM-22沸石、和实施例4制备的复合物的XRD图案;
图4说明了实施例4制备的复合物沸石/TUD-1的中孔孔径分布;和
图5描绘了纯沸石Y和实施例5制备的样品5的XRD图案。
优选实施方案详述
本发明的催化剂具有新的组成,基本上包括三种活性组分:(1)选自元素周期表的VIII、IB、IIB、VIIB和VIB族中的至少一种金属;(2)提供一些酸功能的至少一类微孔沸石;和(3)具有无规互连中孔的非晶态无机氧化物,所述中孔的直径范围为1.5nm至25nm。所述催化剂还可任选地包括硼和/或磷作为另一种组分。为了物理完整性,所述催化剂还可以包括粘合剂。
金属主要选自过渡金属、贵金属及它们的组合。这些金属包括:钛、钒、锆、锰、锌、铜、金、镧、铬、钼、镍、钴、铁、钨、钯、铑、钌和铂。一些金属可位于在中孔无机氧化物的孔表面上;另一些金属可掺入沸石构架内部作为晶格原子的替代物,和/或位于沸石微孔的内部。此外,一些金属可位于催化剂粘合剂上。
催化剂中的金属含量取决于特定的应用,基于催化剂的重量计,金属含量范围为0.3wt%至30wt%。对于贵金属,其含量的优选范围为0.2wt%至5wt%,对于过渡金属,其含量的优选范围为3wt%至30wt%。
本文所述的沸石包括嵌入非晶态多孔无机氧化物中的微孔沸石。所述微孔沸石可以是任何类型的微孔沸石。一些例子为:沸石β、沸石Y(包括“超稳定的Y”--USY)、丝光沸石、沸石L、ZSM-5、ZSM-11、ZSM-12、ZSM-20、θ-1、ZSM-23、ZSM-34、ZSM-35、ZSM-48、SSZ-32、PSH-3、MCM-22、MCM-49、MCM-56、ITQ-1、ITQ-2、ITQ-4、ITQ-21、SAPO-5、SAPO-11、SAPO-37、Breck-6(也称为EMT)、ALPO4-5等。这些沸石在本领域是已知的,许多是市售的。在本发明中,可将沸石掺入无机氧化物中,或可在非晶态多孔氧化物中原位合成沸石。
催化剂的沸石含量可在小于约1wt%至大于约99wt%的范围内,或者在这之间的任何范围内。但是,优选约3wt%至90wt%,更优选约4wt%至约80wt%。具有沸石的催化剂优选包含不大于约10vol%的微孔。
非晶态多孔无机氧化物优选是三维的中孔无机氧化物材料,按无机氧化物材料的微孔和中孔计(即其中并未掺入沸石),其中包含至少97vol%的中孔(即不大于3vol%的微孔),通常包含至少98vol%的中孔。这种材料描述于美国专利6,358,486,并被称为TUD-1。一种用于制备优选的多孔无机氧化物的方法公开于美国专利6,358,486和美国专利申请系列号10/764,797。
优选的多孔无机氧化物(TUD-1)的主要化学组成包括但不限于:二氧化硅、氧化铝、二氧化硅-氧化铝、二氧化钛、氧化锆、氧化镁及它们的组合。多孔无机氧化物TUD-1还可包括钒、锌、铜、金、镓、镧、铬、钼、镍、钴、铁和钨。
TUD-1是非晶态物质(即通过目前可用的X射线衍生技术未观察到晶体)。用N2-孔隙率测定法确定其平均中孔孔径大小范围为约2nm至约25nm。通过BET(N2)确定无机氧化物的表面积的优选范围为约200m2/g至约1200m2/g。其孔体积的优选范围为约0.3cm3/g至约2.2cm3/g。
根据美国专利6,358,486和美国专利申请系列号10/764,797,通常如下制备中孔无机氧化物:将(1)无机氧化物的前体和(2)有机模板剂的混合物加热,所述模板剂与氧化物前体或者由前体产生的氧化物种类充分混合。原料通常是无定型材料,可以由一种或多种无机氧化物如二氧化硅或氧化铝组成,其中具有或不具有其它的金属氧化物。硅原子可以被其它金属原子部分地代替。这些金属包括但不限于:铝、钛、钒、锆、镓、硼、锰、锌、铜、金、镧、铬、钼、镍、钴、铁、钨、钯和铂。可以将这些金属掺入中孔壁内部和/或中孔表面上的无机氧化物中。可以将其它金属任选地掺入材料中,然后引发用于产生包含中孔的结构的过程。而且在制备材料后,可以用其它离子如碱金属(例如钠、钾、锂等)离子任选地代替体系中的阳离子。
有机模板剂是形成中孔的有机化合物,优选为:二醇(包括两个或多个羟基的化合物),例如甘油、二甘醇、三甘醇、四甘醇、丙二醇等,或来自三乙醇胺、三异丙醇胺、环丁砜、四亚乙基五胺和二苯甲酸二乙基乙二醇酯中的成员。优选地,有机模板剂的沸点为至少约150℃。
为了将沸石掺入多孔无机氧化物中,其优选方法描述于美国专利6,762,143和美国专利公开2004/0138051。将预成型的沸石和/或预处理的沸石悬浮在与水的混合物中。然后将悬浮液与无机氧化物或无机氧化物的前体、和至少一种形成中孔的有机化合物混合,以形成混合物。通过老化和/或在室温至100℃的特定温度搅拌、和/或通过在60-120℃的温度干燥,混合物优选地形成凝胶。然后将凝胶加热到高至140℃至200℃的温度,并保持一段足够的时间,以形成中孔的无机氧化物结构。最后,通过萃取或萃取结合煅烧,除去有机成孔剂,以获得将沸石掺入非晶态多孔无机氧化物中的组合物。
此外,美国专利申请系列号10/764,797公开了通过使用络合物来制备非晶态多孔无机氧化物的方法。络合物如杂氮硅三环(silitrane)、杂氮铝三环(alumatrane)、杂氮钛三环(titanatrane),尤其是硅-三乙醇胺、铝-三乙醇胺以及它们的混合物可被用作非晶态多孔无机氧化物的前体。根据美国专利6,762,143和美国专利申请2004/0138051所述的方法,可获得将沸石掺入非晶态多孔无机氧化物(TUD-1)中的组合物。
可在催化剂制备的不同阶段,将具有加氢功能的所述金属引入催化剂中。在制备非晶态多孔无机氧化物中具有沸石的复合物(称为沸石/TUD-1)后,可通过常规的浸渍和离子交换装载金属。还可在将金属引入沸石中后,通过浸渍或离子交换将沸石掺入多孔无机氧化物(TUD-1)中。在实践中,优选使用某些粘合剂如氧化铝将沸石/TUD-1成型。在催化剂成型后,可将金属引入催化剂中。
用至少一种溶液浸渍复合物沸石/TUD-1,所述溶液包含来自VIB、VIIB、IB、IIB和VIII族中的至少一种元素。能够使用的VIB族元素的来源对本领域技术人员是公知的。钼源和钨源的例子为氧化物和氢氧化物、钼酸和钨酸及它们的盐,尤其是铵盐如钼酸铵、七钼酸铵、钨酸铵,磷钼酸、磷钨酸及它们的盐,硅钼酸、硅钨酸及它们的盐。优选地,使用氧化物和铵盐,例如钼酸铵、七钼酸铵和偏钨酸铵。
能够使用的VIII、VIIB、IB和IIB族元素的来源对本领域技术人员是公知的。非贵金属的来源的例子为硝酸盐,硫酸盐,磷酸盐,卤化物如氯化物、溴化物和氟化物,以及羧酸盐如乙酸盐和碳酸盐。贵金属的来源的例子为:卤化物如氯化物,硝酸盐,酸如氯铂酸,和氯氧化物如氨氯氧化钌。
将本发明获得的催化剂成型为不同形状和尺寸的颗粒。它们通常以具有平直或缠绕形状的圆柱形或多叶挤出物(例如双叶物、三叶物、或四叶物)形式使用,但也可以制备它们并以压缩的粉末、片剂、环状物、珠子或轮状物的形式使用。
所述催化剂可用于加氢裂化、加氢处理、和加氢异构化,其中所有的催化剂都是双功能的,组合了酸功能和加氢功能。在某些过程中,平衡这两种功能是重要的。选自过渡金属和贵金属中的金属提供了加氢功能。掺入的沸石提供了酸功能。非晶态多孔氧化物TUD-1可提供酸功能和/或加氢功能,这取决于氧化物的化学组成。例如,多孔氧化物是混合氧化物,二氧化硅-氧化铝,它提供酸功能。多孔氧化物为包含镍和钼的二氧化硅,它提供加氢功能。此外,多孔氧化物也可不提供任何酸功能和加氢功能,例如,如果多孔氧化物为纯的二氧化硅。所以,这种新型的催化剂具有极大的适应性,以调整酸功能和加氢功能。
通过使用非晶态多孔氧化物,所述催化剂的另一个重要特征提供了高度的中孔性,这显著增强了传质,从而改善了催化性能。对于大多数液相过程,粒子间的传质限制减少了催化剂利用,降低了总体催化性能。引入中孔性将提高总体催化性能。而且,许多精炼过程使用重质石油原料,这需要大孔来促进大分子出入催化剂粒子。石油原料可包括例如未脱沥青的石油残渣、脱沥青的石油残渣、焦油砂沥青、页岩油和煤液(coal liquid)。这样的话,具有中孔孔径大小为1.5nm至30nm的非晶态多孔氧化物TUD-1能够满足增加传质的需要。
此外,非晶态多孔氧化物不仅具有可调的中孔,而且具有无规互连的中孔。如美国专利6,358,486所述,其无规互连的中孔结构不同于其它中孔材料如MCM-41。与具有一维或二维孔体系的材料相比,无规互连的中孔减少了孔阻塞的机会。因此,在孔阻塞失活方面,所述新型催化剂将具有长寿优势。
在加氢裂化过程中,酸功能和加氢功能之间的平衡是基本的参数,它同时影响着催化剂的活性和选择性。弱的酸功能和强的加氢功能会产生低活性的催化剂,它通常需要高反应温度(390℃或更高)和低空速(LHSV通常为2h-1或更少),但对于中间馏分通常具有非常好的选择性。相反,强的酸功能和弱的加氢功能会产生非常活泼的催化剂,但对中间馏分的选择性差;这种催化剂组合还会有害地影响老化稳定性。因此,寻找合适催化剂的主要考虑是围绕正确选择每种功能以调整催化剂的活性/选择性/稳定性平衡。
为了在加氢裂化过程中获得对中间馏分的良好选择性,催化剂优选以非晶态二氧化硅-氧化铝作为多孔材料,具有选自沸石Y、ZSM-5、沸石β、MCM-56和/或MCM-22中的沸石,并具有选自周期表VIII和/或VIB族中的金属。在原料包含显著量杂芳族毒物的情况下,甚至优选VIB和VIII族的一些金属是硫化物或氧硫化物形式。
本领域技术人员公知的一种常规的硫化方法由如下组成:通常在横断床反应区域内,在硫化氢(纯的,或者例如在氢/硫化氢混合物或氮/硫化氢混合物的流中)存在的情况下,加热到150℃至800℃的温度,优选在250℃至600℃的范围内。
加氢裂化过程的条件(例如温度、压力、氢循环速率和空速)可广泛变化,这取决于原料的性质、所需产物的质量和精炼人员可利用的设备。温度通常超过200℃,常常在250℃至480℃的范围内。压力超过0.1MPa,常常超过1MPa。氢的量为最少50升氢/升原料,常常在80升至5000升氢/升原料的范围内。每小时的空速通常在0.1至20原料体积/催化剂体积/小时的范围内。加氢裂化产物可包括例如沸点范围为约150℃至约400℃的中间馏分、柴油和润滑油基础油。
通常,加氢异构化催化剂,例如用于升级费-托(Fischer-Tropsh)产物(公开于美国专利6,570,047)的加氢异构化催化剂包括在酸性金属氧化物载体上负载的一种或多种VIII族催化金属组分,以赋予催化剂加氢功能和酸功能,用于烃的加氢异构化。加氢异构化条件通常包括温度为约150℃至约500℃、压力为约1巴至约240巴、和LHSV为约0.1至约20。在相对低的加氢异构化温度下,例如在烃合成反应器的温度下,催化金属组分可以包括VIII族贵金属,如Pt或Pd,优选Pt。但是,在能用于本发明方法的较高温度下,优选催化金属组分包括一种或多种较廉价的VIII族非贵金属,例如Co、Ni和Fe,通常还包括VIB族金属(例如Mo或W)氧化物助催化剂。催化剂还可以包括IB族金属如铜作为氢解作用抑制剂。还可以加入磷以增强金属的溶解性,并辅助总体稳定性。
已经知道,催化剂的裂化和加氢活性取决于其具体的组成。本发明提供了优选的催化剂组成,包括:催化活性的金属如钴和钼;氧化物载体或负载体,包括二氧化硅、氧化铝、二氧化硅-氧化铝、二氧化硅-氧化铝-磷酸盐、二氧化钛、氧化锆、氧化钒和其它II、IV、V或VI族氧化物;以及酸性沸石,例如沸石Y(包括USY)、沸石β和ZSM-5。
下列实施例说明了本发明,但不以任何方式限制本发明的范围。
实施例1
本实施例示范说明将沸石β掺入二氧化硅TUD-1中。首先,将4.6份经煅烧的沸石β悬浮在51份水中,并搅拌30分钟,沸石β中SiO2/Al2O3的摩尔比为75,平均粒度为0.2μm。然后,在搅拌下向悬浮液中添加23份三乙醇胺。在连续搅拌另外30分钟后,添加63.5份原硅酸四乙酯(“TEOS”)。在再次搅拌另外30分钟后,向混合物中滴加12.6份氢氧化四乙铵水溶液(35%)。在搅拌约2小时后,混合物形成不流动的稠凝胶。使该凝胶在室温的静止状态老化24小时。接下来,将凝胶在100℃空气中干燥24小时。将干凝胶转移到高压釜中,在180℃用热水处理4小时。最后,以1℃/min的加热速率在600℃空气煅烧10小时。所得产物称为样品1,其XRD图案示于图1,其中清楚地显示沸石β的两个特征峰。在最终的复合物中,存在约20wt%沸石β。氮吸附揭示其表面积为约730m2/g,孔体积为约1.08cm3/g。样品1的中孔孔径分布示于图2。
实施例2
此处使用的沸石β与实施例1中所用的相同。首先,将12.2份沸石β悬浮在51份水中,搅拌30分钟。然后,在搅拌下向悬浮液中添加23份三乙醇胺。在连续搅拌另外30分钟后,添加63.5份TEOS。在再次搅拌另外30分钟后,向混合物中滴加12.7份氢氧化四乙铵水溶液(35%)。进行与实施例1所述相同的操作。在煅烧后,其XRD图案(对应样品2)示于图1,其中清楚地显示沸石β的两个特征峰。在最终的复合物沸石/TUD-1中,存在约40wt%沸石β。氮吸附揭示其表面积为约637m2/g,孔体积为约1.07cm3/g。其中孔孔径分布示于图2。
实施例3
使用与实施例1所述相同的沸石β和操作,除了化学品的量。化学品用量为:9.2份沸石β、17份水、7.6份三乙醇胺、21.2份TEOS、和4.2份氢氧化四乙铵水溶液(35%)。最终产物称为样品3,通过XRD和气体吸附表现其特征。在图1中,其XRD图案清楚地显示沸石β的两个特征峰。在最终的复合物中,存在约60wt%沸石β。氮吸附揭示其表面积为约639m2/g,孔体积为约0.97cm3/g。其中孔孔径分布示于图2。
实施例4
本实施例示范说明掺入MCM-22。首先,将2.4份合成的沸石MCM-22悬浮在10.5份水中,搅拌30分钟,沸石MCM-22中SiO2/Al2O3的摩尔比为6.4,平均粒度为2.5μm。然后,在搅拌下向上述悬浮液中添加9.2份三乙醇胺。在连续搅拌另外30分钟后,添加12.7份TEOS。在再次搅拌另外30分钟后,向混合物中滴加2.52份氢氧化四乙铵水溶液(35%)。在搅拌约2小时后,混合物形成不流动的稠凝胶。使该凝胶在室温的静止状态老化24小时。接下来,将凝胶98℃空气干燥24小时。将干凝胶转移到高压釜中,在180℃用热水处理4小时。最后,以1℃/min的加热速率在600℃空气煅烧10小时。
所得产物称为样品4,其XRD图案示于图3的最上部图中,其中清楚地显示沸石MCM-22(中间的图)和中孔材料(最下部图)的特征峰。在样品4中,存在约40wt%沸石MCM-22,基于铝含量的元素分析确证了这个数字,其中假设硅质中孔材料中不含铝。氮吸附揭示其表面积为约686m2/g,孔体积为约0.82cm3/g。在图4中,其中孔孔径分布集中在10nm周围。氩吸附显示微孔集中在0.5nm。
实施例5
将SiO2/Al2O3的摩尔比为14.8、表面积为606m2/g的超稳定Y(USY)掺入包含铝的中孔基质中。首先,将2.9份超稳定的沸石Y悬浮在17.0份水中,搅拌30分钟。然后,在搅拌下向上述悬浮液中添加124份三乙醇胺。在连续搅拌另外30分钟后,在搅拌下添加包含171.4份TEOS和28份异丙醇铝的另一混合物。在再次搅拌另外30分钟后,向混合物中滴加34份氢氧化四乙铵水溶液(35%)。在搅拌约2小时后,混合物形成不流动的稠凝胶。使该凝胶在室温和静止状态老化24小时。接下来,将凝胶在100℃空气干燥24小时。将干凝胶转移到高压釜中,在180℃用热水处理2小时。最后,以1℃/min的加热速率在600℃空气煅烧10小时。将最后的材料称为样品5。
样品5的XRD图案示为图5的最上部图,其中清楚地显示沸石Y和中孔结构材料的两个特征峰。下部的图说明沸石Y的XRD图案。在最后的复合物中,存在约5wt%沸石Y。氮吸附揭示其表面积为约694m2/g,孔体积为约1.1cm3/g。
实施例6
该实施例示范说明使用氧化铝作为粘合剂进行的催化剂挤出。通过离子交换,在60℃和搅拌下,将一份复合物5与十份1N硝酸铵溶液混合6小时,获得样品5的质子形式(即H+)。过滤固体材料,洗涤并在110℃干燥,以得到白色粉末。在第二次离子交换后,将固体材料在550℃空气煅烧6小时。
将八份H+-样品5与两份Nyacol形式的氧化铝混合,以提供催化剂。将混合物挤压成1.6mm直径的圆柱形。将挤出物干燥,在550℃煅烧4小时。最后,挤出物包含约4%USY、76wt%含铝的非晶态多孔氧化物和20wt%氧化铝。
实施例7
该实施例示范说明制备二氧化硅前体,即二氧化硅-三乙醇胺络合物。首先,将250份二氧化硅凝胶、697份三乙醇胺(TEA)和286份乙二醇(EG)装入配有冷凝器的烧瓶中。在用机械搅拌器将烧瓶的内容物充分混合后,在搅拌下将混合物加热到高至200-210℃。这个步骤除去了在反应过程中产生的大部分水以及来自冷凝器顶部的小部分EG。同时,大部分EG和TEA保留在反应混合物中。在约六小时后,停止加热;在冷却至55℃后收集反应混合物。该反应混合物为微棕色,显示为二氧化硅-三乙醇胺络合物。
实施例8
本实施例示范说明使用二氧化硅-三乙醇胺络合物作为二氧化硅来源制备沸石/TUD-1。将99份沸石Y(CBV-500)和300份水的悬浮液装入用于湿磨法的研磨装置中。在以3000rpm研磨30分钟后,收集悬浮液,用作掺入二氧化硅TUD-1中的沸石。在搅拌下,将两百零六(206)份该悬浮液(测得为20wt%沸石Y)与实施例7获得的217份络合物混合。在30分钟后,混合物形成稠凝胶,然后在90℃干燥24小时。将干凝胶转移到高压釜中,加热到高至180℃并保持6小时。最后,将凝胶在600℃空气煅烧10小时,最终变成白色粉末。
最后的沸石/TUD-1复合物包含45wt%沸石。氮气吸附显示其BET表面积为约560m2/g,总孔体积为约1.2cm3/g,平均中孔孔径为约5.7nm。
实施例9
该实施例显示了将金属掺入催化剂中。通过用Ni和W浸渍,将实施例6获得的挤出物进一步功能化。在搅拌下,将五(5)份硝酸镍水溶液(14wt%Ni)与8.4份偏钨酸铵溶液(39.8wt%W)混合。然后在搅拌下用9份水稀释混合物。用上述Ni/W溶液浸渍实施例6获得的12.5份挤出物,在118℃干燥2小时,在500℃煅烧2小时。所得的改性挤出物包含4.0wt%Ni和18.7wt%W。
实施例10
该实施例示范说明通过初始润湿制备0.9wt%钯和0.3wt%铂/沸石-TUD-1。用包括0.42份四胺硝酸铂、12.5份四胺硝酸钯水溶液(5%Pd)和43份水的水溶液浸渍实施例2获得的沸石/TUD-1。将经浸渍的沸石/TUD-1在室温下老化5小时,然后在90℃干燥2小时。最后,以1℃/min的加热速率将干材料在350℃空气煅烧4小时。使用CO化学吸附测量贵金属分散;然后将粉末在氢流中于100℃还原1小时,然后以5℃/min加热至350℃,在该温度保持2小时。假设Pt∶CO化学计量比为1,测得分散度为51%。
实施例11
该实施例示范说明通过初始润湿制备0.90wt%铱/沸石/TUD-1催化剂。将0.134份氯化铱(III)溶于5.3份去离子水中。在混合下,将该溶液添加到实施例4获得的8份沸石/TUD-1中。将粉末在25℃干燥。
使用CO化学吸附进行分散度测量,然后将粉末在氢流中于100℃还原1小时,然后以5℃/min加热至350℃,在该温度保持2小时。假设Ir∶CO化学计量比为1,CO化学吸附显示金属分散度为78%。
实施例12
该实施例说明实施例9获得的催化剂作为加氢裂化催化剂的用途,评价其在加氢裂化中对中间馏分的选择性。在流动反应器中,使用经加氢处理的重质真空瓦斯油作为原料,以预硫化形式(常规方式)进行评价。在LHSV为1.5kg/升小时、总压力为140巴(H2S的分压为5.5巴,氨的分压为0.075巴)、气体/原料比率为1500NL/kg运行。原料的性能示于表1中。
表1
经加氢处理的重质真空瓦斯油的性能
蒸馏(D1160): | |
IBP,℃(vol%)10%30%50%70%90%EPKV@100℃,cst碳,wt%氢,wt%总硫,wt%总氮,ppm | 3454024414725085647418.8186.613.40.00816.1 |
在组分净转化为65wt%时评价对中间馏分(例如沸点范围为175℃至345℃)的选择性。令人惊讶地是,选择性达到了72.6wt%。
实施例13
该实施例示范说明了润滑油收率和粘度指数的改善。如实施例9所述,用四胺硝酸铂浸渍实施例6获得的复合物沸石/TUD-1,最终的催化剂包含约0.6wt%Pt。典型的脱油蜡原料的组成示于下面表2中。从300SUS(65cst)中性油的溶剂(MEK)脱蜡中获得这种脱油蜡,所述中性油从Arab Light crude中获得。将来自加氢裂化步骤的总液体产物进一步升级,通过在所获得的低酸性Pt/沸石β/TUD-1催化剂上处理,进行加氢异构化,以有效地加氢异构化并将大多数未转化的蜡转化为非常高品质、非常高VI的润滑油,其基本上包含所有的异链烷烃,主要是单分枝异链烷烃。在一定范围的转化水平下,在400psia H2分压、2500SCF/B氢、和0.5LHSV下,在催化剂上处理总蜡质液体产物。然后将总液体产物蒸馏至700+的额定分馏点。然后将蜡质塔底物进行溶剂脱蜡,以制备具有改善润滑油收率的润滑油。表3包含这些实验的结果,这些实验使用包含沸石的加氢裂化催化剂。
表2
脱油蜡的性能 | |
重力,°API氢,wt%氮,ppm硫,wt%KV@100,cstKV@300,cst倾点,蜡中的油,D3235 | 39.214.0490.016.2943.151203.1 |
模拟分布D2887 | |
Wt% | |
0.55 | 759811 |
10203040506070809095 | 83086087889991793895998310141038 |
表3
经低转化加氢裂化的脱油蜡的Pt/沸石β/TUD-1异构化
1 | 2 | 3 | 4 | 5 | |
反应器温度,700-转化wt%(总计)经溶剂脱蜡的油的性能KV@40℃,cstKV@100℃,cstVI倾点,VI@0倾点Sim Dist(5%pt)组成,wt%石蜡单环烷多环烷芳族化合物润滑油收率,wt%(脱油的蜡原料)蜡转化,% | -1819.044.45715301516749252131.747.1 | 69123.318.054.29915251495579701249.468.9 | 63222.523.25.195164151587329334042.361.4 | 63821.522.335.04162101597058926350.170.1 | 6788.923.075.08915751536239124353.891.2 |
尽管上面的描述包含许多细节,但这些细节不应理解为限制本发明,而仅仅作为本发明优选实施方案的示例。在由所附权利要求书限定的发明范围和精神内,本领域技术人员将预期许多其它实施方案。
Claims (24)
1.一种用于烃类转化的催化剂,包括:
(a)具有加氢功能的至少一种元素;
(b)至少一类微孔沸石;和
(c)多孔的非晶态无机氧化物,其具有无规互连的中孔,且X射线反射的2θ角为0.5度至2.5度。
2.如权利要求1所述的催化剂,其中所述具有加氢功能的至少一种元素是选自元素周期表的VIII、IB、IIB、VIIB和VIB族中的金属。
3.如权利要求1所述的催化剂,其中所述具有加氢功能的至少一种元素是选自Pd、Pt、Ni、Mo、W、Rh、Ru、Cu及其组合中的金属。
4.如权利要求1所述的催化剂,其中所述具有加氢功能的元素的重量百分比组成范围为0.2%至30%。
5.如权利要求1所述的催化剂,其中沸石选自:沸石β、沸石Y、ZSM-5、MCM-22、MCM-36、丝光沸石、沸石L、ZSM-11、ZSM-12、ZSM-20、θ-1、ZSM-23、ZSM-34、ZSM-35、ZSM-48、SSZ-32、PSH-3、MCM-49、MCM-56、ITQ-1、ITQ-2、ITQ-4、ITQ-21、SAPO-5、SAPO-11、SAPO-37、Breck-6和ALPO4-5。
6.如权利要求1所述的催化剂,其中沸石的重量百分比组成范围为约3%至约90%。
7.如权利要求1所述的催化剂,其中无机氧化物具有选自Si、Al、Ti、Co、Zn、La、Cu、Au、Mo、W、Cr、Ga、V、Ni、Fe、Mg、Zr及其组合中的至少一种元素。
8.如权利要求1所述的催化剂,其中无机氧化物选自二氧化硅、氧化铝、二氧化钛、氧化锆及其组合。
9.如权利要求1所述的催化剂,其中无机氧化物为氧化铝-二氧化硅。
10.如权利要求1所述的催化剂,还包括选自硼、磷或其组合中的第四组分。
11.如权利要求1所述的催化剂,还包括用于成型的催化剂粘合剂。
12.一种用于制备催化剂的方法,该方法包括:
(a)制备络合物,作为具有无规互连中孔的非晶态无机氧化物的前体;
(b)使用来自步骤(a)的络合物以制备复合物,该复合物包含掺入至具有无规互连中孔的非晶态无机氧化物中的沸石;
(c)将具有加氢功能的至少一种金属引入步骤(b)制备的复合物中。
13.如权利要求12所述的方法,其中所述络合物选自杂氮硅三环、杂氮铝三环、杂氮钛三环及它们的组合。
14.如权利要求12所述的方法,其中沸石选自:沸石β、沸石Y、ZSM-5、MCM-22、MCM-36、丝光沸石、沸石L、ZSM-11、ZSM-12、ZSM-20、θ-1、ZSM-23、ZSM-34、ZSM-35、ZSM-48、SSZ-32、PSH-3、MCM-49、MCM-56、ITQ-1、ITQ-2、ITQ-4、ITQ-21、SAPO-5、SAPO-11、SAPO-37、Breck-6和ALPO4-5。
15.如权利要求12所述的方法,其中金属选自元素周期表的VIII、IB、IIB、VIIB和VIB族。
16.一种用于处理烃原料的方法,该方法包括:
使包含至少一种烃组分的原料与催化有效量的双功能催化剂接触,该催化剂包括:
a)具有加氢功能的至少一种元素;
b)至少一类微孔沸石;和
c)多孔的非晶态无机氧化物,其具有无规互连的中孔,且X射线反射的2θ角为0.5度至2.5度。
17.如权利要求16所述的方法,其中通过选自加氢裂化、加氢处理和加氢异构化中的反应来实现烃组分的转化。
18.如权利要求17所述的方法,其中所述原料包括石油馏分,反应条件足以实现该馏分的加氢裂化,以产生相对轻质的烃产物。
19.如权利要求18所述的方法,其中所述石油馏分包含沸点高于约260℃的至少一种组分。
20.如权利要求18所述的方法,其中所述石油馏分包含沸点高于约290℃的至少一种组分。
21.如权利要求18所述的方法,其中所述石油馏分包含沸点高于约340℃的至少一种组分。
22.如权利要求21所述的方法,其中所述石油馏分还包括选自未脱沥青的石油残渣、脱沥青的石油残渣、焦油砂沥青、页岩油和煤液中的至少一种组分。
23.如权利要求18所述的方法,其中所述相对轻质的烃产物包括选自沸点范围为150℃至400℃的中间馏分组分、柴油和润滑油基础油中的组分。
24.如权利要求17所述的方法,其中通过加氢异构化来实现烃组分的转化,反应条件包括:温度为约150℃至约500℃,压力为约1巴至约240巴,LHSV为约0.1至约20。
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BR0013787B1 (pt) * | 1999-09-07 | 2010-11-16 | processo para produção de um óxido inorgánico que contenha micro e mesoporos. |
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2005
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- 2005-09-07 KR KR1020077007191A patent/KR20070073758A/ko not_active Application Discontinuation
- 2005-09-07 JP JP2007530469A patent/JP2008512231A/ja active Pending
- 2005-09-07 WO PCT/US2005/031668 patent/WO2006029137A2/en active Application Filing
- 2005-09-07 BR BRPI0514985-1A patent/BRPI0514985A/pt not_active Application Discontinuation
- 2005-09-07 CN CNA2005800341486A patent/CN101035618A/zh active Pending
- 2005-09-07 RU RU2007112928/04A patent/RU2362623C2/ru not_active IP Right Cessation
- 2005-09-07 EP EP05797636A patent/EP1791640A2/en not_active Withdrawn
- 2005-09-07 CA CA002579228A patent/CA2579228A1/en not_active Abandoned
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2007
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Also Published As
Publication number | Publication date |
---|---|
IN2007MU00366A (zh) | 2007-07-20 |
CA2579228A1 (en) | 2006-03-16 |
RU2007112928A (ru) | 2008-10-20 |
KR20070073758A (ko) | 2007-07-10 |
WO2006029137A3 (en) | 2006-04-20 |
EP1791640A2 (en) | 2007-06-06 |
JP2008512231A (ja) | 2008-04-24 |
WO2006029137A2 (en) | 2006-03-16 |
BRPI0514985A (pt) | 2008-07-01 |
IL181780A0 (en) | 2007-07-04 |
RU2362623C2 (ru) | 2009-07-27 |
SG155886A1 (en) | 2009-10-29 |
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