CN115231590A - B-euo/mtw共结晶分子筛及其制备方法和应用 - Google Patents
B-euo/mtw共结晶分子筛及其制备方法和应用 Download PDFInfo
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- CN115231590A CN115231590A CN202110463072.XA CN202110463072A CN115231590A CN 115231590 A CN115231590 A CN 115231590A CN 202110463072 A CN202110463072 A CN 202110463072A CN 115231590 A CN115231590 A CN 115231590A
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- molecular sieve
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- mtw
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 122
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- 239000010703 silicon Substances 0.000 claims description 16
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- AMGNHZVUZWILSB-UHFFFAOYSA-N 1,2-bis(2-chloroethylsulfanyl)ethane Chemical compound ClCCSCCSCCCl AMGNHZVUZWILSB-UHFFFAOYSA-N 0.000 claims description 6
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- 229910001414 potassium ion Inorganic materials 0.000 claims description 6
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- 238000002156 mixing Methods 0.000 claims description 4
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- NEUNOKQNYOCZNP-UHFFFAOYSA-N benzyl-(2-hydroxyethyl)-dimethylazanium Chemical compound OCC[N+](C)(C)CC1=CC=CC=C1 NEUNOKQNYOCZNP-UHFFFAOYSA-N 0.000 claims description 2
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- 238000003756 stirring Methods 0.000 description 22
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 12
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
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- 239000004809 Teflon Substances 0.000 description 2
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- 239000002253 acid Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 239000013078 crystal Substances 0.000 description 2
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- 238000011068 loading method Methods 0.000 description 2
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- 229920000515 polycarbonate Polymers 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
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- 239000007858 starting material Substances 0.000 description 2
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
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- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
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- 238000002050 diffraction method Methods 0.000 description 1
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- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229960002413 ferric citrate Drugs 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
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- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- NXKAMHRHVYEHER-UHFFFAOYSA-J hafnium(4+);disulfate Chemical compound [Hf+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NXKAMHRHVYEHER-UHFFFAOYSA-J 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
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- 238000005342 ion exchange Methods 0.000 description 1
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- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
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- 239000000320 mechanical mixture Substances 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- GYLUMIIRFKDCKI-UHFFFAOYSA-L trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;dihydroxide Chemical compound [OH-].[OH-].C[N+](C)(C)CCCCCC[N+](C)(C)C GYLUMIIRFKDCKI-UHFFFAOYSA-L 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Images
Classifications
-
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Abstract
本发明涉及一种B‑EUO/MTW共结晶分子筛及其制备方法和应用。所述B‑EUO/MTW共结晶分子筛具有如式“SiO2·1/x B2O3·m MOz/2”所示的示意性化学组成,其中,SiO2与B2O3的摩尔比20≤x≤150,M为骨架平衡阳离子,M/Si摩尔比0<m≤1,z为M元素的化合价,z=1~7。该共结晶分子筛具有B‑EUO和MTW分子筛两种物相,两种分子筛在共晶中的相对比例可在1%~99%的范围内进行调节。该共晶分子筛可用作吸附剂或催化剂组分。
Description
技术领域
本发明涉及分子筛领域,具体涉及一种B-EUO/MTW共结晶分子筛及其制备方法和应用。
背景技术
沸石分子筛是一类多孔的结晶材料,具有规整的分子尺寸孔道结构、较强的酸性和高的水热稳定性,被广泛应用于催化、吸附和离子交换等领域中,并起着不可替代的作用。
EUO分子筛是一种中孔高硅分子筛,具有一维网状微孔孔道结构,含有十元环直通孔道(孔口直径为0.54×0.41nm)及与之垂直联通的十二元环侧袋(开口尺寸为0.68×0.58nm,深度为0.81nm)结构。由于孔道的特殊性,EUO分子筛在二甲苯异构,直链烷烃异构化,加氢脱蜡等反应中表现出优异的催化性能,具有良好的工业应用前景。MTW分子筛是一种大孔高硅分子筛,具有一维十二元环直孔道,孔径为0.56nm×0.60nm,具有高抗酸性、良好的热稳定性和水热稳定性,对烃类裂解、异构化、脱水和重整等诸多反应具有良好的催化性能。
EUO结构分子筛包括如EP 0042226A1公开的EU-l、EP 0051318A1公开的TPZ-3和US4640829A1公开的ZSM-50等;MTW结构分子筛包括如US 3832449A1所公开的ZSM-12、EP0059059A1所公开的NU-13、EP 0162719A1所公开的Theta-3和US 4557919A1所公开的TPZ-12等。
共结晶分子筛指的是由两种或多种分子筛形成的共结晶,或具有两种或多种分子筛结构特征的复合晶体,该类分子筛往往具有不同于单种分子筛或者对应分子筛机械混合物的性质。由于共晶分子筛具有多重结构和叠加功能,避免了单一孔道结构体系的缺陷,在分子吸附和扩散方面具有很大优势,在炼油催化领域具有广泛的应用前景。常见的共结晶分子筛如CN 1137022A所公开的ZSM-5/ZSM-11、Micropro.Mesopro.Mater.,2009,121,166-172所公开的MCM-49/ZSM-35以及Chin.J Catal.,2006,27:228-232所公开的BEA/MOR等。
传统合成共晶分子筛的方法是同时加入合成共晶两相分子筛的模板剂,即“双模板剂法”。但是,两种模板剂同时存在于合成凝胶中时存在竞争关系,不利于两相比例的调控。因此,发展单一模板剂法合成两相比例可调控的共晶分子筛是十分重要的。
发明内容
本发明目的在于提供一种B-EUO/MTW共结晶分子筛及其制备方法和应用。该共结晶分子筛中B-EUO、MTW两种分子筛的相对比例可在1%~99%的范围内调节,制备方法简单。
本发明采取的技术方案如下:
本发明第一方面提供了一种B-EUO/MTW共结晶分子筛,所述B-EUO/MTW共结晶分子筛具有如式“SiO2·1/x B2O3·m MOz/2”所示的示意性化学组成,其中,SiO2与B2O3的摩尔比20≤x≤150,M为骨架平衡阳离子,M/Si摩尔比0<m≤1,z为M元素的化合价,z=1~7,优选z=1~2。
进一步地,所述B-EUO/MTW共结晶分子筛的示意性化学组成中SiO2与B2O3的摩尔比优选为31≤x≤80,M为骨架平衡阳离子,M/Si摩尔比优选为0.01≤m≤0.4。
所述B-EUO/MTW共结晶分子筛X射线衍射图谱中包括如下表所示的X射线衍射峰:
进一步地,所述B-EUO/MTW共结晶分子筛中,B-EUO分子筛的重量百分含量为1%~99%,MTW分子筛的重量百分含量为1%~99%;优选B-EUO分子筛的重量百分含量为5%~95%,MTW分子筛的重量百分含量为5%~95%。
进一步地,所述骨架平衡阳离子M选自氢离子、铵根离子、钠离子、钾离子、锂离子、铷离子、铯离子、镁离子、钙离子、锶离子、钡离子中的至少一种,优选至少含有钠离子或至少含有钠离子和钾离子。
进一步地,所述B-EUO/MTW共结晶分子筛中不超过10wt%的Si原子被至少一种非硅四价骨架元素Y取代,所述Y选自锗、锡、钛、锆、铪中的至少一种。
进一步地,所述B-EUO/MTW共结晶分子筛中不超过20wt%的B原子被至少一种非硼三价骨架元素X取代,所述X选自铝、铁、镓、铟、铬中的至少一种。
本发明第二方面提供了一种上述B-EUO/MTW共结晶分子筛的制备方法,其制备过程为:将包含硅源、硼源、骨架平衡阳离子M源、有机模板剂Q和水混合,进行晶化反应,获得B-EUO/MTW共结晶分子筛的步骤。所述有机模板剂Q选自含苄基(2-羟乙基)二甲基铵鎓离子的物质,所述苄基(2-羟乙基)二甲基铵的结构式如下:
进一步地,所述有机模板剂Q、所述硅源(以SiO2计)、所述硼源(以B2O3计)、所述M源(以MOz/2计)和水的摩尔比为Q:SiO2:B2O3:MOz/2:H2O=0.06~0.85:1:0.0067~0.05:0.03~1.2:15~120,优选Q:SiO2:B2O3:MOz/2:H2O=0.16~0.5:1:0.0125~0.032:0.09~0.8:25~100;当B2O3:SiO2=0.025~0.05时,H2O/SiO2>65。
进一步地,所述硅源选自由水玻璃、硅溶胶、固体硅胶、气相白炭黑、无定形二氧化硅、硅藻土、沸石分子筛、四烷氧基硅烷组成的组中的至少一种。
进一步地,所述硼源选自由硼酸、四硼酸钠、无定形氧化硼、硼酸钾、偏硼酸钠、四硼酸铵、有机硼酯组成的组中的至少一种。
进一步地,所述骨架平衡阳离子M选自由氢离子、铵根离子、钠离子、钾离子、锂离子、铷离子、铯离子、镁离子、钙离子、锶离子、钡离子组成的组中的至少一种,优选钠离子和钾离子中的至少一种。
进一步地,所述B-EUO/MTW共结晶分子筛的制备方法中,可选择性地包括将非硅四价骨架元素Y源和/或非硼三价骨架元素X源与所述硅源、硼源、骨架平衡阳离子M源、有机模板剂Q和水混合,进行晶化反应,获得B-EUO/MTW共结晶分子筛的步骤。
进一步地,所述非硅四价骨架元素Y选自由锗、锡、钛、锆、铪、锌组成的组中的至少一种。
进一步地,所述Y源以相应的氧化物YO2计与所述硅源以SiO2计的摩尔比YO2/SiO2=0~0.1,优选0.01~0.09;其中所述锗源选自氧化锗、硝酸锗和四烷氧基锗中的至少一种;所述锡源选自四氯化锡、氯化亚锡、烷基锡、烷氧基锡和有机锡酸酯中的至少一种;所述钛源选自四烷基钛酸酯(如钛酸四甲酯、钛酸四乙酯、钛酸四丙酯、钛酸四正丁酯)、四氯化钛、六氟钛酸、硫酸钛以及它们的水解产物中的至少一种;所述锆源、铪源、锌源选自本领域的常规物质,如硝酸锆、氯氧化锆、硫酸铪、卤化锌、乙酸锌等。
进一步地,所述非硼三价骨架元素X选自由铝、铁、镓、铟、铬组成的组中的至少一种。
进一步地,所述X源以相应的氧化物X2O3计与所述硼源以B2O3计的摩尔比X2O3/B2O3=0~0.2,优选0.01~0.15;其中所述铝源选自硫酸铝、铝酸钠、硝酸铝、氯化铝、拟薄水铝石、氧化铝、氢氧化铝、硅铝沸石分子筛、碳酸铝、单质铝、异丙醇铝、乙酸铝中的至少一种;所述铁源选自硫酸铁、硝酸铁、卤化铁(如三氯化铁)、二茂铁、柠檬酸铁中的至少一种;所述镓源、铟源、铬源选自本领域的常规物质,如氧化镓、硝酸镓、氧化铟、硝酸铟、氯化铬、硝酸铬等。
进一步地,所述晶化条件包括在100~200℃晶化24~300小时;优选110~190℃晶化36~250小时。
进一步地,所述晶化反应结束后进行常规的后处理,如过滤、洗涤、干燥制得所述分子筛的步骤;和任选地,焙烧所述获得的分子筛的步骤。
本发明第三方面提供了一种分子筛组合物,包括按照前述任一方面所述的B-EUO/MTW共结晶分子筛或按照前述任一方面所述的方法制备的B-EUO/MTW共结晶分子筛。所述分子筛组合物中可以含有适量粘结剂。
本发明第四方面提供了一种按照前述任一方面所述的B-EUO/MTW共结晶分子筛、按照前述任一方面所述的方法制备的B-EUO/MTW共结晶分子筛、或者按照前述任一方面所述的B-EUO/MTW共结晶分子筛组合物作为吸附剂或催化剂组分的应用。
根据本发明,涉及的B-EUO/MTW共结晶分子筛及其制备方法,具有有机模板剂结构单一简单、B-EUO和MTW分子筛占该共结晶分子筛的重量百分比在1%~99%的范围内可调的特点。在对骨架中的Si、B元素进行部分取代后,还可以将Al、Ti、Zr、Fe等多种元素引入骨架中,产生不同的催化活性中心,满足不同催化反应的需要。
附图说明
图1为实施例1所获得样品的X射线衍射(XRD)图;
图2为实施例1所获得样品的扫描电子显微镜(SEM)照片;
图3为实施例2所获得样品的X射线衍射(XRD)图;
图4为实施例2所获得样品的扫描电子显微镜(SEM)照片;
图5为对比例1所获得样品的X射线衍射(XRD)图;
图6为对比例2所获得样品的X射线衍射(XRD)图。
具体实施方式
为了便于理解本发明,本发明列举如下实施例。但是本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应该视为对本发明的具体限制。
在本说明书的上下文中,分子筛的结构是由X-射线衍射谱图(XRD)确定的,所述分子筛的X-射线衍射谱图(XRD)由X-射线粉末衍射仪测定,使用Cu-Kα射线源,Kα1波长λ=1.5405980埃镍滤光片。
本发明中,采用的是荷兰帕纳科公司X’Pert PRO型X射线粉末衍射(XRD)仪,工作电压40kV,电流40mA,扫描范围5~40°。产物形貌采用日本HITACHI公司的S-4800型场发射扫描电镜(Fe-SEM)进行拍摄。
需要特别说明的是,在本说明书的上下文中公开的两个或多个方面(或实施方式)可以彼此任意组合,由此而形成的技术方案(比如方法或系统)属于本说明书原始公开内容的一部分,同时也落入本发明的保护范围之内。
在没有明确指明的情况下,本说明书内所提到的所有百分数、份数、比率等都是以重量为基准的,除非以重量为基准时不符合本领域技术人员的常规认识。
【实施例1】
将0.34g硼酸、1.35g氢氧化钠溶液(30wt%)、25g苄基(2-羟乙基)二甲基氢氧化铵溶液(20wt%)加入59g水中溶解,在搅拌下缓慢加入19g Ludox硅溶胶(SiO2 40wt%),继续在常温下搅拌1h,将上述混合物装入带有聚四氟乙烯内衬的晶化釜中,置于160℃烘箱中晶化144小时。反应后固体经过滤、用蒸馏水洗涤、100℃干燥后得到原粉B-EUO/MTW共结晶分子筛,将原粉固体置于马弗炉中在550℃温度下焙烧5小时得到最终产品,其中B-EUO分子筛含量为55%。最终产品的XRD图谱如图1所示,谱图数据如表1所示,SEM照片如图2所示,合成该分子筛的原料组成见表4。
表1
【实施例2】
将0.3g硼酸、3.5g氢氧化钠溶液(30wt%)、37g苄基(2-羟乙基)二甲基氢氧化铵溶液(20wt%)加入30g水中溶解,在搅拌下缓慢加入25g Ludox硅溶胶(SiO2 40wt%),继续在常温下搅拌1h,将上述混合物装入带有聚四氟乙烯内衬的晶化釜中,置于155℃烘箱中晶化168小时。反应后固体经过滤、洗涤、干燥、焙烧后得到B-EUO/MTW共结晶分子筛,其中B-EUO分子筛含量为10%。产品的XRD图谱如图3所示,谱图数据如表2所示,SEM照片如图4所示,合成该分子筛的原料组成见表4。
表2
【实施例3】
将0.42g硼酸、1.5g氢氧化钠溶液(30wt%)、19g苄基(2-羟乙基)二甲基氢氧化铵溶液(20wt%)加入100g水中溶解,在搅拌下缓慢加入16g Ludox硅溶胶(SiO2 40wt%),继续在常温下搅拌1h,将上述混合物装入带有聚四氟乙烯内衬的晶化釜中,置于165℃烘箱中晶化120小时。反应后固体经过滤、洗涤、干燥、焙烧后得到B-EUO/MTW共结晶分子筛,其中B-EUO分子筛含量为90%。合成该分子筛的原料组成见表4,产品的XRD谱图数据如表3所示:
表3
【实施例4】
将0.4g硼酸、0.6g氢氧化钠溶液(30wt%)、0.9g氢氧化钾溶液(30wt%)、29g苄基(2-羟乙基)二甲基氢氧化铵溶液(20wt%)加入64g水中溶解,在搅拌下缓慢加入21g Ludox硅溶胶(SiO2 40wt%),继续在常温下搅拌1h,将上述混合物装入带有聚四氟乙烯内衬的晶化釜中,置于160℃烘箱中晶化168小时。反应后固体经过滤、洗涤、干燥、焙烧后得到B-EUO/MTW共结晶分子筛,具有与图1相似的XRD图谱。其中B-EUO分子筛含量为65%,合成该分子筛的原料组成见表4。
【实施例5】
将0.62g硼酸、7g氢氧化钾溶液(30wt%)、49.3g苄基(2-羟乙基)二甲基氢氧化铵溶液(20wt%)加入117g水中溶解,在搅拌下缓慢加入37.5g Ludox硅溶胶(SiO2 40wt%),继续在常温下搅拌1h,将上述混合物装入带有聚四氟乙烯内衬的晶化釜中,置于170℃烘箱中晶化192小时。反应后固体经过滤、洗涤、干燥、焙烧后得到B-EUO/MTW共结晶分子筛,具有与图1相似的XRD图谱。其中B-EUO分子筛含量为35%,合成该分子筛的原料组成见表4。
【实施例6】
将0.45g硼酸、2.5g氢氧化钠溶液(30wt%)、51g苄基(2-羟乙基)二甲基氢氧化铵溶液(20wt%)加入90g水中溶解,在搅拌下缓慢加入13g发烟硅胶(SiO2 95wt%),继续在常温下搅拌1h,将上述混合物装入带有聚四氟乙烯内衬的晶化釜中,置于150℃烘箱中晶化96小时。反应后固体经过滤、洗涤、干燥、焙烧后得到B-EUO/MTW共结晶分子筛,具有与图1相似的XRD图谱。其中B-EUO分子筛含量为25%,合成该分子筛的原料组成见表4。
【实施例7】
将0.33g硼酸、1.2g氢氧化钠溶液(30wt%)、22g苄基(2-羟乙基)二甲基氢氧化铵溶液(20wt%)加入90g水中溶解,在搅拌下加入0.11g USY分子筛(SiO2/Al2O3=12),继续搅拌30min后缓慢加入16g Ludox硅溶胶(SiO2 40wt%),继续在常温下搅拌1h,将上述混合物装入带有聚四氟乙烯内衬的晶化釜中,置于175℃烘箱中晶化204小时。反应后固体经过滤、洗涤、干燥、焙烧后得到B-EUO/MTW共结晶分子筛,具有与图1相似的XRD图谱。其中B-EUO分子筛含量为80%,合成该分子筛的原料组成见表4。
【实施例8】
将0.32g硼酸、0.3g九水硝酸铁、0.9g氢氧化钠溶液(30wt%)、22g苄基(2-羟乙基)二甲基氢氧化铵溶液(20wt%)加入80g水中溶解,在搅拌缓慢加入16g Ludox AS-40硅溶胶(SiO2 40wt%),继续在常温下搅拌1h,将上述混合物装入带有聚四氟乙烯内衬的晶化釜中,置于165℃烘箱中晶化168小时。反应后固体经过滤、洗涤、干燥、焙烧后得到B-EUO/MTW共结晶分子筛,具有与图1相似的XRD图谱。其中B-EUO分子筛含量为70%,合成该分子筛的原料组成见表4。
【实施例9】
将0.36g硼酸、1.1g硫酸钛、1.35g氢氧化钠溶液(30wt%)、30g苄基(2-羟乙基)二甲基氢氧化铵溶液(20wt%)加入50g水中溶解,在搅拌下缓慢加入20g Ludox硅溶胶(SiO240wt%),继续在常温下搅拌1h,将上述混合物装入带有聚四氟乙烯内衬的晶化釜中,置于160℃烘箱中晶化144小时。反应后固体经过滤、洗涤、干燥、焙烧后得到B-EUO/MTW共结晶分子筛,具有与图1相似的XRD图谱。其中B-EUO分子筛含量为50%,合成该分子筛的原料组成见表4。
【对比例1】
将0.34g硼酸、1.35g氢氧化钠溶液(30wt%)、24g氢氧化六甲双铵模板剂溶液(25wt%)加入61g水中溶解,在搅拌下缓慢加入19g Ludox硅溶胶(SiO2 40wt%),继续在常温下搅拌1h,将上述混合物装入带有聚四氟乙烯内衬的晶化釜中,置于160℃烘箱中晶化144小时。反应后固体经过滤、洗涤、干燥、焙烧后得到无定形物,XRD图谱如图5所示,未能合成出B-EUO分子筛。合成该分子筛的原料组成见表4。
【对比例2】
将0.34g硼酸、1.35g氢氧化钠溶液(30wt%)、9.2g四甲基氢氧化铵溶液(25wt%)加入72g水中溶解,在搅拌下缓慢加入19g Ludox硅溶胶(SiO2 40wt%),继续在常温下搅拌1h,将上述混合物装入带有聚四氟乙烯内衬的晶化釜中,置于160℃烘箱中晶化144小时。反应后固体经过滤、洗涤、干燥、焙烧后得到RUT分子筛,XRD图谱如图6所示,未能合成出B-EUO分子筛。合成该分子筛的原料组成见表4。
表4实施例及对比例分子筛原料摩尔比组成
项目 | SiO<sub>2</sub>/B<sub>2</sub>O<sub>3</sub> | Q/SiO<sub>2</sub> | M/Si | H<sub>2</sub>O/SiO<sub>2</sub> | YO<sub>2</sub>/SiO<sub>2</sub> | X<sub>2</sub>O<sub>3</sub>/B<sub>2</sub>O<sub>3</sub> |
实施例1 | 46.0 | 0.20 | 0.08 | 40.1 | 0 | 0 |
实施例2 | 68.7 | 0.23 | 0.16 | 25.8 | 0 | 0 |
实施例3 | 31.4 | 0.18 | 0.11 | 65.6 | 0 | 0 |
实施例4 | 43.3 | 0.21 | 0.07 | 40.0 | 0 | 0 |
实施例5 | 49.8 | 0.20 | 0.15 | 40.8 | 0 | 0 |
实施例6 | 56.5 | 0.25 | 0.09 | 35.8 | 0 | 0 |
实施例7 | 40.6 | 0.21 | 0.08 | 60.6 | 0 | 0.05 |
实施例8 | 41.2 | 0.21 | 0.06 | 56.2 | 0 | 0.14 |
实施例9 | 45.8 | 0.23 | 0.08 | 36.3 | 0.04 | 0 |
对比例1 | 46.0 | 0.20 | 0.08 | 40.1 | 0 | 0 |
对比例2 | 46.0 | 0.20 | 0.08 | 40.1 | 0 | 0 |
Claims (14)
1.一种B-EUO/MTW共结晶分子筛,其特征在于,所述B-EUO/MTW共结晶分子筛具有如式“SiO2·1/x B2O3·m MOz/2”所示的示意性化学组成,其中,SiO2与B2O3的摩尔比20≤x≤150,M为骨架平衡阳离子,M/Si摩尔比0<m≤1,z为M元素的化合价,z=1~7,优选z=1~2。
2.根据权利要求1所述B-EUO/MTW共结晶分子筛,其特征在于,所述示意性化学组成中SiO2与B2O3的摩尔比为31≤x≤80,M为骨架平衡阳离子,M/Si摩尔比为0.01≤m≤0.4。
4.根据权利要求1所述B-EUO/MTW共结晶分子筛,其特征在于,所述B-EUO/MTW共结晶分子筛中,B-EUO分子筛的重量百分含量为1%~99%,MTW分子筛的重量百分含量为1%~99%;优选B-EUO分子筛的重量百分含量为5%~95%,MTW分子筛的重量百分含量为5%~95%。
5.根据权利要求1所述B-EUO/MTW共结晶分子筛,其特征在于,所述骨架平衡阳离子M选自氢离子、铵根离子、钠离子、钾离子、锂离子、铷离子、铯离子、镁离子、钙离子、锶离子、钡离子中的至少一种,优选至少含有钠离子或至少含有钠离子和钾离子。
6.根据权利要求1所述B-EUO/MTW共结晶分子筛,其特征在于,所述B-EUO/MTW共结晶分子筛中不超过10wt%的Si原子被至少一种非硅四价骨架元素Y取代,所述Y选自锗、锡、钛、锆、铪中的至少一种。
7.根据权利要求1或6所述B-EUO/MTW共结晶分子筛,其特征在于,所述B-EUO/MTW共结晶分子筛中不超过20wt%的B原子被至少一种非硼三价骨架元素X取代,所述X选自铝、铁、镓、铟、铬中的至少一种。
9.根据权利要求8所述的制备方法,其特征在于,所述有机模板剂Q、所述硅源、所述硼源、所述M源和水的摩尔比为Q:SiO2:B2O3:MOz/2:H2O=0.06~0.85:1:0.0067~0.05:0.03~1.2:15~120,优选Q:SiO2:B2O3:MOz/2:H2O=0.16~0.5:1:0.0125~0.032:0.09~0.8:25~100;当B2O3:SiO2=0.025~0.05时,H2O/SiO2>65。
10.根据权利要求8所述的制备方法,其特征在于,所述B-EUO/MTW共结晶分子筛的制备方法中,可选择性地包括将非硅四价骨架元素Y源和/或非硼三价骨架元素X源与所述硅源、硼源、骨架平衡阳离子M源、有机模板剂Q和水混合,进行晶化反应,获得B-EUO/MTW共结晶分子筛的步骤。
11.根据权利要求10所述的制备方法,其特征在于,所述Y源以相应的氧化物YO2计与所述硅源以SiO2计的摩尔比YO2/SiO2=0~0.1,优选0.01~0.09。
12.根据权利要求10所述的制备方法,其特征在于,所述X源以相应的氧化物X2O3计与所述硼源以B2O3计的摩尔比X2O3/B2O3=0~0.2,优选0.01~0.15。
13.一种分子筛组合物,其特征在于,包括按照前述权利要求1-7任一项所述B-EUO/MTW共结晶分子筛,或者按照权利要求8-12任一项所述制备方法所制备的B-EUO/MTW共结晶分子筛以及粘结剂。
14.一种按照前述权利要求1-7任一项所述B-EUO/MTW共结晶分子筛,或者按照权利要求8-12任一项所述制备方法所制备的B-EUO/MTW共结晶分子筛,或者按照权利要求13所述的分子筛组合物作为吸附剂或催化剂组分的应用。
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US20100179361A1 (en) * | 2008-08-14 | 2010-07-15 | Ifp | Zeolitic Catalysts, Their Process for Preparation and their Applications |
CN101519216A (zh) * | 2009-03-26 | 2009-09-02 | 上海大学 | 一种含硼分子筛的合成方法 |
CN102740968A (zh) * | 2009-11-27 | 2012-10-17 | 巴斯夫欧洲公司 | 制备钛沸石催化剂的方法 |
CN103270140A (zh) * | 2010-12-22 | 2013-08-28 | Ifp新能源公司 | 使用困在介孔结构化氧化物载体中的基于杂多阴离子的催化剂对烃馏分进行加氢裂化的方法 |
CN103183354A (zh) * | 2011-12-31 | 2013-07-03 | 上海欣年石化助剂有限公司 | 一种制备 euo 结构沸石的方法 |
CN104379257A (zh) * | 2012-06-18 | 2015-02-25 | 埃克森美孚化学专利公司 | 具有euo骨架类型的结晶分子筛的合成 |
US20180111836A1 (en) * | 2016-10-24 | 2018-04-26 | Chevron U.S.A. Inc. | Synthesis of mtw framework type molecular sieves |
CN112209403A (zh) * | 2019-07-09 | 2021-01-12 | 中国石油化工股份有限公司 | Scm-25/mfi共结晶分子筛、其制备方法及其用途 |
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