CN108097293B - 锡掺杂的mfi结构沸石分子筛的合成方法和应用 - Google Patents
锡掺杂的mfi结构沸石分子筛的合成方法和应用 Download PDFInfo
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 38
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 20
- 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 20
- 239000010457 zeolite Substances 0.000 title claims abstract description 20
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000001509 sodium citrate Substances 0.000 claims abstract description 13
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 13
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
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- 239000012467 final product Substances 0.000 claims abstract description 8
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- 238000000967 suction filtration Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 229910021485 fumed silica Inorganic materials 0.000 claims description 8
- OVBJJZOQPCKUOR-UHFFFAOYSA-L EDTA disodium salt dihydrate Chemical compound O.O.[Na+].[Na+].[O-]C(=O)C[NH+](CC([O-])=O)CC[NH+](CC([O-])=O)CC([O-])=O OVBJJZOQPCKUOR-UHFFFAOYSA-L 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052710 silicon Inorganic materials 0.000 abstract description 11
- 239000010703 silicon Substances 0.000 abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 7
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 abstract description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 abstract description 5
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 abstract description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 2
- 239000010935 stainless steel Substances 0.000 abstract description 2
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- 150000007517 lewis acids Chemical class 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
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- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000007848 Bronsted acid Substances 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229960001484 edetic acid Drugs 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 description 3
- 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 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
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- 239000011268 mixed slurry Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 239000002028 Biomass Substances 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
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000008139 complexing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940120503 dihydroxyacetone Drugs 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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Abstract
本发明涉及一种锡掺杂的MFI结构沸石分子筛的合成方法和应用。合成方法为依次将硅源,氢氧化钠,四丙基氢氧化铵,水,铝源混合搅拌均匀形成凝胶状,再将乙二胺四乙酸二钠和柠檬酸钠与可溶性锡盐的水溶液的混合液加入上述凝胶中,充分搅拌后,转入不锈钢聚四氟乙烯水热高压反应釜中,在恒温烘箱中晶化数天后,自然冷却至室温,抽滤,去离子水洗涤三次,在80℃恒温干燥箱中干燥12‑16小时,然后在550‑600℃马弗炉中焙烧4‑6h,再利用质量分数为6%的NH4Cl溶液交换三次,再在550‑600℃马弗炉中焙烧4‑6h即得到最终产品。本发明可以制得结晶度高,形貌规整的Sn‑MFI和Sn‑Al‑MFI沸石分子筛。该方法制备工艺简单,重复性好,易于大规模应用。
Description
技术领域
本发明涉及一种锡掺杂的MFI结构沸石分子筛的合成方法和应用,具体为Sn-MFI结构沸石分子筛的合成方法和应用。通过水热法一步合成将Sn的物种分布于分子筛的结构中,可用于MFI结构分子筛中Sn物种的构建和多相催化应用,属于分子筛合成领域。
背景技术
近年来,路易斯酸沸石分子筛催化剂由于其在一些酸催化反应中展现出独特优异的催化性能而受到人们的广泛关注。目前对于其制备主要是通过后合成的方式进行,首先将传统的含铝的沸石分子筛(如Beta,ZSM-5,MOR等)利用浓硝酸进行脱铝,然后通过原子种植的方式将高价态的金属如Ti,Zr,Hf和Sn等后补于脱铝后的分子筛留下的缺陷位上,而得到具有路易斯酸的分子筛而应用于一些特定的催化反应,然而该方法需要使用大量的浓硝酸,后期处理过程复杂且对环境造成较大污染,因此该方法不利于大规模推广;另外现有的一步水热直接制备过程中需要引入F-作为矿化剂而促进分子筛的晶化得到路易斯酸分子筛,但由于F-的大量排放引起水体的富营养化而限制了该方法的使用。因此,开发具有制备工艺简单,成本低廉的路易斯酸分子筛催化剂具有重要的现实意义。由于Sn掺杂的MFI结构分子筛对一些生物质分子如二羟基丙酮等转化高附加值的乳酸或乳酸酯的过程展现出了良好的催化活性而被人们所关注,因此开发具有制备过程简单,重现性好,且易于实现的高催化活性的路易斯酸Sn-MFI分子筛的制备方法具有非常重要的应用价值。同时,在一些典型的催化过程中,往往需要布朗斯特酸(Bronsted酸)和路易斯酸(Lewis酸)的协调催化,因此开发具有Bronsted酸和Lewis酸共存的双功能沸石分子筛催化剂也具有重要的现实意义。
发明内容
本发明的目的在于提供一种锡掺杂的MFI结构沸石分子筛的合成方法和应用。该含Sn的Sn-MFI结构沸石分子筛是通过水热合成法一步将金属Sn(IV)引入到MFI结构分子筛的中,合成工艺简单,晶化时间短,得到样品的结晶度高,易于工业化应用。
本发明提供的锡掺杂的MFI结构沸石分子筛是以可溶性锡盐、乙二胺四乙酸二钠、柠檬酸钠、铝源和硅源为原料通过水热法一步合成,Sn-MFI结构沸石分子筛催化剂中Sn含量为0.1-5%。
具体合成方法包括的步骤:依次将硅源,氢氧化钠,四丙基氢氧化铵水溶液(TPAOH,质量百分含量为30%),水,铝源混合搅拌均匀形成凝胶状,再将乙二胺四乙酸二钠和柠檬酸钠的水溶液与可溶性锡盐的水溶液的混合液加入上述凝胶中,充分搅拌后,转入不锈钢聚四氟乙烯水热高压反应釜中,在恒温烘箱中晶化后,自然冷却至室温,抽滤,水洗,干燥,然后在550-600℃马弗炉中焙烧4-6h,用NH4Cl溶液交换三次,再在550-600℃马弗炉中焙烧。
本发明提供的锡掺杂的MFI结构沸石分子筛的具体合成方法包括的步骤:
1)将硅源,氢氧化钠,四丙基氢氧化铵和水混合均匀,搅拌1-3h,然后再加入铝源溶液,搅拌2-3h,然后再将乙二胺四乙酸二钠和柠檬酸钠固体与可溶于水的锡盐与水的混合液加入上述混合浆液中,继续搅拌1-2h,得到混合浆液。
2)将上述浆液装入聚四氟乙烯水热反应釜中,晶化2-15天,然后冷却至室温,抽滤,去离子水洗涤三次,80℃干燥12-16小时,在550-600℃马弗炉中焙烧4-6h。
3)将上述焙烧得到的样品,利用质量分数为4-6%的NH4Cl溶液交换三次,然后550-600℃马弗炉中焙烧4-6h进而得到最终产品。
步骤1) 中所述的可溶性锡盐为五水合四氯化锡或乙酰丙酮锡;硅源为硅溶胶、正硅酸乙酯,气相二氧化硅,水玻璃,和硅酸钠中的任意一种;硅源优选为气相二氧化硅;铝源为偏铝酸钠、异丙醇铝、硝酸铝和硫酸铝中的任意一种;铝源优选为硝酸铝;乙二胺四乙酸二钠为络合剂,柠檬酸钠为配合缓冲剂,四丙基氢氧化铵为结构导向剂。
其中,Sn4+与乙二胺四乙酸二钠络合,Sn4+与乙二胺四乙酸二钠的摩尔比为:1:0.5-10,Sn4+与柠檬酸钠的摩尔比为:1:1-10。
步骤1) 中的物料的物质的量配比为:H2O:SiO2=10-1000;Sn:SiO2=0.01-0.2;NaOH:SiO2=0.05-2;TPAOH:SiO2=0.1-1;Al:SiO2=0.0-0.5。步骤1) 的搅拌温度为25℃-80℃。
步骤2)所述的晶化温度为80-200℃。
本发明提供了锡掺杂的MFI结构沸石分子筛,该骨架含Sn的Sn-MFI沸石分子筛是通过水热合成法一步将金属Sn盐的络合物加入到MFI结构分子筛的合成体系中,得到分子筛结构中含Sn的Sn-MFI结构沸石分子筛催化剂。本发明是无大颗粒Sn金属氧化物的聚集体。将Sn物种引入MFI沸石分子筛的结构中,合成工艺步骤简单,样品的结晶度高,XRD显示合成产物均为MFI型结构的分子筛,结晶度良好。SEM结果显示样品均为椭球形的颗粒100nm左右的球形小颗粒,易于工业化应用。
附图说明
图1:实施例1-5所得样品的XRD图。
图2:实例4中样品3% Sn-MFI(Si/Al=160)的扫描电镜图。
具体实施方式
下面结合具体实施例,进一步详细阐述本发明,但本发明的保护范围并不限于此。实施例中未注明具体条件的实验方法,通常按照常规条件以及手册中所述的条件,或按照制造厂商所建议的条件;所用的通用设备、材料、试剂等,如无特殊说明,均可从商业途径得到。
实施例1:利用气相二氧化硅为硅源合成Sn含量为2%的Sn-MFI样品Si/Al=∞
首先将0.60g氢氧化钠,17.50g四丙基氢氧化铵,5.20g气相二氧化硅和10ml去离子水混合在一起,在50℃下搅拌4h后,将0.35g二水合乙二胺四乙酸二钠,0.30g的柠檬酸钠,0.30g五水合四氯化锡和30ml去离子水的溶液滴加入上述混合液中,再继续搅拌4h,转入聚四氟乙烯反应釜中,在200℃恒温烘箱中晶化3d,然后自然冷却至室温,抽滤,去离子水洗涤三次后,置于80℃恒温干燥箱中干燥24h,在550℃马弗炉中焙烧6h后,再利用质量分数为6%的NH4Cl溶液交换3次,在80℃恒温干燥箱中干燥24h,再置于550℃马弗炉中焙烧6h即得到最终产品。
附图1中a为该样品的XRD,可以看出样品展示出了典型的MFI结构的分子筛的特征衍射峰,具有较高的结晶度。
实施例2:利用气相二氧化硅为硅源制备Sn含量为3%的Sn-MFI样品Si/Al=∞
首先将0.80g氢氧化钠,17.50g四丙基氢氧化铵,5.20g气相二氧化硅和10ml去离子水混合在一起,在50℃下搅拌4h后,将0.50g二水合乙二胺四乙酸二钠,0.80g的柠檬酸钠,0.48g五水合四氯化锡和30ml去离子水的溶液滴加入上述混合液中,再继续搅拌4h,转入聚四氟乙烯反应釜中,在200℃恒温烘箱中晶化3d,然后自然冷却至室温,抽滤,去离子水洗涤三次后,置于80℃恒温干燥箱中干燥24h,在550℃马弗炉中焙烧6h后,再利用质量分数为6%的NH4Cl溶液交换3次,在80℃恒温干燥箱中干燥24h,再置于550℃马弗炉中焙烧6h即得到最终产品。
附图1中b为该样品的XRD,可以看出样品展示出了典型的MFI结构的分子筛的特征衍射峰,具有较高的结晶度。
实施例3:利用硅酸钠为硅源合成Sn含量为2%的Sn-MFI样品Si/Al=∞
首先将0.80g氢氧化钠,17.50g四丙基氢氧化铵,4.6g九水合硅酸钠和10ml去离子水混合在一起,在50℃下搅拌4h后,将0.45g二水合乙二胺四乙酸二钠,0.40g的柠檬酸钠,0.35g五水合四氯化锡和25ml去离子水的溶液滴加入上述混合液中,再继续搅拌4h,转入聚四氟乙烯反应釜中,在200℃恒温烘箱中晶化3d,然后自然冷却至室温,抽滤,去离子水洗涤三次后,置于80℃恒温干燥箱中干燥24h,在550℃马弗炉中焙烧6h后,再利用质量分数为6%的NH4Cl溶液交换3次,在80℃恒温干燥箱中干燥24h,再置于550℃马弗炉中焙烧6h即得到最终产品。
附图1中c为该样品的XRD,可以看出样品展示出了典型的MFI结构的分子筛的特征衍射峰,具有较高的结晶度。
实施例4:利用气相二氧化硅为硅源制备Si/Al=160(Si和Al的摩尔质量比),Sn含量为3%的Sn-MFI样品
首先将0.80g氢氧化钠,17.50g四丙基氢氧化铵,5.20g气相二氧化硅和10ml去离子水混合在一起,在50℃下搅拌4h后,将0.25g的九水合硝酸铝和10ml去离子水的溶液加入上述混合液中,搅拌2h后,将0.50g二水合乙二胺四乙酸二钠,0.80g的柠檬酸钠,0.48g五水合四氯化锡和20ml去离子水的溶液滴加入上述混合液中,再继续搅拌4h,转入聚四氟乙烯反应釜中,在200℃恒温烘箱中晶化3.5d,然后自然冷却至室温,抽滤,去离子水洗涤三次后,置于80℃恒温干燥箱中干燥24h,在550℃马弗炉中焙烧6h后,再利用质量分数为6%的NH4Cl溶液交换3次,在80℃恒温干燥箱中干燥24h,再置于550℃马弗炉中焙烧6h即得到最终产品。
附图1中d为该样品的XRD,可以看出样品展示出了典型的MFI结构的分子筛的特征衍射峰,具有较高的结晶度。附图2为其扫描电镜图,合成的样品为100 nm左右的小颗粒。
实施例5:选择正硅酸四乙酯为硅源合成Si/Al=80,Sn含量为2%的Sn-MFI样品
首先将0.30g氢氧化钠,17.50g四丙基氢氧化铵,18.0g正硅酸四乙酯和10ml去离子水混合在一起,在60℃下搅拌4h后,将0.50g的九水合硝酸铝和10ml去离子水的溶液加入上述混合液中,搅拌2h后,将0.50g二水合乙二胺四乙酸二钠,0.80g的柠檬酸钠,0.48g五水合四氯化锡和20ml去离子水的溶液滴加入上述混合液中,再继续搅拌4h,转入聚四氟乙烯反应釜中,在200℃恒温烘箱中晶化3.5d,然后自然冷却至室温,抽滤,去离子水洗涤三次后,置于80℃恒温干燥箱中干燥24h,在550℃马弗炉中焙烧6h后,再利用质量分数为6%的NH4Cl溶液交换3次,在80℃恒温干燥箱中干燥24h,再置于550℃马弗炉中焙烧6h即得到最终产品。
附图1中e为该样品的XRD,可以看出样品展示出了典型的MFI结构的分子筛的特征衍射峰,具有较高的结晶度。
Claims (1)
1.一种锡掺杂的MFI结构沸石分子筛的合成方法,其特征在于经过如下的步骤:
1)首先将0.80g氢氧化钠,17.50g四丙基氢氧化铵,5.20g气相二氧化硅和10ml去离子水混合在一起,在50℃下搅拌4h;
2)将0.25g的九水合硝酸铝和10ml去离子水的溶液加入上述混合液中,搅拌2h;
3)将0.50g二水合乙二胺四乙酸二钠,0.80g的柠檬酸钠,0.48g五水合四氯化锡和20ml去离子水的溶液滴加入上述混合液中,再继续搅拌4h;
4)转入聚四氟乙烯反应釜中,在200℃恒温烘箱中晶化3.5d,然后自然冷却至室温;
5)抽滤,去离子水洗涤三次后,置于80℃恒温干燥箱中干燥24h,在550℃马弗炉中焙烧6h;
6)再利用质量分数为6%的NH4Cl溶液交换3次,在80℃恒温干燥箱中干燥24h;
7)再置于550℃马弗炉中焙烧6h即得到最终锡掺杂的MFI结构沸石分子筛产品。
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