CN112551538B - 一种纳米级Sn-Beta的合成方法 - Google Patents
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 58
- 230000008025 crystallization Effects 0.000 claims abstract description 58
- 239000002808 molecular sieve Substances 0.000 claims abstract description 41
- 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 41
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
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- 238000011049 filling Methods 0.000 claims abstract description 4
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- 239000010413 mother solution Substances 0.000 claims abstract 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 8
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
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- 229940079864 sodium stannate Drugs 0.000 claims description 3
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 claims description 3
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 claims description 3
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 3
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 3
- 239000002253 acid Substances 0.000 claims 1
- CJGYQECZUAUFSN-UHFFFAOYSA-N oxygen(2-);tin(2+) Chemical compound [O-2].[Sn+2] CJGYQECZUAUFSN-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 6
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- 125000005842 heteroatom Chemical group 0.000 description 10
- 238000011160 research Methods 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 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 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
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- 239000004698 Polyethylene Substances 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
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Abstract
本发明提供了一种纳米级Sn‑Beta的合成方法，主要包括以下步骤：将易溶于醇类的硅源与水解剂混合均匀，再将水与有机模板剂一同加入，将所得到的溶胶在水浴锅中搅拌，加入Beta晶种和含F‑离子化合物，获得晶化前驱混合物；再将晶化前驱混合物快速装入水热反应釜中进行分段晶化，待晶化反应完成后冷却到室温，将固体晶化产物与母液分离，产物洗涤至中性，经干燥，焙烧后即得纳米级Sn‑Beta分子筛原粉。本发明所制得的Sn‑Beta分子筛具有颗粒尺寸小、尺寸均匀、比表面积大等特点，具有广阔的工业化生产前景和巨大的经济价值。
Description
技术领域
本发明涉及化工合成技术及其应用领域，尤其涉及一种纳米级Sn-Beta的合成方法。
背景技术
在现有技术中，将分子筛骨架引入杂原子，特别是具有特定催化性能的过渡金属离子同晶取代所得到的杂原子分子筛，因为金属离子在分子筛骨架上处于孤立的高分散状态，同时也由于与分子筛母体骨架之间的相互作用，使得它们具备了常规的过渡金属氧化物所没有的特殊催化功能，其性能也明显区别于母体分子筛的原有功能，不仅对沸石催化剂的酸性、表面性能起到调节作用，同时有利于沸石催化剂实现多功能催化。在这方面，最典型的例子是钛硅分子筛。1983年，意大利的Taramasso成功地将钛引入MFI拓扑结构硅酸盐体系中，合成得到了TS-1分子筛，从而使分子筛的应用从传统的酸碱催化过程扩展到催化氧化过程，被认为是二十世纪八十年代分子筛催化研究领域的一个里程碑。
除去钛硅分子筛，功能性杂原子分子筛最有学术研究价值和应用潜力的乃是含锡杂原子分子筛，尤其是Sn-Beta杂原子分子筛。众所周知，Beta分子筛是一种微孔高硅分子筛，其骨架由三维十二元环孔道交错而成，一般条件下所合成的Beta沸石是多形体A、多形体B、多形体C共生，是唯一具有三维十二元环直通道体系的高硅沸石。Beta沸石分子筛独特的孔道结构、良好的热及水热稳定性和合适的酸度使其可作为催化材料广泛用于石油炼制及石油化工工程中，如苯和丙烯烷基化、醇类的胺化、烯烃水合、甲苯的岐化及甲基化、加氢裂化和催化脱蜡等，是一种具有广阔应用前景的催化材料。
锡由于其酸性适中，氧化性能优越使得其在催化领域的研究较为活跃，然而含锡的催化剂容易失活，重复使用性较差。将锡引入分子筛骨架，合成含锡杂原子分子筛，从而得以利用锡的独特的催化性能，成为分子筛研究领域的一个热点。近年来对Sn-Beta杂原子沸石的制备及应用探究的报道也越来越多，其中具有代表性和突破性的是西班牙的Corma教授研究组。2001年Corma等人首次报道了Sn-Beta分子筛的合成方法[Corma A.,NemethL.,Renz M.,Valencia S.,Nature,2001,412,423-425]，他们采用正硅酸四乙酯作为硅源，添加HF作为矿化剂，在含氟体系中成功合成出无铝的Sn-Beta，通过对其催化性能的探究，发现该催化剂对Baeyer-Viiliger反应具有优异的催化性能和近乎100％的产物酯或内酯选择性。他们对Sn-Beta分子筛在精细化工等领域的应用进行了系统、持续而深入的研究[CormaA.,Renz M.,Angew.Chem.Int.Ed.2007,46,298-300]。
除了采用水热体系的合成，采用二次合成方法进行难于合成的杂原子分子筛的合成一直被广泛的研究，诸如含钛杂原子分子筛的二次合成。对于含锡杂原子分子筛来说，P.Wu等将经硝酸脱铝的Beta分子筛采用气相SnCl4同晶取代[P.Li,G.Liu,H.Wu,Y.Liu,J.Jiang,and P.Wu,J.Phys.Chem.C,dx.doi.Org/10.1021/jp1076966]，但是该方法存在难于操作以及难以控制的缺点。I.Hermans等则将经硝酸脱铝的Beta分子筛采用固态离子交换的方式进行后合成方法的研究[C.Hammond,S.Conrad,and I.Hermans,Angew.Chem.Int.Ed.,DOI:10.1002/anie.201206193]，该方法则存在着所用锡源容易团聚、不易分散的明显缺点。
发明内容
为解决上述问题，本发明提供了一种纳米级Sn-Beta的合成方法，包括以下步骤：
1)将易溶于醇类的硅源与水解剂在10～120℃的条件下按摩尔比为1:500～1000的比例混合均匀，再将水、有机模板剂一同加入，室温条件下搅拌16～20h，得到溶胶；
2)将步骤1)中所得到的溶胶置于60～90℃的水浴锅中，待搅拌3～7h后，加入Beta晶种和含F-离子化合物，获得晶化前驱混合物；
3)将晶化前驱混合物快速装入水热反应釜中进行分段晶化，晶化采用分段晶化，第一段晶化温度为130～160℃，晶化时间为1～3d，第一段晶化完成后取出反应釜，在釜中加入锡源后，进行第二段晶化，晶化温度为140～170℃，晶化时间为5～10d；
4)晶化完成后冷却到室温，将固体晶化产物与母液分离，产物洗涤至中性，在70～130℃的条件下干燥，然后在马弗炉中以450～650℃的温度焙烧2～6h，得纳米级Sn-Beta分子筛原粉。
进一步地，步骤1)中所述的硅源为有机硅酸酯。
进一步地，步骤2)中所述的有机硅酸酯为正硅酸甲酯、硅酸异丙酯、亚硅酸乙酯、四乙氧基硅烷、正硅酸四乙酯中的一种或几种。
进一步地，步骤1)中所述的水解剂为氨水、氟化铵、有机酸、无机酸中的一种或几种。
进一步地，步骤1)中所述的有机酸为甲酸或酒石酸，无机酸为硝酸或盐酸。
进一步地，步骤1)中所述的模板剂由四乙基氢氧化铵或四乙基氢氧化铵与多乙烯基多胺NH2CH2CH2(NCH2CH2)nNH2按摩尔比为1：5的比例混合制得。
进一步地，步骤3)中所述的锡源为卤化锡、卤化亚锡、硫酸亚锡、硫酸锡、锡酸盐、亚锡酸盐、硝酸锡、氧化锡、氧化亚锡中的一种或几种。
进一步地，步骤3)中所述的锡源为氯化锡、硝酸锡、硫酸锡、锡酸钠中的一种或几种。
进一步地，步骤2)中所述的晶化前驱混合物中各组分的摩尔比为nSiO2:nF-:nSnO2:nTEA+:nH2O＝80.0～150.0:50.0～65.0:0.5～1.0:50.0～70.0:500.0～1000.0。
进一步地，步骤3)中所述的分子筛晶化方式为动态晶化或静态晶化，优选地选择动态晶化。
与现有技术相比，本发明的有益技术效果：
(1)本发明制备出的纳米级Sn-Beta具有颗粒尺寸小、粒径分布均匀、比表面积大的特点，具有较高的催化活性；
(2)本发明制备出的纳米级Sn-Beta结晶度较高，同时通过调整原料和控制反应条件，有效避免了杂晶的产生；
(3)本发明提供的纳米级Sn-Beta的合成方法工艺简单、成本低，得到的纳米级Sn-Beta品质高，具有广阔的应用和工业化生产前景。
附图说明
下面结合附图说明对本发明作进一步说明。
图1为本发明实施例1得到的纳米级Sn-Beta的XRD图谱。
图2为本发明实施例1得到的纳米级Sn-Beta的SEM图谱。
具体实施方式
本发明提供了一种纳米级Sn-Beta的合成方法，包括以下步骤：
1)将易溶于醇类的硅源与水解剂在10～120℃的条件下按摩尔比为1:500～1000的比例混合均匀，再将水、有机模板剂一同加入，室温条件下搅拌16～20h，得到溶胶；
2)将步骤1)中所得到的溶胶置于60～90℃的水浴锅中，待搅拌3～7h后，加入Beta晶种和含F-离子化合物，获得晶化前驱混合物；
3)将晶化前驱混合物快速装入水热反应釜中进行分段晶化，晶化采用分段晶化，第一段晶化温度为130～160℃，晶化时间为1～3d，第一段晶化完成后取出反应釜，在釜中加入锡源后，进行第二段晶化，晶化温度为140～170℃，晶化时间为5～10d；
4)晶化完成后冷却到室温，将固体晶化产物与母液分离，产物洗涤至中性，在70～130℃的条件下干燥，然后在马弗炉中以450～650℃的温度焙烧2～6h，得纳米级Sn-Beta分子筛原粉。
在一个实施例中，步骤1)中的硅源为有机硅酸酯。
在一个实施例中，步骤2)中的有机硅酸酯为正硅酸甲酯、硅酸异丙酯、亚硅酸乙酯、四乙氧基硅烷、正硅酸四乙酯中的一种或几种。
在一个实施例中，步骤1)中的水解剂为氨水、氟化铵、有机酸、无机酸中的一种或几种。
在一个实施例中，步骤1)中的有机酸为甲酸或酒石酸，无机酸为硝酸或盐酸。
在一个实施例中，步骤1)中的模板剂由四乙基氢氧化铵或四乙基氢氧化铵与多乙烯基多胺NH2CH2CH2(NCH2CH2)nNH2按摩尔比为1：5的比例混合制得。
在一个实施例中，步骤3)中的锡源为卤化锡、卤化亚锡、硫酸亚锡、硫酸锡、锡酸盐、亚锡酸盐、硝酸锡、氧化锡、氧化亚锡中的一种或几种。
在一个实施例中，步骤3)中的锡源为锡源为氯化锡、硝酸锡、硫酸锡、锡酸钠中的一种或几种。
在一个实施例中，步骤2)中的晶化前驱混合物中各组分的摩尔比为nSiO2:nF-:nSnO2:nTEA+:nH2O＝80.0～150.0:50.0～65.0:0.5～1.0:50.0～70.0:500.0～1000.0。
在一个实施例中，步骤3)中的分子筛晶化方式为动态晶化或静态晶化，优选地选择动态晶化。
以下结合实施例对本发明提供的纳米级Sn-Beta的合成方法进行进一步说明。
实施例1
将103.32g正硅酸乙酯与6.01g氨水在25℃下混合均匀，然后加入47.61g去离子水和71.49g四乙基氢氧化铵，室温条件下搅拌16h，得到溶胶，将所得溶胶置于60℃水浴锅中搅拌3h，加入1.49g Beta晶种和4.71g氟化铵，搅拌均匀，获得晶化前驱混合物，将晶化前驱混合物装入水热反应釜140℃反应1d后取出，加入1.39g五水四氯化锡，搅拌2h后装入水热反应釜160℃反应5d，晶化完成后冷却到室温，将晶化产物抽滤，洗至中性，80℃干燥，在马弗炉550℃焙烧4h后即得纳米级Sn-Beta分子筛原粉1#。
通过1#纳米级Sn-Beta分子筛原粉的XRD图谱和SEM图谱可以看出，与现有技术相比，采用本发明所述方法制备出的纳米级Sn-Beta分子筛原粉具有颗粒尺寸小、粒径分布均匀、比表面积大的优点，其平均粒径为40～80nm。
实施例2
将103.32g正硅酸乙酯与6.01g氨水在25℃下混合均匀，然后加入47.61g去离子水和71.49g四乙基氢氧化铵，室温条件下搅拌16h，得到溶胶，将所得溶胶置于60℃水浴锅中搅拌3h，加入1.49g Beta晶种和4.71g氟化铵，搅拌均匀，获得晶化前驱混合物，将晶化前驱混合物装入水热反应釜130℃反应1d后取出，加入1.39g五水四氯化锡，搅拌2h后装入水热反应釜140℃反应5d，晶化完成后冷却到室温，将晶化产物抽滤，洗至中性，80℃干燥，在马弗炉550℃焙烧4h后即得纳米级Sn-Beta分子筛原粉2#。经检测，其平均粒径为30～70nm。
本文中应用了具体个例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想；同时，对于本领域的一般技术人员，依据本发明的思想，在具体实施方式及应用范围上均会有改变之处。综上所述，本说明书内容不应理解为对本发明的限制。
Claims (6)
1.一种纳米级Sn-Beta的合成方法，其特征在于，包括以下步骤：
1)将易溶于醇类的硅源与水解剂在10～120℃的条件下混合均匀，再将水、有机模板剂一同加入，室温条件下搅拌16～20h，得到溶胶；其中硅源、水解剂、水与有机模板剂的重量比为103.32:6.01:47.61：71.49；
2)将步骤1)中所得到的溶胶置于60～90℃的水浴锅中，搅拌3～7h后，加入Beta晶种和含F-离子化合物，获得晶化前驱混合物；
3)将晶化前驱混合物快速装入水热反应釜中进行分段晶化，第一段晶化温度为130～160℃，晶化时间为1～3d，第一段晶化完成后取出反应釜，在釜中加入锡源后，进行第二段晶化，晶化温度为140～170℃，晶化时间为5～10d；
4)晶化反应完成后冷却到室温，将固体晶化产物与母液分离，产物洗涤至中性，在70～130℃的条件下干燥，然后在马弗炉中以450～650℃的温度焙烧2～6h，得纳米级Sn-Beta分子筛原粉；
步骤1)中所述的硅源为有机硅酸酯；
步骤1)中所述的水解剂为氨水、氟化铵、有机酸、无机酸中的一种或几种；
步骤1)中所述的模板剂由四乙基氢氧化铵或四乙基氢氧化铵与多乙烯基多胺按摩尔比为1：5的比例混合制得；
2.根据权利要求1所述的一种纳米级Sn-Beta的合成方法，其特征在于，所述的有机硅酸酯为正硅酸甲酯、硅酸异丙酯、亚硅酸乙酯中的一种或几种。
3.根据权利要求1所述的一种纳米级Sn-Beta的合成方法，其特征在于，所述的有机酸为甲酸或酒石酸，无机酸为硝酸或盐酸。
4.根据权利要求1所述的一种纳米级Sn-Beta的合成方法，其特征在于，所述的锡源为卤化锡、卤化亚锡、硫酸亚锡、硫酸锡、锡酸盐、亚锡酸盐、硝酸锡、氧化锡、氧化亚锡中的一种或几种。
5.根据权利要求4所述的一种纳米级Sn-Beta的合成方法，其特征在于，所述的锡源为氯化锡、硝酸锡、硫酸锡、锡酸钠中的一种或几种。
6.根据权利要求1所述的一种纳米级Sn-Beta的合成方法，其特征在于，所述的分子筛晶化方式为动态晶化或静态晶化。
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