CN112619698A - 一种zsm-5/zsm-35复合分子筛及其制备方法 - Google Patents
一种zsm-5/zsm-35复合分子筛及其制备方法 Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 44
- 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 44
- 239000002131 composite material Substances 0.000 title claims abstract description 32
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 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 29
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 24
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- 239000007787 solid Substances 0.000 claims abstract description 23
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims abstract description 20
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- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 11
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- 238000000926 separation method Methods 0.000 claims abstract description 4
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- 238000000034 method Methods 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- 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 claims description 11
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- 229910052708 sodium Inorganic materials 0.000 claims description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 10
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
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- 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 claims description 2
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- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 4
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- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
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- 238000005342 ion exchange Methods 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 238000004098 selected area electron diffraction Methods 0.000 description 1
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- 230000007847 structural defect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
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Abstract
本发明公开了一种ZSM‑5/ZSM‑35复合分子筛及其制备方法，该复合分子筛以ZSM‑5沸石粒子为核相，ZSM‑35沸石为壳层，ZSM‑35沸石为单晶结构，壳层厚度50‑700nm，核相与壳层重量比为1:0.3‑3。本发明的ZSM‑5/ZSM‑35复合分子筛的制备方法，包括如下内容：（1）将硅源、铝源、四丙基氢氧化铵和水混合均匀，得到混合物A，然后晶化，固液分离，得到固相物料；（2）将固相物料分散于混合物B中，加热蒸发部分水分，然后经喷雾干燥处理，得到固体粉末；其中混合物B为硅源、铝源、环己胺和水的混合物；（3）固体粉末经分段晶化处理，过滤、洗涤、干燥和焙烧，得到ZSM‑5/ZSM‑35复合分子筛。该复合分子筛结晶度高，制备方法过程简单，重复性好，易于工业应用。
Description
技术领域
本发明属于分子筛合成领域，具体地涉及一种ZSM-5/ZSM-35复合分子筛及其制备方法。
背景技术
ZSM-5是由美国Mobil公司于1972年首次合成的具有三维交叉孔道体系的高硅沸石。1978年Kokotailo等人首次确定其结构，认为是基本结构单元为硅氧和铝氧四面体组成的五元环通过共用氧桥连接成的骨架结构，然后再连接构成具有二维正交十元环孔道的拓扑结构。ZSM-5沸石孔径大小适中，酸性较强，离子交换性及择形催化性能优良，而且具有良好的热稳定性，水热稳定性及耐酸性。目前ZSM-5主要应用在石油加工领域、煤化工领域和精细化工及环保领域。
ZSM-35分子筛是由 Mobil 公司开发的一种中孔沸石，具有 FER 型骨架结构.它拥有垂直交叉的二维孔道系统，它拥有垂直交叉的二维孔道系统，其中平行于[001]面的十元环孔道的大小为 0.54nm×0.42nm，平行于[010]面的八元环孔道的大小为0.48 nm×0.35nm。ZSM-35分子筛可广泛用于烃类的转化过程，例如异构化、聚合、芳构化和裂化等，具有良好的应用前景。
由于ZSM-5和ZSM-35沸石分子筛在结构和性能上存在一定的差异，将两种沸石分子筛复合使用可以起到调节酸性和亲疏水性、孔道搭配以改善传质等效果。ZSM-5和ZSM-35沸石分子筛进行简单的机械混合，存在两种晶相分布不均匀的问题。而传统的水热附晶生长制备条件苛刻，过程复杂，且无法合成出外壳为单晶结构的核壳复合分子筛，外壳结构不够稳定。
发明内容
针对现有技术的不足，本发明提供了一种ZSM-5/ZSM-35复合分子筛及其制备方法。该复合分子筛以ZSM-5沸石粒子为核，ZSM-35单晶沸石为壳，结晶度高，制备方法过程简单，重复性好，易于工业应用。
本发明的ZSM-5/ZSM-35复合分子筛为核壳结构，以ZSM-5沸石粒子为核相，ZSM-35沸石为壳层，ZSM-35沸石为单晶结构，壳层厚度50-700nm，优选70~300nm，核相与壳层重量比为1:0.3-3。
本发明的ZSM-5/ZSM-35复合分子筛的制备方法，包括如下内容：（1）将硅源、铝源、四丙基氢氧化铵和水混合均匀，得到混合物A，然后晶化，固液分离，得到固相物料；（2）将固相物料分散于混合物B中，加热蒸发部分水分，然后经喷雾干燥处理，得到固体粉末；其中混合物B为硅源、铝源、环己胺和水的混合物；（3）固体粉末经分段晶化处理，过滤、洗涤、干燥和焙烧，得到ZSM-5/ZSM-35复合分子筛。
本发明方法中，所述的硅源是正硅酸四乙酯和/或硅溶胶；所述的铝源是硫酸铝、氯化铝、异丙醇铝或偏铝酸钠一种或多种。
本发明方法中，步骤（1）所述的混合物A以下列物质计的摩尔比为: A12O3：SiO2：四丙基氢氧化铵：水=1:20-150: 8-20: 900-3000。
本发明方法中，步骤（1）所述的晶化条件为：90-120℃晶化5-24小时。
本发明方法中，步骤（1）所述的固液分离方式可以采用离心、过滤等本领域熟知的方式。
本发明方法中，步骤（2）所述的固相物料与混合物B的质量比为1:12-25。
本发明方法中，步骤（2）所述的混合物B以下列物质计的摩尔比为：A12O3: SiO2:环己胺:Na2O:水=1:20-50:3-10: 1-7:300-2000。
本发明方法中，步骤（2）所述的喷雾干燥处理条件为：喷雾压力110-150psi，干燥温度60-90℃。
本发明方法中，步骤（2）所述的加热蒸发部分水分后，体系中的水和硅的摩尔比例为：H2O: SiO2=10-15:1。
本发明方法中，步骤（3）所述的分段晶化处理过程为：依次在80~120℃下晶化3~24小时，140~170℃下晶化1~24小时，110~140℃下晶化8~144小时。
本发明方法中，步骤（3）所述的洗涤、过滤过程为本领域技术人员熟知，一般采用等体积去离子水洗涤2~5次；所述的干燥条件为100~120℃干燥3~6小时，所述的焙烧条件为300-700℃焙烧4-10h，优选的焙烧温度为450-600℃，优选的焙烧时间为5-7h。
本发明的ZSM-5/ZSM-35复合分子筛可用于制备具有脱硫及芳构化功能的催化剂，该催化剂适用于清洁汽油的生产。
本发明利用喷雾干燥和分段晶化相结合的方法成功合成出高结晶度的复合分子筛。先通过水热合成一种沸石分子筛粒子，再利用喷雾干燥使沸石分子筛粒子表面包覆含有模板剂的无定型硅铝。为确保包覆均匀，先在高水含量的体系中分散ZSM-5沸石粒子，然后蒸发掉部分水分，调节反应体系的粘度，通过选择适宜的喷雾压力和干燥温度，使液相能够很好的喷出包裹在沸石离子上，同时包覆层在体系温度下能够以适宜的速度凝固干燥而不破裂，得到了包覆状态合适的固体粉末，能够很好的适用于后期的晶化处理；固体粉末先通过低温预晶化再进行高温快速晶化，预晶化过程为后期晶体快速生长提供条件，高温快速晶化使外层的无定型硅铝快速结晶包覆内部的沸石粒子，进一步防止出现两相分离的现象，晶化的末期重新调低晶化温度，有利于获得高结晶度的沸石分子筛产品。此外，通过固体粉末晶化可在保持原沸石分子筛粒子不变的情况下将无定型硅铝材料晶化出形成另一种沸石分子筛，最终形成ZSM-5/ZSM-35复合沸石分子筛，固相晶化可避免液相晶化中沸石溶解再生不能形成两种晶型及两相分离的问题。合成的ZSM-5/ZSM-35复合沸石分子筛的结构特征为大单晶包覆，此种结构缺陷少，相比于小晶粒的团聚包覆，结构更加稳定。与传统水热合成法相比，该方法过程简单，重复性好，产品结晶度高。
附图说明
图1为实施例1的合成ZSM-5/ ZSM-35复合分子筛的XRD谱图。
图2为实施例1的合成ZSM-5/ ZSM-35复合分子筛的TEM以及选区电子衍射图片。
图3为实施例2的合成ZSM-5/ ZSM-35复合分子筛的XRD谱图。
图4为实施例3的合成ZSM-5/ ZSM-35复合分子筛的XRD谱图。
具体实施方式
以下结合本发明的技术方案和附图说明本发明的具体实施方式。
实施例1
将0.38g偏铝酸钠、15.2g硅溶胶（30wt%二氧化硅）、12.3g四丙基氢氧化铵（含量为25wt%的水溶液）、23.9g去离子水搅拌混合，形成均一的前驱体溶液A。然后转移到聚四氟乙烯为内衬的反应釜中密封，在90℃静态晶化12时间，经过洗涤、过滤，得到ZSM-5粒子。将2.28g偏铝酸钠、91.2g硅溶胶、9.12g环己胺、3.04g氢氧化钠、120g去离子水搅拌混合，形成均一的前驱体溶液B。将制得的ZSM-5粒子均匀分散到B溶液中，搅拌30分钟形成均一的混合液。经加热蒸发部分水分后，喷雾干燥前体系的水和硅的含量为：H2O: SiO2=11:1。通过喷雾干燥装置(压力115psi，干燥温度60℃)将液体转变为喷雾，经干燥得到的固体粉末于依次在90℃下晶化20h， 165℃下晶化3h，120℃下晶化72h，产物经过洗涤、过滤，110℃干燥5小时，540℃焙烧5小时脱除模板剂，得到最终的ZSM-5/ZSM-35复合分子筛产品，壳层的ZSM-35为单晶结构，壳层厚度为50-150，核相与壳层的重量比为1:2.5。
实施例2
将1.53g异丙醇铝、15.6g正硅酸四乙酯、24.45g四丙基氢氧化铵（含量为25wt%的水溶液）、60.75g去离子水搅拌混合，形成均一的前驱体溶液A。然后转移到聚四氟乙烯为内衬的反应釜中密封，在120℃静态晶化8时间，经过洗涤、过滤，得到ZSM-5粒子。将1.53g异丙醇铝、23.4g正硅酸四乙酯、3g环己胺、1.5g氢氧化钠、33.75g去离子水搅拌混合，形成均一的前驱体溶液B。将制得的ZSM-5粒子均匀分散到B溶液中，搅拌30分钟形成均一的混合液。经加热蒸发部分水分后，喷雾干燥前体系的水和硅的含量为：H2O: SiO2=14:1。通过喷雾干燥装置(压力145psi，干燥温度90℃)将液体转变为喷雾，经干燥得到的固体粉末于依次在110℃下晶化3h，145℃下晶化24h，130℃下晶化72h，产物经过洗涤、过滤，100℃干燥5小时，550℃焙烧4小时脱除模板剂，得到最终的ZSM-5/ ZSM-35复合分子筛产品，壳层厚度为80-170，核相与壳层的重量比为1:1.2。
实施例3
将0.97g异丙醇铝、74.1g正硅酸四乙酯、38.8g四丙基氢氧化铵（含量为25wt%的水溶液）、128.3g去离子水搅拌混合，形成均一的前驱体溶液A。然后转移到聚四氟乙烯为内衬的反应釜中密封，在120℃静态晶化8时间，经过洗涤、过滤，得到ZSM-5粒子。将1.94g异丙醇铝、79g正硅酸四乙酯、14.4g环己胺、3.8g氢氧化钠、171g去离子水搅拌混合，形成均一的前驱体溶液B。将制得的ZSM-5粒子均匀分散到B溶液中，搅拌30分钟形成均一的混合液。经加热蒸发部分水分后，喷雾干燥前体系的水和硅的含量为：H2O: SiO2=12:1。通过喷雾干燥装置(压力145psi，干燥温度90℃)将液体转变为喷雾，经干燥得到的固体粉末于依次在110℃下晶化3h，145℃下晶化24h，130℃下晶化72h，产物经过洗涤、过滤，100℃干燥3小时，450℃焙烧4小时脱除模板剂，得到最终的ZSM-5/ ZSM-35复合分子筛产品，壳层厚度为 50-150nm，核相与壳层的重量比为1:0.9。
对比例1
将0.3g偏铝酸钠、12g硅溶胶（30wt%二氧化硅水溶液）、9.7g四丙基氢氧化铵（含量为25wt%的水溶液）、18.8g去离子水搅拌混合，形成均一的前驱体溶液A。然后转移到聚四氟乙烯为内衬的反应釜中密封，在90℃静态晶化12时间，经过洗涤、过滤，得到ZSM-5粒子。将1.8g偏铝酸钠、72g硅溶胶、7.2g环己胺、2.4g氢氧化钠、94.8g去离子水搅拌混合，形成均一的前驱体溶液B。将制得的ZSM-5粒子均匀分散到B溶液中，搅拌30分钟形成均一的混合液。经加热蒸发部分水分后，喷雾干燥前体系的水和硅的含量为：H2O: SiO2=11:1。通过喷雾干燥装置(压力115psi，干燥温度60℃)将液体转变为喷雾，经干燥得到的固体粉末于在165℃下晶化72h，产物经过过滤，110℃干燥5小时，540℃焙烧5小时脱除模板剂，得到最终的ZSM-5粒子和ZSM-35粒子的混合物，未晶化出复合分子筛产品。
对比例2
将0.3g偏铝酸钠、12g硅溶胶（30wt%二氧化硅水溶液）、9.7g四丙基氢氧化铵（含量为25wt%的水溶液）、18.8g去离子水搅拌混合，形成均一的前驱体溶液A。然后转移到聚四氟乙烯为内衬的反应釜中密封，在90℃静态晶化12时间，经过洗涤、过滤，得到ZSM-5粒子。将1.8g偏铝酸钠、72g硅溶胶、7.2g环己胺、2.4g氢氧化钠、94.8g去离子水搅拌混合，形成均一的前驱体溶液B。将制得的ZSM-5粒子均匀分散到B溶液中，搅拌30分钟形成均一的混合液。经加热蒸发部分水分后，喷雾干燥前体系的水和硅的含量为：H2O: SiO2=11:1。通过喷雾干燥装置(压力300psi，干燥温度130℃)将液体转变为喷雾，经干燥得到的固体粉末于依次在90℃下晶化20h，165℃下晶化3h，120℃下晶化72h，产物经过洗涤、过滤，110℃干燥5小时，540℃焙烧5小时脱除模板剂，得到最终的产品未晶化出ZSM-35沸石分子筛，为无定型硅铝和ZSM-5粒子的混合物。
对比例3
将0.3g偏铝酸钠、12g硅溶胶（30wt%二氧化硅水溶液）、9.7g四丙基氢氧化铵（含量为25wt%的水溶液）、18.8g去离子水搅拌混合，形成均一的前驱体溶液A。然后转移到聚四氟乙烯为内衬的反应釜中密封，在90℃静态晶化12时间，经过洗涤、过滤，得到ZSM-5粒子。将1.8g偏铝酸钠、72g硅溶胶、7.2g环己胺、2.4g氢氧化钠、94.8g去离子水搅拌混合，形成均一的前驱体溶液B。将制得的ZSM-5粒子均匀分散到B溶液中，搅拌30分钟形成均一的混合液。经加热蒸发部分水分后，喷雾干燥前体系的水和硅的含量为：H2O: SiO2=20:1。通过喷雾干燥装置(压力115psi，干燥温度60℃)将液体转变为喷雾，经干燥得到的固体粉末于依次在90℃下晶化20h，165℃下晶化3h，120℃下晶化72h，产物经过洗涤、过滤，110℃干燥5小时，540℃焙烧5小时脱除模板剂，得到最终的ZSM-5粒子和ZSM-35粒子的混合物，未晶化出复合分子筛产品。
Claims (13)
1.一种ZSM-5/ZSM-35复合分子筛，其特征在于：以ZSM-5沸石粒子为核相，ZSM-35沸石为壳层，ZSM-35沸石为单晶结构。
2.根据权利要求1所述的复合分子筛，其特征在于：壳层厚度50-700nm，优选70~300nm，核相与壳层重量比为1:0.3-3。
3.一种权利要求1或2所述的ZSM-5/ZSM-35复合分子筛的制备方法，其特征在于包括如下内容：（1）将硅源、铝源、四丙基氢氧化铵和水混合均匀，得到混合物A，然后晶化，固液分离，得到固相物料；（2）将固相物料分散于混合物B中，加热蒸发部分水分，然后经喷雾干燥处理，得到固体粉末；其中混合物B为硅源、铝源、环己胺和水的混合物；（3）固体粉末经分段晶化处理，过滤、洗涤、干燥和焙烧，得到ZSM-5/ZSM-35复合分子筛。
4.根据权利要求3所述的方法，其特征在于：所述的硅源是正硅酸四乙酯和/或硅溶胶；所述的铝源是硫酸铝、氯化铝、异丙醇铝或偏铝酸钠一种或多种。
5.根据权利要求3所述的方法，其特征在于：步骤（1）所述的混合物A以下列物质计的摩尔比为: A12O3：SiO2：四丙基氢氧化铵：水=1:20-150: 8-20: 900-3000。
6.根据权利要求3所述的方法，其特征在于：步骤（1）所述的晶化条件为：90-120℃晶化5-24小时。
7.根据权利要求3所述的方法，其特征在于：步骤（2）所述的固相物料与混合物B的质量比为1:12-25。
8. 根据权利要求3所述的方法，其特征在于：步骤（2）所述的混合物B以下列物质计的摩尔比为：A12O3: SiO2:环己胺:Na2O:水=1:20-50:3-10: 1-7:300-2000。
9.根据权利要求3所述的方法，其特征在于：步骤（2）所述的喷雾干燥处理条件为：喷雾压力110-150psi，干燥温度60-90℃。
10.根据权利要求3所述的方法，其特征在于：步骤（2）所述的加热蒸发部分水分后，体系中的水和硅的摩尔比例为：H2O: SiO2=10-15:1。
11.根据权利要求3所述的方法，其特征在于：步骤（3）所述的分段晶化处理过程为：依次在80~120℃下晶化3~24小时，140~170℃下晶化1~24小时，110~140℃下晶化8~144小时。
12.根据权利要求3所述的方法，其特征在于：步骤（3）所述的干燥条件为100~120℃干燥3~6小时；所述的焙烧条件为300-700℃焙烧4-10h。
13.一种权利要求1或2所述的ZSM-5/ZSM-35复合分子筛在制备具有脱硫及芳构化功能的催化剂中的应用。
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| CN114538462A (zh) * | 2022-02-22 | 2022-05-27 | 复旦大学 | 一种mfi/mel复合分子筛及其制备方法和应用 |
| CN114538462B (zh) * | 2022-02-22 | 2023-06-30 | 复旦大学 | 一种mfi/mel复合分子筛及其制备方法和应用 |
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