CN114054082A - 一种纳米多级孔sapo-11分子筛及其制备方法和应用 - Google Patents
一种纳米多级孔sapo-11分子筛及其制备方法和应用 Download PDFInfo
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- CN114054082A CN114054082A CN202111329641.8A CN202111329641A CN114054082A CN 114054082 A CN114054082 A CN 114054082A CN 202111329641 A CN202111329641 A CN 202111329641A CN 114054082 A CN114054082 A CN 114054082A
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- Prior art keywords
- molecular sieve
- hierarchical pore
- sapo
- pore sapo
- nano hierarchical
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Abstract
本发明公开了一种纳米多级孔SAPO‑11分子筛及其制备方法和应用，所述的纳米多级孔SAPO‑11分子筛的粒径为50～1000nm；介孔体积/微孔体积比为1～5∶1；介孔孔径为50～70nm。本发明合成的纳米多级孔SAPO‑11分子筛具有较小的粒径，同时具有微孔和介孔结构，有利于反应物和产物的扩散、减少积碳生成。本发明通过在制备分子筛的前驱体凝胶时加入表面活性剂，在分段晶化时再加入氟源合成了纳米多级孔SAPO‑11分子筛。本发明制备的纳米多级孔SAPO‑11分子筛可运用于芳烃的烷基化反应和烷基转移反应，与传统的SAPO‑11分子筛相比该催化剂的催化活性更好，目标产物选择性更高，使用寿命更长。
Description
技术领域
本发明属于分子筛技术领域，具体涉及一种纳米多级孔SAPO-11分子筛及其制备方法和应用。
背景技术
SAPO-n系列分子筛具有丰富的结构多样性，已经成为一类重要的分子筛材料。SAPO-11分子筛作为SAPO-n家族中的重要一员，具有类似于AlPO-11的AEL结构，其结构由非相交的椭圆形10元环孔道组成，孔径为0.40×0.65nm，其孔道为一维直孔道。SAPO-11分子筛具有优异的热稳定性、独特的孔道结构和可调变的酸性。因此，SAPO-11分子筛在异构化、催化裂化、加氢裂化和芳烃烷基化等反应中表现出了良好的催化反应性能。
虽然SAPO-11分子筛在上述反应中表现出良好的催化反应性能，但是由于SAPO-11分子筛本身粒径较大(～10μm)和微孔结构限制了传质效率，使得催化剂的活性位点利用率低。为了解决粒径大导致的传质效率低的问题，有研究者尝试制备纳米级的分子筛来缩短反应物和产物的扩散路径，减小传质阻力，增强反应过程中分子的扩散性能。文献(QiyingLiu，Hualiang Zuo，Tiejun Wang，et al.One-step hydrodeoxygenationof palm oil toisomerized hydrocarbon fuels over Ni supported on nano-sized SAPO-11catalysts[J].Applied Catalysis A General，2013，468：68-74.)报道了以二正丙胺为结构导向剂，在十四烷胺-正丙醇-水混合介质中成功合成了粒径为20～50nm的SAPO-11分子筛，在棕榈油加氢脱氧反应中表现出优异的催化性能。
为了增强分子筛的热稳定性，有研究者使用氟离子改性来增强原子间的键强。文献(Liu，Y.X.；Zheng，D.J.；Zhao，L.M.；Peng，P.；Wang，X.S.；Li，L.；Yu，S.T.；Liu，S.W.；Liu，X.M.；Yan，Z.F.，Effect of fluoride ions on the stability of SAPO-11molecular sieves.Micropor Mesopor Mat2020，306.)报道了以研磨法合成了具有氟离子的SAPO-11分子筛，合成的产物具有良好的热稳定性。
为了解决传统SAPO-11分子筛所具有的微孔结构不利于分子的扩散，限制其催化性能的问题。有研究者试图在分子筛中引入介孔，CN106809862A公开了一种制备多级孔SAPO-11分子筛的方法及其分子筛，它采用水蒸气辅助或气相转移法，以介孔磷酸硅铝凝胶为前驱体合成多级孔SAPO-11分子筛。
如果创制纳米多级孔SAPO-11分子筛有望更进一步提高SAPO-11分子筛的传质效率和活性位点利用率。但目前尚没有制备纳米多级孔SAPO-11分子筛的方法公开。
本发明提供一种纳米多级孔SAPO-11分子筛及其制备方法。通过在制备分子筛的前驱体凝胶时加入表面活性剂，在预晶化结束后加入氟源然后再次晶化合成了纳米多级孔SAPO-11分子筛。本说明书中的制备方法操作简单、原料价格低、分子筛收率高，合成的分子筛具有大比表面积、粒径小、同时具有微孔和介孔，且克服了现有技术无法提供和制备纳米多级孔SAPO-11分子筛的技术问题。
本发明提供一种纳米多级孔SAPO-11分子筛及其制备方法，该分子筛可用于催化萘系物烷基化制备2，6-DMN、生产均三甲苯、C7～C9芳烃制二甲苯等反应中。
发明内容
针对现有技术中的不足与难题，本发明旨在提供一种纳米多级孔SAPO-11分子筛及其制备方法和应用。
本发明通过以下技术方案予以实现：
本发明第一方面提供了一种纳米多级孔SAPO-11分子筛，解决了传统SAPO-11分子筛粒径较大和孔道结构单一而限制传质效率的技术问题，其具体方案为：
一种纳米多级孔SAPO-11分子筛，纳米多级孔SAPO-11分子筛的粒径为50～1000nm，优选100～800nm；纳米多级孔SAPO-11分子筛比表面积为1340～1500m2/g，优选1340～1450m2/g，总孔体积为1.525～1.764cm3/g，优选1.56～1.725cm3/g，纳米多级孔SAPO-11分子筛催化剂介孔孔径为55～70nm，优选60～70nm，纳米多级孔SAPO-11分子筛含有微孔和介孔结构，且介孔体积/微孔体积比为1～5∶1，优选1.33～4.45；纳米多级孔SAPO-11分子筛的Al/P比为0.03～30。
本发明第二方面提供了上述纳米多级孔SAPO-11分子筛的制备方法，该方法解决了现有技术无法生产纳米多级孔SAPO-11分子筛的技术问题，其具体方案为：
一种纳米多级孔SAPO-11分子筛的制备方法，分子筛采用水热法合成，其制备过程包括将水、磷源、铝源、模板剂、表面活性剂、硅源按比例混合均匀，经陈化、晶化、加氟再晶化、洗涤、分离、干燥、煅烧，最终得到纳米多级孔SAPO-11分子筛。
所述磷源至少含有磷酸、磷酸钠、磷酸氢钠、磷酸钾、磷酸氢钾、磷酸铵和磷酸氢铵中的至少一种；优选的，所述磷源为磷酸；
所述铝源至少含有拟薄水铝石、异丙醇铝、偏铝酸钠、氢氧化铝、三氯化铝、氧化铝、硫酸铝和硝酸铝中的一种；优选的，所述铝源为拟薄水铝石；
所述模板剂至少含有二正丙胺、二异丙胺和乙二胺中的一种；优选的，所述模板剂为二正丙胺；
所述表面活性剂至少含有异丙醇、乙二醇、聚乙烯醇和甘油中的一种；优选的，所述表面活性剂为异丙醇；
所述硅源至少含有硅溶胶、正硅酸甲酯、正硅酸丙酯、正硅酸四乙酯、白炭黑、高岭土、蒙脱土、硅酸钠、粉煤灰和水玻璃中的一种；优选的，所述硅源为硅溶胶；
所述氟源至少含有氢氟酸，氟化钠，氟化钾，氟化铝，氟化钙，氟化钡，氟化铯中的一种；优选地，所述氟源为氢氟酸；
优选地，合成分子筛所使用的水、磷源、铝源、模板剂、表面活性剂和硅源的原料比按水∶磷源∶铝源∶模板剂∶表面活性剂∶硅源＝(25～500)∶(0.1～3.0)∶(0.1～3.0)∶(0.1～5.0)∶(0.01～3)∶(0.1～3.5)的摩尔比进行配制。
所述陈化温度为10～40℃，陈化时间为0.1～24h。
所述分子筛采用分段晶化合成，在165～200℃预晶化1～120h，晶化结束后取出并加入氟源搅拌均匀，然后再在50～120℃下晶化1～120h；所述分子筛在加氟源后的原料摩尔比为水∶磷源∶铝源∶模板剂∶表面活性剂∶硅源∶氟源＝(25～500)∶(0.1～3.0)∶(0.1～3.0)∶(0.1～5.0)∶(0.01～3)∶(0.1～3.5)∶(0.05～3)。
所述分子筛的干燥温度为20～300℃，干燥时间为0.1～48h。
所述分子筛焙烧的温度为：350～700℃，时间为1～20h。
本发明第三方面提供上述纳米多级孔SAPO-11分子筛的应用，纳米多级孔SAPO-11分子筛在催化剂中的应用，其用于2，6-二甲基萘(2，6-DMN)、均三甲苯、对二甲苯的制备，解决传统分子筛催化芳烃烷基转移及烷基化反应转化率低、选择性低和稳定性差等问题。
其中，2，6-二甲基萘(2，6-DMN)的制备方法具体为：采用上述纳米多级孔SAPO-11分子筛为催化剂，以含有萘系物的物质为主要原料，以甲醇或C7～C10的芳烃为甲基化试剂，在反应温度为200～600℃，反应压力为0.1～4.5MPa，空速为0.05～10.0h-1的条件下，使反应物等与催化剂床层接触，反应生成包含2，6-DMN的产物。
其中，均三甲苯的制备方法具体为：采用上述纳米多级孔SAPO-11分子筛为催化剂，至少含有甲苯、乙苯、二甲苯、C9重芳烃、C10重芳烃中的一种为原料，在反应温度为150～600℃，反应压力为0.1～4.5MPa，空速为0.1～10h-1的条件下，使反应物等与催化剂床层接触，反应生成含有均三甲苯的产物。
其中，对二甲苯的制备方法具体为：采用上述纳米多级孔SAPO-11分子筛为催化剂，以至少含有C7～C9芳烃中的一种为原料，在反应温度为300～600℃，反应压力为0.1～4.5MPa，空速为0.2～20h-1的条件下，使反应物等与催化剂床层接触，反应生成含有对二甲苯的产物。
与现有技术相比，本发明有益效果包括：
(1)本发明所述纳米多级孔SAPO-11分子筛的粒径为50～1000nm；所述纳米多级孔SAPO-11分子筛的比表面积为1340～1500m2/g，总孔体积为1.525～1.764cm3/g，介孔孔径为55～70nm，介孔体积/微孔体积为1～5∶1；本发明合成的纳米多级孔SAPO-11分子筛具有较小的粒径，同时具有微孔和介孔结构，有利于反应物和产物的扩散，有利于减少积碳生成。
(2)本发明采用分段晶化合成了纳米多级孔SAPO-11分子筛。
(3)本发明制备的纳米多级孔SAPO-11分子筛运用于催化芳烃的烷基化反应和烷基转移反应中表现出优异的性能。
附图说明
图1是实施例1中制备的纳米多级孔SAPO-11分子筛的XRD图；
图2是实施例1中制备的纳米多级孔SAPO-11分子筛的SEM图。
具体实施方式
下面结合附图，对本发明作进一步地说明。
【实施例1】
本实施方式中水热法合成是纳米多级孔SAPO-11分子筛的具体方法是按以下步骤进行的；
将14.9g拟薄水铝石加入到用103.5g水稀释的28.7g磷酸溶液中，搅拌混合30min后加入3.0g异丙醇，再用分液漏斗缓慢滴加7.5g硅溶胶，滴加速度约为1滴/s，最后加入12.7g结构导向剂二正丙胺，将凝胶在室温下搅拌陈化2h，所得凝胶的摩尔组成为1.1DPA∶1.1Al2O3∶0.5SiO2∶1.0P2O5∶0.4IPA∶50H2O。将凝胶装入带有聚四氟乙烯内衬的反应釜中，在165℃预晶化5h，晶化结束后取出加入4.3g氢氟酸搅拌均匀，然后在120℃下晶化24h，此时的摩尔组成为1.1DPA∶1.1Al2O3∶0.5SiO2∶1.0P2O5∶0.4IPA∶0.3HF∶50H2O。经多次抽滤洗涤，洗涤至滤液为中性，在120℃干燥12h，最后在马弗炉中600℃煅烧4h得到纳米多级孔SAPO-11分子筛。
本实施例制得的纳米多级孔SAPO-11分子筛的粒径为50～1000nm，比表面积为1340～1500m2/g，总孔体积为1.525～1.764cm3/g，介孔孔径为55～70nm，介孔体积/微孔体积为1～5∶1；；本实施例制得的纳米多级孔SAPO-11分子筛的XRD图和SEM图，如图1和图2所示。
【实施例2-32】
将水、P源、Al源、F源、模板剂、表面活性剂和Si源等原料，按照表1的制备条件，根据实施例1中相同的步骤进行操作，即可得到纳米多级孔SAPO-11分子筛。
对实施例1～32所得的样品进行N2吸附-脱附测试，SEM测试，得到的结果见表1。
表1实施例2-32的制备条件及制得的分子筛性能
【实施例33-64】
将纳米多级孔SAPO-11分子筛用于芳烃烷基化制备2，6-DMN。
以含有萘系物的物质为主要原料，以甲醇或C7～C10的芳烃为甲基化试剂。采用实施例1-32得到的纳米多孔级SAPO-11分子筛，按照下表的反应条件进行催化剂性能评价，可得到富含2，6-二甲基萘的产物。
表2实施例33-64制备2，6-DMN的反应汇总
【实施例65-96】
将纳米多级孔SAPO-11分子筛用于制备均三甲苯。
以至少含有甲苯、乙苯、二甲苯、C9重芳烃、C10重芳烃中的一种物质为原料，采用实施例1-32得到的纳米多级孔SAPO-11分子筛，按照下表的反应条件进行催化剂性能评价，可得到富含均三甲苯的产物。
表3实施例65-96制备均三甲苯的反应汇总
【实施例97-128】
将纳米多级孔SAPO-11分子筛用于制备对二甲苯。
以至少含有C7～C9芳烃中的一种为原料，采用实施例1～32得到的纳米多级孔SAPO-11分子筛，按照下表的反应条件进行催化剂性能评价，可得到富含对二甲苯的产物。
表4实施例97-128制备对二甲苯的反应条件
以上所述仅表达了本发明的优选实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形、改进及替代，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。
Claims (10)
1.一种纳米多级孔SAPO-11分子筛，其特征在于：
(1)所述纳米多级孔SAPO-11分子筛的粒径为50～1000nm；
(2)所述纳米多级孔SAPO-11分子筛含有微孔和介孔结构，比表面积为1340～1500m2/g，总孔体积为1.525～1.764cm3/g，介孔孔径为55～70nm，且介孔体积/微孔体积比为1～5∶1；
(3)所述纳米多级孔SAPO-11分子筛的A1/P比为0.03～30。
2.根据权利要求1所述的一种纳米多级孔SAPO-11分子筛，其特征在于：所述纳米多级孔SAPO-11分子筛的粒径为100～800nm；所述纳米多级孔SAPO-11分子筛比表面积为1340～1450m2/g，所述纳米多级孔SAPO-11分子筛总孔体积为1.56～1.725cm3/g，介孔孔径为60～70nm，介孔体积/微孔体积比为1.33～4.45。
3.根据权利要求1所述的纳米多级孔SAPO-11分子筛的制备方法，其特征在于：所述分子筛采用水热法合成，其制备过程包括将水、磷源、铝源、模板剂、表面活性剂、硅源作为原料按比例混合均匀，经陈化、晶化、加氟再晶化、洗涤、分离、干燥、煅烧，最终得到纳米多级孔SAPO-11分子筛。
4.根据权利要求3所述的纳米多级孔SAPO-11分子筛的制备方法，所述磷源至少含有磷酸、磷酸钠、磷酸氢钠、磷酸钾、磷酸氢钾、磷酸铵和磷酸氢铵中的至少一种；所述铝源至少含有拟薄水铝石、异丙醇铝、偏铝酸钠、氢氧化铝、三氯化铝、氧化铝、硫酸铝和硝酸铝中的一种；所述模板剂至少含有二正丙胺、二异丙胺、乙二胺中的一种；所述表面活性剂至少含有异丙醇、乙二醇、聚乙烯醇和甘油中的一种；所述硅源至少含有硅溶胶、正硅酸甲酯、正硅酸丙酯、正硅酸四乙酯、白炭黑、高岭土、蒙脱土、硅酸钠、粉煤灰和水玻璃中的一种；所述氟源至少含有氢氟酸，氟化钠，氟化钾，氟化铝，氟化钙，氟化钡，氟化铯中的一种。
5.根据权利要求3所述的纳米多级孔SAPO-11分子筛的制备方法，其特征在于：按水∶磷源∶铝源∶氟源∶表面活性剂∶硅源∶模板剂＝(25～500)∶(0.1～3.0)∶(0.1～3.0)∶(0.05～3)∶(0.01～3)∶(0.1～3.5)∶(0.1～5.0)的摩尔比进行配制。
6.根据权利要求3所述的纳米多级孔SAPO-11分子筛的制备方法，其特征在于：所述晶化过程采用分段晶化；按顺序依次加入：水、磷源、铝源、表面活性剂、硅源、模板剂，在温度为10～40℃下陈化0.1～24h；在165～185℃预晶化1～120h，晶化结束后取出并加入氟源搅拌均匀，再在50～120℃下晶化1～120h；所述干燥的温度为20～300℃、时间为0.1～48h；所述煅烧的温度为350～700℃、时间为1～20h。
7.如权利要求1或2所述的纳米多级孔SAPO-11分子筛的应用，其特征在于：所述纳米多级孔SAPO-11分子筛在催化剂中的应用，其用于2，6-二甲基萘、均三甲苯和对二甲苯。的制备。
8.根据权利要求7所述的纳米多级孔SAPO-11分子筛的应用，其特征在于，所述2，6-二甲基萘的制备方法具体为：以所述纳米多级孔SAPO-11分子筛为催化剂，以含有萘系物的物质为主要原料，以甲醇或C7～C10的芳烃为甲基化试剂，在反应温度为200～600℃，反应压力为0.1～4.5MPa，空速为0.05～10.0h-1的条件下，使反应物等与催化剂床层接触，反应生成包含2，6-DMN的产物。
9.根据权利要求7所述的纳米多级孔SAPO-11分子筛的应用，其特征在于，所述均三甲苯的制备方法具体为：以所述纳米多级孔SAPO-11分子筛为催化剂，以至少含有甲苯、乙苯、二甲苯、C9重芳烃、C10重芳烃中的一种为原料，在反应温度为150℃～600℃，反应压力为0.1～4.5MPa，空速为0.1～10h-1的条件下，使反应物等与催化剂床层接触，反应生成含有均三甲苯的产物。
10.根据权利要求7所述的纳米多级孔SAPO-11分子筛的应用，其特征在于，所述对二甲苯的制备方法具体为：以所述纳米多级孔SAPO-11分子筛为催化剂，以至少含有C7～C9芳烃中的一种为原料，在反应温度为300～600℃，反应压力为0.1～4.5MPa，空速为0.2～20h-1的条件下，使反应物等与催化剂床层接触，反应生成含有对二甲苯的产物。
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