CN114602546A - 一种石墨烯封装镍负载的沸石分子筛催化剂的制备方法 - Google Patents
一种石墨烯封装镍负载的沸石分子筛催化剂的制备方法 Download PDFInfo
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- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
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Abstract
本发明公开了一种石墨烯封装镍负载的沸石分子筛催化剂的制备方法，以ZSM‑22、ZSM‑35、SAPO‑11沸石分子筛为载体，将石墨烯封装的镍纳米粒子负载于ZSM‑22、ZSM‑35、SAPO‑11沸石分子筛载体上形成多活性位点协同催化剂，石墨烯封装镍纳米粒子(Ni@C)的活性界面为最外层石墨烯，Ni@C作为金属中心与沸石分子筛载体表面的酸性位点保持了良好的协同催化活性，提高了镍负载型沸石分子筛催化剂在高温高压反应体系下的活性和稳定性。
Description
技术领域：
本发明涉及纳米功能化材料领域，具体涉及一种石墨烯封装镍负载的沸石分子筛催化剂的制备方法。
背景技术：
镍粒子负载型沸石材料是一种常用的金属中心、酸性位点复合型催化剂，该催化剂广泛用于各类加氢、脱氧、热解、裂化、异构等反应。传统镍粒子负载型沸石催化剂通常将镍粒子直接负载于分子筛的表面，反应过程中镍粒子表面作为活性位直接与反应底物接触而反应，这样一来负载的镍粒子很容易在反应过程中受到底物的侵蚀而流失，这是此类催化剂最为常见的失活方式之一。另外，在高温条件下镍粒子很容易发生团聚造成金属中心减少而导致催化剂失活。
发明内容：
本发明的目的是提供一种石墨烯封装镍负载的沸石分子筛催化剂的制备方法，以ZSM-22、ZSM-35、SAPO-11沸石分子筛为载体，将石墨烯封装的镍纳米粒子负载于ZSM-22、ZSM-35、SAPO-11沸石分子筛载体上形成多活性位点协同催化剂，石墨烯封装镍纳米粒子(Ni@C)的活性界面为最外层石墨烯，Ni@C作为金属中心与沸石分子筛载体表面的酸性位点保持了良好的协同催化活性，提高了镍负载型沸石分子筛催化剂在高温高压反应体系下的活性和稳定性。
本发明是通过以下技术方案予以实现的：
一种石墨烯封装镍负载的沸石分子筛催化剂的制备方法，该方法包括以下步骤：
(1)按金属负载量为0.5-20wt％将ZSM-22、ZSM-35、SAPO-11沸石分子筛中的任一种和镍硝酸盐、醋酸镍中的任一种作为镍源添加到烧瓶中，并溶于乙醇中形成溶液A；
(2)将柠檬酸、酒石酸、苹果酸、葡萄糖、蔗糖、果糖、D-山梨糖醇中一种或者多种作为碳源溶解在去离子水中形成溶液B；碳源与镍源的摩尔比范围为0.25-4.5；
(3)将溶液A和溶液B混合并在40-105℃优选为60-80℃温度下搅拌直至液体完全挥发；
(4)在氮气、氩气、氦气等惰性气氛下，在管式炉中将固体混合物进一步在150-800℃，优选为350-750℃下煅烧0.5-10小时，优选为3-5小时，焙烧完成后，将样品在惰性气氛中冷却至室温然后研磨过筛，所得黑色粉末为目标催化剂。
本发明跟现有技术相比，具有如下优点：
(1)本发明催化剂无需氢气进行还原，利用碳源热解产生的无定型碳作为还原剂就可以将分散好的镍粒子原位还原为零价单质。
(2)本发明中碳源热解产生的无定型碳有效的促进了镍粒子的分散，本发明中石墨烯封装的镍粒子的尺度可以调控到3.4纳米左右，镍粒子的高分散大大提高了其催化活性。传统的镍负载型分子筛催化剂的镍粒子大小通常在15-25纳米之间。
(4)本发明采用石墨烯封装的镍粒子作为金属中心，相比传统的镍负载型催化剂可以有效降低镍负载量，传统催化剂镍负载量通常在10-30wt％，本发明催化剂镍的负载量在2wt％-3wt％便达到很好的效果。
(5)本发明的催化剂能有效抑制镍流失从而大大提高催化剂的高温、酸环境中的使用稳定性，多次循环使用镍负载量均没有明显下降。
(6)本发明中石墨烯封装的镍纳米粒子作为金属中心可以与沸石酸性位间建立起良好的协同催化关系，该催化剂可以替代传统镍负载型催化剂在加氢、脱氧、热解、裂化、异构等反应过程中进行应用，具有更好的稳定性、经济性。
附图说明：
图1为按照实施例2制备的典型石墨烯封装的镍粒子的高分辨TEM图像，由图可知镍核的暴露晶面为Ni(1,1,1)面，石墨烯壳层间隔为典型的3.4埃。
图2-图4为实施例1-3制备的催化剂的TEM图。
图5为实施例1-4制备的催化剂的XRD图。
图6为实施例1制备的Ni@CN/ZSM-35催化连续加氢转化产物中烃类含量。
具体实施方式：
以下是对本发明的进一步说明，而不是对本发明的限制。
实施例1
以柠檬酸为碳源的Ni@CN/ZSM-35的制备，包括如下步骤：
将20克ZSM-35和5.8克Ni(CH3COO)2·4H2O添加到100毫升烧瓶中，并溶于50毫升乙醇中以形成溶液A。然后，将5.8克用作碳源的柠檬酸溶解在10毫升去离子水中以形成溶液B。随后，将溶液A和溶液B混合并在80℃温度下搅拌直至液体完全挥发。然后在氦气气氛下，在管式炉中将固体混合物进一步在350℃下煅烧3小时，升温速率保持在10K/min。研磨后，所得黑色粉末为最终的Ni@CN/ZSM-35催化剂，其TEM图如图2所示，XRD图如图5所示。
实施例2
以葡萄糖和柠檬酸为混合碳源的Ni@CPN/SAPO-11的制备，包括如下步骤：
将200克SAPO-11和12.5克Ni(NO3)2·6H2O和10.2克Ni(CH3COO)2·4H2O添加到500毫升烧瓶中，并溶于100毫升乙醇中以形成溶液A。然后，将25克用葡萄糖和15克柠檬酸溶解在100毫升去离子水中以形成溶液B。接下来，将溶液A和溶液B混合并在78℃温度下搅拌直至液体完全挥发。然后在氮气气氛下，在管式炉中将固体混合物进一步在750℃下煅烧5小时，升温速率保持在15K/min。研磨后，所得粉末为最终的Ni@CPN/SAPO-11催化剂，其TEM图如图3所示，XRD图如图5所示。
实施例3
以葡萄糖碳源的Ni@CP/ZSM-22的制备，包括如下步骤：
将200克ZSM-22和12.5克Ni(NO3)2·6H2O和10.2克Ni(CH3COO)2·4H2O添加到500毫升烧瓶中，并溶于100毫升乙醇中以形成溶液A。然后，将25克用葡萄糖溶解在100毫升去离子水中以形成溶液B。接下来，将溶液A和溶液B混合并在78℃温度下搅拌直至液体完全挥发。然后在氮气气氛下，在管式炉中将固体混合物进一步在450℃下煅烧5小时，升温速率保持在20K/min。研磨后，所得粉末为最终的Ni@CP/ZSM-22催化剂，其TEM图如图4所示，XRD图如图5所示。
实施例4
Ni@CPN/SAPO-11催化硬脂酸加氢，具体实施步骤如下：
将0.6克实施例2制备的Ni@CPN/SAPO-11和10克硬脂酸加入180毫升高压反应釜中，充入4Mpa氢气，然后升温至430℃反应2小时。液体产物采用安捷伦7890A和质谱5975C气相色谱-质谱联用仪进行分析。
液体产物中C8-C18烃类产物含量为99.6wt.％，产物异构烷烃的选择性为62.3mol％，芳烃选择性为5.45mol％。
实施例5
Ni@CN/ZSM-35催化菜籽油生物柴油加氢，具体实施步骤如下：
将0.6克实施例1制备的Ni@CN/ZSM-35和10克菜籽油生物柴油加入180毫升高压反应釜中，充入4Mpa氢气，然后升温至400℃反应3小时。液体产物采用安捷伦7890A和质谱5975C气相色谱-质谱联用仪进行分析。
液体产物中C8-C18烃类产物含量为97.8wt.％，产物异构烷烃的选择性为42.3mol％，芳烃选择性为25.45mol％。
实施例6
Ni@CP/ZSM-22催化棕榈酸加氢，具体实施步骤如下：
将0.6克实施例3制备的Ni@CP/ZSM-22和10克棕榈酸加入180毫升高压反应釜中，充入4Mpa氢气，然后升温至420℃反应3小时。液体产物采用安捷伦7890A和质谱5975C气相色谱-质谱联用仪进行分析。
液体产物中C8-C16烃类产物含量为98.6wt.％，产物异构烷烃的选择性为58.1mol％。
实施例7
Ni@CN/ZSM-35催化菜籽油生物柴油连续6次加氢循环反应性能分析，具体实施步骤如下：将0.6克按照实施例1制备的Ni@CN/ZSM-35和10克油酸加入180毫升高压反应釜中，充入4Mpa氢气，然后升温至430℃反应0.5小时。反应后将油脂与催化剂分离，催化剂经乙醇三次洗涤离心分离于50℃干燥后再次使用。液体产物采用安捷伦7890A和质谱5975C气相色谱-质谱联用仪进行分析。
反应后液体C8-C18烃类产物在产物中含量如图6。
实施例8
催化剂金属中心抗酸性测试：将0.5克Ni@CP/ZSM-22加入50毫升浓度为0.5克/毫升的硫酸水溶液中于60℃磁力搅拌5小时，反应后通过XRF分析催化剂的镍流失率为2.35％。
流失率计算方法如下：
Claims (3)
1.一种石墨烯封装镍负载的沸石分子筛催化剂的制备方法，其特征在于，该方法包括以下步骤：
(1)按金属负载量为0.5-20wt％将ZSM-22、ZSM-35、SAPO-11沸石分子筛中的任一种和镍硝酸盐、醋酸镍中的任一种作为镍源添加到烧瓶中，并溶于乙醇中形成溶液A；
(2)将柠檬酸、酒石酸、苹果酸、葡萄糖、蔗糖、果糖、D-山梨糖醇中一种或者多种作为碳源溶解在去离子水中形成溶液B；碳源与镍源的摩尔比范围为0.25-4.5；
(3)将溶液A和溶液B混合并在40-105℃温度下搅拌直至液体完全挥发；
(4)在惰性气氛下，在管式炉中将固体混合物进一步在150-800℃下煅烧0.5-10小时焙烧完成后，将样品在惰性气氛中冷却至室温然后研磨过筛，所得黑色粉末为目标催化剂。
2.根据权利要求1所述石墨烯封装镍负载的沸石分子筛催化剂的制备方法，其特征在于，步骤(3)为将溶液A和溶液B混合并在60-80℃温度下搅拌直至液体完全挥发。
3.根据权利要求1或2所述石墨烯封装镍负载的沸石分子筛催化剂的制备方法，其特征在于，步骤(4)为在氮气、氩气、氦气气氛下，在管式炉中将固体混合物进一步在350-750℃下煅烧3-5小时，焙烧完成后，将样品在惰性气氛中冷却至室温然后研磨过筛，所得黑色粉末为目标催化剂。
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