CN115400786A - 一种微孔分子筛的表面改性方法 - Google Patents
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Abstract
本发明涉及一种微孔分子筛的表面改性方法，该方法以微孔分子筛ZSM‑5或MCM‑22为基体，通过磁控溅射技术将Si、B、Ti薄膜沉积于微孔分子筛外表面，通过调节磁控溅射频率、温度、时间等因素，实现对微孔分子筛外表面的精细调控。本发明得到的表面改性微孔分子筛对合成对二甲苯过程有着很好的择型催化性能。在甲苯烷基化过程中，可以实现20％甲苯转化率的同时对二甲苯的选择性最大达到90％以上，在甲苯歧化过程中实现50％以上的甲苯转化率的同时对二甲苯选择性最大达到90％以上。
Description
技术领域
本发明涉及微孔分子筛的表面改性领域，特别涉及一种用于甲苯与甲醇烷基化或甲苯歧化合成对二甲苯过程的微孔分子筛的表面改性方法。
背景技术
对二甲苯是一种重要的化工原料，传统的合成方式有甲苯歧化，二甲苯异构化和甲苯烷基化。
对二甲苯生产过程中所用到的催化剂主要是ZSM-5和MCM-22等微孔分子筛。烷基化反应可以同时得到邻、间、对三种二甲苯的异构体，这主要是由于反应过程中生成的对二甲苯很容易在催化剂的外表面发生异构化反应而生成邻二甲苯和间二甲苯。因此，要想提高烷基化过程中对二甲苯的选择性，也就是提高催化剂的择型性能，就必须对分子筛进行改性。
对分子筛改性的目的主要有两点：一是降低催化剂外表面的酸性位数量，减少产物对二甲苯在分子筛外表面的异构化反应；二是调变分子筛孔口尺寸，增大邻二甲苯和间二甲苯的扩散阻力。通常改性的方法有化学气相硅沉积、化液相硅沉积、预积碳和金属氧化物改性。预积碳也可以提高分子筛催化剂的择型性能，但是由于再生后的催化剂还必须进行再次预积碳，因此操作烦琐，而且目前也仅限于实验室研究。采用金属氧化物改性来覆盖分子筛外表面酸性位操作非常简单，且一次就可以完成较好的覆盖效果，但该方法在降低外表面酸性的同时也会引起孔道内酸性的降低，因此也未能大规模使用。硅沉积的方法虽然可以有效提高分子筛催化剂的择型性能，但由于分子筛表面羟基和沉积物之间的作用力很弱，往往需要3～4次的沉积才能达到较好的效果，因此操作比较繁琐，能耗较高。
所以，寻找一种高效、便捷的微孔分子筛表面改性的方法，使得到的改性微孔分子筛能更高效地用于合成对二甲苯过程，提高对二甲苯的收率及选择性具有重要的意义。
发明内容
本发明是针对现有技术合成对二甲苯过程中所用微孔分子筛改性过程繁琐，成本高等问题，提供一种方法简单，成本低廉，择型性能好的微孔分子筛表面改性方法。本发明通过磁控溅射技术可以在材料表面形成均匀致密的薄膜，且操作简单、沉积速率高，沉积温度低，材料损伤小等优点，适用于大批的工业化生产。
为解决上述技术问题，本发明具体是按照以下步骤进行的：
(1)将微孔分子筛置于磁控溅射仪基片上；
(2)对溅射腔进行真空处理，使溅射腔压力降至4.5×10-3Pa以下；
(3)打开Ar、O2流量调节阀，调节Ar:O2流量比为10:1～10:4，调节溅射腔工作气压为0.2Pa；
(4)调节射频功率为50～150W，使溅射腔温度保持在40～70℃；
(5)对微孔分子筛进行15～60分钟的溅射处理，即得到表面改性的微孔分子筛材料。
作为对本发明的限定，本发明所述磁控溅射过程所用的靶材是Si、B或Ti。
作为对本发明的限定，本发明所述的微孔分子筛是ZSM-5或MCM-22，两种分子筛都是自制分子筛。
其中所述的微孔分子筛MCM-22制备方法如下：
将13.3g氢氧化钠溶于443ml去离子水中；随后向上述溶液中加入4g偏铝酸钠和38mL的六亚甲基亚胺，并剧烈搅拌；在强烈搅拌下将195ml硅溶胶缓慢滴加到上述溶液，继续强烈搅拌30min，将所得白色凝胶移入聚四氟乙烯内衬的晶化釜中，在烘箱150℃晶化7天；然后过滤，洗涤至pH＝8.0，110℃烘干24h，随后在马弗炉中550℃焙烧8h，即得微孔分子筛MCM-22。
所述的微孔分子筛ZSM-5制备方法如下：
先将12.5g氢氧化钠溶于288mL去离子水中；随后向溶液中加入3.7g的NaAlO2和195mL的四丙基氢氧化铵溶液，并剧烈搅拌；在强烈搅拌下将195mL的硅胶溶液缓慢滴加到溶液中，继续强烈搅拌30min，随后将白色凝胶移入聚四氟乙烯内衬的晶化釜中，在烘箱160℃晶化3天；过滤，洗涤至pH＝9.0，110℃烘干24h，随后在马弗炉中550℃焙烧8h即得微孔分子筛ZSM-5。
一般为了提高微孔分子筛在对二甲苯合成过程的择型性能，对微孔分子筛外表面酸性位的改性覆盖是关键。常规的改性覆盖微孔分子筛外表面酸性位的方法，大多数是采用浸渍法制备SiO2、MgO改性微孔分子筛。但浸渍过程常会导致分子筛孔道堵塞，从而引起微孔分子筛活性降低。
而采用本发明所述的技术方案后，得到的表面改性微孔分子筛可用于甲苯烷基化合成对二甲苯的过程中，对对二甲苯有较好的择形性能。本发明利用磁控溅射技术获取的改性微孔分子筛，沉积速率高，沉积温度低，分子筛材料损伤小，工作气压较低，沉积制备的薄膜均匀致密，适用于大批的工业化生产。
附图说明
附图1为磁控溅射Si改性后ZSM-5微孔分子筛材料的XRD表征图；
附图2为磁控溅射Ti改性后ZSM-5微孔分子筛材料的XRD表征图。
从图上可以看出，通过磁控溅射技术对微孔分子筛进行表面改性处理，不会对微孔分子筛本身的结构造成损坏。
具体实施方式
本发明将就以下实施例作进一步说明，但应了解的是，这些实施例仅为例示说明之用，而不应被解释为本发明实施的限制。
实施例1
将微孔分子筛ZSM-5平铺在基片上，以Si为靶材，在射频功率为100W，氩氧比例为10:1，溅射腔温度分别为40℃、55℃、70℃条件下磁控溅射30分钟，制备Si改性ZSM-5微孔分子筛，所得催化剂记为Cat1、Cat2、Cat3。
实施例2
将微孔分子筛MCM-22平铺在基片上，以B为靶材，在射频功率为150W，氩氧比例为10:4，溅射腔温度分别为50℃条件下分别进行磁控溅射15分钟、30分钟和60分钟，制备B改性MCM-22微孔分子筛，所得催化剂记为Cat4、Cat5、Cat6。
实施例3
将微孔分子筛ZSM-5平铺在基片上，以Ti为靶材，在射频功率为50W，氩氧比例为10:3，溅射腔温度分别为70℃条件下分别进行磁控溅射30分钟和60分钟，制备Ti改性ZSM-5微孔分子筛，所得催化剂记为Cat7、Cat8。
将上述实施例中的得到的改性微孔分子筛用于甲苯烷基化合成对二甲苯过程中，典型反应条件为：反应温度400℃，甲苯与甲醇摩尔比为4:1，原料质量空速为1h-1，所得到的微孔分子筛催化性能如下表1所示：
表1表面改性微孔分子筛催化剂的活性评价
| 催化剂 | 甲苯转化率/％ | 对二甲苯选择性/％ |
| Cat1 | 24.1 | 40.2 |
| Cat2 | 21.7 | 57.5 |
| Cat3 | 20.1 | 83.5 |
| Cat4 | 23.3 | 45.4 |
| Cat5 | 21.2 | 60.6 |
| Cat6 | 20.0 | 90.1 |
| Cat7 | 20.9 | 83.5 |
| Cat8 | 21.2 | 88.7 |
将上述实施例中的得到的改性微孔分子筛用于甲苯歧化合成对二甲苯过程中，典型反应条件为：反应温度400℃，原料质量空速为1h-1，所得到的催化性能如下表2所示：
表2表面改性微孔分子筛催化剂的活性评价
| 催化剂 | 甲苯转化率/％ | 对二甲苯选择性/％ |
| Cat1 | 71.1 | 52.2 |
| Cat2 | 64.5 | 60.7 |
| Cat3 | 60.1 | 80.3 |
| Cat4 | 73.4 | 71.1 |
| Cat5 | 66.5 | 88.3 |
| Cat6 | 57.4 | 91.2 |
| Cat7 | 55.3 | 87.1 |
| Cat8 | 51.7 | 90.5 |
从表1和表2数据可以看出：通过磁控溅射制备的Si、B、Ti改性微孔分子筛在合成对二甲苯过程中有较好的表现，对二甲苯选择性最高可以达到90％以上，说明该方法可以对微孔分子筛的外表面进行有效的覆盖，且对分子筛孔道影响较小。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (4)
1.一种微孔分子筛的表面改性方法，其特征在于该方法是按照下述步骤进行的：
(1)将微孔分子筛置于磁控溅射仪基片上；
(2)对溅射腔进行真空处理，使溅射腔压力降至4.5×10-3Pa以下；
(3)打开Ar、O2流量调节阀，调节Ar：O2流量比为10:1～10:4，调节溅射腔工作气压为0.2Pa；
(4)调节射频功率为50～150W，使溅射腔温度保持在40～70℃；
(5)对微孔分子筛进行15～60分钟的溅射处理，即得到表面改性的微孔分子筛材料。
2.根据权利要求1所述的一种微孔分子筛的表面改性方法，其特征在于磁控溅射过程所用的靶材是Si、B或Ti。
3.根据权利要求1所述的一种微孔分子筛的表面改性方法，其特征在于所述的微孔分子筛是ZSM-5或MCM-22。
4.根据权利要求1所述的一种微孔分子筛的表面改性方法，其特征在于所述表面改性的微孔分子筛材料可用于甲苯与甲醇烷基化或甲苯歧化合成对二甲苯的过程。
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