CN111017953A - 氟化的硅铝分子筛及其制备方法和应用 - Google Patents

氟化的硅铝分子筛及其制备方法和应用 Download PDF

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CN111017953A
CN111017953A CN201911320320.4A CN201911320320A CN111017953A CN 111017953 A CN111017953 A CN 111017953A CN 201911320320 A CN201911320320 A CN 201911320320A CN 111017953 A CN111017953 A CN 111017953A
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molecular sieve
fluorinated
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fluorination
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CN111017953B (zh
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陈爽
姚素梅
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Tianjin Changlu Chemical New Material Co ltd
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Abstract

本发明属于催化剂制备领域，具体涉及一种氟化的硅铝分子筛及其制备方法和应用。氟化的硅铝分子筛的制备方法包括下述步骤：将分子筛在烘箱中干燥后，放入管式炉中，通入N2升温至200‑500℃，改通CHClF2气体进行氟化，氟化完成后改通N2降温至室温。压片成型取20‑40目。本申请通过将氟化气体通CHClF2(R22)通入管式炉和分子筛作用后形成氟化的硅铝分子筛，操作方便，且得到的硅铝分子筛作为制备六氟丙酮的催化剂催化效率高，选择性高，稳定型强。

Description

氟化的硅铝分子筛及其制备方法和应用
技术领域
本发明属于催化剂制备领域，具体涉及一种氟化的硅铝分子筛及其制备方法和应用。
背景技术
分子筛问世以来，由于其具有丰富的微孔结构，良好的水热稳定性和强酸性等特点，作为催化、吸附分离材料已经广泛应用于石油加工、煤化工、环境保护与精细化工等催化领域。尤其是ZSM-5型、Y型分子筛等分子筛已经广泛应用于裂解，异构，烷基化，芳构化等反应中，但是氟化后的分子筛却鲜有报道。
发明内容
本发明的目的在于提供一种氟化的硅铝分子筛及其制备方法和应用。
本发明为实现上述目的，采用以下技术方案：
一种氟化的硅铝分子筛的制备方法，包括下述步骤：将分子筛在烘箱中干燥后，放入管式炉中，通入N2升温至200-500℃，改通CHClF2(R22)气体进行氟化，氟化完成后改通N2降温至室温。压片成型取20-40目。
干燥温度为90-140℃，干燥时间为2-5小时，氟化温度为200-500℃，氟化气体流量为10-50ml/min，氟化时间为2-5小时。
优选，的包括下述步骤：将ZSM-5分子筛在烘箱中120℃干燥4小时，取10g放入管式炉中，通入N2升温至350℃，改通CHClF2气体，流量为30ml/min，氟化4小时，改通N2降温至室温。压片取20-40目。
所述的分子筛的硅铝摩尔比SiO2/Al2O3＝10-100。
优选的，分子筛的硅铝摩尔比SiO2/Al2O3＝50。
所述的分子筛为ZSM-5型或Y型分子筛。
本申请还包括一种所述的制备方法得到的氟化的硅铝分子筛。
本申请还包括一种所述的氟化的硅铝分子筛的应用，应用于制备六氟丙酮。
与现有技术相比，本发明的有益效果是：
本申请通过将氟化气体通CHClF2(R22)通入管式炉和分子筛作用后形成氟化的硅铝分子筛，操作方便，且得到的硅铝分子筛作为制备六氟丙酮的催化剂催化效率高，选择性高，稳定型强。
具体实施方式
为了使本技术领域的技术人员更好地理解本发明的技术方案，下面结合最佳实施例对本发明作进一步的详细说明。
实施例一：将ZSM-5分子筛(硅铝比为10)在烘箱中120℃干燥4小时，取10g放入管式炉中，通入N2升温至350℃，改通CHClF2(R22)气体，流量为30ml/min，氟化4小时，改通N2降温至室温。压片取20-40目，为催化剂A。
实施例二：具体步骤与实施例一制备步骤相同，只是选用的ZSM-5分子筛硅铝比为50。此为催化剂B。
实施例三：具体步骤与实施例一制备步骤相同，只是选用的分子筛为Y型。此为催化剂C。
实施例四：此为对比例，按照专利US2004186322制备TiO2作为催化剂。此为催化剂D。
分别对催化剂A、B、C、D进行六氟环氧丙烷异构化反应。
反应试验在固定床反应器内进行，不锈钢反应管(内径10mm，长度300mm)，分别装入由上述方法(实施例1、2、3、4)制成的样品各5.0ml(20-40目)，反应温度为20℃，60℃，100℃，150℃，200℃，操作压力为常压，反应空速为300h-1。反应产物采用气相色谱分析方法分析测定，然后通入去离子水中吸收生成六氟丙酮水合物。反应结果如表1所示。
表1
Figure BDA0002326975560000021
考察催化剂A的反应稳定性，装填催化剂5.0ml(20-40目)，反应温度为60℃，，操作压力为常压，反应空速为300h-1。反应活性随时间的变化如表2所示。
表2
Figure BDA0002326975560000031
结果表明，在500小时的反应时间内，催化剂一直表现出较高的反应活性，具体很强的催化稳定性。
以上内容仅为本发明的较佳实施例，对于本领域的普通技术人员，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，本说明书内容不应理解为对本发明的限制。

Claims (8)

1.一种氟化的硅铝分子筛的制备方法，其特征在于，包括下述步骤：将分子筛在烘箱中干燥后，放入管式炉中，通入N2升温至200-500℃，改通CHClF2气体进行氟化，氟化完成后改通N2降温至室温。压片成型取20-40目。
2.根据权利要求1所述的氟化的硅铝分子筛的制备方法，其特征在于，干燥温度为90-140℃，干燥时间为2-5小时，氟化温度为200-500℃，氟化气体流量为10-50ml/min，氟化时间为2-5小时。
3.根据权利要求1所述的氟化的硅铝分子筛的制备方法，其特征在于，包括下述步骤：将ZSM-5分子筛在烘箱中120℃干燥4小时，取10g放入管式炉中，通入N2升温至350℃，改通CHClF2气体，流量为30ml/min，氟化4小时，改通N2降温至室温。压片取20-40目。
4.根据权利要求1所述的氟化的硅铝分子筛的制备方法，其特征在于，所述的分子筛为ZSM-5型或Y型分子筛。
5.根据权利要求1所述的氟化的硅铝分子筛的制备方法，其特征在于，所述的分子筛的硅铝摩尔比SiO2/Al2O3＝10-100。
6.根据权利要求1所述的氟化的硅铝分子筛的制备方法，其特征在于，所述的分子筛的硅铝摩尔比SiO2/Al2O3＝50。
7.一种权利要求1-6任一项所述的制备方法得到的氟化的硅铝分子筛。
8.一种权利要求7所述的氟化的硅铝分子筛的应用，其特征在于，应用于制备六氟丙酮。
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN112745194A (zh) * 2020-12-31 2021-05-04 山东华夏神舟新材料有限公司 以六氟环氧丙烷为原料连续生产六氟异丙醇的工艺方法

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