CN102093222A - 固体酸催化剂SO42-/TiO2-HNbMoO6催化甲苯选择性硝化的方法 - Google Patents

固体酸催化剂SO42-/TiO2-HNbMoO6催化甲苯选择性硝化的方法 Download PDF

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CN102093222A
CN102093222A CN2010106010140A CN201010601014A CN102093222A CN 102093222 A CN102093222 A CN 102093222A CN 2010106010140 A CN2010106010140 A CN 2010106010140A CN 201010601014 A CN201010601014 A CN 201010601014A CN 102093222 A CN102093222 A CN 102093222A
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toluene
nitrotoluene
acid
hnbmoo
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何杰
唐元
张忠良
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Yangzhou Institute Of Chemistry And Chemical Engineering Of Nanjing University
Anhui University of Science and Technology
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Yangzhou Institute Of Chemistry And Chemical Engineering Of Nanjing University
Anhui University of Science and Technology
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Abstract

一种固体酸催化剂SO4 2-/TiO2-HNbMoO6催化甲苯选择性硝化的方法，用SO4 2-/TiO2-HNbMoO6作催化剂,CCl4、醋酸酐与甲苯的体积比为3:1.2:1,发烟硝酸与甲苯的摩尔比为0.5~3:1，催化剂用量是甲苯和硝酸总质量的2-10%,甲苯转化率达到80~100%，对硝基甲苯与邻硝基甲苯的质量比达到1.23~1.54。

Description

固体酸催化剂SO<sub>4</sub><sup>2-</sup>/TiO<sub>2</sub>-HNbMoO<sub>6</sub>催化甲苯选择性硝化的方法
一、技术领域
本发明涉及一种SO4 2-/TiO2-HNbMoO6固体酸催化剂用于甲苯选择性硝化的方法。
二、背景技术
甲苯选择性硝化提高产物中对硝基甲苯比例是目前研究热点，固体酸催化剂替代硫酸往往可以提高产物中对硝基甲苯比例。刘丽荣等(刘丽荣，吕春绪，李霞.固体铌酸催化下甲苯的硝化，应用化学.2007，24(12)：1374～1377)研究了铌酸(Nb2O5.nH2O)上甲苯的硝酸选择性硝化，对、邻硝基甲苯比例达到0.79，反应转化率为99.3％。层状铌钼酸(HNbMoO6)几乎具有层状铌酸的所有性质且前者酸性远远强于后者。2009年Caio Tagusagawa(Caio Tagusagawa，Atsushi Takagaki.Catal.Today.2009，267-231)研究了HNbMoO6催化甲苯与苄醇付克烷基化反应，结果表明催化活性高于Nb2O5-MoO3、铌酸(Nb2O5.nH2O)。
三、发明内容
本发明提供了一种SO4 2-/TiO2-HNbMoO6固体酸催化剂催化甲苯选择性硝化的方法。甲苯选择性硝化反应：在容器中加入CCl4、醋酸酐、甲苯、质量分数为95％的发烟硝酸和SO4 2-/TiO2-HNbMoO6催化剂，CCl4、醋酸酐与甲苯的体积比为3∶1.2∶1，发烟硝酸与甲苯的摩尔比为0.5～3∶1，催化剂用量是甲苯和硝酸总质量的2-10％，搅拌，30-50℃下滴加发烟硝酸，滴加完毕后，反应温度控制在30-50℃，继续搅拌0.5-2小时，反应结束后过滤分出液相，液相用NaHCO3水溶液中和至中性，分出有机相，有机相用无水硫酸钠干燥后，过滤得到硝基甲苯混合物，气相色谱进样分析。分析结果：甲苯转化率达到80～100％，对硝基甲苯与邻硝基甲苯的质量比达到1.23～1.54。
Figure BDA0000040083620000011
固体酸SO4 2-/TiO2-HNbMoO6的合成：室温下将19.32g钛酸正丁酯缓慢滴加到200mL1mol/L盐酸溶液中，滴加2.5小时，继续搅拌0.5小时得到混合液，将2克C4H9NH2-HNbMoO6(参考：N.S.P.Bhuvanesh，J.Gopalakrishnan.Inorg.Chem.1995，34，3160-3164)加入到混合液中搅拌3小时，过滤分离，水洗至无氯离子，室温干燥得到固体酸TiO2-HNbMoO6。将1.2克TiO2-HNbMoO6置于容器中，加入1.8mL 0.4mol/L硫酸混合，80℃水浴上蒸干，500℃焙烧3小时得到固体酸SO4 2-/TiO2-HNbMoO61克。
四、具体实施方式
实施例1：甲苯选择性硝化反应：在容器中加入CCl415mL、醋酸酐6mL、甲苯5mL和SO4 2-/TiO2-HNbMoO6催化剂1克，搅拌，40℃水浴下滴加质量分数为95％的发烟硝酸5mL，滴加完毕后，反应温度控制在40℃，继续搅拌1.5小时，反应结束后过滤分出液相，液相用NaHCO3水溶液中和至中性，分出有机相，有机相用无水硫酸钠干燥后，过滤得到硝基甲苯混合物。气相色谱进样分析，甲苯转化率达到100％，对硝基甲苯与邻硝基甲苯的质量比达到1.54。
实施例2：甲苯选择性硝化反应：在容器中加入CCl415mL、醋酸酐6mL、甲苯5mL和SO4 2-/TiO2-HNbMoO6催化剂0.45克，搅拌，40℃水浴下滴加质量分数为95％的发烟硝酸5mL，滴加完毕后，反应温度控制在40℃，继续搅拌1.5小时，反应结束后过滤分出液相，液相用NaHCO3水溶液中和至中性，分出有机相，有机相用无水硫酸钠干燥后，过滤得到硝基甲苯混合物。气相色谱进样分析，甲苯转化率达到80％，对硝基甲苯与邻硝基甲苯的质量比达到1.23。
实施例3：甲苯选择性硝化反应：在容器中加入CCl415mL、醋酸酐6mL、甲苯5mL和SO4 2-/TiO2-HNbMoO6催化剂1克，搅拌，40℃水浴下滴加质量分数为95％的发烟硝酸2mL，滴加完毕后，反应温度控制在40℃，继续搅拌1.5小时，反应结束后过滤分出液相，液相用NaHCO3水溶液中和至中性，分出有机相，有机相用无水硫酸钠干燥后，过滤得到硝基甲苯混合物。气相色谱进样分析，甲苯转化率达到86％，对硝基甲苯与邻硝基甲苯的质量比达到1.37。
实施例4：甲苯选择性硝化反应：在容器中加入CCl415mL、醋酸酐6mL、甲苯5mL和SO4 2-/TiO2-HNbMoO6催化剂1克，搅拌，40℃水浴下滴加质量分数为95％的发烟硝酸5mL，滴加完毕后，反应温度控制在40℃，继续搅拌0.5小时，反应结束后过滤分出液相，液相用NaHCO3水溶液中和至中性，分出有机相，有机相用无水硫酸钠干燥后，过滤得到硝基甲苯混合物。气相色谱进样分析，甲苯转化率达到93％，对硝基甲苯与邻硝基甲苯的质量比达到1.26。

Claims (1)

1.一种固体酸催化剂SO4 2-/TiO2-HNbMoO6催化甲苯选择性硝化的方法，
在容器中加入CCl4、醋酸酐、甲苯、质量分数为95%的发烟硝酸，其特征是用SO4 2-/TiO2-HNbMoO6作催化剂, CCl4、醋酸酐与甲苯的体积比为3:1.2:1, 发烟硝酸与甲苯的摩尔比为0.5~3:1，催化剂用量是甲苯和硝酸总质量的2-10%,搅拌,30-50℃下滴加发烟硝酸,滴加完毕后, 反应温度控制在30-50℃，继续搅拌0.5-2小时后，过滤分出液相，液相用NaHCO3水溶液中和至中性，分出有机相，有机相用无水硫酸钠干燥后，过滤得到硝基甲苯混合物，硝基甲苯混合物中对硝基甲苯与邻硝基甲苯的质量比达到1.23~1.54，甲苯转化率达到80~100%。
CN2010106010140A 2010-12-23 2010-12-23 固体酸催化剂SO42-/TiO2-HNbMoO6催化甲苯选择性硝化的方法 Pending CN102093222A (zh)

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CN106146357A (zh) * 2015-04-14 2016-11-23 上海合丽亚日化技术有限公司 一种dsd酸的制备方法

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106146357A (zh) * 2015-04-14 2016-11-23 上海合丽亚日化技术有限公司 一种dsd酸的制备方法
CN106146357B (zh) * 2015-04-14 2017-12-26 上海合丽亚日化技术有限公司 一种dsd酸的制备方法

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