CN109053379A - 一种用于甲苯氧化制备高附加值产物的还原型氧化物材料 - Google Patents

一种用于甲苯氧化制备高附加值产物的还原型氧化物材料 Download PDF

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CN109053379A
CN109053379A CN201811017987.2A CN201811017987A CN109053379A CN 109053379 A CN109053379 A CN 109053379A CN 201811017987 A CN201811017987 A CN 201811017987A CN 109053379 A CN109053379 A CN 109053379A
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麻春艳
宋茂勇
杨成功
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Research Center for Eco Environmental Sciences of CAS
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Abstract

本发明公开了甲苯选择氧化制备苯甲醇、苯甲醛、苯甲酸、苯甲酸苄酯的还原型氧化物材料，属于纳米材料技术领域。以甲苯为原料，无溶剂，分子氧(氧气、空气等含氧气体)为氧化剂，在还原型氧化物材料的催化作用下，选择性氧化甲苯制备苯甲醇、苯甲醛、苯甲酸、苯甲酸苄酯。通过调变氧化物的还原度，以及添加金属助剂，在最佳反应条件下，甲苯转化率最高可达到60％，苯甲醇、苯甲醛、苯甲酸、苯甲酸苄酯四种产物选择性加和可以达到100％。

Description

一种用于甲苯氧化制备高附加值产物的还原型氧化物材料
技术领域
本发明涉及一种甲苯液相选择氧化制备苯甲醇、苯甲醛、苯甲酸、苯甲酸苄酯的还原型氧化物材料。该材料在无有机溶剂、分子氧氧化剂作用下实现甲苯的选择性氧化制备苯甲醇、苯甲醛、苯甲酸、苯甲酸苄酯，无需添加酸碱助剂。
背景介绍：
甲苯，有机化工的重要原料，利用甲苯的选择氧化，可合成苯甲醇、苯甲醛、苯甲酸和苯甲酸苄酯。苯甲醇主要作为化妆品定香剂，医用药膏和药物防腐剂；苯甲醛主要作为有机溶剂，香料等；苯甲酸主要用于医药行业及染料载体和增塑剂等的生产；苯甲酸苄酯主要用作疥疮的治疗也用于调合香料。因而，苯甲醛、苯甲酸和苯甲酸苄酯这些产品是具有较高的商业价值，开发甲苯为附加值较高的下游产品具有重要研究意义和经济价值。
工业上，甲苯液相氧化多采用Fe、Co、Ni、V等金属盐作为催化剂，在强碱或者强酸条件下反应，易腐蚀设备且产物不易分离，后续处理过程复杂。因此，在去酸碱助剂的条件下，液相甲苯直接以分子氧作为氧化剂，选择氧化制备甲苯下游产物符合绿色化学和清洁生产需求。
目前无溶剂、无酸碱助剂，分子氧催化选择氧化甲苯的方法是一种最为理想，最为清洁的方法。但是，与该方法有关的相关研究还不成熟，几乎没有实际工业化应用。专利号为CN 102219662的中国专利公布了一种无溶剂空气氧化甲苯制备苯甲醇、苯甲醛、苯甲酸、苯甲酸苄酯的方法，该方法采用的催化剂为可溶性锰盐，造成产物不易分离提纯，锰盐不易去除，且转化率仅为10％。专利号为CN 106883116的中国专利提出用以铁氧化物负载金为催化剂，分子氧为氧源，实现了温和条件下液相甲苯的选择氧化，但产物没有苯甲醇，产物多样性不足，影响工业化的扩展性。
文献(Science,2011,311,195)提出Au-Pd/C和Au-Pd/TiO2表现出很好的，甲苯氧化活性，且不同的载体和不同的Au-Pd配比表现出很好的产物选择性，但催化剂的贵金属负载量较高(1％)，经济性不好。
发明内容
本发明的目的是在无溶剂条件下，以含氧气体为氧化剂，在还原型氧化物材料以及还原型氧化物负载金属助剂材料的催化剂作用下，选择性氧化甲苯制备苯甲醇、苯甲醛、苯甲酸、苯甲酸苄酯。
本发明采用以下技术实现上述目的：
以还原型氧化物为催化剂(氧化物可以为钛氧化物、铜氧化物、铈氧化物、锰氧化物、钨氧化物、钼氧化物等金属氧化物)，采用浸渍法或静电吸附法添加金属助剂(金属可以为铁、钴、镍、铂、金、钯等)，负载量≤0.15％。
反应在具有搅拌功能的高压反应釜中进行，反应温度为25-300℃，反应压力为0.1-10MPa，可使用辅助光源，辅助光源功率为50-200W，光的范围可以为紫外光(<400nm)，可见光或者全波段光。反应时间≥2h。
催化剂均匀混在甲苯中，浓度为0.5-100mg/mL。
与现有技术相比，本发明的优点是：
1)还原型氧化物催化剂制备简单，成本低，以分子氧(氧气、空气等含氧气体)为氧化剂，生产过程更加清洁，可以利用光能，能源利用更加多样化。
2)在最佳反应条件下，甲苯转化率最高可达60％，主要高附加值产物有四种，更加丰富了工业生产的扩展选择性，并且苯甲醇、苯甲醛、苯甲酸、苯甲酸苄酯四种产物选择性加和可达到100％。
具体实施方式
下列实施方式对本发明做进一步解释，并非限定本发明的应用范围。
实施例1
40毫升甲苯加入到100毫升高压反应釜，加入40毫克还原型TiO2催化剂，反应温度160℃，维持氧气压力在1MPa，磁力搅拌速率为1500转/分钟，反应10小时后，甲苯转化率达到23％，其中苯甲醇选择性达到19％，苯甲醛选择性为42％，苯甲酸选择性为33％，苯甲酸苄酯选择性为6％。
实施例2
40毫升甲苯加入到100毫升高压反应釜，加入40毫克还原型TiO2催化剂，反应温度25℃，维持氧气压力在1MPa，50W辅助光照(氙灯光源，全波段)，磁力搅拌速率为1500转/分钟，反应10小时后，甲苯转化率达到14％，其中苯甲醇选择性达到46％，苯甲醛选择性为37％，苯甲酸选择性为15％，苯甲酸苄酯选择性为2％。
实施例3
40毫升甲苯加入到100毫升高压反应釜，加入40毫克还原型TiO2催化剂，反应温度160℃，维持氧气压力在1MPa，50W辅助光照(氙灯光源，全波段)，磁力搅拌速率为1500转/分钟，反应5小时后，甲苯转化率达到56％，其中苯甲醇选择性达到7％，苯甲醛选择性为5％，苯甲酸选择性为76％，苯甲酸苄酯选择性为12％。
实施例4
40毫升甲苯加入到100毫升高压反应釜，加入40毫克还原型WO3催化剂，反应温度160℃，维持氧气压力在1MPa，50W辅助光照(氙灯光源，全波段)，磁力搅拌速率为1500转/分钟，反应5小时后，甲苯转化率达到58％，其中苯甲醇选择性达到9％，苯甲醛选择性为7％，苯甲酸选择性为73％，苯甲酸苄酯选择性为11％。
实施例5
40毫升甲苯加入到100毫升高压反应釜，加入30毫克还原型MoO2催化剂，反应温度160℃，维持氧气压力在1MPa，50W辅助光照(氙灯光源，全波段)，磁力搅拌速率为1500转/分钟，反应5小时后，甲苯转化率达到54％，其中苯甲醇选择性达到13％，苯甲醛选择性为11％，苯甲酸选择性为67％，苯甲酸苄酯选择性为9％。
实施例6
40毫升甲苯加入到100毫升高压反应釜，加入40毫克还原型Pt/TiO2催化剂，反应温度160℃，维持氧气压力在1MPa，50W辅助光照(氙灯光源，全波段)，磁力搅拌速率为1500转/分钟，反应5小时后，甲苯转化率达到60％，其中苯甲醇选择性达到5％，苯甲醛选择性为8％，苯甲酸选择性为72％，苯甲酸苄酯选择性为15％。
实施例7
40毫升甲苯加入到100毫升高压反应釜，加入40毫克还原型Pt/WO3催化剂，反应温度160℃，维持氧气压力在1MPa，50W辅助光照(氙灯光源，全波段)，磁力搅拌速率为1500转/分钟，反应5小时后，甲苯转化率达到59％，其中苯甲醇选择性达到6％，苯甲醛选择性为13％，苯甲酸选择性为69％，苯甲酸苄酯选择性为12％。
实施例8
40毫升甲苯加入到100毫升高压反应釜，加入40毫克还原型Co/WO3催化剂，反应温度160℃，维持氧气压力在1MPa，50W辅助光照(氙灯光源，全波段)，磁力搅拌速率为1500转/分钟，反应5小时后，甲苯转化率达到57％，其中苯甲醇选择性达到9％，苯甲醛选择性为16％，苯甲酸选择性为67％，苯甲酸苄酯选择性为8％。
上述实施例仅为本发明的最佳实施条件，不局限于实施例。凡是与本发明原则相同的等同替换、相关参数优化等，均应在本发明的保护范围之内。

Claims (7)

1.一种用于甲苯液相选择氧化制备苯甲醇、苯甲醛、苯甲酸、苯甲酸苄酯的还原型氧化物材料，具体包括：甲苯为原料，含氧气体为氧化剂(氧气或空气等)，温度为25-300℃，压力为0.1-10MPa，可辅助紫外或可见光协同作用，在还原型氧化物材料以及添加助剂的还原型氧化物材料的催化作用下使甲苯氧化，得到苯甲醇、苯甲醛、苯甲酸、苯甲酸苄酯中的一种或两种以上。
2.根据权利要求1所述的方法，其特征在于：所述还原型金属氧化物为表面富含氧空位和低价态金属的金属氧化物，包括TiO2、CuO、CeO2、MnO2、WO3、MoO2等氧化物。
3.根据权利要求1所述的方法，其特征在于：所述还原型氧化物为经过还原剂(硼氢化钠、碱金属、氢气等)还原处理的氧化物。
4.根据权利要求3所述的方法，其特征在于：所述还原型氧化物的还原度根据还原剂的用量，还原温度，还原时间调变而不同。
5.根据权利要求4所述的方法，其特征在于：所述的还原温度20-900℃，所述还原时间10-720分钟。
6.根据权利要求1所述的方法，其特征在于：所述助剂为过渡金属(Co、Ni、Fe等)和贵金属(Pt、Au、Pd等)，助剂负载量≤0.15％。
7.根据权利要求1所述，其特征在于：所述辅助紫外或可见光的光源功率为50-200W，光的范围可以为紫外光(<400nm)，可见光或者全波段光。
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