CN109225272B - 一种Pt-ZnS/C催化剂及其制备方法和应用 - Google Patents
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Abstract
本发明公开了一种Pt‑ZnS/C催化剂，该催化剂的制备方法包括：步骤1)活性炭预处理；步骤2)ZnS改性活性炭；步骤3)光还原负载Pt。该催化剂中Pt与ZnS存在SMSI效应(金属‑载体强相互作用)，活性组分与载体结合牢固、粒径小、分布窄、分散性好。该催化剂用于氯代硝基苯加氢制备氯代苯胺反应，氯代苯胺选择性在99.5％以上。
Description
技术领域
本发明属于催化剂领域，具体涉及一种Pt-ZnS/C催化剂及其制备方法和应用。
背景技术
硫化铂族金属催化剂在很多有机化合物的气相或液相选择加氢反应中都表现出良好的催化性能，加氢条件下比普通贵金属催化剂和非硫化贵金属催化剂有更好的加氢选择性和稳定性。硫化铂族金属催化剂可以提高有机液相加氢反应选择性，能使含羰基、羟基和卤素等官能团化合物催化加氢反应的选择性大大提高，在还原胺化、卤代芳硝基物的选择加氢等反应中都有广泛的应用。
氯代苯胺是用于合成染料、医药和农药等的重要中间体，市场需求量很大，传统的铁粉还原法和硫化碱还原法制备卤代苯胺环境污染十分严重，逐渐被污染小的催化加氢法所替代。但催化加氢法存在脱卤问题，脱卤严重会造成设备腐蚀和产品纯度下降，因此如何抑制氯代硝基苯催化加氢中的脱氯，是现在研究的重点和难点。目前主要有两种方法：一是向反应体系中加入助剂来抑制脱卤，但助剂会污染产品，分离困难；二是改善催化剂的性能，以达到抑制脱卤的目的。例如专利CN1199935提供一种卤代硝基苯催化加氢合成卤代苯胺的生产方法，该方法以炭纳米管为载体，Pt、Pd为活性组分制备催化剂。该催化剂能有效抑制脱卤，但是碳纳米管生产成本较高，不利于产业化。专利CN103349983A提供一种卤代硝基苯催化加氢制卤代苯胺用催化剂及应用，该催化剂载体经过无机酸回流处理、碳酸盐溶液浸泡，该方法制备的催化剂能较好的抑制脱卤，活性炭预处理工艺比较复杂。
发明内容
为达到以上目的，本发明提供了一种用于氯代硝基催化加氢制备氯代苯胺的Pt-ZnS/C催化剂，该催化剂以Pt为活性组分，以ZnS改性的活性炭为载体，纳米ZnS以单层或亚单层状态分散于活性炭表面上，Pt与ZnS之间存在SMSI效应(金属-载体强相互作用)，存在协同催化效应，大大提高了催化加氢反应的选择性，活性组分通过硫化锌的桥接作用与载体结合牢固，不易脱落流失，活性组分粒径小、分布窄、分散性好。该催化剂在氯代硝基苯加氢制备氯代苯胺反应，转化率为100％，氯代苯胺选择性在99.5％以上。
本发明提供的Pt-ZnS/C催化剂通过下述技术方案予以实现：
Pt-ZnS/C催化剂，该催化剂以Pt纳米颗粒为活性组分，以纳米ZnS改性修饰的活性炭为载体，其中Pt纳米颗粒占催化剂总质量的0.5～5％，Zn/Pt的质量比为0.5～2:1。
其中，上述Pt-ZnS/C催化剂中，所述活性炭的比表面为1000～1800m2/g，例如1200～1600m2/g。
其中，上述Pt-ZnS/C催化剂中，所述Pt纳米颗粒的粒径为1～5nm，所述纳米ZnS的粒径为20～400nm。
其中，上述Pt-ZnS/C催化剂中，所述纳米ZnS以单层或亚单层状态分散于活性炭表面上。
本发明还提供上述Pt-ZnS/C催化剂的制备方法，该方法包括以下步骤：
(1)活性炭预处理：对活性炭进行氧化预处理，处理后洗涤至中性，得到预处理的活性炭，干燥备用；
(2)ZnS改性活性炭：将上述预处理的活性炭分散于去离子水中浆化，向浆化液中加入锌源、硫化剂，搅拌后静置陈化，过滤洗涤干燥，煅烧后得到改性载体ZnS/C；
(3)光还原负载Pt：将上述改性载体ZnS/C分散于去离子水中，加入空穴清除剂，搅拌后再加入氯铂酸溶液，常温紫外光照射，过滤、洗涤、干燥，得到Pt-ZnS/C催化剂。
其中，上述Pt-ZnS/C催化剂的制备方法，步骤(1)中所述氧化预处理使用的氧化剂为双氧水或者硝酸，优选为硝酸，例如质量浓度8～15％的硝酸。
其中，上述Pt-ZnS/C催化剂的制备方法，步骤(1)中所述氧化预处理的时间为1～3h，温度为50～65℃。
其中，上述Pt-ZnS/C催化剂的制备方法，步骤(2)中所述锌源可以为氯化锌、醋酸锌和硝酸锌中的至少一种。其中，所述浆化液中锌离子的浓度可以为1～20g/L。
其中，上述Pt-ZnS/C催化剂的制备方法，步骤(2)中所述锌源中还含有聚乙烯吡咯烷酮(PVP)，所述PVP在浆化液中的浓度为0.01～2wt％。
其中，上述Pt-ZnS/C催化剂的制备方法，步骤(2)中加入锌源后搅拌1～3h，再滴加硫化剂，硫化剂加完后，继续搅拌1～2h。
其中，上述Pt-ZnS/C催化剂的制备方法，步骤(2)中所述硫化剂可以为硫化钠、硫化铵和硫脲中的至少一种；所述硫化剂加入量以硫计，锌与硫的摩尔比为1:1～10。
其中，上述Pt-ZnS/C催化剂的制备方法，步骤(2)中所述煅烧为在200～500℃的氮气气氛下锻烧1～3h。
其中，上述Pt-ZnS/C催化剂的制备方法，步骤(2)中所述静置陈化的时间为1～3h。
其中，上述Pt-ZnS/C催化剂的制备方法，步骤(3)中所述改性载体ZnS/C和去离子水的液固比(mL/g)为20～100:1。
其中，上述Pt-ZnS/C催化剂的制备方法，步骤(3)中所述空穴清除剂为甲醇和/或乙醇，空穴清除剂在体系中的体积分数为1～5％。
其中，上述Pt-ZnS/C催化剂的制备方法，步骤(3)中所述紫外光下照射的时间为8～12h。
本发明还提供上述Pt-ZnS/C催化剂应用于氯代硝基苯加氢制备氯代苯胺反应，优选无溶剂条件下氯代硝基苯液相加氢制备氯代苯胺：所述加氢反应在无溶剂条件下进行，催化剂用量为反应底物质量的0.5～3％，18％氨水用量为反应底物质量的1～3％，反应温度为60～120℃，加氢压力为0.6～1.2MPa，反应时间为60～120min。
本发明的有益效果是：
本发明提供的Pt-ZnS/C催化剂通过ZnS修饰载体，大大提高了催化加氢的选择性和稳定性；铂前驱体在ZnS光催化剂作用下还原为单质铂Pt0过程中，不需要加入保护剂；纳米铂与ZnS之间存在金属-载体强相互作用，结合牢固，改变了纳米铂的电子状态，同时限制了催化剂使用过程中纳米铂粒子的迁移与团聚；铂纳米晶粒径小，为1-5nm，分布窄，分散性好。该催化剂邻氯硝基苯加氢反应中，转化率为100％，邻氯苯胺选择性大于99.5％。
具体实施方式
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
除非另有说明，以下实施例中使用的原料和试剂均为市售商品，或者可以通过已知方法制备。
实施例1
1)活性炭预处理：将活性炭用10％硝酸在60℃下氧化预处理1～3h，洗涤至中性，干燥后备用；
2)ZnS改性活性炭：将6.70g氯化锌和0.5g PVP溶解于1000mL去离子水中，加入50g预处理的活性炭分散于其中，搅拌2h，滴加4％硫化铵溶液120mL，继续搅拌1.5h，静置陈化2h，过滤洗涤干燥后，于450℃的氮气下锻烧2h，得到改性载体ZnS/C，锌含量为6％；
3)光还原负载Pt：将步骤2)中的ZnS/C改性载体4.75g分散于500mL去离子水中，加入8mL甲醇，继续搅拌30min，再加入含0.25gPt的氯铂酸溶液，常温下在紫外光下照射10h，过滤、洗涤，70℃下真空干燥，得到5％Pt-ZnS/C催化剂。
实施例2
具体实施过程同实施例1，不同的是锌源为醋酸锌，改性载体ZnS/C中锌含量为4％，催化剂Pt-ZnS/C中铂含量为5％。
实施例3
具体实施过程同实施例1，不同的是锌源为硝酸锌，改性载体ZnS/C中锌含量为6％，催化剂Pt-ZnS/C中铂含量为5％。
实施例4
具体实施过程同实施例1，不同的是改性载体ZnS/C中锌含量为4％，催化剂Pt-ZnS/C中铂含量为3％。
实施例5
具体实施过程同实施例1，不同的是锌源为醋酸锌，改性载体ZnS/C中锌含量为4％，催化剂Pt-ZnS/C中铂含量为2％。
活性测试
将实施例1～5中的Pt-ZnS/C催化剂及传统5％Pt/C用于催化邻氯硝基苯加氢制备邻氯苯胺的反应中。反应在500mL高压釜中进行。向釜中投入催化剂0.5～1.5g、邻氯硝基苯100g、18％氨水1.6mL，封闭高压釜。抽真空氮气置换3次，开搅拌升温，转速800r/min。当釜温达到80℃时，通氢气充压至1.2MPa开始反应，保持釜温80℃～90℃，当不吸氢时停止反应，将高压釜骤冷至50℃以下，卸压开釜，将反应液离心分离后取样，气相色谱分析各产物含量。结果如下表1所示。
表1
| 催化剂样品 | 转化率 | 邻氯苯胺选择性 |
| 实施例1 | 100％ | 99.7％ |
| 实施例2 | 100％ | 99.3％ |
| 实施例3 | 100％ | 99.5％ |
| 实施例4 | 100％ | 99.6％ |
| 实施例5 | 100％ | 99.4％ |
| 传统5％Pt/C | 100％ | 80.3％ |
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (7)
1.Pt-ZnS/C催化剂，其特征在于，该催化剂以Pt纳米颗粒为活性组分，以纳米ZnS改性修饰的活性炭为载体，其中Pt纳米颗粒占催化剂总质量的0.5~5％，Zn/Pt的质量比为0.5~2:1；
所述活性炭的比表面为1000~1800m2/g；
所述Pt纳米颗粒的粒径为1~5nm，所述纳米ZnS的粒径为20~400nm；
所述纳米ZnS以单层或亚单层状态分散于活性炭表面上。
2.权利要求1所述Pt-ZnS/C催化剂的制备方法，其特征在于，该方法包括以下步骤：
(1)活性炭预处理：对活性炭进行氧化预处理，处理后洗涤至中性，得到预处理的活性炭，干燥备用；
(2)ZnS改性活性炭：将上述预处理的活性炭分散于去离子水中浆化，向浆化液中加入锌源、硫化剂，搅拌后静置陈化，过滤洗涤干燥，煅烧后得到改性载体ZnS/C；
(3)光还原负载Pt：将上述改性载体ZnS/C分散于去离子水中，加入空穴清除剂，搅拌后再加入氯铂酸溶液，常温紫外光照射，过滤、洗涤、干燥，得到Pt-ZnS/C催化剂。
3.根据权利要求2所述的制备方法，其特征在于，步骤(1)中所述氧化预处理使用的氧化剂为双氧水或者硝酸；所述氧化预处理的时间为1~3h，温度为50~65℃。
4.根据权利要求2所述的制备方法，其特征在于，步骤(2)中所述锌源为氯化锌、醋酸锌和硝酸锌中的至少一种；所述浆化液中锌离子的浓度为1~20g/L；
所述锌源中还含有聚乙烯吡咯烷酮(PVP)，所述PVP在浆化液中的浓度为0.01~2wt％；
加入锌源后搅拌1~3h，再滴加硫化剂，硫化剂加完后，继续搅拌1~2h。
5.根据权利要求2所述的制备方法，其特征在于，步骤(2)中所述硫化剂为硫化钠、硫化铵和硫脲中的至少一种；所述硫化剂加入量以硫计，锌与硫的摩尔比为1:1~10；
所述煅烧为在200~500℃的氮气气氛下锻烧1~3h；
所述静置陈化的时间为1~3h。
6.根据权利要求2所述的制备方法，其特征在于，步骤(3)中所述改性载体ZnS/C和去离子水的液固比为20~100:1mL/g；
所述空穴清除剂为甲醇和/或乙醇，空穴清除剂在体系中的体积分数为1~5％；
所述紫外光下照射的时间为8~12h。
7.权利要求1所述Pt-ZnS/C催化剂应用于氯代硝基苯加氢制备氯代苯胺反应。
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