CN107983370B - 一种MoS2微米花在催化硝基苯加氢制苯胺反应中的应用 - Google Patents
一种MoS2微米花在催化硝基苯加氢制苯胺反应中的应用 Download PDFInfo
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Abstract
本发明涉及一种MoS2微米花在催化硝基苯加氢制苯胺反应中的应用，具体的说是通过MoS2微米花可高效催化硝基苯制苯胺。本发明所述的MoS2微米花是以Na2MoO4·2H2O、铜试剂(C5H10NS2Na·3H2O)为前驱体，通过水热方法合成的，能够有效催化硝基苯加氢制苯胺，选择性为100％，无副产物产生。
Description
技术领域
本发明涉及MoS2微米花及其在催化硝基苯加氢反应中的应用，属于催化剂的制备与应用领域。
背景技术
苯胺又称阿尼林油、氨基苯，在室温下为无色油状液体。苯胺是有机化工过程特别是精细化工过程中的重要原料和中间体，广泛应用于聚氨酯、医药、农药、染料、香料、橡胶等领域。目前,工业上通常采用硝基苯铁粉还原法、苯酚氨解法、硝基苯催化加氢还原法生产苯胺。其中化工工艺成本高、环境污染严重限制了硝基苯铁粉还原法、苯酚氨解法的使用，硝基苯催化氢化法以清洁H2为氢源，具有原料成本低、工序少、收率高、环境友好等优点，成为苯胺主要的合成方法。
硝基苯催化加氢制备苯胺主要方法有：硝基苯气相加氢和硝基苯液相加氢。其中气相加氢法是将硝基苯原料气化后与H2混合，通过装有催化剂的固定床或流化床反应器，在200-300 ℃，2-4MPa H2下进行加氢还原生成苯胺和水蒸气，再经冷凝、分离、脱水及精馏而得到苯胺，该工艺具有技术成熟、操作简单、维修费用低、不需要分离催化剂及产品质量好等优点，但反应过程需要压力较高，易发生局部过热而引起副反应和催化剂失活。另一类硝基苯液相催化加氢在100-200℃，0.5-3.0MPa压力下，采用催化剂，在无水条件下硝基苯进行加氢反应生成苯胺。硝基苯液相催化加氢工艺的优点是反应温度较低，副反应少，催化剂寿命长。从环境友好和反应效率的角度考虑，硝基苯液相催化加氢的研究具有重要的应用价值，而且还有助于对硝基苯苯加氢制备苯胺反应机理的认识。
目前，能够有效催化硝基苯加氢制苯胺的固体催化剂主要是贵重金属体系和Ni基催化剂体系。例如：Serp等报道C60负载的Ru催化剂在80℃，3MPa H2下反应20h，硝基苯转化率为 100％，苯胺选择性为96％(P.Serp,et al.,ACS Catal.,2016,6,6018-6024)。Mizukoshi等报道石墨烯负载的Pd催化剂在25℃，1MPa H2下反应5h，硝基苯转化率为100％，苯胺选择性为 100％(Y.Mizukoshi,et al.,Mater.Lett.,2017,199,24–27)。Sun等报道CoNi双金属催化剂在 120℃，3MPa H2下反应6h，硝基苯为100％，苯胺选择性为100％(Y.Sun,et al.,Nanoscale,2016, 8,3949-3953)。Qiu等报道C负载的Ni催化剂在140℃，2MPa H2下反应2h，硝基苯转化率为 73％，苯胺选择性为96.9％(J.Qiu,et al.,Phys.Chem.Chem.Phys.,2015,17,145-150)。
尽管这些负载型金属催化剂可高效催化硝基苯加氢制备苯胺，但贵金属价格昂贵，储量有限，且需求量逐年增加，而Ni基催化剂中活性物种Ni需要通过高温(>400℃)还原含Ni 前驱体获得，因此寻找非贵金属且合成路径简单有效的催化剂是硝基苯加氢制苯胺反应的研究热点。过渡金属硫化物特别是MoS2作为一类新催化材料引起了人们的关注，在某些加氢、脱氢反应中表现出优异的催化性能，但以用H2为氢源，硝基苯加氢制备苯胺体系中还研究的较少。因此，研究MoS2催化剂的制备及结构调控，使其能够高活性高选择性的催化硝基苯生成苯胺，具有潜在的实用价值。
发明内容：
本发明旨在提供一种新型的硝基苯加氢的MoS2催化剂，所制备的微米花状结构MoS2可高效催化硝基苯加氢制备苯胺，实现100％的苯胺选择性。
基于上述目的，本发明所涉及的技术方案如下：
1)MoS2微米花的制备：在烧杯中加入5mmol Na2MoO4·2H2O、10mmol铜试剂(C5H10NS2Na·3H2O)和60mL水，搅拌至溶解，将所得液体转入100ml以聚四氟乙烯为内衬的不锈钢反应釜中于240℃水热处理24h，然后自然冷却至室温，产物经离心洗涤，50℃真空干燥得到MoS2微米花，直径为3.9-5.8μm，表面积为23.74m2/g。
2)将MoS2微米花催化剂用于催化硝基苯加氢制苯胺反应。MoS2微米花在100℃，3MPa H2下反应6h，硝基苯转化率达100％，苯胺选择性为100％。
本发明具有如下优点：
1)利用铜试剂(C5H10NS2Na·3H2O)为硫源，水热合成了MoS2微米花，有效的拓展了MoS2的制备方法。
2)通过合成微米花状结构MoS2，实现了硝基苯加氢制备苯胺，转化率100％，选择性为 100％。
3)有效的拓展了该反应的催化剂范围，使其不再主要局限于贵重金属催化剂和Ni基催化剂，MoS2微米花也可高效催化该反应。
4)本发明具有环境友好、原子利用率和过程效率高的特点。
附图说明：
图1是MoS2微米花催化剂的表征结果，(a)XRD,(b,c)SEM和(d)HRTEM。
具体实施方式
下列实施例用来进一步说明本发明，但不因此而限制本发明。
实施例1
所述MoS2微米花的制备：
在烧杯中加入5mmol Na2MoO4·2H2O、10mmol铜试剂(C5H10NS2Na·3H2O)和60mL 水，搅拌至溶解，将所得液体转入100ml以聚四氟乙烯为内衬的不锈钢反应釜中于240℃水热处理24h，然后自然冷却至室温，产物经离心洗涤，50℃真空干燥可得到MoS2微米花。材料表征结果如图1所示。
实施例2-5
实施例1所制备的材料用于催化硝基苯加氢制备苯胺反应。
将60mg实施例1中的材料加入到含有4mL甲苯，1mmol硝基苯的50mL高压反应釜中，通入H2除掉体系中的空气，最终保持3MPa H2。置于油浴锅内，搅拌条件下100℃反应一定时间(1-6h)，反应产物离心分离后取上层清夜，用气相色谱分析其组成。色谱分析条件如下：气相色谱，OV-1701毛细管柱(50m×0.25mm×0.25μm)，色谱用H2为燃烧气，空气为助燃气，保护气为氦气。反应结果见表1。
表1 MoS2微米花催化硝基苯加氢制苯胺的反应结果
由表1可以看出：MoS2微米花催化硝基苯加氢，在100℃时反应1h、2h、4h、6h，硝基苯的转化率为23％、42％、89％、100％，苯胺的选择性均为100％，且没有副产物生成。
实施例6
实验步骤同实施例5，催化反应结束后，离心处理得到MoS2微米花催化剂，重复实施例 5的实验步骤，共进行了3次重复实验。硝基苯的转化率和苯胺的选择性均为100％。
对比例1
将商品化的MoS2作为对比催化剂，实验步骤同实施例5。将60mg商品化的MoS2加入到含有4mL甲苯，1mmol硝基苯的50mL高压反应釜中，通入H2除掉体系中的空气，最终保持3MPa H2。置于油浴锅内，搅拌条件下100℃反应6h，反应产物离心分离后取上层清夜，用气相色谱分析其组成，发现硝基苯转化率为52％，苯胺选择性为100％。
Claims (1)
1.一种MoS2微米花催化硝基苯加氢制苯胺的方法，其特征在于：包括如下步骤：（1）MoS2微米花由如下步骤制得：在烧杯中加入5 mmol Na2MoO4·2H2O、10 mmol 铜试剂C5H10NS2Na·3H2O 和 60 mL 水，搅拌至溶解，将所得液体转入100 mL以聚四氟乙烯为内衬的不锈钢反应釜中于240 oC水热处理24 h，然后自然冷却至室温，产物经离心洗涤，50 oC真空干燥得到MoS2微米花，直径为3.9-5.8 μm，表面积为23.74 m²/g；
（2）MoS2微米花催化硝基苯加氢制苯胺反应，在100 oC，3 MPa H2下反应6 h，硝基苯转化率为100%，苯胺选择性为100%。
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