CN115254201A - 一种氢还原再生纳米金属-磷-碳催化剂的方法 - Google Patents
一种氢还原再生纳米金属-磷-碳催化剂的方法 Download PDFInfo
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Abstract
本发明公开了一种氢还原再生纳米金属‑磷‑碳催化剂的方法，是将已经失活的纳米金属‑磷‑碳催化剂，置于氢气气氛下，于200~1200℃还原1‑24h，获得纳米金属‑磷‑碳催化剂。实验表明，纳米金属‑磷‑碳催化剂通过氢化还原再生后保持很高的催化活性，用于加氢催化还原不饱和化合物的反应中，使用多次后依然保持很高的催化效果。而且，该方法成本低、操作简易，普适性好，可以对多种有机化合物的不饱和键实现全加氢和选择性加氢，适用于进行工业化生产。
Description
技术领域
本发明属于催化剂制备技术领域，具体涉及一种金属再分散法纳米金属-磷-碳催化剂及其制备与应用。
背景技术
纳米金属催化材料在催化反应中具有广泛的应用（石油的深加工及其精炼、生物的加氢转化、二氧化碳转化利用等），但其在相对苛刻条件下（高温、高压、酸性、氢气等）容易在反应过程中发生金属的团聚、流失以及载体的坍塌、结构转变等引起失活，这些失活的催化材料大部分被当做固体废弃物进行处理，这样既不利于环境保护有，又导致了大量的金属流失，无形中增加了企业生产的成本。针对纳米金属催化材料的回收再利用已经有一些研究，例如，针对碳基催化剂一般采用直接煅烧回收金属；而非碳基催化剂的回收更加复杂，一般采用先煅烧、再强酸/强碱浸出的方法回收金属。针对因积碳失活的催化剂可在含氧气氛下高温煅烧催化剂；对因金属流失失活的催化剂，通过对催化剂再次补加适当的金属，但是，因金属团聚失活的催化相应的再生技术缺乏，因此，无论是从应用还是基础研究的角度看，发展一种针对因金属团聚失活的催化剂再生技术都具有很强的必要性和急迫性。
纳米金属-磷-碳催化剂，是由催化活性组分、协同催化组分分布于碳载体上形成的催化剂，其中催化活性组分为加氢金属，包括钌、铂、钴、镍、铱、金、铜、钯、银、铁、锌和铑等，协同催化组分为磷，主要用于加氢催化还原不饱和化合物的反应中。然而，在加氢催化还原反应中，纳米金属-磷-碳催化剂会因金属团聚导致催化活性降低或失活，从而使得催化剂不能回收利用。
发明内容
本发明的目的是针对纳米金属-磷-碳催化剂因发生金属团聚导致催化活性降低/失活的问题，提供一种氢还原再生纳米金属-磷-碳催化剂的方法。
本发明再生纳米金属-磷-碳催化剂的方法，是将已经失活的纳米金属-磷-碳催化剂，置于氢气气氛下，于200~1200℃还原1-24h，获得再生纳米金属-磷-碳催化剂。
所述纳米金属-磷-碳催化剂中，活性组分纳米金属为钌、铂、钴、镍、铱、金、铜、钯、银、铁、锌和铑中的至少一种，其含量为0.001~40wt.%。
所述协同催化组分磷的含量为0.01~40wt.%
所述碳载体为活性碳、石墨烯、碳纳米管、碳球、微孔碳、介孔碳、大孔碳、多级孔碳中的至少一种。
纳米金属-磷-碳催化剂通过氢化还原再生的原理：首先是活化的氢与载体中磷作用，形成P-H活性物种，P-H活性物种进一步和已经团聚的活性金属作用，使其进行再分散，形成纳米级别的金属颗粒，从而使催化剂再生。
TEM图显示，再生金属-磷-活性炭催化剂中的金属的粒径在5纳米以下，实现了催化剂的再生，使催化剂的活性位点增加，催化剂的活性明显提高。用于加氢催化还原不饱和化合物的反应中，使用多次后依然保持很高的催化效果。
附图说明
图1是本发明实施例1制备的催化剂的TEM图；
图2是本发明实施例2制备的催化剂的TEM图；
图3是本发明实施例2中循环使用催化剂的结果图；
图4是本发明实施例3制备的催化剂的TEM图。
具体实施方式
实施例1
纳米钌/磷-碳纳米管催化剂制备：将已经失活的1g钌-磷-碳纳米管（失活原因铁的粒径长大）催化剂，于氢气气中600℃碳4h，得到再生催化剂，该催化剂的电镜照片如图1。从图1可见，从图1可见，再生钌-磷-活性炭催化剂中的钌的粒径在4纳米以下，实现了催化剂的再生，使催化剂的活性位点增加，催化剂的活性明显提高。
称取该再生催化剂0.5g、1-己炔20mmol、四氢呋喃30ml加入高压反应釜中，通入高纯氢气置换3次气体后，充氢气至3.0MPa，升温到80℃，反应10h，反应结束后，快速冷却至室温，然后将反应液进行离心分离，取溶液对反应体系进行重结晶定量计算，1-己烯的产率为95%。
称取该再生催化剂0.5g、二苯乙炔20mmolg、甲苯30ml加入高压反应釜中，通入高纯氢气置换3次气体后，充氢气至3.0MPa，升温到140℃，反应10h，反应结束后，快速冷却至室温，然后将反应液进行离心分离，取溶液对反应体系进行重结晶定量计算，二苯乙烯的产率为98%。
实施例2
纳米铁/磷-活性碳催化剂制备：将已经失活的1g铁-磷-活性碳催化剂（失活原因铁的粒径长大），于氢气气中500℃碳3h，得到再生催化剂，其电镜照片如图2。从图2可见，再生铁-磷-活性炭催化剂中的铁的粒径在5纳米以下，实现了催化剂的再生，使催化剂的活性位点增加，催化剂的活性明显提高。
称取该再生催化剂0.5g、苯酐20mmol、四氢呋喃40ml加入高压反应釜中，通入高纯氢气置换3次气体后，充氢气至4MPa，升温到150℃，反应2h，反应结束后，快速冷却至室温，然后将反应液进行离心分离，对反应液进行色谱分析，反应液采用agilent6980气相色谱配备SE-54毛细管柱，循环使用催化剂的产物的产率如图3所示，可以看出，本发明制备的催化剂在使用八次后依然保持很高的催化效果。
实施例3
纳米铂/磷-石墨烯催化剂制备：将已经失活的1g铂-磷-石墨烯（失活原因铁的粒径长大）催化剂，于氢气气中500℃碳4h，得到再生催化剂，其电镜照片如图4。从图4可见，再生铂-磷-活性炭催化剂中的钌的粒径在4纳米以下，实现了催化剂的再生，使催化剂的活性位点增加，催化剂的活性明显提高。
称取该再生催化剂1.0g和二氧化硅2.0均匀混合后、压片制备出40-60目的催化剂颗粒、装入固定床反应管内、充入3.0MPa的氢气，氢气流速50ml/min，升温至110℃，将对氯硝基苯200g溶于1000ml的甲苯溶剂中，利用高压注射泵连续向反应器中注入，空速30g/g.h，在装置的储液罐收集反应液，对反应液进行色谱分析，反应液采用agilent6980气相色谱配备SE-54毛细管柱，对氯苯胺的收率97%。
实施例4
纳米钌/磷-多级孔碳催化剂制备：将已经失活的1g钌-磷-多级孔碳（失活原因钌的粒径长大）催化剂，于氢气气中600℃碳4h，得到再生催化剂。
称取该再生催化剂0.5g、乙酰丙酸20mmol、乙醇30ml加入高压反应釜中，通入高纯氢气置换3次气体后，充氢气至3.0MPa，升温到150℃，反应10h，反应结束后，快速冷却至室温，然后将反应液进行离心分离，对反应液进行色谱分析，反应液采用agilent6980气相色谱配备SE-54毛细管柱，伽马-戊内酯的收率94%。
实施例5
纳米钌/磷-石墨烯催化剂制备：将已经失活的1g钌-磷-石墨烯（失活原因钌的粒径长大）催化剂，于氢气气中500℃碳6h，得到再生催化剂。
称取该再生催化剂0.5g、呋喃乙酸甲酯20mmol、异丙醇30ml加入高压反应釜中，通入高纯氢气置换3次气体后，充氢气至3.0MPa，升温到120℃，反应15h，反应结束后，快速冷却至室温，然后将反应液进行离心分离，对反应液进行色谱分析，反应液采用agilent6980气相色谱配备SE-54毛细管柱，四氢呋喃乙酸甲酯的收率91%。
实施例6
纳米铂/磷-碳球催化剂制备：将已经失活的1g铂-磷-碳球（失活原因铂的粒径长）催化剂，于氢气气中400℃碳10h，得到再生催化剂。
称取该再生催化剂0.5g、硝基苯20mmol、异丙醇30ml加入高压反应釜中，通入高纯氢气置换3次气体后，充氢气至3.0MPa，升温到120℃，反应15h，反应结束后，快速冷却至室温，然后将反应液进行离心分离，对反应液进行色谱分析，反应液采用agilent6980气相色谱配备SE-54毛细管柱，苯胺的收率96%。
实施例7纳米铁/磷-介孔碳催化剂制备：将已经失活的1g钌-磷-介孔碳（失活原因铁的粒径长大）催化剂，于氢气气中600℃碳4h，得到再生催化剂。
称取该再生催化剂0.5g、乙酰丙酸20mmol、乙醇30ml加入高压反应釜中，通入高纯氢气置换3次气体后，充氢气至3.0MPa，升温到150℃，反应10h，反应结束后，快速冷却至室温，然后将反应液进行离心分离，对反应液进行色谱分析，反应液采用agilent6980气相色谱配备SE-54毛细管柱，伽马-戊内酯的收率94%。
此外，本案发明人还参照前述实施例，以本说明书述及的其它原料、工艺操作、工艺条件进行了试验，并均获得了较为理想的结果。
Claims (4)
1.一种氢还原再生纳米金属-磷-碳催化剂的方法，是将已经失活的纳米金属-磷-碳催化剂，置于氢气气氛下，于200~1200℃还原1~24h，获得再生纳米金属-磷-碳催化剂。
2.如权利要求1所述一种氢还原再生纳米金属-磷-碳催化剂的方法，其特征在于：所述纳米金属-磷-碳催化剂中，活性组分纳米金属为钌、铂、钴、镍、铱、金、铜、钯、银、铁、锌和铑中的至少一种，其含量为0.001~40wt.%。
3.如权利要求1所述一种氢还原再生纳米金属-磷-碳催化剂的方法，其特征在于：所述协同催化组分磷的含量为0.01~40wt.%。
4.如权利要求1所述一种氢还原再生纳米金属-磷-碳催化剂的方法，其特征在于：所述碳载体为活性碳、石墨烯、碳纳米管、碳球、微孔碳、介孔碳、大孔碳、多级孔碳中的至少一种。
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