金属有机骨架材料的制备及在乙炔氢氯化反应中的应用
发布时间：2019-03-04 13:52
【摘要】：聚氯乙烯(PVC)是世界五大工程塑料之一,因为其良好的物理和化学性质而受到人们广泛关注。目前制备聚氯乙烯的氯乙烯单体的制备主要采用以下三种方法:乙烯法、乙烷法和乙炔法。基于我国当前“富煤,贫油,少气”的基本能源结构,乙炔法将在很长一段时期内作为生产氯乙烯单体的主要合成方法。该方法所使用的催化剂基于活性炭载体,负载活性组分HgCl_2。但由于在高温条件下,HgCl_2极易升华,从而造成了活性组分的流失,以及汞金属对环境和人体有巨大危害,因此,寻找一种无汞催化剂替代汞催化剂是当前实验研究和实际生产的当务之急。本论文针对PVC领域汞催化剂存在匮乏以及污染环境的问题,秉承绿色可持续发展的理念,设计了一条新型绿色环保无汞催化剂的技术线路。本论文内容主要通过综述金属有机骨架材料的合成方法及在催化领域的应用,以Cu-BTC为主要研究对象,使用浸渍法、沉积沉淀法,制备了以金属有机骨架材料为载体的铋基和金基催化剂,并对原料,合成条件等进行优化,结合多项表征手段,探讨了催化剂的内部结构,活性组分存在形式,以及影响催化剂活性和稳定性的因素,也对催化剂失活的主要原因进行了讨论。主要内容包括:(1)采用了水热法合成了金属有机多孔材料Cu-BTC,通过XRD、IR、BET、SEM、TEM、TG等多种手段对Cu-BTC进行表征。讨论了Cu-BTC作为催化剂在乙炔氢氯化反应中的催化活性和稳定性。在T=180℃、GHSV(C_2H_2)=331 h-1、VHCl/VC_2H_2=1.05:1、p=0.2 MPa的反应条件下,Cu-BTC催化剂最高的初始催化活性为工业汞催化剂初始活性的66.3%,持续了4 h后,已经下降为工业汞活性的10%以下。催化剂活性不高并且迅速失活的原因有两点:一是该催化剂活性组分催化效果不佳,二是Cu-BTC催化剂在高温条件下骨架结构的坍塌。(2)以BiCl_3为主要活性组分,金属有机骨架材料Cu-BTC为载体,分别采用等体积浸渍法和沉积沉淀法制备了负载型无汞催化剂,考察了影响这两种催化剂催化活性和稳定性的因素。结果表明,在T=180℃、GHSV(C_2H_2)=331 h-1、VHCl/VC_2H_2=1.05:1、p=0.2 MPa的反应条件下,当采用等体积浸渍法时,活性组分Bi原子负载量(质量分数)达到15%时催化剂的催化活性最好,能达到相同条件下工业汞催化剂催化活性的1.6倍左右,并且催化剂寿命能持续500 min左右;当采用沉积沉淀法时,Bi原子负载量达到20%时,催化剂的催化活性,能达到相同条件工业汞催化剂催化活性的2.2倍左右,催化剂寿命能持续800 min左右。在采用沉积沉淀法制备催化剂的基础上,通过添加B、K、Na等元素的化合物,考察助剂对该催化剂催化活性的影响。(3)选取多种不同的金属有机骨架材料作为载体,以Au作为活性组分,采用浸渍法制备负载型Au基催化剂,并考察其催化活性。在T=180℃、GHSV(C_2H_2)=331 h-1、VHCl/VC_2H_2=1.05:1、p=0.2 MPa的反应条件下,Au基催化剂的初始活性最高能达到相同条件下工业汞催化剂的60%-70%,但催化剂的寿命都普遍较短,大多数在3h内完全失活。
[Abstract]:Polyvinyl chloride (PVC) is one of the world's five major engineering plastics because of its good physical and chemical properties. At present, the preparation of vinyl chloride monomer for polyvinyl chloride mainly adopts the following three methods: ethylene method, ethane method and acetylene method. Based on the basic energy structure of the present "rich coal, lean oil and less gas" in China, the acetylene method is the main synthetic method for producing vinyl chloride monomer for a long period of time. The catalyst used in the method is based on an active carbon carrier and a load active component HgCl _ 2. However, because of the easy sublimation of HgCl _ 2 under high temperature, the loss of active component and the great harm to the environment and human body caused by the mercury metal, it is urgent to find a mercury-free catalyst to replace the mercury catalyst. Aiming at the shortage of mercury catalyst in the field of PVC and the problem of environmental pollution, the paper designs a new technology for green and environment-friendly mercury-free catalyst in the light of the concept of green sustainable development. In this paper, the synthesis method of metal organic framework material and its application in the field of catalysis are reviewed. Cu-BTC is used as the main research object, and the base and the gold base catalyst with the metal organic framework material as the carrier are prepared by using the impregnation method and the deposition precipitation method, and the raw materials, The structure of the catalyst, the form of active component, and the factors that affect the activity and stability of the catalyst are discussed, and the main causes of the deactivation of the catalyst are also discussed. The main contents of this paper are as follows: (1) Cu-BTC is synthesized by hydrothermal method, and Cu-BTC is characterized by XRD, IR, BET, SEM, TEM and TG. The catalytic activity and stability of Cu-BTC as catalyst in the chlorination of acetylene was discussed. Under the reaction conditions of T = 180 鈩，
本文编号：2434321
[Abstract]:Polyvinyl chloride (PVC) is one of the world's five major engineering plastics because of its good physical and chemical properties. At present, the preparation of vinyl chloride monomer for polyvinyl chloride mainly adopts the following three methods: ethylene method, ethane method and acetylene method. Based on the basic energy structure of the present "rich coal, lean oil and less gas" in China, the acetylene method is the main synthetic method for producing vinyl chloride monomer for a long period of time. The catalyst used in the method is based on an active carbon carrier and a load active component HgCl _ 2. However, because of the easy sublimation of HgCl _ 2 under high temperature, the loss of active component and the great harm to the environment and human body caused by the mercury metal, it is urgent to find a mercury-free catalyst to replace the mercury catalyst. Aiming at the shortage of mercury catalyst in the field of PVC and the problem of environmental pollution, the paper designs a new technology for green and environment-friendly mercury-free catalyst in the light of the concept of green sustainable development. In this paper, the synthesis method of metal organic framework material and its application in the field of catalysis are reviewed. Cu-BTC is used as the main research object, and the base and the gold base catalyst with the metal organic framework material as the carrier are prepared by using the impregnation method and the deposition precipitation method, and the raw materials, The structure of the catalyst, the form of active component, and the factors that affect the activity and stability of the catalyst are discussed, and the main causes of the deactivation of the catalyst are also discussed. The main contents of this paper are as follows: (1) Cu-BTC is synthesized by hydrothermal method, and Cu-BTC is characterized by XRD, IR, BET, SEM, TEM and TG. The catalytic activity and stability of Cu-BTC as catalyst in the chlorination of acetylene was discussed. Under the reaction conditions of T = 180 鈩，
本文编号：2434321
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