【摘要】：聚氯乙烯(PVC)是世界五大工程塑料之一,因?yàn)槠淞己玫奈锢砗突瘜W(xué)性質(zhì)而受到人們廣泛關(guān)注。目前制備聚氯乙烯的氯乙烯單體的制備主要采用以下三種方法:乙烯法、乙烷法和乙炔法�；谖覈�(guó)當(dāng)前“富煤,貧油,少氣”的基本能源結(jié)構(gòu),乙炔法將在很長(zhǎng)一段時(shí)期內(nèi)作為生產(chǎn)氯乙烯單體的主要合成方法。該方法所使用的催化劑基于活性炭載體,負(fù)載活性組分HgCl_2。但由于在高溫條件下,HgCl_2極易升華,從而造成了活性組分的流失,以及汞金屬對(duì)環(huán)境和人體有巨大危害,因此,尋找一種無(wú)汞催化劑替代汞催化劑是當(dāng)前實(shí)驗(yàn)研究和實(shí)際生產(chǎn)的當(dāng)務(wù)之急。本論文針對(duì)PVC領(lǐng)域汞催化劑存在匱乏以及污染環(huán)境的問(wèn)題,秉承綠色可持續(xù)發(fā)展的理念,設(shè)計(jì)了一條新型綠色環(huán)保無(wú)汞催化劑的技術(shù)線路。本論文內(nèi)容主要通過(guò)綜述金屬有機(jī)骨架材料的合成方法及在催化領(lǐng)域的應(yīng)用,以Cu-BTC為主要研究對(duì)象,使用浸漬法、沉積沉淀法,制備了以金屬有機(jī)骨架材料為載體的鉍基和金基催化劑,并對(duì)原料,合成條件等進(jìn)行優(yōu)化,結(jié)合多項(xiàng)表征手段,探討了催化劑的內(nèi)部結(jié)構(gòu),活性組分存在形式,以及影響催化劑活性和穩(wěn)定性的因素,也對(duì)催化劑失活的主要原因進(jìn)行了討論。主要內(nèi)容包括:(1)采用了水熱法合成了金屬有機(jī)多孔材料Cu-BTC,通過(guò)XRD、IR、BET、SEM、TEM、TG等多種手段對(duì)Cu-BTC進(jìn)行表征。討論了Cu-BTC作為催化劑在乙炔氫氯化反應(yīng)中的催化活性和穩(wěn)定性。在T=180℃、GHSV(C_2H_2)=331 h-1、VHCl/VC_2H_2=1.05:1、p=0.2 MPa的反應(yīng)條件下,Cu-BTC催化劑最高的初始催化活性為工業(yè)汞催化劑初始活性的66.3%,持續(xù)了4 h后,已經(jīng)下降為工業(yè)汞活性的10%以下。催化劑活性不高并且迅速失活的原因有兩點(diǎn):一是該催化劑活性組分催化效果不佳,二是Cu-BTC催化劑在高溫條件下骨架結(jié)構(gòu)的坍塌。(2)以BiCl_3為主要活性組分,金屬有機(jī)骨架材料Cu-BTC為載體,分別采用等體積浸漬法和沉積沉淀法制備了負(fù)載型無(wú)汞催化劑,考察了影響這兩種催化劑催化活性和穩(wěn)定性的因素。結(jié)果表明,在T=180℃、GHSV(C_2H_2)=331 h-1、VHCl/VC_2H_2=1.05:1、p=0.2 MPa的反應(yīng)條件下,當(dāng)采用等體積浸漬法時(shí),活性組分Bi原子負(fù)載量(質(zhì)量分?jǐn)?shù))達(dá)到15%時(shí)催化劑的催化活性最好,能達(dá)到相同條件下工業(yè)汞催化劑催化活性的1.6倍左右,并且催化劑壽命能持續(xù)500 min左右;當(dāng)采用沉積沉淀法時(shí),Bi原子負(fù)載量達(dá)到20%時(shí),催化劑的催化活性,能達(dá)到相同條件工業(yè)汞催化劑催化活性的2.2倍左右,催化劑壽命能持續(xù)800 min左右。在采用沉積沉淀法制備催化劑的基礎(chǔ)上,通過(guò)添加B、K、Na等元素的化合物,考察助劑對(duì)該催化劑催化活性的影響。(3)選取多種不同的金屬有機(jī)骨架材料作為載體,以Au作為活性組分,采用浸漬法制備負(fù)載型Au基催化劑,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的反應(yīng)條件下,Au基催化劑的初始活性最高能達(dá)到相同條件下工業(yè)汞催化劑的60%-70%,但催化劑的壽命都普遍較短,大多數(shù)在3h內(nèi)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，

本文編號(hào)：2434321