乙炔氢氯化反应低金含量无汞催化剂的制备及其性能研究-应用化学专业论文.docx

内蒙古大学硕士学位论文的还原活化能(45．5 kJ／m01)高于Au／C中Au3+--,Auo的还原活化能(35．6 kJ／mol、)，表明Au．Cu相互作用使得Au3+更难被还原。XPS测试进一步证明 Au．Cu／C催化剂中Au3+物种的相对含量(28％)高于其在Au／C催化剂中的相对含量(16％)。进一步推测了Au．Cu／C在乙炔与氯化氢加成反应中的催化机理。 (3)分析了活性组分Au、Cu负载顺序对催化剂表面活性组分存在形式和催化性能的影响，发现采用Au、Cu一步负载的方法比Au、Cu分步负载的方法具 有更好的催化性能，Au、Cu同时负载更有助于发挥Au．Cu协同作用从而增加了 Au在催化剂表面的分散度，使得更多的Au3+活性物种存在于催化剂表面。在T=150℃，VHcl／Vc2H2=1．08，GHSV(C2H2、)=720 h-1的条件下乙炔转化率高达 97．4％，氯乙烯选择性在150 h反应时间内一直稳定在99．0％左右。(4)表征了氧化物Ti02掺杂对Au-Cu／C催化性能的影响，发现Ti02掺杂量 为9％时Au(0．45％)Cu(4％)Ti02(9％)／C表现出最好的催化性能，TPR测试表明 Au、Cu和Ti02的相互作用使得Au3+的含量增加并且更难被还原，XPS分析表明Ti02为Au提供电子增强Au对氯化氢反应物的吸附能力，从而表现出更好的 催化性能。关键词：乙炔氢氯化反应；低金含量；无汞催化剂；协同作用万方数据内蒙古大学硕士学位论文PREPARATION AND CATALYTIC EVALUATION OF MERCURY．FREE LOW．GOLD．CONTENT CATALYSTS FOR ACETYLENE HYDROCHLORINATIONABSTRACTHighly toxic mercury catalysts used for acetylene hydrochlorination to produce vinyl chloride pollute the environment seriously and it is hazardous to human health． Therefore，the development of environmentally friendly mercury-free catalystsbecomes the most important issue in the entire vinyl chloride industry．In this paper，HAuCl4·4H20 and CuCl2·2H20 were the precursor of active ingredients，supported catalysts were prepared by ultrasonic—assisted impregnation method for acetylene hydrochlorination to VCM．Influences of the supports (activated carbon，A1203 and Ti02)，loading amount and synergistic effect of theactive components were investigated．Besides，we investigated the effects of the loading order of the active ingredients and Ti02 additive on the existing form of active ingredients and catalytic activity of catalysts．We have obtained the followingresults：(1)We prepared Au．Cu／C(A1203 and Ti02)catalysts by ultrasonic-assistedIII万方数据内蒙古大学硕士学位论文impregnation method．XRD analysis shows that Au active component supported onactivated carbon exists in the form of AU3+and on A1203 and Ti02 exists in the form of Au0．BET results indicated that Au active component supported on activated carbon exhibits larger specific surface area(5 62