【正文】 CH4合成氣在連續(xù)式步階反應(yīng)器上直接合成 C2+含氧化合物的研究ICH4合成氣在連續(xù)式步階反應(yīng)器上直接合成 C2+含氧化合物的研究摘 要 從節(jié)能減排、清潔環(huán)保及 CH4合成氣的利用角度來看，CH 4合成氣低溫轉(zhuǎn)化直接合成含氧有機物是 研究領(lǐng)域最具挑戰(zhàn)性的課題之一。本課1C題組采用了兩步梯階轉(zhuǎn)化工藝，其核心思想是首先使 CH4 在催化劑表面解離，生成表面 CHX 物種；然后再通入 CO2(CO)與表面 CHX 物種反應(yīng)生成含氧化合物。本文借鑒兩步法，在前期研究的基礎(chǔ)上，重點研究了 CH4合成氣直接轉(zhuǎn)化合成 C2+含氧化合物的反應(yīng)，調(diào)變催化劑以獲得更高的催化活性。本文采用等體積浸漬法制備了 CuCo 基催化劑，在連續(xù)式固定床兩步梯階反應(yīng)裝置上，對制備的所有催化劑進行了活性評價，利用表征手段 XRD、NH 3TPD、H 2TPR、BET 等對催化劑測試，并結(jié)合活性數(shù)據(jù)和各種表征結(jié)果進行了分析。主要研究結(jié)論如下：（1）適宜的中強酸強度和酸量有助于 CH4合成氣直接轉(zhuǎn)化合成 C2+含氧化合物的反應(yīng)，強酸阻礙了該反應(yīng)的進行。（2）負(fù)載在載體 TiO2 上的金屬顆粒，在高溫還原后，與載體間的適度相互作用及活性金屬 Cu 和 Co 在載體上良好的分散性與還原性，提高了 CuCo/TiO2 催化劑的催化活性。CH4合成氣在連續(xù)式步階反應(yīng)器上直接合成 C2+含氧化合物的研究II（3）催化劑表面上高度分散的 CuO 微晶顆粒有利于催化加氫和脫氫反應(yīng)的進行，對 CH4合成氣轉(zhuǎn)化反應(yīng)有重要的促進作用。（4）負(fù)載在不同載體的雙金屬 CuCo 催化劑上 C2+含氧化合物的選擇性和時空收率的高低順序為 CuCo/TiO CuCo/Al2OCuCo/SiO 2。（5）先浸漬 Cu 后浸漬 Co 的催化劑的催化性能最好，其 C2+含氧化合物的時空收率較高可達 mgh1，選擇性為 %。（6）浸漬順序?qū)Υ呋瘎┧嵝缘挠绊戄^大，先浸漬 Cu 后浸漬 Co 的方式有利于中強酸的產(chǎn)生，而 CuCo 同時浸漬的方式有利于強酸的形成。中強酸有利于 CH4合成氣轉(zhuǎn)化反應(yīng)，而強酸阻礙了該反應(yīng)的進行。關(guān)鍵詞：甲烷，合成氣，直接轉(zhuǎn)化，C 2+含氧化合物，CuCo 催化劑CH4合成氣在連續(xù)式步階反應(yīng)器上直接合成 C2+含氧化合物的研究IIISYNTHESIS OF C2+ OXYGENATESFROM CH4 AND SYNGAS BY A CONTINUOUSSTEPWISE REACTORABSTRACTFrom the perspective of energysaving emission reduction, clean environment and the utilization of CH4synthesis gas, CH4syngas conversion directly synthesis of oxygencontaining anic pounds in low temperature is one of the most challenging topic in research research group proposed two step ladder conversion process,It39。s core idea is to first make CH4 in the catalyst surface dissociation,generation of surface CHx species。And CO2 (Co) generation of oxygen containing pounds with the surface CHX species the basis of previous research, we studied the direct synthesis of C2+ oxygenates from the CH4 and synthesis gas by the lights of the new technology, and focused on the catalysts improvement to enhance the catalytic property in this dissertation. CuCo Catalysts were prepared by equivoluminal impregnation method. The activity of all the catalysts was evaluated in the fixed bed reaction device with a continuous, stepwise reactor. Then these catalysts were characterized by the techniques of XRD、NH 3TPD、 H2TPR and BET, binding CH4合成氣在連續(xù)式步階反應(yīng)器上直接合成 C2+含氧化合物的研究IVtheir activity data and a variety of characterization results to analyse the catalyst performances. The main conclusions were as follows：(1) On the CuCo bimetallic catalysts with various carriers, the order of C2+ oxygenates yield and selectivity is CuCo/TiO2 CuCo/Al2O3 CuCo/SiO2.(2) The suitable medium acidity and acid strength is beneficial to improving catalytic activity of the catalysts for the synthesis of C2+ oxygenate with CH4 and synthesis gas.(3) It is concluded that the interaction between the TiO2 and the active metal CoCu and the good dispersion of CoCu/TiO2 in the catalysts improve the catalytic activity.(4) The catalyst sample impregnated first with Cu has the highest activity and the yield of C2+ oxygenate is mgh1.(5) The impregnation sequence influences the acidity of the catalyst. The way impregnated first with Cu then Co is beneficial to the formation of medium acid and the medium acid is beneficial to the conversion of CH4 and syngas. Then that coimpregnated with Cu and Co is conducive to the formation of strong acid, but the strong acid restrains the conversion.(6) The impregnation sequence influences the existing state of Cu, The way impregnated first with Cu then Co is conducive to the formation of highly dispersed CuO fragmented crystallite particles or clusters.CH4合成氣在連續(xù)式步階反應(yīng)器上直接合成 C2+含氧化合物的研究VKEY WORDS：CH 4, syngas, direct synthesis, C2+ oxygenates, CuCo catalystCH4合成氣在連續(xù)式步階反應(yīng)器上直接合成 C2+含氧化合物的研究VI目 錄摘 要 ...........................................................................................................................................IABSTRACT................................................................................................................................I第一章 前 言 .........................................................................................................................1 選題背景及意義 ...............................................................................................................................1 文獻綜述 ...........................................................................................................................................3 甲烷活化的研究概述 ..................................................................................................................3 CH4 活化催化劑活性金屬的研究 ...........................................................................................6 CH4 活化催化劑載體的研究 ...................................................................................................9 一氧化碳的活化與轉(zhuǎn)化 ............................................................................................................10 CO 與催化劑表面的相互作用 ..............................................................................................10 H2 與 CO 的共吸附 ................................................................................................................11 甲烷，一氧化碳共活化轉(zhuǎn)化 ....................................................................................................12 CH4CO 直接合成乙酸的研究 ..............................................................................................12 CH4CO 直接合成乙醛的研究 ..............................................................................................14 本研究已有的工作基礎(chǔ)及本論文研究重點 ...............................................................................15第二章 實驗部分 .....................................................................................................................17 實驗所用化學(xué)試劑、原料與儀器設(shè)備 .......................................................................................17 化學(xué)試劑與原料一覽表 ...............