化工学报
化工學報
화공학보
JOURNAL OF CHEMICAL INDUSY AND ENGINEERING (CHINA)
2014年
7期
2770-2775
,共6页
胡菊%潘亚林%黎汉生%吴芹%王金福
鬍菊%潘亞林%黎漢生%吳芹%王金福
호국%반아림%려한생%오근%왕금복
反加共沉淀法%铈改性%铜基催化剂%甲醇合成
反加共沉澱法%鈰改性%銅基催化劑%甲醇閤成
반가공침정법%시개성%동기최화제%갑순합성
anti-coprecipitation%Ce modification%Cu-based catalysts%methanol synthesis
采用反加共沉淀法,以硝酸铜、硝酸锌、硝酸铝溶液为原料,碳酸钠溶液为沉淀剂,硝酸铈为助剂,制备了铈(Ce)改性的甲醇合成铜基催化剂(CuZnAlCe),并通过X射线衍射(XRD)、N2等温吸附、热重-差热分析(TG-DTA)、扫描电子显微镜(SEM)、程序升温还原(TPR)等手段进行表征,采用微型固定床反应装置进行催化活性及稳定性评价,考察了Ce含量对CuZnAlCe催化剂结构和催化性能的影响。结果表明,Ce的引入可以改善催化剂活性中心的分散度,使催化剂比表面积增加,整体的结构变得更加松散,催化剂更容易被还原。随着Ce含量的增加,CO的转化率不断增大,当Ce含量为2%时CO转化率最大,可达47.6%。但Ce含量过量时使催化剂还原温度升高,CO的转化率降低。此外,适当的Ce含量改性可以提高铜基催化剂的热稳定性。
採用反加共沉澱法,以硝痠銅、硝痠鋅、硝痠鋁溶液為原料,碳痠鈉溶液為沉澱劑,硝痠鈰為助劑,製備瞭鈰(Ce)改性的甲醇閤成銅基催化劑(CuZnAlCe),併通過X射線衍射(XRD)、N2等溫吸附、熱重-差熱分析(TG-DTA)、掃描電子顯微鏡(SEM)、程序升溫還原(TPR)等手段進行錶徵,採用微型固定床反應裝置進行催化活性及穩定性評價,攷察瞭Ce含量對CuZnAlCe催化劑結構和催化性能的影響。結果錶明,Ce的引入可以改善催化劑活性中心的分散度,使催化劑比錶麵積增加,整體的結構變得更加鬆散,催化劑更容易被還原。隨著Ce含量的增加,CO的轉化率不斷增大,噹Ce含量為2%時CO轉化率最大,可達47.6%。但Ce含量過量時使催化劑還原溫度升高,CO的轉化率降低。此外,適噹的Ce含量改性可以提高銅基催化劑的熱穩定性。
채용반가공침정법,이초산동、초산자、초산려용액위원료,탄산납용액위침정제,초산시위조제,제비료시(Ce)개성적갑순합성동기최화제(CuZnAlCe),병통과X사선연사(XRD)、N2등온흡부、열중-차열분석(TG-DTA)、소묘전자현미경(SEM)、정서승온환원(TPR)등수단진행표정,채용미형고정상반응장치진행최화활성급은정성평개,고찰료Ce함량대CuZnAlCe최화제결구화최화성능적영향。결과표명,Ce적인입가이개선최화제활성중심적분산도,사최화제비표면적증가,정체적결구변득경가송산,최화제경용역피환원。수착Ce함량적증가,CO적전화솔불단증대,당Ce함량위2%시CO전화솔최대,가체47.6%。단Ce함량과량시사최화제환원온도승고,CO적전화솔강저。차외,괄당적Ce함량개성가이제고동기최화제적열은정성。
Cerium modified Cu-based catalysts (CuZnAlCe) for methanol synthesis from syngas were prepared by anti-coprecipitation method with Na2CO3 solution as a precipitant, Cu(NO3)2, Zn(NO3)2 and Al2(NO3)3 solution as raw materials. The structure and morphology of CuZnAlCe were studied by X-ray diffraction, thermal gravimetry-differential thermal analysis, N2 adsorption-desorption measurement, scanning electron microscopy, and temperature programmed reduction. The catalytic activities of the prepared catalysts for methanol synthesis were evaluated on micro fixed-bed reaction system. It showed that the addition of Ce improved the dispersion of active sites and provided a high surface area, which play an important role in the stability and activity of CuZnAlCe. The CO conversion reached an optimum value to 47.6% over the Ce modified Cu-based catalyst at the Cu/Ce molar ratio of 1:0.02, while the catalytic activity and stability decreased when the loading of Ce was excessive. Proper loadings of Ce could improve the thermal stability of Cu-based catalysts.