第41卷第6期
燃料化学学报
Vol 41 No 6
2013年6月
Journal of Fuel Chemistry and Technology
Jun.2013
文章编号:0253-2409(2013)06-0703-07
nCr基催化剤煅烧温度对
异丁醇合成性能的影响
寇永利2,解红娟,刘广波12,武应全12,张欣悦3,韩怡卓, Noritatsu Tsubaki,谭猗生
(1.中国科学院山西煤炭化学研究所媟转化国家重点实验室,山西太原0830001;2.中国科学院大学,北京10009;
3.中南大学化学化工学院,湖南长沙410012;4.寓山大学应用化学系,日本富山930-8555
摘要:研究了煅烧温度对Zn○r基催化剂合成
异丁醇性能的影响。结果表明,随着煅烧温度的升高,催化剂的活性和产物分
布都发生了较大的变化。催化剂在较低的温度下煅烧,液相产物中醇主要是甲醇和
异丁醇;在较高的温度下煅烧,液相产物
醇的分布符合A-S-F方程。用BET、XRD、H2-TPR、XPS等技术手段对催化剂织构参数体相结构、还原性能、表面组成进行表
征。结果表明,在300℃煅烧时,催化剂中的Zn0和Cr2O3未完全形成非计量尖晶石Zn.CraO;:400℃煅烧时,催化剂中
形成了最多量非计量尖晶石Zn,Cr2aO;当煅烧温度高于400℃时,随着燈烧温度进一步升高;非计量尖晶石Zn, Cr2/a4- 3O
逐步发生了分解,生成了更多量的Zn0和C2O3,导致催化剂的活性随之下降。进一步证明了非计量尖晶石ZnC2;O是
该催化反应活性相。
关键词:ZnCr基催化剂;C0加氢;异丁醇;合成气;非计量尖晶石Zn-Cr2ausO
中图分类号:O643文献标识码:A
Effect of calcination temperature on the
performance of Zncr based catalyst in isobutanol synthesis
KOU Yong-li 2, XIE Hong-juan LIU Guang-bo'2, WU Ying-quan
ZHANG Xin-yue, HAN Yi-zhuo, Noritatsu Tsubaki, TAN Yi-sheng
(1. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry,
Chinese Academy of Sciences, Taiyuan 030001, China;
2. University of Chinese Academy of Sciences, Beijing 100049, China
3. School of Chemistry and Chemical Engineering, University of Central South, Changsha 410012, China
4. Department of Applied Chemistry, University of Toyama, Toyama 930-8555, Japan)
Abstract The effect of calcination temperature on the performance of Zncr based catalysts in isobutanol
synthesis was investigated; the texture properties, bulk structure, reducibility and surface composition of the
catalysts were characterized by BET, XRD, H -TPR and XPS. The results indicate that both the activity an
product selectivity of the Zncr catalyst are greatly influenced by its calcination temperature. The catalyst calcined
at low temperature shows high selectivity to methanol and isobutanol, while the product distribution over the
catalyst calcined at high temperature obeys the A-S-F equation. Calcination at 300 C is insufficient to, get a
complete formation of non-stoicheiometric spinel Zn, Cr a O while calcination at 400t gives the maximum
amount of non-stoichiometric spinel Zn, Cro in the Zncr based catalyst; however, further increasing the
calcination temperature may cause the decomposition of certain non-stoicheiometric spinel Zn; Cr O to Zno
and Cr, O,, which will reduce its catalytic activity in isobutanol synthesis. Such results suggest that non-
stoicheiometric spinel Zn, Cr2/(-) O is possibly the active phase of the Zncr based catalyst in isobutanol synthesis
Key words Zncr based catalyst; carbon monoxide hydrogenation; isobutanol synthesis; syngas; non
stoicheiometric spinel Zn, Cr2/3(1-,0
异丁醇是基本有机化工原料,用于制造抗氧剂、的添加剂,2010年已经被美国环保署列人燃料添加
合成橡胶、人造縻香、果子精油和合成药物等。中国剂目录。
是稀土资源大国,异丁醇作为溶剂广泛用于稀土生
目前,
工业异丁醇主要来自丙烯羰基合成法制
产中锶钡和锂等盐类的提纯。异丁醇是最好的助丁醇时的副产品,由于该法是以生产正丁醇为目标,
溶剂之一,可与同时生成的甲醇反应制取甲基叔丁因此,获得的异丁醇量很少,不能满足对异丁醇日益
基醚(MTBE)汽油添加剂,或异丁烯二聚和加氢制增长的需要们,而且生产异丁醇的原料大多是石油
取
异辛烷-。异丁醇亦可作为油品添加剂及航油基产品丙烯。富煤少油是中国能源结构的主要特
收稿日期:2012-12-12;修回日期:2013-0202
甚金项目:中国科学院西山西煤炭化学研究所前瞻性布局项目(2011 SQZBJ13
联系作者:谭猗生,Tel/Fax:0351-4044287,E-mail:tan@sxic.ac.cn。
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