无机盐工业
主管:中海油天津化工研究设计院有限公司
主办:中海油天津化工研究设计院有限公司
   中海油炼油化工科学研究院(北京)有限公司
   中国化工学会无机酸碱盐专业委员会
ISSN 1006-4990 CN 12-1069/TQ

无机盐工业 ›› 2024, Vol. 56 ›› Issue (9): 164-170.doi: 10.19964/j.issn.1006-4990.2024-0139

• 催化材料 • 上一篇    

不同烧制气氛对丙烯酸催化剂性质影响的研究

王静(), 苏晋, 张利杰, 周鹏, 孙彦民, 李佳   

  1. 中海油天津化工研究设计院有限公司,天津 300131
  • 收稿日期:2024-03-11 出版日期:2024-09-10 发布日期:2024-09-26
  • 作者简介:王静(1986— ),女,博士,工程师,研究方向为催化材料的分析表征;E-mail:wangjing99@cnooc.com.cn

Study on effect of different calcination atmospheres on properties of acrylic acid catalysts

WANG Jing(), SU Jin, ZHANG Lijie, ZHOU Peng, SUN Yanmin, LI Jia   

  1. CNOOC Tianjin Chemical Research and Design Insititute Co.,Ltd.,Tianjin 300131,China
  • Received:2024-03-11 Published:2024-09-10 Online:2024-09-26

摘要:

采用溶液法制备了含Mo-V的复合氧化物前驱体,经喷雾干燥后的前驱体在不同气氛(5%H2+95%N2、N2、5%O2+95%N2、空气和O2)中焙烧处理,获得Mo-V-W-Sb系列复合金属氧化物催化剂,并将其应用于丙烯醛气相氧化制丙烯酸反应。采用电感耦合等离子体发射光谱仪(ICP-OES)、X射线荧光光谱仪(XRF)、X射线衍射仪(XRD)、氮气物理吸附仪、透射电子显微镜(TEM)、化学吸附仪和电位滴定仪对催化剂进行了表征。实验结果表明,不同的焙烧气氛对Mo-V-W-Sb系列催化剂的晶相结构、物化性质及催化性能均产生了明显的影响。前驱体在弱氧化性气氛(5%O2+95%N2)中烧制时,有利于制备出含有较纯Mo3VO11+x 活性相、相对较大比表面积(6.8 m2/g)、适中结晶度和还原温度(约415 ℃),以及最适宜n(V5+)/[n(V3+)+n(V4+)+n(V5+)]为0.019的催化剂,且该催化剂表现出最佳的催化性能,高达99.5%的丙烯醛转化率和88.7%的丙烯酸收率。

关键词: 复合氧化物, 气相氧化, 丙烯酸, 催化性能

Abstract:

The composite oxide precursors containing Mo-V were prepared by solution method,and the precursors after spray drying were calcined under different atmospheres(5%H2+95%N2,N2,5%O2+95%N2,air and O2) to obtain Mo-V-W-Sb series composite metal oxide catalysts.And they were applied to the vapor phase oxidation of acrolein to acrylic acid.The catalysts were characterized by inductively coupled plasma-optical emission spectrometer(ICP-OES),X-ray fluorescence spectrometer(XRF),X-ray diffractometer(XRD),nitrogen physical adsorption analyzer,transmission electron microscope(TEM),temperature program reduction(H2-TPR) and potentiometric titrator.The experimental results indicated that the calcination atmosphere had a significant impact on the crystal structure,physicochemical properties,and catalytic performance of the Mo-V-W-Sb series catalysts.When the precursor was thermotreated in a weakly oxidizing atmosphere(5%O2+95%N2),it was beneficial to prepare a catalyst with pure Mo3VO11+x active phase,relatively larger specific surface area(6.8 m2/g),moderate crystallinity and reduction temperature(about 415 ℃),and the most suitable n(V5+)/[n(V3+)+n(V4+)+ n(V5+)]=0.019.Furthermore,this catalyst exhibited the best reaction performance in the oxidation of acrolein to acrylic acid,with a conversion rate of 99.5% acrolein and a yield of 88.7% acrylic acid.

Key words: composite oxides, vapor phase oxidation, acrylic acid, catalytic performance

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