固定床甲醇氧化制甲醛铁钼催化剂的应用与研究进展
Application and research progress of iron-molybdenum catalysts for methanol oxidation to formaldehyde in fixed bed
- 低碳化学与化工 2024, 49(1): 12-24.
- 作者机构：
西南化工研究设计院有限公司 国家碳一化学工程技术研究中心，工业排放气综合利用国家重点实验室， 四川 成都 610225
- 作者简介：
程金燮（1989—），硕士，高级工程师，研究方向为碳一与低碳催化转化，E-mail：chengjx@swchem.com。
赵安民（1983—），博士，正高级工程师，研究方向为催化及新材料，E-mail：zhaoanmin@swchem.com。
- 基金信息：
DOI：10.12434/j.issn.2097-2547.20220385
中图分类号：
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程金燮,黄宏,王华等.固定床甲醇氧化制甲醛铁钼催化剂的应用与研究进展[J].低碳化学与化工,2024,49(01):12-24.
CHENG Jinxie,HUANG Hong,WANG Hua,et al.Application and research progress of iron-molybdenum catalysts for methanol oxidation to formaldehyde in fixed bed[J].Low-carbon Chemistry and Chemical Engineering,2024,49(01):12-24.
程金燮,黄宏,王华等.固定床甲醇氧化制甲醛铁钼催化剂的应用与研究进展[J].低碳化学与化工,2024,49(01):12-24. DOI： 10.12434/j.issn.2097-2547.20220385.
CHENG Jinxie,HUANG Hong,WANG Hua,et al.Application and research progress of iron-molybdenum catalysts for methanol oxidation to formaldehyde in fixed bed[J].Low-carbon Chemistry and Chemical Engineering,2024,49(01):12-24. DOI： 10.12434/j.issn.2097-2547.20220385.
摘要
为突破铁钼甲醛催化剂“卡脖子”技术，实现其国产化和大面积推广应用，综述了国内外铁钼甲醛催化剂的工业应用、实验室制备和反应及失活机理的研究进展。分析发现，国外铁钼甲醛催化剂经过70年的工业应用与改进，甲醛收率可达93.3%，而国产铁钼甲醛催化剂在开展工业试用后仍未实现大面积的进口替代；共沉淀法是制备该催化剂的主流方法，钼铁比（,n,(Mo):,n,(Fe)）、助剂种类、沉淀温度、pH值、搅拌速率、陈化时间和煅烧温度等都会影响该催化剂的结构和性能；甲醇在该催化剂上氧化生成甲醛的反应遵循氧化还原机理，晶格氧在其中扮演氧化活性位的角色，甲氧基生成、甲氧基脱氢和晶格氧传递等过程均有可能是反应速控步骤，反应过程中的钼挥发流失是造成该催化剂失活的重要原因。进一步指出国内需针对工业试用出现的问题，加强对铁钼甲醛催化剂形成机制、制备过程对催化剂结构与性能的影响规律和催化反应及失活机理等问题的研究，以提升该催化剂性能，特别是催化剂稳定性。
Abstract
To break through the “neck jamming” technology of iron-molybdenum formaldehyde catalysts and realize its localization and widespread application, the research progress of industrial application, laboratory preparation, reaction and deactivation mechanism of iron-molybdenum formaldehyde catalysts at home and abroad was reviewed. It is found that foreign iron-molybdenum formaldehyde catalysts achieve a formaldehyde yield of 93.3% after 70 years of industrial application and improvement, while domestic catalysts don’t realize large-scale import substitution yet after industrial trials. Co-precipitation method is the mainstream method for preparing the catalyst, and the structure and performance of the catalyst will be affected by ,n,(Mo):,n,(Fe), additives, precipitation temperature, pH value, stirring speed, aging time and calcination temperature. The reaction of methanol oxidation to formaldehyde on the catalyst followed redox mechanism, in which lattice oxygen plays a role of oxidizing active site, and the rate-determining step of the reaction is may be methoxy generation, methoxy dehydrogenation, or lattice oxygen transfer process, and the loss of molybdenum volatilization during reaction is an important reason for catalyst deactivation. It is pointed out that it’s necessary at home to strengthen the research on iron-molybdenum formaldehyde catalysts formation mechanism, the influence law of preparation process on structure and performance of the catalyst, and the catalytic reaction and deactivation mechanism aimed at issues arising from industrial trials, so as to improve the catalyst performance, especially the catalyst stability.
关键词
催化剂铁钼法甲醛甲醇氧化
Keywords
catalystiron-molybdenum processformaldehydemethanol oxidation
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