甲醇氧化制甲醛工艺及催化剂研究进展

doi:10.19964/j.issn.1006-4990.2023-0146

Abstract

Abstract:

The silver method and ferro-molybdenum method for producing formaldehyde by air oxidation of methanol were summarized and compared.Silver method was employed as the main technology of formaldehyde production in China for its maturity.Ferro-molybdenum method was more suitable for the planning and development of formaldehyde industry for its low methanol consumption，high formaldehyde yield，long catalyst life and good economic benefit.Nevertheless，domestic technology of ferro-molybdenum method was not mature.The research progresses of silver，ferro-molybdenum and vanadium catalysts were reviewed.Silver catalyst was difficult to be improved greatly.Ferro-molybdenum was researched as a hotspot，and vanadium catalyst was still far away from industrial application.Further study on reaction mechanism for performance improvement of ferro-molybdenum catalyst was proposed as an important subject of methanol oxidation to formaldehyde.The development of ferro-molybdenum catalyst which was more compatible with the existing silver method process was suggested as the main research direction of formaldehyde production technology in the future.

Key words: methanol oxidation, silver method, ferro-molybdenum method, catalyst for methanol to formaldehyde, production technology

CLC Number:

TQ426.94

LI He, ZHANG Lijie, ZHANG Kai, SU Jin, YAO Zhaoyang, ZENG Xianjun, GUO Chunlei, SUN Yanmin. Advances in technology and catalyst for methanol oxidized to formaldehyde[J]. Inorganic Chemicals Industry, 2023, 55(11): 12-18.

Figures/Tables 3

References 43

1	邵青楠，迟子怡，李学刚，等.铁钼法甲醇制甲醛催化动力学研究及反应器模拟［J］.天然气化工（C1化学与化工），2021，46（5）：121-128.
	SHAO Qingnan， CHI Ziyi， LI Xuegang，et al.Kinetic study and reactor simulation of methanol to formaldehyde over Fe-Mo catalysts［J］.Natural Gas Chemical Industry，2021，46（5）：121-128.
2	周泽乾，查抒言.铁钼法制甲醛催化剂专利技术综述［J］.广东化工，2019，46（19）：248-249.
	ZHOU Zeqian， ZHA Shuyan.Patents review on iron-molybdenum oxide catalyst of methanol to formaldehyde［J］.Guangdong Chemical Industry，2019，46（19）：248-249.
3	SANTOS O S， MASCARENHAS A J S， ANDRADE H M C.N₂O-assisted methanol selective oxidation to formaldehyde on cobalt oxide catalysts derived from layered double hydroxides［J］.Catalysis Communications，2018，113：32-35.
4	冯晓波.甲醛市场现状及发展趋势刍议［J］.中氮肥，2017（6）：51-54.
	FENG Xiaobo.Discussion on the present situation and development trend of formaldehyde market［J］.M-Sized Nitrogenous Fertilizer Progress，2017（6）：51-54.
5	许永成，肖敦峰，刘广智.甲醇氧化制甲醛工艺技术探讨［J］.化肥设计，2012，50（3）：24-26，29.
	XU Yongcheng， XIAO Dunfeng， LIU Guangzhi.Discussion on process technology of formaldehyde made by methanol oxidation［J］.Chemical Fertilizer Design，2012，50（3）：24-26，29.
6	黄政，金国杰，高焕新.Fe₂（MoO₄）₃/MoO₃纳米棒催化剂的制备及应用［J］.工业催化，2017，25（2）：37-41.
	HUANG Zheng， JIN Guojie， GAO Huanxin.Preparation and application of Fe₂（MoO₄）₃/MoO₃ nano-rod catalysts［J］.Industrial Catalysis，2017，25（2）：37-41.
7	XIAO Yang， WANG Yuan， VARMA A.Low-temperature selective oxidation of methanol over Pt-Bi bimetallic catalysts［J］.Journal of Catalysis，2018，363：144-153.
8	贾镜渤.铁钼法甲醛装置甲醛反应器闪爆及防范措施［J］.化工管理，2022（28）：138-141.
	JIA Jingbo.Reactor flash explosion and preventive measures of Fe-Mo catalyst formaldehyde preparation plant［J］.Chemical Management，2022（28）：138-141.
9	PHAM T T P， NGUYEN P H D， VO T T，et al.Preparation of NO-doped β-MoO₃ and its methanol oxidation property［J］.Materials Chemistry and Physics，2016，184：5-11.
10	江秀美.甲醛生产用铁钼催化剂的活性及其影响因素探索［J］.化工管理，2019（10）：84-85.
	JIANG Xiumei.Activity of Fe-Mo catalyst for formaldehyde production and its influencing factors［J］.Chemical Enterprise Management，2019（10）：84-85.
11	李洪亮，房海霞.铁钼法制甲醛的甲醇单耗控制与影响因素［J］.化工管理，2021（27）：142-143.
	LI Hongliang， FANG Haixia.Methanol unit consumption control and influencing factors of formaldehyde by Fe-Mo method［J］.Chemical Enterprise Management，2021（27）：142-143.
12	RIETZ F，张华民.铁钼法制备甲醛技术的优势探讨［J］.林产工业，2016，43（1）：44-46.
	RIETZ F， ZHANG Huamin.Discussion on the technical advantages of iron-molybdenum catalytic processes［J］.China Forest Products Industry，2016，43（1）：44-46.
13	孔令吉.铁钼法甲醛生产中甲醇转化率提升工艺技术研究［J］.生物化工，2021，7（3）：150-152，156.
	KONG Lingji.Research on process technology for increasing methanol conversion rate in iron-molybdenum formaldehyde production［J］.Biological Chemical Engineering，2021，7（3）：150-152，156.
14	PAPES FILHO A C， MACIEL FILHO R.Hybrid training approach for artificial neural networks using genetic algorithms for rate of reaction estimation：Application to industrial methanol oxidation to formaldehyde on silver catalyst［J］.Chemical Engineering Journal，2010，157（2/3）：501-508.
15	QIAN Min， LIAUW M A， EMIG G.Formaldehyde synthesis from methanol over silver catalysts［J］.Applied Catalysis A：General，2003，238（2）：211-222.
16	SUN Qiuyan， Yong MEN， WANG Jinguo，et al.Support effect of Ag/ZnO catalysts for partial oxidation of methanol［J］.Inorganic Chemistry Communications，2018，92：51-54.
17	周立国，刘凯.甲醇中Fe²⁺、S^2-杂质对催化氧化生产甲醛催化剂活性的影响［J］.山东化工，2011，40（1）：11-15.
	ZHOU Liguo， LIU Kai.The influence of impurities of Fe²⁺，S^2- in methanol on the activity of the catalyst in producing formaldehyde［J］.Shandong Chemical Industry，2011，40（1）：11-15.
18	杨占奇.延长银催化剂使用寿命的方法探讨［J］.化工管理，2013（24）：102-103.
	YANG Zhanqi.Discussion on the method of prolonging the service life of silver catalyst［J］.Chemical Enterprise Management，2013（24）：102-103.
19	WATERHOUSE G I N， BOWMAKER G A， METSON J B.Influence of catalyst morphology on the performance of electrolytic silver catalysts for the partial oxidation of methanol to formaldehyde［J］.Applied Catalysis A：General，2004，266（2）：257-273.
20	ROUTRAY K， ZHOU Wu， KIELY C J，et al.Origin of the synergistic interaction between MoO₃ and iron molybdate for the selective oxidation of methanol to formaldehyde［J］.Journal of Catalysis，2010，275（1）：84-98.
21	YANG Wenjuan， LI Junjun， CUI Xiaoya，et al.Fine-tuning inverse metal-support interaction boosts electrochemical transformation of methanol into formaldehyde based on density functional theory［J］.Chinese Chemical Letters，2021，32（8）：2489-2494.
22	张薛诗蕴，袁善良，刘照，等.焙烧温度对甲醇氧化制甲醛铁钼催化剂结构及性能的影响［J］.天然气化工（C1化学与化工），2021，46（3）：35-40，87.
	ZHANG Xueshiyun， YUAN Shanliang， LIU Zhao，et al.Effect of calcination temperature on structure and activity of iron-molybdenum catalysts for methanol oxidation to formaldehyde［J］.Natural Gas Chemical Industry，2021，46（3）：35-40，87.
23	KONG Lingtao， XU Shengtao， LIU Xue，et al.Effects of iron precursors on the structure and catalytic performance of iron molybdate prepared by mechanochemical route for methanol to formaldehyde［J］.Chinese Journal of Chemical Engineering，2020，28（6）：1603-1611.
24	殷惠琴，贺健，董天雷.甲醇氧化制甲醛催化剂性能的影响因素分析［J］.能源化工，2021，42（3）：26-29.
	YIN Huiqin， HE Jian， DONG Tianlei.Analysis of factors affecting the performance of catalysts for methanol oxidation to formaldehyde［J］.Energy Chemical Industry，2021，42（3）：26-29.
25	卫敏，程丽军，袁善良，等.调控制备pH值对铁钼催化剂结构及性能的影响［J］.燃料化学学报，2019，47（2）：209-214.
	WEI Min， CHENG Lijun， YUAN Shanliang，et al.Effect of pH value on the structure and properties of iron-molybdenum catalysts during preparation［J］.Journal of Fuel Chemistry and Technology，2019，47（2）：209-214.
26	刘雪.机械化学法制备铁钼催化剂及其催化甲醇部分氧化制甲醛性能研究［D］.乌鲁木齐：新疆大学，2021.
	LIU Xue.Study on iron molybdate catalytic prepared by mechanochemical method and their catalytic performance for partial oxidation of methanol to formaldehyde［D］.Urumqi：Xinjiang University，2021.
27	李高林，邓少亮，周振华，等.高活性铁钼法甲醛催化剂的研究［J］.辽宁化工，2019，48（8）：760-762.
	LI Gaolin， DENG Shaoliang， ZHOU Zhenhua，et al.Study on the ferric molybdate formaldehyde catalyst with high activity［J］.Liaoning Chemical Industry，2019，48（8）：760-762.
28	韩双双，闫真真，孔令涛，等.球磨时间对甲醇氧化制甲醛铁钼催化剂结构及性能的影响［J］.现代化工，2018，38（10）：114-117.
	HAN Shuangshuang， YAN Zhenzhen， KONG Lingtao，et al.Effects of milling time on structure and performance of iron molybdate catalyst for methanol to formaldehyde［J］.Modern Chemical Industry，2018，38（10）：114-117.
29	KONG Lingtao， ZHANG Mei， LIU Xue，et al.Green and rapid synthesis of iron molybdate catalyst by mechanochemistry and their catalytic performance for the oxidation of methanol to formaldehyde［J］.Chemical Engineering Journal，2019，364：390-400.
30	王峰，李书双.一种甲醇氧化制甲醛铁钼基催化剂的制备方法及应用：中国，108097259B［P］.2020-11-24.
31	DIAS A P S， MONTEMOR F， PORTELA M F，et al.The role of the suprastoichiometric molybdenum during methanol to formaldehyde oxidation over Mo-Fe mixed oxides［J］.Journal of Molecular Catalysis A：Chemical，2015，397：93-98.
32	RAUN K V， JOHANNESSEN J， MCCORMACK K，et al.Modeling of the molybdenum loss in iron molybdate catalyst pellets for selective oxidation of methanol to formaldehyde［J］.Chemical Engineering Journal，2019，361：1285-1295.
33	刘经伟，李泽壮，杨爱武，等.一种以SiC为载体的铁钼氧化物、其制备方法及其应用：中国，106552658B［P］.2019-09-06.
34	尹育，初乃波，万毅，等.一种甲醇氧化制甲醛催化剂及其制备方法：中国，107952445B［P］.2020-07-24.
35	余科，李耀会，吕小婉，等.EQ-101型甲醛催化剂的研究［C］//中部四省化学化工学会2016年学术年会摘要集.南昌，2016：124.
36	张雄斌，林涛海，邓建康，等.EQ-101型铁钼甲醛合成催化剂的工业应用［J］.煤化工，2019，47（1）：32-34.
	ZHANG Xiongbin， LIN Taohai， DENG Jiankang，et al.Industrial application of EQ-101 iron-molybdenum formaldehyde synthesis catalyst［J］.Coal Chemical Industry，2019，47（1）：32-34.
37	LERVOLD S， LØDENG R， YANG Jia，et al.Partial oxidation of methanol to formaldehyde in an annular reactor［J］.Chemical Engineering Journal，2021，423：130141.
38	VERNIKOVSKAYA N V， SHEBOLTASOV A G，OVCHINNIKOVA E V，et al.Experimental and theoretical investigation of the oxidation of methanol to formaldehyde in a microstructured slit-type catalytic reactor［J］.Chemical Engineering Journal，2023，451：138368.
39	BEHERA G C， PARIDA K.Selective gas phase oxidation of methanol to formaldehyde over aluminum promoted vanadium phosphate［J］.Chemical Engineering Journal，2012，180：270-276.
40	ALI T T， BASAHEL S N， MAHMOUD H A，et al.Influence of preparation conditions on the catalytic activity of high surface area silica in partial methanol oxidation［J］.Chemical Engineering Journal，2017，330：852-862.
41	LI Zizhen， IVANENKO A， MENG Xiangchao，et al.Photocatalytic oxidation of methanol to formaldehyde on bismuth-based semiconductors［J］.Journal of Hazardous Materials，2019，380：120822.
42	MAHDI H I， RAMLEE N N， SILVA SANTOS D H DA，et al.Formaldehyde production using methanol and heterogeneous solid catalysts：A comprehensive review［J］.Molecular Catalysis，2023，537：112944.
43	YANG Z Y， WOJTASZEK-GURDAK A， YANG C M，et al.Enhancement of selectivity in methanol oxidation over copper containing SBA-15 by doping with boron species［J］.Catalysis Today，2020，356：122-131.

工艺类型	反应温度/℃	反应器类型	催化剂使用周期/月	甲醇转化率/%	反应选择性/%	甲醛收率/%	甲醇单耗（以37% 甲醛计）/（kg·t^-1）	副产中压蒸汽量（以37%甲醛计）/（kg·t^-1）
银法	600~680	固定床绝热	3~6	92~96	95~97	87~90	440~450	300~500
铁钼法	250~350	列管式固定床换热	12~18	97~99	95~99	91~94	424~438	600~800
工艺类型	副产蒸汽压力/MPa	耗电量（以37%甲醛计）/（KW·h·t^-1）	产品中甲醛质量分数/%	产品中甲醇质量分数（以37%甲醛计）/%		产品中甲酸质量分数（以 37%甲醛计）/%	催化剂对毒物敏感程度	催化剂失活原因
银法	0.15	18~30	37~50	1.5~3.6		0.01~0.02	敏感	Ag晶粒烧结，原料中Fe、S中毒
铁钼法	2.5	70~120	37~60	0.4~1.3		0.02~0.03	不敏感	Mo升华

[1]	Chen Yao,Peng Can,Wu Lijue,Fu Haikuo. Progress in production technologies of battery grade cobalt sulfate [J]. Inorganic Chemicals Industry, 2019, 51(3): 7-11.
[2]	Peng Zhanying;Yan Xin. New ‘green’ tetragenous coproduction technology for nano-sized calcium carbonate in soda plant using Hou′s process [J]. INORGANICCHEMICALSINDUSTRY, 2009, 0(10): 0-0.

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Advances in technology and catalyst for methanol oxidized to formaldehyde

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 3

References 43

Related Articles 2

Metrics

Comments

Recommended 0