丁烯氧化脱氢钼铋系催化剂：晶相之间的协同效应

doi:10.16085/j.issn.1000-6613.2018-1280

化工进展 ›› 2019, Vol. 38 ›› Issue (01): 334-343.DOI: 10.16085/j.issn.1000-6613.2018-1280

丁烯氧化脱氢钼铋系催化剂：晶相之间的协同效应

张思泽¹(),万超¹,曾亮²,程党国¹(),陈丰秋¹,巩金龙²()

1. 浙江大学化学工程与生物工程学院，浙江杭州 310027
2. 天津大学化工学院，天津化学化工协同创新中心，天津300072

收稿日期:2018-06-21 修回日期:2018-10-12 出版日期:2019-01-05 发布日期:2019-01-05
通讯作者: 程党国,巩金龙
作者简介:张思泽（1994—），男，硕士研究生。E-mail：<email>21628025@zju.edu.cn</email>。|程党国，教授。E-mail：<email>dgcheng@zju.edu.cn</email>|巩金龙，教授。E-mail：<email>jlgong@tju.edu.cn</email>
基金资助:
国家自然科学基金(21622606);国家自然科学基金（21622606）。

Oxidative dehydrogenation of butene over bismuth molybdate catalysts: synergetic effect between different crystalline phases

Size ZHANG¹(),Chao WAN¹,Liang ZENG²,Dangguo CHENG¹(),Fengqiu CHEN¹,Jinlong GONG²()

1. College of Chemical and Biological Engineering，Zhejiang University，Hangzhou 310027，Zhejiang，China
2. Collaborative Innovation Centre of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

Received:2018-06-21 Revised:2018-10-12 Online:2019-01-05 Published:2019-01-05
Contact: Dangguo CHENG,Jinlong GONG

摘要/Abstract

摘要：

钼铋系催化剂以其优良的性能一直以来都是丁烯氧化脱氢研究和应用的热点。本文简述了已有研究中对钼铋系催化剂及改性后的多组分催化剂的晶相结构及其与反应性能间关系的研究进展。指出在钼铋催化剂中，有较多晶格缺陷的α-Bi₂(MoO₄)₃提供吸附位，氧流动性较强的γ-Bi₂MoO₆提供晶格氧，二者的协同作用提高了催化剂的活性。而在改性后的多组分钼铋系催化剂中，添加的组分与钼铋元素结合生成新的晶相，产生了更多的晶格缺陷及氧供体，从而提升了催化性能。对于钼铋系催化剂进一步改进的方向，本文认为在添加组分的方法基础上，还可以从催化剂表面结构方面入手，进行进一步的深入探究。

关键词: 烯烃, 氧化脱氢, 催化剂, 晶型结构

Abstract:

Due to the excellent catalytic performance, the multicomponent bismuth molybdate catalysts have attracted much attention in oxidative dehydrogenation of butene. This review describes the recent progress about the crystalline phases and its relationship with the reaction performance for both single and multicomponent bismuth molybdates. The results indicate that in bismuth molybdate, α-Bi₂(MoO₄)₃ provides adsorption sites because of the presence of more lattice defects, and γ-Bi₂MoO₆ provides lattice oxygen because of higher oxygen mobility. The synergistic effect of the two phases enhances the activity of the catalysts. In multicomponent bismuth molybdate catalysts, the added elements combine bismuth and molybdenum to form new crystalline phases, resulting in more lattice defects and oxygen donors, and thus improving the catalytic performance. As for the further improvement of multicomponent bismuth molybdate catalysts, it is believed that, on the basis of the method of adding components, the surface structure of the catalysts can be further explored.

Key words: alkene, oxidative dehydrogenation, catalyst, crystalline phases

中图分类号:

张思泽, 万超, 曾亮, 程党国, 陈丰秋, 巩金龙. 丁烯氧化脱氢钼铋系催化剂：晶相之间的协同效应[J]. 化工进展, 2019, 38(01): 334-343.

Size ZHANG, Chao WAN, Liang ZENG, Dangguo CHENG, Fengqiu CHEN, Jinlong GONG. Oxidative dehydrogenation of butene over bismuth molybdate catalysts: synergetic effect between different crystalline phases[J]. Chemical Industry and Engineering Progress, 2019, 38(01): 334-343.

图/表 9

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催化剂	反应温度/℃	实验变量	最优活性^①
催化剂	反应温度/℃	实验变量	S/%	Y/%	TOS/h
α-Bi₂(MoO₄)₃ ^[4]	420	单相	74	27	48
β-Bi₂Mo₂O₉ ^[3]	420	单相（不稳定）	92	60	100
γ-Bi₂MoO₆ ^[30,31]	420	制备pH = 3	90	46	12
	440	丁烯∶氧气 = 1∶0.75	91	47	48
β-Bi₂Mo₂O₉ + γ-Bi₂MoO₆ ^[32]	420	β + 32% γ 混合相（摩尔分数）	73	29	null
α-Bi₂(MoO₄)₃ + γ-Bi₂MoO₆ ^[3]	420	α + 90% γ 混合相（质量分数）	90	59	null

催化剂	反应温度/℃	实验变量	最优活性^①
催化剂	反应温度/℃	实验变量	S/%	Y/%	TOS/h
α-Bi₂(MoO₄)₃ ^[4]	420	单相	74	27	48
β-Bi₂Mo₂O₉ ^[3]	420	单相（不稳定）	92	60	100
γ-Bi₂MoO₆ ^[30,31]	420	制备pH = 3	90	46	12
	440	丁烯∶氧气 = 1∶0.75	91	47	48
β-Bi₂Mo₂O₉ + γ-Bi₂MoO₆ ^[32]	420	β + 32% γ 混合相（摩尔分数）	73	29	null
α-Bi₂(MoO₄)₃ + γ-Bi₂MoO₆ ^[3]	420	α + 90% γ 混合相（质量分数）	90	59	null

项目	金属
项目	Ni	Co	Fe	Mg	Mn	Cd	Ca	Pb
离子半径 /?	0.69	0.72	0.74	0.66	0.80	0.97	0.99	1.20
稳定性结构	α-CoMoO₄型（单斜晶系） M(Ⅱ)：6-配位； M⁶⁺：6-配位					CaWO₄型（白钨矿，四方晶系） M(Ⅱ)∶8-配位；M⁶⁺∶4-配位
α-MnMoO4型 M(Ⅱ)：6-配位； M6+：4-配位

项目	金属
项目	Ni	Co	Fe	Mg	Mn	Cd	Ca	Pb
离子半径 /?	0.69	0.72	0.74	0.66	0.80	0.97	0.99	1.20
稳定性结构	α-CoMoO₄型（单斜晶系） M(Ⅱ)：6-配位； M⁶⁺：6-配位					CaWO₄型（白钨矿，四方晶系） M(Ⅱ)∶8-配位；M⁶⁺∶4-配位
α-MnMoO4型 M(Ⅱ)：6-配位； M6+：4-配位

催化剂	晶相	反应温度/℃	最优活性^①			TPRO峰/℃
催化剂	晶相	反应温度/℃	S/%	Y/%	TOS/h	TPRO峰/℃
BiMoCe_0.2 ^[7]	Ce(MoO₄)₂, α-Bi₂(MoO₄)₃, β-Bi₂Mo₂O₉, γ-Bi₂MoO₆	440	96	70	2	183
BiMoLa_0.2 ^[8]	La₂(MoO₄)₃, α-Bi₂(MoO₄)₃, β-Bi₂Mo₂O₉, γ-Bi₂MoO₆	440	95	71	100	174
BiMoZr_0.4 ^[11]	Zr(MoO₄)₂, α-Bi₂(MoO₄)₃, β-Bi₂Mo₂O₉, γ-Bi₂MoO₆	440	91	68	2	171
BiV_0.6Mo_0.4 ^[12]	Bi_0.93Mo_0.21V_0.79O₄, γ-Bi₂MoO₆	420	89	64	8	181
BiMoV_0.15 ^[14]	BiVO₄, α-Bi₂(MoO₄)₃, β-Bi₂Mo₂O₉, γ-Bi₂MoO₆	440	96	73	2	180
BiMoFe_0.65 ^[48]	Fe₂(MoO₄)₃, α-Bi₂(MoO₄)₃, β-Bi₂Mo₂O₉, γ-Bi₂MoO₆	420	91	63	6	155

丁烯氧化脱氢钼铋系催化剂：晶相之间的协同效应

Oxidative dehydrogenation of butene over bismuth molybdate catalysts: synergetic effect between different crystalline phases

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催化剂	晶相	最优活性^①
催化剂	晶相	S/%	Y/%	TOS/h
Co₉Fe₃Bi₁Mo₁₂O₅₁ ^[9]	α-CoMoO₄, β-CoMoO₄, α-Bi₂(MoO₄)₃, γ-Bi₂MoO₆, Fe₂(MoO₄)₃	93	61	6
Ni₉Fe₃Bi₁Mo₁₂O₅₁ ^[9]	α-NiMoO₄, β-NiMoO₄, α-Bi₂(MoO₄)₃, γ-Bi₂MoO₆, Fe₂(MoO₄)₃	90	53	6
Mn₉Fe₃Bi₁Mo₁₂O₅₁ ^[9]	α-MnMoO₄, α-Bi₂(MoO₄)₃, γ-Bi₂MoO₆, Fe₂(MoO₄)₃	90	48	6
Mg₉Fe₃Bi₁Mo₁₂O₅₁ ^[9]	β-MgMoO₄,α-Bi₂(MoO₄)₃, γ-Bi₂MoO₆, Fe₂(MoO₄)₃	91	47	6
Zn₉Fe₃Bi₁Mo₁₂O₅₁ ^[9]	α-ZnMoO₄, α-Bi₂(MoO₄)₃, γ-Bi₂MoO₆, Fe₂(MoO₄)₃	92	40	6
BiFe_0.65Ni_0.05Mo^[13,53]	Bi₃Mo₂Fe₁O₁₂[derived α-Bi₂(MoO₄)₃], Fe₂(MoO₄)₃, NiMoO₄	84	72	14
BiFe_0.65Co_0.05Mo^[13]	Bi₃Mo₂Fe₁O₁₂[derived α-Bi₂(MoO₄)₃], Fe₂(MoO₄)₃, CoMoO₄	82	68	14
BiFe_0.65Zn_0.05Mo^[13]	Bi₃Mo₂Fe₁O₁₂[derived α-Bi₂(MoO₄)₃], Fe₂(MoO₄)₃, ZnMoO₄	86	67	14
BiFe_0.65Mn_0.05Mo^[13]	Bi₃Mo₂Fe₁O₁₂[derived α-Bi₂(MoO₄)₃], Fe₂(MoO₄)₃, MnMoO₄	85	64	14
BiFe_0.65Cu_0.05Mo^[13]	Bi₃Mo₂Fe₁O₁₂[derived α-Bi₂(MoO₄)₃], Fe₂(MoO₄)₃, CuMoO₄	78	46	14

催化剂	晶相	最优活性^①
催化剂	晶相	S/%	Y/%	TOS/h
Co₉Fe₃Bi₁Mo₁₂O₅₁ ^[9]	α-CoMoO₄, β-CoMoO₄, α-Bi₂(MoO₄)₃, γ-Bi₂MoO₆, Fe₂(MoO₄)₃	93	61	6
Ni₉Fe₃Bi₁Mo₁₂O₅₁ ^[9]	α-NiMoO₄, β-NiMoO₄, α-Bi₂(MoO₄)₃, γ-Bi₂MoO₆, Fe₂(MoO₄)₃	90	53	6
Mn₉Fe₃Bi₁Mo₁₂O₅₁ ^[9]	α-MnMoO₄, α-Bi₂(MoO₄)₃, γ-Bi₂MoO₆, Fe₂(MoO₄)₃	90	48	6
Mg₉Fe₃Bi₁Mo₁₂O₅₁ ^[9]	β-MgMoO₄,α-Bi₂(MoO₄)₃, γ-Bi₂MoO₆, Fe₂(MoO₄)₃	91	47	6
Zn₉Fe₃Bi₁Mo₁₂O₅₁ ^[9]	α-ZnMoO₄, α-Bi₂(MoO₄)₃, γ-Bi₂MoO₆, Fe₂(MoO₄)₃	92	40	6
BiFe_0.65Ni_0.05Mo^[13,53]	Bi₃Mo₂Fe₁O₁₂[derived α-Bi₂(MoO₄)₃], Fe₂(MoO₄)₃, NiMoO₄	84	72	14
BiFe_0.65Co_0.05Mo^[13]	Bi₃Mo₂Fe₁O₁₂[derived α-Bi₂(MoO₄)₃], Fe₂(MoO₄)₃, CoMoO₄	82	68	14
BiFe_0.65Zn_0.05Mo^[13]	Bi₃Mo₂Fe₁O₁₂[derived α-Bi₂(MoO₄)₃], Fe₂(MoO₄)₃, ZnMoO₄	86	67	14
BiFe_0.65Mn_0.05Mo^[13]	Bi₃Mo₂Fe₁O₁₂[derived α-Bi₂(MoO₄)₃], Fe₂(MoO₄)₃, MnMoO₄	85	64	14
BiFe_0.65Cu_0.05Mo^[13]	Bi₃Mo₂Fe₁O₁₂[derived α-Bi₂(MoO₄)₃], Fe₂(MoO₄)₃, CuMoO₄	78	46	14