Advances in chemical-looping oxidative dehydrogenation of light alkanes

doi:10.11949/0438-1157.20221311

Abstract

Abstract:

The production capacity of light olefins can reflect the technology level of the chemical industry. With the growing market demand for light olefins, novel and efficient light olefin production processes have attracted extensive attention. With chemical-looping light alkane oxidative dehydrogenation technology, through the reaction of lattice oxygen in the oxygen carrier and reactant molecules, the selective conversion of alkane molecules to olefin molecules can be realized, which can increase the yield of olefins and effectively reduce the process energy consumption and CO₂ emission. This review analyzes the current research progress on the screening and theoretical design of oxygen carrier materials, the regulation mechanism of surface active sites and lattice oxygen transport in the bulk phase, and the optimization of reactors and processes for chemical-looping light alkane oxidative dehydrogenation technology. The future development trends of chemical-looping light alkane oxidative dehydrogenation technologies are systematically summarized to provide instructive perspectives for the advance of relevant technologies.

Key words: chemical-looping, oxygen carrier, oxidative dehydrogenation, selective hydrogen combustion, light alkanes

摘要：

低碳烯烃生产能力是化工行业技术水平的重要标志。随着低碳烯烃市场需求的增加，新型高效的低碳烯烃生产工艺得到了广泛关注。化学链低碳烷烃氧化脱氢技术，通过载氧体中的晶格氧与反应物分子发生反应，实现烷烃分子向烯烃分子的选择性转化，可以提高烯烃产率，有效降低过程能耗和CO₂排放。本文针对化学链低碳烷烃氧化脱氢技术，深入分析了载氧体材料的筛选和理论设计、表面活性位和体相氧传输的调控机制、循环稳定性、载氧体的制备、化学链烷烃脱氢反应器和工艺设计优化等方向的研究现状和进展，并系统总结了未来化学链低碳烷烃脱氢技术及相关领域的发展趋势，为化学链烷烃脱氢领域的技术进步提供参考和借鉴。

关键词: 化学链, 载氧体, 氧化脱氢, 选择性氢燃烧, 低碳烷烃

CLC Number:

TQ 511

Jiachen SUN, Chunlei PEI, Sai CHEN, Zhijian ZHAO, Shengbao HE, Jinlong GONG. Advances in chemical-looping oxidative dehydrogenation of light alkanes[J]. CIESC Journal, 2023, 74(1): 205-223.

孙嘉辰, 裴春雷, 陈赛, 赵志坚, 何盛宝, 巩金龙. 化学链低碳烷烃氧化脱氢技术进展[J]. 化工学报, 2023, 74(1): 205-223.

Figures/Tables 13

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模式	载氧体	温度/℃	气相组成	转化率（H₂或C _n H₂_n₊₂）/%	选择性/%	文献
选择性氢燃烧	Na₂WO₄/CaMnO₃	850	40% H₂，40% C₂H₄，Ar平衡气（100 ml/L）	>85 (H₂)	~90	[24]
	Na₂WO₄/Mg₆MnO₈	850	80% C₂H₆，Ar平衡气（4500 h^-1）	81.8（C₂H₄）	76.0	[25]
	Na₂WO₄/LaMnO₃	800	40% C₂H₄，Ar平衡气（3400 h^-1）	70（C₂H₆）	85	[26]
	Co_0.3Mo_0.7/Fe₂O₃	825	12.5% C₂H₆，Ar平衡气（40 ml/min）	56.2（C₂H₆）	87.4	[27]
	Bi-Ce_0.75Zr_0.25O₂	550	2.5% C₂H₄，2.5% H₂，N₂平衡气（100 ml/min）	90（H₂）	—	[28]
	Ni-HY	600	10% C₂H₆, He平衡气（5100 h^-1）	18（C₂H₆）	97	[29]
	Na₂WO₄/CuMn₂O₄	720	10% C₂H₆，N₂平衡气（50 ml/min）	58.8（C₂H₆）	86.4	[30]
氧化脱氢	V-TiO₂	500	19% C₃H₈，N₂平衡气（21 ml/min）	~17（C₃H₈）	90	[31]
	MoVO _x -Al₂O₃	500	19% C₃H₈，N₂平衡气（21 ml/min）	36（C₃H₈）	89	[32]
	H₃PMo₁₂O₄₀/Al₂O₃	450	19% C₃H₈，N₂平衡气（21 ml/min）	~7（C₃H₈）	>90	[33]
	MoO _x -Fe₂O₃	600	80% C₂H₆，Ar平衡气（1500 h^-1）	4.9（C₂H₆）	62.2	[34]
	Mg-La_1.6Sr_0.4FeCoO₆	725	40% C₂H₆，N₂平衡气（10 ml/min）	52.9（C₂H₆）	89.4	[35]
	LiBr-La_0.8Sr_0.2FeO₃	500	80% C₄H₁₀，Ar平衡气（30 ml/min）	75.6（C₄H₁₀）	56.2	[36]
	Li₂O-La _x Sr_2-_x FeO_4-_δ	700	37.5% C₂H₆，N₂平衡气（40 ml/min）	61（C₂H₆）	90	[37-38]
	Li₂CO₃-La_0.8Sr_0.2FeO₃	700	80% C₂H₆，Ar平衡气（40 ml/min）	50（C₂H₆）	91	[39]
	Cr-Ce-K/Al₂O₃	630	50% C₃H₈，N₂平衡气（17 ml/min）	57.5（C₃H₈）	78	[40]
	Ce-SrFeO₃	725	80% C₂H₆，Ar平衡气（20 ml/min）	29（C₂H₆）	82	[41]

模式	载氧体	温度/℃	气相组成	转化率（H₂或C _n H₂_n₊₂）/%	选择性/%	文献
选择性氢燃烧	Na₂WO₄/CaMnO₃	850	40% H₂，40% C₂H₄，Ar平衡气（100 ml/L）	>85 (H₂)	~90	[24]
	Na₂WO₄/Mg₆MnO₈	850	80% C₂H₆，Ar平衡气（4500 h^-1）	81.8（C₂H₄）	76.0	[25]
	Na₂WO₄/LaMnO₃	800	40% C₂H₄，Ar平衡气（3400 h^-1）	70（C₂H₆）	85	[26]
	Co_0.3Mo_0.7/Fe₂O₃	825	12.5% C₂H₆，Ar平衡气（40 ml/min）	56.2（C₂H₆）	87.4	[27]
	Bi-Ce_0.75Zr_0.25O₂	550	2.5% C₂H₄，2.5% H₂，N₂平衡气（100 ml/min）	90（H₂）	—	[28]
	Ni-HY	600	10% C₂H₆, He平衡气（5100 h^-1）	18（C₂H₆）	97	[29]
	Na₂WO₄/CuMn₂O₄	720	10% C₂H₆，N₂平衡气（50 ml/min）	58.8（C₂H₆）	86.4	[30]
氧化脱氢	V-TiO₂	500	19% C₃H₈，N₂平衡气（21 ml/min）	~17（C₃H₈）	90	[31]
	MoVO _x -Al₂O₃	500	19% C₃H₈，N₂平衡气（21 ml/min）	36（C₃H₈）	89	[32]
	H₃PMo₁₂O₄₀/Al₂O₃	450	19% C₃H₈，N₂平衡气（21 ml/min）	~7（C₃H₈）	>90	[33]
	MoO _x -Fe₂O₃	600	80% C₂H₆，Ar平衡气（1500 h^-1）	4.9（C₂H₆）	62.2	[34]
	Mg-La_1.6Sr_0.4FeCoO₆	725	40% C₂H₆，N₂平衡气（10 ml/min）	52.9（C₂H₆）	89.4	[35]
	LiBr-La_0.8Sr_0.2FeO₃	500	80% C₄H₁₀，Ar平衡气（30 ml/min）	75.6（C₄H₁₀）	56.2	[36]
	Li₂O-La _x Sr_2-_x FeO_4-_δ	700	37.5% C₂H₆，N₂平衡气（40 ml/min）	61（C₂H₆）	90	[37-38]
	Li₂CO₃-La_0.8Sr_0.2FeO₃	700	80% C₂H₆，Ar平衡气（40 ml/min）	50（C₂H₆）	91	[39]
	Cr-Ce-K/Al₂O₃	630	50% C₃H₈，N₂平衡气（17 ml/min）	57.5（C₃H₈）	78	[40]
	Ce-SrFeO₃	725	80% C₂H₆，Ar平衡气（20 ml/min）	29（C₂H₆）	82	[41]

名称	反应模型	微分形式f(x)=1/k_app×dx/dt	积分形式g(x)=k_app dt
F1	First-order or Avrami–Erofe’ev (n=1)	(1-x)	-ln(1-x)
F1.5	Three-halves order	(1-x)^3/2	2[(1-x)^-1/2-1]
F2	Second-order	(1-x)²	1/(1-x)-1
F3	Third-order	(1-x)³	(1/2)[(1-x)^-2-1]
R1	Zero-order	1	x
R2	Contracting area	2(1-x)^1/2	1-(1-x)^1/2
R3	Contracting volume	3(1-x)^2/3	1-(1-x)^1/3
D1	1-D diffusion	1/(2x)	x²
D2	2-D diﬀusion, Valensi equation	1/[-ln(1-x)]	(1-x)ln(1-x)+x
D3	3-D diffusion, Jander equation	3(1-x)^1/3/[2(1-x)^-1/3-1]	[1-(1-x)^1/3]²
D4	Ginstling-Brounshtein equation	3/[2(1-x)^-1/3-1]	1-2x/3-(1-x)^2/3
AE0.5	Avrami-Erofe’ev (n=0.5)	(1/2)(1-x)[-ln(1-x)]^-1	[-ln(1-x)]²
AE1.5	Avrami-Erofe’ev (n=1.5)	(3/2)(1-x)[-ln(1-x)]^1/3	[-ln(1-x)]^2/3
AE2	Avrami-Erofe’ev (n=2)	2(1-x)[-ln(1-x)]^1/2	[-ln(1-x)]^1/2
AE3	Avrami-Erofe’ev (n=3)	3(1-x)[-ln(1-x)]^2/3	[-ln(1-x)]^1/3

名称	反应模型	微分形式f(x)=1/k_app×dx/dt	积分形式g(x)=k_app dt
F1	First-order or Avrami–Erofe’ev (n=1)	(1-x)	-ln(1-x)
F1.5	Three-halves order	(1-x)^3/2	2[(1-x)^-1/2-1]
F2	Second-order	(1-x)²	1/(1-x)-1
F3	Third-order	(1-x)³	(1/2)[(1-x)^-2-1]
R1	Zero-order	1	x
R2	Contracting area	2(1-x)^1/2	1-(1-x)^1/2
R3	Contracting volume	3(1-x)^2/3	1-(1-x)^1/3
D1	1-D diffusion	1/(2x)	x²
D2	2-D diﬀusion, Valensi equation	1/[-ln(1-x)]	(1-x)ln(1-x)+x
D3	3-D diffusion, Jander equation	3(1-x)^1/3/[2(1-x)^-1/3-1]	[1-(1-x)^1/3]²
D4	Ginstling-Brounshtein equation	3/[2(1-x)^-1/3-1]	1-2x/3-(1-x)^2/3
AE0.5	Avrami-Erofe’ev (n=0.5)	(1/2)(1-x)[-ln(1-x)]^-1	[-ln(1-x)]²
AE1.5	Avrami-Erofe’ev (n=1.5)	(3/2)(1-x)[-ln(1-x)]^1/3	[-ln(1-x)]^2/3
AE2	Avrami-Erofe’ev (n=2)	2(1-x)[-ln(1-x)]^1/2	[-ln(1-x)]^1/2
AE3	Avrami-Erofe’ev (n=3)	3(1-x)[-ln(1-x)]^2/3	[-ln(1-x)]^1/3

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