Advances in MoVTeNbO x catalyst for oxidative dehydrogenation of ethane to ethylene

doi:10.16085/j.issn.1000-6613.2022-2368

Abstract

Abstract:

It is a promising way for ethylene production by oxidative dehydrogenation of ethane. MoVTeNbO _x catalyst has the advantages of high activity and strong redox ability, and it is currently the research focus of oxidative dehydrogenation of low carbon alkanes. In this work, the research progress of MoVTeNbO _x composite metal oxide in the oxidative dehydrogenation of ethane to ethylene was systematically reviewed, including the crystalline phase structure and the active center of catalyst, the preparation of catalysts, influencing factors of catalytic conversion of ethane and the improvement of catalyst performance. The main research directions at present are the regulation strategy of the active center of polymetallic oxide catalyst, the optimization of the interactions among the oxides, optimizing the preparation conditions, improving the redox ability of the catalyst and the content of V⁵⁺ on the surface through the regulation of additives, and thus improving the oxidative dehydrogenation activity and operational stability, so as to provide the foundation for the large-scale production and industrial application of the catalyst. Finally, the development prospect of MoVTeNbO _x mixed metal oxide in oxidative dehydrogenation is given.

Key words: ethane, oxidative dehydrogenation, ethylene, MoVTeNbO _x mixed metal oxides

摘要：

乙烷氧化脱氢制乙烯是非常有应用前景的乙烯生产途径，MoVTeNbO _x 催化剂具有活性高、氧化还原能力强等特点，是当前低碳烷烃氧化脱氢的研究热点。本工作系统综述了MoVTeNbO _x 复合金属氧化物在乙烷氧化脱氢制乙烯反应中的应用研究情况，包括催化剂晶相结构与活性中心、催化剂制备和催化乙烷转化的影响因素及反应性能优化提升等方面。研究多金属氧化物催化剂活性中心的调控策略，实现各组分氧化物相互作用的最优化，优化制备条件，通过助剂调控策略提高催化剂氧化还原能力及表面V⁵⁺含量，进而提高乙烷氧化脱氢活性和运行稳定性，为催化剂的规模化生产和工业应用奠定基础，是当前的主要研究方向。最后展望了MoVTeNbO _x 复合金属氧化物催化剂在氧化脱氢领域的发展前景。

关键词: 乙烷, 氧化脱氢, 乙烯, MoVTeNbO _x 复合金属氧化物

CLC Number:

TQ032.41

BU Tingting, DONG Bingli, ZHOU Ying, MA An, ZHOU Hongjun. Advances in MoVTeNbO _x catalyst for oxidative dehydrogenation of ethane to ethylene[J]. Chemical Industry and Engineering Progress, 2023, 42(11): 5707-5721.

卜婷婷, 董炳利, 周颖, 马安, 周红军. MoVTeNbO _x 催化剂应用于乙烷氧化脱氢制乙烯的研究进展[J]. 化工进展, 2023, 42(11): 5707-5721.

Figures/Tables 15

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催化剂	反应条件	转化率（摩尔分数）/%	选择性（摩尔分数）/%
MoVTeNbO（M1）^[5]	400℃，C₂H₆/O₂/He=30/20/50	58.4	91.2
M1（机械处理）^[6]	400℃，C₂H₆/O₂/He=30/20/50	57.6	90.6
M1-1.0（1.0表示草酸浓度）^[7]	400℃，C₂H₆/O₂/He=30/20/50（摩尔比），v=30mL/min	73	85
MoVTeNbCeO-0.1^[8]	400℃，C₂H₆/O₂/(He+N₂)=10/5/85	56.2	95.4
M1/CeO₂^[5]	400℃，C₂H₆/O₂/He=30/20/50（摩尔比），v=30mL/min	59.4	89.3
M1@CeO₂@堇青石^[9]	400℃，C₂H₆/O₂/He=30/20/50	60	85
MoVTeNbBiO^[10]	400℃，C₂H₆/O₂/N₂=10/10/80（体积比），v=30mL/min	50	94
Cr/CeO₂^[11]	740℃，C₂H₆/CO₂=1/7，v(C₂H₆)=10mL/min，v(CO₂)=70mL/min	36.6	97
Cr/TiO₂-ZrO₂^[12]	700℃，C₂H₆/O₂/N₂=10/50/40（体积比），v=75mL/min	48	95
Cr/MCM-41^[13]	700℃，C₂H₆/O₂/N₂=10/50/40，v=75mL/min	56	94
Nb-NiO^[14]	450℃，C₂H₆/O₂/He=5/5/90（摩尔比）	9	84
Nb₂O₅-NiO/Ni-泡沫^[15]	450℃，C₂H₆/O₂/N₂=1/1/8（体积比），GHSV=9000h^-1	60	68
Nd₂O₃-LiCl/SZ^[16]	650℃，C₂H₆/O₂/N₂=1/1/8（体积比），v=60mL/min	93	83
NiO/Al₂O₃^[17]	450℃，C₂H₆/O₂/N₂=10/10/80（体积比）	59.1	65.3
NiFe-1.0/γ-Al₂O₃^[18]	400℃，C₂H₆/O₂=1./1（体积比），W/F=0.48g·s/mL	41.7	75.0
Ni40Si40Al^[19]	400℃，C₂H₆/O₂=1（体积比），W/F=0.6g·s/cm³	17.4	78.3
P_0.15‐Ni‐Al‐O^[20]	475℃，C₂H₆/O₂/N₂=10/10/80（体积比）	31.9	61.4
VO _x /c-Al₂O₃^[21]	600℃，C₂H₆=20ml/次（脉冲进料），反应时间35s	25.84	61.80
VCoAPO-18^[22]	600℃，C₂H₆/O₂/He=4/8/88（摩尔比）	27.8	74.3
Ga₂O₃/HZSM-5^[23]	650℃，C₂H₆/CO₂/Ar=3/15/82（体积比），v=30mL/min	15	94
MoO₃-TiO₂^[24]	550℃，C₂H₆/O₂/He=1/1/8（体积比），GHSV=10000mL/g·h	55.2	92.1
Na₂WO₄/Mn/B_5.0Si₉₅^[25]	700℃，C₂H₆/O₂/N₂=1.5/1/2（体积比），GHSV=15000h^-1	66.12	70.32

催化剂	反应条件	转化率（摩尔分数）/%	选择性（摩尔分数）/%
MoVTeNbO（M1）^[5]	400℃，C₂H₆/O₂/He=30/20/50	58.4	91.2
M1（机械处理）^[6]	400℃，C₂H₆/O₂/He=30/20/50	57.6	90.6
M1-1.0（1.0表示草酸浓度）^[7]	400℃，C₂H₆/O₂/He=30/20/50（摩尔比），v=30mL/min	73	85
MoVTeNbCeO-0.1^[8]	400℃，C₂H₆/O₂/(He+N₂)=10/5/85	56.2	95.4
M1/CeO₂^[5]	400℃，C₂H₆/O₂/He=30/20/50（摩尔比），v=30mL/min	59.4	89.3
M1@CeO₂@堇青石^[9]	400℃，C₂H₆/O₂/He=30/20/50	60	85
MoVTeNbBiO^[10]	400℃，C₂H₆/O₂/N₂=10/10/80（体积比），v=30mL/min	50	94
Cr/CeO₂^[11]	740℃，C₂H₆/CO₂=1/7，v(C₂H₆)=10mL/min，v(CO₂)=70mL/min	36.6	97
Cr/TiO₂-ZrO₂^[12]	700℃，C₂H₆/O₂/N₂=10/50/40（体积比），v=75mL/min	48	95
Cr/MCM-41^[13]	700℃，C₂H₆/O₂/N₂=10/50/40，v=75mL/min	56	94
Nb-NiO^[14]	450℃，C₂H₆/O₂/He=5/5/90（摩尔比）	9	84
Nb₂O₅-NiO/Ni-泡沫^[15]	450℃，C₂H₆/O₂/N₂=1/1/8（体积比），GHSV=9000h^-1	60	68
Nd₂O₃-LiCl/SZ^[16]	650℃，C₂H₆/O₂/N₂=1/1/8（体积比），v=60mL/min	93	83
NiO/Al₂O₃^[17]	450℃，C₂H₆/O₂/N₂=10/10/80（体积比）	59.1	65.3
NiFe-1.0/γ-Al₂O₃^[18]	400℃，C₂H₆/O₂=1./1（体积比），W/F=0.48g·s/mL	41.7	75.0
Ni40Si40Al^[19]	400℃，C₂H₆/O₂=1（体积比），W/F=0.6g·s/cm³	17.4	78.3
P_0.15‐Ni‐Al‐O^[20]	475℃，C₂H₆/O₂/N₂=10/10/80（体积比）	31.9	61.4
VO _x /c-Al₂O₃^[21]	600℃，C₂H₆=20ml/次（脉冲进料），反应时间35s	25.84	61.80
VCoAPO-18^[22]	600℃，C₂H₆/O₂/He=4/8/88（摩尔比）	27.8	74.3
Ga₂O₃/HZSM-5^[23]	650℃，C₂H₆/CO₂/Ar=3/15/82（体积比），v=30mL/min	15	94
MoO₃-TiO₂^[24]	550℃，C₂H₆/O₂/He=1/1/8（体积比），GHSV=10000mL/g·h	55.2	92.1
Na₂WO₄/Mn/B_5.0Si₉₅^[25]	700℃，C₂H₆/O₂/N₂=1.5/1/2（体积比），GHSV=15000h^-1	66.12	70.32

催化剂	反应条件	乙烷转化率/%	乙烯选择性/%	CO _x 选择性/%
MoV_0.24Te_0.24Nb_0.18O _x^[29]	440℃，常压，C₂H₆/O₂/N₂=9/7/84	45	93	7
MoV_0.25Te_0.23Nb_0.12O _x^[5]	400℃，常压，C₂H₆/O₂/He=30/20/50	58.4	91.2	8.8
MoV_0.25Te_0.23Nb_0.18O _x^[60]	400℃，常压，C₂H₆/O₂/He=30/20/50	24.2	94.6	5.4
MoV_0.27Te_0.16Nb_0.14O _x^[78]	380℃，常压，C₂H₆/O₂/He+Ne=30/20/50	35	92	8
MoV_0.29Nb_0.15O _x^[79]	400℃，常压，C₂H₆/O₂=3/1	21	70	30
MoV_0.3Te_0.23Nb_0.12O _x^[80]	400℃，常压，C₂H₆/O₂/N₂=5/5/90	55	92	8
MoV_0.37Te_0.17Nb_0.15O _x^[81]	400℃，常压，C₂H₆︰O₂=75︰25(v/v)	37	85	15

催化剂	反应条件	乙烷转化率/%	乙烯选择性/%	CO _x 选择性/%
MoV_0.24Te_0.24Nb_0.18O _x^[29]	440℃，常压，C₂H₆/O₂/N₂=9/7/84	45	93	7
MoV_0.25Te_0.23Nb_0.12O _x^[5]	400℃，常压，C₂H₆/O₂/He=30/20/50	58.4	91.2	8.8
MoV_0.25Te_0.23Nb_0.18O _x^[60]	400℃，常压，C₂H₆/O₂/He=30/20/50	24.2	94.6	5.4
MoV_0.27Te_0.16Nb_0.14O _x^[78]	380℃，常压，C₂H₆/O₂/He+Ne=30/20/50	35	92	8
MoV_0.29Nb_0.15O _x^[79]	400℃，常压，C₂H₆/O₂=3/1	21	70	30
MoV_0.3Te_0.23Nb_0.12O _x^[80]	400℃，常压，C₂H₆/O₂/N₂=5/5/90	55	92	8
MoV_0.37Te_0.17Nb_0.15O _x^[81]	400℃，常压，C₂H₆︰O₂=75︰25(v/v)	37	85	15

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