柱撑型钒基催化剂的制备及其丙烷氧化脱氢催化性能

doi:10.16085/j.issn.1000-6613.2018-2145

摘要/Abstract

摘要：

以人工合成的3种不同层板组成的层状双羟基金属氢氧化物MgAl-CO₃-LDHs、CoAl-CO₃-LDHs和NiCr-CO₃-LDHs为载体，以偏钒酸钠NaVO₃为柱撑剂和钒前体，采用离子交换法制备了钒柱撑的催化剂样品（MgAlVO、CoAlVO和NiCrVO），通过XRD、FTIR、XPS和Raman等手段表征了样品的物相、钒物种的存在形态以及钒的价态，以丙烷氧化脱氢制丙烯为模型反应，表征了所制备的催化剂样品的催化性能，着重探讨了LDHs载体的层板组成以及钒的含量对催化剂样品中的钒氧物种存在形态及其丙烷氧化脱氢催化性能的影响。结果表明：以20%理论含量的钒柱撑MgAl-CO₃-LDHs所制备的催化剂样品20%MgAlVO对丙烷氧化脱氢反应的催化性能较好，当反应温度为560℃时，丙烯收率可以达到11.3%，Raman光谱显示该催化剂样品中的钒以Mg₃V₂O₈和α-Mg₂V₂O₇两种形式共存，且晶格氧O^2-和吸附氧O^-所占的比例较为均衡，有利于获得较好的丙烷氧化脱氢催化性能，而在同样条件下制备的催化剂样品20%CoAlVO和20%NiCrVO中的钒物种只观察到分别以Co₃V₂O₈和Ni₃V₂O₈存在的正钒酸盐，前者对丙烯的收率不到8%，后者甚至完全得不到丙烯。

关键词: 催化剂, 催化剂载体, 选择性, 层状双羟基金属氢氧化物, 丙烷氧化脱氢制丙烯

Abstract:

Three types of vanadium-based catalyst samples were prepared through ionic exchange by using three layer double hydroxides with different layer composition as carrier, which was MgAl-CO₃-LDHs、CoAl-CO₃-LDHs and NiCr-CO₃-LDHs, and NaVO₃ as pillar reagent as well as vanadium precursor. The physical phase and the state of vanadium species were characterized by XRD, FTIR, XPS and Raman spectra. The catalytic performance of the prepared catalyst samples were tested by using oxidative dehydrogenation of propane to propylene as probe reaction, and the influence of the layer composition of LDHs and the content of vanadium on the state of vanadium species as well as on its catalytic performance were discussed. The results showed that a propylene yield of 11.3% was obtained at 560℃ on the catalyst sample of 20%MgAlVO, and the Raman spectra showed that two types of vanadium species of Mg₃V₂O₈ and α-Mg₂V₂O₇ coexisted in this sample. Besides, the XPS spectra showed that the ratio of lattice oxygen to the adsorbed oxygen was ideal. Both of them were beneficial to obtain high catalytic performance. However, vanadium species of Co₃V₂O₈ and Ni₃V₂O₈ were observed in the samples of 20%CoAlVO and NiCrVO. The propylene yield was lower than 8% on the catalyst samples of 20%CoAlVO and even no propylene produced on the catalyst samples of 20%NiCrVO at the same conditions.

Key words: catalyst, catalyst support, selectivity, layer double hydroxides（LDHs）, oxidative dehydrogenation of propane to propylene

中图分类号:

TQ032

祝琳华,贺召宏,司甜,何艳萍. 柱撑型钒基催化剂的制备及其丙烷氧化脱氢催化性能[J]. 化工进展, 2019, 38(08): 3711-3719.

Linhua ZHU,Zhaohong HE,Tian SI,Yanping HE. Preparation of vanadia pillared catalysts and the catalytic performance in the oxidative dehydrogenation of propane to propylene[J]. Chemical Industry and Engineering Progress, 2019, 38(08): 3711-3719.

图/表 9

图1 载体及其钒柱撑后样品的XRD谱图

图2 载体及其钒柱撑后样品的FTIR谱图

图3 3种不同层板组成的钒催化剂上的丙烷氧化脱氢性能

图4 催化剂样品的V2p3/2的XPS谱图

图5 催化剂样品的O1s的XPS谱图

表1 钒基催化剂样品的V2p3/2和O1s的分峰拟合结果

样品	结合能/eV					晶格氧与吸附氧所占比例/%			V⁵⁺/V⁴⁺
样品	V⁵⁺	V⁴⁺	O^2-	O^-	$O 2 -$	O^2-	O^-	$O 2 -$	V⁵⁺/V⁴⁺
20%MgAlVO	517.2	516.5	529.8	531.1	—	59.82	40.18	—	1.40
20%CoAlVO	517.3	516.4	530.1	531.1	532.2	47.69	25.92	26.39	1.07
20%NiCrVO	517.2	516.5	530.0	531.6	—	84.00	16.00	—	0.78

表1 钒基催化剂样品的V2p3/2和O1s的分峰拟合结果

样品	结合能/eV					晶格氧与吸附氧所占比例/%			V⁵⁺/V⁴⁺
样品	V⁵⁺	V⁴⁺	O^2-	O^-	$O 2 -$	O^2-	O^-	$O 2 -$	V⁵⁺/V⁴⁺
20%MgAlVO	517.2	516.5	529.8	531.1	—	59.82	40.18	—	1.40
20%CoAlVO	517.3	516.4	530.1	531.1	532.2	47.69	25.92	26.39	1.07
20%NiCrVO	517.2	516.5	530.0	531.6	—	84.00	16.00	—	0.78

图6 MgAlVO、CoAlVO和NiCrVO的Raman谱图

图7 不同钒含量催化剂上丙烷氧化脱氢反应的丙烯转化率（X）、丙烯选择性（S）和收率（Y）

图8 不同钒含量催化剂样品的Raman谱图

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