Preparation of vanadia pillared catalysts and the catalytic performance in the oxidative dehydrogenation of propane to propylene

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

Abstract

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

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

CLC Number:

TQ032

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.

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.

Figures/Tables 9

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

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

References 25

1	杨英，彭蓉，肖立桢 . 丙烷脱氢制丙烯工艺及其经济性分析[J]. 石油化工技术与经济, 2014, 30(3): 6-10.
	YANG Y , PENG R , XIAO L Z . Technology and economic analysis of dehydrogenation of propane[J]. Technology &Economics in Petrochemicals, 2014, 30(3):6-10.
2	TURAKULOVA A O , KHARLANOV A N , LEVANOV A V , et al . Catalytic properties of the VO _х /Ce_0.46Zr_0.54O₂, oxide system in the oxidative dehydrogenation of propane[J]. Russian Journal of Physical Chemistry A, 2017, 91(1): 17-25.
3	邵高耸，顾建峰 . VO _x /焦磷酸镧催化剂的丙烷氧化脱氢制丙烯催化性能[J]. 工业催化, 2016, 24(11): 27-31.
	SHAO G S , GU J F . Catalytic performance of VO _x /lanthanum pyrophosphate catalyst for oxidative dehydrogenation of propane to propene[J]. Industrial Catalysis, 2016, 24(11): 27-31
4	KOOTENAEI A H S , TWOFIGHI J , KHODADI A , et al . Stability and catalytic performance of vanadia supported on nanostructured titania catalyst in oxidative dehydrogenation of propane[J]. Applied Surface Science, 2014, 298(14): 26-35.
5	HOY M, JENSEN A D , GRUNWALDT J D . Structure of alumina supported vanadia catalysts for oxidative dehydrogenation of propane prepared by flame spray pyrolysis[J]. Applied Catalysis A: General, 2013, 451: 207-215.
6	KARAKOULIA S A , TRIANTAFYLLIDIS K S , TSILOMELEKIS G , et al . Propane oxidative dehydrogenation over vanadia catalysts supported on mesoporous silicas with varying pore structure and size[J]. Catalysis Today, 2009, 141(3): 245-253.
7	DINSE A , FRANK B , HESS C , et al . Oxidative dehydrogenation of propane over low-loaded vanadia catalysts: impact of the support material on kinetics and selectivity[J]. Journal of Molecular Catalysis A: Chemical, 2008, 289(1/2): 28-37.
8	NIETO J M L . The selective oxidative activation of light alkanes. From supported vanadia to multicomponent bulk V-containing catalysts[J]. Topics in Catalysis, 2006, 41(1): 3-15.
9	HERACLEOUS E , MACHLI M , LWMONIDOU A A , et al . Oxidative dehydrogenation of ethane and propane over vanadia and molybdena supported catalysts[J]. Journal of Molecular Catalysis A: Chemical, 2005, 232(1-2): 29-39.
10	EVANS O R , BELL A T , TILLEY T D . Oxidative dehydrogenation of propane over vanadia-based catalysts supported on high-surface-area mesoporous MgAl₂O₄ [J]. Journal of Catalysis, 2004, 226(2): 292-300.
11	DAI H , BELL A T , IGLESIA E . Effects of molybdena on the catalytic properties of vanadia domains supported on alumina for oxidative dehydrogenation of propane[J]. Journal of Catalysis, 2004, 221(2): 491-499.
12	LIU Y M , YONG C , YAN S R , et al . Highly effective oxidative dehydrogenation of propane over vanadia supported on mesoporous SBA-15 silica[J]. Catalysis Letters, 2003, 88(1): 61-67.
13	段雪, 张法智 . 插层组装与功能材料[M].北京: 化学工业出版社, 2007.
	DUAN X , ZHANG F ZH . Intercalation assembly and function materials[M]. Beijing: Chemical Industry Press, 2007.
14	VALVERDE J A , ECHAVARRIA A , EON J G . V-Mg-Al catalyst from hydrotalcite for the oxidative dehydrogenation of propane[J]. Reac. Kinet. Mech. Cat., 2014, 111: 679-696.
15	VALVERDE J A , Adriana ECHAVARRIA A , EON J G . Decavanadate-intercalated Ni-Al hydrotalcites as precursors of mixed oxides for the oxidative dehydrogenation of propane[J]. Catalysis Today,2012, 192: 36-43.
16	BLANCO S , CARRAZAN S R G , RIVES V . Oxidative dehydrogenation of propane on Mg-V-Al mixed oxides[J]. Applied Catalysis A: General, 2008, 342: 93-98.
17	DULA R , WCISLO K , SERWICKA E M . Layered double hydroxide-derived vanadium catalysts for oxidative dehydrogenation of propane influence of interlayer-doping versus layer-doping[J] Applied Catalysis A: General, 2002, 230:281-291.
18	霍彦杉 . 纳米金在LDHs上的液相插层组装及其催化活性研究[D].昆明: 昆明理工大学, 2013.
	HUO Y SH . Intercalation assembly of gold nanoparticles on the LDHs and catalytic performance[D]. Kunming：Kunming University of Science and Technology, 2013.
19	MACIUCA A L , CIOCAN C E , DUMITRIU E , et al . V-, Mo- and W-containing layered double hydroxides as effective catalysts for mild oxidation of thioethers and thiophenes with H₂O₂ [J]. Catalysis Today, 2008, 138(1/2): 33-37.
20	NARITA E , KAVIRATNA P , PINNAVAIA T J , et al . Synthesis of heteropolyoxometalate pillared layered double hydroxides via calcined zinc-aluminium oxide precursors[J]. Chemistry Letters, 2006, 5(5): 805-808.
21	ÖZER N . Electrochemical properties of sol-gel deposited vanadium pentoxide films[J]. Thin Solid Films, 1997, 305(1/2): 80-87.
22	MENDIALDUA J , CASANOVA R , BARBAUX Y . XPS studies of V₂O₅, V₆O₁₃, VO₂, and V₂O₃ [J]. Journal of Electron Spectroscopy & Related Phenomena, 1995, 71(3): 249-261.
23	MAGG N , IMMARAPORN B , GIORGI J B , et al . Vibrational spectra of alumina- and silica-supported vanadia revisited: an experimental and theoretical model catalyst study[J]. Journal of Catalysis, 2004, 226(1): 88-100.
24	GAO X , RUIZ P , XIN Q , et al . Preparation and characterization of three pure magnesium vanadate phases as catalysts for selective oxidation of propane to propene[J]. Catalysis Letters, 1994, 23(3): 321-337.
25	TIAN H , WACHS I E , BRIAND L E . Comparison of UV and visible Raman spectroscopy of bulk metal molybdate and metal vanadate catalysts[J]. Journal of Physical Chemistry B, 2005, 109(49): 23491-23499.

[1]	ZHANG Mingyan, LIU Yan, ZHANG Xueting, LIU Yake, LI Congju, ZHANG Xiuling. Research progress of non-noble metal bifunctional catalysts in zinc-air batteries [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 276-286.
[2]	SHI Yongxing, LIN Gang, SUN Xiaohang, JIANG Weigeng, QIAO Dawei, YAN Binhang. Research progress on active sites in Cu-based catalysts for CO₂ hydrogenation to methanol [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 287-298.
[3]	XIE Luyao, CHEN Songzhe, WANG Laijun, ZHANG Ping. Platinum-based catalysts for SO₂ depolarized electrolysis [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 299-309.
[4]	YANG Xiazhen, PENG Yifan, LIU Huazhang, HUO Chao. Regulation of active phase of fused iron catalyst and its catalytic performance of Fischer-Tropsch synthesis [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 310-318.
[5]	WANG Lele, YANG Wanrong, YAO Yan, LIU Tao, HE Chuan, LIU Xiao, SU Sheng, KONG Fanhai, ZHU Canghai, XIANG Jun. Influence of spent SCR catalyst blending on the characteristics and deNO _x performance for new SCR catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 489-497.
[6]	DENG Liping, SHI Haoyu, LIU Xiaolong, CHEN Yaoji, YAN Jingying. Non-noble metal modified vanadium titanium-based catalyst for NH₃-SCR denitrification simultaneous control VOCs [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 542-548.
[7]	CHENG Tao, CUI Ruili, SONG Junnan, ZHANG Tianqi, ZHANG Yunhe, LIANG Shijie, PU Shi. Analysis of impurity deposition and pressure drop increase mechanisms in residue hydrotreating unit [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4616-4627.
[8]	WANG Peng, SHI Huibing, ZHAO Deming, FENG Baolin, CHEN Qian, YANG Da. Recent advances on transition metal catalyzed carbonylation of chlorinated compounds [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4649-4666.
[9]	ZHANG Qi, ZHAO Hong, RONG Junfeng. Research progress of anti-toxicity electrocatalysts for oxygen reduction reaction in PEMFC [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4677-4691.
[10]	GE Quanqian, XU Mai, LIANG Xian, WANG Fengwu. Research progress on the application of MOFs in photoelectrocatalysis [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4692-4705.
[11]	WANG Weitao, BAO Tingyu, JIANG Xulu, HE Zhenhong, WANG Kuan, YANG Yang, LIU Zhaotie. Oxidation of benzene to phenol over aldehyde-ketone resin based metal-free catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4706-4715.
[12]	GE Yafen, SUN Yu, XIAO Peng, LIU Qi, LIU Bo, SUN Chengying, GONG Yanjun. Research progress of zeolite for VOCs removal [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4716-4730.
[13]	ZHU Chuanqiang, RU Jinbo, SUN Tingting, XIE Xingwang, LI Changming, GAO Shiqiu. Characteristics of selective non-catalytic reduction of NO _x with solid polymer denitration agent [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4939-4946.
[14]	WU Haibo, WANG Xilun, FANG Yanxiong, JI Hongbing. Progress of the development and application of 3D printing catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 3956-3964.
[15]	MAO Shanjun, WANG Zhe, WANG Yong. Group recognition hydrogenation: From concept to application [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 3917-3922.