Sn对V2O5/Al2O3催化剂在异丁烷脱氢反应中的影响

doi:10.16085/j.issn.1000-6613.2018-1815

摘要/Abstract

摘要：

以Al₂O₃为载体，采用等体积浸渍法制备了负载型高分散氧化钒催化剂（12%V₂O₅/Al₂O₃），并选择Sn作为助剂对12%V₂O₅/Al₂O₃催化剂的表面性质进行调控，采用XRD、N₂等温吸脱附、NH₃-TPD、H₂-TPR、XPS、TEM和Raman光谱等方法对催化剂进行表征，结合活性评价实验，研究了催化剂表面物种分散状态、酸性和活性物种价态的变化与异丁烷脱氢活性和稳定性之间的关系。表征结果显示，Sn对V₂O₅/Al₂O₃表面的酸性和V物种在催化剂表面的分布和价态具有一定的调节作用，当Sn质量分数为1%时，氧化锡在催化剂表面分散均匀，对表面积和孔结构影响较小，同时，表面酸性变化较小，表面低价态的钒物种增多。活性评价结果表明，该催化剂在临氢反应条件下保持了最佳的脱氢活性及稳定性，异丁烷脱氢反应480min后，异丁烷转化率为46.8%，异丁烯收率为39.8%。

关键词: 烷烃, 催化剂, 活性, 五氧化二钒, 脱氢

Abstract:

The highly dispersed vanadium oxide catalyst (12%V₂O₅/Al₂O₃) supported by Al₂O₃ was prepared by impregnation. The surface properties of 12%V₂O₅/Al₂O₃ catalyst were controlled by using Sn as an auxiliary agent. The changes in the dispersion state, acidity, and the valence of active species of the catalyst were studied, and their influences on the dehydrogenation activity and stability of isobutane were discussed. The catalysts were characterized by XRD, N₂ adsorption-desorption isotherms, NH₃-TPD, H₂-TPR, XPS, TEM and Raman spectra. The characterization results showed that Sn could regulate the surface acidity of V₂O₅/Al₂O₃ and the distribution and valence state of V species on the surface of the catalyst. When 1% (wt) Sn was added, SnO₂ was uniformly dispersed on the surface of the catalyst, and it show little impact on the specific surface area and pore structure. At the same time, the change in surface acidity was small and the vanadium species with low valence increased. The performance evaluation results showed that the catalyst maintained the best reactivity and stability with the presence of hydrogen. After dehydrogenation of isobutane for 480min, the isobutane conversion was 46.8% and the isobutene yield was 39.8%.

Key words: alkane, catalyst, reactivity, vanadium pentoxide（V₂O₅）, dehydrogenation

中图分类号:

TQ221.21

夏成杰,刘洋,柯明,王奇,刘稳,张蕾. Sn对V₂O₅/Al₂O₃催化剂在异丁烷脱氢反应中的影响[J]. 化工进展, 2019, 38(08): 3679-3687.

Chengjie XIA,Yang LIU,Ming KE,Qi WANG,Wen LIU,Lei ZHANG. Effect of Sn on V₂O₅/Al₂O₃ catalyst in dehydrogenation of isobutane[J]. Chemical Industry and Engineering Progress, 2019, 38(08): 3679-3687.

图/表 14

参考文献 44

16	WACHS I E , WECKHUYSEN B M . Structure and reactivity of surface vanadium oxide species on oxide supports[J]. Applied Catalysis A: General, 1997, 157(1/2): 67-90.
17	TIAN Y P , BAI P , LIU S M , et al . VO _x -K₂O/γ-Al₂O₃ catalyst for nonoxidative dehydrogenation of isobutane[J]. Fuel Processing Technology, 2016, 151: 31-39.
18	马红超, 刘子玉, 王振旅, 等 . 镧对V₂O₅/γ-Al₂O₃催化剂在异丁烷脱氢中活性的影响[J]. 高等学校化学学报, 2002, 23(5): 857-860.
	Hongchao MA , LIU Ziyu , WANG Zhenlü , et al . Effect of La on the activity of V₂O₅/γ-Al₂O₃ catalyst in dehydrogenation of isobutane[J]. Chemical Journal of Chinese Universities, 2002, 23(5): 857-860.
19	WU T F , LIU G , ZENG L , et al . Structure and catalytic consequence of Mg-modified VO _x /Al₂O₃ catalysts for propane dehydrogenation[J]. AIChE Journal, 2017, 63(11): 4911-4919.
20	HARLIN M E , NIEMI V M , KRAUSE A O I , et al . Effect of Mg and Zr modification on the activity of VO _x /Al₂O₃ catalysts in the dehydrogenation of butanes[J]. Journal of Catalysis, 2001, 203(1): 242-252.
21	GUERREROP REZ M O , KIM T , BA ARES M A , et al . Nature of catalytic active sites for Sb-V-O mixed metal oxides[J]. Journal of Physical Chemistry C, 2008, 112(43): 16858-16863.
22	庞玉锋 . 混合C₄烷烃脱氢制混合C₄烯烃[D]. 北京: 中国石油大学, 2011.
	PANG Yufeng . Dehydrogenation of mixed C₄ alkanes to mixed C₄ olefins[D]. Beijing: China University of Petroleum, 2011.
23	马红超 . 异丁烷脱氢制异丁烯钒基催化剂的研究[D]. 长春: 吉林大学, 2003.
	Hongchao MA . Study on vanadium-based catalyst for dehydrogenation of isobutylene to isobutylene[D]. Changchun: Jilin University, 2003.
24	BAO K V , SONG M B , AHN I Y, et al . Propane dehydrogenation over Pt-Sn/rare-earth-doped Al₂O₃: influence of La, Ce or Y on the formation and stability of Pt-Sn alloys[J]. Catalysis Today, 2011, 164(1): 214-220.
1	李丽, 阎子峰 . 异丁烷脱氢催化剂的研究[J]. 化学进展, 2005, 17(4):651-659.
	LI Li , YAN Zifeng . Review of catalytic dehydrogenation of isobutene[J]. Progress in Chemistry, 2005, 17(4): 651-659.
2	栗士瑞 . 异丁烷脱氢制异丁烯生产技术问题探析[J]. 化工设计通讯, 2016, 42(4): 177.
	LI Shirui . Production of technical problems isobutene dehydrogenation of isobutane[J]. Chemical Engineering Design Communications, 2016, 42(4): 177.
3	刘洋, 柯明 . 异丁烷氧化脱氢制异丁烯催化剂研究进展[J]. 化工进展, 2017, 36(3): 909-917.
	LIU Yang , KE Ming . Research progress on catalysts for oxydehydrogenation of isobutane to isobutene[J]. Chemical Industry and Engineering Progress, 2017, 36(3): 909-917.
4	周庆祥, 刘洋, 柯明 . 异丁烷直接脱氢制异丁烯的催化剂的研究进展[J]. 化学通报, 2017(9): 835-844.
	ZHOU Qingxiang , LIU Yang , KE Ming . Research progress of catalysts for isobutane direct dehydrogenation to isobutene[J]. Chemistry Bulletin, 2017(9): 835-844.
5	SATTLER J J , RUIZ-MARTINEZ J , SANTILLAN-JIMENEZ E , et al . Catalytic dehydrogenation of light alkanes on metals and metal oxides[J]. Chemical Reviews, 2014, 114(20): 106-113.
6	WANG G J , MA H C, LI Y , et al . Dehydrogenation of isobutane over V₂O₅/γ-Al₂O₃ catalyst[J]. Reaction Kinetics& Catalysis Letters, 2001, 74(1): 103-10.
7	曾铁强, 缪长喜, 吴文海, 等 . 高分散型钒氧化物催化剂上异丁烷催化脱氢的研究[J]. 化学世界, 2014, 55(9): 524-529.
	ZENG Tieqiang , MIAO Changxi , WU Wenhai , et al . Dehydrogenation of isobutane to isobutene over highly dispersed VO _x spercies[J]. Chemical World, 2014, 55(9): 524-529.
8	孙楠楠, 王国玮, 韩东敏, 等 . V₂O₅负载量对VO _x /MgAl₂O₄催化异丁烷脱氢制异丁烯的影响[J]. 石油炼制与化工, 2014, 45(4): 45-49.
	SUN Nannan , WANG Guowei , HAN Dongmin , et al . Effect of V₂O₅ load on VO _x /MgAl₂O₄ catalytic dehydrogenation of isobutane to isobutylene[J]. China Petroleum Processing Petrochemical Technology, 2014, 45(4): 45-49.
9	RODEMERCK U , SOKOLOV S , STOYANOVA M , et al . Influence of support and kind of VO _x species on isobutene selectivity and coke deposition in non-oxidative dehydrogenation of isobutane[J]. Journal of Catalysis, 2016, 338: 174-183.
10	MCGREGOR J , HUANG Z , SHIKO G , et al . The role of surface vanadia species in butane dehydrogenation over VO _x /Al₂O₃ [J]. Catalysis Today, 2009, 142(3/4): 143-151.
11	WACHS I E , WECKHUYSEN B M . Structure and reactivity of surface vandium oxide species on oxide supports[J]. Applied Catalysis A: General, 1997, 157(1/2): 67-90.
12	马红超, 王振旅, 朱万春, 等 . 异丁烷脱氢催化剂V-O-Al水热-流体干燥法合成[J]. 高等学校化学学报, 2003, 24(6): 1103-1105.
	Hongchao MA , WANG Zhenglü , ZHU Wanchun , et al . Hydrothermal-fluid drying aynthesis of V-O-Al catalyst for isobutane dehydrogenation[J]. Chemical Journal of Chinese Universities, 2003, 24(6): 1103-1105.
13	MURGIA V , TORRES E M F , GOTTIFREDI J C , et al . Sol-gel synthesis of V₂O₅-SiO₂ catalyst in the oxidative dehydrogenation of n-butane[J]. Applied Catalysis A: General, 2006, 312(1):134-143.
14	QIAO K , PENG P , HU C , et al . Synthesis of vanadium-based catalysts and their excellent catalytic behaviors on dehydrogenation of C₄hydrocarbons[J]. Applied Petrochemical Research, 2015, 5(4): 321-327.
15	SOKOLOV S , STOYANOVA M , RODEMERCK U , et al . Comparative study of propane dehydrogenation over V-, Cr-, and Pt-based catalysts: time on-stream behavior and origins of deactivation[J]. Journal of Catalysis, 2012, 293(9): 67-75.
25	LEE M H, NAGARAJA B M , LEE K Y, et al . Dehydrogenation of alkane to light olefin over PtSn/θ-Al₂O₃ catalyst: effects of Sn loading[J]. Catalysis Today, 2014, 232(4): 53-62.
26	NAGARAJA B M , SHIN C H , JUNG K D . Selective and stable bimetallic PtSn/θ-Al₂O₃ catalyst for dehydrogenation of n-butane to n-butenes[J]. Applied Catalysis A: General, 2013, 467: 211-223.
27	ZHANG Y , ZHOU Y , SHI J , et al . Comparative study of bimetallic Pt-Sn catalysts supported on different supports for propane dehydrogenation [J]. Journal of Molecular Catalysis A: Chemical, 2014, 381(1): 138-147.
28	FU Y , MA H, WANG Z L , et al . Characterization and reactivity of SnO₂-doped V₂O₅/γ-Al₂O₃ catalysts in dehydrogenation of isobutane to isobutene[J]. Journal of Molecular Catalysis A: Chemical, 2004, 221(1): 163-168.
29	陈桂芳, 李静, 杨向光 . V₂O₅/Al₂O₃上异丁烷脱氢反应研究[J]. 工业催化, 2007, 15(9): 30-32.
	CHEN Guifang , LI Jing , YANG Xiangguang . Study on dehydrogenation of isobutane over V₂O₅/Al₂O₃ catalyst[J]. Industrial Catalysis, 2007, 15(9): 30-32.
30	SONKER R K , SHARMA A , TOMAR M , et al . Low temperature operated NO₂ gas sensor based on SnO₂-ZnO nanocomposite thin film[J]. Journal of Computational & Theoretical Nanoscience, 2014, 20(5). DOI: 10.1166/asl.2014.5461 . DOI URL
31	NARAYANAN S , SULTANA A , LE Q T , et al . A comparative and multitechnical approach to the acid character of templated and non-templated ZSM-5 zeolites[J]. Applied Catalysis A: General, 1998, 168(168): 373-384.
32	罗沙, 李先如, 周波, 等 . 异丁烷脱氢制异丁烯反应过程Pt-Sn-K/γ-Al₂O₃催化剂的失活分析[J]. 工业催化, 2014, 22(7): 541-545.
	LUO Sha , LI Xianru , ZHOU Bo , et al . Deactivation reason analysis of Pt-Sn-K/γ-Al₂O₃ catalysts during the dehydrogenation of isobutane to isobutylene[J]. Industrial Catalysis, 2014, 22(7): 541-545.
33	MAHDAVI V , MONAJEMI A . Gas phase dehydration of glycerol catalyzed by gamma Al₂O₃ supported V₂O₅: a statistical approach for simultaneous optimization[J]. RSC Advances, 2016, 6:115.
34	尉继英, 马军, 朱月香, 等 . SnO₂-Al₂O₃复合氧化物催化剂的一氧化氮选择催化还原性能[J]. 分子催化, 2001, 15(1): 1-5.
	Jiying DIAN , Jun MA , ZHU Yuexiang , et al . Selective catalytic reduction of nitric oxide over SnO₂-Al₂O₃ composite oxide catalyst[J]. Journal of Molecular Catalysis, 2001, 15(1): 1-5.
35	张林, 秦枫, 黄镇, 等 . V₂O₅/γ-Al₂O₃表面酸性和钒价态的调控及其异丁烷脱氢性能[J]. 石油化工, 2016, 45(9): 1043-1049.
	ZHANG Lin , QIN Feng , HUANG Zhen , et al . Modification of acidity and vanadium valence of V₂O₅/γ-Al₂O₃ catalyst for dehydrogenation of isobutane[J]. Petrochemical Technology, 2016, 45(9): 1043-1049.
36	TIAN Y P , LIU X M , ROOD M J , et al . Study of coke deposited on a VO _x -K₂O/γ-Al₂O₃ catalyst in the non-oxidative dehydrogenation of isobutane[J]. Applied Catalysis A: General, 2017, 545: 1-9.
37	HARLIN M E , NIEMI V M , KRAUSE A O I . Alumina-supported vanadium oxide in the dehydrogenation of butanes[J]. Journal of Catalysis, 2000, 195(1): 67-78.
38	郭锡坤, 王小明, 陈庆生 . Sn/Al₂O₃催化剂结构与选择性催化还原NO性能[J]. 催化学报, 2007, 28(5): 417-422.
	GUO Xikun , WANG Xiaoming , CHEN Qingsheng . Structure of Sn/Al₂O₃ Catalyst and its activity for selective catalytic reduction of NO[J]. Chinese Journal of Catalysis, 2007, 28(5): 417-422.
39	季静, 柴忠义, 纪玉国 . 异丁烷脱氢制异丁烯催化剂的研究进展[J]. 石油化工, 2012, 41(s1): 172-174.
	JI Jing , CHAI Zhongyi , JI Yuguo . Progress in catalysts for dehydrogenation of Isobutane to Isobutene[J] Petrochemical Technology, 2012, 41(s1): 172-174.
40	TAKITA Y , SANO K I , KUROSAKI K , et al . Oxidative dehydrogenation of iso-butane to iso-butene Ⅰ. Metal phosphate catalysts[J]. Applied Catalysis A: General, 1998, 167(1): 49-56.
41	刘坚, 赵震, 徐春明,等 . Al₂O₃或SiO₂负载钒氧化物催化剂的紫外-拉曼光谱比较研究[J]. 工业催化, 2008, 16(10): 35-37.
	LIU Jian , ZHAO Zhen , XU Chun ming , et al . Comparative study on UV-Raman spectroscopy of Al₂O₃ or SiO₂ supported vanadium oxide catalysts[J]. Industrial Catalysis, 2008,16(10): 35-37.
42	YANG S , IGLESIA E , BELL A T . Oxidative dehydrogenation of propane over V₂O₅/MoO₃/Al₂O₃ and V₂O₅/Cr₂O₃/Al₂O₃: structural characterization and catalytic function[J]. Journal of Physical Chemistry B, 2005, 109(18): 8987-9000.
43	宋威 . PtSn/Al₂O₃催化剂制备及异丁烷脱氢性能研究[D]. 大连: 大连理工大学, 2017.
	SONG Wei . Preparation of PtSn/Al₂O₃ catalyst and dehydrogenation of isobutane[D]. Dalian: Dalian University of Technology, 2017.
44	SADEZKY A , MUCKENHUBER H , GROTHE H , et al . Raman microspectroscopy of soot and related carbonaceous materials: spectral analysis and structural information[J]. Carbon, 2005, 43(8): 1731-1742.

催化剂	比表面积/m²·g^-1	孔容/cm·g^-1	孔径/nm
Al₂O₃	280.7	0.42	5.96
12%V₂O₅/Al₂O₃	260.8	0.39	5.92
0.5%Sn-12%V₂O₅/Al₂O₃	256.6	0.38	7.65
1%Sn-12%V₂O₅/Al₂O₃	254.3	0.38	8.03
2%Sn-12%V₂O₅/Al₂O₃	241.8	0.37	6.09
4%Sn-12%V₂O₅/Al₂O₃	174.3	0.34	7.89

催化剂	比表面积/m²·g^-1	孔容/cm·g^-1	孔径/nm
Al₂O₃	280.7	0.42	5.96
12%V₂O₅/Al₂O₃	260.8	0.39	5.92
0.5%Sn-12%V₂O₅/Al₂O₃	256.6	0.38	7.65
1%Sn-12%V₂O₅/Al₂O₃	254.3	0.38	8.03
2%Sn-12%V₂O₅/Al₂O₃	241.8	0.37	6.09
4%Sn-12%V₂O₅/Al₂O₃	174.3	0.34	7.89

催化剂	部分酸量/μmol·g^-1			总酸量/μmol·g^-1
催化剂	弱酸	中强酸	强酸	总酸量/μmol·g^-1
12%V₂O₅/Al₂O₃	959.9	268.9	328.7	1557.5
0.5%Sn-12%V₂O₅/Al₂O₃	952.1	235.5	410.4	1598.0
1%Sn-12%V₂O₅/Al₂O₃	941.6	203.9	482.7	1628.2
2%Sn-12%V₂O₅/Al₂O₃	779.9	166.7	616.0	1562.6
4%Sn-12%V₂O₅/Al₂O₃	712.9	150.5	745.5	1608.9

催化剂	部分酸量/μmol·g^-1			总酸量/μmol·g^-1
催化剂	弱酸	中强酸	强酸	总酸量/μmol·g^-1
12%V₂O₅/Al₂O₃	959.9	268.9	328.7	1557.5
0.5%Sn-12%V₂O₅/Al₂O₃	952.1	235.5	410.4	1598.0
1%Sn-12%V₂O₅/Al₂O₃	941.6	203.9	482.7	1628.2
2%Sn-12%V₂O₅/Al₂O₃	779.9	166.7	616.0	1562.6
4%Sn-12%V₂O₅/Al₂O₃	712.9	150.5	745.5	1608.9

催化剂	H₂-TPR表征
催化剂	温度_peak/℃	耗氢量/mmol·g^-1	温度_peak/℃	耗氢量/mmol·g^-1
12%V₂O₅/Al₂O₃	—	—	456.2	0.9614
0.5%Sn-12%V₂O₅/Al₂O₃	329.3	0.5315	456.7	0.4704
1%Sn-12%V₂O₅/Al₂O₃	330.2	0.6367	457.9	0.4293
2%Sn-12%V₂O₅/Al₂O₃	332.7	0.8174	467.4	0.3836
4%Sn-12%V₂O₅/Al₂O₃	336.6	1.0105	472.5	0.3184

Sn对V₂O₅/Al₂O₃催化剂在异丁烷脱氢反应中的影响

Effect of Sn on V₂O₅/Al₂O₃ catalyst in dehydrogenation of isobutane

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 14

参考文献 44

相关文章 15

编辑推荐

Metrics

本文评价

催化剂	甲烷/%	乙烷/%	乙烯/%	丙烷/%	丙烯/%	正丁烷/%	异丁烯/%	其他/%
12%V₂O₅/Al₂O₃	2.52	0.42	0.13	2.80	2.35	2.36	81.81	7.61
0.5%Sn-12%V₂O₅/Al₂O₃	2.36	0.40	0.11	2.82	2.70	2.35	82.72	6.54
1%Sn-12%V₂O₅/Al₂O₃	2.35	0.29	0.18	2.41	2.66	2.22	84.29	5.60
2%Sn-12%V₂O₅/Al₂O₃	2.27	0.33	0.17	2.18	2.69	1.70	85.20	5.46
4%Sn-12%V₂O₅/Al₂O₃	2.17	0.18	0.19	2.09	2.98	0.98	85.96	5.45

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	高雨飞, 鲁金凤. 非均相催化臭氧氧化作用机理研究进展[J]. 化工进展, 2023, 42(S1): 430-438.
[6]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[7]	赵景超, 谭明. 表面活性剂对电渗析减量化工业含盐废水的影响[J]. 化工进展, 2023, 42(S1): 529-535.
[8]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[9]	许友好, 王维, 鲁波娜, 徐惠, 何鸣元. 中国炼油创新技术MIP的开发策略及启示[J]. 化工进展, 2023, 42(9): 4465-4470.
[10]	王谨航, 何勇, 史伶俐, 龙臻, 梁德青. 气体水合物阻聚剂研究进展[J]. 化工进展, 2023, 42(9): 4587-4602.
[11]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[12]	王鹏, 史会兵, 赵德明, 冯保林, 陈倩, 杨妲. 过渡金属催化氯代物的羰基化反应研究进展[J]. 化工进展, 2023, 42(9): 4649-4666.
[13]	张启, 赵红, 荣峻峰. 质子交换膜燃料电池中氧还原反应抗毒性电催化剂研究进展[J]. 化工进展, 2023, 42(9): 4677-4691.
[14]	王伟涛, 鲍婷玉, 姜旭禄, 何珍红, 王宽, 杨阳, 刘昭铁. 醛酮树脂基非金属催化剂催化氧气氧化苯制备苯酚[J]. 化工进展, 2023, 42(9): 4706-4715.
[15]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.