气凝胶骨架镶嵌的CeO2纳米团簇催化氧化HCl制Cl2

doi:10.11949/j.issn.0438-1157.20150902

化工学报 ›› 2015, Vol. 66 ›› Issue (9): 3421-3427.DOI: 10.11949/j.issn.0438-1157.20150902

• 催化、动力学与反应器 • 上一篇下一篇

气凝胶骨架镶嵌的CeO₂纳米团簇催化氧化HCl制Cl₂

徐希化¹, 费兆阳¹, 陈献², 汤吉海¹, 崔咪芬², 乔旭^1,2

1 南京工业大学材料化学工程国家重点实验室, 江苏南京 210009;
2 南京工业大学化工学院, 江苏南京 210009

收稿日期:2015-06-11 修回日期:2015-06-30 出版日期:2015-09-05 发布日期:2015-09-05
通讯作者: 费兆阳, 乔旭
基金资助:
国家科技支撑计划项目(2011BAE18B01);国家自然科学基金项目(21306089);江苏省高校自然科学基金项目(13KJB530006);江苏高校优势学科建设工程资助项目。

CeO₂ nanoclusters stabilized in aerogel matrix as catalysts for Cl₂ production from HCl oxidation

XU Xihua¹, FEI Zhaoyang¹, CHEN Xian², TANG Jihai¹, CUI Mifen², QIAO Xu^1,2

1 State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009, Jiangsu, China;
2 College of Chemical Engineering, Nanjing Tech University, Nanjing 210009, Jiangsu, China

Received:2015-06-11 Revised:2015-06-30 Online:2015-09-05 Published:2015-09-05
Supported by:
supported by the National Key Technology Research and Development Program of the Ministry of Science and Technology of China (2011BAE18B01), the National Natural Science Foundation of China (21306089), the Higher Education Natural Science Foundation of Jiangsu Province (13KJB530006) and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).

摘要/Abstract

摘要：

采用一步溶胶-凝胶法制备了镶嵌于气凝胶骨架内的CeO₂纳米团簇催化材料(CeO₂@M_xO_y, M_xO_y= SiO₂、ZrO₂、Al₂O₃)用于HCl催化氧化反应。镶嵌于气凝胶骨架内的CeO₂纳米团簇显著的量子尺寸效应导致其表现出不同于晶相CeO₂的特性,H₂-TPR测试结果显示在晶相CeO₂表面氧物种还原温区内CeO₂纳米团簇即可被充分还原。优异的氧化还原性能导致CeO₂@M_xO_y在HCl氧化过程具有良好的催化活性,其中,40CeO₂@SiO₂的活性最高,在接触时间为0.1598 h,V_O₂/V_HCl为1,430℃时,Cl₂空时产率可以达到2.10 g·(g cat)^-1·h^-1。催化剂表面的HCl氧化反应同时受O₂分压和HCl分压的影响,这表明Cl₂从催化剂表面的脱附是该反应的决速步骤。

关键词: 氧化铈, 纳米团簇, 气凝胶, 氯循环, 催化氧化, 动力学

Abstract:

CeO₂ nanoclusters inserted into aerogel matrix (CeO₂@M_xO_y, M_xO_y= SiO₂, ZrO₂, Al₂O₃) prepared by a single-step sol-gel method were used as catalysts for recycling Cl₂ from HCl oxidation. Due to their remarkable quantum-size effects, the properties of CeO₂ nanoclusters were significantly different from crystal phase CeO₂. The CeO₂ nanoclusters could be completely reduced at the temperature range for reduction of the surface oxygen species of crystal phase CeO₂. The unique properties of CeO₂ nanoclusters resulted in the high activity of CeO₂@M_xO_y in the process of HCl oxidation reaction. 40CeO₂@SiO₂ exhibited the highest activity and the STY (space time yield of Cl₂) reached to 2.10 g·(g cat)^-1·h^-1 at 430℃ with V_O₂/V_HCl of 1 and contact time of 0.1598 h. Kinetic studies showed that both O₂ and HCl competed for the active sites rendering desorption of surface Cl as the rate-determining step.

Key words: CeO₂, nanoclusters, aerogel, chlorine recycle, catalytic oxidation, kinetics

中图分类号:

O643

徐希化, 费兆阳, 陈献, 汤吉海, 崔咪芬, 乔旭. 气凝胶骨架镶嵌的CeO₂纳米团簇催化氧化HCl制Cl₂[J]. 化工学报, 2015, 66(9): 3421-3427.

XU Xihua, FEI Zhaoyang, CHEN Xian, TANG Jihai, CUI Mifen, QIAO Xu. CeO₂ nanoclusters stabilized in aerogel matrix as catalysts for Cl₂ production from HCl oxidation[J]. CIESC Journal, 2015, 66(9): 3421-3427.

参考文献 23

[1]	Mortensen M K, Minet R G, Tsotsis T T, Benson S. A two-stage process for catalytic oxidation of hydrogen chloride to chlorine [J]. Chemical Engineering Science, 1996, 51(10):2031-2039.
[2]	Wu Liding(吴礼定). Production presents status of TDI and its research development [J]. China Chlor-Alkali(中国氯碱), 2011, (10): 19-21.
[3]	Zhang Linhao(张林浩), Liang Rizhong(梁日忠). Eco-industry mode study on the process of polyurethane intermediate production with chlorine element recycle [J]. Chemical Industry and Engineering Progress(化工进展), 2012, 30(12): 2799-2803.
[4]	Amrute A P, Mondelli C, Hevia M A G, Pérez-Ramírez J. Mechanism-performance relationships of metal oxides in catalyzed HCl oxidation [J]. ACS Catalysis, 2011, 1(6): 583-590.
[5]	Tang J H, Chen X, Fei Z Y, Zhao J H, Cui M F, Qiao X. HCl oxidation to recycle Cl2 over a Cu/Ce composite oxide catalyst(Ⅰ): Interinsic kinetic study [J]. Industrial & Engineering Chemistry Research, 2013, 52(34): 11897-11903.
[6]	Pérez-Ramírez J, Mondelli C, Schmidt T, Schlüter O F K, Wolf A, Mleczko L, Dreier T. Sustainable chlorine recycling via catalysed HCl oxidation: from fundamentals to implementation [J]. Energy & Environmental Science, 2011, 4(12): 4786.
[7]	Li H L, Wu C Y, Li L Q, Li Y, Zhao Y C, Zhang J Y. Kinetic modeling of mercury oxidation by chlorine over CeO2-TiO2 catalysts [J]. Fuel, 2013, 113:726-732.
[8]	Yin Fengxiang(银凤翔), Ji Shengfu(季生福), Chen Nengzhan(陈能展), Zhao Liping(赵丽萍), Wang Wei(王伟), Li Chengyue(李成岳), Liu Hui(刘辉). Catalytic combustion of methane over Ce1-xCuxO2-x/ Al2O3 solid solution catalyst [J]. Journal of Chemical Industry and Engineering (China) (化工学报), 2006, 57(4): 744-750.
[9]	Meng Yingqin(孟英芹), Zhao Xiaobing(赵晓兵), Li Xiazhang(李霞章). Catalytic properties of CeO2-TiO2/attapulgite nanocomposites prepared by sol-gel method [J]. CIESC Journal(化工学报), 2013, 64(7): 2679-2686.
[10]	Amrute A P, Mondelli C, Moser M, Novell-Leruth G, Lopez N, Rosenthal D, Farr R, Schuster M E, Teschner D, Shmidt T, Pérez-Ramírez J. Performance, structure, and mechanism of CeO2 in HCl oxidation to Cl2 [J]. Journal of Catalysis, 2012, 286: 287-297.
[11]	Moser M, Mondelli C, Schmidt T, Girgsdies F, Schuster M E, Farra R, Szentmiklosi L, Tesschner D, Pérez-Ramírez J. Supported CeO2 catalysts in technical form for sustainable chlorine production [J]. Applied Catalysis B, 2013, 132/133: 123-131.
[12]	Fei Z Y, Xie X X, Dai Y, Liu H Y, Chen X, Tang J H, Cui M F, Qiao X. HCl oxidation for sustainable Cl2 recycle over CexZr1-xO2 catalysts: effects of Ce/Zr ratio on the activity and stability [J]. Industrial & Engineering Chemistry Research, 2014, 53: 19438-19445.
[13]	Shan W, Liu F, He H, Shi X Y, Zhang C B. An environmentally- benign CeO2-TiO2 catalyst for the selective catalytic reduction of NOx with NH3 in simulated diesel exhaust [J]. Catal. Today, 2012, 184(1): 160-165.
[14]	Fang J, Bi X, Si D, et al. Spectroscopic studies of interfacial structures of CeO2-TiO2 mixed oxides [J]. Appl. Surf. Sci., 2007, 253(22): 8952-8961.
[15]	Kaneko H, Muiura T, Ishihar H, Taku S, Yokoyama T, Nakajima H, Tamaura Y. Reactive ceramics of CeO2-Mox(M=Mn, Fe, Ni, Cu) for H2 generation by two-step water splitting using concentrated solar thermal energy [J]. Energy, 2007, 32:656-663.
[16]	Katta L, Sudarsanam P, Thrimurthulu G, Reddy B M. Doped nanosized ceria solid solutions for low temperature soot oxidation: zirconium versus lanthanum promoters [J]. Applied Catalysis B: Environmental, 2010, 101(1/2): 101-108.
[17]	Liu Chuntao(刘春涛), Shi Pengfei(史鹏飞). CO selective oxidation in hydrogen-rich gas over CuO/CeO2 catalysts [J]. Journal of Chemical Industry and Engineering(China)(化工学报), 2004, 55(S1): 284-286.
[18]	Aramendia M A, Borau V, Jimenez C, Jimenez C, Marinas J M, Porras A, Urbano F J. Synthesis and characterization of ZrO2 as an acid-base catalyst dehydration-dehydrogenation of propan-2-ol [J]. Journal of the Chemical Society, 1997, 93 (7): 1431-1438.
[19]	Bang Y, Seo J G, Youn M H, Song I K.Hydrogen production by steam reforming of liquefied natural gas (LNG) over mesoporous Ni-Al2O3 aerogel catalyst prepared by a single-step epoxide-driven sol-gel method [J]. International Journal of Hydrogen Energy, 2012, 37(2): 1436-1443.
[20]	Jampaiah D, Tur K M, Ippolito S J, Sabri Y M, Tardio J, Bhargava S K, Reddy B M. Structure characterization and catalytic evaluation of transition and rare earth metal doped ceria-based solid solutions for elemental mercury oxidation [J]. RSC Advavaces, 2013, 3: 12963-12974.
[21]	Si R, Zhang Y W, Li S J, Lin B X, Yan C H. Urea-based hydrothermally derived homogeneous nanostructured Ce1-xZrxO2 (x= 0-0.8) solid solutions: a strong correlation between oxygen storage capacity and lattice strain [J]. Journal of Physical Chemistry B, 2004, 108(33): 12481-12488.
[22]	Urban S, Tarabanko N, Kanzler C H, Zalewska-Wierzbicka K, Ellinghaus R, Rohrlack S F, Chen L, Klar P J, Smarsly B M, Over H. Stable and active mixed Zr-Ce oxides for catalyzing the gas phase oxidation of HCl [J]. Catalysis Letters, 2013, 143(12): 1362-1367.
[23]	Xie Xingxing(谢兴星), Fei Zhaoyang(费兆阳), Dai Yong(戴勇), Xu Xihua(徐希化), Chen Xian(陈献), Tang Jihai(汤吉海), Cui Mifen(崔咪芬), Qiao Xu(乔旭). Structure of ceria-based mixed catalytic oxidation performance [J]. Journal of Molecular Catalysis(China)(分子催化), 2014, 28(6):507-514.

气凝胶骨架镶嵌的CeO₂纳米团簇催化氧化HCl制Cl₂

CeO₂ nanoclusters stabilized in aerogel matrix as catalysts for Cl₂ production from HCl oxidation

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