研究生: |
吳信賢 Wu, Hsin-Hsien |
---|---|
論文名稱: |
氧化錳-氧化鈰擔載銀觸媒應用於揮發性有機物完全氧化之研究 Deep oxidation of volatile organic compounds using manganese oxide - cerium oxide supported silver catalysts |
指導教授: |
周更生
Chou, Ken-Sen 談駿嵩 Tan, Chung-Sung |
口試委員: |
陳郁文
Chen, Yu-Wen 沈克鵬 Shen, Keh-Perng 黃國柱 Hwang, Kuo-Chu |
學位類別: |
博士 Doctor |
系所名稱: |
工學院 - 化學工程學系 Department of Chemical Engineering |
論文出版年: | 2017 |
畢業學年度: | 105 |
語文別: | 中文 |
論文頁數: | 131 |
中文關鍵詞: | 揮發性有機物 、銀觸媒 、氧化錳 、氧化鈰 、奈米銀絲 、中孔洞氧化矽 、洗塗 |
外文關鍵詞: | Volatile Organic Compounds, silver catalysts, Manganese oxide, Cerium oxide, Silver nanowire, SBA-15, Wash-coating |
相關次數: | 點閱:3 下載:0 |
分享至: |
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報 |
本研究成功製備氧化錳-氧化鈰擔載銀觸媒,並藉由觸媒分析和活性測試,掌握作為VOCs完全氧化反應觸媒的特性。
首先利用沉積沉澱法和共沈澱法製備金屬氧化物(鈰、錳和鐵等)擔載銀觸媒,結果顯示金屬氧化物擔載銀觸媒,其活性皆高於銀觸媒,其中以Ag/MnOx-CeO2應用於低溫VOCs觸媒氧化反應之可行性最高,可在175℃將丙酮(1000 ppm)完全氧化。
此外奈米銀絲,因具有特殊晶面結構,本研究證明奈米銀絲作為VOCs觸媒具有優於一般銀粒子的催化活性,兩者將異丙醇完全氧化的溫度分別為200℃(奈米銀絲)及310℃(一般銀粒)。並進一步以多元醇法披覆金屬氧化物殼層之方式,合成核殼結構銀觸媒,並探討核殼結構對奈米銀絲的結構及活性的幫助程度。研究結果顯示,此方式讓奈米銀絲的結構特徵在披覆金屬氧化物殼層後,不會發生顯著變化,而且異丙醇(125 ppm)完全氧化的溫度可進一步降低至175℃。
中孔洞氧化矽SBA-15具有高表面積、高熱穩定性及孔洞大小具一致性的優點。本研究利用TEOS為粘著劑將SBA-15洗塗於陶瓷紙,利用超音波測試其粘著效果發現SBA-15損失率極低。再將其含浸觸媒後應用於廢氣處理結果顯示,可有效減少觸媒用量20%。
從工業廢氣處理的角度,上述觸媒研究結果各有其特點。核殼結構銀觸媒活性高,但目前的製備程序較複雜而不易實施。以SBA-15洗塗於陶瓷紙並含浸觸媒的方式相對簡單,而且陶瓷紙相較於堇青石蜂巢陶瓷具有達93%之輕量化效果,更具有放大實施之優勢。
A catalyst, Ag/MnOx-CeO2 was successfully prepared in this study. The characterization and activity test of catalyst were also conducted to understand the reactivity for the treatment of VOCs.
The catalyst with metal oxide (such as Ce, Mn, and Fe) and Ag were prepared by deposition-precipitation method and co-precipitation method. Our results showed that the catalytic activity of this Ag/MnOx-CeO2 catalyst were higher than the Ag catalyst. Ag/MnOx-CeO2 showed a very high removal efficiency for VOCs at low temperature. Acetone (1000 ppm) can be completely oxidized at 175 °C.
In addition, we also tried silver nanowire as the catalyst, its catalytic activity was higher than the Ag particles due to the special crystal structure of the nanowire. The temperatures for complete oxidation of isopropanol were 200 °C and 310 °C for Ag nanowire and Ag particles, respectively.
The synthesis of core-shell structure of silver nanowire by polyol method was also conducted in this study. The results indicated that the structure of silver nanowire did not change after the polyol process and the temperature for complete oxidation of isopropanol (125 ppm) was further reduced to 175 °C from 200 °C.
The advantages of SBA-15 as support are high surface area, high thermal stability, and homogeneous pore size. In this study, SBA-15 was wash-coated on ceramic paper with TEOS as the adhesive agent. The results showed that the lost rate of SBA-15 was extremely low by an ultrasonic test. Using impregnation method to prepare SBA-15 supported catalyst and used it to treat VOCs exhaust, the results show the amount of catalyst could be reduced by 20%.
From the perspective of industrial waste gas treatment, the various catalysts show their own characteristics from the test results of this study. The silver nanowire with core-shell structure shows a high activity, but it requires a complex preparation process, and might be difficult result to implement industrially. On the other hand, the use of SBA-15 coated on ceramic paper and subsequent impregnation method to prepare SBA-15 catalyst is relatively easy. The weight of ceramic paper was light than the cordierite honeycomb-like ceramic by 93%, which should be advantageous to the scale up for industrial waste gas treatment.
Alia S. M., K. Duong, T. Liu, K. Jensen, and Y. Yan. "Supportless silver nanowires as oxygen reduction reaction catalysts for hydroxide-exchange membrane fuel cells" Chem. Sus. Chem. 5 (2012) 1619-1624.
Bal’zhinimaev B. S., E. V. Kovalyov, V. V. Kaichev, A. P. Suknev and V. I. Zaikovskii. "Catalytic abatement of VOC over novel Pt fiberglass catalysts" Top. Catal. 60 (2017) 73-82.
Bonelli R., C. Lucarelli, T. Pasini, L.F. Liotta, S. Zacchini, S. Albonetti. "Total oxidation of volatile organic compounds on Au/FeOx catalysts supported on mesoporous SBA-15 silica" Appl. Catal. A 400 (2011) 54-60.
Bratlie K. M., H. Lee, K. K., P. Yang, and G. A. Somorjai. “Platinum nanoparticle shape effects on benzene hydrogenation selectivity” Nano Lett. 7 (2007) 3097-3101
M.A. Campesi, N.J. Mariani, M.C. Pramparo, B.P. Barbero, L.E. Cadús, O.M. Martínez, G.F. Barreto. "Combustion of volatile organic compounds on a MnCu catalyst: a kinetic study" Catal. Today 176 (2011) 225.
Chimentão R. J., I. Kirm, F. Medina, X. Rodríguez, Y. Cesteros, P. Salagre and J. E. Sueiras. "Different morphologies of silver nanoparticles as catalysts for the selective oxidation of styrene in the gas phase" Chem. Commun. 0 (2004) 846–847
Choi K.-H., D.-H. Lee, H.-S. Kim, Y.-C. Yoon, C.-S. Park, and Y. H. Kim. "Reaction characteristics of precious-metal-free ternary Mn–Cu–M (M=Ce, Co, Cr, and Fe) oxide catalysts for low-temperature CO oxidation." Ind. Eng. Chem. Res. 55 (2016) 4443-4450.
Chou, K.-S., C.-C. Chen. "Fabrication and characterization of silver core and porous silica shell nanocomposite particles" Microporous Mesoporous Mater. 98 (2007) 208-213.
Chou K.-S., M.-Y. Lin, H.-H. Wu. "Studies on the removal of 2-propanol by Ag@Fe2O3 core–shell structured catalyst" J. Taiwan Inst. Chem. Eng. 44 (2013) 228–232
Chuang, K. T., B. Zhou, S. Tong. "Kinetics and mechanism of catalytic oxidation of formaldehyde over hydrophobic catalysts" Ind. Eng. Chem. Res. 33 (2002) 1680-1686.
Cordi, E. M., J. L. Falconer. "Oxidation of volatile organic compounds on a Ag/Al2O3 catalyst" Appl. Catal. A 151 (1997) 179-191.
Das, D. P., K. M. Parida. "Mn(III) oxide pillared titanium phosphate (TiP) for catalytic deep oxidation of VOCs" Appl. Catal. A 324 (2007) 1-8.
Duprez D., F. Cavani. "Handbook of advanced methods and processes in oxidation catylysis" Imperial College Press (2014)
Einaga H., A. Ogata. "Catalytic oxidation of benzene in the gas phase over alumina-supported silver catalysts" Environ. Sci. Technol. 44 (2010) 2612-2617
German, E., I. Efremenko. "Calculation of the activation energies of dissociative oxygen adsorption on the surfaces of rhodium (111), silver (111) and (110), and gold (111)" J. Mol. Struct. THEOCHEM 711 (2004) 159-165.
German, E. D.. "Adiabatic and non-adiabatic models for dissociative adsorption kinetics of diatomic molecules X2 on solid surface" Chem. Phys. 319 (2005) 167-177.
Hamoudi S., A. Sayari, K. Belkacemi, L. Bonneviot, F. Larachi. "Catalytic wet oxidation of phenol over PtxAg1−xMnO2/CeO2 catalysts" Catal. Today 62 (2000) 379-388
Han W., J. Deng, S. Xie, H. Yang, H. Dai, C. T. Au. "Gold supported on iron oxide nanodisk as efficient catalyst for the removal of toluene" Ind. Eng. Chem. Res. 53 (2014) 3486-3494.
Hong H., L. Hu, M. Li, J. Zheng, X. Sun, X. Lu, X. Cao, J. Lu, H. Gu. "Preparation of Pt@Fe2O3 Nanowires and their Catalysis of Selective Oxidation of Olefins and Alcohols" Chem. Eur. J. 17 (2011) 8726 - 8730
Imamura, S., H. Yamada, K. Utani. "Combustion activity of Ag/CeO2 composite catalyst" Appl. Catal. A 192 (2000) 221-226.
Jarrah N. A.. "Studying the influence of process parameters on the catalytic carbon nanofibers formation using factorial design" Chem. Eng. J. 151 (2009) 367-371
Jiang N., J. Hu, J. L., K. Shang, N. Lu, Y. Wu. "Plasma-catalytic degradation of benzene over Ag-Ce bimetallic oxide catalysts using hybrid surface/packed-bed discharge plasmas" Appl. Catal. B 184 (2016) 355-363
Kamal M. S., S. A. Razzak, M. M. Hossain. "Catalytic oxidation of volatile organic compounds (VOCs) - A review" Atmos, Environ. 140 (2016) 117-134
Larlus, O., V. Valtchev, J. Patarin, A.-C. Faust, B. Maquin. "Preparation of silicalite-1/glass fiber composites by one- and two-step hydrothermal syntheses" Microporous Mesoporous Mater. 56 (2002) 175-184.
Li, W.-X., C. Stampfl, M. Scheffler. "Why is a noble metal catalytically active? The role of the O-Ag interaction in the function of silver as an oxidation catalyst" Phys. Rev. Lett. 90 (2003) 256102.
Li W. B., J. X. Wang, H. Gong. "Catalytic combustion of VOCs on non-noble metal catalysts" Catal. Today 148 (2009) 81-87.
Lou, J.-C., S.-W. Huang. "Treating isopropyl alcohol by a regenerative catalytic oxidizer" Sep. Purif. Technol. 62 (2008) 71-78.
Lu Y.-C., K.-S. Chou, M. Nogami. "Process window for the synthesis of Ag wires through polyol process" Mater. Chem. Phys. 116 (2009) 1-5
Luo, M.-f., X.-x. Yuan, X.-m. Zheng. "Catalyst characterization and activity of Ag-Mn, Ag-Co and Ag-Ce composite oxides for oxidation of volatile organic compounds" Appl. Catal. A 175 (1998) 121-129.
Minicò S., S. Scirè, C. Crisafulli, R. Maggiore, S. Galvagno. "Catalytic combustion of volatile organic compounds on gold/iron oxide catalysts" Appl. Catal. B 28 (2000) 245-251.
Moretti E. C.. "Reduce VOC and HAP Emissions" Chem. Eng. Prog. 98 (2002) 33-40
Moulder J. F.. "Handbook of x-ray photoelectron spectroscopy: a reference book of standard spectra for identification and interpretation of XPS data" Perkin-Elmer Corporation (1992)
Na, H., Z. Zhi-You, S.-G. Sun, Y. Ding, Z. L. Wang. "Synthesis of tetrahexahedral platinum nanocrystals with high-index facets and high electro-oxidation activity" Science 316 (2007) 732-735.
Nagy, A. J., G. Mestl, R. Schlögl. "The role of subsurface oxygen in the silver-catalyzed, oxidative coupling of methane" J. Catal. 188 (1999) 58-68.
Nanba, T., S. Masukawa, J. Uchisawa, A. Obuchi. "Effect of support materials on Ag catalysts used for acrylonitrile decomposition" J. Catal. 259 (2008) 50-259.
Ousmane M., L.F. Liotta, G. Pantaleo, A.M. Venezia, G. Di Carlo, M. Aouine, L. Retailleau, A. Giroir-Fendler. "Supported Au catalysts for propene total oxidation: Study of support morphology and gold particle size effects" Catal. Today 176 (2011a) 7-13.
Ousmane M., L. F. Liotta, G. Di Carlo, G. Pantaleo, A. M. Venezia, G. Deganello, L. Retailleau, A. Boreave, A. Giroir-Fendler. "Supported Au catalysts for low-temperature abatement of propene and toluene, as model VOCs: Support effect" Appl. Catal. B 101 (2011b) 629-637.
Papadakis K., C.U.I. Odenbrand, J. Sjoblom, D. Creaser. "Development of a dosing strategy for a heavy-duty diesel exhaust cleaning system based on NOx storage and reduction technology by Design of Experiments" Appl. Catal. B 70 (2007) 215-225.
Pearce R., W. R. Patterson “Catalysis and Chemical Process” New York Wiley (1981) 261.
Peng P.-Y., Y.-C. Tsai, J.-T. Yeh, Y.-S. Lin, C.-M. Huang. "Influence of Sr substitution on catalytic performance of LaMnO3/Ni metal foam composite for CO oxidation" Aerosol Air Qual. Res. 15 (2015) 1662-1671.
Péreza H., P. Navarrob, M. Montes. "Deposition of SBA-15 layers on Fecralloy monoliths by washcoating" Chem. Eng. J. 158 (2010) 325-332.
Piumetti M., Bensaid S., Andana T., Russo N., Pirone R. and Fino D. Cerium-copper oxides prepared by solution combustion synthesis for total oxidation reactions: From powder catalysts to structured reactors. Appl. Catal. B 205 (2017) 455-468
Pulido A., P. Concepcion, M. Boronat, A. Corma. "Aerobic epoxidation of propene over silver (111) and (100) facet catalysts" J Catal. 292 (2012) 138–147.
Qu Z., Y. Bu, Y. Qin, Y. Wang, Q. Fu. "The improved reactivity of manganese catalysts by Ag in catalytic oxidation of toluene" Appl. Catal. B 132-133 (2013) 353-362.
Ramnani, S. P., S. Sabharwal, J.Vinod Kumar, K.H. Prasad Reddy, K.S.Rama Rao, P.S.Sai Prasad. "Advantage of radiolysis over impregnation method for the synthesis of SiO2 supported nano-Ag catalyst for direct decomposition of N2O" Catal. Commun. 9 (2008) 756-761.
N. Rezlescu, E. Rezlescu, L. Sachelarie, P. D. Popa, C. Doroftei, M. Ignat. "Nanocrystalline mixed oxides containing magnesium prepared by a combined Sol-Gel and self-combustion method for catalyst applications" Materials Sci. Appl. 4 (2013) 447-452. Rodríguez M. L., Luis E. Cadús, D. O. Borio. "Monolithic reactor for VOCs abatement: Influence of non-uniformity in the coating" J. Environ. Chem. Eng.5 (2017) 292-302.
Rufer A., W. Reschetilowski. "Application of design of experiments in heterogeneous catalysis: Using the isomerization of n-decane for a parameter screening" Chem. Eng. Sci. 75 (2012) 364–375.
Rybak P., B. Tomaszewska, A. Machocki, W. Grzegorczyk, A. Denis. "Conversion of ethanol over supported cobalt oxide catalysts" Catal. Today 176 (2011) 14-20.
Salazar, M. R., C. Saravanan, J. D. Kress, A. Redondo. "Molecular and atomic oxygen on unpromoted and cesium promoted Ag(111) surfaces" Surf. Sci. 449 (2000a) 75-92.
Salazar, M. R., J. D. Kress, A. Redondo. "Dissociation of molecular oxygen on unpromoted and cesium promoted Ag(110) surfaces" Surf. Sci. 469 (2000b) 80-90.
Samantaray, S. K., K. Parida. "Modified TiO2-SiO2 mixed oxides: 1. Effect of manganese concentration and activation temperature towards catalytic combustion of volatile organic compounds" Appl. Catal. B 57 (2005) 83-91.
Scir, S., S. Minic, C. Crisafulli, S. Galvagno. "Catalytic combustion of volatile organic compounds over group IB metal catalysts on Fe2O3" Catal. Commun. 2 (2001) 229-232.
Spinicci, R., M. Faticanti, P. Marini, S. D. Rossi, P. Porta. "Catalytic activity of LaMnO3 and LaCoO3 perovskites towards VOCs combustion" J. Mol. Catal. A 197 (2003) 147-155.
Spivey J. J.. "Complete Catalytic Oxidation of Volatile Organicst" Ind. Eng. Chem. Res. 26 (1987) 2165-2180.
Sterte, J., J. Hedlund, D. Creaser, O. Öhrman, W. Zheng, M. Lassinantti, Q. Li., F. Jareman. "Application of the seed-film method for the preparation of structured molecular sieve catalysts" Catal. Today 69 (2001) 323-329.
Sun Y., B. Mayers, T. Herricks, Y. Xia. "Polyol synthesis of uniform silver nanowires: A plausible growth mechanism and the supporting evidence" Nano Lett. 3 (2003) 955-960.
Tang, X., J. Chen, Y. Li, Y. Li., Y. Xu, W. Shen. "Complete oxidation of formaldehyde over Ag/MnOx-CeO2 catalysts" Chem. Eng. J. 118 (2006) 119-125.
Tang X., Y. Li, X. Huang, Y. Xu, H. Zhu, J. Wang, W. Shen. "MnOx–CeO2 mixed oxide catalysts for complete oxidation of formaldehyde: Effect of preparation method and calcination temperature" Appl. Catal. B 62 (2006) 265–273.
Tu, Y.-J. and Y.-W. Chen. "Effects of Alkaline-Earth Oxide Additives on Silica-Supported Copper Catalysts in Ethanol Dehydrogenation" Ind. Eng. Chem. Res. 37 (1998) 2618-2622.
Tzitzios, V. K. and V. Georgakilas. "Catalytic reduction of N2O over Ag-Pd/Al2O3 bimetallic catalysts" Chemosphere 59 (2005) 887-891.
Waterhouse, G. I. N., G. A. Bowmaker, J. B. Metson. "Mechanism and active sites for the partial oxidation of methanol to formaldehyde over an electrolytic silver catalyst" Appl. Catal. A 265 (2004) 85-101.
Widmann D., R. J. Behm. "Active oxygen on a Au/TiO2 catalyst: formation, stability, and CO oxidation activity" Angew. Chem. Int. Ed. 50 (2011) 10241-10245.
Wiley B., Y. Sun, B. Mayers, Y. Xia. "Shape-controlled synthesis of metal nanostructures: The case of silver" Chem. Eur. J. 11 (2005) 454–463.
Wiley B., T. Herricks, Y. Sun, Y. Xia. "Polyol synthesis of silver nanoparticles: use of chloride and oxygen to ppromote the formation of single-crystal, truncated cubes and tetrahedrons" Nano Lett. 4 (2004) 1733-1739.
Xia, G. G., Y. G. Yin, W. S. Willis, J. Y. Wang, S. L. Suiba, "Efficient stable catalysts for low temperature carbon monoxide oxidation" J. Catal. 185 (1999) 91-105.
Xia Y., Y. Xiong, B. Lim, S. E. Skrabalak. "Shape-controlled synthesis of metal nanocrystals: Simple chemistry meets complex physics." Angew. Chem. Int. Ed. 48 (2009) 60-103.
Xu, Y., C. H. Langford. "Photoactivity of titanium dioxide supported on MCM 41, Zeolite X, and Zeolite Y" J. Phys. Chem. B 101 (1997) 3115-3121.
Yano H., M. Shoda. "Selection and substantiation of an organic solvent removal apparatus at a print shop by comparative experiments using the activated carbon adsorption and catalytic oxidation methods" J. Air Waste Manage. Assoc. 49 (1999) 324–331.
Yunarti R. T., M. Lee, Y. J. Hwang, J.-W. Choi, D. J. Suh, J. Lee, I. W. Kim, J.-M. Ha. "Transition metal-doped TiO2 nanowire catalysts for the oxidative coupling of methane" Catal. Commun. 50 (2014) 54–58.
Zhang, R., J. A. Schwarz. "Design of inhomogeneous metal distributions within catalyst particles" Appl. Catal. A 91 (1992) 57-65.
Zhao, D., J. Feng, Q. Huo, N. Melosh, G. H. Fredrickson, B. F. Chmelka, G. D. Stucky. "Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores" Science 279 (1998) 548-552.
Zhu, W., Y. Han, L. An. "Silver nanoparticles synthesized from mesoporous Ag/SBA-15 composites" Microporous Mesoporous Mater. 80 (2005) 221-226.
Zhu Y., W. Zhao, H. Chen, J. Shi. "A Simple One-Pot Self-Assembly Route to Nanoporous and Monodispersed Fe3O4 Particles with Oriented Attachment Structure and Magnetic Property" J. Phys. Chem. C 111 (2007) 5281-5285.
沈明宗(2001),實場蓄熱式焚化爐處理排氣中揮發性有機物之操作性能研究,國立中山大學,環境工程研究所碩士論文
陳信宏(2002),奈米銀微粒之化學合成與應用研究,國立清華大學,化學工程學系,碩士論文
李賢學(2005),化學還原法製備奈米銀及其應用,國立清華大學,化學工程學系,博士論文
陳貞志(2007),單一粒徑分佈二氧化矽膠體和銀-二氧化矽核-殼結構奈米粒子的製備及應用,國立清華大學,化學工程學系,博士論文
許誌麟(2009),銀-二氧化矽核殼結構奈米粒子觸媒應用,國立清華大學,化學工程學系,碩士論文
盧育杰(2010),溶液相法合成奈米銀及半導體量子點之研究與應用,國立清華大學,化學工程學系,博士論文
林明佑(2010),銀/三氧化二鐵觸媒合成及於易揮發性有機氣體全氧化之應用,國立清華大學,化學工程學系,碩士論文
張雅欣(2011),奈米級銀粒子與銀絲於量子點及透明導電塗層之應用研究,國立清華大學,化學工程學系,碩士論文
吳駿源(2012),奈米銀絲尺寸控制與其應用,國立清華大學,化學工程學系,碩士論文
徐仲彥(2014),奈米銀絲連續化製程與其應用研究,國立清華大學,化學工程學系,碩士論文