CuO/PSSF复合催化剂的制备及其在苯酚降解中的应用
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摘要
以纸状不锈钢微纤材料(paper-like sintered stainless steel fibers,PSSF)为载体,采用化学气相沉积法(chemical vapor depositon,CVD)制备CuO/PSSF复合催化剂并在固定床反应器上进行苯酚湿式催化氧化降解研究。采用SEM、XRD、XPS等技术对催化剂的表面形态、物相结构、元素价态进行分析,改变流量及床层高度考察停留时间对湿式催化氧化降解苯酚过程中苯酚转化率、H_2O_2转化率、TOC转化率及Cu2+浸出浓度的影响规律。催化剂表征结果表明,活性组分CuO成功负载在PSSF微纤材料上;活性评价测试结果表明,低流量条件对各活性指标变化影响十分明显;随床层高度增加各活性指标均显著提高,4cm床层高度下达到最高苯酚转化率和TOC转化率,分别为96.5%和47.4%,同时没有高毒副产物产生。本文初步探究了复合催化剂与固定床反应器结合的工艺可行性,旨在为工业化含酚废水的降解提供一些思路。
Supported by PSSF(paper-like sintered stainless steel fibers), novel CuO/PSSF composite catalysts were synthesized by chemical vapor deposition(CVD) and applied in the catalytic wet peroxide oxidation(CWPO) of phenol in a fixed-bed reactor. The physical structure, morphology, and element valence state of the catalysts were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM) and X-ray photoelectron spectra(XPS), respectively. The influence of residence time has been studied by modifying the feed flow rate and catalyst bed height, while the conversion of phenol,H_2O_2 and TOC as well as the leaching concentration of Cu2+were analyzed to investigate the catalytic activity of the CuO/PSSF composite catalysts. Characterization results indicated that CuO was deposited on PSSF successfully and the activity evaluation results showed that conversion of phenol, H_2O_2 and TOC changed significantly at low feed flow rate but increased as the catalyst bed height increased and the highest phenol and TOC conversion(96.5% and 47.4%, respectively) were obtained with 4 cm catalyst bed height, meanwhile the intermediates of high toxicity were not observed. This study preliminarily supported the application of the CuO/PSSF composite catalysts in fixed-bed reactor, and thus provided some new solutions for the degradation of phenol-containing wastewater.
Supported by PSSF(paper-like sintered stainless steel fibers), novel CuO/PSSF composite catalysts were synthesized by chemical vapor deposition(CVD) and applied in the catalytic wet peroxide oxidation(CWPO) of phenol in a fixed-bed reactor. The physical structure, morphology, and element valence state of the catalysts were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM) and X-ray photoelectron spectra(XPS), respectively. The influence of residence time has been studied by modifying the feed flow rate and catalyst bed height, while the conversion of phenol,H_2O_2 and TOC as well as the leaching concentration of Cu2+were analyzed to investigate the catalytic activity of the CuO/PSSF composite catalysts. Characterization results indicated that CuO was deposited on PSSF successfully and the activity evaluation results showed that conversion of phenol, H_2O_2 and TOC changed significantly at low feed flow rate but increased as the catalyst bed height increased and the highest phenol and TOC conversion(96.5% and 47.4%, respectively) were obtained with 4 cm catalyst bed height, meanwhile the intermediates of high toxicity were not observed. This study preliminarily supported the application of the CuO/PSSF composite catalysts in fixed-bed reactor, and thus provided some new solutions for the degradation of phenol-containing wastewater.
引文
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[22]SASHKINA K A,PARKHOMCHUK E V,RUDINA N A,et al.The role of zeolite Fe-ZSM-5 porous structure for heterogeneous Fenton catalyst activity and stability[J].Microporous and Mesoporous Materials,2014,189:181-188.
[23]VALKAJ K M,KATOVI?A,ZRN?EVI?S.Catalytic properties of Cu/13X zeolite based catalyst in catalytic wet peroxide oxidation of phenol[J].Industrial&Engineering Chemistry Research,2011,50(8):4390-4397.
[24]INCHAURRONDO N,CECHINI J,FONT J,et al.Strategies for enhanced CWPO of phenol solutions[J].Applied Catalysis B:Environmental,2012,111/112:641-648.
[25]LAM L Y F.Development of MCM-41 based catalysts for the photoFenton’s degradation of dye pollutants[D].Hongkong:The Hong Kong University of Science and Technology,2005.
[26]李宝杰.MOCVD工艺制备高温抗氧化铱涂层的研究[D].长沙:国防科学技术大学,2006.LI B J.Study on MOCVD process of preparing anti-oxidation Ir coatings[D].Changsha:National University of Defense Technology,2006.
[27]CHEN A P,LONG H,LI X C,et al.Controlled growth and characteristics of single-phase Cu2O and CuO films by pulsed laser deposition[J].Vacuum,2009,83(6):927-930.
[28]CHEN H H,ZHANG H P,YAN Y.Preparation and characterization of a novel gradient porous ZSM-5 zeolite membrane/PSSF composite and its application for toluene adsorption[J].Chemical Engineering Journal,2012,209:372-378.
[29]LIU H,WANG G,PARK J,et al.Electrochemical performance ofα-Fe2O3nanorods as anode material for lithium-ion cells[J].Electrochimica Acta,2009,54(6):1733-1736.
[30]WAHID S,TATARCHUK B J.Catalytic material with enhanced contacting efficiency for volatile organic compound removal at ultrashort contact time[J].Industrial&Engineering Chemistry Research,2013,52(44):15494-15503.
[31]RALLAN C,ALRUBAYE R,GARFORTH A.Generation of catalytic films of alumina and zeolites on FeCralloy rods[J].Chemical Engineering Transactions,2015,43:907-912.
[32]凌敏,赵国锋,曹发海,等.新型微纤结构催化/吸附填料研究进展[J].催化学报,2010,31(7):717-724.LING M,ZHAO G F,CAO F H,et al.Advances in research on novel microfibrousstructuredcatalytic/adsorbentpackings[J].Chinese Journal of Catalysis,2010,31(7):717-724.
[33]BARRECA D,GASPAROTTO A,TONDELLO E.CVD Cu2O and CuO nanosystems characterized by XPS[J].Surface Science Spectra,2008,14:41-51.
[34]MORALES J,SANCHEZ L,MARTIN F,et al.Use of lowtemperature nanostructured CuO thin films deposited by spraypyrolysis in lithium cells[J].Thin Solid Films,2005,474(1/2):133-140.
[35]LIU S,HOU H Y,LIU X X,et al.High-performance hierarchical cypress-like CuO/Cu2O/Cu anode for lithium ion battery[J].Ionics,2017,23(5):1075-1082.
[36]SANTOS A,YUSTOS P,DURBAN B,et al.Catalytic wet oxidation of phenol:kinetics of the mineralization rate[J].Industrial&Engineering Chemistry Research,2001,40(13):2773-2781.
[37]SANTOS A,YUSTOS P,QUINTANILLA A,et al.Study of the copper leaching in the wet oxidation of phenol with CuO-based catalysts:causes and effects[J].Applied Catalysis B:Environmental,2005,61(3/4):323-333.
[38]MARTíNEZ F,MELERO J A,BOTAS Já,et al.Treatment of phenolic effluents by catalytic wet hydrogen peroxide oxidation over Fe2O3/SBA-15 extruded catalyst in a fixed-bed reactor[J].Industrial&Engineering Chemistry Research,2007,46(13):4396-4405.
[39]ZAZO J A,CASAS J A,MOHEDANO A F,et al.Catalytic wet peroxide oxidation of phenol with a Fe/active carbon catalyst[J].Applied Catalysis B:Environmental,2006,65(3/4):261-268.
[40]HE D L,ZHANG H P,YAN Y.Preparation of Cu-ZSM-5 catalysts by chemical vapour deposition for catalytic wet peroxide oxidation of phenol in a fixed bed reactor[J].Royal Society Open Science,2018,5(4):172364.
[41]YAN Y,JIANG S S,ZHANG H P.Efficient catalytic wet peroxide oxidation of phenol over Fe-ZSM-5 catalyst in a fixed bed reactor[J].Separation and Purification Technology,2014,133:365-374.
[42]YAN Y,WU X W,ZHANG H P.Catalytic wet peroxide oxidation of phenol over Fe2O3/MCM-41 in a fixed bed reactor[J].Separation and Purification Technology,2016,171:52-61.
[2]HUANG K,WANG J J,WU D F,et al.Copper hydroxyl sulfate as a heterogeneous catalyst for the catalytic wet peroxide oxidation of phenol[J].RSC Advances,2015,5(11):8455-8462.
[3]MASSA P,IVORRA F,HAURE P,et al.Catalytic wet peroxide oxidation of phenol solutions over CuO/CeO2systems[J].Journal of Hazardous Materials,2011,190(1/3):1068-1073.
[4]BOTAS J A,MELERO J A,MARTINEZ F,et al.Assessment of Fe2O3/SiO2catalysts for the continuous treatment of phenol aqueous solutions in a fixed bed reactor[J].Catalysis Today,2010,149(3/4):334-340.
[5]CAUDO S,CENTI G,GENOVESE C,et al.Homogeneous versus heterogeneous catalytic reactions to eliminate organics from waste water using H2O2[J].Topics in Catalysis,2006,40(1/4):207-219.
[6]INCHAURRONDO N,CONTRERAS E,HAURE P.Catalyst reutilization in phenol homogeneous cupro-Fenton oxidation[J].Chemical Engineering Journal,2014,251:146-157.
[7]LIOU R,CHEN S.CuO impregnated activated carbon for catalytic wet peroxide oxidation of phenol[J].Journal of Hazardous Materials,2009,172(1):498-506.
[8]ZHONG X,BARBIER J,DUPREZ D,et al.Modulating the copper oxide morphology and accessibility by using micro-/mesoporous SBA-15 structures as host support:effect on the activity for the CWPO of phenol reaction[J].Applied Catalysis B:Environmental,2012,121/122:123-134.
[9]LUO X,WU S,YANG Y Q,et al.Deposition of titanium coating on SiCfiber by chemical vapor deposition with Ti-I2 system[J].Applied Surface Science,2017,406:62-68.
[10]胡小龙,孙青,徐春宏,等.纳米TiO2/沸石复合材料光催化降解苯酚的性能[J].化工进展,2016,35(5):1519-1523.HU X L,SUN Q,XU C H,et al.Photocatalytic degradation of phenol with nano-TiO2/zeolite composite material[J].Chemical Industry and Engineering Progress,2016,35(5):1519-1523.
[11]SONG H,WANG J,WANG Z D,et al.Effect of titanium content on dibenzothiophene HDS performance over Ni2P/Ti-MCM-41 catalyst[J].Journal of Catalysis,2014,311:257-265.
[12]PRINCE J,TZOMPANTZI F,MENDOZA-DAMIáN G,et al.Photocatalytic degradation of phenol by semiconducting mixed oxides derived from Zn(Ga)Al layered double hydroxides[J].Applied Catalysis B:Environmental,2015,163:352-360.
[13]NICKELL R A,TATARCHUK B J.High surface area,supported precious metal cathodes utilizing metal microfibrous collectors for application in chlor-alkali cells[J].Journal of Applied Electrochemistry,2005,35(6):581-587.
[14]KALLURI R R,CAHELA D R,TATARCHUK B J.Microfibrous entrapped small particle adsorbents for high efficiency heterogeneous contacting[J].Separation and Purification Technology,2008,62(2):304-316.
[15]MAIONE A,ANDRéF,RUIZ P.Structured bimetallic Pd-Pt/γ-Al2O3catalysts on FeCrAlloy fibers for total combustion of methane[J].Applied Catalysis B:Environmental,2007,75(1/2):59-70.
[16]BRUNEEL E,BRABANT J,LE M T,et al.Deposition of a Cu/Mo/Ce catalyst for diesel soot oxidation on a sintered metal fiber filter with a CeO2anti corrosion coating[J].Catalysis Communications,2012,25:111-117.
[17]CHEN H H,ZHANG H P,YAN Y.Adsorption dynamics of toluene in structured fixed bed with ZSM-5 membrane/PSSF composites[J].Chemical Engineering Journal,2013,228:336-344.
[18]LIU J,YAN Y,ZHANG H P.Adsorption dynamics of toluene in composite bed with microfibrous entrapped activated carbon[J].Chemical Engineering Journal,2011,173(2):456-462.
[19]LU M H,YAO Y,GAO L L,et al.Continuous treatment of phenol over an Fe2O3/γ-Al2O3catalyst in a fixed-bed reactor[J].Water,Air&Soil Pollution,2015,226(4):1-13.
[20]TARAN O P,ZAGORUIKO A N,AYUSHEEV A B,et al.Wet peroxide oxidation of phenol over Cu-ZSM-5 catalyst in a flow reactor.Kinetics and diffusion study[J].Chemical Engineering Journal,2015,282:108-115.
[21]GONZALEZ-OLMOS R,HOLZER F,KOPINKE F D,et al.Indications of the reactive species in a heterogeneous Fenton-like reaction using Fe-containing zeolites[J].Applied Catalysis A:General,2011,398(1/2):44-53.
[22]SASHKINA K A,PARKHOMCHUK E V,RUDINA N A,et al.The role of zeolite Fe-ZSM-5 porous structure for heterogeneous Fenton catalyst activity and stability[J].Microporous and Mesoporous Materials,2014,189:181-188.
[23]VALKAJ K M,KATOVI?A,ZRN?EVI?S.Catalytic properties of Cu/13X zeolite based catalyst in catalytic wet peroxide oxidation of phenol[J].Industrial&Engineering Chemistry Research,2011,50(8):4390-4397.
[24]INCHAURRONDO N,CECHINI J,FONT J,et al.Strategies for enhanced CWPO of phenol solutions[J].Applied Catalysis B:Environmental,2012,111/112:641-648.
[25]LAM L Y F.Development of MCM-41 based catalysts for the photoFenton’s degradation of dye pollutants[D].Hongkong:The Hong Kong University of Science and Technology,2005.
[26]李宝杰.MOCVD工艺制备高温抗氧化铱涂层的研究[D].长沙:国防科学技术大学,2006.LI B J.Study on MOCVD process of preparing anti-oxidation Ir coatings[D].Changsha:National University of Defense Technology,2006.
[27]CHEN A P,LONG H,LI X C,et al.Controlled growth and characteristics of single-phase Cu2O and CuO films by pulsed laser deposition[J].Vacuum,2009,83(6):927-930.
[28]CHEN H H,ZHANG H P,YAN Y.Preparation and characterization of a novel gradient porous ZSM-5 zeolite membrane/PSSF composite and its application for toluene adsorption[J].Chemical Engineering Journal,2012,209:372-378.
[29]LIU H,WANG G,PARK J,et al.Electrochemical performance ofα-Fe2O3nanorods as anode material for lithium-ion cells[J].Electrochimica Acta,2009,54(6):1733-1736.
[30]WAHID S,TATARCHUK B J.Catalytic material with enhanced contacting efficiency for volatile organic compound removal at ultrashort contact time[J].Industrial&Engineering Chemistry Research,2013,52(44):15494-15503.
[31]RALLAN C,ALRUBAYE R,GARFORTH A.Generation of catalytic films of alumina and zeolites on FeCralloy rods[J].Chemical Engineering Transactions,2015,43:907-912.
[32]凌敏,赵国锋,曹发海,等.新型微纤结构催化/吸附填料研究进展[J].催化学报,2010,31(7):717-724.LING M,ZHAO G F,CAO F H,et al.Advances in research on novel microfibrousstructuredcatalytic/adsorbentpackings[J].Chinese Journal of Catalysis,2010,31(7):717-724.
[33]BARRECA D,GASPAROTTO A,TONDELLO E.CVD Cu2O and CuO nanosystems characterized by XPS[J].Surface Science Spectra,2008,14:41-51.
[34]MORALES J,SANCHEZ L,MARTIN F,et al.Use of lowtemperature nanostructured CuO thin films deposited by spraypyrolysis in lithium cells[J].Thin Solid Films,2005,474(1/2):133-140.
[35]LIU S,HOU H Y,LIU X X,et al.High-performance hierarchical cypress-like CuO/Cu2O/Cu anode for lithium ion battery[J].Ionics,2017,23(5):1075-1082.
[36]SANTOS A,YUSTOS P,DURBAN B,et al.Catalytic wet oxidation of phenol:kinetics of the mineralization rate[J].Industrial&Engineering Chemistry Research,2001,40(13):2773-2781.
[37]SANTOS A,YUSTOS P,QUINTANILLA A,et al.Study of the copper leaching in the wet oxidation of phenol with CuO-based catalysts:causes and effects[J].Applied Catalysis B:Environmental,2005,61(3/4):323-333.
[38]MARTíNEZ F,MELERO J A,BOTAS Já,et al.Treatment of phenolic effluents by catalytic wet hydrogen peroxide oxidation over Fe2O3/SBA-15 extruded catalyst in a fixed-bed reactor[J].Industrial&Engineering Chemistry Research,2007,46(13):4396-4405.
[39]ZAZO J A,CASAS J A,MOHEDANO A F,et al.Catalytic wet peroxide oxidation of phenol with a Fe/active carbon catalyst[J].Applied Catalysis B:Environmental,2006,65(3/4):261-268.
[40]HE D L,ZHANG H P,YAN Y.Preparation of Cu-ZSM-5 catalysts by chemical vapour deposition for catalytic wet peroxide oxidation of phenol in a fixed bed reactor[J].Royal Society Open Science,2018,5(4):172364.
[41]YAN Y,JIANG S S,ZHANG H P.Efficient catalytic wet peroxide oxidation of phenol over Fe-ZSM-5 catalyst in a fixed bed reactor[J].Separation and Purification Technology,2014,133:365-374.
[42]YAN Y,WU X W,ZHANG H P.Catalytic wet peroxide oxidation of phenol over Fe2O3/MCM-41 in a fixed bed reactor[J].Separation and Purification Technology,2016,171:52-61.