络合-溶剂热法制备钯基催化剂及其催化氧化间二甲苯性能
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摘要
通过采用络合-溶剂热法、水热法和浸渍法三种方法制备了负载量为0.6%(质量分数)的Pd/Al_2O_3催化剂,重点考察不同制备方法催化氧化间二甲苯作为典型的挥发性有机化合物的能力。结果表明:络合-溶剂热法制备的Pd/Al_2O_3-com催化剂催化氧化间二甲苯的能力最强,间二甲苯体积分数为0.002%时完全转化温度(T100)为130℃,低于浸渍法制备催化剂的完全转化温度30℃。对Pd/Al_2O_3催化剂进行了比表面积(BET)、X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)等表征分析,发现Pd/Al_2O_3-com中Pd主要以还原态Pd~0高度分散于载体表面,而另两种方法制备的催化剂均有明显的Pd~(2+)存在。结合性能测试及表征分析,表明络合-溶剂热法制备的Pd/Al_2O_3-com催化剂活性组分Pd的高度分散,增强了催化活性,可满足高浓度间二甲苯、宽气体体积空速条件下催化氧化脱除间二甲苯的工业应用要求。
The Pd/Al_2O_3 catalysts with a loading of 0.6%(mass fraction) were prepared by complexation-solvent thermal method, hydrothermal method and impregnation method. The effect of different preparation methods on the performance of the catalyst was evaluated by using m-xylene as the representative of volatile organic compounds(VOCs). The results showed that the most effective catalyst Pd/Al_2O_3-com was prepared by complexingsolvothermal.The m-xylene with volume fraction of 0.002% can completely converted to CO_2 and H20(T100) at130℃ over Pd/Al_2O_3-com catalyst from the complexing-solvothermal method, which was lower about 30℃ than the catalyst(Pd/Al_2O_3-imp) from the impregnation method. X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), Brunauer-Emmett-Teller(BET) and scanning electron microscopy(SEM) techniques were performed to characterize the physio-chemical properties of synthesized Pd/Al_2O_3 catalysts. The results indicated that the Pd element of Pd/Al_2O_3-com was mainly dispersed on the surface of the support at the reduction state Pd~0, while the Pd element of Pd/Al_2O_3-imp and Pd/Al_2O_3-hyd catalyst was at the form of Pd~(2+) with poor dispersion. Combined with the catalytic activity performance and evaluation results, a highly dispersed and reduction state form of Pd active component on the surface of the carrier resulted in a remarkable catalytic activity on m-xylene conversion. The Pd/Al_2O_3-com catalyst with these features exhibit good activity for removing VOCs under high concentration(0.02%-0.07%, vol) and wide space velocity(5×10~4-10×10~4 h~(-1)) conditions, and thus meet well the requirements of industrial application.
The Pd/Al_2O_3 catalysts with a loading of 0.6%(mass fraction) were prepared by complexation-solvent thermal method, hydrothermal method and impregnation method. The effect of different preparation methods on the performance of the catalyst was evaluated by using m-xylene as the representative of volatile organic compounds(VOCs). The results showed that the most effective catalyst Pd/Al_2O_3-com was prepared by complexingsolvothermal.The m-xylene with volume fraction of 0.002% can completely converted to CO_2 and H20(T100) at130℃ over Pd/Al_2O_3-com catalyst from the complexing-solvothermal method, which was lower about 30℃ than the catalyst(Pd/Al_2O_3-imp) from the impregnation method. X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), Brunauer-Emmett-Teller(BET) and scanning electron microscopy(SEM) techniques were performed to characterize the physio-chemical properties of synthesized Pd/Al_2O_3 catalysts. The results indicated that the Pd element of Pd/Al_2O_3-com was mainly dispersed on the surface of the support at the reduction state Pd~0, while the Pd element of Pd/Al_2O_3-imp and Pd/Al_2O_3-hyd catalyst was at the form of Pd~(2+) with poor dispersion. Combined with the catalytic activity performance and evaluation results, a highly dispersed and reduction state form of Pd active component on the surface of the carrier resulted in a remarkable catalytic activity on m-xylene conversion. The Pd/Al_2O_3-com catalyst with these features exhibit good activity for removing VOCs under high concentration(0.02%-0.07%, vol) and wide space velocity(5×10~4-10×10~4 h~(-1)) conditions, and thus meet well the requirements of industrial application.
引文
[1]Lu C,Wey M,Chen L.Application of polyol process to prepare AC-supported nanocatalyst for VOC oxidation[J].Applied Catalysis A:General,2007,325(1):163-174.
[2]Aziz A,Park H,Kim S,et al.Phenol and ammonium removal by using Fe-ZSM-5 synthesized by ammonium citrate iron source[J].International Journal of Environmental Science and Technology,2016,13(12):2805-2816.
[3]ScirèS,Liotta L F.Supported gold catalysts for the total oxidation of volatile organic compounds[J].Applied Catalysis B:Environmental,2012,125(2):222-246.
[4]Liao Y,Jia L,Chen R,et al.Charcoal-supported catalyst with enhanced thermal-stability for the catalytic combustion of volatile organic compounds[J].Applied Catalysis A:General,2016,522:32-39.
[5]芮泽宝,纪红兵.有机废气催化燃烧过程中多尺度效应和催化剂设计[J].化工学报,2018,69(1):317-326.Rui Z B,Ji H B.Multi-scale effect and catalyst design in catalytic combustion of organic waste gas[J].CIESC Journal,2018,69(1):317-326.
[6]Tidahy H,Siffert S,Lamonier J,et al.New Pd/hierarchical macromesoporous ZrO2,TiO2and ZrO2-TiO2catalysts for VOCs total oxidation[J].Applied Catalysis A:General,2006,310:61-69.
[7]Gil A,Vicentem A,Lambert J F,et al.Platinum catalysts supported on Al-pillared clays:application to the catalytic combustion of acetone and methyl-ethyl-ketone[J].Catalysis Today,2001,68(1/2/3):41-51.
[8]Pozan G S.Effect of support on the catalytic activity of manganese oxide catalysts for toluene combustion[J].Journal of Hazardous Materials,2012,221:124-130.
[9]Tang W,Deng Y,Li W,et al.Importance of porous structure and synergistic effect on the catalytic oxidation activities over hierarchical Mn-Ni composite oxides[J].Catalysis Science&Technology,2016,6(6):1710-1718.
[10]Hu C,Zhu Q,Jiang Z,et al.Catalytic combustion of dilute acetone over Cu-doped ceria catalysts[J].Chemical Engineering Journal,2009,152(2/3):583-590.
[11]Pan H,Li Z,Xia Q,et al.Catalytic activity of copper based catalysts pretreated with H2reduction for catalytic combustion of styrene[J].Catalysis Communications,2009,10(8):1166-1169.
[12]Sedjame H,Fontaine C,Lafaye G,et al.On the promoting effect of the addition of ceria to platinum based alumina catalysts for VOCs oxidation[J].Applied Catalysis B:Environmental,2014,144:233-242.
[13]Hosseini M,Haghighi M,Kahforoushan D,et al.Sono-dispersion of ceria and palladium in preparation and characterization of Pd/Al2O3-clinoptilolite-CeO2nanocatalyst for treatment of polluted air via low temperature VOC oxidation[J].Process Safety and Environmental Protection,2017,106:284-293.
[14]Liu Y,Dai H,Deng J,et al.Mesoporous Co3O4-supported gold nanocatalysts:highly active for the oxidation of carbon monoxide,benzene,toluene,and o-xylene[J].Journal of Catalysis,2014,309:408-418.
[15]Bal Zhinimaev B S,Kovalyov E V,Kaichev V V,et al.Catalytic abatement of VOC over novel Pt fiber glass catalysts[J].Topics in Catalysis,2017,60(1/2):73-82.
[16]Beck I E,Bukhtiyarov V I,Parkharukov I Y,et al.Platinum nanoparticles on Al2O3:correlation between the particle size and activity in total methane oxidation[J].Journal of Catalysis,2009,268(1):60-67.
[17]Komvokis V G,Marti M,Delimitis A,et al.Catalytic decomposition of N2O over highly active supported Ru nanoparticles(≤3 nm)prepared by chemical reduction with ethylene glycol[J].Applied Catalysis B:Environmental,2011,103(1/2):62-71.
[18]Huang S,Zhang C,He H.Complete oxidation of o-xylene over Pd/Al2O3catalyst at low temperature[J].Catalysis Today,2008,139(1/2):15-23.
[19]胡凌霄,王莲,王飞,等.Pd/γ-Al2O3催化剂催化氧化邻-二甲苯[J].物理化学学报,2017,33(8):1681-1688.Hu L X,Wang L,Wang F,et al.Catalytic oxidation of o-xylene over Pd/γ-Al2O3catalysts[J].Acta Physico-Chimica Sinica,2017,33(8):1681-1688.
[20]?ztürk S,K?semen A,K?semen Z A,et al.Electrochemically growth of Pd doped ZnO nanorods on QCM for room temperature VOC sensors[J].Sensors and Actuators B:Chemical,2016,222:280-289.
[21]Kim J,Parl J,Kim H S,et al.A new route to preparation of palladium catalysts for VOC combustion[J].Journal of Industrial and Engineering Chemistry,2012,18(1):425-428.
[22]Ońska M J,Król A,C E K,et al.Zeolites Y modified with palladium as effective catalysts for low-temperature methanol incineration[J].Applied Catalysis B:Environmental,2015,166:353-365.
[23]Huang S,Zhang C,He H.Effect of pretreatment on Pd/Al2O3catalyst for catalytic oxidation of o-xylene at low temperature[J].Journal of Environmental Sciences,2013,25(6):1206-1212.
[24]Barakat T,Rooke J C,Cousin R,et al.Investigation of the elimination of VOC mixtures over a Pd-loaded V-doped TiO2support[J].New Journal of Chemistry,2014,38(5):266-274.
[25]Demoulin O,Rupprechter G,Seunier I,et al.Investigation of parameters influencing the activation of a Pd/γ-Alumina catalyst during methane combustion[J].The Journal of Physical Chemistry B,2005,109(43):20454-20462.
[26]Padilla J M,Del Angel G,Navarrete J.Improved Pd/γ-Al2O3-Ce catalysts for benzene combustion[J].Catalysis Today,2008,133/134/135:541-547.
[27]Kim S C,Shim W G.Properties and performance of Pd based catalysts for catalytic oxidation of volatile organic compounds[J].Applied Catalysis B:Environmental,2009,92(3/4):429-436.
[28]Huang H,Leung D Y C.Complete oxidation of formaldehyde at room temperature using TiO2supported metallic Pd nanoparticles[J].ACS Catalysis,2011,1(4):348-354.
[29]Wang Y,Zhang C,He H.Insight into the role of Pd state on Pdbased catalysts in o-xylene oxidation at low temperature[J].ChemCatChem,2018,10(5):998-1004.
[30]夏燎原,吴义强,胡云楚.锡掺杂介孔分子筛在木材阻燃中的烟气转化作用[J].无机材料学报,2013,28(5):532-536.Xia L Y,Wu Y Q,Hu C Y.Study on smoke catalytic conversion by Sn-substituted mesoporous silica composite in wood fire retardance[J].Journal of Inorganic Materials,2013,28(5):532-536.
[31]叶青,霍飞飞,王海平,等.x Au/α-MnO2催化剂的结构及催化氧化VOCs气体性能[J].高等学校化学学报,2013,34(5):1187-1194.Ye Q,Huo F F,Wang H P,et al.Structure of x Au/α-MnO2catalyst and performance of catalytic oxidation of VOCs[J].Chemical Journal of Chinese Universities,2013,34(5):1187-1194.
[32]Shim W G,Lee J W,Kim S C.Analysis of catalytic oxidation of aromatic hydrocarbons over supported palladium catalyst with different pretreatments based on heterogeneous adsorption properties[J].Applied Catalysis B:Environmental,2008,84(1/2):133-141.
[33]Kundakovic L,Flytzani-Stephanoulos M.Reduction characteristics of copper oxide in cerium and zirconium oxide systems[J].Applied Catalysis A:General,1998,171(1):13-29.
[34]陈静,张庆红,方文浩,等.水滑石负载钯催化剂上的醇无氧脱氢反应[J].催化学报,2010,31(8):1061-1070.Chen J,Zhang Q H,Fang W H,et al.Oxidant-free dehydrogenation of alcohols over hydrotalcite-supported palladium catalysts[J].Chinese Journal of Catalysis,2010,31(8):1061-1070.
[35]Hirai H,Chawanya H,Toshima N.Colloidal palladium protected with poly(N-vinyl-2-pyrrolidone)for selective hydrogenation of cyclopentadiene[J].Reactive Polymers,1985,3(2):127-141.
[36]Roberts G W,Satterfield C N.Effectiveness factor for porous catalysts Langmuir-Hinshelwood kinetic expressions[J].Industrial&Engineering Chemistry Fundamentals,1966,5(3):317-325.
[37]Kratzer P,Brening W.Highly excited molecules from Eley-Rideal reactions[J].Surface Science Letters,1991,254(1/2/3):275-280.
[38]Saqlain M A,Hussain A,Siddiq M,et al.A DFT+U study of the mars van Krevelen mechanism of CO oxidation on Au/TiO2catalysts[J].Applied Catalysis A:General,2016,519:27-33.
[2]Aziz A,Park H,Kim S,et al.Phenol and ammonium removal by using Fe-ZSM-5 synthesized by ammonium citrate iron source[J].International Journal of Environmental Science and Technology,2016,13(12):2805-2816.
[3]ScirèS,Liotta L F.Supported gold catalysts for the total oxidation of volatile organic compounds[J].Applied Catalysis B:Environmental,2012,125(2):222-246.
[4]Liao Y,Jia L,Chen R,et al.Charcoal-supported catalyst with enhanced thermal-stability for the catalytic combustion of volatile organic compounds[J].Applied Catalysis A:General,2016,522:32-39.
[5]芮泽宝,纪红兵.有机废气催化燃烧过程中多尺度效应和催化剂设计[J].化工学报,2018,69(1):317-326.Rui Z B,Ji H B.Multi-scale effect and catalyst design in catalytic combustion of organic waste gas[J].CIESC Journal,2018,69(1):317-326.
[6]Tidahy H,Siffert S,Lamonier J,et al.New Pd/hierarchical macromesoporous ZrO2,TiO2and ZrO2-TiO2catalysts for VOCs total oxidation[J].Applied Catalysis A:General,2006,310:61-69.
[7]Gil A,Vicentem A,Lambert J F,et al.Platinum catalysts supported on Al-pillared clays:application to the catalytic combustion of acetone and methyl-ethyl-ketone[J].Catalysis Today,2001,68(1/2/3):41-51.
[8]Pozan G S.Effect of support on the catalytic activity of manganese oxide catalysts for toluene combustion[J].Journal of Hazardous Materials,2012,221:124-130.
[9]Tang W,Deng Y,Li W,et al.Importance of porous structure and synergistic effect on the catalytic oxidation activities over hierarchical Mn-Ni composite oxides[J].Catalysis Science&Technology,2016,6(6):1710-1718.
[10]Hu C,Zhu Q,Jiang Z,et al.Catalytic combustion of dilute acetone over Cu-doped ceria catalysts[J].Chemical Engineering Journal,2009,152(2/3):583-590.
[11]Pan H,Li Z,Xia Q,et al.Catalytic activity of copper based catalysts pretreated with H2reduction for catalytic combustion of styrene[J].Catalysis Communications,2009,10(8):1166-1169.
[12]Sedjame H,Fontaine C,Lafaye G,et al.On the promoting effect of the addition of ceria to platinum based alumina catalysts for VOCs oxidation[J].Applied Catalysis B:Environmental,2014,144:233-242.
[13]Hosseini M,Haghighi M,Kahforoushan D,et al.Sono-dispersion of ceria and palladium in preparation and characterization of Pd/Al2O3-clinoptilolite-CeO2nanocatalyst for treatment of polluted air via low temperature VOC oxidation[J].Process Safety and Environmental Protection,2017,106:284-293.
[14]Liu Y,Dai H,Deng J,et al.Mesoporous Co3O4-supported gold nanocatalysts:highly active for the oxidation of carbon monoxide,benzene,toluene,and o-xylene[J].Journal of Catalysis,2014,309:408-418.
[15]Bal Zhinimaev B S,Kovalyov E V,Kaichev V V,et al.Catalytic abatement of VOC over novel Pt fiber glass catalysts[J].Topics in Catalysis,2017,60(1/2):73-82.
[16]Beck I E,Bukhtiyarov V I,Parkharukov I Y,et al.Platinum nanoparticles on Al2O3:correlation between the particle size and activity in total methane oxidation[J].Journal of Catalysis,2009,268(1):60-67.
[17]Komvokis V G,Marti M,Delimitis A,et al.Catalytic decomposition of N2O over highly active supported Ru nanoparticles(≤3 nm)prepared by chemical reduction with ethylene glycol[J].Applied Catalysis B:Environmental,2011,103(1/2):62-71.
[18]Huang S,Zhang C,He H.Complete oxidation of o-xylene over Pd/Al2O3catalyst at low temperature[J].Catalysis Today,2008,139(1/2):15-23.
[19]胡凌霄,王莲,王飞,等.Pd/γ-Al2O3催化剂催化氧化邻-二甲苯[J].物理化学学报,2017,33(8):1681-1688.Hu L X,Wang L,Wang F,et al.Catalytic oxidation of o-xylene over Pd/γ-Al2O3catalysts[J].Acta Physico-Chimica Sinica,2017,33(8):1681-1688.
[20]?ztürk S,K?semen A,K?semen Z A,et al.Electrochemically growth of Pd doped ZnO nanorods on QCM for room temperature VOC sensors[J].Sensors and Actuators B:Chemical,2016,222:280-289.
[21]Kim J,Parl J,Kim H S,et al.A new route to preparation of palladium catalysts for VOC combustion[J].Journal of Industrial and Engineering Chemistry,2012,18(1):425-428.
[22]Ońska M J,Król A,C E K,et al.Zeolites Y modified with palladium as effective catalysts for low-temperature methanol incineration[J].Applied Catalysis B:Environmental,2015,166:353-365.
[23]Huang S,Zhang C,He H.Effect of pretreatment on Pd/Al2O3catalyst for catalytic oxidation of o-xylene at low temperature[J].Journal of Environmental Sciences,2013,25(6):1206-1212.
[24]Barakat T,Rooke J C,Cousin R,et al.Investigation of the elimination of VOC mixtures over a Pd-loaded V-doped TiO2support[J].New Journal of Chemistry,2014,38(5):266-274.
[25]Demoulin O,Rupprechter G,Seunier I,et al.Investigation of parameters influencing the activation of a Pd/γ-Alumina catalyst during methane combustion[J].The Journal of Physical Chemistry B,2005,109(43):20454-20462.
[26]Padilla J M,Del Angel G,Navarrete J.Improved Pd/γ-Al2O3-Ce catalysts for benzene combustion[J].Catalysis Today,2008,133/134/135:541-547.
[27]Kim S C,Shim W G.Properties and performance of Pd based catalysts for catalytic oxidation of volatile organic compounds[J].Applied Catalysis B:Environmental,2009,92(3/4):429-436.
[28]Huang H,Leung D Y C.Complete oxidation of formaldehyde at room temperature using TiO2supported metallic Pd nanoparticles[J].ACS Catalysis,2011,1(4):348-354.
[29]Wang Y,Zhang C,He H.Insight into the role of Pd state on Pdbased catalysts in o-xylene oxidation at low temperature[J].ChemCatChem,2018,10(5):998-1004.
[30]夏燎原,吴义强,胡云楚.锡掺杂介孔分子筛在木材阻燃中的烟气转化作用[J].无机材料学报,2013,28(5):532-536.Xia L Y,Wu Y Q,Hu C Y.Study on smoke catalytic conversion by Sn-substituted mesoporous silica composite in wood fire retardance[J].Journal of Inorganic Materials,2013,28(5):532-536.
[31]叶青,霍飞飞,王海平,等.x Au/α-MnO2催化剂的结构及催化氧化VOCs气体性能[J].高等学校化学学报,2013,34(5):1187-1194.Ye Q,Huo F F,Wang H P,et al.Structure of x Au/α-MnO2catalyst and performance of catalytic oxidation of VOCs[J].Chemical Journal of Chinese Universities,2013,34(5):1187-1194.
[32]Shim W G,Lee J W,Kim S C.Analysis of catalytic oxidation of aromatic hydrocarbons over supported palladium catalyst with different pretreatments based on heterogeneous adsorption properties[J].Applied Catalysis B:Environmental,2008,84(1/2):133-141.
[33]Kundakovic L,Flytzani-Stephanoulos M.Reduction characteristics of copper oxide in cerium and zirconium oxide systems[J].Applied Catalysis A:General,1998,171(1):13-29.
[34]陈静,张庆红,方文浩,等.水滑石负载钯催化剂上的醇无氧脱氢反应[J].催化学报,2010,31(8):1061-1070.Chen J,Zhang Q H,Fang W H,et al.Oxidant-free dehydrogenation of alcohols over hydrotalcite-supported palladium catalysts[J].Chinese Journal of Catalysis,2010,31(8):1061-1070.
[35]Hirai H,Chawanya H,Toshima N.Colloidal palladium protected with poly(N-vinyl-2-pyrrolidone)for selective hydrogenation of cyclopentadiene[J].Reactive Polymers,1985,3(2):127-141.
[36]Roberts G W,Satterfield C N.Effectiveness factor for porous catalysts Langmuir-Hinshelwood kinetic expressions[J].Industrial&Engineering Chemistry Fundamentals,1966,5(3):317-325.
[37]Kratzer P,Brening W.Highly excited molecules from Eley-Rideal reactions[J].Surface Science Letters,1991,254(1/2/3):275-280.
[38]Saqlain M A,Hussain A,Siddiq M,et al.A DFT+U study of the mars van Krevelen mechanism of CO oxidation on Au/TiO2catalysts[J].Applied Catalysis A:General,2016,519:27-33.
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