Cu/Co复合氧化物催化降解正庚烷
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摘要
采用不同沉淀剂及Cu/Co比例,以共沉淀法制备了系列Cu/Co复合氧化物催化剂。对催化剂进行了XRD、SEM、H_2-TPR和O_2-TPD表征,探究了不同沉淀剂对催化剂物理化学性质的影响,结果表明,以氨水为沉淀剂制备的催化剂氧化还原性较强且具有更多的化学吸附氧。当反应空速15 000 h~(-1),氧气体积分数10%,温度150~275℃时,在固定床连续反应器-气相色谱在线检测装置上,考察了Cu/Co催化剂对正庚烷的催化燃烧降解活性,结果表明:Cu_1Co_4催化剂[n(Cu)∶n(Co)=1∶4]活性最优,温度为185.61℃时其对正庚烷转化率达90%。Cu_1Co_4寿命实验结果表明:其稳定性良好;XRD表征及热重分析(TG)结果表明:反应前后催化剂结构稳定且表面无积炭生成。
A series of copper-cobalt composite oxides with various mole proportion of Cu/Co were synthesized by co-precipitation in the presence of different precipitants.Obtained catalysts were characterized by XRD,SEM,H_2-TPR and O_2-TPD.The effects of different precipitants on the physical and chemical properties of catalyst were also investigated.The results indicated that the catalysts using ammonia as precipitant exhibited stronger redox properties and had more chemisorption oxygen.The catalytic activity of the catalysts for oxidative degradation of n-heptane was investigated in a continuous fixed bed reactor with GHSV of 15 000 h~(-1),oxygen concentration of 10%(volume fraction) at 150 ~275℃.It was found that Cu_1Co_4 catalyst[n(Cu) ∶ n(Co) = 1∶4]performed the best activity in the case of reaction temperature of 185.61 ℃ and the conversion of n-heptane was 90%.Moreover,the stability test showed that Cu_1Co_4 had good stability.The characterization results of XRD and TG implied that Cu_1Co_4 was stable before and after reaction,and there was no carbon deposition formation on its surface.
A series of copper-cobalt composite oxides with various mole proportion of Cu/Co were synthesized by co-precipitation in the presence of different precipitants.Obtained catalysts were characterized by XRD,SEM,H_2-TPR and O_2-TPD.The effects of different precipitants on the physical and chemical properties of catalyst were also investigated.The results indicated that the catalysts using ammonia as precipitant exhibited stronger redox properties and had more chemisorption oxygen.The catalytic activity of the catalysts for oxidative degradation of n-heptane was investigated in a continuous fixed bed reactor with GHSV of 15 000 h~(-1),oxygen concentration of 10%(volume fraction) at 150 ~275℃.It was found that Cu_1Co_4 catalyst[n(Cu) ∶ n(Co) = 1∶4]performed the best activity in the case of reaction temperature of 185.61 ℃ and the conversion of n-heptane was 90%.Moreover,the stability test showed that Cu_1Co_4 had good stability.The characterization results of XRD and TG implied that Cu_1Co_4 was stable before and after reaction,and there was no carbon deposition formation on its surface.
引文
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[31]Liu Qixian(刘启宪),Tang Xiaosu(唐小苏),Duan Yankang(段言康),et al.Effects of precipitations on the structure and catalytic activities of Co3O4catalysts for the N2O decomposition[J].J Mol Catal(分子催化),2016,30(4):363-371.
[32]Palacios-Hernandez T,Hirata-Flores G A,Contreras-López O E,et al.Synthesis of Cu and Co metal oxide nanoparticles from thermal decomposition of tartrate complexes[J].Inorg Chim Acta,2012,392(392):277-282.
[33]Zhang F,Wang X,Zhang X,et al.The catalytic activity of Ni O for N2O decomposition doubly promoted by barium and cerium[J].Chem Eng J,2014,256(8):365-371.
[34]Solsona B,Vazquez I,Garcia T,et al.Complete oxidation of short chain alkanes using a nanocrystalline cobalt oxide catalyst[J].Catal Lett,2007,116(3/4):116-121.
[35]T9rncrona A,Skoglundh M,Thormhlen P,et al.Low temperature catalytic activity of cobalt oxide and ceria promoted Pt and Pd:-influence of pretreatment and gas composition[J].Appl Catal B,1997,14(1):131-145.
[36]Belkouch J,Ould-Dris A,Taouk B.Removal of hazardous chlorinated VOCs over Mn-Cu mixed oxide based catalyst[J].J Hazard Mater,2009,169(1/2/3):758-765.
[37]Li T Y,Chiang S J,Liaw B J,et al.Catalytic oxidation of benzene over Cu O/Ce1-xMnxO2catalysts[J].Ald Aaly B Nvronmnal,2011,103(1/2):143-148.
[2]Carter W P L,Atkinson R.Atmospheric chemistry of alkanes[J].J Atmos Chem,1985,3(3):377-405.
[3]Aristizabal B H,Maya C,de Correa C M,et al.Orthodichlorobenzene oxidation over Pd/Co loaded sulfated zirconia and mordenite catalysts[J].Appl Catal A,2008,335(2):211-219.
[4]Aristizabal B H,de Correa C M,Serykh A I,et al.In situ FTIR study of the adsorption and reaction of ortho-dichlorobenzene on Pd-Co sulfated zirconia catalysts[J].Chin J Catal,2008,258(1):95-102.
[5]Luo J Y,Meng M,Li X,et al.Mesoporous Co3O4-Ce O2and Pd/Co3O4-Ce O2catalysts:Synthesis,characterization and mechanistic study of their catalytic properties for low-temperature CO oxidation[J].J Catal,2008,254(2):310-324.
[6]Abbasi Z,Haghighi M,Fatehifar E,et al.Synthesis and physicochemical characterizations of nanostructured Pt/Al2O3-Ce O2catalysts for total oxidation of VOCs[J].J Hazard Mater,2011,186(2/3):1445-1454.
[7]YaoRui(姚瑞),Ying Tao(尹涛),Bai Zilong(柏子龙),et al.The Efectt of Ce-doping on NO catalytic Oxidation on Mn-Co/Ti O2[J].Chem World(化学世界),2015,56(10):601-604.
[8]Li J,Zhao P,Liu S.Sn Ox-Mn Ox-Ti O2catalysts with high resistance to chlorine poisoning for low-temperature chlorobenzene oxidation[J].Appl Catal A,2014,482(7):363-369.
[9]Solsona B,Davies T E,Garcia T,et al.Total oxidation of propane using nanocrystalline cobalt oxide and supported cobalt oxide catalysts[J].Appl Catal,B,2008,84(1/2):176-184.
[10]Kodziej A,jewska J,Tyczkowski J,et al.Coupled engineering and chemical approach to the design of a catalytic structured reactor for combustion of VOCs:Cobalt oxide catalyst on knitted wire gauzes[J].Chem Eng J,2012,s 200-202(200):329-337.
[11]Liu Q,Wang L C,Chen M,et al.Dry citrate-precursor synthesized nanocrystalline cobalt oxide as highly active catalyst for total oxidation of propane[J].Chin J Catal,2009,263(1):104-113.
[12]Zhao Fuzhen(赵福真),Zhang Guanghong(张广宏),Zeng Penghui(曾鹏辉),et al.Preparation of CuxCo1-x/Al2O3/cordierite monolithic catalysts and the catalytic combustion of toluene[J].Chineese J Catal(催化学报),2011,32(5):821-826.
[13]Zhu J,Gao Q.Mesoporous MCo2O4(M=Cu,Mn and Ni)spinels:Structural replication,characterization and catalytic application in CO oxidation[J].Microporous Mesoporous Mater,2009,124(1/2/3):144-152.
[14]Feng Qi(丰奇),Wang Qian(王倩),Yu Yang(于洋),et al.Catalytic Degradation of 1,2,4-Trichlorobenzene with Co-Mn Polyhedral Composite by Sol-Gel Progrss[J].Chem World(化学世界),2017,58(1):7-12.
[15]Liu Dayong(刘大永),Fang Zhigang(方志刚),Zhao Zhenning(赵振宁),et al.Study on composition and catalytic property of Co-PB amorphous alloy[J].Chem World(化学世界),2015,56(11):641-645.
[16]Behar S,Gómez-Mendoza N A,Gómez-García M,et al.Study and modelling of kinetics of the oxidation of VOC catalyzed by nanosized Cu--Mn spinels prepared via an alginate route[J].Appl Catal A,2014,504(9):203-210.
[17]De Rivas B,López-Fonseca R,Jiménez-Gonzlez C,et al.Synthesis,characterisation and catalytic performance of nanocrystalline Co3O4for gas-phase chlorinated VOC abatement[J].J Catal,2011,281(1):88-97.
[18]Cai T,Huang H,Deng W,et al.Catalytic combustion of 1,2-dichlorobenzene at low temperature over Mn-modified Co3O4catalysts[J].Appl Catal B,2015,166-167(5),393-405.
[19]Shaheen W M,Ali A A.Characterization of solid-solid interactions and physico-chemical properties of copper-cobalt mixed oxides and CuxCo3-xO4spinels[J].Mater Res Bull,2001,36(9):1703-1716.
[20]Morales F,Grandjean D,Mens A,et al.X-ray absorption spectroscopy of Mn/Co/Ti O2Fischer-Tropsch catalysts:relationships between preparation method,molecular structure,and catalyst performance[J].J Phys Chem B,2006,110(17):8626-8639.
[21]Wang Y,Zhang C,Liu F,et al.Well-dispersed palladium supported on ordered mesoporous Co3O4for catalytic oxidation of o-xylene[J].Appl Catal B,2013,142-143(10):72-79.
[22]Carrillo A M,Carriazo J G.Cu and Co oxides supported on halloysite for the total oxidation of toluene[J].Appl Catal B,2015,164(4):443-452.
[23]Wang Hong(王虹),Zhao Zhen(赵震),Xu Chunming(徐春明),et al.Simultaneous Removal of Soot Particles and NO feom Diesel Engines over La BO3Perovskite-Type Oxides[J].Chineese J Catal(催化学报),2008,29(7):649-654.
[24]Hosseini S,Niaei A,Salari D.Preparation and characterization of nano-and non-nanoscale Co3O4spinels obtained from different methods and study of their performance in combustion of aromatics from polluted air-A comparison with Pt/gamma-Al2O3performance[J].J Environ Sci Health Part A Toxic/Hazard Subst Environ Eng,2012,47(12):1728-1732.
[25]Li S,Wang H,Li W,et al.Effect of Cu substitution on promoted benzene oxidation over porous Cu Co-based catalysts derived from layered double hydroxide with resistance of water vapor[J].Appl Catal B,2015,166-167(5):260-269.
[26]Khassin A A,Yurieva T M,Kustova G N,et al.Cobalt-aluminum coprecipitated catalysts and their performance in the Fischer-Tropsch synthesis[J].J Mol Catal A:Chem,2001,168(1/2):193-207.
[27]Huang H,Dai Q,Wang X.Morphology effect of Ru/Ce O2catalysts for the catalytic combustion of chlorobenzene[J].Appl Catal B,2014,158-159(3):96-105.
[28]Xie X,Shen W.Cheminform abstract:Morphology control of cobalt oxide nanocrystals for promoting their catalytic performance[J].Nanoscale,2010,41(3):50.
[29]Huang H,Dai Q,Wang X.Morphology effect of Ru/Ce O2catalysts for the catalytic combustion of chlorobenzene[J].Appl Catal B,2014,158-159(3):96-105.
[30]Li P,He C,Cheng J,et al.Catalytic oxidation of toluene over Pd/Co3Al O catalysts derived from hydrotalcite-like compounds:Effects of preparation methods[J].Appl Catal B,2011,101(3/4):570-579.
[31]Liu Qixian(刘启宪),Tang Xiaosu(唐小苏),Duan Yankang(段言康),et al.Effects of precipitations on the structure and catalytic activities of Co3O4catalysts for the N2O decomposition[J].J Mol Catal(分子催化),2016,30(4):363-371.
[32]Palacios-Hernandez T,Hirata-Flores G A,Contreras-López O E,et al.Synthesis of Cu and Co metal oxide nanoparticles from thermal decomposition of tartrate complexes[J].Inorg Chim Acta,2012,392(392):277-282.
[33]Zhang F,Wang X,Zhang X,et al.The catalytic activity of Ni O for N2O decomposition doubly promoted by barium and cerium[J].Chem Eng J,2014,256(8):365-371.
[34]Solsona B,Vazquez I,Garcia T,et al.Complete oxidation of short chain alkanes using a nanocrystalline cobalt oxide catalyst[J].Catal Lett,2007,116(3/4):116-121.
[35]T9rncrona A,Skoglundh M,Thormhlen P,et al.Low temperature catalytic activity of cobalt oxide and ceria promoted Pt and Pd:-influence of pretreatment and gas composition[J].Appl Catal B,1997,14(1):131-145.
[36]Belkouch J,Ould-Dris A,Taouk B.Removal of hazardous chlorinated VOCs over Mn-Cu mixed oxide based catalyst[J].J Hazard Mater,2009,169(1/2/3):758-765.
[37]Li T Y,Chiang S J,Liaw B J,et al.Catalytic oxidation of benzene over Cu O/Ce1-xMnxO2catalysts[J].Ald Aaly B Nvronmnal,2011,103(1/2):143-148.