钯基阳极氧化改性铝片催化剂制备及甲苯催化燃烧性能

Hans Journal of Chemical Engineering and Technology 化学工程与技术, 2019, 9(4), 299-304Published Online July 2019 in Hans. /journal/hjcethttps:///10.12677/hjcet.2019.94042Study on Catalytic Combustion of Toluene on Co-Based CatalystsShengkang Wang, Hua Pan*, Yiping Mao, Zhongyu Yang, Dingsheng Zhang, Yu MeiCollege of Biology and Environmental Engineering, Zhejiang Shuren University, Hangzhou ZhejiangReceived: Jun. 14th, 2019; accepted: Jun. 28th, 2019; published: Jul. 4th, 2019AbstractCo/CeO2 and Co/TiO2 catalysts were prepared by impregnation method. The catalytic behavior of Co/CeO2 and Co/TiO2 catalysts for catalytic combustion of toluene was investigated. It shows that the activity of Co/CeO2 catalyst is higher than that of Co/TiO2 catalyst. Co/CeO2 catalyst has a lower light-off temperature (T50= 210˚C), while the conversion of toluene can be stabilized at 80% at 225˚C on Co/CeO2. Co/CeO2 has a larger specific surface area, which increases the contact area of the reactants with the catalyst, resulting in the higher activity of the catalyst. The active compo-nent in the Co/CeO2and Co/TiO2catalysts is Co3O4. The higher content of O surf and Co3O4on the surface of Co/CeO2 catalyst may be the main reason for the higher activity of Co/CeO2 catalyst.KeywordsCobalt, Catalytic Combustion, TolueneCo基催化剂上甲苯催化燃烧的研究王晟康，潘华*，毛益萍，杨仲余，张鼎盛，梅瑜浙江树人大学生物与环境工程学院，浙江杭州收稿日期：2019年6月14日；录用日期：2019年6月28日；发布日期：2019年7月4日摘要采用浸渍法制备了Co/CeO2和Co/TiO2催化剂，考察了Co/CeO2和Co/TiO2催化剂催化燃烧甲苯的催化行为。

Cu x Co 1-x /Al 2O 3/FeCrAl 整体式催化剂上甲苯催化燃烧赵福真1曾鹏辉1,2季生福1,*杨肖1李成岳1(1北京化工大学化工资源有效利用国家重点实验室,北京100029;2中国石油大学(北京)重质油国家重点实验室,北京102200)摘要：以FeCrAl 合金薄片为基底,Al 2O 3浆料为过渡胶体,不同摩尔比的Cu 、Co 为催化活性组分,制备了一系列Cu x Co 1-x /Al 2O 3/FeCrAl(x =0-1)新型整体式催化剂.采用X 射线粉末衍射(XRD),扫描电子显微镜(SEM),X 光电子能谱(XPS)和程序升温还原(TPR)等手段对催化剂的结构进行了表征.在微型固定床反应器上评价了催化剂的催化甲苯燃烧性能.研究结果表明:在所制备的整体式催化剂上,当Cu 含量比较低时,形成了Cu-Co-O 固溶体;当Cu 含量比较高时,可以测得CuO 的衍射峰.催化剂表面颗粒大小和形貌与Cu 、Co 摩尔比密切相关.在催化剂表面,Co 以Co 2+和Co 3+价态存在,而Cu 主要以Cu 2+价态存在.催化剂中的Cu 可以改善Co 的氧化还原性,从而有利于催化剂活性的提高.在所制备的催化剂中,Cu 0.5Co 0.5/Al 2O 3/FeCrAl 催化剂具有最好的活性,甲苯在374o C 可以完全催化燃烧消除.关键词：FeCrAl;整体式催化剂;甲苯催化燃烧;X 射线粉末衍射;X 光电子能谱中图分类号：O643Catalytic Combustion of Toluene over Cu x Co 1−x /Al 2O 3/FeCrAl Monolithic CatalystsZHAO Fu-Zhen 1ZENG Peng-Hui 1,2JI Sheng-Fu 1,*YANG Xiao 1LI Cheng-Yue 1(1State Key Laboratory of Chemical Resource Engineering,Beijing University of Chemical Technology,Beijing 100029,P .R.China ;2State Key Laboratory of Heavy Oil Processing,China University of Petroleum,Beijing 102200,P .R.China )Abstract ：A series of Cu x Co 1-x /Al 2O 3/FeCrAl (x =0-1)catalysts were prepared using an FeCrAl alloy as support,a boehmite primer sol as the first washcoat layer and copper as well as cobalt oxides as the active washcoat layer.The structure of the catalysts was characterized using X-ray powder diffraction (XRD),scanning electron microscope (SEM),X-ray photoelectron spectroscopy (XPS)and temperature-programmed reduction (TPR).Toluene was chosen as the model compound to evaluate the catalytic activity in a conventional fixed-bed quartz reactor.Results indicate that a Cu-Co-O solid solution phase was present when the content of Cu in the catalysts was low and a CuO phase was present when the content of Cu was high.Both Co 2+and Co 3+were present on the surface of the obtained monolithic catalysts while Cu 2+was the main Cu species.The addition of a proper amount of copper oxide improved the reducibility of the cobalt oxide,which enhanced the catalytic activity of the catalysts.All the obtained catalysts showed good activity for the catalytic combustion of toluene.The Cu 0.5Co 0.5/Al 2O 3/FeCrAl catalyst had the best catalytic activity,and toluene was totally oxidized at 374°C over it.Key Words ：FeCrAl;Monolithic catalyst;Toluene catalytic combustion;X-ray powder diffraction;X-ray photoelectron spectroscopy[Article]物理化学学报(Wuli Huaxue Xuebao )Acta Phys.⁃Chim.Sin .,2010,26(12)：3285-3290December Received:June 9,2010;Revised:July 29,2010;Published on Web:October 19,2010.∗Corresponding author.Email:jisf@;Tel/Fax:+86-10-64419619.The project was supported by the National Natural Science Foundation of China (20473009).国家自然科学基金(20473009)资助项目ⒸEditorial office of Acta Physico ⁃Chimica Sinica3285Vol.26 Acta Phys.⁃Chim.Sin.2010V olatile organic compounds(VOCs)produced from many chemical and petrochemical industries are one of the major air pollutants.Besides their own malodorous and carcinogenic na-ture,they act as main precursors of ozone and smog formation[1-3]. Among all the methods for treatment of VOCs,catalytic com-bustion has been recognized as one of the most effective and economic technologies.This method has many advantages such as low temperature required for combustion ignition,high-er selectivity,and high energy efficiency[4-5].At present,the cat-alysts investigated for catalytic combustion of VOCs are main-ly noble metals and metal oxides[6].Although noble metal cata-lysts show good activity for the complete oxidation of VOCs, the high cost and the sensitivity to poisoning have led to the de-velopment of base metal catalysts for this application.Recent-ly,the development of transition metal oxides for catalytic oxi-dation of VOCs has been widely reported,and copper-contain-ing catalysts show high activity for the combustion of VOCs. Antunes et al.[7]reported catalytic oxidation of toluene over Cu-NaHY zeolites and found that a higher copper loading led to a higher catalytic activity.The toluene could be completely oxi-dized to CO2at350℃,when the copper loading was5%. Kovanda et al.[8]also concluded that the oxidation activity in toluene combustion increased with the increasing amount of easily reducible copper component.Lu et al.[9]prepared a se-ries of transition-metal catalysts using activated carbon(AC) as the support material,and copper,cobalt,iron,and nickel as the catalytic active phases.In their work,they observed that the activity of metal/AC followed a particular order:Cu>Co> Fe>Ni.However,the conventional pellet or granule catalysts loaded in fixed-bed reactors have high pressure drops and high gradi-ent of temperature thus depressed the activity of the catalysts. Recently,monolithic catalysts have increasingly attracted the attention of paring to the conventional cata-lysts,the monolithic catalysts have distinct advantages:better mechanical strength,lower capacity of mass and heat transfer, lower thermal expansion coefficient leading to a higher ther-mal shock resistance[10].The most widely used monolithic sub-strate is the monoliths made of ceramic or metallic materials. The metallic monoliths present a smaller wall thickness and higher thermal conductivity than the ceramic monoliths[11],thus for the reactions with high space velocity and heat exchange, such as toluene combustion reaction,the metallic monolithic catalysts have a promising application.In this work,a series of copper-cobalt mixed oxide catalysts with different Cu/Co ratios washcoated on metallic monoliths were reported.The performance of the obtained catalysts for the toluene catalytic combustion was evaluated and the cata-lysts were characterized by XRD,SEM,XPS,and TPR tech-niques.1Experimental1.1Catalyst preparationThe metallic monolithic catalysts were prepared using the FeCrAl alloy foils(OC404,Sandvik Steel,Sweden)as sup-ports.The alloy foils were rolled into several cylinders in dif-ferent diameters and50mm in length.The supports were pre-treated successively in basic,acidic and ethanol solution,and then thoroughly rinsed in de-ionized water,and finally the pre-treated supports were calcined at950℃for15h in air.In or-der to improve the adhesion between the washcoat layers and the heat-treated metallic supports,a boehmite primer sol was used as first washcoat layer,then dried at room temperature in air and thereafter at120℃for3h and calcined at500o C for4 h,and the monolithic support(Al2O3/FeCrAl)was formed.The Cu x Co1-x/Al2O3/FeCrAl(x=0-1)catalysts were prepared as follows:the solutions of Cu(NO3)2·3H2O(analytical re-agent)and Co(NO3)2·6H2O(analytical reagent)were mixed in appropriate ratios.The mixture was added into the boehmite primer sol with a total40%(w)metal content to obtain the slur-ry.The monolithic support(Al2O3/FeCrAl)was inserted into the above slurry and held for1min,taken out at the constant speed of3cm·min-1,then dried at room temperature in air and thereafter at120℃for3h,and then calcined at500℃for4h. The coating procedure should be repeated to achieve the de-sired coating amount.Finally,the Cu x Co1-x/Al2O3/FeCrAl metal support monolithic catalysts were obtained.The compositions of the catalysts were listed in Table1.1.2Catalytic activity measurementsCatalytic combustion experiments were performed in a con-ventional fixed-bed quartz reactor(i.d.,8mm;length,300 mm)at atmospheric pressure.The reactant gas mixture was prepared by passing air through a conical flask filled with liq-uid toluene,which was kept at0o C.The reaction feed consist-ed of1000μL·L-1of toluene in dry air and the space velocity was5.6×104mL·g-1·h-1.The reaction was stabilized for20Table1Compositions of Cu x Co1−x/Al2O3/FeCrAl catalystsSample1234567CompositionCu/Al2O3/FeCrAlCu0.9Co0.1/Al2O3/FeCrAlCu0.75Co0.25/Al2O3/FeCrAlCu0.5Co0.5/Al2O3/FeCrAlCu0.25Co0.75/Al2O3/FeCrAlCu0.1Co0.9/Al2O3/FeCrAlCo/Al2O3/FeCrAln(Cu)/(n(Cu)+n(Co))10.890.740.480.240.09Cu loding(%)8.07.26.04.02.00.8d(311)/nm--0.244730.244550.244030.243900.243783286２Ｏ３Ｏ４０５Ｏ６Ｏ７Ｏ８０一．３∞一＞＝∽ｃ①一ｃZHAO Fu-Zhen et al .：Catalytic Combustion of Toluene over Cu x Co 1-x /Al 2O 3/FeCrAl Monolithic CatalystsNo.12min at the required temperature,and the outlet products weremeasured with online gas chromatography (Beijing East and West Electronics Institute,GC-4000A)equipped with a flame ionization detector (FID).The catalyst temperature was con-trolled with a K-type thermocouple placed in the vicinity of the catalyst bed.In every case,carbon dioxide and water were the only reaction products detected along the whole experiment.1.3Catalysts characterizationThe phase structure of the samples was characterized by X-ray diffraction (XRD)using a Japan Rigaku D/Max 2500VB2+/PC diffractometer with a Cu K αradiation operating at 200mA and 40kV .The morphology of the samples was ob-served by a Japan HITACHI S-4700scanning electron micro-scope (SEM).X-ray photoelectron spectroscopy (XPS)experi-ments were carried out on an UK ESCALAB250instrument (Thermo Electron Co.)using Mg K αas the exciting radiation at the constant pass energy of 30eV .Binding energies were cal-ibrated using the carbon present as a contaminant (binding en-ergy of C 1s is 285.0eV).The surface atomic compositions of all samples were calculated from photoelectron peak areas for each element after correction for instrument parameters.The temperature-programmed reduction (TPR)measurements were carried out using America Thermo Electron Corporation TPD/R/O 1100series catalytic surfaces analyzer equipped with a TCD detector.0.08g of the sample was loaded and preheated with 10%(volume fraction,same as below)O 2/He mixture at 500℃for 1.5h.After cooling down to room temperature,5%H 2/N 2mixture was introduced into the instrument and the tem-perature was ramped to 800℃at a heating rate of 5℃·min -1.Water produced by the sample reduction was condensed in a cold trap before reaching the detectors.Only H 2was detected in the outlet gas confirming the effectiveness of the cold trap.2Results and discussion2.1XRD measurementsThe XRD patterns of the pre-oxidized FeCrAl metal support and Cu x Co 1-x /Al 2O 3/FeCrAl monolithic catalysts are presented in Fig.1.For FeCrAl metal suppor t,after the heat treatment at950℃for 15h,the characteristic peaks of FeCr (JCPDS 34-0396)and α-Al 2O 3(JCPDS 88-0826)were observed.The diffraction peaks of Co 3O 4(2θ=31.20°,36.84°,44.63°,59.46°and 65.35°,JCPDS 42-1467)could be seen when x =0(Co/Al 2O 3/FeCrAl).With the increase of x ,the diffraction peaks had a little shift.Take the most intense peak at 2θ=36.84°as an example:when x =0,the d value for (311)plane is 0.24378nm (Table 1);when x =0.5,the d value for (311)plane is 0.24455nm;when x =0.75,the d value for (311)plane is 0.24473nm.This is because the radius of Cu 2+(0.062nm)is larger than that of Co 3+(0.052nm),which leads to the expansion of Co 3O 4lat-tice when Cu 2+migrates partially into the cubic structure.There-fore,changes in the d (311)value of the samples indicate that the missing CuO phase at low Cu loading formed the Ce-Co-O sol-id solution in these catalysts [12].Cu and Co can form a Cu-Co-O solid solution that was also been found by Rad-wan [13].When x >0.5,the most intense peaks of bulk CuO at 35.5°and 38.8°[4]were detected.2.2Surface morphology of the samplesFig.2shows the morphology of the FeCrAl support and Cu x Co 1-x /Al 2O 3/FeCrAl monolithic catalysts.From the surface view of FeCrAl (Fig.3(A,B)),it can be seen that after pretreatment in air at 950℃for 15h,the surface became more coarse and had more macropores.This benefited the coating of Cu x Co 1-x /Al 2O 3.As for Cu x Co 1-x /Al 2O 3/FeCrAl (x =0-1)monolithic catalysts,the surface morphology changed significantly with the x value.For the catalyst with x =1,namely Cu/Al 2O 3/FeCrAl (sample 1),the surface was quite homogenous and smooth,only several large particles could be found.However,the surface morpholo-gy of the catalysts changed greatly with the decrease of Cu con-tent.When x =0.9,although the surface was still smooth,there were some small particles appeared (sample 2).When x =0.75and x =0.5(samples 3and 4),the surface became inhomoge-nous gradually,the particles became bigger and the heap of par-ticles were very loose.When x further decreased to 0.25(sam-ple 5),the surface morphology of the catalyst became smooth again and almost no particles could be found.When x =0.1(sample 6),the surface feature was different from other cata-lysts,there appeared the big clusters of particles,the dispersion was inhomogenous and the particle size was large.When x =0(sample 7),the particles of the catalyst decreased obviously,the clusters increased and the heap of the particles was com-pact.2.3X-ray photoelectron spectroscopyXPS spectra of Cu 2p of catalysts 1,4,and 6are shown in Fig.3(A).The presence of a higher Cu 2p 3/2binding energy (933.0-933.8eV)and the pronounced shake-up peak (940.0-945.0eV)are the characteristics of CuO,while a lower Cu 2p 3/2binding energy (932.2-933.1eV)and the absence of the shake-up peak are the characteristics of Cu 2O [15-16].After the Gauss model fitting,it can be noticed that the given catalysts exhibit the Cu 2p 3/2main peak at about 933.2eV with thechar-Fig.1XRD spectra of the samples(a)FeCrAl foil pre-oxidized at 950℃for 15h;(1-7)Cu x Co 1-x /Al 2O 3/FeCrAlcatalysts;(★)FeCr,(▼)Cu-Co-O,(●)a -Al 2O 3.(◆)CuO3287Ａ２５哥３霞尊Ⅺ’●Ｌ‘。

CHEMICAL INDUSTRY AND ENGINEERING PROGRESS 2010年第29卷第11期·2090·化工进展TiO2-SiO2/ZrO2催化剂的制备及催化燃烧甲苯性能刘媛1，龙千明1，白云鹤2，吕斯濠2，范洪波2（1华南理工大学环境科学与工程学院，广东广州 510006；2东莞理工学院化学与环境工程学院，广东东莞 523808）摘要：以ZrO2为载体，制备出TiO2-SiO2/ZrO2催化剂，用XRD和SEM对其进行表征；并将催化剂用于甲苯的催化燃烧，探讨了温度、气流速率、进气浓度等因素对甲苯催化效率和反应产物CO、CO2选择性的影响。

结果表明：催化剂中的TiO2呈锐钛矿晶型，催化剂颗粒成功负载于ZrO2表面；随着温度升高，甲苯催化效率增大，350 ℃时能达到最大值100%，CO2选择性随之增大，但CO选择性却减少；气流速率增大导致甲苯催化效率增大，CO选择性稍稍增大，而CO2选择性减小；进气浓度从25 mg/L增加到100 mg/L时，甲苯催化效率逐渐减小，CO2选择性减小，CO选择性稍有增大。

关键词：TiO2-SiO2/ZrO2催化剂；催化燃烧；甲苯中图分类号：X 511 文献标志码：A 文章编号：1000–6613（2010）11–2090–06Preparation of TiO2-SiO2/ZrO2 catalyst for catalytic combustion of toluene LIU Yuan1，LONG Qianming1，BAI Yunhe 2，LÜ Sihao2，F AN Hongbo2（1College of Environmental Science and Engineering，South China University of Technology，Guangzhou 510006，Guangdong，China；2College of Chemistry and Environmental Engineering，Dongguan University of Technology，Dongguan 523808，Guangdong，China）Abstract：TiO2-SiO2/ZrO2 catalyst was prepared using ZrO2 as carrier and characterized with XRD and SEM. The catalyst was used for catalytic combustion of toluene，and the effect of temperature，gas flow rate and inlet concentration of toluene was investigated. Results showed that the TiO2 particles with anatase phase have been successfully fixed on the surface of ZrO2. As the increase in temperature，both the catalytic rate of toluene and the productivity of CO2 were increased，while the productivity of CO was decreased. 100% catalytic rate of toluene was achieved at 350℃. The increase in gas flow rate could lead to the increase in catalytic rate of toluene，the productivity of CO was a little increased while the productivity of CO2 was decreased. When the inlet concentration of toluene was increased from 25 mg/L to 100 mg/L，the catalytic rate of toluene was decreased gradually，the productivity of CO2 was decreased and the productivity of CO was a little increased.Key words：TiO2-SiO2/ZrO2 catalyst；catalytic combustion；toluene工业企业和汽车排放的挥发性有机废气VOCs 是大气的主要污染物之一，不仅会造成大气的光化学污染，而且毒性大，严重影响人体健康[1]。

[19]中华人民共和国国家知识产权局[12]发明专利申请公开说明书[11]公开号CN 1623655A [43]公开日2005年6月8日[21]申请号200410061031.4[22]申请日2004.10.26[21]申请号200410061031.4[71]申请人福州大学地址350015福建省福州市工业路523号[72]发明人王榕 李敏超 林墀昌 陈天文 林建新 [74]专利代理机构福州智理专利代理有限公司代理人丁秀丽[51]Int.CI 7B01J 23/44B01J 37/02权利要求书 2 页 说明书 7 页[54]发明名称钯—氧化铝催化剂及其制备方法[57]摘要本发明公开了一种钯－氧化铝催化剂及其制备方法，它涉及一种以预先涂覆适宜量碱土金属氧化物，并经900－995℃(起始氧化铝为γ－Al 2O 3)或500－850℃(起始氧化铝为δ，θ－Al 2O 3)高温焙烧过的Al 2O 3为载体(比表面积约60－130m 2/g，孔容积≥0.5ml/g，Na 2O含量＜0.05％)，以钯为主活性成分，担载量为0.15－0.24％(wt)，采用浸渍方法制备。

该催化剂可在保持合理的金属钯层厚度(30－60μm)和较高催化活性的前提下将贵金属Pd降低到0.2％左右。

200410061031.4权 利 要 求 书第1/2页 1.一种钯-氧化铝催化剂，其特征在于：以预先涂覆碱土金属氧化物，并且当起始氧化铝为γ-A l2O3经过900-995℃高温煅烧、或当起始氧化铝为δ，θ-Al2O3经过500--850℃高温煅烧的氧化铝为载体，以干的氧化铝载体重量为基准，碱土金属氧化物涂覆量为0.1～10％wt；以金属钯为主活性成份，以干的氧化铝载体重量为基准，钯的担载量为0.15-0.24％wt；金属钯层厚度为30--90μm。

2.按照权利要求1所述的钯-氧化铝催化剂，其特征在于：高温煅烧后的氧化铝的B E T表面积为60-130m2/g，平均孔半径为10-14n m，N a2O含量＜0.05％，以干的载体氧化铝重量为基准，碱土金属氧化物涂覆量最好是0.1～5％wt，更好是0.1～3％wt。

专利名称：用于催化燃烧甲苯的复合型非贵金属氧化物催化剂及其制备方法和应用
专利类型：发明专利
发明人：刘程,李飞,仵静,侯鑫,黄伟,兰力强,庞菊玲,满雪,高明明
申请号：CN201611073528.7
申请日：20161129
公开号：CN106732539A
公开日：
20170531
专利内容由知识产权出版社提供
摘要：本发明提供了一种用于催化燃烧甲苯的复合型非贵金属氧化物催化剂，该催化剂以TiO为载体，以负载在TiO上的复合型非贵金属氧化物为活性组分，所述复合型非贵金属氧化物的结构式为：SnMnO，x满足：0.05≤x≤0.5，所述复合型非贵金属氧化物的质量占催化剂质量的10％～30％。

本发明还提供了一种制备上述催化剂的方法，以及利用该催化剂对甲苯进行催化燃烧的方法。

本发明催化剂为复合型非贵金属氧化物催化剂，能够快速、高效地消除工业尾气中的甲苯。

申请人：西安元创化工科技股份有限公司
地址：710061 陕西省西安市雁塔区雁翔路99号
国籍：CN
代理机构：西安创知专利事务所
代理人：谭文琰
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