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1.
Large amounts of water containing-ammonium nitrogen(NH4+-N)have attracted increasing attention.Catalytic ozonation technology,involving the generation of hydroxyl radical(OH)with strong oxidation ability,was originally utilized to degrade organic-containing wastewater.In this paper,Ce/MnOx composite metal oxide catalysts prepared with different preparation conditions were used to degrade wastewater containing inorganic pollutant(NH4+-N).The as-prepared catalyst features were characterized using X-ray diffraction(XRD),Brunauer-Emmett-Teller method(BET),scanning electron microscopy(SEM),energy dispersive X-ray spectroscopy(EDS),Fourier transform infrared spectroscopy(FTIR),X-ray photoelectron spectroscopy(XPS)and H2-temperature programmed reduction(H2-TPR)techniques.The results show that the catalyst,prepared by conditions with precipitant Na2CO3 and Ce/Mn molar ratio 1:2 calcined at 400℃for 3 h in pH 11.0,displays the optimal performance,with the removal rate of NH4+-N and selectivity to gaseous nitrogen,88.14 wt%and 53.67 wt%,respectively.The effects of several operating factors including solution pH,initial NH4+-N concentrations and scavengers were evaluated.In addition,XRD patterns of catalyst with the best performance and the comparative study on decontamination of NH4+-N by various processes(O3,catalyst and catalyst/O3)show that the primary metal oxides are CeO2 and MnO2 in Ce/MnOx composite metal oxide catalysts,which have a synergistic effect on the catalytic ozonation of NH4+-N,and the new phase MnO2 plays a great role.After 5 consecutive use cycles,the degradation efficiency is declined slightly,and can still achieve better than 70 wt%over 1 h reaction.Additionally,the application of catalytic ozonation for actual wastewater on the removal rate of NH4+-N was investigated.Possible mechanism and degradation pathway of NH4+-N were also proposed.In a word,the application of CeO2-MnO2 composite metal oxide catalysts in catalytic ozonation can be regarded as an effective,feasible and promising method for the treatment of NH4+-N.  相似文献   

2.
A series of 3DOM CeMnO_3 perovskite catalysts were prepared by poly(methyl methacrylate) hardtemplating-excessive impregnation method at calcination temperature of x℃(x=600,700,800) and the heating rate of y ℃/min(y=1,2,5,10).The samples were characterized by Brunauer-Emmett-Teller method,scanning electron microscopy,transmission electron microscopy,H_2-temperature programmed reduction,X-ray photoelectron spectroscopy,X-ray diffraction,moreover,the effect of the calcination process on the catalytic activity of the samples were discussed by the catalytic combustion of toluene.The results show that the 3DOM CeMnO_3 catalysts calcined at 600℃ promote the formation of a perovskite structure,inhibit the reduction of the Mn~(4+) species in the catalyst with high temperature.The catalyst expresses the complete macroporous structure,large specific surface area(38.8 m~2/g),higher adsorption oxygen concentration and Mn~(4+) substance concentration,with a low T_(90%)=172℃.By preparing the catalysts at different calcination heating rates,it can be concluded that the catalyst possesses a high concentration of adsorbed oxygen and a low reduction temperature and a large specific surface area(40.42 m~2/g) greatly promotes adsorption stage catalytic oxidation reaction and catalytic combustion of toluene at low temperature under the heating rate of 5℃/min.When the heating rate is 1 ℃/min,the catalyst has a complete macroporous structure(250 nm),which is beneficial to the exchange of macromolecular substances during the catalytic reaction and the catalyst has a high concentration of lattice oxygen suitable for the catalysis of toluene in high temperature flue gas combustion.  相似文献   

3.
The effect of manganese and/or ceria loading of V_2 O_5-Mo_O_3/TiO_2 catalysts was investigated for selective catalytic reduction(SCR) of NO_x by NH_3.The manganese and/or ceria loaded V_2 O_5-MoO_3/TiO_2 catalysts we re prepared by the wetness impregnation method.The physicochemical characteristics of the catalysts were thoroughly characterized.The catalytic performance of 1.5 wt% V_2 O_5-3 wt% MoO_3/TiO_2(V1.5 Mo3/Ti) is greatly enhanced by addition of 2.5 wt% MnO_x and 3.0 wt% CeO_2(V1.5 Mo3 Mn2.5 Ce3/Ti) below450℃.Compared with the V1.5 Mo3/Ti catalyst with NO_x conversion of 75% at 275 ℃,V1.5 Mo3 Mn2.5 Ce3/Ti exhibits higher NO_x conversion of 84% with good resistance to SO_2 and H_2 O at a gas hourly space velocity value of 150000 h~(-1).The active manganese,cerium,molybdenum,and vanadium oxide species are highly dispersed on the catalyst surface and some synergistic effects exist among these species.Addition of MnO_x significantly enhances the redox ability of the cerium,vanadium,and molybdenum species.Addition of Ce increases the acidity of the catalyst.More active oxygen species,including surface chemisorbed oxygen,form with addition of Mn and/or Ce.Because of the synergistic effects,appropriate proportions of manganese in different valence states exist in the catalysts.In summary,the good redox ability and the strong acidity contribute to the high NH3-SCR activity and N2 selectivity of the V1.5 Mo3 Mn2.5 Ce3/Ti catalyst in a wide temperature range.And the V1.5 Mo3 Mn2.5 Ce3/Ti catalyst shows good resistance to H_2 O and SO2 in long-time catalytic testing,which can be ascribed to the highly sulfated species adsorbed on the catalyst.  相似文献   

4.
Mesoporous CeMnOx composite oxides catalysts were prepared by surfactant-assisted co-precipitation method and used for the catalytic oxidation of toluene.The effect of different cerium precursors[Ce(NO_3)_3 and(NH_4)_2 Ce(NO_3)_6] on catalyst structure,surface properties and toluene combustion activities of mesoporous CeMnO_x catalysts were investigated.The Ce(Ⅲ)MnO_x catalyst prepared from Ce(NO_3)_3 precursor shows higher catalytic activity,with a 90% conversion temperature of 240℃,which is better than the Ce(Ⅳ)MnO_x catalyst derived from(NH_4)_2 Ce(NO_3)_6] precursor.On the basis of characterizations,it reveals that abundant surface content of Mn~(4+),better redox behavior and larger concentration of surface active oxygen species are responsible for the excellent catalytic performance.  相似文献   

5.
崔永康  邢奕  苏伟  王嘉庆 《工程科学学报》2021,43(11):1534-1542
ZSM-5是一种常用来吸附甲苯的微孔吸附剂,选择三种碱金属Li、Na和K对ZSM-5进行改性,结合表征手段和数学模型的方式研究引入ZSM-5中的碱金属对微孔结构和吸附甲苯的影响。在此实验中,分别从吸附容量、放热能量、扩散阻力和脱附活化能四方面深入探讨碱金属对吸附甲苯的影响规律。基于实验结果得知:碱金属的引入改变了ZSM-5分子筛的微孔结构并呈现出一定的规律。随着离子半径(Li+ Na?ZSM-5 > K?ZSM-5。静态饱和吸附量呈Li?ZSM-5(0.363 mmol·g?1)>Na?ZSM-5(0.360 mmol·g?1)>K?ZSM-5(0.325 mmol·g?1)排序。恒定浓度波模型很好的描述甲苯在ZSM-5上的吸附扩散行为,空间位阻和静电束缚力分别在高低进气浓度条件下对甲苯在ZSM-5孔道中的扩散占据主导作用,较高进气质量浓度(155 mg·m?3)条件下,碱金属改性对扩散阻力影响规律为Li?ZSM-5Na?ZSM-5>K?ZSM-5。结合脱附动力学分析,Na?ZSM-5因具有较大的孔径和适中的吸附强度,表现出更好的再生潜能。本研究从空间位阻和吸附强度两方面系统阐述了碱金属改性对甲苯吸附行为的影响机理,为在复杂的实际环境应用中选择合适的吸附剂提供了一定的参考意义。   相似文献   

6.
This work was devoted to the study of the selective catalytic reduction of NO by NH_3 on calcined and hydrothermal treated cerium loaded zeolite catalysts.The parent faujasite zeolite Na-F(Si/Al=1.32 and S_(BET)=749 m~2/g) used as support for the preparation of the catalysts was obtained from industrial sodium metasilicate and aluminum scraps.As expected,the NO conversion increases with increasing the percentage of cerium in the structure of the faujasite zeolite.Total NO conversion into N_2 is reached at 400℃at a space velocity of 250 000 h~(-1).The high conversion is due to the redox shift between Ce~(3+)/Ce~(4+)and the strong acid sites related to the rare earth present in the framework that is the key in SCR of NO process.Moreover,the highest loaded cerium catalyst retains almost its activity after hydrothermal treatment at 850℃.This higher loading is desirable for both activity and stability provided that two stages of preparation are used to put the Ce ions in the sodalite cages.  相似文献   

7.
Cu/ZSM-5 and CeO_2-modified Cu/ZSM-5 catalysts were prepared by a wetness impregnation method. The addition of CeO_2 was found to enhance the NO_x selective catalytic reduction(SCR) activity of the catalyst at low temperatures, but the high-temperature activity was weakened. The catalysts were characterized by X-ray diffraction(XRD), nitrogen physisorption, inductively coupled plasma optical emission spectrometry(ICP-OES), X-ray photoelectron spectroscopy(XPS), electron paramagnetic resonance(EPR), H_2 temperature-programmed reduction(TPR) and NH_3 temperature-programmed desorption(TPD). The results showed that more CuO clusters instead of isolated Cu~(2+) species were obtained on the modified catalyst. These active CuO clusters, as well as the Cu-Ce synergistic effect, improved the redox property of the catalyst and low-temperatures SCR activity via promoting the oxidation of NO to NO_2 and fast SCR reaction. The loss in high-temperatures activity was attributed to the enhanced competitive oxidation of NH_3 by O_2 and decreased surface acidity of the catalyst.  相似文献   

8.
In this paper,MCM-41 was synthesized by a soft template technique and MCM-41 supported CuO-CeO_2 nano-sized catalysts with different Cu/Ce molar ratios were prepared by a deposition-precipitation method.N_2 adsorption,HRTEM-EDS,H_2-TPR,XPS characterization,as well as catalytic activity and durability tests for the catalytic combustion of chlorobenzene(CB) were conducted to explore the relationship between the structure and catalytic performance of the catalysts.It is revealed that cuCe(6:1)/MCM-41 has the highest activity and can completely catalyze the degradation of CB at 260℃.The reasons for the high activity of the catalysts are as follows:MCM-41,a type of mesoporous material which has large pore size and large specific surface area,is suitable as a catalyst carrier.The average diameter of nano-sized CuO and CeO_2 particles is about 3-5 nm and adding CeO_2 improves the dispersion of active component CuO,which are highly and evenly dispersed on the surface of MCM-41.Characterization results also explain why MCM-41 supported CuO-CeO_2 with appropriate proportion can highly enhance the catalytic activity.The reason is that CeO_2 acting as an oxygen-rich material can improve the mobility of oxygen species through continuous redox between Ce~(4+)and Ce~(3+),and improve the catalytic performance of CuO for CB combustion.Besides,CuCe(6:1)/MCM-41 also displays good durability for CB combustion,both in the humid condition and in the presence of benzene,making it a promising catalytic material for the elimination of chlorinated VOCs.  相似文献   

9.
Hierarchical ZSM-5(HZ) molecular sieves based on fly ash were synthesized using a method combining water heat treatment with step-by-step calcination.The coupling catalysts between La_(1-x)Ce_xMn_(0.8)-Ni_(0.2)O_3(x ≤ 0.5) perovskites and HZ were prepared through the impregnation method,which were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),high-resolution transmission electron microscopy(HRTEM),N_2 adsorption,X-ray photoelectron spectroscopy(XPS),NH_3-temperature programmed desoprtion(NH_3-TPD),H_2-temperature programmed reduction(H_2-TPR) and O_2-TPD techniques and investigated regarding pentanal oxidation at 120-390℃ to explore the effects of Ce doping on the catalytic activity and the active oxygen species of the coupling catalysts,meanwhile,the reaction mechanism and pathway of pentanal oxidation were also studied.The results reveal that Ce substitution at La sites can change the electronic interactions between all the elements and promote the electronic transfer among La,Ce,Ni,Mn and HZ,influencing directly the physicochemical characteristics of the catalysts.Moreover,the amount and transfer ability of surface adsorbed oxygen(O_2~-and O~-)regarded as the reactive oxygen species and the low temperature reducibility are the main influence factors in pentanal oxidation.Additionally,La_(0.8)Ce_(0.2)Mn_(0.8)Ni_(0.2)O_3/HZ exhibits the best catalytic activity and deep oxidation capacity as well as a better water resistance due to its larger amount of surface adsorbed oxygen species and higher low temperature reducibility.What's more,appropriate Ce substitution can significantly enhance the amount of O_2~-ions,which can distinctly enhance the catalytic activity of the catalyst,and moderate acid strength and appropriate acid amount can also facilitate the improvement of the pentanal oxidation activity.It is found that there is a synergic catalytic effect between surface acidity and redox ability of the catalyst.According to the in situ DRIFTS and GC/MS analyses,pentanal can be oxidized gradually to CO_2 and H_2 O by the surface oxygen species with the form of adsorption in air following the Langmuir-Hinshelwood(L-H) reaction mechanism.Two reaction pathways for the pentanal oxidation process are proposed,and the conversion of the formates to carbonates may be one of the main rate-determining steps.  相似文献   

10.
So far,it is still a controversial issue which status of gold species is a better active site for catalyzing CO oxidation.Herein,the influence of the different atmospheres pretreatment(oxidative and reductive)on gold state of Au/La-CeOx(1 wt%gold loading)catalyst during CO oxidation was studied.The changes of Au species were monitored by combined in situ diffuse reflectance infrared Fourier transform spectroscopy(in situ DRIFTS)and X-ray photoelectron spectroscopy(XPS).For the sample pretreated with oxidative atmosphere,the data show that the initial Au3+is transformed to Auδ+(0<δ<1)during CO oxidation,which is a key step to lead to higher reactivity.For the sample after reductive atmosphere pretreatment,Auδ+is mixed with a small amount of Au0which can be converted to Auδ+with the increase of temperature in reaction.Meanwhile,the sample always maintains high activity during the reaction.Therefore,the Au?+obtained by reductive pretreatment is more active than the Au3+obtained by oxidative treatment in catalyzing CO oxidation.  相似文献   

11.
The effect of Ce on the structure of MoVNbCeO multi-metal oxide catalysts and the performance of ethane selective oxidation was investigated. These multi-metal oxide catalysts with superior oxidizability exhibit high catalytic activity, and vanadium acts as the active center for ethane oxidation reaction. The improved catalytic activity is related to the increased V5+ content on the catalyst surface, which results from the enhanced transformation of the electrons between V and Ce. Moreover, Ce effectively promotes oxygen adsorption, activation, and mobility. And the presence of Ce can also prevent MoO3 formation and stabilize the Mo5O14-like structure. In addition, the catalyst with a moderate amount of Ce exhibits outstanding catalytic performance. Especially, the MVN-Ce catalyst with a Ce/V ratio of 0.1 exhibits the best performance: the total selectivity of the catalyst toward C2H4 and CH3COOH is the highest (72%) at the ethane conversion of 31%. Therefore, MoVNbCeO multi-metal oxides are promising candidates for selective oxidation.  相似文献   

12.
CuMn mixed oxides catalysts doped with La were prepared following a co-precipitation method and used for the catalytic oxidation of toluene. Catalysts properties of the catalysts were investigated by X-ray diffraction, N_2 adsorption/desorption,scanning electron microscopy, H_2-temperature-programmed reduction(H_2-TPR), O_2-temperature-programmed desorption(O_2-TPD) and X-ray photoelectron spectroscopy techniques. Characterization data reveal that the phase change and decrease in crystallinity of the La-doped catalysts increase the number of oxygen vacancies. Improvements in reducibility and an increase in the amount of chemisorbed oxygen of the La-doped catalysts were also verified by H_2-TPR and O_2-TPD. The activity of the CuMn mixed oxides catalysts is significantly improved by the addition of a nominal amount of La. The CuMn/La-4 mol% catalyst exhibits the best catalytic activity, with a 90%conversion temperature of 255 ℃,attributed to a high Mn~(3+)ratio, superficial chemisorbed oxygen,and high surface area. This study indicates La to be a promising dopant for Cu-Mn catalysts toward toluene oxidation.  相似文献   

13.
The interaction between Pt and its various supports can regulate the intrinsic electronic structure of Pt particles and their catalytic performance.Herein,Pt/CeO_2 and Pt/SiC catalysts were successfully prepared via a facile Pt colloidal particle deposition method,and their catalytic performance in CO oxidation was investigated.XRD,TEM,XPS and H_2-TPR were used to identify the states of Pt particles on the support surface,as well as their effect on the performance of the catalysts.Formation of the Pt-O-Ce interaction is one of the factors controlling catalyst activity.Under the oxidative treatment at low temperature,the Pt-O-Ce interaction plays an important role in improving the catalytic activity.After calcining at high temperature,enhanced Pt-O-Ce interaction results in the absence of metallic Pt~0 on the support surface,as evidenced by the appearance of Pt~(2+) species.It is consistent with the XPS data of Pt/CeO_2,and is the main reason behind the deactivation of the catalyst.By contrast,either no interaction is formed between Pt and SiC or Pt nanoparticles remain in the metallic Pt~0 state on the SiC surface even after aging at 800℃in an oxidizing atmosphere.Thus,the Pt/SiC shows better thermal stability than Pt/CeO_2.The interaction between Pt and the active support may be concluded to be essential for CO oxidation at low temperature,but strong interactions may induce serious deactivation of catalytic activity.  相似文献   

14.
CeO2,La2O3,and CeO2-Y2O3 oxides were coated on the surface of spherical granular AI2O3(3-5 mm)through impregnation method,and proved as better supports of Pd and Pt catalysts.The influences of rare earth metal doping on the adsorption rates of Pd and Pt ions,as well as the catalytic performance,were investigated.Results show that the H2PtCl6·6H2O adsorption rates of the Al  相似文献   

15.
The utilization of pure hydrogen as an energy source in fuel cells gave rise to renewed interest in developing active and stable water-gas shift catalysts. Gold catalysts have proven to be very efficient for water-gas shift reaction at low temperature. The aim of the present study was to investigate the effect of:(i) different preparation methods(impregnation and coprecipitation) to obtain a modified ceria support,and(ii) the amount of Y_2 O_3(1.0 wt%, 2.5 wt%, 5.0 wt% and 7.5 wt%) as dopant on the water-gas shift activity of Au/CeO_2 catalysts. An extended characterization by means of S_(BET), XRD, HRTEM/HAADF, FTIR,H_2-TPR and CO-TPR measurements in combination with careful evaluation of the catalyst behavior allowed to shed light on the parameters governing the water-gas shift activity. The catalysts show very high activity(90% CO conversion) in the temperature range 180-220 ℃,with a slightly better performance of the gold catalysts on supports prepared by impregnation. The decreased activity with increasing Y_2 O_3 concentration is related to the hindering of oxygen mobility due to ordering of surface oxygen vacancies in vicinity of segregated Y~(3+). The effect of catalyst pre-treatments and the stability of the best performing samples were examined as well.  相似文献   

16.
SAPO-34,SAPO-5/34 based catalysts doped with Cu,Ce as active components were synthesized via a one-pot hydrothermal method by using different amounts of additive(a-cellulose),and their catalytic activities were measured for selective catalytic reduction(SCR) of NO with NH3.The synthesized Cu-Ce co-doped products switch from cubic SAPO-34,to flower-like aggregated SAPO-5/34,hybrid crystal SAPO-5/34,and finally to spherical aggregated SAPO-34 with the increase of α-cellulose amount.The Cu-Ce co-doped SAPO-5/34 hybrid crystal structure catalysts with 0.75 mol ratios of C/P(Cu-Ce/SP-0.75)exhibit excellent NH3-SCR activity with higher than 90% NO_x conversion in the temperature range of 180-450℃,at WHSV of 20000 mL/(g·h).Furthermore,the catalyst displays outstanding sulfur resistance and NO_X conversion maintains above 90% at 200-450℃ after adding 100 ppm of SO_2.The characteristic results suggest that the high deNO_X performance of Cu-Ce/SP-0.75 is due to the enhanced accessibility,abundant activity species,excellent redox property and high adsorptive and activated capacity for NH3.  相似文献   

17.
Cerium-promoted silica supported copper chromite catalyst was synthesized from acid hydrolysis of sodium silicate by sol-gel method.The catalyst was characterized by Brunauer-Emmett-Teller(BET)method,field-emission scanning electron microscopy(FESEM),X-ray diffraction(XRD),H2-temperature programmed reduction(H2-TPR),NH3-temperature programmed desorption(NH3-TPD)and pyridine adsorbed Fourier transform infrared spectroscopy(Py-FTIR).Among cerium doped catalysts,5 wt%of Ce promoted copper chromite supported by 40 wt%of silica(SiCuCr40-Ce5)shows the largest BET surface area.XRD analysis of the reduced form of the catalyst shows both CeO2/Ce2O3 redox system and CuO/Cu2O/Cu redox system.Py-FTIR shows the maximum number of Lewis acid sites for SiCuCr40-Ce5 than others.The highest acetol selectivity with analytical reagent(AR)grade glycerol conversion is observed for SiCuCr40-Ce5 at 200℃for 3 h in a batch reactor at atmospheric pressure.Cerium promotion lowers the reaction te mperature with enhanced glycerol conve rsion and increased acetol selectivity.Though the above catalyst shows higher conversion for laboratory reagent(LR)grade glycerol but it reduces acetol selectivity.The addition of glucose into the LR grade glycerol further reduces glycerol conversion and decreases the acetol selectivity to zero.This may be due to the presence of iron as impurity in LR grade glycerol.XRD analysis of spent catalyst shows the absence of redox catalytic system and the pore volume reduces identified by BET analysis.Raman analysis of the spent catalyst shows graphite-like carbon deposition in the spent catalvst.  相似文献   

18.
A series of MnCeOx catalysts supported on cordierite honeycomb (Cord) were prepared by a combustion synthesis method using Mn(NO3)2 , Ce(NO3 )2·6H2O and citric acid. The effect of the molar ratio of Mn/Ce, calcination time, the amount of citric acid and the effect of water vapor on the catalytic properties for the complete oxidation of benzene were investigated. These catalysts were characterized by X-ray diffraction (XRD), H 2 temperature-programmed reduction (H2 -TPR), O2 temperature programmed desorption (O2 -TPD) and scanning electron microscopy (SEM) techniques. The results indicated that the MnCeOx /Cord catalyst with Mn/Ce molar ratio of 1:1, calcining for 7h and M n+ /(citric acid) molar ratio of 6 exhibited the highest catalytic activity. When the concentration of benzene was 1500 ppm and the gaseous hourly space velocity was 20000h -1 , the conversion of toluene was 99.1% at the reaction temperature of 300 oC.  相似文献   

19.
Active new ceria-promoted platinum supported on ZSM-5 catalysts were prepared and characterized by X-ray diffraction(XRD),Fourier transform infrared spectra(FTIR),transform electron microscopy(TEM),temperature programmed desorption(TPD),and FTIR of CO adsorption.The samples were prepared by the incipient wetness impregnation method and calcined at 500℃.The XRD patterns and FTIR spectra prove that the zeolite framework is kept unaltered after metal loadings.TEM images prove the presence of Pt nan...  相似文献   

20.
In this paper,CeO2 substrate was prepared by the sol-gel method,further CuO was introduced by adding the copper complexes with chelating agents into the sol-gel precursors of CeO2,in which different chelating agents(β-cyclodextrin,glucose and trimesic acid) were tried.This synthesis method helps the CuO species to disperse very uniformly in the CeO2 substrates.When the amount of copper oxide is up to33 mol%,the CuO/CeO2 samples can still maintain a hig...  相似文献   

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