CO and C3H8 total oxidation over Pd/La-Al2O3 catalysts： Effect of calcination temperature and hydrothermal treatment

A series of Pd/La-Al2O3（PLA） catalysts with La-Al2O3（LA） support calcined at different temperatures（500, 700, 900 and 1050 oC） were prepared using an incipient wetness impregnation method. The activity of the fresh and hydrothermally aged PLA catalysts were tested for total oxidation of CO and C3H8. The activity of the fresh PLA catalysts for CO and C3H8 oxidation increased with increasing calcination temperature of the support, while the activities of the aged catalysts declined and became essentially the same. CO chemisorption results revealed that the suppressed activities of the aged catalysts were mainly due to the decline of palladium dispersion. The turnover frequency（TOF） of CO oxidation increased with increasing reduction ability of the catalysts, with a fresh catalyst calcined at 1050 oC having the highest value（0.048 s–1）. However, the TOF of C3H8 total oxidation was affected by not only the redox properties of catalysts but also the size of Pd particle, and large Pd particles possessed higher TOF value of C3H8 oxidation, with the highest value（0.125 s–1） being obtained on an aged catalyst calcined at 500 oC.     

Hydrothermal stability of MOx-Ce0.75Zr0.25O2 catalysts for NOx reduction by ammonia

Various acidic components（MOx：phosphate,sulfate,tungstate and niobate） were loaded on Ce0.75 Zr0.25 O2 powders by an impregnation method.The as-prepared catalysts were hydrothermally treated at 760 oC for 48 h in air containing 10 vol.% H2 O to obtain the aged catalysts.The catalysts were characterized by X-ray diffraction,Fourier transform infrared spectroscopy,H2 programmed-reduction,NH3 adsorption and deNOx activity measurements.The results showed that,among the catalysts investigated,the phosphated Ce0.75 Zr0.25 O2 catalyst showed the highest hydrothermal stability.The remained high acidity of the phosphated catalyst with moderate redox property helped to maintain the excellent NH3-SCR activity of hydrothermally aged catalyst.Cerium tungstate led to the poor redox property of the tungstated catalyst although the acidity of catalyst was still high.The decomposition of sulfates at temperatures higher than 600 °C restrained the usage of sulfated catalysts in high temperature conditions.The overall dehydration of niobate to niobium oxides led to the low acidity of hydrothermally aged Nb2 O5-Ce0.75 Zr0.25 O2 catalyst.     

Influence of Ce0.35Zr0.55Y0.10 Solid Solution on Performance of Pt-Rh Three-Way Catalysts

Ce0.35Zr0.55Y0. 10 solid solution was prepared by co-precipitation technique and characterized by specific surface area measurements （BET） and X-ray diffraction （XRD）. Ce0.35Zr0.55Y0.10 was used to prepare low Pt-Rh threeway catalyst （TWC）, and its influence on the performance of TWC was investigated. The results revealed that Ce0.35 Zr0.55Y0.10 had a cubic structure similar to Ce0.50Zr0.50O2 and its specific surface area can maintain higher than Ce0.50 Zr0.50O2 after 1000 ℃ calcination for 5 h. Being hydrothermal aged at 1000 ℃ for 5 h, the catalyst containing Ce0.35 Zr0.55Y0.10 still exhibited higher conversion of C3H8, CO and NO and lower light-off temperature in comparison with Ce0.50Zr0.50O2 TWC.     

Effect of Fe2O3 Loading Amount on Catalytic Properties of Monolithic Fe2O3/Ce0.67Zr0.33O2 -Al2O3 Catalyst for Methane Combustion

Ce0.67Zr0.33O2-Al2O3 solid solution was prepared by the co-precipitation method. Fe2O3-based catalysts supported on the solid solution were obtained by the impregnation method. The article revealed that the optimal loading amount of Fe2O3 on Ce0.67Zr0.33 O2-Al2O3 in our experimental condition for catalytic combustion of methane was 8% （ mass fraction）. The prepared catalysts were characterized by BET, TPR, XRD analyses, and their catalytic activity was investigated after being calcined at 873 K and after being aged in water gas at 1273 K. When the loading amount of Fe203 was 8% （ mass fraction）, the catalyst held the highest activity, and the best temperature speciality and thermal stability. The complete-conversion temperature of methane for fresh and aged sample was 788 and 838 K, respectively. The range between the light-off temperature and the complete-conversion temperature was only 15 K. The characterization results of XRD indicated that Fe2O3 was well dispersed on the Ce0.67Zr0.33O2-Al2O3 matrix. The results of BET and TPR were in good harmony with the catalytic activity results.     

Effect of high temperature pretreatment on the thermal resistance properties of Pd/CeO_2/Al_2O_3 close-coupled catalysts

Fresh Pd/CeO_2/Al_2O_3 close coupled catalyst was prepared by the stepwise impregnation method and calcined at 550 °C for 3 h, which was then pretreated at 700, 800, and 900 °C for 3 h, respectively. Finally, these pretreated catalysts were aged at 1000 °C for 3 h to study their anti-aging properties. The catalytic activities of the catalysts were investigated detailedly, and the results showed that the catalyst pretreated at 800 °C before aging treatment possessed the best anti-aging performance for C_3H_8 oxidation. XRD and XPS results indicated that well-crystallized CeO_2 particles were formed during calcinations at 800 °C, which made CeO_2 an effective promoter. HRTEM revealed that Pd particles found on the edge of CeO_2 over the aged catalyst pretreated at 800 °C were relatively smaller than those over the catalysts without pretreatment. H_2-TPR and XPS results also implied that the interaction between well-crystallized CeO_2 and Pd suppressed the deactivation of PdO sites and further enhanced the catalytic performance.     

Process Simulation and Microstructure Analysis of Low Carbon Si-Mn Quenched and Partitioned Steel

The quenching and partitioning （Q＆P） process was experimentally investigated on the thermomechanical simulator （Gleeble3800）. The microstructure and fracture mechanism of the sheets were investigated by means of TEM. It was found that the microstructure of quenched and partitioned steel consists of fine lath martensite and thin inter-lath austenite films. The optimum quenching temperature of producing the maximum amount of retained austenite after final quenching at room temperature was predicted by Matlab software package. It was found that the calculations by Matlab software can provide guidance for experimental processing design reliably. The volume fraction of retained austenite at room temperature was approximately 8%, which was measured easily by the software VC6.0＋＋ programming. The results verified that quenched and partitioned steel possesses a good combination of strength and plasticity due to its fine microstructure. This steel exhibited high ultimate tensile strength （exceeding 1 000 MPa） and good elongation of 25%. The results showed that the fracture mechanism of the sheets is typical tough fracture under the condition of tensile failure.     

Hydrothermal and sulfur aging of CeTi/CeWTi catalysts for selective catalytic reduction of NO_x with NH_3

The CeO_2-TiO_2(CeTi)and CeO_2/WO_3-TiO_2(CeWTi)catalysts were prepared by sol-gel method.The asprepared catalysts were hydrothermally treated at 760 ℃ for 48 h in air containing 10 vol% H_2O to obtain the hydrothermal aged catalysts.The sulfur aged catalysts were treated at 400 ℃ with 100 ppm SO_2,10%water vapor,air balance for 48 h and catalysts.The powder X-ray diffraction(XRD)and Raman results indicate that the crystallization of hydrothermal aged catalysts is more serious than sulfur aged catalysts.In addition,tungsten species can stabilize the CeTi catalyst from grain growth.According to the results of in situ diffuse reflectance infrared Fourier transform spectra(DRIFTS),temperatureprogrammed desorption of ammonia(NH_3-TPD),H_2 temperature-programmed reduction(H_2-TPR)and ammonia oxidation,the aging process leads to loss of surface area,redox properties,surface acidities and surface ceria concentration,especially for the hyd rothermal aging.The NH_3-NO/NO_2 SCR perfo rmances of sulfur aged catalysts are better than that of hydrothermal aged catalysts.Compared with CeTi catalyst,the addition of tungsten inhibits the crystallization of catalyst.So that more acid sites and active sites are retained.This is also the reason why tungsten addition improves the NH_3-NO/NO_2 SCR performance of CeTi catalyst.     

Effect of BaO on catalytic performance of Pd-based catalysts for purification of gasoline-methanol exhaust

Barium oxide was developed successfully to modify palladium catalysts supported on CeO2-ZrO2-La2O3-Al2O3（CZLA） compound oxides by impregnation method. N2 adsorption（BET）, X-ray diffraction（XRD）, H2-temperature-programmed reduction（H2-TPR） and X-ray photoelectron spectroscopy（XPS） were employed to characterize the influence of BaO on the physicochemical properties of catalyst. And catalytic activity tests for methanol, CO, C3H8 and NO conversion were evaluated. Catalytic activity results showed that BaO had a positive effect on the conversion of all pollutants. H2-TPR results suggested that the addition of BaO increased the reductive ability of the palladium catalysts. The XPS results indicated that doping BaO also improved the dispersion of Pd species and increased the amounts of Ce3＋ on the Pd-Ba/CZLA catalyst surface, which led to a better redox property. The excellent redox property helped to improve the catalytic activities toward all the pollutants over Pd-based catalysts.     

NiO-Ce0.5Zr0.5O2 catalysts prepared by citric acid method for steam reforming of ethanol

NiO-Ce0.5Zr0.5O2 catalysts were prepared by citrate method and used for hydrogen production from steam reforming of ethanol （SRE）. The effect of nickel content and space velocity on the catalytic performance was investigated. The prepared catalysts were characterized with XRD and thermal analysis techniques. 20%NiO-Ce0.5Zr0.5O2catalyst was very active and selective for hydrogen production via SRE, in which ethanol conversion of 100% could be obtained with feed component of 20% （H2O＋EtOH） and 80% N2, water/ethanol of 3/1 in molar ratio at 350 ℃. Also, the catalyst showed good stability for anti-sintering and carbon-resistance. The XRD illuminated that both NiO and Ce0.5Zr0.5O2 crystal sizes were very small in NiO-Ce0.5Zr0.5O2 catalyst, and Ce0.5Zr0.5O2 solid solution was formed.     

Catalytic performance of cerium iron complex oxides for partial oxidation of methane to synthesis gas

The cerium iron complex oxides oxygen carrier was prepared by the co-precipitation method. The reactions between methane and lattice oxygen from the complex oxides were investigated in a fixed micro-reactor system. The reduced oxygen carder could be re-oxidized by air and its initial state could be restored. The characterizations of the oxygen carders were studied using XRD, O2-TPD, and H2-TPR. The results showed that the bulk lattice oxygen of CeO2-Fe2O3 was found to be suitable for the partial oxidation of methane to synthesis gas. There were two kinds of oxygen species on the oxygen carrier： the stronger oxygen species that was responsible for the complete oxidation of methane, and the weaker oxygen species （bulk lattice oxygen） that was responsible for the selective oxidation of methane to CO and H2 at a higher temperature. Then, the lost bulk lattice oxygen could be selectively supplemented by air re-oxidation at an appropriate reaction condition. CeFeO3 appeared on the oxygen carrier after 10 successive redox cycles, however, it was not bad for the selectivity of CO and H2.     

Durability of three-way and close-coupled catalysts for Euro Ⅳ regulation

The durability of three-way catalyst (TWC) and corresponding close-coupled catalyst (CCC) for Euro Ⅳ stage regulation was in-vestigated through Vehicle Road Running Mode tests, whereas emissions of regulated pollutants of three car fleet were investigated at every 100,000 km miles. The results showed that HC, NOx, and CO emission values could meet Euro Ⅳ regulation limits at every point. The redox properties of TWC and CCC were measured by CO reduction during each isothermal. It was obvious that both aged TWC and aged CCC behaved a good redox property at 673 and 773 K. Based on XRD and BET measurement results, TWC and CCC washcoat were character-ized with good thermal stability.     

Low-content and highly effective zoned Rh and Pd three-way catalysts for gasoline particulate filter potentially meeting Euro 7

The next-generation Euro 7 standard proposed much lower pollutant limits from gasoline vehicles,specifically for CO and NO_x,which would be challenging for the three-way catalysts(TWCs) utilized commercially to eliminate these pollutants.TWCs with reductive(Rh) and oxidative(Pd) active components on gasoline particulate filters(TWC on GPF) play importantly auxiliary roles in the remediation of CO and NO_x downstream the close coupled TWCs to meet their emission targets.Here,a...     

Construction of bimetallic Pt-Pd/CeO2-ZrO2-La2O3 catalysts with different Pt/Pd ratios and its structure-activity correlations for three-way catalytic performance

A series of Pt-Pd bimetallic catalysts supported on CeO₂-ZrO₂-La₂O₃ mixed oxides were synthesized through the conventional impregnation method.Three-way catalytic performance evaluations along with detailed physio-chemical characterizations were carried out to establish possible structure-activity correlations.Results show that on the one hand,different Pt/Pd ratios can strongly affect the TWC behaviors of Pt-Pd/CZL catalysts by modulating the synergis...     

Ce–Ti catalysts modified with copper and vanadium to effectively remove slip NH3 and NOx from coal-fired plants

In this work, V/Ce–Ti catalysts were modified with different kinds of transition metals (Cu, Fe, Co, Mn) by sol–gel and impregnation methods. The NH₃ oxidation performance of them was tested to select the most active catalyst in NH₃-selective catalytic oxidation (NH₃–SCO). The effect of NO, SO₂ and H₂O was also investigated. The experimental results indicate that 1% Cu–V/Ce–Ti catalyst exhibits the most significant ability to remove slip ammonia discharged from coal-fired plants and its NH₃ conversion efficiency reaches 90% at 300 °C. In addition, 97% NO_x can be removed when NO is introduced in the gas. Cu–V/Ce–Ti catalyst also obtains good resistance to H₂O and SO₂. Based on the characterization experiment, the introduced Cu and V are highly dispersed on Ce–Ti catalyst and they can increase the redox properties and the number of acidic sites. Besides, the redox cycles among Cu, V and Ce species on Cu–V/Ce–Ti catalyst surface are conducive to generating more active oxygen and promoting the oxidation capacity of the catalyst.     

Effect of preparation method on physicochemical properties and catalytic performances of LaCoO_3 perovskite for CO oxidation

Perovskite oxides LaCoO_3 prepared by templating, co-precipitation and sol-gel method with different complexants were systematically characterized and its catalytic performances for CO oxidation were investigated. The samples were characterized by X-ray diffraction, thermogravimetry analysis and differential scanning calorimetry, N_2 physisorption, transmission electron microscopy, temperature program reduction of hydrogen, temperature program desorption of oxygen and X-ray photoelectron spectroscopy measurement, results of which show that the properties of LaCoO_3, such as surface morphology, surface area, surface compositions, redox capability, oxygen vacancy, as well as the calcination temperature and formation mechanism, depend intimately on the preparation method. Catalytic tests indicate that the sample prepared by carbon templating method shows the best activity for CO oxidation, with full CO conversion obtained at 135 ℃. In particular, the catalyst can be activated and significant increase of activity can be obtained with the increase of reaction time. The cyclic and longterm stability of catalysts were discussed and compared.     

SO42–-modified La,Y-doped ceria-zirconia with high oxygen storage capacity and its application in Pd-only three-way catalysts

As the oxygen redox ability shows great effects on the catalytic performances of ceria-zirconia based materials, many strategies have been utilized to improve the oxygen storage capacity. Here in this study, we report a simple and facile approach to prepare a SO₄^2–-modified La, Y-doped ceria-zirconia material (SO/CZLY-f) with high oxygen storage capacity. Due to the additional redox process between SO₄^2? and S^2?, oxygen storage capacity of SO/CZLY-f (745.3 μmol O₂/g) is about 1.6 times higher than that of La, Y-doped ceria-zirconia material without SO₄^2– modification. Moreover, the catalytic activities and stability of the corresponding Pd-only three-way catalyst were measured. Compared to that of Pd@CZLY-f, the operation window of CO, full conversion temperature of HC and NO over Pd@SO/CZLY-f are obviously widened and lowered, respectively. After aging treatment at 1100 °C for 4 h, the superiority of aged Pd-loading composite is still maintained.