用于环戊烯氧化合成戊二醛反应的钨基催化剂的表征

Tungsten-containing hexagonal mesoporous silica （W-HMS） supported tungsten oxide catalysts （WOx/W-HMS） was prepared for the selective oxidation of cyclopentene with aqueous hydrogen peroxide to glutaraldehyde. X-ray diffraction （XRD） results indicated that the crystal form of the active phase （tungsten oxide） of the WOx/W-HMS catalysts was dependent on the W loading and calcination temperature. X-ray photoelectron spec- troscopy （XPS） analysis revealed that the dispersed tungsten oxides on the surface of W-HMS support consisted of a mixture of W（V） and W（VI）. It was found that a high content of amorphous W species in （5＋） oxidation state resuited in the high catalytic activity. When the W loading was up to 12% （by mass） or the catalyst precursor was treated at temperature of 623 K, the catalytic activity decreased due to the presence of WO3 crystallites and the oxidation of W（V） to W（VI） on the catalyst surface. Furthermore, NH3-temperature-programmed-desorption （NH3-TPD） analysis showed that the effects of W loading and calcination temperature on the acidity of the catalysts were related to the catalytic activity. A high selectivity of 80.2% for glutaraldehyde with a complete conversion of cyclopentene was obtained over 8%WOx/W-HMS catalyst calcined at 573 K after 14 h of reaction.     

Effects of porous oxide layer on performance of Pd-based monolithic catalysts for 2-ethylanthraquinone hydrogenation

Pd/oxide/cordierite monolithic catalysts(oxide = Al_2O_3, SiO_2 and SiO_2\\Al_2O_3) were prepared by the impregnation method. The results of ICP, XRD, SEM–EDX, XPS and N_2 adsorption–desorption measurements revealed that the Pd penetration depth increased with increasing the thickness of oxide layer, and the catalysts with Al_2O_3 layers had the larger pore size than those with SiO_2 and SiO_2\\Al_2O_3 layers. Catalytic hydrogenation of 2-ethylanthraquinone(eA Q), a key step of the H_2O_2 production by the anthraquinone process, over the various monolithic catalysts(60 °C, atmosphere pressure) showed that the monolithic catalyst with the moderate thickness of Al_2O_3 layer(about 6 μm) exhibited the highest conversion of e AQ(99.1%) and hydrogenation efficiency(10.0 g·L~(-1)). This could be ascribed to the suitable Pd penetration depth and the larger pore size, which provides a balance between the distribution of Pd and accessibility of active sites by the reactants.     

Carbon nanotubes loaded with vanadium oxide for reduction NO with NH3 at low temperature☆

The catalytic activity of carbon nanotubes-supported vanadium oxide (V2O5/CNTs) catalysts in the selective catalytic reduction (SCR) of NO with NH3 at low temperatures (≤250 °C) was investigated. The effects of V2O5 loading, reaction temperature, and presence of SO2 on the SCR activity were evaluated. The results show that V2O5/CNTs catalysts exhibit high activity for NO reduction with NH3 at low-temperatures. The catalysts also show very high stability in the presence of SO2. More interestingly, their activities are significantly promoted in-stead of being poisoned by SO2. The promoting effect of SO2 is distinctly associated with V2O5 loading, particularly maximized at low V2O5 loading, which indicated the role of CNTs support in this effect. The promoting effect of SO2 at low temperatures suggests that V2O5/CNTs catalysts are promising catalytic materials for low-temperature SCR reactions.     

CO_2 methanation over TiO_2–Al_2O_3 binary oxides supported Ru catalysts

TiO_2 modified Al_2O_3 binary oxide was prepared by a wet-impregnation method and used as the support for ruthenium catalyst. The catalytic performance of Ru/TiO_2–Al_2O_3catalyst in CO_2 methanation reaction was investigated. Compared with Ru/Al_2O_3 catalyst, the Ru/TiO_2–Al_2O_3catalytic system exhibited a much higher activity in CO_2 methanation reaction. The reaction rate over Ru/TiO_2–Al_2O_3 was 0.59 mol CO_2·(g Ru)1·h-1, 3.1 times higher than that on Ru/Al_2O_3[0.19 mol CO_2·(gRu)-1·h-1]. The effect of TiO_2 content and TiO_2–Al_2O_3calcination temperature on catalytic performance was addressed. The corresponding structures of each catalyst were characterized by means of H_2-TPR, XRD, and TEM. Results indicated that the averaged particle size of the Ru on TiO_2–Al_2O_3support is 2.8 nm, smaller than that on Al_2O_3 support of 4.3 nm. Therefore, we conclude that the improved activity over Ru/TiO_2–Al_2O_3catalyst is originated from the smaller particle size of ruthenium resulting from a strong interaction between Ru and the rutile-TiO_2 support, which hindered the aggregation of Ru nanoparticles.     

Catalytically active membranes for esterification: A review

Esterification is an important process in the food industry and can be carried out via homogeneous or heterogeneous catalysis. The homogeneous catalyst, despite providing high conversion, can cause corrosion in reactors, which is not observed with the use of heterogeneous catalysts. However, some of these catalysts require a high process temperature and may lose their catalytic activity with reuse. Thus, catalytic membranes have been proposed as a promising alternative. The combination of cataly...     

Preparation and characterization of sulfated TiO2 with rhodium modification used in esterification reaction and decomposition of methyl orange☆

A unique Rh/TiO_2 solid acid catalyst modified with H_2SO_4 was synthesized and evaluated in the esterification reaction of propylene glycol methyl ether and decomposition of methyl orange(MO) in aqueous phase under halogen lamp irradiation. For this purpose, rhodium(Rh) nanoparticles were loaded on SO_4~(2-)/TiO_2 via the photo-deposition method. It was found that SO_4~(2-)/Rh–TiO_2 exhibited stronger catalytic activity than SO_4~(2-)/TiO_2. The new catalysts were characterized by X-ray powder diffraction(XRD), Brunauer–Emmett–Teller(BET), Transmission electron microscopy(TEM) and high-resolution(HRTEM), X-ray photoelectron spectroscopy(XPS) and Fourier Transform infrared spectroscopy(FTIR). Results from XRD and BET show that SO_4~(2-)/Rh–TiO_2 has higher specific surface area and smaller pore size than SO42-/TiO_2. The distribution of loaded Rh was found to be uniform with a particle size of 2–4 nm. Data from XPS reveal that Rh primarily exists as Rh~0 and Rh~(3+)in Rh–TiO_2 and SO_4~(2)-/Rh–TiO_2. These valence forms of Rh likely contribute to the enhanced catalytic activity. Furthermore, FT-IR spectra of the catalysts show an abundance of surface hydroxyl groups, which help the formation of hydroxyl radicals and the enhancement of surface acid density. The results show that more acid sites are formed on the sulfated Rh–TiO_2, and these acidic sites are largely responsible for improving the catalytic performance. This superior SO_4~(2-)/Rh–TiO_2 catalyst has potential applications in reactions requiring efficient acid catalysts, including esterification reactions and waste water treatment.     

Effect of boron addition on the MoO_3/CeO_2–Al_2O_3 catalyst in the sulfur-resistant methanation

The effect of boron on the performance of MoO_3/CeO_2–Al_2O_3 catalysts, which were prepared with impregnation method, was investigated. The catalysts were characterized with N_2 adsorption–desorption, XRD, H_2-TPR, and NH_3-TPD, and were tested in sulfur-resistant methanation. The results indicated that the MoO_3/CeO_2–Al_2O_3 catalysts modified by boron showed higher catalytic performance in sulfur-resistant methanation. The CO conversion increased from 47% to 62% with 0.5 wt% boron content. When the content of boron was under 0.5 wt%, the results suggested there was an increase in the amorphous form of MoO_3 caused by the generation of weak and intermediate acid sites, which had weakened the interaction between the active components and supports. While, the catalyst added 2.0 wt% boron showed the strong acid sites and the largest crystalline size resulting in the uneven distribution of ceria.     

Microwave-assisted catalytic oxidation of gaseous toluene with a Cu-Mn-Ce/cordierite honeycomb catalyst

A novel Cu-Mn-Ce/cordierite honeycomb catalyst was prepared by an incipient wetness method and the catalyst was characterized. The active ingredients were present as various spinel species of Cu, Mn and Ce oxides with different valences and they were unevenly dispersed over the surface of the catalyst. The catalytic oxidation of gaseous toluene was primarily investigated using a fixed bed reactor under microwave heating in the continuous flow mode. Under the optimal conditions of 6.7 wt-% loading of the active component, a bed temperature of 200℃, a flow rate of 0.12 m^3 · h^-1 and an initial concentration of toluene of 1000 mg·m^-3, the removal and mineralization efficiencies of toluene were 98% and 70%, respectively. Thus the use of the microwave effectively improved the oxidation of toluene and this is attributed to dipole polarization and hotspot effects. After four consecutive cycles (a total of 1980 min), the Cu-Mn- Ce/cordierite catalyst still exhibited excellent catalytic activity and structural stability, and the toluene removal was higher than 90%. This work demonstrates the possibility of treating volatile organic compounds in exhaust gases by microwave-assisted catalytic oxidation.     

Influence factors on activity of Ru–Zn catalysts in selective hydrogenation of benzene

Selective hydrogenation of benzene is an atom economic green route to produce cyclohexene. The control of Zn species is the key to the catalytic performance of Ru–Zn catalysts. The influences of ZnO crystals on selective hydrogenation of benzene were explored. A series of Ru–Zn catalysts with different Zn contents and ZnO morphologies were prepared by changing the amount of NaOH in the co-precipitation process. The catalysts were characterized by N_2 physisorption, X-ray powder diffraction(XRD), inductively coupled plasma optical emission spectrometer(ICP-OES), scanning electron microscope(SEM), temperature-programmed reduction(H_2-TPR)and Malvern laser particle size analyzer. It is found that with increasing the amount of NaOH, the Zn content first increased then decreased, and the ZnO crystals changed from relatively thicker pyramidal-shaped crystals to slimmer needle-shaped crystals. The catalyst had the highest Zn content(22.1%) and strongest interaction between ZnO crystals and Ru particles at pH 10.6 of the solution after reduction. As a result, it had the lowest activity. The activity of Ru–Zn catalysts is affected by both the Zn content and the interaction between ZnO crystals and Ru particles. The effect of reduction time was also investigated. Prolonging the reduction time caused no significant growth of ZnO crystals but the aggregation of catalyst particles and growth of Ru nanocrystals, thus resulting in the decrease of catalytic activity.     

带有磺酸基团和羰基酸团的新固体酸的合成及其在缩醛化反应中的催化性能简

The novel solid acid with both sulfonic and carbonyl acid groups has been synthesized from 3-（（2-sulfoethoxy） carbonyl）acrylic acid and tetraethyl orthosilicate （TEOS）. The catalytic activities were investigated through the acetalization. The results showed that the novel solid acid was very efficient for the reactions with the high yields. The high acidity, high stability and reusability were the key feature of the novel solid acid. Moreover, the sulfonic and carbonyl acid groups could cooperate during the catalytic process, which improved its catalytic activities. The catalyst shows recyclability, and hold great potential for replacement of homogeneous catalysts.     

Cobalt catalysts for Fischer–Tropsch synthesis: The effect of support,precipitant and pH value

In this report,Co-based catalysts supported on ZnO,Al_2O_3 and ZrO_2 as well as the ZrO_2 derived from different precipitants and different pH values were prepared by co-precipitation method.Their catalytic Fischer–Tropsch synthesis(FTS)performance was investigated in a fixed-bed reactor.The results revealed that Co catalyst supported on ZrO_2 exhibited better FTS catalytic performance than that supported on ZnO or Al_2O_3.For the Co/ZrO_2catalyst,different precipitants showed the following an activity order of NaOHNa_2CO_3NH_4OH,and the best pH value is 13.The catalysts were characterized by N_2adsorption–desorption,XRF,XRD,H_2-TPR,H_2-TPD and TEM.It was found that the main factor affecting the CO conversion of the catalyst was the amounts of low-temperature active adsorption sites.Moreover,the selectivity of C_5~+hydrocarbons had a positive relationship with the peak temperature of the weak hydrogen adsorption sites.The higher the peak temperature,the higher the C_5~+selectivity is.     

中温H2S-空气燃料电池阴极催化剂的研究

Abstract Cathode catalysts comprising composite NiO, NiO-Pt, or LiNiO2 have been developed for electro- chemical oxidation of hydrogen sulfide in intermediate-temperature solid oxide fuel cells （ITSOFCs）. All catalysts exhibited good electrical conductivity and catalytic activity at operating temperature. Composite NiO catalysts were found to be more active and have lower over potential and higller current density than pure Pt although the electrical conductivity of NiO itself is lower than that of Pt. This problem has been overcome by either admixing as high as 10% （by mass）Ag powder into NiO_ cathode layer or using composite NiO c atalysts such as NiO-Pt and LiNiO2 catalysts. Composite catalysts like NiO with Ag, electrolyte and starch admixed, NiO-Pt, which was prepared from a mixture of NiO and Pt powders, by admixing electrolyte and starch, and LiNiO2, which is derived from the reaction of LiOH-H2O and NiO with electrolyte and starch admix_ed have been shown to be feasible and effective in an intermediate-temperature H2S-air fuel cell. A fuel cell using Li2SO4-based proton-conducting membrane as electrolyte, metal sulfides as anode catalysts, and composite NiO as cathode catalysts produced a maximum current density about 300mA·cm^-2 and maximum power density over 80 mW-cm-2 at 680℃.     

相对湿度对不同载体的负载Cu催化剂催化燃烧甲苯的影响

The copper based catalysts, CuO/γ-Al2O3, CuO/γ-Al2O3-cordierite (Cord) and CuO/Cord, were prepared by impregnation method. The catalytic activity of the catalysts was tested in absence and presence of water vapor, and the catalysts were characterized. Temperature program desorption (TPD) experiments of toluene and water on the catalysts were carried out. The influence of water vapor on the activity of the catalysts was discussed. Results showed that addition of the water vapor has a significant negative effect on the catalytic activity of the catalysts. The higher the concentration of the water vapor in feed steam was, the lower the catalytic activity of the copper based catalysts became, which could be mainly ascribed to the competition of water molecules with toluene molecules for adsorption on the catalyst surfaces. TPD experiments showed that the strength of the interaction between water mole-cules and three catalysts followed the order: CuO/γ-Al2O3>CuO/γ-Al2O3-Cord>CuO/Cord. As a consequence of that, the degree of degradation in the catalytic activity of these three catalysts by the water vapor followed the order: CuO/γ-Al2O3>CuO/γ-Al2O3-Cord>CuO/Cord. However, the negative effect of the water vapor was reversible.     

Catalytic cracking of 1-butene to propylene by Ag modified HZSM-5

Silver modified HZSM-5 (AgHZ) zeolite catalysts were prepared by ion exchange method and their catalytic properties in the 1-butene cracking reaction were measured. The catalysts were characterized by infrared spec-troscopy with pyridine adsorption (Py-IR), N2 adsorption and X-ray diffraction (XRD). The effects of Ag loading and steaming treatment on catalytic performances were studied. It is found that the activity of HZSM-5 (HZ) cat-alyst significantly decreases with the steaming time, whereas AgHZ catalysts show stable activity in the steaming time of 24–48 h and their activities increase with the Ag loading. When the steaming time is 24–48 h, the yield of propylene over HZ catalyst significantly decreases, whereas it is stable over AgHZ catalysts. The AgHZ catalysts with Ag loadings of 0.28%–0.43%(by mass) show similar propylene yields (~30%), which are higher than that over the AgHZ catalyst with a Ag loading of 0.55%(by mass). These results indicate that the steam-treated AgHZ catalysts with optimum Ag loadings have higher yield of propylene and are more stable than the steam-treated HZ catalyst. The regeneration stability measurement in butene cracking also shows that the AgHZ catalyst steam-treated under a suitable condition has better stability than the HZ catalyst.     

Structure,characterization, and dynamic performance of a wet air oxidation catalyst Cu–Fe–La/γ-Al_2O_3

A Cu–Fe–La/γ-Al_2O_3(CFLA) catalyst was prepared by the excessive impregnation method and characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The results indicate that the catalyst contained mostly Cu~(2+), Fe~(3+), and La~(3+)and a small amount of Cu~+, Fe~(2+), and La. The active components were uniformly distributed in the catalyst, and the particle size of the components was approximately 7.5 nm. The CFLA catalyst was used for the treatment of methyl orange(MO) solution by catalytic wet air oxidation(CWAO), and it exhibited a high catalytic activity. The catalytic reaction involved variable valence states of metals and free-radical reaction mechanism. The CWAO reaction of MO solution was fitted by a segmented first-order dynamic model, and the rapid reaction apparent activation energy was 13.9 k J·mol~(-1).     

A SHORT-CUT OF EXPLORING THE OPTIMUM ACTIVITY FOR COMMERCIAL METHANATION CATALYST Ni/Al_2O_3

Two commercial methanation catalysts Ni/Al_2O_3 were taken as example for examination. Both crushed and pelleted catalyst were used. Their catalytic activities were evaluated under different reduction conditions. It was found that the reduction process is of vital importance in developing the activity. Each catalyst has its own appropriate condition to display its intrinsic property. So it is really unreasonable to compare the activity of different catalysts under same testing condition. In this paper we present a procedure for exploring the optimum activity of the two catalysts with their corresponding data, which are quite different from each other and from the previous ones.     

High-performance phosphate supported on HZSM-5 catalyst for dehydration of glycerol to acrolein

The purpose of this study is to increase acrolein yield and capability of coking resistance in the reaction of glycerol dehydration to acrolein by assembling metal phosphate supported on HZSM-5 catalyst.The as-prepared catalysts were characterized by XRD,SEM,EDS,BET,NH3-TPD,CO2-TPD and Py-IR techniques.It was found that metal phosphate species were incorporated into the porous structure of HZSM-5 zeolites,thus influencing the surface and textural physico-chemical properties of the supporters.The alkaline-treated HZSM-5 catalyst promoted the dispersion of phosphate species on the carriers.Moreover,the amount of strong aridity was tremendously improved by adding the different metal hydrophosphates and the catalysts show high catalytic activity.In this present work,the Sn1/4H2PO4/HZSM-5 catalyst exhibited good performance in the catalytic activity and coking resistant ability,which resulted in a high acrolein yield of 83％ initially and acrolein yield of 68％ after 30 h.The aridity,especially the ratio of strong to weak acid,plays an important role in promoting acrolein yield and stability simultaneously.     

WP/γ-Al2O3催化剂的制备、表征及加氢脱硫和加氢脱氮活性

Two series of WP/Al2O3 catalyst precursors with WP mass loading in the range 18.5%-37.1% were prepared using the impregnation method and mixing method, respectively, and the catalysts were then obtained by temperature-programmed reduction of supported tungsten phosphate (precursor of WP/Al2O3 catatlysts) in H2 at 650℃ for 4h. The catalysts were characterized by XRD, BET, TG/DTA, XPS and 31p MAS-NMR. The activities of these catalysts were tested in the hydrodenitrogenation (HDN) of pyridine and hydrodesulfurization (HDS) of thiophene at 340℃ and 3.0MPa. The results showed that owing to the stronger interaction of the support with the active species, the precursor of WP/Al2O3 catalyst was more difficultly phosphided and a greater amount of W species was in a high valence state W6 on the surface of the catalyst prepared by the impregnation method than that by the mixing method. 31p MAS-NMR results indicated that 31p shift from 85% H3PO4 of 2.55 × 10-4 for WP and 2.57 × 10-4 for WP/γ-Al2O3 catalysts prepared by mixing method. Such WP/Al2O3 catalysts showed higher HDN activities and lower HDS activities than those prepared by the impregnation method under the same loading of WP.WP/γ-Al2O3 catalysts with weak interaction between support and active species were favorable for HDN reaction while the WP/γ-Al2O3 catalysts with strong interaction were favorable for HDS reaction.     

Pt-Sn/SBA-15催化剂的制备、表征和长链烷烃脱氢催化性能

A series of the Pt-Sn/SBA-15 catalysts were prepared and their properties characterized by using X-ray powder diffraction （XRD）, N2 adsorption-desorption, high resolution transmission electron microscope, X-ray photoelectron spectroscopy （XPS） and H2-temperature programmed reduction. Their performances in long chain alkane dehydrogenation were evaluated in a fixed-bed microreactor with dodecane as a model alkane. The results indicated that SBA-15 maintained the well-order mesoporous structure during the reaction. The performance of the catalyst was found not dominated by its textural properties, but by the molar ratio of Sn to Pt which governed the degree of Sn reduction. Owing to the highest degree of Sn reduction, 1% （by mass） Pt-1.8% （by mass） Sn/SBA-15 showed the best catalytic activity. At 0.1 MPa and 470℃, the molar ratio of hydrogen to alkane at 4, and liquid hourly space velocity （LHSV） 20 h^-1, the dodecane conversion is 10%, and the dodecene selectivity is about 70%.     

载体二氧化钛的晶型对对硝基苯酚加氢催化剂Ni/TiO2的影响

The catalytic hydrogenation ofp-nitrophenol to p-aminophenol was investigated over Ni/TiO2 catalysts prepared by a liquid-phase chemical reduction method. The catalysts were characterized by inductively coupled plasma （ICP）, X-ray powder diffraction （XRD）, transmission electron microscopy （TEM）, X-ray photoelectron spectra （XPS） and temperature-programmed reduction （TPR）. Results show that the titania structure has favorable influence on physio-chemical and catalytic properties of Ni/TiO2 catalysts. Compared to commercial Raney nickel, the catalytic activity of Ni/TiO2 catalyst is much superior, irrespective of the titania structure. The catalytic activity of anatase titania supported nickel catalyst Ni/TiO2（A） is higher than that of rutile titania supported nickel catalyst Ni/TiO2（R）, possibly because the reduction of nickel oxide to metallic nickel for Ni/TiO2（A） is easier than that for Ni/TiO2（R） at similar reaction conditions.