Mesoporous Co3O4 and Au/Co3O4 catalysts for low-temperature oxidation of trace ethylene.

Low-temperature catalysts of mesoporous Co(3)O(4) and Au/Co(3)O(4) with high catalytic activities for the trace ethylene oxidation at 0 degrees C are reported in this paper. The catalysts were prepared by using the nanocasting method, and the mesostructure was replicated from three-dimensional (3D) cubic KIT-6 silicas. High resolution transmission electron microscopy (HRTEM) studies revealed that {110} facets were the exposed active surfaces in the mesoporous Co(3)O(4), whereas the Co(3)O(4) nanosheets prepared by the precipitation method exhibited the most exposed {112} facets. We found that the mesoporous Co(3)O(4) was significantly more active for ethylene oxidation than the Co(3)O(4) nanosheets. The results indicated that the crystal facet {110} of Co(3)O(4) played an essential role in determining its catalytic oxidation performance. The synthesized Au/Co(3)O(4) materials, in which the gold nanoparticles were assembled into the pore walls of the Co(3)O(4) mesoporous support, exhibited stable, highly dispersed, and exposed gold sites. Gold nanoparticles present on Co(3)O(4) readily produced surface-active oxygen species and promoted ethylene oxidation to achieve a 76% conversion at 0 degrees C, which is the highest conversion reported yet.

[Hydrolysis of COS over MgAl Mixed Oxides Derived from Hydrotalcites].

A series of MgAl hydrotalcite-derived composite oxides were prepared by co-precipitation methods. The effects of calcination temperature, reaction temperature, water vapor volume fraction, and alkali metal addition on the hydrolysis activity of the samples were investigated. The crystal structure, specific surface area, pore structure, and basic position distribution of the composite oxides were characterized using XRD, BET, TPD, and XPS. The results shown that the catalytic activity firstly increased and then decreased with the rise of calcination temperature. Furthermore, the sample that calcined at 650℃ can achieve the best catalytic activity (complete removal of COS lasted for 180 min). Increasing the reaction temperature improved the catalytic activity, which can present excellent catalytic activity and stability at temperatures above 70℃. In addition, the doping of the alkali metal Cs improved the catalytic activity, the complete removal time for COS can be maintained for 480 min.

Unsteady-state direct partial oxidation of methane to synthesis gas in a fixed-bed reactor using AFeO3 (A = La, Nd, Eu) perovskite-type oxides as oxygen storage.

Direct partial oxidation of methane to synthesis gas on AFeO(3) (A = La, Nd, Eu) oxides by a novel sequential redox cyclic reaction in the absence of gaseous oxygen was investigated over a fixed-bed reactor. These oxides were prepared by the sol-gel method and characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques. XRD analysis showed that all AFeO(3) (A = La, Nd, Eu) oxides, calcined at 1173 K, are single-phase perovskites. The CH(4)-TPSR/MS and continuous reaction experiments indicated that the AFeO(3) (A = La, Nd, Eu) oxides provide mostly oxygen species, as the sole oxidant originated from lattice oxygen instead of gaseous oxygen, which can oxidize CH(4) to synthesis gas with high selectivity in the absence of gaseous oxygen. In terms of material economics and the amount of oxygen species for synthesis gas formation, the LaFeO(3) sample exhibits the best performance among these tested AFeO(3) oxides for synthesis gas production. The pulse experiments at different temperatures showed that the rate of oxygen migration during the CH(4) reaction with LaFeO(3) is strongly affected by the reaction temperature, and increases with rising temperature, which is favorable to much more CH(4) selective oxidation at high temperature. The two types of oxygen species are identified by experiments of continuous reactions and pulses, and confirmed by XPS. Methane can be converted selectively to synthesis gas by consumption of lattice oxygen, and general carbonaceous deposits on the catalyst surface do not occur under the appropriate reaction conditions by sequential redox cycles. The performance of selective oxidation of CH(4) to synthesis gas can be recovered by reoxidation using gaseous molecular oxygen; the LaFeO(3) oxide maintains relatively high catalytic activity and structural stability in redox atmospheres.

Hydrogen production from a combination of the water-gas shift and redox cycle process of methane partial oxidation via lattice oxygen over LaFeO3 perovskite catalyst.

A redox cycle process, in which CH4 and air are periodically brought into contact with a solid oxide packed in a fixed-bed reactor, combined with the water-gas shift (WGS) reaction, is proposed for hydrogen production. The sole oxidant for partial oxidation of methane (POM) is found to be lattice oxygen instead of gaseous oxygen. A perovskite-type LaFeO3 oxide was prepared by a sol-gel method and employed as an oxygen storage material in this process. The results indicate that, under appropriate reaction conditions, methane can be oxidized to CO and H2 by the lattice oxygen of LaFeO3 perovskite oxide with a selectivity higher than 95% and the consumed lattice oxygen can be replenished in a reoxidation procedure by a redox operation. It is suggested that the POM to H2/CO by using the lattice oxygen of the oxygen storage materials instead of gaseous oxygen should be possibly applicable. The LaFeO3 perovskite oxide maintained relatively high catalytic activity and structural stability, while the carbonaceous deposits, which come from the dissociation of CH4 in the pulse reaction, occurred due to the low migration rate of lattice oxygen from the bulk toward the surface. A new dissociation-oxidation mechanism for this POM without gaseous oxygen is proposed based on the transient responses of the products checked at different surface states via both pulse reaction and switch reaction over the LaFeO3 catalyst. In the absence of gaseous-phase oxygen, the rate-determining step of methane conversion is the migration rate of lattice oxygen, but the process can be carried out in optimized cycles. The product distribution for POM over LaFeO3 catalyst in the absence of gaseous oxygen was determined by the concentration of surface oxygen, which is relevant with the migration rate of lattice oxygen from the bulk toward the surface. This process of hydrogen production via selective oxidation of methane by lattice oxygen is better in avoiding the deep oxidation (to CO2) and enhancing the selectivity. Therefore, this new route is superior to general POM in stability (resistance to carbonaceous deposition), safety (effectively avoiding accidental explosion), ease of operation and optimization, and low cost (making use of air not oxygen).

Adsorption/desorption studies of NOx on well-mixed oxides derived from Co-Mg/Al Hydrotalcite-like compounds.

CoxMg3-x/Al hydrotalcite-like compounds (where x=0.0, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0) were synthesized by the coprecipitation method and characterized by the XRD and TGA techniques. Incorporation of Co for x=0.0-3.0 gradually decreased the transformation temperature of the hydrotalcites to the corresponding oxides from 444 to 246 degrees C and also decreased the surface area from 162.7 to 21.6 m2/g upon calcination at 800 degrees C for 4 h in air. The resultant oxide was generally composed of a poor MgO phase and a spinel phase, with more spinel phase at higher Co incorporation. The derived oxides were tested as the storage/reduction catalysts for NOx adsorption/desorption. The storage capacity for NOx was highly dependent on the catalyst composition and storage temperature. In general, more NOx was stored at lower temperature (100 degrees C) than that at higher temperature (300 degrees C), and tertiary catalysts (x=0.5-2.5) stored more NOx than binary catalyst (x=0.0 or 3.0). The catalytic conversion of NO to NO2 and the catalytic decomposition of NOx were observed on the tertiary catalysts during NOx adsorption at 300 degrees C, which was highly related to the loading of cobalt. The reducibility of catalysts was determined by TPR experiments, and the reduction of cobalt cations started at 150-200 degrees C in H2. In situ IR spectra of catalysts adsorbing NOx revealed that the major NOx species formed on the catalysts were various kinds of nitrites and nitrates, together with some forms of dimers, such as N2O2(2-) and N2O4 (or NO+NO3-). The storage/reduction mechanism and the function of Co in the mixed oxides are proposed and discussed on the basis of these observations.

The observation of abnormal signals in laser flash photolysis: a type of probable synchronized nuclear spin signals.

In laser flash photolysis (LFP) work, noise-like signals were observed together with transient absorption decay spectra in time domain. Analyzed results show that it is a valuable resonance spectrum of excited state molecules, in which four molecular cases are given here. We proposed that this kind signal might originate from nuclear or nuclear and electron spin resonance features in the excited molecules based on radio wave frequency spectrum levels and the significant interaction with static magnetic field.

[Source Apportionment and Health Risk Assessment of VOCs During the Haze Period in the Winter in Beijing].

A method for determining volatile organic compounds (VOCs) by cryogenic dynamic adsorption in solid adsorbent tubes, subsequent thermal desorption with cryofocusing in a cold trap and analysis by gas chromatography and mass spectrometry was adapted for continuous ambient air monitoring. VOCs pollution characteristics and health risk assessment (HRA)were researched in detail. Moreover, the sources apportionment was reliably analyzed by positive matrix factorization (PMF) model. The results showed that the average concentration of VOCs was 332.34 µg·m-3 per day, the concentrations of aromatic hydrocarbon and halo hydrocarbon were remarkably high compared to the other VOCs. Particularly, the PMF analysis results revealed that solvent/paint use emission, biomass or coal combustion and motor vehicle exhaust emissions were the main pollutants emission sources. Additionally, the cancer risk index of all carcinogenic substances was higher than the suggested value of USEPA(1×10-6), which could cause potential harm to human health.

[Comparison Analysis of Economic and Engineering Control of Industrial VOCs].

Volatile organic compounds (VOCs) pollutant has become China's major air pollutant in key urban areas like sulfur dioxide, nitrogen oxides and particulate matter. It is mainly produced from industry sectors, and engineering control is one of the most important reduction measures. During the 12th Five-Year Plan, China decides to invest 40 billion RMB to build pollution control projects in key industry sectors with annual emission reduction of 605 000 t x a(-1). It shows that China attaches a great importance to emission reduction by engineering projects and highlights the awareness of engineering reduction technologies. In this paper, a macroeconomic model, namely computable general equilibrium model, (CGE model) was employed to simulate engineering control and economic control (imposing environmental tax). We aim to compare the pros and cons of the two reduction policies. Considering the economic loss of the whole country, the environmental tax has more impacts on the economy system than engineering reduction measures. We suggest that the central government provides 7 500 RMB x t(-1) as subsidy for enterprises in industry sectors to encourage engineering reduction.

Simultaneous catalytic removal of NOx and diesel soot particulate over perovskite-type oxides and supported Ag catalysts.

A series of perovskite-type oxides and supported Ag catalysts were prepared, and characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The catalytic activities of the catalysts as well as influencing factors on catalytic activity have been investigated for the simultaneous removal of NOx and diesel soot particulate. An increase in catalytic activity for the selective reduction of NOx was observed with Ag addition in these perovskite oxides, especially with 5% Ag loading. This catalyst could be a promising candidate of catalytic material for the simultaneous elimination of NOx and diesel soot.

Preparation and catalytic properties of ZrO2-Al2O3 composite oxide supported nickel catalysts for methane reforming with carbon dioxide.

ZrO2-Al2O3 composite oxides and supported Ni catalysts were prepared, and characterized by N2 adsorption/desorption, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques. The catalytic performance and carbon deposition was also investigated. This mesoporous composite oxide is shown to be a promising catalyst support. An increase in the catalytic activity and stability of methane and carbon dioxide reforming reaction was resulted from the zirconia addition, especially at 5wt% ZrO2 content. The Ni catalyst supported ZrO2-Al2O3 has a strong resistance to sintering and the carbon deposition in a relatively long-term reaction.

In situ IR, pulse reaction and TPD-ITD study of catalytic performance of room-temperature carbon monoxide oxidation on supported gold catalysts.

With in situ IR, two different CO adsorption bands were detected on various chemical state gold catalysts. One band is attributed to the linear CO on an oxidized gold catalyst(2100 cm-1), the other one is ascribed to the bridged CO on metallic gold (2085 cm-1), CO pulse reaction showed that Au/Fe2O3 catalyst had a room-temperature activity even in the presence of moisture. The produced CO2 was detained and more easily desorbed from supported gold catalyst than support oxide. TPD-IDT results indicated that the O2- superoxide ions are the possible active oxygen species.

[Fe-ZSM-5 catalysts with different silica-alumina ratios for N2O, catalytic decomposition].

The Fe-ZSM-5 catalysts were prepared with H-ZSM-5 of different Si/Al ratios by wet ion exchange and chemical vapor deposition. Then the catalysts were investigated by XRD, BET, TEM, UV-vis and NH3-TPD technologies to analyze the iron states in Fe-ZSM-5 zeolites. The results showed that after H-ZSM-5 zeolites were prepared by chemical vapor deposition and heating wet ion exchange, the nano Fe2 O3 particles were uniformly dispersed with the sizes of 8 nm in the Fe-ZSM-5-25 (Si/A1-25). Moreover, there were more oligonuclear Fe3+ Oy clusters in the Fe-ZSM-5-25 catalysts than in Fe-ZSM-5-300 (Si/Al-300). The results of catalytic performance on N2O decomposition showed that Fe-ZSM-5-25 catalysts had higher catalytic activities than Fe-ZSM-5-300 catalysts. The Fe-ZSM-5 catalysts prepared by chemical vapor deposition achieved the best catalytic activity in N2O decomposition among the catalysts prepared by the three methods. Moreover, the presence of O2 only slightly reduced N2O conversion, while NO promoted the N2O decomposition. Finally, after reaction for more than 100 h, Fe-ZSM-5 catalyst showed no obvious deactivation under simulated emission conditions.

[Evaluation and selection of VOCs treatment technologies in packaging and printing industry].

Volatile organic compounds (VOCs) play an important role in urban air pollution. Activities of industries including the packaging and printing industries are regarded as the major sources. How to select the suitable treating techniques is the major problem for emission control. In this article, based on the VOCs emission characteristics of the packaging and printing industry and the existing treatment technologies, using the analytic hierarchy process (AHP) model, an evaluation system for VOCs selection was established and all the technologies used for treatment were assessed. It showed that the priority selection was in the following order: Carbon Fiber Adsorption-Desorption > Granular Carbon Adsorption-Desorption > Thermal Combustion > Regenerative Combustion > Catalytic combustion > Rotary adsorption-concentration and combustion > Granular Carbon adsorption-concentration and combustion. Carbon Fiber Adsorption-Desorption was selected as the best available technology due to its highest weight among those technologies.

[Selective catalytic oxidation of H2S over supported Fe catalysts on CeO2-intercalated laponite clay].

A series of Fe/CeO2-intercalated clay catalysts were synthesized successfully, the physicochemical properties of the catalysts were characterized by XRD, BET, XRF, TG, FT-IR, O2-TPD, H2-TPR and XPS methods. The catalytic performances for selective catalytic oxidation of H2S were further investigated, all catalysts exhibited high catalytic activities. Among them 5% Fe/Ce-Lap presented the best activity at 180 degreeC and the maximum sulfur yield was up to 96% due to the interaction between iron and cerium, which improved the redox ability of Fe3+ . Moreover, the strong oxygen adsorption capacity and the well dispersion of iron species improved the catalytic performance efficiently.

[Study of VOCs emission prediction and control based on dynamic CGE].

Researches on controlling volatile organic compounds (VOCs) through macroeconomic policy from the view of cost-benefit analysis are very important for our country to improve the air environment. Based on our previous study, this paper predicted future VOCs emissions until 2020 under current policies with 2007 as reference year by using dynamic CGE model. Meanwhile, environmental tax was imposed in ten industries with high emission and the impacts of emissions and economic system were discussed. Finally, policy implementations for VOCs emission control were suggested for policy-makers. The results showed that environment tax could mitigate VOCs emission, but it also resulted in high cost. Owing to the highly related relationship between different sectors, although transport sector was not taxed, it also suffered a great economic influence. Thus, when using the tax policy for reducing VOCs, subsidy for special sector is necessary.

[Current research situation of H2S selective catalytic oxidation technologies and catalysts].

This review summarizes and discusses different selective catalytic oxidation technologies and various catalysts for removing H2S, the undesirable byproduct of the fluid catalytic cracking (FCC) processing. Currently the selective oxidation technologies used include Superclaus, Euroclaus, Clinsulf-Do, BSR/Hi-Activity, Selectox and Modop techniques, which have various characteristics and application areas. Catalysts for H2S selective oxidation mainly contain the following systems: carbon, supported SiC, zeolite, oxide, and pillared clay. Former studies focused on carbon and oxide systems. The research interest on zeolite system decreased in recent years, while SiC is regarded as a typical support with great potential for this reaction and continues to be attractive. Pillared clay system is at the preliminary research stage, and is still far from practical application.

[Evaluation of treatment technology of volatile organic compounds for fixed industrial resources].

The reduction of the emission of volatile organic compounds (VOCs) from fixed industrial resources is considered more necessary than before. The traditional treatment techniques, newly developed ones and some combinations of these treatment techniques are reviewed in this paper. The applying conditions, developing trend and existing problems of these techniques are also evaluated.

[Health risk assessment of atmospheric volatile organic compounds in urban-rural juncture belt area].

A method for determining volatile organic compounds (VOCs) by cryogenic dynamic adsorption in solid adsorbent tubes, subsequent thermal desorption with cryofocusing in a cold trap and analysis by gas chromatography and mass spectrometry was adapted. An internationally recognized four-step evaluation model of health risk assessment (HRA) was adapted to preliminarily assess the health risks caused by volatile organic compounds (VOCs) in urban-rural juncture belt area in Beijing. Results of HRA indicated that non-carcinogenic risk indexes of VOCs are below 1 and non-carcinogenic risk indexes of aromatic substances range from 10(-4)-10(-5), halohydrocarbons in the 10(-4)-10(-1). Volatile pollutants would not cause non-carcinogenic health hazard to exposed population. However, the cancer risk index exposed to carcinogenic benzene was 2.21 x 10(-5), which is higher than that suggested value of USEPA (1x10(-6)) and may cause potential harm to human health. The greatest health risk is in winter, followed by autumn, summer minimum.

[Pollution and source of atmospheric volatile organic compounds in urban-rural juncture belt area in Beijing].

A method for determining volatile organic compounds (VOCs) by cryogenic dynamic adsorption in solid adsorbent tubes, subsequent thermal desorption with cryofocusing in a cold trap and analysis by gas chromatography and mass spectrometry was adapted. Volatile organic content levels, spatial and temporal distribution and sources were studied. Results indicated that 265 species were detected in atmospheric environment of this area, including alkanes, alkenes, aromatics, halohydrocarbons and oxygenated compounds. The average concentration of VOCs is 431.7 microg x m(-3), followed by aromatics 248.1 microg x m(-3), alkanes 130.5 microg x m(-3) alkenes 11.7 microg x m(-3), halohydrocarbons 22.4 microg x m(-3), oxygenated compounds 18.6 microg x m(-3), respectively. Benzene, toluene, ethylbenzene, xylene and so on have a comparatively high content. Aromatics and alkanes are the most abundant VOCs; Organic pollutants generally occurred at a relatively high level in the morning and evening traffic rush hours. VOCs varied with seasons: winter maximum, followed by autumn, summer minimum. Source analysis showed that atmospheric VOCs mainly come from vehicular exhaust, gasoline evaporation, use of adhesive and solvent and vegetation emission. They accounted for 53.4%, 20.1%, 11.0% and 5.93%, respectively.

[Study on foreign regulations and standards of stationary sources VOCs emission control].

By investigating volatile organic compounds (VOCs) emission control regulations and standards of the United States, the European Union and Japan, the suggestions on VOCs emission control and standards formulating in China were presented. Referencing foreign successful environmental management approach and experience, as well as the corresponding regulations and standards, the author believed that China can find a simple and highly effective way for controlling VOCs, through establishing the emission standards system, innovating VOCs emission control approach, improving VOCs emission control efficiency and unifying VOCs monitoring methods.