Nickel catalysts supported on MgO with different specific surface area for carbon dioxide reforming of methane

In this paper, three kinds of MgO with different specific surface area were prepared, and their effects on the catalytic performance of nickel catalysts for the carbon dioxide reforming of methane were investigated. The results showed that MgO support with the higher specific surface area led to the higher dispersion of the active metal, which resulted in the higher initial activity. On the other hand, the specific surface area of MgO materials might not be the dominant factor for the basicity of support to chemisorb and activate CO2, which was another important factor for the performance of catalysts. Herein, Ni/MgO(CA) catalyst with proper specific surface area and strong ability to activate CO2exhibited stable catalytic property and the carbon species deposited on the Ni/MgO(CA) catalyst after 10 h of reaction at 650 ?C were mainly activated carbon species.

Carbon dioxide reforming of methane over bimetallic catalysts of Pt-Ru/γ-Al_2O_3 for thermochemical energy storage

The reaction of CO2 reforming of CH4 has been investigated with y-A1203-supported platinum and ruthenium bimetallic catalysts, with the specific purpose of thermochemical energy storage. The catalysts were prepared by using the wetness impregnation method. The prepared catalysts were characterized by a series of physico-chemical characterization techniques such as BET surface area, thermo-gravimetric （TG）, transmission electron microscope （TEM） and X-ray photoelectron spectroscopy （XPS）. In addition, the amount of carbon deposits on the surface of the catalysts and the type of the carbonaceous species were discussed by TG. It was found that the bimetallic Pt-Ru/7-A1203 catalysts exhibit both superior catalytic activity and remarkable stability by comparison of monometallic catalysts. During the 500 h stability test, the bimetallic catalyst showed a good performance at 800 ~C in CO2 reforming of CH4, exhibiting an excellent anti-carbon performance with the mass loss of less than 8.5%. The results also indicate that CO2 and CH4 have quite stable conversions of 96.0 % and 94.0 %, respectively. Also, the selectivity of the catalysts is excellent with the products ratio of CO/H2 maintaining at 1.02. Furthermore, it was found in TEM images that the active carbonaceous species were formed during the catalytic reaction, and well-distributed dot-shaped metallic particles with a relatively uniform size of about 3 nm as well as amorphous carbon structures were observed. Combined with BET, TG, TEM tests, it is concluded that the selected bimetallic catalysts can work continuously in a stable state at the high temperature, which has a potential to be utilized for the closed-loop cycle of the solar thermochemical energy storage in future industry applications.

Adsorption behavior of carbon dioxide and methane in bituminous coal:A molecular simulation study

The adsorption behavior of CO_2, CH_4 and their mixtures in bituminous coal was investigated in this study. First, a bituminous coal model was built through molecular dynamic(MD) simulations, and it was confirmed to be reasonable by comparing the simulated results with the experimental data. Grand Canonical Monte Carlo(GCMC)simulations were then carried out to investigate the single and binary component adsorption of CO_2 and CH_4with the built bituminous coal model. For the single component adsorption, the isosteric heat of CO_2 adsorption is greater than that of CH_4 adsorption. CO_2 also exhibits stronger electrostatic interactions with the heteroatom groups in the bituminous coal model compared with CH_4, which can account for the larger adsorption capacity of CO_2 in the bituminous coal model. In the case of binary adsorption of CO_2 and CH_4mixtures, CO_2 exhibits the preferential adsorption compared with CH_4 under the studied conditions. The adsorption selectivity of CO_2 exhibited obvious change with increasing pressure. At lower pressure, the adsorption selectivity of CO_2 shows a rapid decrease with increasing the temperature, whereas it becomes insensitive to temperature at higher pressure. Additionally, the adsorption selectivity of CO_2 decreases gradually with the increase of the bulk CO_2 mole fraction and the depth of CO_2 injection site.

Diurnal variations of carbon dioxide,methane,and nitrous oxide fluxes from invasive Spartina alterniflora dominated coastal wetland in northern Jiangsu Province

The invasions of the alien species such as Spartina alterniflora along the northern Jiangsu coastlines have posed a threat to biodiversity and the ecosystem function.Yet,limited attention has been given to their potential influence on greenhouse gas（GHG） emissions,including the diurnal variations of GHG fluxes that are fundamental in estimating the carbon and nitrogen budget.In this study,we examined the diurnal variation in fluxes of carbon dioxide（CO_2）,methane（CH_4）,and nitrous oxide（N2O） from a S.alterniflora intertidal flat in June,October,and December of 2013 and April of 2014 representing the summer,autumn,winter,and spring seasons,respectively.We found that the average CH_4 fluxes on the diurnal scale were positive during the growing season while negative otherwise.The tidal flat of S.alterniflora acted as a source of CH_4 in summer（June） and a combination of source and sink in other seasons.We observed higher diurnal variations in the CO_2 and N_2O fluxes during the growing season（1 536.5 mg CO_2 m^（–2） h^（–1） and 25.6 μg N_2O m^（–2） h^（–1）） compared with those measured in the non-growing season（379.1 mg CO_2 m^（–2） h^（–1） and 16.5 μg N_2O m^（–2） h^（–1））.The mean fluxes of CH_4 were higher at night than that in the daytime during all the seasons but October.The diurnal variation in the fluxes of CO_2 in June and N_2O in December fluctuated more than that in October and April.However,two peak curves in October and April were observed for the diurnal changes in CO_2 and N_2O fluxes（prominent peaks were found in the morning of October and in the afternoon of April,respectively）.The highest diurnal variation in the N_2O fluxes took place at 15：00（86.4 μg N_2O m^（–2） h^（–1）） in June with an unimodal distribution.Water logging in October increased the emission of CO_2（especially at nighttime）,yet decreased N_2O and CH_4 emissions to a different degree on the daily scale because of the restrained diffusion rates of the gases.The seasonal and diurnal variations of CH_4 and CO_2 fluxes did not correlate to the air and soil temperatures,whereas the seasonal and diurnal variation of the fluxes of N_2O in June exhibited a significant correlation with air temperature.When N_2O and CH_4 fluxes were converted to CO_2-e equivalents,the emissions of N_2O had a remarkable potential to impact the global warming.The mean daily flux（MF） and total daily flux（TDF） were higher in the growing season,nevertheless,the MF and TDF of CO_2 were higher in October and those of CH_4 and N_2O were higher in June.In spite of the difference in the optimal sampling times throughout the observation period,our results obtained have implications for sampling and scaling strategies in estimating the GHG fluxes in coastal saline wetlands.

Diel and seasonal variation of methane and carbon dioxide fluxes at Site Guojiaba, the Three Gorges Reservoir

In order to investigate the CH4 and CO2 fluxes across the water-gas interface and identify their controlling factors, four diel field campaigns and one monthly sampling campaign during June 2010-May 2011 were carried out at a site near the Three Gorges Dam, China. The averaged CH4 and CO2 fluxes across the air-water interface from the site were much less than those reported from reservoirs in tropic and temperate regions, and from the natural river channels of the Yangtze River. CH4 Fluxes at the site were very low compared to most other reservoirs or natural lakes. One of the most important reasons may be due to the oxidation of CH4 in the water column owing to the great water depth and high DO in water in the Three Gorges Reservoir. The averaged monthly CH4 and CO2 fluxes at the site during the observation year were 0.05 mg/（m^2·hr） and 104.43 mg/（m^2·hr） respectively with the maximum occurred in July 2010. The monthly CO2 fluxes during the observation year were positively correlated to the surface water temperature, and negatively correlated to the air pressure and the surface water pH. The CO2 flux showed a positive correlation with DOC to some extent, although not significantly, which indicated that allochthonous organic C was a major source of CO2 and biogeochemical processes in this reservoir were C-limited. The significantly positive correlation between the reservoir outflow and the seasonal gas flux indicate the disturbance condition of the water body dominated the seasonal gas emission.

Effect of barley straw biochar application on greenhouse gas emissions from upland soil for Chinese cabbage cultivation in short-term laboratory experiments

Chinese cabbage was cultivated in upland soil with the addition of biochar in order to investigate the potential for reduction of greenhouse gas emissions. Barley straw biochar(BSB) was introduced in a Wagner pot(1/5000a) in amounts of 0(BSB0, control), 100(BSB100), 300(BSB300), and 500(BSB500) kg 10a^(-1). After the addition of BSB into the upland soil, carbon dioxide(CO_2) emission increased while methane(CH_4) and nitrous oxide(N_2O) emissions decreased. The highest CO2 flux was measured for the BSB500 sample,(84.6 g m^(-2)) followed by BSB300, BSB100, and BSB0 in decreasing order. Relative to those of control, the total CH_4 flux and N_2O flux for the BSB500 treatment were lower by 31.6% and 26.1%, respectively. The global warming potential(GWP) of the treatment without biochar was 281.4 g CO_2 m-2 and those for treatments with biochar were in the range from 194.1 to 224.9 g CO_2 m^(-2). Therefore, introducing BSB into upland soil to cultivate Chinese cabbages can reduce the global warming potential.

Low-temperature utilization of CO_2 and CH_4 by combining partial oxidation with reforming of methane over Ru-based catalysts

Combination of partial oxidation of methane （POM） with carbon dioxide reforming of methane （CRM） has been studied over Ru-based catalysts at 550℃.POM,CRM and combined reaction were performed over 8wt%Ru/γ-Al2O 3 and the results show that both POM and CRM contribute to the combined reaction,between which POM plays a more important role.Moreover,the addition of Ce to Ru-based catalyst results in an improvement in the activity and CO selectivity under the adopted reaction conditions.The Ce-doped catalyst was characterized by N2 adsorption-desorption,SEM,XRD,TPR,XPS and in situ DRIFTS.The mechanism has been studied by in situ DRIFTS together with the temperature distribution of catalyst bed.The mechanism of the combined reaction is more complicated and it is the combination of POM and CRM mechanisms in nature.The present paper provides a new catalytic system to activate CH4 and CO2 at a rather low temperature.

Modification of Ni/SiO_2 Catalysts by Means of a Novel Plasma Technology

Atmospheric high frequency cold plasma jet was applied to modify Ni/SiO2 catalysts. The catalysts prepared by two different methods with plasma jet were compared with conventional catalysts. BET, XRD, H2-TPD and high-resolution transmission electron microscopy （HRTEM） were used to characterize these catalysts. The results showed that the catalyst prepared with plasma jet had higher nickel dispersion, larger specific surface area and smaller nickel particle size, about 5 nanometres. Detailed analyses revealed that improved structure and characteristic of the plasma catalyst were benefited from the large amount of hydrogen atoms in the plasma jet, by which the catalyst reduction can be easily achieved in shorter period of time at lower temperature, thus avoiding sintering and conglomeration of the active particles and the support. The activity of catalysts was investigated in the methane reforming with CO2. It is shown that the conversions of CH4 and CO2, the yields of H2 and CO were all significantly increased for the plasma catalysts.

Ground-based remote sensing of atmospheric total column CO_2 and CH_4 by direct sunlight in Hefei

Fourier transform spectrometry has played an important role in the three-dimensional greenhouse gas monitoring as the focus of attention on global warming in the past few years. In this paper, a ground-based low-resolution remote sensing system measuring the total columns of CO2 and CH4 is developed, which tracks the sun automatically and records the spectra in real-time and has the advantages of portability and low cost. A spectral inversion algorithm based on nonlinear least squares spectral fitting procedure for determining the column concentrations of these species is described. Atmospheric transmittance spectra are computed line-by-line in the forward model and observed on-line by direct solar radiation. Also, the wavelength shifts are introduced and the influence of spectral resolution is discussed. Based on this system and algorithm, the vertical columns of O2, CO2, and CH4 are calculated from total atmospheric observation transmittance spectra in Hefei, and the results show that the column averaged dry-air mole fractions of CO2 and CH4 are measured with accuracies of 3.7% and 5%, respectively. Finally, the H2O columns are compared with the results observed by solar radiometer at the same site and the calculated correlation coefficient is 0.92, which proves that this system is suitable for field campaigns and used to monitor the local greenhouse gas sources under the condition of higher accuracy, indirectly.

Characteristics of greenhouse gas emission in three full-scale wastewater treatment processes

Three full-scale wastewater treatment processes, Orbal oxidation ditch, anoxic/anaerobic/aerobic （reversed A^2O） and anaerobic/anoxic/aerobic （A^2O）, were selected to investigate the emission characteristics of greenhouse gases （GHG）, including carbon dioxide （CO2）, methane （CH4） and nitrous oxide （N2O）. Results showed that although the processes were different, the units presenting high GHG emission fluxes were remarkably similar, namely the highest CO2 and N2O emission fluxes occurred in the aerobic areas, and the highest CH4 emission fluxes occurred in the grit tanks. The GHG emission amount of each unit can be calculated from its area and GHG emission flux. The calculation results revealed that the maximum emission amounts of CO2, CH4 and N2O in the three wastewater treatment processes appeared in the aerobic areas in all cases. Theoretically, CH4 should be produced in anaerobic conditions, rather than aerobic conditions. However, results in this study showed that the CH4 emission fluxes in the forepart of the aerobic area were distinctly higher than in the anaerobic area. The situation for N2O was similar to that of CH4： the N2O emission flux in the aerobic area was also higher than that in the anoxic area. Through analysis of the GHG mass balance, it was found that the flow of dissolved GHG in the wastewater treatment processes and aerators may be the main reason for this phenomenon. Based on the monitoring and calculation results, GHG emission factors for the three wastewater treatment processes were determined. The A^2O process had the highest CO2 emission factor of 319.3 g CO2/kg CODremoved, and the highest CH4 and N2O emission factors of 3.3 g CH4/kg CODremoved and 3.6 g N2O/kg TNremoved were observed in the Orbal oxidation ditch process.

Study of atmospheric CO2 and CH4 at Longfengshan WMO/GAW regional station： The variations, trends, influence of local sources/sinks, and transport

Atmospheric CO_2 and CH_4 have been continuously measured since 2009 at Longfengshan WMO/GAW station(LFS) in China. Variations of the mole fractions, influence of long-distance transport, effects of local sources/sinks and the characteristics of synoptic scale variations have been studied based on the records from 2009 to 2013. Both the CO_2 and CH_4 mole fractions display increasing trends in the last five years, with growth rates of 3.1±0.02 ppm yr.1 for CO_2 and 8±0.04 ppb yr.1(standard error, 1-σ)for CH_4. In summer, the regional CO_2 mole fractions are apparently lower than the Marine Boundary Layer reference, with the lowest value of.13.6±0.7 ppm in July, while the CH_4 values are higher than the MBL reference, with the maximum of 139±6 ppb.From 9 to 17(Local time, LT) in summer, the atmospheric CO_2 mole fractions at 10 m a.g.l. are always lower than at 80 m, with a mean difference of.1.1±0.2 ppm, indicating that the flask sampling approach deployed may underestimate the background mole fractions in summer. In winter, anthropogenic emissions dominate the regional CO_2 and CH_4 mole fractions. Cluster analysis of backward trajectories shows that atmospheric CO_2 and CH_4 at LFS are influenced by anthropogenic emissions from the southwest(Changchun and Jilin city) all year. The synoptic scale variations indicate that the northeastern China plain acts as an important source of atmospheric CO_2 and CH_4 in winter.

Effects of Pits and Mounds Following Windthrow Events on Soil Features and Greenhouse Gas Fluxes in a Temperate Forest

Pit and mound micro-relief(resultant microsites from trees uprooted by windthrow) could have regimes of microclimate and soil features that differ from areas of undisturbed soil. In an attempt to provide a comprehensive evaluation of the significance of pits and mounds on soil features and also the dynamics of greenhouse gas(GHG) fluxes at local scale, this study was carried out in a reserved area of Darabkola forest in Mazandaran Province, northern Iran. The age of a pit and mound was considered equal to the degree of decay of the blown down tree. Three microsites were distinguished, consisting of pit bottom(PB), mound top(MT) and undisturbed area(UA). Soil samples were taken at 0–15 and 15–30 cm depths from all microsites and analysed for soil physical, chemical and biological features. Our findings suggested that in context of forest ecology, pits and mounds following windthrow events should be considered as an effective factor influencing soil features(i.e., density, texture, water content, p H, organic C, total N, available nutrients and earthworm density/biomass) and especially GHG fluxes. Results showed that MT acted as a sink for N2O(-0.010 mg N2 O m-2d-1) and CH4(-0.257 mg CH4m-2d-1) fluxes and also produced lower CO2 concentrations(0.095 mg CO2 m-2d-1) than PB(0.207 mg CO2 m-2d-1) and UA(0.098 mg CO2 m-2d-1). As a consequence, a separation into pits/mounds would be important for a precise budgeting of greenhouse gases.

Ammonia and greenhouse gas emissions from a subtropical wheat field under different nitrogen fertilization strategies

Minimizing soil ammonia（NH_3） and nitrous oxide（N_2O） emission factors（EFs） has significant implications in regional air quality and greenhouse gas（GHG） emissions besides nitrogen（N） nutrient loss.The aim of this study was to investigate the impacts of different N fertilizer treatments of conventional urea,polymer-coated urea,ammonia sulfate,urease inhibitor（NBPT,N-（n-butyl） thiophosphoric triamide）-treated urea,and nitrification inhibitor（DCD,dicyandiamide）-treated urea on emissions of NH_3 and GHGs from subtropical wheat cultivation.A field study was established in a Cancienne silt loam soil.During growth season,NH_3 emission following N fertilization was characterized using active chamber method whereas GHG emissions of N_2O,carbon dioxide（CO_2）,and methane（CH_4） were by passive chamber method.The results showed that coated urea exhibited the largest reduction（49%） in the EF of NH_3-N followed by NBPT-treated urea（39%） and DCD-treated urea（24%） over conventional urea,whereas DCD-treated urea had the greatest suppression on N_2O-N（87%） followed by coated urea（76%） and NBPT-treated urea（69%）.Split fertilization of ammonium sulfate-urea significantly lowered both NH_3-N and N_2O-N EF values but split urea treatment had no impact over one-time application of urea.Both NBPT and DCD-treated urea treatments lowered CO_2-C flux but had no effect on CH_4-C flux.Overall,application of coated urea or urea with NPBT or DCD could be used as a mitigation strategy for reducing NH_3 and N_2O emissions in subtropical wheat production in Southern USA.

Greenhouse gas emissions from oilfield-produced water in Shengli Oilfield,Eastern China

Greenhouse gas（GHG） emissions from oil and gas systems are an important component of the GHG emission inventory. To assess the carbon emissions from oilfield-produced water under atmospheric conditions correctly, in situ detection and simulation experiments were developed to study the natural release of GHG into the atmosphere in the Shengli Oilfield,the second largest oilfield in China. The results showed that methane（CH4） and carbon dioxide（CO2） were the primary gases released naturally from the oilfield-produced water.The atmospheric temperature and release time played important roles in determining the CH4 and CO2emissions under atmospheric conditions. Higher temperatures enhanced the carbon emissions. The emissions of both CH4 and CO2from oilfield-produced water were highest at 27°C and lowest at 3°C. The bulk of CH4 and CO2was released from the oilfield-produced water during the first release period, 0–2 hr, for each temperature, with a maximum average emission rate of 0.415 g CH4/（m3·hr） and 3.934 g CO2/（m3·hr）, respectively. Then the carbon emissions at other time periods gradually decreased with the extension of time. The higher solubility of CO2 in water than CH4 results in a higher emission rate of CH4 than CO2over the same release duration. The simulation proved that oilfield-produced water is one of the potential emission sources that should be given great attention in oil and gas systems.

Rh doping effect on coking resistance of Ni/SBA-15 catalysts in dry reforming of methane

A series of SBA-15 supported bimetallic Rh–Ni catalysts with different weight ratio of Rh/Ni in the range of 0–0.04 were prepared for carbon dioxide reforming of methane. The doping effect of Rh on catalytic activity as well as carbon accumulation and removal over the catalysts was studied. The characterization results indicated that the addition of a small amount of Rh promoted the reducibility of Ni particles and decreased the Ni particle size. During the dry reforming reaction, the carbon deposition was originated from CH4 decomposition and CO disproportionation. The Rh–Ni catalyst with small metallic particle size inhibited the carbon formation and exhibited high efficiency in the removal of coke. In comparison with bare Ni-based catalyst, the Rh–Ni bimetallic catalysts showed high activity and stability in the dry reforming of methane.