For more and purer hydrogen-the progress and challenges in water gas shift reaction

The water gas shift(WGS) reaction is a standard reaction that is widely used in industrial hydrogen production and removal of carbon monoxide. The improved catalytic performance of WGS reaction also contributes to ammonia synthesis and other reactions. Advanced catalysts have been developed for both high and low-temperature reactions and are widely used in industry. In recent years, supported metal nanoparticle catalysts have been researched due to their high metal utilization. Low-temperature catalysts have shown promising results, including high selectivity, high shift rates, and higher activity potential. Additionally, significant progress has been made in removing trace CO through the redox reaction in electrolytic cell. This paper reviews the development of WGS reaction catalysts, including the reaction mechanism, catalyst design, and innovative research methods. The catalyst plays a crucial role in the WGS reaction, and this paper provides an instant of catalyst design under different conditions. The progress of catalysts is closely related to the development of advanced characterization techniques.Furthermore, modifying the catalyst surface to enhance activity and significantly increase reaction kinetics is a current research direction. This review goals to stimulate a better understanding of catalyst design, performance optimization, and driving mechanisms, leading to further progress in this field.

Adaptability of Development Methods for Offshore Gas Cap Edge Water Reservoirs under Different Permeability Levels

The BZ 34-1 oilfield is a typical gas cap edge water reservoir in the Bohai oilfield. The main characteristics of the oilfield were multi-phase sand body stacking and the sand body was composed of three parts: gas cap, oil reservoir, and edge water. The actual production site results show that the permeability difference of multi-layer sand bodies has a serious impact on the development effect. This article establishes a typical reservoir model numerical model based on the total recovery degree of the reservoir and the recovery degree of each layer, and analyzes the impact of permeability gradient. As the permeability gradient increases, the total recovery degree of all four well patterns decreases, and the total recovery degree gradually decreases. The recovery degree of low permeability layers gradually decreases, and the recovery degree of high permeability layers gradually increases. As the permeability gradient increases, the degree of recovery gradually decreases under different water contents. As the permeability gradient increases, the reduction rate of remaining oil saturation in low permeability layers is slower, while the reduction rate of remaining oil saturation in high permeability layers was faster. By analyzing the impact of permeability gradient on the development effect of oil fields, we could further deepen our understanding of gas cap edge water reservoirs and guide the development of this type of oil field.

Effect of Mg/Al atom ratio of support on catalytic performance of Co-Mo/MgO-Al_2O_3 catalyst for water gas shift reaction

Co-Mo-based catalysts supported on mixed oxide supports MgO-Al2O3 with different Mg/Al atom ratios for water gas shift reaction were studied by means of TPR, Raman, XPS and ESR. It was found that the octahedral Mo species in oxidized Co-Mo/MgO（x）-Al2O3 catalyst and the contents of Mo^5＋, Mo^4＋, S^2- and S^2-2 species in the functioning catalysts increased with increasing the Mg/Al atom ratio of the support under the studied experimental conditions. This is favorable for the formation of the active Co-Mo-S phase of the catalysts. Catalytic performance testing results showed that the catalysts Co-Mo/MgO-Al2O3 with the Mg/Al atom ratio of the support in the range of 0.475-0.525 exhibited optimal catalytic activity for the reaction.

Reverse water gas shift reaction over Co-precipitated Ni-CeO_2 catalysts

The Ni-CeO2 catalysts with different Ni contents were prepared by a co-precipitation method and used for Reverse Water Gas Shift （RWGS） reaction. 2wt.%Ni-CeO2 showed excellent catalytic performance in terms of activity, selectivity, and stability for RWGS reaction. Characterizations of the catalyst samples were conducted by XRD and TPR. The results indicated that, in Ni-CeO2 catalysts, there were three kinds of nickel, nickel ions in ceria lattice, highly dispersed NiO and bulk NiO. Oxygen vacancies were formed in CeO2 lattice due to the incorporation of Ni^2＋ ions into ceria lattice. Oxygen vacancies formed in ceria lattice and highly dispersed Ni were key active components for RWGS, and bulk Ni was key active component for methanation of CO2.

A novel steady-state productivity equation for horizontal wells in bottom water drive gas reservoirs

It is known that there is a discrepancy between field data and the results predicted from the previous equations derived by simplifying three-dimensional（3-D） flow into two-dimensions（2-D）.This paper presents a new steady-state productivity equation for horizontal wells in bottom water drive gas reservoirs.Firstly,the fundamental solution to the 3-D steady-state Laplace equation is derived with the philosophy of source and the Green function for a horizontal well located at the center of the laterally infinite gas reservoir.Then,using the fundamental solution and the Simpson integral formula,the average pseudo-pressure equation and the steady-state productivity equation are achieved for the horizontal section.Two case-studies are given in the paper,the results calculated from the newly-derived formula are very close to the numerical simulation performed with the Canadian software CMG and the real production data,indicating that the new formula can be used to predict the steady-state productivity of such horizontal gas wells.

Ceria modified three-dimensionally ordered macro-porous Pt/TiO_2 catalysts for water-gas shift reaction

Three-dimensionally ordered macro-porous （3DOM） TiO2 and ceria-modified 3DOM TiO2 supported platinum catalysts were prepared with template and impregnation methods, and the resultant samples were characterized by scanning electron microscopy（SEM）, X-ray diffractometer（XRD）, high-resolution transmission electron microscopy（HRTEM） and temperature programmed reducfion（TPR） techniques. The catalytic performances over the platinum-based catalysts were investigated for water-gas shift （WGS） reaction in a wide temperature range （180-360 ℃）. The results showed that 3DOM Pt/TiO2 catalyst exhibited obviously better catalytic performance than the corresponding non macro-porous catalyst, owing to the macro-porous structure favoring mass transfer. Addition of celia into 3DOM Pt/TiO2 led to improvement of catalytic activity. TPR and HRTEM results showed that the interaction existed between ceria and titanium oxide and addition of ceria promoted the reducibility of platinum oxide and TiO2 on the interface of platinum and TiO2 particles, which contributed to high activity of the celia modified catalysts. The results indicated that ceria-modified 3DOM Pt/TiO2 was a promising candidate of fuel cell oriented WGS catalyst.

Underwater gas self-transportation along femtosecond laser-written open superhydrophobic surface microchannels(<100μm)for bubble/gas manipulation

Underwater transportation of bubbles and gases has essential applications in manipulating and using gas,but achieving this function at the microscopic level remains a significant challenge.Here,we report a strategy to self-transport gas in water along a laser-induced open superhydrophobic microchannel with a width less than 100μm.The femtosecond laser can directly write superhydrophobic and underwater superaerophilic microgrooves on the polytetrafluoroethylene(PTFE)surfaces.In water,the single laser-induced microgroove and water medium generate a hollow microchannel.When the microchannel connects two superhydrophobic regions in water,the gas spontaneously travels from the small region to the large area along this hollow microchannel.Gas self-transportation can be extended to laser-drilled microholes through a thin PTFE sheet,which can even achieve anti-buoyancy unidirectional penetration.The gas can overcome the bubble’s buoyance and spontaneously travel downward.The Laplace pressure difference drives the processes of spontaneous gas transportation and unidirectional bubble passage.We believe the property of gas self-transportation in the femtosecond laser-structured open superhydrophobic and underwater superaerophilic microgrooves/microholes has significant potential applications related to manipulating underwater gas.

Boosting the water gas shift reaction on Pt/CeO_(2)-based nanocatalysts by compositional modification: Support doping versus bimetallic alloying

The water gas shift reaction is of vital significance for the generation and transition of energy due to the application in hydrogen production and industries such as ammonia synthesis and fuel cells.The influence of support doping and bimetallic alloying on the catalytic performance of Pt/Ce O_(2)-based nanocatalysts in water gas shift reaction was reported in this work.Various lanthanide ions and 3d transition metals were respectively introduced into the Ce O_(2)support or Pt to form Pt/Ce O_(2):Ln(Ln=La,Nd,Gd,Tb,Yb)and Pt M/Ce O_(2)(M=Fe,Co,Ni)nanocatalysts.The sample of Pt/Ce O_(2):Tb showed the highest activity(TOF at 200℃=0.051 s^(-1))among the Pt/Ce O_(2):Ln and the undoped Pt/Ce O_(2)catalysts.Besides,the sample of Pt Fe/Ce O_(2)exhibited the highest activity(TOF at 200℃=0.12 s^(-1))among Pt M/Ce O_(2)catalysts.The results of the multiple characterizations indicated that the catalytic activity of Pt/Ce O_(2):Ln catalysts was closely correlated with the amount of oxygen vacancies in doped ceria support.However,the different activity of Pt M/Ce O_(2)bimetallic catalysts was owing to the various Pt oxidation states of the bimetals dispersed on ceria.The study of the reaction pathway indicated that both the samples of Pt/Ce O_(2)and Pt/Ce O_(2):Tb catalyzed the reaction through the formate pathway,and the enhanced activity of the latter derived from the increased concentration of oxygen vacancies along with promoted water dissociation.As for the sample of Pt Fe/Ce O_(2),its catalytic mechanism was the carboxyl route with a higher reaction rate due to the moderate valence of Pt along with improved CO activation.

Monolithic macroporous catalysts—a new route for miniaturization of water-gas shift reactor

Monolithic macroporous Pt/CeO2/Al2O3 catalysts were prepared using concentrated emulsions synthesis route, and the obtained samples were characterized with SEM, TG, TEM, XRD and TPR techniques. These monolithic catalysts were applied to water gas shift （WGS） reaction in reformed gases. The SEM and TEM results indicated that the monoliths possessed macroporosity, and that the platinum particles homogeneously dispersed on the supports with the particle size in the range of 1-2 nm. The reducibility of the catalysts was characterized by TPR method, and it was shown that the monolithic PtOx/CeO2/Al2O3 exhibited the similar reducibility property to that of the particle PtOx/CeO2 reported in literatures. The CO conversion over the monolithic catalysts is higher than that over micro-reactor catalysts for WGS reaction in the reformed gases conditions, indicating that the monolithic macroporous catalysts is a potential new route for miniaturization of WGS reactor.

Experimental study on total dissolved gas supersaturation in water

More and more high dams have been constructed and operated in China. The total dissolved gas （TDG） supersaturation caused by dam discharge leads to gas bubble disease or even death of fish, Through a series of experiments, the conditions and requirements of supersaturated TDG generation were examined in this study. The results show that pressure （water depth）, aeration, and bubble dissolution time are required for supersaturated TDG generation, and the air-water contact area and turbulence intensity are the main factors that affect the generation rate of supersaturated TDG. The TDG supersaturation levels can be reduced by discharging water to shallow shoals downstream of the dam or using negative pressure pipelines. Furthermore, the TDG supersaturation levels in stilling basins have no direct relationship with those in reservoirs. These results are of great importance for further research on the prediction of supersaturated TDG generation caused by dam discharge and aquatic protection.

A three dimensional visualized physical simulation for natural gas charging in the micro-nano pore system

A micro-nano pore three-dimensional visualized real-time physical simulation of natural gas charging, in-situ pore-scale computation, pore network modelling, and apparent permeability evaluation theory were used to investigate laws of gas and water flow and their distribution, and controlling factors during the gas charging process in low-permeability(tight) sandstone reservoir. By describing features of gas-water flow and distribution and their variations in the micro-nano pore system, it is found that the gas charging in the low permeability(tight) sandstone can be divided into two stages, expansion stage and stable stage. In the expansion stage, the gas flows continuously first into large-sized pores then small-sized pores, and first into centers of the pores then edges of pores;pore-throats greater than 20 μm in radius make up the major pathway for gas charging. With the increase of charging pressure, movable water in the edges of large-sized pores and in the centers of small pores is displaced out successively. Pore-throats of 20-50 μm in radius and pore-throats less than 20 μm in radius dominate the expansion of gas charging channels at different stages of charging in turn, leading to reductions in pore-throat radius, throat length and coordination number of the pathway, which is the main increase stage of gas permeability and gas saturation. Among which, pore-throats 30-50 μm in radius control the increase pattern of gas saturation. In the stable stage, gas charging pathways have expanded to the maximum, so the pathways keep stable in pore-throat radius, throat length, and coordination number, and irreducible water remains in the pore system, the gas phase is in concentrated clusters, while the water phase is in the form of dispersed thin film, and the gas saturation and gas permeability tend stable. Connected pore-throats less than 20 μm in radius control the expansion limit of the charging pathways, the formation of stable gas-water distribution, and the maximum gas saturation. The heterogeneity of connected pore-throats affects the dynamic variations of gas phase charging and gas-water distribution. It can be concluded that the pore-throat configuration and heterogeneity of the micro-nanometer pore system control the dynamic variations of the low-permeability(tight) sandstone gas charging process and gas-water distribution features.

An experimental and numerical study of chemically enhanced water alternating gas injection

In this work, an experimental study combined with numerical simulation was conducted to investigate the potential of chemically enhanced water alternating gas （CWAG） injection as a new enhanced oil recovery method. The unique feature of this new method is that it uses alkaline, surfactant, and polymer additives as a chemical slug which is injected during the water alternating gas （WAG） process to reduce the interfacial tension （IFT） and simultaneously improve the mobility ratio. In essence, the proposed CWAG process involves a combination of chemical flooding and immiscible carbon dioxide （CO2） injection and helps in IFT reduction, water blocking reduction, mobility control, oil swelling, and oil viscosity reduction due to CO2 dissolution. Its performance was compared with the conventional immiscible water alter- nating gas （I-WAG） flooding. Oil recovery utilizing CWAG was better by 26 % of the remaining oil in place after waterflooding compared to the recovery using WAG conducted under similar conditions. The coreflood data （cumulative oil and water production） were history mat- ched via a commercial simulator by adjusting the relative permeability curves and assigning the values of the rock and fluid properties such as porosity, permeability, and the experimentally determined IFT data. History matching ofthe coreflood model helped us optimize the experiments and was useful in determining the importance of the parameters influencing sweep efficiency in the CWAG process. The effectiveness of the CWAG process in pro- viding enhancement of displacement efficiency is evident in the oil recovery and pressure response observed in the coreflood. The results of sensitivity analysis on CWAG slug patterns show that the alkaline-surfactant-polymer injection is more beneficial after CO2 slug injection due to oil swelling and viscosity reduction. The CO2 slug size analysis shows that there is an optimum CO2 slug size, around 25 % pore volume which leads to a maximum oil recovery in the CWAG process. This study shows that the ultralow IFT system, i.e., IFT equaling 10 2 or 10 3 mN/ m, is a very important parameter in CWAG process since the water blocking effect can be minimized.

Promotion effect of Re additive on the bifunctional Ni catalysts for methanation coupling with water gas shift of biogas: Insights from activation energy

The cheap manganese sand was first modified by H2O2 and was further creatively utilized as Ni-based catalyst support.In order to enhance the catalytic performance,Re was added into the Ni-based catalyst and the promotion effect of Re on the methanation coupling with water gas shift of biogas was investigated from the perspective of activation energy.It was found that CH4 and CO2 formation rates,which separately represented the reaction rate of methanation and water gas shift,were both enhanced after Re addition compared to non-added catalyst.Two kinetics models including empirical model and K-model were employed and from the results of calculation,it showed that Re selectively decreased the activation energy of methanation reaction and had little impact on the activation energy of water gas shift.The increased CO2 formation rate was owing to the assistance of accelerated H2O production from methanation rather than the activation energy change in water gas shift.

Synthesis of Dimethyl Ether from CO Hydrogenation: a Thermodynamic Analysis of the Influence of Water Gas Shift Reaction

Three reactions involved in dimethyl ether (DME) synthesis from COhydrogenation: methanol synthesis reaction (MSR), methanol dehydration reaction (MDR) and water gasshift reaction (WGSR) are studied by thermodynamic calculation. For demonstrating this process indetail, three models, MSR, MSR+MDR, MSR+MDR+WGSR, are used. Their basic characteristics can beobtained by varying widely the ratios of H_2 to CO in the feed (no CO_2). Through thermodynamicanalysis a chemical synergic effect obviously exists in the second and third models. By comparisonbetween two models it is found that WGSR plays a special role in dimethyl ether synthesis. It ispossible for the two models to shift one to the other by regulating CO_2 concentration in feed. ForModel 2, the selectivity for DME in oxygenates (DME+methanol) does not change with the ratio of H_2to CO.

Study on the Quality Characteristics of Gas Field Water in Eastern Sichuan

Gas field water is the formation water produced together with natural gas in the process of natural gas exploitation.The gas field water treated is difficult to reach the standard due to its wide sources,numerous types and complex composition.In addition,it can pollute soil,surface water and groundwater.In this study,the quality and pollution characteristics of gas field water in eastern Sichuan were studied by conventional water quality determination and GC-MS.The results show that the main components of gas field water in eastern Sichuan were chloride,COD Cr,SS,anionic surfactant,sulfide and other substances.The gas field water could be divided into two types according to the characteristics of water quality,of which one had high mineralization and high organic compounds,and the other had high sulfur and high organic compounds.There were 17 kinds of organic pollutants in the gas field water,mainly including alkanes,alcohols,esters and a small amount of acids.

Selective synthesis of carbon monoxide via formates in reverse water–gas shift reaction over alumina-supported gold catalyst

Thermal decomposition of formic acid on SiO2, CeO2 and γ-Al2O3 was studied as an elementary step of reverse water–gas shit reaction（RWGS） over supported Au catalysts. γ-Al2O3 showed the highest CO selectivity among the tested oxides in the decomposition of formic acid. Infrared spectroscopy showed the formation of four formate species on γ-Al2O3： three η~1-type and one μ~2-type species, and these formates decomposed to CO at 473 K or higher. Au-loaded γ-Al2O3 samples were prepared by a depositionprecipitation method and used as catalysts for RWGS. The supported Au catalyst gave CO with high selectivity over 99% from CO2 and H2, which is attributed to the formation of formates on Au and subsequent decomposition to CO on γ-Al2O3.

Study on the Monitoring Malfunction of Water Pollution during Drought or Flood Period and Low-carbon and High-value Methodology--A Case Study of the Correlation Test of Water,Soil and Gas Pollution in Xiangxiang County

Based on the low-carbon and high-value methodology of chemical ecology and chemical informatics,combining theory and methods,taking saving,environmental protection,low carbon,high production,high value and circulation as values and aims,the relationship between human and land as a basis,ecosystem as a center,overall control as a goal and agricultural ecological engineering as a mean,environmental pollution detection,as one of bottlenecks for agricultural products and food security,should be solved firstly;through the field survey in dry years from 2009 to 2010 when drought and flood were frequent and the frequency of drought was higher than that of flood,plus the determination of surface water flow and water quantity in a small typical river basin,the correlation of local water,soil and gas in the county could be found,and the transfer of monitoring focus from water environment to atmospheric environment was possible and necessary.The study would promote the quantitative research on the correlation among water,soil and gas,and the results were in accordance with the conclusions of related studies.

MOLECULAR DYNAMICS SIMULATIONS OF FILLED AND EMPTY CAGE-LIKE WATER CLUSTERS IN LIQUID WATER AND THEIR SIGNIFICANCE TO GAS HYDRATE FORMATION MECHANISMS

Molecular dynamics simulations are performed to observe the evolutions of 512 and 51262 cage-like water clusters filled with or without a methane molecule immersed in bulk liquid water at 250 K and 230 K. The lifetimes of these clusters are calculated according to their Lindemann index δ (t) using the criteria of δ≥0.07. For both the filled and empty clusters, we find the dynamics of bulk water determines the lifetimes of cage-like water clusters, and that the lifetime of 512 62 cage-like cluster is the same as that of 512 cage-like cluster. Although the methane molecule indeed makes the filled cage-like cluster more stable than the empty one, the empty cage-like cluster still has chance to be long-lived compared with the filled clusters. These observations support the labile cluster hypothesis on the formation mechanisms of gas hydrates.

Three-stage pyrolysis–steam reforming–water gas shift processing of household,commercial and industrial waste plastics for hydrogen production

Five common single plastics and nine different household,commercial and industrial waste plastics were processed using a three-stage(i)pyrolysis,(ii)catalytic steam reforming and(iii)water gas shift reaction system to produce hydrogen.Pyrolysis of plastics produces a range of different hydrocarbon species which are subsequently catalytically steam reformed to produce H_(2)and CO and then undergo water gas shift reaction to produce further H_(2).The process mimics the commercial process for hydrogen production from natural gas.Processing of the single polyalkene plastics(high-density polyethylene(HDPE),low-density polyethylene(LDPE),and polypropylene(PP))produced similar H_(2)yields between 115 mmol and 120 mmol per gram plastic.Even though PS produced an aromatic product slate from the pyrolysis stage,further stages of reforming and water gas shift reaction produced a gas yield and composition similar to that of the polyalkene plastics(115 mmol H_(2)per gram plastic).PET gave significantly lower H_(2)yield(41 mmol per gram plastic)due to the formation of mainly CO,CO_(2)and organic acids from the pyrolysis stage which were not conducive to further reforming and water gas shift reaction.A mixture of the single plastics typical of that found in municipal solid waste produced a H_(2)yield of 102 mmol per gram plastic.Knowing the gas yields and composition from the single plastics enabled an estimation of the yields from a simulated waste plastic mixture and a‘real-world’waste plastic mixture to be determined.The different household,commercial and industrial waste plastic mixtures produced H_(2)yields between 70 mmol and 107 mmol per gram plastic.The H_(2)yield and gas composition from the single waste plastics gave an indication of the type of plastics in the mixed waste plastic samples.

Experimental study of the effects of a multistage pore-throat structure on the seepage characteristics of sandstones in the Beibuwan Basin:Insights into the flooding mode

To investigate the relationship between grain sizes, seepage capacity, and oil-displacement efficiency in the Liushagang Formation of the Beibuwan Basin, this study identifies the multistage pore-throat structure as a crucial factor through a comparison of oil displacement in microscopic pore-throat experiments. The two-phase flow evaluation method based on the Li-Horne model is utilized to effectively characterize and quantify the seepage characteristics of different reservoirs, closely relating them to the distribution of microscopic pores and throats. It is observed that conglomerate sandstones at different stages exhibit significant heterogeneity and noticeable differences in seepage capacity, highlighting the crucial role played by certain large pore throats in determining seepage capacity and oil displacement efficiency. Furthermore, it was found that the displacement effects of conglomeratic sandstones with strong heterogeneity were inferior to those of conventional homogeneous sandstone, as evidenced by multiple displacement experiments conducted on core samples with varying granularities and flooding systems. Subsequently, core-based experiments on associated gas flooding after water flooding were conducted to address the challenge of achieving satisfactory results in a single displacement mode for reservoirs with significant heterogeneity. The results indicate that the oil recovery rates for associated gas flooding after water flooding increased by 7.3%-16.4% compared with water flooding alone at a gas-oil ratio of approximately 7000 m^(3)/m^(3). Therefore, considering the advantages of gas flooding in terms of seepage capacity, oil exchange ratio, and the potential for two-phase production, gas flooding is recommended as an energy supplement mode for homogeneous reservoirs in the presence of sufficient gas source and appropriate tectonic angle. On the other hand, associated gas flooding after water flooding is suggested to achieve a more favorable development effect compared to a single mode of energy supplementation for strongly heterogeneous sandstone reservoirs.