Ca and Sr co-doping induced oxygen vacancies in 3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts for boosting low-temperature oxidative coupling of methane

It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.

Methane Emission from Rice Fields:Necessity for Molecular Approach for Mitigation

Anthropogenic methane emissions are a leading cause of the increase in global averagetemperatures,often referred to as global warming.Flooded soils play a significant role in methaneproduction,where the anaerobic conditions promote the production of methane by methanogenicmicroorganisms.Rice fields contribute a considerable portion of agricultural methane emissions,as riceplants provide both factors that enhance and limit methane production.Rice plants harbor both methaneproducingand methane-oxidizing microorganisms.Exudates from rice roots provide source for methaneproduction,while oxygen delivered from the root aerenchyma enhances methane oxidation.Studies haveshown that the diversity of these microorganisms depends on rice cultivars with some genes characterizedas harboring specific groups of microorganisms related to methane emissions.However,there is still aneed for research to determine the balance between methane production and oxidation,as rice plantspossess the ability to regulate net methane production.Various agronomical practices,such as fertilizerand water management,have been employed to mitigate methane emissions.Nevertheless,studiescorrelating agronomic and chemical management of methane with productivity are limited.Moreover,evidences for breeding low-methane-emitting rice varieties are scattered largely due to the absence ofcoordinated breeding programs.Research has indicated that phenotypic characteristics,such as rootbiomass,shoot architecture,and aerenchyma,are highly correlated with methane emissions.This reviewdiscusses available studies that involve the correlation between plant characteristics and methaneemissions.It emphasizes the necessity and importance of breeding low-methane-emitting rice varieties inaddition to existing agronomic,biological,and chemical practices.The review also delves into the idealphenotypic and physiological characteristics of low-methane-emitting rice and potential breeding techniques,drawing from studies conducted with diverse varieties,mutants,and transgenic plants.

Investigation of oxy-fuel combustion for methane and acid gas in a diffusion flame

Co-combustion of methane(CH4)and acid gas(AG)is required to sustain the temperature in Claus reaction furnace.In this study,oxy-fuel combustion of methane and acid gas has been experimentally studied in a diffusion flame.Three equivalence ratios(ER=1.0,1.5,2.0)and CH_(4)-addition ratios(CH_(4)/AG=0.3,0.5,0.7)were examined and the flame was interpreted by analyzing the distributions of the temperature and species concentration along central axial.CH_(4)-AG diffusion flame could be classified into three sections namely initial reaction,oxidation and complex reaction sections.Competitive oxidation of CH_(4)and H_(2)S was noted in the first section wherein H_(2)S was preferred and both were mainly proceeding decomposition and partial oxidation.SO_(2)was formed at oxidation section together with obvious presence of H2 and CO.However,H2 and CO were inclined to be sustained under fuel rich condition in the complex reaction section.Reducing ER and increasing CH4/AG contributed to higher temperature,H_(2)S and CH_(4)oxidation and CO_(2)reactivity.Hence a growing trend for CH_(4)and AG to convert into H_(2),CO and SO_(2)could be witnessed.And this factor enhanced the generation of CS2 and COS in the flame inner core by interactions of CH4 and CO_(2)with sulfur species.COS was formed through the interactions of CO and CO_(2)with sulfur species.The CS_(2)production directly relied on reaction of CH_(4)with sulfur species.The concentration of COS was greater than CS_(2)since CS_(2)was probably inhibited due to the presence of H_(2).COS and CS_(2)could be consumed by further oxidation or other complex reactions.

Micro segment analysis of supercritical methane thermal-hydraulic performance and pseudo-boiling in a PCHE straight channel

The printed circuit heat exchanger(PCHE) is receiving wide attention as a new kind of compact heat exchanger and is considered as a promising vaporizer in the LNG process. In this paper, a PCHE straight channel in the length of 500 mm is established, with a semicircular cross section in a diameter of 1.2 mm.Numerical simulation is employed to investigate the flow and heat transfer performance of supercritical methane in the channel. The pseudo-boiling theory is adopted and the liquid-like, two-phase-like, and vapor-like regimes are divided for supercritical methane to analyze the heat transfer and flow features.The results are presented in micro segment to show the local convective heat transfer coefficient and pressure drop. It shows that the convective heat transfer coefficient in segments along the channel has a significant peak feature near the pseudo-critical point and a heat transfer deterioration when the average fluid temperature in the segment is higher than the pseudo-critical point. The reason is explained with the generation of vapor-like film near the channel wall that the peak feature related to a nucleateboiling-like state and heat transfer deterioration related to a film-boiling-like state. The effects of parameters, including mass flow rate, pressure, and wall heat flux on flow and heat transfer were analyzed.In calculating of the averaged heat transfer coefficient of the whole channel, the traditional method shows significant deviation and the micro segment weighted average method is adopted. The pressure drop can mainly be affected by the mass flux and pressure and little affected by the wall heat flux. The peak of the convective heat transfer coefficient can only form at high mass flux, low wall heat flux, and near critical pressure, in which condition the nucleate-boiling-like state is easier to appear. Moreover,heat transfer deterioration will always appear, since the supercritical flow will finally develop into a filmboiling-like state. So heat transfer deterioration should be taken seriously in the design and safe operation of vaporizer PCHE. The study of this work clarified the local heat transfer and flow feature of supercritical methane in microchannel and contributed to the deep understanding of supercritical methane flow of the vaporization process in PCHE.

Extreme massive hydraulic fracturing in deep coalbed methane horizontal wells:A case study of the Linxing Block,eastern Ordos Basin,NW China

Deep coal seams show low permeability,low elastic modulus,high Poisson’s ratio,strong plasticity,high fracture initiation pressure,difficulty in fracture extension,and difficulty in proppants addition.We proposed the concept of large-scale stimulation by fracture network,balanced propagation and effective support of fracture network in fracturing design and developed the extreme massive hydraulic fracturing technique for deep coalbed methane(CBM)horizontal wells.This technique involves massive injection with high pumping rate+high-intensity proppant injection+perforation with equal apertures and limited flow+temporary plugging and diverting fractures+slick water with integrated variable viscosity+graded proppants with multiple sizes.The technique was applied in the pioneering test of a multi-stage fracturing horizontal well in deep CBM of Linxing Block,eastern margin of the Ordos Basin.The injection flow rate is 18 m^(3)/min,proppant intensity is 2.1 m^(3)/m,and fracturing fluid intensity is 16.5 m^(3)/m.After fracturing,a complex fracture network was formed,with an average fracture length of 205 m.The stimulated reservoir volume was 1987×10^(4)m^(3),and the peak gas production rate reached 6.0×10^(4)m^(3)/d,which achieved efficient development of deep CBM.

Increased Oxygen Vacancies in CuO-ZnO Snowflake-like Composites Drive the Hydrogenation of CO_(2) to Methanol

Cu/ZnO is widely used in the hydrogenation of carbon dioxide (CO_(2)) to methanol (CH_(3)OH) to improve the lowconversion rate and selectivity generally observed. In this work, a series of In, Zr, Co, and Ni-doped CuO-ZnO catalysts wassynthesized via a hydrothermal method. By introducing a second metal element, the activity and dispersion of the activesites can be adjusted and the synergy between the metal and the carrier can be enhanced, forming an abundance of oxygenvacancies. Oxygen vacancies not only adsorb CO_(2) but also activate the intermediates in methanol synthesis, playing a keyrole in the entire reaction. Co3O4-CuO-ZnO had the best catalytic performance (a CO_(2) conversion rate of 9.17%;a CH_(3)OHselectivity of 92.77%). This study describes a typical strategy for multi-component doping to construct a catalyst with anabundance of oxygen vacancies, allowing more effective catalysis to synthesize CH_(3)OH from CO_(2).

Decorating Single-Atom Catalysts with CO for Efficient Methane Conversion

Direct methane conversion has advantages such as low energy consumption,less processes,and being more economical.However,it is difficult to activate methane at room temperature due to the high dissociation energy of C-H bonds of methane.Additionally,the target products,such as methanol,acetic acid,and other oxygenates,are prone to overoxidation,resulting in the generation of CO_(2).Therefore,the design of catalysts with high activity and selectivity is important.

Oxygen vacancies enriched Ni-Co/SiO_(2)@CeO_(2) redox catalyst for cycling methane partial oxidation and CO_(2) splitting

Redox catalysts play a vital role in the interconversion of two significant greenhouse gases,CO_(2)and CH_(4),via chemical looping methane dry reforming technology.Herein,a series of transition metals-alloyed and core-shell structured Ni-M/SiO_(2)@CeO_(2)(M=Fe,Co,Cu,Mn,Zr)redox catalyst were fabricated and evaluated in a gas-solid fixed-bed reactor for cycling CH_(4)partial oxidation(PO_(x))and CO_(2)splitting.The catalysts are composed of spherical SiO_(2)core and CeO_(2)shell,and the highly dispersed Ni alloy nanoparticles are the interlayer between core and shell.The oxygen vacancy concentration of Ni-M/SiO_(2)@CeO_(2)followed the order of Co>Cu>Fe>Mn>Zr,and Ni alloying with transition metals significantly enhanced oxygen storage capacity(OSC).Ni-Co/SiO_(2)@CeO_(2)catalyst with abundant oxygen vacancies and a high OSC showed the lowest temperatures of CH_(4)activation(610℃)and CO_(2)decomposition(590℃),thus demonstrating excellent redox reactivity.The catalyst exhibited superior activity and structural stability in the continuous CH_(4)/CO_(2)redox cycles at 615℃,achieving 87%CH_(4)conversion and 83%CO selectivity.The proposed catalyst shows great potential for the utilization of CH_(4)and CO_(2)in a redox mode,providing a new sight for design redox catalyst in chemical looping or related fields.

Methanation of CO/CO_(2)for power to methane process:Fundamentals,status,and perspectives

Power-to-methane(P2M)processes,by converting electricity from renewable energy to H2and then into other high value-added and energy-intense chemicals in the presence of active catalysts,have become an effective solution for energy storage.However,the fluctuating electricity from intermittent renewable energy leads to a dynamic composition of reactants for downstream methanation,which requires an excellent heterogeneous catalyst to withstand the harsh conditions.Based on these findings,the objective of this review is to classify the fundamentals and status of CO/CO_(2)methanation and identify the pathways in the presence of various catalysts for methane production.In addition,this review sheds insight into the future development and challenges of CO_(2)or CO methanation,including the deactivation mechanisms and catalyst performance under dynamically harsh conditions.Finally,we elaborated on the advantages and development prospects of P2M,and then we summarized the current stage and ongoing industrialization projects of P2M.

Probing deactivation by coking in catalyst pellets for dry reforming of methane using a pore network model

Dry reforming of methane(DRM) is an attractive technology for utilizing the greenhouse gases(CO_(2) and CH_(4)) to produce syngas. However, the catalyst pellets for DRM are heavily plagued by deactivation by coking, which prevents this technology from commercialization. In this work, a pore network model is developed to probe the catalyst deactivation by coking in a Ni/Al_(2)O_(3) catalyst pellet for DRM. The reaction conditions can significantly change the coking rate and then affect the catalyst deactivation. The catalyst lifetime is higher under lower temperature, pressure, and CH_(4)/CO_(2) molar ratio, but the maximum coke content in a catalyst pellet is independent of these reaction conditions. The catalyst pellet with larger pore diameter, narrower pore size distribution and higher pore connectivity is more robust against catalyst deactivation by coking, as the pores in this pellet are more difficult to be plugged or inaccessible.The maximum coke content is also higher for narrower pore size distribution and higher pore connectivity, as the number of inaccessible pores is lower. Besides, the catalyst pellet radius only slightly affects the coke content, although the diffusion limitation increases with the pellet radius. These results should serve to guide the rational design of robust DRM catalyst pellets against deactivation by coking.

Methane Oxidation to Synthesis Gas Using Lattice Oxygen of La_(1-x)Sr_xMO_(3-λ)(M =Fe,Mn) Perovskite Oxides Instead of Molecular Oxygen

In this paper, the partial oxidation of methane to synthesis gas using lattice oxygen of La1- SrxMO3-λ (M=Fe, x Mn) perovskite oxides instead of molecular oxygen was investigated. The redox circulation between 11% O2/Ar flow and 11% CH4/He flow at 900℃ shows that methane can be oxidized to CO and H2 with a selectivity of over 90.7% using the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite oxides in an appropriate reaction condition, while the lost lattice x oxygen can be supplemented by air re-oxidation. It is viable for the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite x oxides instead of molecular oxygen to react with methane to synthesis gas in the redox mode.

Selective Hydrogenation of Polycyclic Aromatics to Monocyclic Aromatics over NiMoC/HβCatalysts in a Methane and Hydrogen Environment

To obtain high yields of monocyclic aromatic hydrocarbons with methyl side chains,such as toluene and xylene,methane(CH_(4))can be introduced into the hydrocracking of polycyclic aromatic hydrocarbons.CH_(4)can participate in the reaction,supply methyl side chains to the product,and improve product distribution.In this study,the hydrogenation reaction of polycyclic aromatic hydrocarbons over a carbonized NiMo/Hβcatalyst in a CH_(4)and hydrogen(H_(2))environment was investigated to study the promotional effect of CH_(4)on the hydrocracking of polycyclic aromatics.Under conditions of 3.5 MPa,380℃,volume air velocity of 4 h^(-1),gas-oil volume ratio of 800,and H_(2):CH_(4)molar ratio of 1:1,the conversion rate of naphthalene was 99.97%,the liquid phase yield was 93.62%,and the selectivity of BTX were 17.76%,25.17%,and 20.47%,respectively.In comparison to the use of a H_(2)atmosphere,the selectivity of benzene was significantly decreased,whereas the selectivity of toluene and xylene were increased.It was shown that CH_(4)can participate in the hydrocracking of naphthalene and improve the selectivity of toluene and xylene in the liquid product.The carbonized NiMo/Hβcatalyst was characterized by a range of analytical methods(such as X-ray diffraction(XRD),ammonia-temperature-programmed desorption(NH3-TPD),hydrogen-temperature-programmed reduction(H_(2)-TPR),and X-ray photoelectron spectroscopy(XPS)).The results indicated that Ni and Mo carbides were the major species in the carbonized NiMo/Hβcatalyst and were considered to be active sites for the activation of CH_(4)and H_(2).After loading the metal components,the catalyst displayed prominent weak acidic sites,which may be suitable locations for cracking,alkylation,and other related reactions.Therefore,the carbonized NiMo/Hβcatalyst displayed multiple functions during the hydrocracking of polycyclic aromatic hydrocarbons in a CH_(4)and H_(2)environment.These results could be used to develop a new way to efficiently utilize polycyclic aromatic hydrocarbons and natural gas resources.

Dietary supplementation with xylooligosaccharides and exogenous enzyme improves milk production,energy utilization efficiency and reduces enteric methane emissions of Jersey cows

Background Sustainable strategies for enteric methane(CH_(4))mitigation of dairy cows have been extensively explored to improve production performance and alleviate environmental pressure.The present study aimed to investigate the effects of dietary xylooligosaccharides(XOS)and exogenous enzyme(EXE)supplementation on milk production,nutrient digestibility,enteric CH_(4) emissions,energy utilization efficiency of lactating Jersey dairy cows.Forty-eight lactating cows were randomly assigned to one of 4 treatments:(1)control diet(CON),(2)CON with 25 g/d XOS(XOS),(3)CON with 15 g/d EXE(EXE),and(4)CON with 25 g/d XOS and 15 g/d EXE(XOS+EXE).The 60-d experimental period consisted of a 14-d adaptation period and a 46-d sampling period.The enteric CO_(2)and CH_(4) emissions and O2 consumption were measured using two GreenFeed units,which were further used to determine the energy utilization efficiency of cows.Results Compared with CON,cows fed XOS,EXE or XOS+EXE significantly(P<0.05)increased milk yield,true protein and fat concentration,and energy-corrected milk yield(ECM)/DM intake,which could be reflected by the significant improvement(P<0.05)of dietary NDF and ADF digestibility.The results showed that dietary supplementation of XOS,EXE or XOS+EXE significantly(P<0.05)reduced CH_(4) emission,CH_(4)/milk yield,and CH_(4)/ECM.Furthermore,cows fed XOS demonstrated highest(P<0.05)metabolizable energy intake,milk energy output but lowest(P<0.05)of CH_(4) energy output and CH_(4) energy output as a proportion of gross energy intake compared with the remaining treatments.Conclusions Dietary supplementary of XOS,EXE or combination of XOS and EXE contributed to the improvement of lactation performance,nutrient digestibility,and energy utilization efficiency,as well as reduction of enteric CH_(4) emissions of lactating Jersey cows.This promising mitigation method may need further research to validate its long-term effect and mode of action for dairy cows.

Interactions of Microplastics and Methane Seepage in the Deep-Sea Environment

Microplastics(MPs)are important exempla of the Anthropocene and are exerting an increasing impact on Earth’s carbon cycle.The huge imbalance between the MPs floating on the marine surface and those that are estimated to have been introduced into the ocean necessitates a detailed assessment of marine MP sinks.Here,we demonstrate that cold seep sediments,which are characterized by methane fluid seepage and a chemosynthetic ecosystem,effectively capture and accommodate small-scale(<100μm)MPs,with 16 types of MPs being detected.The abundance of MPs in the surface of the sediment is higher in methane-seepage locations than in non-seepage areas.Methane seepage is beneficial to the accumulation,fragmentation,increased diversity,and aging of MPs.In turn,the rough surfaces of MPs contribute to the sequestration of the electron acceptor ferric oxide,which is associated with the anaerobic oxidation of methane(AOM).The efficiency of the AOM determines whether the seeping methane(which has a greenhouse effect 83 times greater than that of CO_(2)over a 20-year period)can enter the atmosphere,which is important to the global methane cycle,since the deep-sea environment is regarded as the largest methane reservoir associated with natural gas hydrates.

High surface area biocarbon monoliths for methane storage

New energy sources that reduce the volume of harmful gases such as SO_(x)and NO_(x)released into the atmosphere are in constant development.Natural gas,primarily made up of methane,is being widely used as one reliable energy source for heating and electricity generation due to its high combustion value.Currently,natural gas accounts for a large portion of electricity generation and chemical feedstock in manufacturing plastics and other commercially important organic chemicals.In the near future,natural gas will be widely used as a fuel for vehicles.Therefore,a practical storage device for its storage and transportation is very beneficial to the deployment of natural gas as an energy source for new technologies.In this tutorial review,biomaterials-based carbon monoliths(CMs),one kind of carbonaceous material,was reviewed as an adsorbent for natural gas(methane)adsorption and storage.

Comparison of LaFeO_3,La_(0.8)Sr_(0.2)FeO_3,and La_(0.8)Sr_(0.2)Fe_(0.9)CO_(0.1)O_3 perovskite oxides as oxygen carrier for partial oxidation of methane

Comparison of LaFeO3, La0.8Sr0.2FeO3, and La0.8Sr0.2Fe0.9CO0.1O3 perovskite oxides as oxygen carrier for partial oxidation of methane in the absence of gaseous oxygen was investigated by continuous flow reaction and sequential redox reaction, Methane was oxidized to syngas with high selectivity by oxygen species of perovskite oxides in the absence of gaseous oxygen. The sequential redox reaction revealed that the structural stability and continuous oxygen supply in redox reaction decreased over La0.8Sr0.2Fe0.9Co0. 1O3 oxide, while LaFeO3 and La0.8Sr0.2FeO3 exhibited excellent structural stability and continuous oxygen supply.

CeO_2 as the Oxygen Carrier for Partial Oxidation of Methane to Synthesis Gas in Molten Salts: Thermodynamic Analysis and Experimental Investigation

A new technique -- the direct partial oxidation of methane to synthesis gas using lattice oxygen in molten salts medium has been introduced. Using CeO2 as the oxygen carrier, thermodynamic data were calculated in the reaction process, and the results indicated that direct partial oxidation of methane to synthesis gas using lattice oxygen of cerium oxide is feasible in theory. In a stainless steel reactor, the effects of temperature and varying amounts of γ-Al2O3 supported CeO2 on cn4 conversion, H2 and CO selectivity, were investigated, respectively. The results show that 10% CeO2/γ-Al2O3 has the maximal reaction activity at a temperature of 865 ℃ and above, the H2/CO ratio in the gas that has been produced reaches 2 and the CH4 conversion, H2 and CO selectivity reached the following percentages： i.e. 61%, 89%, and 91% at 870 ℃, respectively. In addition, increase of reaction temperature is favorable for the partial oxidation of methane.

The status and development strategy of coalbed methane industry in China

To achieve the goals of carbon peaking and carbon neutrality under the backgrounds of poor resource endowments, weak theoretical basis and other factors, the development of the coalbed methane industry of China faces many bottlenecks and challenges. This paper systematically analyzes the coalbed methane resources, key technologies and progress, exploration effect and production performance in China and abroad. The main problems are summarized as low exploration degree, low technical adaptability, low return on investment and small development scale. This study suggests that the coalbed methane industry in China should follow the “two-step”(short-term and long-term) development strategy. The short-term action before 2030, can be divided into two stages:(1) From the present to 2025, to achieve new breakthroughs in theory and technology, and accomplish the target of annual production of 10 billion cubic meters;(2) From 2025 to 2030, to form the technologies suitable for most geological conditions, further expand the industry scale, and achieve an annual output of 30 billion cubic meters, improving the proportion of coalbed methane in the total natural gas production. The long-term action after 2030 is to gradually realize an annual production of 100 billion cubic meters. The strategic countermeasure to achieve the above goals is to adhere to “technology+management dual wheel drive”, realize the synchronous progress of technology and management, and promote the high-quality development of the coalbed methane industry. Technically, the efforts will focus on fine and effective development of coalbed methane in the medium to shallow layers of mature fields, effective development of coalbed methane in new fields, extensive and beneficial development of deep coalbed methane, three-dimensional comingled development of coalbed methane, applying new technologies such as coalbed methane displacement by carbon dioxide, microwave heating and stimulation technology, ultrasonic stimulation, high-temperature heat injection stimulation, rock breaking by high-energy laser. In terms of management, the efforts will focus on coordinative innovation of resource, technology, talent, policy and investment, with technological innovation as the core, to realize an all-round and integrated management and promote the development of coalbed methane industry at a high level.

Perovskite-type oxygen-permeable membrane BaCo_(0.7)Fe_(0.2)Nb_(0.1)O_(3-δ) for partial oxidation of methane in coke oven gas to hydrogen

Perovskite-type oxygen-permeable membrane reactors of BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） packed with Ru-based catalyst had high oxygen permeability and could be used for hydrogen production by partial oxidation of methane in coke oven gas （COG）. At 1173 K, 94% of methane conversion, 85% of H2 selectivity, 107% of CO selectivity, and as high as 15.4 mL·cm^-2·min^-1 of oxygen permeation flux were obtained. The BCFNO membrane itself had poor catalytic activity to partial oxidation of CH4 in COG. During continuous operation for 70 h at 1173 K, no degradation of the membrane reaction performance was observed. XRD and SEM characterization also demonstrated that the BCFNO membrane reactor exhibited good stability in partial oxidation of methane in COG.