Intensified shape selectivity and alkylation reaction for the two-step conversion of methanol aromatization to p-xylene

Two-step conversion of methanol to aromatics via light hydrocarbons can significantly improve the conversion stability compared with direct aromatization of methanol,but it remains a challenge to achieve a high p-xylene(PX)selectivity.Herein,silica coating was firstly used to passivate external acid sites of ZSM-5 catalyst for the aromatization of light hydrocarbons by the chemical liquid deposition method.With the increase of SiO_(2) deposition,the density of the external acid sites of the catalyst was decreased from 0.1 to 0.03 mmol·g^(-1),which inhibited the surface secondary reactions and increased the PX/X from 34.6% to 60.0%.In view of the fact that the aromatization process in the second step was partly inhibited as methanol was consumed in advance in the upper methanol-to-light hydrocarbons catalyst layer,part of methanol was directly introduced into the lower aromatization catalyst layer to promote the alkylation process during the aromatization,which decreased the toluene selectivity from 34.5% to 14.3% but increased the xylene selectivity from 40.0%to 55.3%.It was also found that an appropriate external acid density was needed for aromatization catalyst to strengthen the alkylation process and improve the selectivity of xylene under the conditions of methanol introduction.

Effect of silicon carbide-based iron catalyst on reactor optimization for non-oxidative direct conversion of methane

The conversion of methane to olefins,aromatics,and hydrogen(MTOAH)can be used to stably obtain hydrocarbons when the effect of the catalytic surface is optimized from the reaction engineering perspective.In this study,Fe/Si C catalysts were packed into a quartz tube reactor.The catalytic surfaces of Si C and the impregnated Fe species decreased the apparent activation energies(E_a)of methane consumption in the blank reactor between 965 and 1020℃.Consequently,the hydrocarbon yield increased by 2.4times at 1020℃.Based on the model reactions of ethane,ethylene,and acetylene mixed with hydrogen in the range of 500-1020℃,an excess amount of Fe in the reactor favored the C-C coupling reaction over the selective hydrogenation of acetylene;consequently,coke formation was favored over the hydrogenation reaction.The gas-phase reactions and catalyst properties were optimized to increase hydrocarbon yields while reducing coke selectivity.The 0.2Fe catalyst-packed reactor(0.26 wt%Fe)resulted in a hydrocarbon yield of 7.1%and a coke selectivity of<2%when the ratio of the void space of the postcatalyst zone to the catalyst space was adjusted to be≥2.Based on these findings,the facile approach of decoupling the reaction zone between the catalyst surface and the gas-phase reaction can provide insights into catalytic reactor design,thereby facilitating the scale-up from the laboratory to the commercial scale.

Chemical looping conversion of methane via Fe_(2)O_(3)-LaFeO_(3)calcined from LaFe-MOF precursor

The effective utilization of natural gas resources is a promising option for the implementation of the"dual carbon"strategy.However,the capture of carbon dioxide with relatively lower concentration after the combustion of natural gas is the crucial step.Fortunately,the lattice oxygen is used for chemical cycle conversion of methane to overcome the shortcomings mentioned above.A method was proposed to synthesize perovskite for methane cycle conversion using metal organic framework as a precursor.Morphology and pore structure of Fe_(2)O_(3)-LaFeO_(3)composite oxides were regulated by precursor synthesis conditions and calcination process.Moreover,the chemical looping conversion performance of methane was evaluated.The results showed that the pure phase precursor of La[Fe(CN)_(6)]·5H_(2)O was synthesized with the specific surface area of 23.91 m^(2)·g^(-1)under the crystallization of 10 h and the pH value of10.5.Fe_(2)O_(3)-LaFeO_(3)was obtained by controlled calcination of La[Fe(CN)_(6)]·5H_(2)O and Fe_(2)O_(3)with variable mass ratio.The selectivity of CO_(2)can reach more than 99%under the optimal parameters of methane chemical looping conversion:m(Fe_(2)O_(3)):m(LaFeO_(3))=2:1,the reaction temperature is 900℃,the lattice oxygen conversion is less than 40%.Fe_(2)O_(3)-LaFeO_(3)still has good phase and structure stability after five redox reaction and regeneration cycles.

Characterization and Activity of Cr, Cu and Ga Modified ZSM-5 for Direct Conversion of Methane to Liquid Hydrocarbons

Direct conversion of methane using a metal-loaded ZSM-5 zeolite prepared viaacidic ion exchange was investigated to elucidate the roles of metal and acidity in the formation ofliquid hydrocarbons. ZSM-5 (SiO_2/Al_2O_3=30) was loaded with different metals (Cr, Cu and Ga)according to the acidic ion-exchange method to produce metal-loaded ZSM-5 zeolite catalysts. XRD,NMR, FT-IR and N_2 adsorption analyses indicated that Cr and Ga species managed to occupy thealuminum positions in the ZSM-5 framework. In addition, Cr species were deposited in the pores ofthe structure. However, Cu oxides were deposited on the surface and in the mesopores of the ZSM-5zeolite. An acidity study using TPD-NH_3, FT-IR, and IR-pyridine analyses revealed that the totalnumber of acid sites and the strengths of the Broensted and Lewis acid sites were significantlydifferent after the acidic ion exchange treatment. Cu loaded HZSM-5 is a potential catalyst fordirect conversion of methane to liquid hydrocarbons. The successful production of gasoline via thedirect conversion of methane depends on the amount of aluminum in the zeolite framework and thestrength of the Broensted acid sites.

Selective electrocatalytic conversion of methane to fuels and chemicals

The increase in natural gas reserves makes methane a significant hydrocarbon feedstock. However, thedirect catalytic conversion of methane into liquid fuels and useful chemicals remains a great challenge,and many studies have been devoted to this field in the past decades. Electrocatalysis is considered asan important alternative approach for the direct conversion of methane into value-added chemicals, al-though many other innovative methods have been developed. This review highlights recent advances inelectrocatalytic conversion of methane to ethylene and methanol, two important chemicals. The electro-catalytic systems efficient for methane conversions are summarized with an emphasis on catalysts andelectrolytes. The effects of reaction conditions such as the temperature and the acid-base property of thereaction medium are also discussed,

Methane Conversion Using Dielectric Barrier Discharge: Comparison with Thermal Process and Catalyst Effects

The direct conversion of methane using a dielectric barrier discharge has been experimentally studied. Experiments with different values of flow rates and discharge voltages have been performed to investigate the effects on the conversion and reaction products both qualitatively and quantitatively. Experimental results indicate that the maximum conversion of methane has been 80% at an input flow rate of 5 ml/min and a discharge voltage of 4 kV. Experimental results also show that the optimum condition has occurred at a high discharge voltage and higher input flow rate. In terms of product distribution, a higher flow rate or shorter residence time can increase the selectivity for higher hydrocarbons. No hydrocarbon product was detected using the thermal method, except hydrogen and carbon. Increasing selectivity for ethane was found when Pt and Ru catalysts presented in the plasma reaction. Hydrogenation of acetylene in the catalyst surface could have been the reason for this phenomenon as the selectivity for acetylene in the products was decreasing.

Preparation and Performance of Ce/Zr Mixed Oxides for Direct Conversion of Methane to Syngas

CexZr1-xO2 mixed oxides with different Ce/Zr ratios were prepared by coprecipitation. The characterizations of mixed oxides were studied by X-ray diffraction (XRD) and H2-TPR. And the performances were tested in a fixed-bed quartz reactor. The results indicated that lattice oxygen of CexZr1-xO2 could oxidate methane to syngas and the incorporation of zirconium into the ceria lattice could improve the O2- mobility. The Ce0.7Zr0.3O2 had the best activity in investigative temperature ranging from 600 to 900 ℃. Effects of reaction time on H2/CO ratio were studied at 850 ℃ when using Ce0.7Zr0.3O2 as catalyst. The results indicated that the ratio was closed to 2 values in the first 10 min, however, it rapidly increased with reaction time after >10 min. The possible reason was that the direct partial oxidation of methane reaction was dominant in the first 10 min. However, the methane pyrogenation was responsible for the rapid increase of H2/CO ratio after 10 min. Thus, if syngas with H2/CO ratio of 2 wanted to be obtained, the reaction time needed to be controlled.

Plasma-assisted methane conversion in an atmospheric pressure dielectric barrier discharge reactor

In this paper, a cylindrical dielectric barrier discharge （DBD） reactor has been developed for the conversion of methane into hydrogen and other valuable chemicals. The effects of a wide range of processing parameters including discharge power, residence time and frequency on the performance of plasma methane conversion reaction have been investigated. The results show that the CH4 DBD could be characterized as a typical filamentary discharge with a microdis-charge zone in each half-cycle of the applied voltage. The conversion of CH4 reaches a maximum of 25.2% at a feed flow rate of 50 mL-min-1, a discharge power of 45 W and an excitation frequency of 20 kHz. It is found that the residence time of methane in the discharge zone has the most significant effect on both methane conversion and hydrogen yield, which are significantly higher at higher residence time.

Research progress on methane conversion coupling photocatalysis and thermocatalysis

Conversion of methane into value-added chemicals is of significance for methane utilization and industrial demand of primary chemical products.The barrier associated with the nonpolar structure of methane and the high bond energy C-H bond(4.57 eV)makes it difficult to realize methane conversion and activation under mild conditions.The photothermal synergetic strategy by combining photon energy and thermo energy provides an advanced philosophy to achieve efficient methane conversion.In this review,we overview the current pioneering studies of photothermal methane indirect conversion and present the methane direct conversion by the way of photocatalysis and thermocatalysis to provide a fundamental understanding of methane activation.Finally,we end this review with a discussion on the remaining challenges and perspectives of methane direct conversion over single-atom catalysts via photothermal synergetic strategy.

Kinetic Modeling of Plasma Methane Conversion Using Gliding Arc

Plasma methane (CH_4) conversion in gliding arc discharge was examined. Theresult data of experiments regarding the performance of gliding arc discharge were presented in thispaper. A simulation which is consisted some chemical kinetic mechanisms has been provided toanalyze and describe the plasma process. The effect of total gas flow rate and input frequencyrefers to power consumption have been studied to evaluate the performance of gliding arc plasmasystem and the reaction mechanism of decomposition. Experiment results indicated that the maximumconversion of CH_4 reached 50% at the total gas flow rate of 1 L/min. The plasma reaction wasoccurred at the atmospheric pressure and the main products were C (solid), hydrogen, and acetylene(C_2H_2). The plasma reaction of methane conversion was exothermic reaction which increased theproduct stream temperature around 30-50℃.

Influence of extra-framework Al in Fe-MOR catalysts for the direct conversion of methane to oxygenates by nitrous oxide

Iron-containing zeolites play an important role in the selective oxidation of methane to oxygenates by nitrous oxide.A solid-state ion exchange method is adopted to prepare Fe-MOR zeolite catalysts with different amounts of extra-framework Al.EPR spectra and UV-vis spectra show that the percentage of iron ions in tetrahedral or octahedral coordination increases while those of clustered Fe species decrease by the addition of extra-framework Al species.Nitrous oxide titration reveals that more active Fe centers are formed,which promote the nitrous oxide consumption.The number of active centers in the catalyst with the introduction of extra-framework Al is about four times that of the catalyst without the addition of extra-framework Al.Due to this,there is an increase in the methane conversion,total selectivity and yield of oxygenates.

Methane Conversion to C_2 Hydrocarbons by Abnormal Glow Discharge at Atmospheric Pressure

Methane conversion to C2 hydrocarbons has been investigated with the addition of hydrogen in a plasma reactor of abnormal glow discharge at atmospheric pressure. The aim of this experiment is to minimize coke formation and improve discharge stability. The typical conditions in the experiment are 300 ml of total feed flux and 400 W of discharge power. The experimental results show that methane conversion is from 91.6% to 35.2% in mol, acetylene selectivity is from 90.2% to 57.6%, and ethylene selectivity is approximately from 7.8% to 3.6%, where the coke increases gradually along with the increase of CH4/H2 from 2 ： 8 to 9 ： 1. A stable discharge for a considerable running time can be obtained only at a lower ratio of CH4/H2 = 2：8 or 3： 7. These phenomena indicate that the coke deposition during methane conversion is obviously reduced by adding a large amount of hydrogen during an abnormal glow discharge. A qualitative interpretation is presented, namely, with abundant hydrogen, the possibility that hydrogen molecules are activated to hydrogen radicals is increased with the help of the abnormal glow discharge. These hydrogen radicals react with carbon radicals to form C2 hydrocarbon products. Therefore, the deposition of coke is restrained.

Experimental study on characteristics of pore water conversion during methane hydrates formation in unsaturated sand

Understanding the pore water conversion characteristics during hydrate formation in porous media is important to study the accumulation mechanism of marine gas hydrate.In this study,low-field NMR was used to study the pore water conversion characteristics during methane hydrate formation in unsaturated sand samples.Results show that the signal intensity of T_(2) distribution isn’t affected by sediment type and pore pressure,but is affected by temperature.The increase in the pressure of hydrogen-containing gas can cause the increase in the signal intensity of T_(2) distribution.The heterogeneity of pore structure is aggravated due to the hydrate formation in porous media.The water conversion rate fluctuates during the hydrate formation.The sand size affects the water conversion ratio and rate by affecting the specific surface of sand in unsaturated porous media.For the fine sand sample,the large specific surface causes a large gas-water contact area resulting in a higher water conversion rate,but causes a large water-sand contact area resulting in a low water conversion ratio(C_(w)=96.2%).The clay can reduce the water conversion rate and ratio,especially montmorillonite(C_(w)=95.8%).The crystal layer of montmorillonite affects the pore water conversion characteristics by hindering the conversion of interlayer water.

Oxygen-Free Conversion of Methane to Ethylene in a Plasma-Followed-by-Catalyst (PFC) Reactor

Oxygen-free conversion of methane to ethylene was investigated in a two-stage plasma-followed-by-catalyst （PFC） reactor. In the absence of catalyst, pulsed spark discharges and pulsed corona discharges were compared for methane conversion. The results showed that methane was mainly converted to acetylene, but pulsed spark discharges exhibited distinct advantages over the pulsed corona discharges in methane conversion. Thereby, pulsed spark discharges were employed and followed by Ag-Pd/SiO2 catalyst for achieving ethylene as a target product in the PFC reactor. Using the PFC reactor, a steady single-pass ethylene yield of 57% was obtained at a rate of methane conversion of 74%.

Direct conversion of methane to methanol by electrochemical methods

A convenient method for methane(CH_(4))direct conversion to methanol(CH_(3)OH)is of great significance to use methane-rich resources,especially clathrates and stranded shale gas resources located in remote regions.Theoretically,the activation of CH_(4) and the selectivity to the CH_(3)OH product are challenging due to the extreme stability of CH_(4) and relatively high reactivity of CH_(3)OH.The state-of-the-art‘methane reforming-methanol synthesis’process adopts a two-step strategy to avoid the further reaction of CH_(3)OH under the harsh conditions required for CH_(4) activation.In the electrochemical field,researchers are trying to develop conversion pathways under mild conditions.They have found suitable catalysts to activate the C–H bonds in methane with the help of external charge and have designed the electrode reactions to continuously generate certain active oxygen species.These active oxygen species attack the activated methane and convert it to CH_(3)OH,with the benefit of avoiding over-oxidation of CH_(3)OH,and thus obtain a high conversion efficiency of CH_(4) to CH_(3)OH.This mini-review focuses on the advantages and challenges of electrochemical conversion of CH4 to CH_(3)OH,especially the strategies for supplying electro-generated active oxygen species in-situ to react with the activated methane.

Formation of Methane and Ethylene in Methanol Conversion over HZSM-5 Catalyst

Primary formation of methane and secondary formation of ethylene in methanol conversion are evidenced by temperature-programmed-surface- reaction of adsorbed methanol on HZSM-5 catalyst.A reaction mechanism accounts for the observed results is described.

Jet Plasma-Chemical Reactor for the Conversion of Methane: the Use of Clustering

The research results of processes proceeding in supersonic jets of light hydrocarbons, activated by an electron beam are presented. It is shown, that condensation suppressed at activation by electrons in the initial stage of condensation. The developed condensation conditions mode leads to increasing of a part of heavy corpuscles in activated stream and not only owing to stimulation of condensation but because of formation of heavy hydrocarbonic molecules.

Kinetic contribution of CO_2/O_2 additive in methane conversion activated by non-equilibrium plasmas

A temperature-controlled and pressure-controlled coaxial dielectric barrier discharge(DBD) reactor was developed to decouple the thermal and kinetic effects of radio frequency(RF) discharge on methane conversion,and further to compare the kinetic behaviors of the mechanistically similar reactions of methane conversion with O_2 and CO_2 additives. A kinetic mechanism for RF plasma assisted methane conversion was assembled. The formation of products in the RF plasma reactor was measured with Gas Chromatography(GC–TCD) and the data were used to validate the kinetic model. The experimental and computational results showed the different kinetic roles of carbon dioxide and oxygen additives in methane conversion, due to the different dissociation and ionization energy of the two additive gases, as well as the thus produced electron energy distribution function(EEDF). Fuel oxidation by plasma generated O, O(~1 D), O_2(a^1Δg), O_2(b^1Σ_g^+) and O+in partial oxidation of methane was observed essential for methane consumption, which resulted in an increase in methane conversion rate,compared to pure methane pyrolysis and dry reforming of methane with CO_2 additive. It was also found that dry reforming of methane with CO_2 was by far the easier to produce the syngas as well as C_2 hydrocarbon species,due to the weak oxidation ability of CO_2 and also the significant deposition of the electron energy on CH_4 dissociation in a dry reforming discharge mixture. This kinetic study produced comparative data to demonstrate the contribution of CO_2/O_2 additive in non-equilibrium plasma assisted methane conversion.

Plasma-based CO_(2) conversion:How to correctly analyze the performance?

Plasma-based CO_(2)conversion is promising for carbon capture and utilization.However,inconsistent reporting of the performance metrics makes it difficult to compare plasma processes systematically,complicates elucidating the underlying mechanisms and compromises further development of this technology.Therefore,this critical review summarizes the correct definitions for gas conversion in plasma reactors and highlights common errors and inconsistencies observed throughout literature.This is done for pure CO_(2)splitting,dry reforming of methane and CO_(2)hydrogenation.We demonstrate that the change in volumetric flow rate is a critical aspect,inherent to these reactions,that is often not correctly taken into account.For dry reforming of methane and CO_(2)hydrogenation,we also demonstrate inconsistent reporting of energy efficiency,and through numerical examples,we show the significance of these deviations.Furthermore,we discuss how to measure changes in volumetric flow rate,supported by data from two experimental examples,showing that the sensitivity inherent to a standard component and a flow meter is essential to consider when deriving the performance metrics.Finally,some general recommendations and good practices are provided.This paper aims to be a comprehensive guideline for authors,to encourage more consistent calculations and stimulate the further development of this technology.

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.