On the Formation of Vanadium Ferrites in CaO–SiO2–FeO–V2O5 Slags

Selective extraction of valuable elements (such as V, Cr, Mn, etc.) and their compounds from metallurgical slag is in a focus of many researchers. Although vanadium may be present in slag as oxides and/or complex spinels with Fe, Mn, etc. during an alloyed steel production, the majority of vanadium in metallurgical slags typically exists as V₂O₅, which comprises up to 3–5 wt% of the slag in some cases. Due to the vanadium toxicity, these slags are forbidden in many civil engineering applications. As a result, hundreds of thousand tonnes of V₂O₅‐bearing slags are landfilled every year. In the present work, the formation of vanadium ferrites (FeV₂O₄ and Fe₂VO₄) in synthesized CaO–SiO₂–FeO–V₂O₅ slags containing 5 wt% V₂O₅ was examined under different partial pressures of oxygen. For the current slag chemistry range, an XRD analysis confirmed the presence of vanadium ferrite in slag samples treated at 1773 K in an argon atmosphere (PO₂ = 10^?1–10^?2 Pa) while no solid was noted in samples treated in air. Results were discussed based on thermodynamic consistency.     

A microstructural characterization of scale formed on austenitic Fe–29.7Mn–8.7Al–1.04C and duplex Fe–29Mn–10Al–0.4C alloys in oxidizing-sulfidizing environments

Austenitic Fe–29.7Mn–8.7Al–1.04C and duplex Fe–29Mn–10Al–0.4C alloys were exposed to the SO₂–O₂ mixed gas environments at 900 °C. The morphology of the scales formed on these alloys under oxidizing-sulfidizing conditions were examined by SEM and X-ray mapping techniques. The results showed that the addition of carbon up to 1 wt.% to the Fe–29.7Mn–8.7Al–1.04C alloy led to the formation of internal sulfidation and intergranular oxidation in the mixed oxidant gas environments. On the other hand, no evidence of intergranular oxidation could be detected in the duplex Fe–29Mn–10Al–0.4C alloy with lower carbon concentration.     

Thermodynamics of manganese distribution between liquid iron and the CaO–Al2O3–SiO2–FeO–MnO system

The thermodynamics of distribution of constituents between liquid iron and the CaO–Al₂O₃–SiO₂–FeO–MnO system at 1600°C was studied using electrochemical indication of the equilibrium partial pressure of oxygen in both phases. The results show that oxidation potential of the Fe(l)–CaO–Al₂O₃–SiO₂–FeO–MnO system, expressed in terms of log p(O₂), is directly proportional to log (x(MnO) · x(FeO)/w| Mn |). Manganese distribution coefficient, L'_mn, in intersection CaO/Al₂O₃ = 1 decreases with increasing slag basicity expressed in terms of activity a(CaO) or 1/γ(MnO). Experimentally determined equilibrium constant K_Mn/Fe is equal to 2.7 for 1600°C. The number of exchanged electrons between Fe-O-Mn-Si electrode and the slag approaches the theoretical value.     

Influence of manganese rate on structural,optical and electrochemical properties of CeO2 thin films deposited by spray pyrolysis: Supercapacitor applications

The present work aimed to investigate the electrochemical properties of ITO substrates in propylene carbonate (PC) with 0.5 mol/L lithium perchlorate (LiClO₄) medium in the presence of elaborated thin films of cerium dioxide pure and doped with manganese at varying percentages. Ce_1–xMn_xO₂ (x = 0 wt%, 2 wt%, 4 wt% and 6 wt%) were successfully deposited by the spray pyrolysis (SP) technique on the glass substrate and ITO at 450 °C. The effects of manganese (Mn) doped thin films Ce_1–xMn_xO₂ were studied and investigated by using different analyses namely X-ray diffraction (XRD) analysis, Raman spectroscopy method, UV–Vis spectrophotometer technique, atomic force microscopy (AFM) analysis and electrochemical properties. XRD data obtained present a polycrystalline with a face-centred cubic structure of fluorite type. Raman results of undoped and Mn doped thin films show two peaks at 465 and 600 cm^?1, due to the formation of extrinsic oxygen vacancies by the incorporation of Mn into Ce_1–xMn_xO₂ matrix. Energy dispersive spectroscopy (EDS) data show the presence of Ce, O, and Mn elements in the elaborated films. The AFM results reveal that the surface roughness decreases with increasing Mn rate. Further, band gap energy of thin films decreases with increasing in Mn rate due to the formation of defect state between valence and conduction band. The storage capacity of the elaborated Ce_1–xMn_xO₂/ITO/PC + LiClO₄ electrode reaches a maximum of 1.997 mF in the presence of 6 wt% of Mn.     

Manganese Distribution between FeO‐MnO‐SiO2–CaO–MgO‐Al2O3 Slags and Molten Iron

Pretreatment of high manganese hot metal is suggested to produce hot metal suitable for further processing to steel in conventional LD converter and rich manganese slags satisfy the requirements for the production of silicomanganese alloys. Manganese distribution between slag and iron represents the efficiency of manganese oxidation from hot metal. The present study has been done to investigate the effect of temperature, slag basicity and composition of oxidizer mixture on the distribution coefficient of manganese between slag and iron. Ferrous oxide activity was determined in molten synthetic slag mixtures of FeO‐MnO‐SiO₂–CaO–MgO‐Al₂O₃. The investigated slags had chemical compositions similar to either oxidizer mixture or slags expected to result from the treatment of high manganese hot metal. The technique used to measure the ferrous oxide activity in the investigated slag systems was the well established one of gas‐slag‐metal equilibration in which molten slags contained in armco iron crucibles are exposed to a flowing gas mixture with a known oxygen potential until equilibrium has been attained. After equilibration, the final chemical analysis of the slags gave compositions having a particular ferrous oxide activity corresponding to the oxygen potential of the gas mixture. The determined values of ferrous oxide activity were used to calculate the equilibrium distribution of manganese between slag and iron. Higher manganese distribution between slag and iron was found to be obtained by using oxidizer containing high active iron oxide under acidic slag and relatively low temperature of about 1350°C.     

Fundamental thermodynamic aspects of the CaO–Al2O3–SiO2 system

The most important metallurgical effects of ladle treatment of aluminium-killed steels with calcium, are associated with the modification of alumina inclusion. For the development of the deoxidation-control model for inclusions, the thermodynamic slag model, based on the Gibbs energy minimization and modelling approaches postulated from J. Hastie et al., was used to calculate component oxide activities in the system CaO–Al₂O₃ and part of systems 3CaO · Al₂O₃ – SiO₂, 12 CaO · 7Al₂O₃ – SiO₂ and CaO · Al₂O₃ – SiO₂ at 1600°C.     

Study of Structural and Mechanical Properties of Al/Nano-Al2O3 Metal Matrix Nanocomposite Fabricated by Powder Metallurgy Method

In this work, the (1???x) Al–xAl₂O₃ (x?=?0, 1, 2, 3, and 4 wt%) of metal matrix nanocomposites (MMNCs) has been manufactured using the powder metallurgy technique. Aluminium metal powder (Al) was used as the matrix material, and alumina nanoparticles (Al₂O₃) synthesized by the sol–gel method were used as the reinforcing material to produce the MMNCs. Two phases of Al₂O₃ have been identified, i.e. the α-phase (rhombohedral structure) and the δ-phase (orthorhombic structure) by X-ray diffraction patterns (XRD) of synthesized Al₂O₃ nanoparticles with an average crystallite size of 31.33 nm. The average particle size of the Al₂O₃ nanoparticle is obtained as 39.6 nm. The XRD patterns of the Al–Al₂O₃ nanocomposites contain the Al and Al₂O₃ peaks that confirm the development of the MMNC without any solid-state reaction during the manufacturing process. FESEM micrographs show an almost uniform distribution of Al₂O₃ particles in the Al metal matrix. The reinforcement of the Al₂O₃ nanoparticles in the Al metal matrix has shown an improvement in hardness by increasing the wt% of Al₂O₃ in Al matrix, and a maximum 24.8% improvement in hardness is observed for 4 wt% Al₂O₃ sample. An increase in wear rate is observed with the increasing wt% of Al₂O₃ in the Al metal matrix in Al–Al₂O₃ nanocomposite. The addition of Al₂O₃ nanoparticles in the Al matrix has resulted in improved corrosion performance of the samples with a maximum corrosion resistance efficiency of 85.6% for 4 wt% Al₂O₃ in Al metal matrix.

     

Effect of FeO and Al2O3 on the MgO Solubility in CaO–SiO2–FeO–Al2O3–MgO Slag System at 1823 K

The MgO solubility in CaO–SiO₂–FeO–Al₂O₃–MgO quinary slag system at 1823 K was measured to evaluate the effect of FeO and Al₂O₃ on the MgO solubility. It was found that the MgO solubility was decreased with higher optical basicity, FeO concentration, and increased with higher Al₂O₃ concentration. The MgO solubility was affected by activity coefficient of Mg²⁺ ($\gamma _{{\rm Mg}_{{\rm 2 + }} } $ ). Increase of the activity coefficient of Mg²⁺ ($\gamma _{{\rm Mg}_{{\rm 2 + }} } $ ) with higher FeO or lower Al₂O₃ decreased the MgO solubility. The increment in MgO solubility is remarkably reduced beyond a critical $X_{{\rm Al}_{2} {\rm O}_{{\rm 3}} } /(X_{{\rm Al}_{2} {\rm O}_{{\rm 3}} } + X_{{\rm FeO}} )$ ratio. The significant decrease of the increment of MgO solubility is caused by the change of the molten slag structure. The excess stability function of Al₂O₃ and the Fourier transform infrared (FT‐IR) analysis were applied to indirectly verify the existence of the spinel structure in the CaO–SiO₂–FeO–Al₂O₃–MgO slag system.     

Verlauf der Kalksättigung im System FeO–Fe2O3–CaO–SiO2–P2O5–MgO–MnO beim Gleichgewicht mit einer Eisenschmelze

Durch Auswertung zahlreicher, in Laborversuchen bei 1580–1650°C erschmolzener kalkgesättigter Schlacken mit gleichzeitigen Gehalten an FeO, Fe₂O₃, SiO₂, P₂O₅, MgO und MnO ist die aus metallurgischen Gründen angestrebte Kalksättigung komplexer Schlacken der Stahlerzeugung für 1600°C neu festgelegt worden. Ausgehend von der Beschreibung der Schlackenzusammensetzungen in den Grundsystemen CaO′–FeO′_n–SiO′₂ und CaO′–FeO′_n–P₂O₅ wird dabei die Beeinflussung der Kalksättigung durch MgO und MnO sowie qualitativ durch dreiwertige Eisenanteile angegeben. Die untersuchten Schlacken lassen in beiden Grundsystemen einen stetigen, von hohen FeO′_n-Gehalten bis hinunter zu Massengehalten von 8% gültigen Verlauf der Kalksättigung ohne einsetzende Dicalciumsilikat- bzw. Tetracalciumphosphatausscheidung erkennen. Durch die bewertende Umrechnung der P₂O₅-, MgO- und MnO-Gehalte wird eine nahezu alle Komponenten erfassende Darstellung komplexer kalkgesättigter Schlacken in einem einfachen Quasidreistoffsystem CaO^*–FeO^*-SiO^*₂ erreicht und die resultierende, dicht belegte Kalksättigungslinie mathematisch beschrieben. Der Einfluß von Al₂O₃-Gehalten auf die Kalksättigung wird abgeschätzt sowie das maximale Lösungsvermögen der kalkgesättigten Schlacke für MgO durch die Berechnung der Schnittlinie zwischen der Kalk- und der Magnesiowüstitsättigungsfläche festgelegt. Ein Ansatz zur Erfassung des Temperatureinflusses auf die Kalksättigung erlaubt schließlich eine vollständige mathematische Beschreibung der Kalksättigungsgehalte im System CaO^*–FeO^*_n–SiO₂ sowohl in Abhängigkeit von der Schlackenzusammensetzung als auch von der Temperatur. Damit können die Kalkgehalte komplexer Betriebsschlacken unterschiedlicher Temperatur mit den erreichbaren Gleichgewichtssättigungswerten verglichen und die Sättigungszustände der Schlacken nach Berechnung eines Sättigungsgrades S_CaO beurteilt werden.     

Effect of manganese and/or ceria loading on V_2O_5-MoO_3/TiO_2 NH_3 selective catalytic reduction catalyst

The effect of manganese and/or ceria loading of V_2 O_5-Mo_O_3/TiO_2 catalysts was investigated for selective catalytic reduction(SCR) of NO_x by NH_3.The manganese and/or ceria loaded V_2 O_5-MoO_3/TiO_2 catalysts we re prepared by the wetness impregnation method.The physicochemical characteristics of the catalysts were thoroughly characterized.The catalytic performance of 1.5 wt% V_2 O_5-3 wt% MoO_3/TiO_2(V1.5 Mo3/Ti) is greatly enhanced by addition of 2.5 wt% MnO_x and 3.0 wt% CeO_2(V1.5 Mo3 Mn2.5 Ce3/Ti) below450℃.Compared with the V1.5 Mo3/Ti catalyst with NO_x conversion of 75% at 275 ℃,V1.5 Mo3 Mn2.5 Ce3/Ti exhibits higher NO_x conversion of 84% with good resistance to SO_2 and H_2 O at a gas hourly space velocity value of 150000 h~(-1).The active manganese,cerium,molybdenum,and vanadium oxide species are highly dispersed on the catalyst surface and some synergistic effects exist among these species.Addition of MnO_x significantly enhances the redox ability of the cerium,vanadium,and molybdenum species.Addition of Ce increases the acidity of the catalyst.More active oxygen species,including surface chemisorbed oxygen,form with addition of Mn and/or Ce.Because of the synergistic effects,appropriate proportions of manganese in different valence states exist in the catalysts.In summary,the good redox ability and the strong acidity contribute to the high NH3-SCR activity and N2 selectivity of the V1.5 Mo3 Mn2.5 Ce3/Ti catalyst in a wide temperature range.And the V1.5 Mo3 Mn2.5 Ce3/Ti catalyst shows good resistance to H_2 O and SO2 in long-time catalytic testing,which can be ascribed to the highly sulfated species adsorbed on the catalyst.     

Nitride capacities in CaO–SiO2 and CaO–SiO2–Al2O3 melts

Nitride capacities, , defined by (mass-% N) · in the CaO–SiO₂ and CaO–SiO₂–AI₂O₃ melts were measured in the temperature range of 1 723 to 1 923 K by a gas-slag equilibration technique using CaO, Al₂O₃, and Mo crucibles. Nitrogen content in slag, (mass-% N), was proportional to oxygen partial pressure, , to the power of ?3/4 at constant nitrogen partial pressure, . The values for increased linearly with increasing temperature and increased with the content of nitride formers, SiO₂ and Al₂O₃, but the effect of SiO₂ on value was found to be greater than that of Al₂O₃. The activity coefficients of Si_3/4N in the CaO–SiO₂ melts tended to increase with increasing the content of SiO₂.     

Fluorine‐Free Mould Powders for Slab Casting: Crystallization Control in the CaO–SiO2–TiO2–Na2O–Al2O3 System

The main problem related to the development of fluorine‐free mould powders for slab casting is effectively controlling the heat transfer between the steel shell and mould. In commercial mould powders crystallization of cuspidine (Ca₄Si₂O₇F₂) from mould slag has a great effect on heat‐transfer control. In industrial process the crystallization rate for a fluorine‐free mould slag should be similar to the crystallization rate of cuspidine. To evaluate the crystallization rate for slags time‐temperature‐transformation (TTT) diagrams can be constructed using the Single Hot Thermocouple Technique by in situ observation. In the present work, fundamental information related to crystallization control in the CaO–SiO₂–TiO₂–Na₂O–Al₂O₃ system was obtained. It was observed that the addition of Na₂O in CaO–SiO₂–TiO₂ slags dramatically shortens the crystals' incubation times in TTT diagrams to the range of seconds. It is possible to control the crystallization kinetics in CaO–SiO₂–TiO₂ slags by changing the Na₂O content. Some observations for the crystals' morphology are reported.     

Solid-state preparation of mesoporous Ce-Mn-Co ternary mixed oxide nanoparticles for catalytic degradation of methylene blue

Mesoporous Ce-Mn-Co ternary metal oxide was fabricated via an efficient oxalate-precursor-based soft reactive grinding route and used to activate H_2 O_2 for advanced oxidation of methylene blue in water.In addition,Mn-Co binary oxide and pure Co_3 O_4 and Mn_3 O_4 were also synthesized as reference catalysts.These catalysts were characterized by X-ray diffraction,N2 adsorption-desorption,H2-temperature programmed reduction,transmission electron microscopy,scanning electron microscopy and X-ray photoelectron spectroscopy.The results demonstrate that part of the Ce and Mn can be incorporated into the lattice of Co_3 O_4 and cause severe lattice distortion of the unit cell.Compared with the single or binary system,Ce-Mn-Co ternary metal oxide exhibits the best activity in methylene blue removal and nearly100% decomposition rate and 84% COD removal rate can be achieved in 12 h,and with degradation rate of93.5% after three rounds.These results are primarily attributed to the synergistic effect of Ce,Mn and Co,which can promote the formation of more lattice defects,higher specific surface area and smaller particle size.Quenching tests show that hydroxyl radicals(·OH) play more dominant role than superoxide radicals(·O_2~-).Kinetic studies were studied and the activation energies of all the catalysts were calculated.     

Contribution to the phase diagram CaF2–CaO–Al2O3

Critical review of the available data. Determination of the liquidus line of CaF₂-Al₂O₃ mixtures and of the CaO liquidus line in the CaF₂–CaO binary. Investigation of the heterogeneous equilibria in the CaF₂–CaO–Al₂O₃ ternary by using different techniques. Determination of the 1600°C liquidus isotherms of CaO, CaO · 2Al₂O₃, CaO · 6Al₂O₃, Al₂O₃ and of the miscibility gap.     

Isothermal reduction behaviour of MnO2 doped Fe2O3 compacts with H2 at 1073–1373 K

Abstract

Pure Fe₂O₃ and Fe₂O₃ doped with 2, 4, and 6 mass% of MnO₂ (>99%) compacts annealed at 1473 K for 6 h were isothermally reduced with H₂ at 1073–1373 K. The O₂ weight loss resulted from the reduction of compacts was continuously recorded as a function of time using thermogravimetric analysis (TGA). High pressure mercury porosimeter, optical and scanning electron microscopes, X-ray phase analysis and vibrating sample magnetometer were used to characterise both the annealed and reduced samples. In MnO₂ containing samples, manganese ferrite (MnFe₂O₄) was identified. The rate of reduction of pure and doped compacts increased with temperature and decreased with the increase in MnO₂ content. Unlike in pure compacts, the reduction of MnO₂ containing samples was not completed and stopped at different extents depending on MnO₂ (mass%). At initial reduction stages, the decrease in the rate was due to the presence of poorly reducible manganese ferrite (MnFe₂O₄) phase which was partially reduced to iron manganese oxide (FeO_0.899, MnO_0.101) at the final stages. The reduction mechanism was predicted from the correlation between the reduction kinetics and the structure of partially reduced samples at different temperatures. The reduction of pure and doped samples was controlled by a combined effect of interfacial chemical reaction and gaseous diffusion mechanism at their initial stages. At final stages, the interfacial chemical reaction was the rate controlling mechanism.     

Dissolution of water vapour in ESR-slags of the systems CaO–Al2O3 and CaF2–CaO–Al2O3 by application of Fourier-Transform-Infrared-Spectroscopy

In CaO–Al₂O₃- and CaF₂–CaO–Al₂O₃-slags the soluted water vapour was quantitatively determined with Fourier-Transform-lnfrared-(FT-IR-)spectroscopy. The slags were equilibrated at 1500 and 1600 °C with definite H₂O- and H₂O/HF-partial pressures, respectively. The liquid slags were quenched in liquid D₂O. They solidified glassily. Water vapour exists in the slags soluted as OH^?-ion. For all slags investigated a linear dependence of the integral extinction upon the square root of the H₂O-partial pressure, respectively upon HF-partial pressure, was determined. The values of the integral extinction (CaF₂–CaO–Al₂O₃-slags) are calibrated by a H₂O-doping-technique. The solution enthalpy of H₂O in CaO–Al₂O₃-slags was estimated: endothermal reactions. Interpretation of the vibrational range yielded in a mainly tetrahedral coordination of Al³⁺ with O^2?- and F^? -ions in the glassy state. By heating the glassily solidified CaO–Al₂O₃-slags were transformed into their crystalline products: shifting of IR-peaks. The CaO–Al₂O₃- and CaF₂–CaO-slags were compared with a CaO–SiO₂–Al₂O₃-slag. The FT-IR-method is quick. The water content can be estimated with an uncertainty of less than ± 5% and is, therefore, suitable for process control of metallurgical procedures.     

Oxidation of molten copper matte

An amount of 80 mg of molten copper matte of a pseudo-ternary Cu₂S-FeS-Fe system contained in a slender alumina sample tube was oxidized at 1503 and 1533 K in a mixed O₂-Ar gas stream and the oxidation path was followed, comparing the overall rate of oxidation with the gaseous diffusion in the sample tube. The following successive reactions were found to be controlled by gas diffusion. Initially, Fe was oxidized to form FeO. After the melt composition reached a pseudo-ternary Cu₂S-FeS-FeO system, FeS was oxidized to form FeO. As the amount of FeO increased, Fe₃O₄ was also formed and subsequently Cu was produced by the oxidation of Cu₂S. In the latter stage, the Cu was oxidized, and the final product under the condition of gas diffusion control was composed of Cu₂O, Fe₃O₄, and CuFeO₂. On the other hand, the rate of formation of Fe₂O₃, CuO, and CuFe₂O₄ was much slower and they were not formed during the oxidation duration where the overall rate of oxidation was controlled by gas diffusion.     

MECHANISMS OF THE REDUCTION OF ZINC FERRITES IN H2/N2 GAS MIXTURES

The rates of reduction of dense pure zinc ferrite and zinc ferrite containing 1 wt% of CaO, MgO, MnO, and Al₂O₃ in solid solution reduced with H₂/N₂ gas mixtures have been investigated at temperatures between 500 and 1100°C. The rate measurements obtained in these studies were complemented with the structural characterization of the partially reduced zinc ferrite samples. The presence of impurity oxides in ZnFe₂O₄ solid solution influenced the conditions for formation of the porous iron morphology. Where porous iron-type microstructures were formed during the reduction reaction, the pore structure of the reduced samples was found to be dependent on reduction temperature, hydrogen partial pressure, and type of impurity oxide added into the solid solution. The reduction plots of zinc ferrite solid solutions exhibited an initial linear rate followed by a gradual decrease in rate with increased percentage reduction. The changes in growth mechanisms and reduction kinetics that occur with changing reduction conditions are discussed.     

Effects of basicity,MgO and MnO on mineralogical phases of CaO–FeOx–SiO2–P2O5 slag

The selective separation phosphorous rich phase from steel slag could be an effective way to utilise the steel slag. The mineralogical phase after cooling of steel slag is essential to selective separation of steel slag. In the present work, the mineralogical phases of CaO–FeO_x–SiO₂–P₂O₅ slag after controlled cooling were investigated by X-ray diffraction and scanning electronic microscopy and energy dispersed spectroscopy technique. It was found that the heat treatment at 1573?K would lead to the precipitation of Ca₂SiO₄–Ca₃P₂O₈ (C2S-C3P) solid solution for all samples. The heat treatment at 1273?K would lead to the precipitation of C2S-C3P, CaSiO₃ and Fe₂O₃. The increase of basicity would promote the crystallisation of CaO–FeO_x–SiO₂–P₂O₅ slag. The Effects of additions of MgO and MnO on phase formations of CaO–FeO_x–SiO₂–P₂O₅ slag were also studied. Fe₂O₃ gradually transformed into MgFe₂O₄ and MnFe₂O₄ in slag after crystallisation with addition of MgO and MnO, respectively. The sizes of MgFe₂O₄ and MnFe₂O₄ crystals increased with increases of MgO and MnO content. The increase of MgO and MnO content would promote the precipitation of MgFe₂O₄ phase and MnFe₂O_4, respectively. The precipitation of crystals from slag during cooling was interpreted by the kinetic and thermodynamic factors. It was proposed that addition of MgO and MnO in slag would be beneficial to magnetic separation of steel slag.     

Comparative studies on promotional effect of Pr6O11,Nd2O3 and Sm2O3 on Ni-SiO2 for pressurized carbon dioxide reforming of methane

The 7 wt% rare earth metal oxide promoted Ni-SiO₂ catalysts of Ni-7Pr₆O₁₁-SiO₂,Ni-7Nd₂O₃-SiO₂,and Ni-7Sm₂O₃-SiO₂ were prepared by the complex-decomposition method,and were comparatively evaluated for pressurized carbon dioxide reforming of methane(CRM) under severe conditions of 750℃,1.0 MPa,CH₄/CO₂=1,and gas hourly space velocity of 53200 mL/(g·h).The addition of r...