Partial Oxidation of Methane to Synthesis Gas over Hexaaluminates LaMAl_(11)O_(19-δ) catalysts

A series of M-substituted hexaaluminates LaMAl11O19-δ （M=Fe, Co, Ni, Mn, and Cu） were prepared and characterized by XRD, XPS, TPR and TGA techniques, respectively. They exhibited different reducibility and catalytic activity for partial oxidation of methane （POM） to synthesis gas. Among the LaMAl11019-δ samples, LaNiAl11O19-δ showed the best catalytic activity for the topic reaction and selectivity for synthesis gas at 780 ℃ for 2 h. The conversion of CH4 was over 99.2%, and the product selectivity for both CO and H2 was above 90.3%.

Fast grain growth phenomenon in high-entropy ceramics:A case study in rare-earth hexaaluminates

It is generally reported that the grain growth in high-entropy ceramics at high temperatures is relatively slower than that in the corresponding single-component ceramics owing to the so-called sluggish diffusion effect.In this study,we report a fast grain growth phenomenon in the high-entropy ceramics(La_(0.2)Nd_(0.2)Sm_(0.2)Eu_(0.2)Gd_(0.2))MgAl_(11)O_(19)(HEMA)prepared by a conventional solid-state reaction method.The results demonstrate that the grain sizes of the as-sintered HEMA ceramics are larger than those of the corresponding five single-component ceramics prepared by the same pressureless sintering process,and the grain growth rate of HEMA ceramics is obviously higher than those of the five single-component ceramics during the subsequent heat treatment.Such fast grain growth phenomenon indicates that the sluggish diffusion effect cannot dominate the grain growth behavior of the current high-entropy ceramics.The X-ray photoelectron spectroscopy(XPS)analysis reveals that there are more oxygen vacancies(OV)in the high-entropy ceramics than those in the single-component ceramics owing to the variable valance states of Eu ion.The high-temperature electrical conductivities of the HEMA ceramics support this analysis.It is considered that the high concentration of OV and its high mobility in HEMA ceramics contribute to the accelerated migration and diffusion of cations and consequently increase the grain growth rate.Based on this study,it is believed that multiple intrinsic factors for the high-entropy ceramic system will simultaneously determine the grain growth behavior at high temperatures.

Catalytic activity of Mn-substituted barium hexaaluminates for methane combustion

The catalysts of hexaaluminate (BaMn x Al12?x O19?δ , x = 1.0, 2.0, 3.0, 4.0) to be used in methane combustion have been successfully synthesized by co-precipitation method and supercritical drying. The crystalline structure and surface area of catalyst were characterized by X-ray diffraction (XRD) and nitrogen adsorption analysis of BET method. BET analysis revealed that the preparing and drying method proposed here provides stable materials with higher surface area of 51.4 m2/g in comparison to materials prepared using conventional ambient drying method for BaMn x Al12?x O19?δ calcined at 1200° under oxygen. XRD analysis indicated that formation of a pure single phase BaMn x Al12?x O19?δ occurred up to x = 3 in the case of Mn-substituted barium hexaaluminates. Incorporation of Mn in excess leads to BaAl2O4 phase formation. As far as the valence state of Manganese ions was concerned, the introduced Mn ions were either divalent or trivalent. The first Mn ions were introduced in the matrix essentially as Mn2+ and only for BaMn3Al9O19?δ does manganese exist exclusively as Mn3+; the higher the Mn concentration, the higher the proportion of Mn3+. Catalytic activity for methane combustion has been measured for Mn-substituted barium hexaaluminates, light-off temperature was observed in the 512?624°C range. The highest activity was obtained for catalysts containing 3 Mn ions per unit cell, which reveals that the BaMn x Al12?x O19?δ catalyst was a promising methane combustion catalyst with high activity and good thermal stability. Temperature programmed reduction (TPR) under hydrogen has been used to correlate the catalytic activity with the amount of easily reducible species.

Alkali Vapor Corrosion of Different Refractories at High Temperatures

Commercial high purity corundum brick,corundum-mullite brick,mullite brick,calcium hexaaluminate brick and calcium hexaaluminate-corundum brick were studied to investigate their reaction state and alkali vapor corrosion mechanism at 1370 and 1500℃.The results show that:(1)served in hot alkali vapor,the high-purity corundum brick has no obvious slag layer but expands dramatically;(2)the corundum-mullite brick shows obvious reactive expansion at 1370℃and melting corrosion happens at 1500℃;(3)at 1370℃alkali vapor and mullite brick react and form a slag layer without volume effect;when the temperature increases to 1500℃,the reaction melting corrosion intensifies;(4)the calcium hexaaluminate brick and the calcium hexaaluminate-corundum brick form a thin slag layer in alkali vapor,and the sample surface absorbs Na+to form a dense layer with small volume effect.

Crystallization behavior of plasma-sprayed lanthanide magnesium hexaaluminate coatings

LaMgAl11O19 thermal barrier coatings （TBCs） were prepared by atmospheric plasma spraying. The crystallization behavior of the coatings and the synthesis mechanism of LaMgAl11O19 powders were researched. The results showed that the plasma-sprayed coatings conmined some amorphous phase, and LaMgAl11O19 powders were partially decomposed into Al2O3, LaAlO3, and MgAl2O4 in the plasma spraying process. The amorphous phase was reerystallized at a temperature of approximately 1174.9℃, at which level the decomposed Al2O3, LaAl2O3, and MgAl2O4 reacted again. The resynthesis temperature of LaMgAl11O19 in the plasma-sprayed coatings was lower than that of LaMgAl11O19 in the original raw powders. The synthesis mechanism of LaMgAl11O19 powders can be summarized as follows： during the first part of the overall reaction, La2O3 reacts with Al2O3 to form LaAl2O3 at approximately 900℃, and then LaAl2O3 further reacts with Al2O3 and MgAl2O4 to produce LaMgAl11O19 at approximately 1200℃.

Effect of Preparation Methods on Activation of Catalysts BaNi0.2Mn0.8Al11O19-δ for Dimethyl Ether Combustion

Catalytic combustion of dimethyl ether （DME） over hexaaluminate catalyst BaNi0.2Mn0.8Al11O19-δ has been investigated. The catalysts were prepared with the sol-gel method and reverse microemulsion method respectively and characterized by thermogravimetry-differential thermal analysis, X-ray diffraction and transimission electron microscope. It was found that the formation of Mn, Ni modified hexaaluminate was a relatively slow process via two solid state reactions and spinel structure was a transition phase. At the same calcined temperature and time, the catalyst prepared with the reverse microemulsion method could form the hexaaluminate phase more easily than that prepared with the sol-gel method. The catalyst BaNi0.2Mn0.8Al11O19-δ prepared with the reverse micro-emulsion method appeared a plate-like morphology, while it appeared a needle-like morphology when using the sol-gel method. The catalytic activities of catalysts BaNi0.2Mn0.8Al11O19-δ prepared with two different methods for DME combustion were tested. It showed that catalyst prepared with the reverse microemulsion method had better catalytic activity, i.e. T10% of DME had decreased by 45℃, about 90% conversion of diemthyl ether at 380℃.

ZrO_2-modified Ni/LaAl_(11)O_(18) catalyst for CO methanation: Effects of catalyst structure on catalytic performance

We report Ni/LaHA@ZrO2catalysts prepared by a facile modified successive adsorption and reaction method for CO methanation.N2adsorption,X‐ray diffraction,transmission electron microscopy,scanning electron microscopy,thermogravimetric analysis,H2temperature‐programmed reduction,H2temperature‐programmed desorption,X‐ray photoelectron spectroscopy,thermogravimetric analysis,and inductively coupled plasma atomic emission spectrometry were used to characterize the samples.The results indicated that the ZrO2nanoparticles were distributed over the surface of the Ni/LaHA@ZrO2catalyst and even partially covered some Ni particles,resulting in the coating exerting a confinement effect.The excess ZrO2had an adverse effect on the enhancement of CO conversion because of the coverage of the surface Ni particles;however,the Ni/LaHA@ZrO2catalyst displayed much higher CH4selectivity than Ni/LaHA because of the activation of the byproduct CO2molecules by ZrO2species.Therefore,even though20Ni/LaHA@ZrO2‐5exhibited similar CO conversion as20Ni/LaHA,the use of the former resulted in a higher CH4yield than the use of the latter.A107‐h‐lifetime test revealed that the Ni/LaHA@ZrO2catalyst was highly stable with superior anti‐sintering and anti‐coking properties because of its coating structure and the promoter effect of ZrO2.

Preparation and Properties of Calcium Hexaaluminate Porous Ceramics

In this paper,calcium hexaaluminate(CA6)porous ceramics were prepared by a foaming method combined with cement solidification molding.The effects of the foaming agent addition on the microstructure and the properties of the ceramics were studied.The results show that the microstructure and the porosity of the ceramics can be controlled by adjusting the addition of the foaming agent.As the addition of the foaming agent increased,the bulk density reduced from 1 g·cm^-3 to 0.35 g·cm^-3,the porosity increased from 70.4%to 89.6%,the compressive strength reduced from 18.46 MPa to 1.66 MPa,and the thermal conductivity at 1000°C decreased from 0.382 W·m^-1·K^-1 to 0.144 W·m^-1·K^-1.It is indicated that calcium hexaaluminate porous ceramics with low density,high strength and low thermal conductivity can be obtained by the foaming method.As the lining material of high temperature electric furnaces,the ceramic has excellent energy saving effect.

Preparation of Different Metal Substituted Hexaaluminate and Its Catalytic Performance of Methane Combustion

Different metal substituted hexaaluminate catalysts （Ba0.8 La0.2 MAl11 O19-α） were the M = Mn, Fe, Co, Cu were prepared using alumina sol as the （NH4）2CO3 coprecipitation precursor and supercritical drying （SCD） method. Meanwhile the catalysts were characterized using BET, XRD, TEM, UV-Vis-DR and O2-TPD techniques. The rod-like hexaaluminate nanoparticles with high surface area ranging from 42 to 73 m^2·g^-1 were obtained after calcinations at 1200℃. The XRD results reveal that the main crystal phase of the catalyst is hexaaluminate and small amount of α-Al2O3 existed except for Ba0.8La0.2MnAl11O19-α catalyst. Moreover, the UV-Vis-DR results verify that Fe^3＋ , Mn^3＋ occupy the Oh sites in the hexaaluminate structure while Co^3＋ , Cu^2＋ locate at the Oh and Td sites.

Effects of SnO₂Addition on the Properties of Alumina-Magnesia Refractory Castables

Alumina-magnesia refractory castables have been widely used in the wall and bottom impact pad of steel ladles. The properties of alumina-magnesia refractory castables with SnO2 additive in 0 - 5 wt% range were investigated. The phase composition, microstructure, physical and mechanical properties of these refractories were studied. The results showed that the addition of SnO2 could have a great influence on the properties of alumina-magnesia refractory castables. The expansion, apparent porosity and strength of refractories with SnO2 were all more prominent than those of reference samples, which were attributed to the formation of CA6 and enhanced bonding. Meanwhile SnO2 could react with spinel and CA6 to form solid solution.

Effect of Complex Agents on Structure and Activity of Fe-Substituted Rare Earth Hexaaluminate Catalysts for Methane Combustion

A series of catalysts were prepared by using complex sol-gel methods.Experimental results confirm the effect of different agents on structure and activity of Fe-substituted rare earth hexaaluminate catalyst (LaFeAl11 O19 ) for methane combustion.The catalyst is yielded by complex sol-gel, respectively using three different complex agents (maltose, glucose and citric acid).XRD demonstrated that haxaaluminate is the major phase of catalyst prepared by maltose,while LaAlO3 is the major one of the catalyst by glucose and citric acid.At the same time, there is a little LaFeO3 and surface areas as well as 29.5 nm particle diameter when the complex agent is maltose.However, T10 ( temperature for 10% conversion of methane) and T100 ( temperature for 100% conversion of methane) for catalyst by glucose is 543 and 758 ℃, which is the best among the three complex agents for methane combustion.

Fe-substituted Ba-hexaaluminate with enhanced oxygen mobility for CO_2 capture by chemical looping combustion of methane

While Fe-based oxygen carriers(OC) are regarded to be promising for chemical looping combustion(CLC),the decrease of CO_2 selectivity during deep reduction process and the severe agglomeration of Fe_2O_3 often occur after multiple redox cycles due to the low oxygen mobility.Herein,Fe-substituted Bahexaaluminates(Ba Fe_xAl_(12)– xO_(19),denoted as BF_xA-H,x = 1 and 2) prepared by a modified two-step method exhibited not only higher amount of converted oxygen(Ot) and CH_4 conversion(77% and 81% vs.17%and 75%) than those prepared by the traditional co-precipitation method(BF_xA-C,x = 1 and 2) but also high CO_2 selectivity above 92% during the nearly whole reduction from Fe^(3+) to Fe^(2+).Furthermore,the BFxA-H exhibited the excellent recyclability during 50 cycles.The better performance was ascribed to the markedly enhanced oxygen mobility which resulted from dominant occupancy of Fe cations in Al(5) sites(Fe^5: 71% and 70% vs.49% and 41%) in mirror planes of hexaaluminate leading to larger amount of lattice oxygen coordinated with Fe^5(O–Fe^5)(0.45 and 0.85 mmol/g vs.0.31 and 0.50 mmol/g).The improvement of oxygen mobility also favored the preservation of chemical state of Fe cations in hexaaluminate structure in the re-oxidation step,resulting in the excellent recyclability of BF_xA-H.

Effect of Drying Methods on the Structure and Combustion Activity of Mn-Substituted Hexaaluminate Catalysts

Conventional oven drying (COD) and supercritical drying (SCD) methods wereapplied to the preparation of Mn-substituted hexaaluminate (BaMnAl_(11)O_(19-α)) catalysts. Theeffect of drying methods on phase composition, specific surface area, pore structure, reductionbehavior of Mn^(3+) ions, and combustion activity of the samples was investigated. The homogenousmixing of the components in the sol-gel process could be maintained by SCD, and the hexaaluminatephase was almost the only phase of the resulting materials after calcination. H_2-TPR revealed thatthe Mn^(3+) ions in the sample obtained by SCD were easier to be reduced than that by COD. Moreover,the samples obtained by SCD have higher surface area, narrower pore size distribution, and highercombustion activity than those obtained by COD.

Kinetics of Carbon Deposition on Hexaaluminate LaNiAl_(11)O_(19) Catalyst During CO_2 Reforming of Methane

In this paper, the properties of carbon deposited on hexaaluminateLaNiAl_(11)O_(19) catalyst were characterized by X-ray photoelectron spectroscopy (XPS), and in themeantime, the amount of carbon deposited on the catalyst, after both CH_4 decomposition and CO_2reforming of CH_4, was determined by means of thermogravimetric analysis (TGA), respectively. Therates of carbon deposited on the catalyst were also investigated and the apparent kinetic equationof CO_2 reforming of CH_4: ν_c = kp^(0.72)(CH_4)·p^(-0.55)(CO_2), was established by analyzing therelation between the rates of deposited carbon and the pressure ratio of CH_4 and CO_2.

Synthesis of hexaaluminate catalysts for methane combustion by reverse microemulsion medium

The aim of this study is to synthesize the catalysts of Fe- and Mn-substituted hexaaluminate by reverse microemulsion medium for methane catalytic combustion application. Pseudo-ternary phase diagrams in quaternary microemulsion systems of cetyltrimethylammonium bromide (CTAB), n-butanol, n-octane, and water [or Al(NO3)3 solution] were presented. The effects of the alcohol chain length, ratio of sur-factant to cosurfactant, and salt concentration on the formation and stability of microemulsion systems were studied. The phase behavior of microemulsion systems was confirmed through the varying of the conductivity with the water content. The performance and structure of the catalysts, La(Mn x /Fe x )Al12?x ? O19-δ synthesized with the optimal parameter in the phase diagrams of microemulsions systems were characterized by BET, TG-DTA, and XRD. The micro fix-bed reactor was used to measure the catalytic activities of catalysts to methane combustion. The results showed that this synthesis method could yield non-agglomerated and highly dispersed precursors that would undergo crystallization at the lower temperature of 950°C. When temperature was raised up to 1050°C, the complete crystalline La-hexaaluminate was shaped. The hexaaluminate substituted with Fe had high-catalytic activity and stability at high temperature, while the Mn-substituted had higher catalytic activity at lower temperature. When the cooperation of Fe and Mn occurred, i.e., LaFeMnAl10O19?δ exhibited a high surface area and catalytic activity to CH4 combustion, the CH4 light-off temperature was only 475°C and the complete combustion temperature was 660°C. This was attributed to the synergistic effect between Fe and Mn.

Effect of intermediate layer on the activity and adhesion stability of metal monolith supported LaMn-hexaaluminate catalyst for methane combustion

Al2O3 and La2O3 layers were coated respectively on a FeCrAl alloy foil by a dip-coating technique and used as the second support for the active LaMnAl11O19 hexaaluminate （HA） phase in a metallic monolithic catalyst. A sample without an intermediate layer was employed for comparison. The properties and performances of the catalyst were examined with X-ray diffraction （XRD）, scanning electron microscopy （SEM）, ultrasonic vibration and thermal shock techniques. Methane catalytic combustion was performed to evaluate the activity of the catalyst. The results showed that the activity and adhesion of the HA to the alloy foil could be improved with the introduction of the intermediate layer. Al2O3 provided a strong adhesion, while La2O3 weakened the interaction between the active component and alloy foil. For the activity, the catalysts made with the two different intermediate materials also showed difference.

Influence of synthesis temperatures on the crystalline grain growth and morphology of lanthanum magnesium hexaaluminate

Lanthanum magnesium hexaaluminate（LaMgAl（11）O（19）, LMA） was prepared at different temperatures by solid-state reaction. Phase compositions and crystal morphologies of specimens synthesized at different temperatures were investigated using X-ray diffraction（XRD）, scanning electron microscopy（SEM）. It was observed that the crystalline grain size of LMA was not only dependent on the preparation temperature but also on its powder morphology. In the temperature range of 1300 e1550℃, LMA showed platelet grain and the average crystalline grain size increases with the increase in temperature. At1600℃, if the powder was sintered for two times, the equiaxed grain could be found with the decrease in grain space, resulting in the reduction of the crystalline grain size. Styles of specimens（powder or disk） might have no obvious influence on morphologies and sizes of LMA crystalline grains which were synthesized with the well-dispersed raw material mixtures. The synthesis temperature played a key role in influencing the free space for the formation and growth of crystalline grains.

High temperature H_(2)S selective oxidation on a copper-substituted hexaaluminate catalyst: A facile process for treating low concentration acid gas

H_(2)S selective catalytic oxidation technology is a prospective way for the treatment of low concentration acid gas with simple process operation and low investment. However, undesirable results such as large formation of SO_(2) and catalyst deactivation inevitably occur, due to the temperature rise of fixed reaction bed caused by the exothermic reaction. Catalyst with high activity in wide operating temperature window, especially in high temperature range, is urgently needed. In this paper, a series of copper-substituted hexaaluminate catalysts (LaCu_(x), x = 0, 0.5, 1, 1.5, 2, 2.5) were prepared and investigated for the H_(2)S selective oxidation reaction at high temperature conditions (300-550℃). The LaCu_(1) catalyst exhibited excellent catalytic performance and great stability, which was attributed to the best reductive properties and proper pore structure. Besides, two facile deep processing paths were proposed to eliminate the remaining H_(2)S and SO_(2) in the tail gas.