High Temperature Properties and Microstructures of Si_3N_4 with AZ-Type Non-Toxic, Non-Oxide Additives

A new type of Si3N4 ceramics (ZAN) is developed in our laboratory. Densification of ZAN is promoted by non-toxic, non-oxide AZ-type additives. In this work high temperature (HT) properties and microstructures of ZAN are investigated.

GLASS FORMATION AND STRUCTURE OF NON-OXIDE GLASSES

In this paper the characteristics of glass formation and structure of non-oxide glasses, have been summarized and some basic points have been discussed. The main points are as follows-Chemical bond nature is a deter-minative factor of formation and structure of glass ;Calcu-lation of glass formation ability by chemical bond paramiters; Classification of inorganic glass systems by characteristics of short range order of the glass structure; Structural models of non-oxide glasses.

Research Status of Non-oxides in Resin-bonded Al-Al2O3 Refractories with TiO2 Added

Ti(C,N)is a raw material for refractories with excellent properties.The preparation of Ti(C,N)by reducing TiO2 has the characteristics of low cost and simple process.In this paper,the research status of resin-bonded Al-Al2O3 refractories containing TiO2 under high temperatures and low oxygen partial pressure was introduced.

Thermodynamic Properties of Non-Oxide Composite Refractories

For initiative application of non-oxides in refractories, it is essential to study thermodynamic properties of non-oxides. The stability and stable order of non-ox- ides under oxidized atmosphere are analyzed firstly and then a new process, “converse reaction sintering”, is proposed. The results of study on oxidation mechanism of silicon and aluminum nitrides indicate that the gaseous suboxides can be produced observably when the oxygen partial pressure is lower than “conversion oxygen partial pressure”. The suboxides can be deposited near the surface of composite to become a compact layer. This causes the material possessing a performance of “self-impedient oxidation”. Metal Si and Al are the better additives for increasing the density and width of compact layer and increasing the ability of anti-oxidation and anti-corrosion. The study on Si3 N4-Al2O3, Si3N4-MgO, Si3 N4-SiC systems is also enumerated as examples in the paper. The experimental results show that the converse reaction sintering is able to make high performance composites and metal Si and Al not only can promote the sintering but also increase the density and width of compact layer.

CHEMICAL DURABILITY OF NON-OXIDE GLASSES

This paper reviews the chemical durability of non-oxide glasses including fluoride, non-fluoride halide, chalcogenide and chalcohalide glasses. Their kinetics and mechanism of corrosion are described and discussed. (Author abstract) 14 Refs.

Synthesis of Non-oxide Porous Ceramics Using Random Copolymers as Precursors

In this paper,we reported a novel method for synthesis of non-oxide porous ceramics by using random copolymers as precursors.A silazane oligomer and styrene monomer were used as starting materials,which were copolymerized at 120 ℃ to form random polysilazane-polystyrene copolymers.The copolymers were then pyrolyzed at 500 ℃ to obtain porous ceramics by completely decomposing polystyrene（PS） and converting polysilazane（PSZ） into non-oxide Si-C-N ceramics.The obtained material contained a bi-model pore-structure consisting of both micro-sized and nano-sized pores with very high surface area of more than500 m;/g.We also demonstrated that the pore structure and surface area of the materials can be tailored by changing the ratio of the two blocks.Current results suggest a promising simple method for making multiscaled porous non-oxide materials.

Direct experimental detection of hydrogen radicals in non-oxidative methane catalytic reaction

Non-oxidative conversion of methane to olefins,aromatics and hydrogen(MTOAH) has been reported recently over metal single sites such as iron and platinum.The reaction was proposed to involve catalytic activation of methane followed by gas phase C-C coupling of methyl radicals.This study using H atom Rydberg Tagging time-of-flight technique provides direct experimental evidence for the formation of hydrogen radicals during MTOAH reaction over a catalytic quartz wall reactor containing embedded iron species(denoted as Fe-reactor).Fe-reactor gives 7.3% methane conversion at 1273 K with 41.2% selectivity toward C2(ethane,ethylene and acetylene) and 31.8% toward BTX(benzene,toluene and xylene),respectively.The enhancing effects of hydrogen radicals on overall MTOAH performance are validated by cofeeding hydrogen donor benzene,which provides an additional route of methane activation apart from catalytic activation.

Intrinsic kinetics of methane aromatization under non-oxidative conditions over modified Mo/HZSM-5 catalysts

The intrinsic reaction kinetics of methane aromatization under non-oxidative conditions over modified Mo/HZSM-5 catalysts was studied in the quartz pipe-reactor under ordinary pressure with the temperature ranging from 913.15 to 973.15 K and the space velocity from 700 to 2100 ml/（g·h）. The Langmuir-Hinshelwood model was chosen to describe the intrinsic kinetics while Levenberg-Marquardt method was selected to determine the parameters in the kinetic model. Statistical test and residual error distribution diagrams showed that experimental data were in good agreement with calculated data, and Langmuir-Hinshelwood model was suitable for the description of the intrinsic kinetics of methane aromatization under the reaction conditions discussed in this article.

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.

Innovation and Development of Refractories for Ironmaking Industry in Sinosteel Luonai

Since China’s Reform and Opening-up,the innovation and development of refractories for ironmaking industry in Sinosteel Luonai were narrated,including silica materials,Al_(2)O_(3)-SiO_(2) refractories and non-oxide composites;and the development direction of refractories for ironmaking industry was prospected.

Phase Reconstruction and Microstructure Evolution of Magnesia-carbon Refractories at High Temperatures in Nitrogen

Magnesia-carbon refractories were prepared using fused magnesia,flake graphite and metal aluminum powder as starting materials,phenolic resin as the binder,heat-treating at 1300-1600℃in nitrogen atmosphere.The phase reconstruction and the microstructure evolution of the obtained magnesia-carbon refractories were analyzed.The formation mechanisms of magnesia crystals with different morphologies by chemical vapor deposition were revealed.The results show that at 1300-1500℃,the non-oxides within the specimens are aluminum carbide(Al_(4)C_(3)),aluminum nitride(AlN)and magnesium aluminum nitride(Mg_(3)Al_(n)N_(n+2),n=2 or 3);at 1600℃,the diffraction characteristic peak intensity of Al_(4)C_(3) and AlN decreases sharply,and sharp diffraction characteristic peaks of nitrogen aluminum carbide(Al_(7)C_(3)N_(3))appear.Mg(g)is produced by the aluminothermic reduction and carbothermal reduction of magnesia.On the surface of the specimens,Mg(g)reacts with oxygen to form MgO whiskers.Inside the specimens,Mg(g)and O_(2)(g)undergo a CVD chemical deposition reaction to form cubic MgO crystals.There is a phase relationship between flake AlN and flake Mg3AlnNn+2,and they are so associated with each other that the morphology is difficult to distinguish.

Energy-Efficient coaromatization of methane and propane

Development of highly effective catalysts for one-stage conversion of methane with high selectivity to valuable products and energy efficiency will provide an efficient way to utilize natural gas and oil-associated gases and to protect environment. In recent years, there have been many efforts on direct catalytic transformations of methane into higher hydrocarbons by feeding additives together with methane under non-oxidative conditions. This paper reviewed the advances in recent research on non-oxidative aromatization of methane in the presence of propane over different modified HZSM-5 catalysts. The thermodynamic consideration, the isotope verification and the mechanism of the activation of methane in the presence of propane are discussed in the paper in detail.

Non-oxidative dehydro-oligomerization of methane to higher molecular weight hydrocarbons at low temperatures

The non-oxidative dehydro-oligomerization of methane to higher molecular weight hydrocarbons such as aroma tics and C2 hydrocarbons in a low temperature range of 773-973 K with Mo/HZSM-5,Mo-Zr/HZSM-5 and Mo-W/HZSM-5 catalysts is studied.The means for enhancing the activity and stability of the Mo-containing catalysts under the reaction conditions is reported.Quite a stable methane conversion rate of over 10% with a high selectivity to the higher hydrocarbons has been obtained at a temperature of 973 K.Pure methane conversions of about 5.2% and 2.0% have been obtained at 923 and 873 K,respectively.In addition,accompanied by the C2-C3 mixture,tht- methane reaction can be initiated even at a lower temperature and the conversion rate of methane is enhanced by the presence of tne initiator of C2-C3 hydrocarbons.Compared with methane oxidative coupling to ethylene,the novel way for methane transformation is significant and reasonable for its lower reaction temperatures and high selectivity to the desired products.

Oxygen vacancy self-doped single crystal-like TiO_(2) nanotube arrays for efficient light-driven methane non-oxidative coupling

Photocatalytic non-oxidative coupling of methane(PNOCM)is a mild and cost-effective method for the production of multicarbon compounds.However,the separation of photogenerated charges and activation of methane(CH4)are the main challenges for this reaction.Here,single crystal-like TiO_(2) nanotubes(VO-p-TNTs)with oxygen vacancies(VO)and preferential orientation were prepared and applied to PNOCM.The results demonstrate that the significantly enhanced photocatalytic performance is mainly related to the strong synergistic effect between preferential orientation and VO.The preferential orientation of VO-p-TNT along the[001]direction reduces the formation of complex centers at grain boundaries as the form of interfacial states and potential barriers,which improves the separation and transport of photogenerated carriers.Meanwhile,VO provides abundant coordination unsaturated sites for CH4 chemisorption and also acts as electron traps to hinder the recombination of electrons and holes,establishing an effective electron transfer channel between the adsorbed CH4 molecule and photocatalyst,thus weakening the C–H bond.In addition,the introduction of VO broadens the light absorption range.As a result,VO-p-TNT exhibits excellent PNOCM performance and provides new insights into catalyst design for CH4 conversion.

Recent progress in synthesis of composite powders and their applications in low-carbon refractories

The development of low-carbon refractories is of great significance,but it is limited by the deteriorated properties that resulted from the decreased graphite content.Incorporating composite powders has proved to be effective in improving the properties of low-carbon refractories.The recent progress in the synthesis of composite powders including modified graphite,nanocarbon-containing composite powders,oxide/non-oxide and non-oxide composite powders and their applications in low-carbon refractories were reviewed,and the future development of composite powder technology was prospected.

Preparation of patterned SiC and SiCN microstructures

Patterned SiC and SiCN microstructures were successfully fabricated on the silicon substrates by using polydimethylsiloxane (PDMS) elastometric stamp as template, polycarbosilane (PCS) and polysilazane (PSZ) as preceramic polymers. The preparing process was followed by precursor infiltration, the curing of the precursor, demolding of the template and pyrolysis of the cured preceramic polymer pattern. It shows that the dimen- sions of the ceramic patterns can be tailored by using the PDMS molds with different di- mensions. The produced ceramic microstructures can be potentially applied in high tem- perature and high pressure environments due to the advanced properties of the SiC and SiCN ceramics.

Biodegradation of organochlorine pesticide endosulfan by bacterial strain Alcaligenes faecalis JBW4

The recently discovered endosulfan-degrading bacterial strain Alcaligenesfaecalis JBW4 was isolated from activated sludge. This strain is able to use endosulfan as a carbon and energy source. The optimal conditions for the growth of strain JBW4 and for biodegradation by this strain were identified, and the metabolic products of endosulfan degradation were studied in detail. The maximum level of endosulfan biodegradation by strain JBW4 was obtained using broth at an initial pH of 7.0, an incubation temperature of 40℃ and an endosulfan concentration of I00 mg/L. The concentration of endosulfan was determined by gas chromatography. Strain JBW4 was able to degrade 87.5% of α-endosulfan and 83.9% of β-endosulfan within 5 days. These degradation rates are much higher than the previously reported bacterial strains. Endosulfan diol and endosulfan lactone were the major metabolites detected by gas chromatography-mass spectrometry; endosulfan sulfate, which is a persistent and toxic metabolite, was not detected. These results suggested that A. faecalis JBW4 degrades endosulfan via a non-oxidative pathway. The biodegradation of endosulfan by A. faecalis is reported for the first time. Additionally, the present study indicates that strain JBW4 may have potential for the biodegradation of endosulfan residues.

The triggering of catalysis via structural engineering at atomic level: Direct propane dehydrogenation on Fe-N_(3)P-C

The on-purpose direct propane dehydrogenation(PDH) has received extensive attention to meet the everincreasing demand of propylene.In this work,by means of density functional theory(DFT) calculations,we systematically studied the intrinsic coordinating effect of Fe single-atom catalysts in PDH.Interestingly,the N and P dual-coordinated single Fe(Fe-N_(3)P-C) significantly outperform the Fe-N_(4-)C site in catalysis and exhibit desired activity and selectivity at industrial PDH temperatures.The mechanistic origin of different performance on Fe-N_(3)P-C and Fe-N_(4-)C has been ascribed to the geometric effect.To be specific,the in-plane configuration of Fe-N_(4) site exhibits low H affinity,which results in poor activity in C-H bond activations.By contrast,the out-of-plane structure of Fe-N_(3)P-C site exhibits moderate H affinity,which not only promote the C-H bond scission but also offer a platform for obtaining appropriate H diffusion rate which ensures the high selectivity of propylene and the regeneration of catalysts.This work demonstrates promising applications of dual-coordinated single-atom catalysts for highly selective propane dehydrogenation.