Towards carbon neutrality of calcium carbide-based acetylene production with sustainable biomass resources

Acetylene is produced from the reaction between calcium carbide(CaC_(2))and water,while the production of CaC_(2) generates significant amount of carbon dioxide not only because it is an energy-intensive process but also the raw material for CaC_(2) synthesis is from coal.Here,a comprehensive biomass-to-acetylene process was constructed that integrated several units including biomass pyrolysis,oxygen-thermal CaC_(2) fabrication and calcium looping.For comparison,a coal-to-acetylene process was also established by using coal as feedstock.The carbon efficiency,energy efficiency and environmental impacts of the bio-based calcium carbide acetylene(BCCA)and coal-based calcium carbide acetylene(CCCA)processes were systematically analyzed.Moreover,the environmental impacts were further evaluated by applying thermal integration at system level and energy substitution in CaC_(2) furnace.Even though the BCCA process showed lower carbon efficiency and energy efficiency than that of the CCCA process,life cycle assessment demonstrated the BCCA(1.873 kgCO_(2eq) kg-prod^(-1))a lower carbon footprint process which is 0.366 kgCO_(2eq) kg-prod^(-1) lower compared to the CCCA process.With sustainable energy(biomass power)substitution in CaC_(2) furnace,an even lower GWP value of 1.377 kgCO_(2eq) kg-prod^(-1) can be achieved in BCCA process.This work performed a systematic analysis on integrating biomass into industrial acetylene production,and revealed the positive role of biomass as raw material(carbon)and energy supplier.

Pulsed laser interference patterning of transition-metal carbides for stable alkaline water electrolysis kinetics

We investigated the role of metal atomization and solvent decomposition into reductive species and carbon clusters in the phase formation of transition-metal carbides(TMCs;namely,Co_(3)C,Fe_(3)C,TiC,and MoC)by pulsed laser ablation of Co,Fe,Ti,and Mo metals in acetone.The interaction between carbon s-p-orbitals and metal d-orbitals causes a redistribution of valence structure through charge transfer,leading to the formation of surface defects as observed by X-ray photoelectron spectroscopy.These defects influence the evolved TMCs,making them effective for hydrogen and oxygen evolution reactions(HER and OER)in an alkaline medium.Co_(3)C with more oxygen affinity promoted CoO(OH)intermediates,and the electrochemical surface oxidation to Co_(3)O_(4)was captured via in situ/operando electrochemical Raman probes,increasing the number of active sites for OER activity.MoC with more d-vacancies exhibits strong hydrogen binding,promoting HER kinetics,whereas Fe_(3)C and TiC with more defect states to trap charge carriers may hinder both OER and HER activities.The results show that the assembled membrane-less electrolyzer with Co_(3)C∥Co_(3)C and MoC∥MoC electrodes requires~2.01 and 1.99 V,respectively,to deliver a 10 mA cm−2 with excellent electrochemical and structural stability.In addition,the ascertained pulsed laser synthesis mechanism and unit-cell packing relations will open up sustainable pathways for obtaining highly stable electrocatalysts for electrolyzers.

The electrical characteristics of a 4H-silicon carbide metal-insulator-semiconductor structure with Al_2O_3 as the gate dielectric

A 4H-silicon carbide metal-insulator-semiconductor structure with ultra-thin Al2O3 as the gate dielectric, deposited by atomic layer deposition on tile epitaxial layer of a 4H-SiC （0001） 80N-/N＋ substrate, has been fabricated. The experimental results indicate that the prepared ultra-thin Al2O3 gate dielectric exhibits good physical and electrical characteristics, including a high breakdown electrical field of 25 MV/cm, excellent interface properties （1 × 10^14 cm^-2） and low gate-leakage current （IG = 1 × 10^-3 A/cm 2@Eox = 8 MV/cm）. Analysis of the current conduction mecha- nism on the deposited Al2O3 gate dielectric was also systematically performed. The confirmed conduction mechanisms consisted of Fowler-Nordheim （FN） tuaneling, the Frenkel-Poole mechanism, direct tunneling and Schottky emission, and the dominant current conduction mechanism depends on the applied electrical field. When the gate leakage current mechanism is dominated by FN tunneling, the barrier height of SiC/Al2O3 is 1.4 eV, which can meet the requirements of silicon carbide metal-insulator-semiconductor transistor devices.

Mo_(2)C添加量对YG6细晶硬质合金组织结构及性能的影响

采用传统粉末冶金方法制备了不同Mo_(2)C添加量的YG6细晶硬质合金。通过对合金显微结构的观察及物理力学性能的检测,研究了Mo_(2)C添加量对YG6细晶硬质合金组织结构及性能的影响。结果表明:随着Mo_(2)C添加量的增加,合金中WC晶粒度逐渐细化并趋于稳定。当合金中Mo_(2)C添加量超过3.5%时,Mo_(2)C对WC晶粒形貌具有球化作用。另外,添加Mo_(2)C会降低合金致密度,合金矫顽磁力随Mo_(2)C含量的增加而逐渐增加。Mo_(2)C添加量为5.0%时,合金综合力学性能最好,其硬度达92.7 HRA,抗弯强度为3 600 MPa,磨粒磨损值为0.81 cm^(3)/(10^(5)r)。

基于碳化钼材料CO_(2)加氢制备高附加值化学品的热催化研究进展

CO_(2)加氢对于CO_(2)转化制备高附加值化学品和燃料以实现二氧化碳利用及能源储存至关重要。CO_(2)加氢包括甲烷化、逆水煤气变换、甲醇化和CO_(2)直接费托合成等。碳化钼,尤其是其二维材料,由于其低成本和良好的性能而备受关注。在CO_(2)加氢反应中,由于碳的渗入,导致晶格膨胀以及价电子增加,碳化钼基催化剂展现出了类似于贵金属催化剂的性质。碳化钼可以通过程序升温渗碳法、选择性蚀刻法、机械合金合成法、化学气相沉积法、原位热渗碳法以及溶液相合成法等来制备。到目前为止,学者已经对基于碳化钼的材料的CO_(2)转化进行大量研究,这些材料具有良好的CO_(2)转化活性和对目标产物的选择性。碳化钼材料的催化性能可以通过调节碳化钼中的C/Mo比、在碳化钼与负载金属之间建立强的金属-载体相互作用以及调整材料的界面结构来实现。然而,基于碳化钼的热催化CO_(2)转化仍处于初级阶段。本文综述基于碳化钼的热催化CO_(2)加氢制备高附加值化学品和燃料的研究进展,并分析其面临的挑战和机遇。

Effect of SiO_2 on the Preparation and Properties of Pure Carbon Reaction Bonded Silicon Carbide Ceramics

Effect of SiO 2 content and sintering process on the composition and properties of Pure Carbon Reaction Bonded Silicon Carbide (PCRBSC) ceramics prepared with C-SiO 2 green body by infiltrating silicon was presented.The infiltrating mechanism of C-SiO 2 preform was also explored.The experimental results indicate that the shaping pressure increases with the addition of SiO 2 to the preform,and the pore size of the body turned finer and distributed in a narrower range,which is beneficial to decreasing the residual silicon content in the sintered materials and to avoiding shock off,thus increasing the conversion rate of SiC.SiO 2 was deoxidized by carbon at a high temperature and the gaseous SiO and CO produced are the main reason to the crack of the body at an elevated temperature.If the green body is deposited at 1800℃ in vacuum before infiltration crack will not be produced in the preform and fully dense RBSC can be obtained.The ultimate material has the following properties:a density of 3.05-3.12g/cm3,a strength of 580±32MPa and a hardness of (HRA)91-92.3.

Preparation, Characterization and Catalytic Properties of S_2O_8^(2-)/ZrO_2 Supported by Tungsten Carbide

A WC-supported S_2O 2-_8/ZrO_2(PSZ) catalyst was prepared and characterized by means of XRD, BET, FTIR and XPS. The isomerization of n-pentane over the catalyst was investigated as well. The results show that the skeletal isomerization and the crack of n-pentane proceed simultaneously on WC-supported S_2O 2-_8/ZrO_2 catalyst. The addition of tungsten carbide showed a significant enhancement in the activity and stability of the catalyst for n-pentane isomerization. The catalyst showed evidently a better activity than S_2O 2-_8/ZrO_2 supported by Pt and WO_3. The results can be interpreted by the existence of the tungsten oxycarbide compound(WC_xO_y) with carbidic, oxide and acidic sites.

CO_(2) mineralization of carbide slag for the production of light calcium carbonates

The production of polyvinyl chloride by calcium carbide method is a typical chemical process with high coal consumption,leading to massive flue gas and carbide slag emissions.Currently,the carbide slag with high CaO content is usually stacked in residue field,easily draining away with the rain and corroding the soil.In this work,we coupled the treatment of flue gas and carbide slag to propose a facile CO_(2)mineralization route to prepare light calcium carbonate.And the route feasibility was comprehensively evaluated via experiments and simulation.Through experimental investigation,the Ca^(2+) leaching and mineralization reaction parameters were determined.Based on the experiment,a process was built and optimized through Aspen Plus,and the energy was integrated to obtain the overall process energy and material consumption.Finally,the net CO_(2)emission reduction rate of the entire process through the life-cycle assessment method was analyzed.Moreover,the relationship between the parameters and the CO_(2)emission life-cycle assessment was established.The final optimization results showed that the mineralization process required 1154.69 kW·h·(t CO_(2))^(-1) of energy(including heat energy of 979.32 kW·h·(t CO_(2))^(-1) and electrical energy of 175.37 kW·h·(t CO_(2))^(-1)),and the net CO_(2)emission reduction rate was 35.8%.The light CaCO_(3)product can be sold as a high value-added product.According to preliminary economic analysis,the profit of mineralizing can reach more than 2,100 CNY·(t CO_(2))^(-1).

Molybdenum carbide clusters for thermal conversion of CO2 to CO via reverse water-gas shift reaction

Molybdenum carbides are highly active for CO2 conversion to CO via the reverse water-gas shift(RWGS)reaction, however the large grain size up to micrometers renders its relatively lower active sites utilization efficiency while generating CH4 as a by-product. In this work, a homogeneously dispersed molybdenum carbide hybrid catalyst with sub-nanosized cluster(the average size as small as 0.5 nm) is prepared via a facile carbothermal treatment for highly selective CO2-CO reduction. The partially disordered Mo2C clusters are characterized by synchrotron high-resolution XRD and atomic resolution HAADF-STEM analysis, for which the source cause of the disorder is pinpointed by XAFS analysis to be the nitrogen intercalants from the carbonaceous precursor. The partially disordered Mo2C clusters show a RWGS rate as high as 184.4 μmol gMo2C-1s-1 at 400 ℃ with a superior selectivity toward CO(> 99.5%). This work 2 highlights a facile strategy for fabricating highly dispersed and partially disordered Mo2C clusters at a sub-nano size with beneficial N-doping for delivering high catalytic activity and operational stability.

电石渣改性制备高效CO_(2)复合吸收剂

电石渣是典型的高钙工业固体废弃物,具有优异的CO_(2)吸收性能,但是在钙循环中纯电石渣的反应活性和CO_(2)吸收性能会随着循环次数的增加而降低。本文以电石渣为钙源,以MgO和ZnO为掺杂剂合成高效稳定的钙镁锌复合吸收剂,在固定床反应器中探究了合成工艺条件及掺杂量对复合吸收剂CO_(2)吸收性能的影响,以及循环吸收过程中吸收剂内部结构的变化。结果表明,利用干物理混合法合成的吸收剂比湿混合法具有更丰富的孔隙结构,Mg和Zn元素在电石渣表面分散均匀,有效改善了电石渣的抗烧结性能和反应活性,改性后的复合吸收剂在循环过程中具有更高的CO_(2)吸收性能,且20次循环后,干物理混合法合成的复合吸收剂CO_(2)吸收量仍可达0.42 g/g。

Simultaneous CO_(2) capture and thermochemical heat storage by modified carbide slag in coupled calcium looping and CaO/Ca(OH)2 cycles

The simultaneous CO_(2) capture and heat storage performances of the modified carbide slag with byproduct of biodiesel were investigated in the process coupled calcium looping and CaO/Ca(OH)2 thermochemical heat storage using air as the heat transfer fluid.The modified carbide slag with by-product of biodiesel exhibits superior CO_(2) capture and heat storage capacities in the coupled calcium looping and heat storage cycles.The hydration conversion and heat storage density of the modified carbide slag after 30 heat storage cycles are 0.65 mol·mol^(-1) and 1.14 GJ·t^(-1),respectively,which are 1.6 times as high as those of calcined carbide slag.The negative effect of CO_(2) in air as the heat storage fluid on the heat storage capacity of the modified carbide slag is overcome by introducing CO_(2) capture cycles.In addition,the CO_(2) capture reactivity of the modified carbide slag after the multiple calcium looping cycles is enhanced by the introduction of heat storage cycles.By introducing 10 heat storage cycles after the 10th and 15th CO_(2) capture cycles,the CO_(2) capture capacities of the modified carbide slag are subsequently improved by 32%and 43%,respectively.The porous and loose structure of modified carbide slag reduces the diffusion resistances of CO_(2) and steam in the material in the coupled process.The formed CaCO_(3)in the modified carbide slag as a result of air as the heat transfer fluid in heat storage cycles decomposes to regenerate CaO in calcium looping cycles,which improves heat storage capacity.Therefore,the modified carbide slag with by-product of biodiesel seems promising in the coupled calcium looping and CaO/Ca(OH)_(2) heat storage cycles.

Fabrication of High-purity Ternary Carbide Ti_3AlC_2 by Spark Plasma Sintering(SPS)Technique

The effect of silicon on synthesis of Ti3AlC2 by spark plasma sintering （SPS） from TiC/Ti/Al powders was investigated. X-ray diffraction （XRD） and scanning electron microscope （SEM） were used for phase identification and microstructure evaluation. The results show that addition of silicon can considerably accelerate the synthesis reaction of Ti3AlC2 and fully dense, essentially single-phase （purity 〉98%） polycrystalline Ti3AlC2 could be successfully obtained by sintering 2TiC/lTi/lAl/0.2Si powders at 1 200- 1 250 ℃ under a pressure of 30 MPa. SEM photographs show that the obtained Ti3AlC2 samples from mixtures powders are in plane-shape with a size of about 2-5 μm and 10-25 μm in the thickness dimension and elongated dimension, respectively.

Temperature Fluctuation Synthesis/Simultaneous Densification and Microstructure Control of Titanium Silicon Carbide (Ti_3SiC_2) Ceramics

A novel temperature fluctuation synthesis/simultaneous densification process was developed for the preparation of Ti3SiC2 bulk ceramics. In this process. Si is used as an in-situ liquid forming phase and it is favorable for both the solid-liquid synthesis and the densification of Ti3SiC2 rainies. The present work demonstrated that the temperature fluctuation synthesis/simultaneous densification process is one of the most effective and simple methods for the preparation of Ti3SiC2 bulk materials providing relatively low synthesis temperature. short reaction time; and simultaneous synthesis and densification. This work also showed the capability to control the microstructure, e.g., the preferred orientation, of the bulk Ti3SiC2 materials simply by applying the hot pressing pressure at different Stages of the temperature fluctuation process. And textured Ti3SiC2 bulk materials with {002} faces of laminated Ti3SiC2 grains normal to the hot pressing axis were prepared.

Ti_(3)C_(2)MXene纳米片制备、改性及其光催化应用研究

近年来,利用光催化缓解环境污染和能源短缺问题受到广泛关注。Ti_(3)C_(2)MXene作为一种新型二维材料,具有丰富的表面基团、多活性位点以及优异的光热和导电性能,在光催化应用研究上逐渐深入。本文概述了Ti_(3)C_(2)MXene纳米片的结构、光电特性及合成方法,讨论了二维Ti_(3)C_(2)纳米片及其改性材料的复合结构,重点分析了Ti_(3)C_(2)纳米片在新型有机污染物降解、水分解产氢和CO_(2)还原的光催化应用研究进展,对Ti_(3)C_(2)纳米片的深入研究提供一定的参考价值。

Instrumented oscillographic study on impact toughness of an axle steel DZ2 with different tempering temperatures

Compared with the conventional Charpy impact test method,the oscillographic impact test can help in the behavioral analysis of materials during the fracture process.In this study,the trade-off relationship between the strength and toughness of a DZ2 axle steel at various tempering temperatures and the cause of the improvement in impact toughness was evaluated.The tempering process dramatically influenced carbide precipitation behavior,which resulted in different aspect ratios of carbides.Impact toughness improved along with the rise in tempering temperature mainly due to the increase in energy required in impact crack propagation.The characteristics of the impact crack propagation process were studied through a comprehensive analysis of stress distribution,oscilloscopic impact statistics,fracture morphology,and carbide morphology.The poor impact toughness of low-tempering-temperature specimens was attributed to the increased number of stress concentration points caused by carbide morphology in the small plastic zone during the propagation process,which resulted in a mixed distribution of brittle and ductile fractures on the fracture surface.

2H-SiC Dendritic Nanocrystals In Situ Formation from Amorphous Silicon Carbide under Electron Beam Irradiation

Under electron beam irradiation, the in-situ formation of 2H-SiC dentritic nanocrystals from amorphous silicon carbide at room temperature was observed. The homogenous transition mainly occurs at the thin edge and on the surface of specimen where the energy obtained from electron beam irradiation is high enough to cause the amorphous crystallizing into 2H-SiC.

Abnormal gradient microstructure in Cr_3C_2 based cemented carbide

With OLYMPUS PMG3 metallograph, an abnormal three layer gradient structure ,i.e. coarse grain zone, binder enrichment zone and normal structure zone from the surface to the inner, was observed in Cr 3C 2 based cemented carbide. In the binder enrichment zone, three different shapes of anomalous coarse carbides were observed. It is shown that the transverse rupture strength can be raised remarkably, up 20.7% from the alloy with abnormal gradient structure by removing the abnormal gradient structure. It is suggested that the abnormal gradient structure in the surface, especially the anomalous coarse carbides in the binder enrichment zone is the main reasons for the lower strength.

Conversion of CO_(2)to added value products via rWGS using Fe-promoted catalysts:Carbide,metallic Fe or a mixture?

Fe-based catalysts are efficient systems for CO_(2)conversion via reverse water-gas shift(rWGS)reaction.Nevertheless,the nature of the active phase,namely metallic iron,iron oxide or iron carbide remains a subject of debate which our paper is meant to close.Fe0 is a much better catalyst for the rWGS than Fe_(3)C.The activity of Fe0 can be promoted by the addition of Cs and Cu whose presence hinders iron carburisation while favouring both higher conversion and enhanced selectivity.When the samples are aged in the rWGS reaction mixture during stability test a new phase appear:Fe_(5)C_(2),resulting in a more active but less selective catalysts than Fe0 for the rWGS reaction.Hence our results indicate that we could potentially achieve an optimal activity/selective balance upon finely tuning the proportion Fe/Fe_(5)C_(2).Beyond the fundamental information concerning active phase we have observed the presence of advanced Fischer-Tropsch-like products at ambient pressure opening new opportunities for the design of hybrid rWGS/Fischer-Tropsch systems.

微量Y_(2)O_(3)对WC−6Co非均匀结构硬质合金微观结构及性能的影响

采用低压烧结法制备了不同Y_(2)O_(3)添加量(质量分数)的WC-6Co非均匀硬质合金,并通过扫描电子显微镜、X射线衍射仪、能谱仪、金相显微镜、电子万能力学试验机、硬度计、矫顽磁力仪等设备研究了Y_(2)O_(3)质量分数对WC-6Co非均匀硬质合金微观结构、相成分及性能的影响。结果表明:Y_(2)O_(3)不会对合金相对密度和相组成产生影响;Y_(2)O_(3)与合金中杂质元素硫、氧等形成稳定的化合物,弥散分散于WC晶界,阻碍WC晶粒的融合长大,降低WC晶粒粒度,抑制WC晶粒非均匀结构的均匀化。随着Y_(2)O_(3)添加量的增加,合金的硬度逐渐增加,而抗弯强度呈现出先迅速上升后下降的趋势。Y_(2)O_(3)质量分数为0.048%对WC-6Co非均匀硬质合金性能提升最明显,硬度和抗弯强度分别达到1530 kgf·mm-2和2902 MPa。

Structural, mechanical, electronic properties, and Debye temperature of quaternary carbide Ti3NiAl2C ceramics under high pressure: A first-principles study

Quaternary carbide Ti3NiAl2C ceramics has been investigated as a potential nuclear fusion structural material,and it has advantages in certain aspects compared with Ti2AlC,Ti3AlC2,and Ti3SiC2 structural materials.In this paper,quaternary carbide Ti3NiAl2C ceramics is pressurized to investigate its structural,mechanical,electronic properties,and Debye temperature.Quaternary carbide Ti3NiAl2C ceramics still maintains a cubic structure under pressure(0–110 GPa).At zero pressure,quaternary carbide Ti3NiAl2C ceramics only has three bonds:Ti–Al,Ni–Al,and Ti–C.However,at pressures of 20 GPa,30 GPa,40 GPa,60 GPa,and 70 GPa,new Ti–Ni,Ti–Ti,Al–Al,Ti–Al,and Ti–Ti bonds form.When the pressure reaches 20 GPa,the covalent bonds change to metallic bonds.The volume of quaternary carbide Ti3NiAl2C ceramics can be compressed to 72%of its original volume at most.Pressurization can improve the mechanical strength and ductility of quaternary carbide Ti3NiAl2C ceramics.At 50–60 GPa,its mechanical strength can be comparable to pure tungsten,and the material changes from brittleness to ductility.However,the degree of anisotropy of quaternary carbide Ti3NiAl2C ceramics increases with the increasing pressure.In addition,we also investigated the Debye temperature,density,melting point,hardness,and wear resistance of quaternary carbide Ti3NiAl2C ceramics under pressure.