Catalytic combustion synthesis of CNTs/MgO composite powders and the influences on the thermal shock resistance of low-carbon Al2O3–C refractories

Using MgC₂O₄, Mg powders as raw materials and Ni(NO₃)₂?6H₂O as a catalyst, CNTs/MgO composite powders were prepared by a catalytic combustion synthesis method. The CNTs/MgO composite powders were characterized by XRD, Raman spectroscopy, FESEM/EDS and HRTEM. The effects of catalyst content on the degree of graphitization and aspect ratio of the CNTs in composite powders were investigated. Moreover, the thermal shock resistance of low-carbon Al₂O₃–C refractories after adding the composite powder was investigated. The results indicated that the CNTs prepared with 1 wt% Ni(NO₃)₂?6H₂O addition had a higher degree of graphitization and aspect ratio. In particular, the aspect ratio could reach approximately 200. The growth mechanism of hollow bamboo-like CNTs in the composite powders was proven to be a V-L-S mechanism. The thermal shock resistance of Al₂O₃–C samples could be improved significantly after adding CNTs/MgO composite powders. In particular, compared with CM0, the residual strength ratio of Al₂O₃–C samples with added 2.5 wt% composite powders could be increased 63.9%.     

Process parameters influence on zone refining and thermodynamics analysis of 1,2-diphenylethane

Effective distribution coefficients of 9 impurities in 1,2-diphenylethane have been calculated by directional crystallization under different ambient frozen temperature. The effect of varied zone size, temperature difference between the melt and ambient frozen environment, number of zone on purity of 1,2-diphenylethane have been also investigated during the process of zone refining. The results indicate that the product purity in the intermediate purified region with varied zone size is higher 0.04%-0.2% than that with constant zone size. The product purity increases with temperature difference between the melt and ambient frozen environment. The appropriate temperature difference is adopted 50℃. The product purity in the intermediate region of sample bar with 2 molten zones is higher 0.05%-0.43% than that with 1 molten zone. In addition, the change of enthalpy and entropy between impurities and 1,2-diphenylethane have been determined.     

Microwave-assisted metal-catalyzed pyrolysis of low-rank coal: Promising option towards obtaining high-quality products

Microwave-assisted catalytic pyrolysis is considered to be a promising technology for coal-staged conversion due to its high efficiency and selectivity. This work was undertaken to investigate the pyrolysis behavior and products quality of microwave-assisted pyrolysis of low rank coal catalyzed by metallic catalysts (K, Ca and Fe) with both dielectric response and catalytic effect via a microwave tube furnace. The mechanism of metallic catalysts on catalytic cracking tar under microwave radiation was also investigated. The dielectric properties and physicochemical structure of coal chars were characterized by a vector network analyzer, XRD, FT-IR, SEM, EDS, and Raman. The chemical structure characteristics of generated tars were determined by FT-IR and GC-MS. Results manifested that microwave interacted preferentially with metal catalysts by polarization and conductivity loss could efficiently induce the occurrence of catalytic pyrolysis reactions to generate high yield syngas (CO + H₂). Specifically, the dielectric loss factor of resultant chars was considerably improved with the introduction of metallic catalysts especial for Ca and Fe. Furthermore, it is found that metal catalysts dramatically enriched the amorphous carbon structure in produced chars whereas in favour of suppressing the trend of carbon graphitization. Additionally, the transformation of larger polycyclic aromatic compounds into lighter tar species was catalytically accelerated, resulting in the large proportion of single-ring aromatics in tar under the synergistic effect between microwave and metal catalysts.     

锌冶炼铜烟灰中铟氧化浸出研究

以锌冶炼过程中的铜烟灰为原料,研究了硫酸浸出含铟铜烟灰过程中硫酸浓度、硫酸用量、浸出温度、浸出时间、氧化剂高锰酸钾用量等因素对铟浸出效果的影响。结果表明,当硫酸浓度300 g/L、液固比6 mL/g、反应温度90 ℃、反应时间5 h、高锰酸钾添加量0.3%时,铜烟灰中铟浸出率为65.73%。     

Microstructure and mechanical properties of Mo coating deposited by supersonic plasma spraying

The inherent technological limitations of traditional thermal spraying technologies have the relatively high oxidation degree and porosity of prepared Molybdenum (Mo) coating. Hence, in this study, a Mo coating was fabricated using supersonic plasma spraying technology. Scanning electron microscopy (SEM), X-ray diffraction (XRD), tensile testing machine, high-precision macro/micro-indentation tester and ball-on-disc tribometer were used to investigate the microstructure, phase composition, mechanical and tribological properties of the coating. The results showed that the Mo coating had dense structure and highly diminished oxidation degree. The phase composition was pure Mo. The tensile strength failure occurred within the coating layer. In the meanwhile, the Mo coating exhibited a superior hardness, a high elastic work/total work (W_e/W_t), and excellent tribological properties. The wear mechanisms were fatigue wear and adhesive wear.     

Lewis acid-oxygen vacancy interfacial synergistic catalysis over SO42−/Ce0.84Zr0.16O2–WO3–ZrO2 for N,N-diethylation of aniline with ethanol

Herein, a new mechanism involving Lewis acid-oxygen vacancy interfacial synergistic catalysis for aniline N,N-diethylation with ethanol was proposed, and the SO₄²⁻/Ce_0.84Zr_0.16O₂–WO₃–ZrO₂ catalyst (SCWZ) with both Lewis acid sites and oxygen vacancies was synthesized by the hydrothermal method, which shows better catalytic activity than the reported solid acidic catalysts. Besides, the SO₄²⁻/ZrO₂ (SZ) and SO₄²⁻/WO₃–ZrO₂ (SWZ) catalysts were also prepared and compared with SCWZ to investigate the synergistic effect of each component. The SO₄²⁻ and WO₃ mainly generate Lewis acid by bonding with ZrO₂, which is beneficial for the fracture of the N–H bond in aniline. The Ce_0.84Zr_0.16O₂ solid solution mainly plays a vital role in generating the oxygen vacancies as the interface active species, which can participate in stripping –OH from ethanol, then the carbocation will also be released, which only needs 1.3805 kcal/mol energy, calculated by density functional theory (DFT), to be input. In comparison, the traditional reaction mechanism needs the Brønsted acidic sites to promote the protonation of ethanol, then dehydration and subsequent formation of carbocation followed, and 108.6846 kcal/mol energy needs to be input, which is far higher than that of the new mechanism. The apparent activation energy (E_a) over SCWZ was measured by experiment to be 34.09 kJ/mol, which is much lower than that of SWZ (47.10 kJ/mol) and SZ (54.37 kJ/mol), illustrating comparatively preferable kinetics for SCWZ than that of SWZ and SZ. Besides, the conversion of aniline and selectivity to N,N-diethylaniline over SCWZ reach almost 100% and 73%, respectively. The SCWZ can be renewed for 4 times without rapid deactivation, and the longevity of SCWZ is longer than that of SWZ and SZ, as the loaded SO₄²⁻ and tetragonal ZrO₂ are stabilized by Ce_0.84Zr_0.16O₂ and WO₃, respectively.     

Impact of gas formation on the transfer of Ti and O from TiO2-bearing basic-fluoride fluxes to submerged arc welded metals: A thermodynamic approach

Gas-slag-metal equilibrium calculations are performed to investigate the transfer of Ti and O to submerged arc welded metals with increasing TiO₂ addition in basic-fluoride fluxes. The results indicate that activities of TiO₂ and Ti₂O₃ considering slag-metal reactions alone do not account for Ti transfer behaviors since TiF₃ gas tends to form and reduce Ti-oxide activities. Thermodynamic simulation indicates that consideration of gases is essential to improve the prediction accuracy of Ti and O concentrations.     

Synthesis,characterization, and ceramization of a carbon-rich SiCw-ZrC-ZrB2 preceramic polymer precursor

A precursor (PBSZ) for SiC_w-ZrC-ZrB₂ hybrid powder was synthesized by chemical reaction of phenol, paraformaldehyde, zirconium oxychloride, boric acid and tetraethylorthosilicate. Results show that zirconium, silicon and boron atoms have been successfully introduced into the branched structure. Decomposition of PBSZ is completed at 800 °C, and it gives amorphous carbon, SiO₂, B₂O₃ and ZrO₂ with a yield of 38% at 1200 °C. During the pyrolysis process, ZrB₂ and SiC form at about 1500 °C, followed by the appearance of ZrC when the amount of B₂O₃ is limited. Highly crystallized ZrB₂–ZrC–C powder with ZrB₂ and ZrC grains evenly distributed in the carbon matrix together with randomly distributed SiC whiskers are obtained after heat-treated at 1800 °C. Further heated at 1900 °C, ZrB₂ and ZrC grains grow from 200 to 500 nm, while SiC whiskers show a much smaller diameter size and tend to grow on the ZrB₂–ZrC–C block surface. The morphology difference is caused by the larger gas supersaturation and accommodation coefficient of the pore channels on the block surface. In addition, defects of the carbon matrix are cumulated to the highest at 1500 °C and the structure-ordered carbon is obtained after heat treated at 1900 °C.     

不同热解工艺下半焦的微观结构特点及其对燃烧性能的影响

摘要：对比研究了3种直立内热炉半焦(熄焦方式分别为水泡熄焦、喷水熄焦及烟气干熄焦)及一种流化床热解半焦的微观结构及燃烧性能。通过对半焦组成、孔隙结构、有机官能团、碳化学结构及半焦微晶结构分析，获得了不同低温热解工艺半焦的组成及微观结构特点，明确了组成及微观结构与燃烧性能之间的关系。结果表明，不同热解工艺半焦的组成和微观结构差异明显，其对半焦的燃烧性能影响显著。干熄焦碳化学结构缺陷比例大，快速热解半焦孔隙结构发0达、挥发分高，与水喷焦相比水泡焦石墨化程度低；水喷焦燃烧性能优于水泡焦，干法所得半焦的燃烧性优于湿法；半焦的挥发分含量决定其燃点，在快升温速率条件下孔隙结构对半焦的燃烧性能影响较大，而慢升温速率条件下有序化度对半焦的燃烧性能影响较大。