转炉中钼氧化物直接合金化炼钢热力学分析

基于转炉炼钢工艺,对MoO3直接合金化炼钢进行热力学分析.分别计算了在标准状态和实际条件下,铁水中存在的几种可能作为还原剂的元素还原MoO3的吉布斯能.分析了终点钢水中[C]和熔渣中(FeO)含量对MoO3还原反应的影响以及还原反应对钢水温度的影响.结果表明,在标准状态下,铁水中[Si],[C],[Mn],[Fe]都可还原MoO3;在实际条件下,钢水中[C],[Fe]在无外配还原剂的情况下也可还原MoO3且转炉终点[Mo]不会被渣中(FeO)再次氧化.为了提高铁的收得率,计算得到了现场终点钢水中[C]和熔渣中(FeO)合适的含量控制范围.热化学计算发现实际条件下还原反应对钢水温度的影响较小.     

工业硅生产过程的热力学分析与优化

为了优化现有矿热炉碳热还原炼硅工艺,提高工业硅的产出量,利用热力学软件HSC,基于平衡常数法,对二氧化硅碳热还原制取工业硅的反应过程进行了热力学计算,并用HSC软件的化学反应平衡模块模拟分析了在煅烧的石英石和碳质还原剂中添加碳化硅对反应的影响.通过软件模拟,分析加入SiC作为原始物料后,不同物料配比对硅产出率的影响.结果表明:在煅烧的石英石和碳质还原剂中添加适量碳化硅可以促进反应的进行,以SiO2、SiC、C为炉料,当输入摩尔比为m(SiO2/C/SiC)=3∶1∶2时,硅产出量相对最高.     

氧化锌烟尘碳基还原同步回收铅锡

采用碳基还原实现氧化锌烟尘中铅锡与锌的同步分离回收,考察了预处理脱氟氯硫(Na2CO3碱洗、煅烧)和配加添加剂(CaO、膨润土)对碳基还原过程铅锡挥发率的影响。结果表明,当烟尘未经预处理,实验条件为温度1300℃、焦粉用量14.04%和保温时间120min时,铅锡挥发率分别为78.58%和95.97%。同一实验条件下,相比于无预处理,碱洗和煅烧均能使铅锡挥发率降低。烟尘经碱洗后,铅锡挥发率分别降至12.97%、16.99%;煅烧使铅锡挥发率分别降至30.46%、57.83%。CaO用量增加有利于降低铅锡挥发率,当CaO用量为5%时,铅锡挥发率分别降至32.16%、57.7%;膨润土用量增加促进铅挥发率的降低,对锡挥发率无明显影响,当膨润土用量为5%时,铅锡挥发率分别降至37.44%、83.25%。采用该工艺,最终同时获得铅锡合金(Pb＞70%,Sn＞5%)和粗锌(Zn＞63%,Pb＞9%)。     

熔盐镁热还原制备SiC纳米粉体及其氧化动力学

以SiO_2及活性炭粉为反应物、Mg粉为还原剂、NaCl-KCl二元盐为反应介质,采用熔盐镁热还原法低温制备了SiC纳米粉体,并采用TG–DSC非等温氧化法对所合成SiC纳米粉体的氧化动力学进行了研究。结果表明:所合成SiC纳米粉体的主晶相为2H-SiC;合成2H-SiC的最佳工艺条件为n(C)和n(Si)摩尔比为1.3:1.0,Mg粉过量60%(质量分数)、反应条件为1 373 K保温3 h时合成粉体中2H-SiC的相对含量最高约为72%,所合成SiC的晶粒大小约为20~50 nm。Kissinger法和Ozawa法的计算结果表明:所合成SiC纳米粉体的氧化反应表观活化能分别约为267.96和270.33 kJ/mol。     

CA对Co-Mo/SiO_2加氢脱硫性能的影响

以柱层层析硅胶为原料,添加粘合剂制备了大孔SiO2载体,用等体积浸渍法制备了CoMo-CA/SiO2催化剂(CoO,MoO3质量分数分别为3%,12%,n(CA):n(MoO3)=1:1)。利用BET和XRD技术进行物化性能表征,以噻吩硫脱除率考察了柠檬酸(CA)对催化剂加氢脱硫性能的影响。结果表明:制备的大孔SiO2载体比表面积380m2/g,孔容0.39cm3/g,中孔(2~50nm)占据90.2%;添加CA后,活性组分均匀分散在载体表面,XRD谱无CoO和MoO3特征峰;在T为300℃、P为3.0MPa、LHSV为2h-1及氢油体积比为600时对噻吩硫脱除率达到96%以上。     

Ti3SiC2陶瓷的制备

Ti3SiC2陶瓷由于具有非常优越的性能而受到广泛关注,但到目前对于反应合成Ti3SiC2的热力学和动力学仍缺乏系统地研究.本文对反应合成Ti3SiC2进行了热力学计算和动力学分析,利用Ti、Si、C混合粉末进行热压,制备了较高纯度的Ti3SiC2陶瓷,并对烧结试样进行XRD和断口SEM分析.热力学计算结果表明:在常用的反应合成Ti3SiC2的材料体系中,Ti-Si-C三元粉末的反应热力学驱动力最大,据此选择Ti、Si、C粉末,按照3:1.2:2的原子比混合作为反应合成Ti3SiC2的原料;动力学分析结果表明:Ti-Si-C三元元素粉末的反应动力学要求必须有较高的升温速度,才能获得Ti3SiC2材料.根据动力学分析结果设计反应合成工艺,利用真空热压获得了纯度达到89%(体积分数,下同)以上的Ti3SiC2材料.     

硅铝合金还原含钛提钒尾渣制备Ti-Si-(Al)合金

以含钛提钒尾渣为原料、铝硅合金为还原剂,于管式电阻炉内氩气气氛下制备Ti-Si-(Al)合金,研究了保温时间、还原剂成分、助溶剂添加量对钛回收率的影响及随还原剂成分变化所制合金中含钛物相的转变规律.结果表明,在温度1550℃、渣金质量比3:1时,最优还原条件为保温时间2 h、还原剂成分Si-70%Al、助溶剂(CaO)添加量45%,该条件下钛回收率最大,为89.23%,此时合金中钛含量为42.32%,渣中TiO_2含量由28.8%降至2.2%;随还原剂中铝含量增加,所制合金中含钛物相的主要变化为TiSi_2→Ti_7Al_5Si_(12)→(TiAl_3,Ti_5Si_3).     

纳米SiC陶瓷的超高压烧结研究(英文)

以纳米SiC为原料,用两面项压机在不同工艺条件下(1 000～1 300℃,4.0～4.5 GPa,15～35 min)实现了40(质量分数,下同)Al2O3烧结助剂添加的SiC陶瓷体的烧结.研究了烧结工艺对SiC陶瓷性能的影响.用X射线衍射、扫描电镜、显微硬度测试仪等对SiC高压烧结体进行了表征.结果表明:Al2O3是有效的低温烧结助剂,在超高压工艺下添加4%Al2O3即可实现SiC陶瓷全致密化烧结;烧结体晶粒长大得到抑制,维持在纳米级,晶格常数收缩了约0.45%;烧结体显微硬度和密度随烧结温度、烧结压力的升高或保温时间的延长而提高.     

残余碳对碳化硅陶瓷光学表面加工性能的影响

为深入了解碳化硅陶瓷的光学表面加工性能,采用常压固相烧结法制备了碳化硅陶瓷,在保证致密度的前提下,通过改变碳的含量,研究了残余碳对SiC陶瓷抛光面的表面质量和光学性能的影响。研究发现,C的质量含量为3%～7%时,SiC陶瓷抛光表面的RMS(root mean square)粗糙度均约为2nm。当C含量为3%～6%时,SiC陶瓷抛光表面在400～750nm波段的全反射率、漫反射率和镜面反射率无明显变化;当C含量升至7%时,全反射率稍有降低,漫反射率稍有上升,镜面反射率稍有降低。其原因可能是过多的残余碳引起SiC陶瓷的折射率下降和产生光学散射,最终造成镜面反射率降低。     

生物质炭对聚丙烯热解挥发分的催化重整分析

应用生物质衍生焦炭对聚丙烯挥发分进行催化重整,分别将Na_2CO_3、CaO和Fe_2O_3负载在炭中以实现催化效果的强化。通过对比液相产率、产气率可以看出:生物质炭对聚丙烯挥发分有显著的催化重整效果,温度为750℃时液相产率为11.80%,较无催化时下降了13.60%。Na_2CO_3作用下随着温度的升高,750℃时液相产率为8.66%,较聚丙烯单独热解时下降了16.74%,产气率最高可达50.86%。负载Fe基的生物质衍生焦炭,在高温阶段对聚丙烯热解挥发分的降解效果不明显,液相产率750℃时为11.64%,产气率为47.91%。添加CaO,随着热解温度的提升液相产率最低可至9.36%,较单独热解时下降了16.04%,产气率最高可达50.18%。在本实验条件下,生物质炭中负载Na基对聚丙烯挥发分催化重整效果最为明显。     

Silicon Carbide Oxidation in Steam up to 2 MPa

Growth and microstructure of a protective or nonprotective SiO₂ scale and the subsequent volatilization of scale formed on high‐purity chemical vapor deposited (CVD) SiC and nuclear‐grade SiC/SiC composites have been studied during high‐temperature 100% steam exposure. The environmental parameters of interest were temperature from 1200°C to 1700°C, pressure of 0.1 to 2 MPa and flow velocities of 0.23 to 145 cm/s. Scale microstructure was characterized via electron microscopy and X‐ray diffractometry. The Arrhenius dependence of the parabolic oxidation and linear volatilization rate constants were determined. The linear volatilization rate exhibited a strong dependence on steam partial pressure with a weaker dependence on flow velocity. At high steam pressures, the oxide scale developed substantial porosity, which significantly accelerated material recession. The dominant oxide phase for the conditions studied was cristobalite. The oxidation behavior of SiC/SiC composite was strongly dependent on the state of the surface, specifically whether steam could find easy entry into the material via surface‐exposed interface layers. For the case where these as‐machined interfaces were surface coated with matrix CVD SiC, composite recession was found to be essentially that of high‐purity CVD SiC.     

高碳镍钼矿碱性还原熔炼-水浸分离与提取镍钼

在理论分析的基础上,以贵州遵义镍钼矿为原料,提出了镍钼矿碱性还原熔炼?水浸提钼的清洁冶金新工艺,考察了Na2CO3用量、温度、还原剂用量、反应时间对镍还原率及钼浸出率的影响,在最优条件下进行了扩大实验. 结果表明,在碱性介质及强还原气氛下,镍钼矿中的镍被还原成高品位镍铁合金,钼转化为可溶性的钼酸盐;最佳工艺条件为Na2CO3用量为理论量的2倍、熔炼温度1000℃、还原剂添加量为镍钼矿的5wt%、反应时间1.5 h. 最佳条件下扩大实验金属镍回收率为94.92%,金属钼挥发率为9.36%,浸出率为99.94%,固硫率接近100%,得到了高品位镍铁合金和含钼浸出液,镍钼有效分离.     

Volatilization of components from zirconia ceramics

Conclusions We investigated volatilization in isothermal conditions of solid solutions of oxides of calcium and yttrium in ZrO₂.The calcium oxide is intensely sublimited from the solid solution of zirconium dioxide, stabilized with CaO at 2000–2100°C. However, during soaking and rapid cooling, destabilization does not occur, even during sublimation of 70–75% CaO. With rise in temperature to 2400–2500°C and a 4 h soak, only 0.5% CaO is preserved in the solid solution, which leads to destabilization and conversion of a large part of the cubic form of ZrO₂ with calcium oxide by fusion, we note sublimation of part of the CaO, and the remaining quantity (3%) is adequate for complete conversion of the zirconia into the stable cubic form.Volatilization of the stabilizing additive occurs in the form of YO at substantially higher temperatures than volatilization of the calcium oxide from the solid solution of zirconium dioxide, stabilized with yttrium oxide. Simultaneously with this we note volatilization of zirconium dioxide in the form of ZrO and ZrO₂.For the use of zirconium dioxide at elevated service temperatures, we would recommend yttrium oxide as a stabilizing additive.Translated from Ogneupory, No. 1, pp. 49–52, January, 1968.     

Oxidation Behavior of Boron-Modified Mo5Si3 at 800°–1300°C

Mo₅Si₃ shows promise as a high-temperature creep-resistant material. The high-temperature oxidation resistance of Mo₅Si₃ has been found to be poor, however, limiting its use in oxidizing atmospheres. Undoped Mo₅Si₃ exhibits pest oxidation at 800°C. Mass loss occurs in the temperature range 900°–1200°C due to volatilization of molybdenum oxide, indicating that the silica scale that forms does not provide a passivating layer. The addition of boron results in protective scale formation and parabolic oxidation kinetics in the temperature range of 1050°–1300°C. The oxidation rate of Mo₅Si₃ was decreased by 5 orders of magnitude at 1200°C by doping with less than 2 wt% boron. Boron doping eliminates catastrophic pest oxidation at 800°C. The mechanism for improved oxidation resistance of borondoped Mo₅Si₃ is viscous sintering of the scale to close pores that form during the initial transient oxidation period, due to volatilization of molybdenum oxide.     

Investigation of the volatilization of Mgo and Zro2 in oxidizing atmospheres

Conclusions The rates of volatilization of refractories made from magnesia and zirconia stabilized with CaO in an oxidizing atmosphere (in air) up to 1900°C are similar; above 2000°C the volatilization rate of magnesia sharply increases; and at 2200°C its magnitude is an order greater than in the specimens of zirconia.The volatilization rate of zirconium dioxide in an oxidizing atmosphere at the temperature of intensive volatilization (2300°C) is about the same as in an inert atmosphere.Translated from Ogneupory, No. 2, pp. 49–53, February, 1971.     

Magnesothermic synthesis of disperse molybdenum carbide in sodium carbonate melts

The physicochemical aspects of the synthesis of molybdenum carbide powders through the magnesothermic reduction of molybdenum oxide in sodium carbonate melts are considered. The reduction reactions are thermodynamically characterized. The composition of the ionic melt is shown to influence the phase composition of the products. In sodium carbonate melts Mo₂C is formed, while sodium chloride melts under the same conditions yield molybdenum powders. The product yield reaches 97% with an about 30% excess of the reducing agent relative to the stoichiometry. Minor metal concentrations are within ～2%. The particle sizes of the powders are determined. The specific surface area of molybdenum carbide powders is 5.53 × 10⁵ m^?1; that of molybdenum is 20.19 × 10⁵ m^?1.     

Identification of a new oxidation/ dissolution mechanism for boria-accelerated SiC oxidation

Boria effects on accelerated SiC oxidation kinetics were investigated by conducting thermogravimetric analysis on SiC substrates coated with sol-gel derived borosilicate glass isothermally exposed to dry O₂ and argon at 800°C and 1200°C for 100 hours. Boria concentrations in the glass coatings were 0, 14-38, and 92-94 mol%, balance silica. Accelerated weight gain was observed for SiC exposures in dry O₂ at 800°C when boria concentrations were ≥ 92 mol%, corroborated by oxide thickness ranging from 3.5 to 10 µm. The oxide thickness predicted for pure SiC exposed to these conditions in the absence of boria is 0.15 µm. Microstructural analysis of SiC surfaces after oxide removal revealed that boria etched the underlying SiC substrate. Oxidation exposures at 1200°C in dry O₂ suppressed boria effects on accelerating SiC oxidation kinetics due to rapid boria volatilization coupled with the formation of a protective thermally grown silica scale. Accelerated weight gain or oxide growth did not occur with argon exposures at either temperature. A new mechanism for boria-accelerated SiC surface-reaction kinetics is presented based on evidence for boria etching of SiC.     

PbO-FeOx-CaO-SiO2-ZnO挥发性高铅渣的挥发动力学

为揭示高铅渣的高温挥发行为,以PbO?FeOx?CaO?SiO2?ZnO为基本渣系,借助热重分析技术,建立了质量比FeO/SiO2=1.8和CaO/SiO2=0.6、不同PbO含量的高铅渣高温挥发本征动力学模型,探讨了不同PbO含量下随温度变化熔渣的挥发特性,结合挥发后熔渣物相和元素分析,揭示了高铅渣的挥发规律. 结果表明,温度高于700℃时,高铅渣中PbO挥发最剧烈,造成渣成分波动导致测定结果偏差;含铅量为20wt%、温度700?1450℃的平均挥发率为18.58%;高铅渣高温挥发受三维扩散控制,影响因素为PbO和硅氧复合离子的含量.     

In situ observation of the dissolution phenomena of SiC particle in CaO–SiO2–MnO slag

The dissolution of SiC particle at 1600 °C in the CaO–SiO₂–MnO slag was observed in situ by means of confocal scanning laser microscopy in order to make the determination of dissolution mechanism. The SiC particle is initially wetted by molten slag from the outer surface and the wetting between SiC and slag phase is more dominant in the composition of higher CaO/SiO₂ ratio. When the SiC particle is wetted by molten slag, the gas bubbles that are mainly CO gas is generated by the reaction between SiC and MnO in slag phase and are continuously evolved at the wetted area, which is pronounced as the CaO/SiO₂ ratio increases. The dissolution of SiC particle in the slag through the reaction with MnO is enhanced in the composition of higher CaO/SiO₂ ratio not only due to greater thermodynamic driving force but also due to accelerated mass transport kinetics.