CO2热力学性质的量子化学计算

采用MP2,QCISD和密度泛函B3LYP方法,在6-311g**和6-311+g**水平上优化和计算了CO2和O2平衡几何结构、能量和谐性振动频率,导出了在标准条件(T=298.15 K,p=1.013×105Pa)下的熵、热焓和热容,并由此计算得到了CO2的标准生成焓和标准生成自由焓.结果显示,B3LYP/6-311G**方法计算得到的CO2和O2的平衡几何结构、能量、谐性振动频率、熵和热容与实验值符合最好;而MP2/6-311G**方法计算得到的CO2标准生成焓和标准生成自由焓与实验值符合最好.     

Ni-Ga二元系的热力学计算

采用CALPHAD技术评估了Ni-Ga二元系的相图和热力学性质.用双亚晶格模型描述2个有序相(L1 2-Ni3Ga和B2-NiGa)的热力学行为,并在优化过程中考虑了fc-(Ni)和LI2-Ni3Ga相的有序-无序转变.溶液相(液相、fcc-(Ni)固溶体)的热力学模型采用Redlich-Kister方程,其余5个中间化合物被视为整比化合物.     

考虑传搁能耗的304不锈钢电炉冶炼流程最优连浇炉数计算方法

分析了304不锈钢电炉冶炼流程的传搁时间和传搁过程温降情况,建立各个工序冶炼温度制度与连浇炉数的关系,得知已有温度制度下的连浇炉数仅为2炉,并以6炉连浇为例给出不同连浇炉数情况下温度制度.通过计算流程中传搁能耗,讨论了连浇炉数与浇次总传搁能耗和平均传搁能耗的关系.提出了一种考虑传搁能耗确定最优连浇炉数的方法.对比发现,当增加连浇炉数的传搁能耗小于开浇一次耗材消耗的能耗时,最大连浇炉数为最为合理的连浇炉数.     

W-Ni-Cu三元系相图的热力学计算

从热力学上估算了W-Cu二元系中液相,bcc(W),fcc(Cu)的相互作用参数,并计算了其相图。应用所估算的参数,结合Kaufman等人提供的W-Ni,Cu-Ni系热力学数据,计算了W-Ni-Cu三元系1100℃,1200℃,1300℃,1400℃,1480℃,1500℃,1600℃时bcc(W)/fcc(Cu,Ni),bcc(W)/liq。两组相平衡,作出了相应温度下的等温截面图,并由它们构筑了该三元系合理的立体示意图。计算结果与实验结果吻合很好。     

不锈钢熔体中氮溶解度的热力学计算模型

在实验研究和前人研究工作的基础上,建立了一个新的不锈钢熔体中氮溶解度与体系温度、氮分压和合金成分的热力学计算模型,在该模型中引入了氮分压对氮活度系数的作用系数.该模型的计算结果与实验值吻合很好.基于该模型的计算结果,讨论了氮分压、温度、合金成分对不锈钢熔体中氮溶解度的影响规律.在压力较高(大于0.1 MPa)特别是合金元素较高的不锈钢熔体中,氮分压与氮的溶解度关系不符合Sievert定律.在一定氮分压下,温度对不锈钢熔体中氮溶解度的影响取决于合金体系的化学成分.在常压(氮分压为0.1 MPa)下,20%Cr-20%Mn的合金体系在1 873 K可获得氮质量分数为0.8%的高氮无镍奥氏体不锈钢.     

水氯镁石脱水反应的热力学计算和动力学分析

为了以水氯镁石为原料制备无水氯化镁提供理论依据,对水氯镁石在脱水过程中可能存在的化学反应进行了热力学计算和动力学分析,得出了温度较低时,水氯镁石不易脱水;温度较高时,在脱水的同时不可避免地发生水解反应;无保护气氛条件下110-200℃时,选择适宜的脱水时间可将MgCl2·6H2O转化为MgCl2·2H2O而无水解反应发生;若继续脱水必须在保护气氛下进行,否则脱水的同时会水解。     

CaO－B_2O_3熔渣中氮的热力学计算模型

根据炉渣结构的共存理论，推导了ＣａＯ－Ｂ_２Ｏ_３渣系热力学计算模型，并且理论计算的ＣａＯ，Ｂ_２Ｏ_３的作用浓度与实测的活度值非常一致。由此说明了该模型的合理性。在此基础上，找出了炉渣结构与渣中氮含量的关系，并分析了其有关的物理意义。研究结果认为：渣中氮含量与炉渣结构密切相关。     

相转化法聚合物/溶剂/非溶剂铸膜体系的热力学计算

计算了相转化法铸膜体系中常见的典型三元相图,分析了聚合物与溶剂之间、聚合物与非溶剂之间、溶剂与非溶剂之间的相互作用参数对聚合物／溶剂／非溶剂铸膜液体系相图的影响,以及体系温度和聚合物摩尔体积对聚合物／溶剂／非溶剂铸膜液体系相图的影响。根据溶剂-非溶剂汽液平衡数据和溶解度参数得到了溶剂-非溶剂、溶剂与聚合物以及非溶剂与聚合物之间的Flory—Huggins相互作用参数,从而获得了几种常见铸膜液体系的相图。同时,利用聚合物／溶剂／非溶剂铸膜液体系的相图数据对热力学模型的参数进行了优化,取得了与实验结果较一致的计算结果     

低碳钢碳氮析出物的热力学计算

钢中的碳氮析出物通过细晶强化和析出强化方式对钢的力学性能有非常重要的作用. 基于规则溶液的双亚点阵模型(其中一个为金属亚点阵,另一个为间隙原子亚点阵)建立了碳氮化钛、氮化铝以及硫化锰的热力学计算模型用以研究析出物的析出开始温度、给定温度的奥氏体成分,并将这一结果应用于CSP过程. 经计算得Ti(CxN1-x),MnS和 AlN的析出温度分别是1 200 ℃,1 440 ℃和1 010 ℃,最大的体积分数分别为2.315×10-5,4.18×10-4和3.1×10-4. 对比发现热力学的计算结果与Thermo-Calc的计算结果和有关文献的实验数据有较好的一致性.     

3,6-二氯-2-甲氧基苯甲酸甲酯合成的热力学计算与分析

采用Benson、Fedors和Rozicka-Domalski基团贡献法对3,6-二氯-2-甲氧基苯甲酸甲酯合成进行热力学计算与分析,得到了反应温度为298.5～383.15 K时的反应焓变、吉布斯自由能变以及平衡常数与温度的关系.结果表明:该合成反应为吸热反应,反应吉布斯自由能变为负值,反应平衡常数数量级为10(2...     

含碳球团还原法处理含锌电炉粉尘的试验分析

为综合利用含锌电炉粉尘,提出运用含碳球团的还原处理方法,并进行了扩大性试验,得到了还原焙烧法的合理工艺条件.试验表明:配碳的碳氧比C/O=1.2、还原温度1 150 ℃、料层厚度30 mm、加热时间65 min可取得较好的效果;还原后的球团为半金属化球团,其w(TFe)为50%左右,金属化率60%～70%,球团的残Zn含量在2%以下,是较好的高炉原料;Zn的还原挥发率达到90%左右,收集粉中ZnO含量在90%左右;PbO含量在2%以下,已达到等级氧化锌的标准,实现了含锌电炉粉尘的无害化和资源化利用.     

New pyrometallurgical process of EAF dust treatment with CaO addition

The non-carbothermic zinc pyrometallurgical processing of electric arc furnace (EAF) dust was investigated on a laboratory scale. The main objective of this process was to convert highly stable zinc ferrite (ZnFe₂O₄), which accounts for more than half of total zinc in the EAF dust, into ZnO and Ca₂Fe₂O₅ by CaO addition. The EAF dust was mixed with CaO powder in various ratios, pressed into pellets, and heated in a muffle furnace in air at temperatures ranging from 700 to 1100℃ for a predetermined holding time. All ZnFe₂O₄ was transformed into ZnO and Ca₂Fe₂O₅ at a minimum temperature of 900℃ within 1 h when sufficient CaO to achieve a Ca/Fe molar ratio of 1.1 was added. However, at higher temperatures, excess CaO beyond the stoichiometric ratio was required because it was consumed by reactions leading to the formation of compounds other than ZnFe₂O₄. The evaporation of halides and heavy metals in the EAF dust was also studied. These components could be preferentially volatilized into the gas phase at 1100℃ when CaO was added.     

Ultrasound effects on zinc recovery from EAF dust by sulfuric acid leaching

In this work, an ultrasound-assisted leaching process was studied for the recovery of zinc from electric arc furnace (EAF) dust, in which zinc was mainly present in the form of franklinite (60%). Hydrometallurgy is emerging as a preferred process for the recovery of a variety of metals, and the use of ultrasound could offer advantages over the conventional leaching process, especially for the dissolution of franklinite. Franklinite is a refractory phase that is difficult to leach and represents the main obstacle in conventional hydrometallurgy processing. Atmospheric leaching with different sulfuric acid concentrations (0.2-2.0 M) at two temperatures (323 and 353 K) was performed. The tests were conducted using both conventional and ultrasound-assisted leaching. After the leaching tests, the solid residues were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques, whereas the leach liquor was analyzed by inductively coupled plasma spectroscopy (ICP). The use of ultrasound facilitated the dissolution of franklinite at low acid concentrations and resulted in a greater zinc recovery under all of the investigated operating conditions.     

含锌电炉粉尘配碳球团的冶金特性

以某钢铁公司含锌电炉粉尘为原料,配入适当的无烟煤制成含碳球团,焙烧球团通过还原煤保护冷却至室温后进行化学分析·研究了1150℃～1300℃的范围内,温度、时间和内配煤量对锌、铁的还原速率以及球团抗压强度的影响·研究结果表明:锌、铁的还原率均随焙烧温度、焙烧时间以及内配煤量的增加而提高;抗压强度随焙烧温度、焙烧时间的增加而增高,但随内配煤量的增加出现极值点·焙烧球团最佳的工艺参数:焙烧时间为15min,内配煤量为13 04%,焙烧温度为1250℃·此时锌的还原率为98 43%,金属化率为94 51%,抗压强度为800 6N/球·     

电弧炉粉尘直接还原炉渣氧化和脱硫能力计算热力学

电孤炉炼钢粉尘中含有多种重金属，若填埋弃置会对环境造成污染．将粉尘与还原剂碳粉混合制粒后返回电弧炉，并补充硅铁还原粉尘中难还原的金属，有价金属还原后回收于钢液中，不仅能生产不锈钢或特种钢，而且能保护环境．制粒时使用木质磺酸钙作为粘结剂，而木质磺酸钙中含有硫，可能影响钢材质量，影响程度取决于冶炼过程中炉渣的条件．经改变初始熔铁、球团、硅铁和石灰加入的量比关系进行实验，采用X射线荧光分析仪检测炉渣成分进行计算热力学研究，确定了1550℃时CaO-MgO-FeO-Fe     

高炉含锌烟尘还原挥发处理技术

用韦氏炉还原挥发法从高炉废弃烟尘中回收锌,成功产出了含Zn量为50%以上的富锌二次粉尘,可直接用于冶金化工生产,实现了高炉烟尘的无害化和资源化,具有良好的经济效益和社会效益。     

底吹条件对电弧炉熔池表面突起高度的影响

用３０ｔ底吹电弧炉１：７水模型探讨了底吹喷嘴孔数，孔径，气体搅拌功率及熔池深度对液面突起高度及上升速度的影响；得到了液面突起高度液体上升速度与气体搅拌功率的关系分别为：Δｈ＝０．３６１，Ｗ＾０．６６４，ｖＬ＝８４．１４４．Ｗ＾０．３３２，液面突起高度与气体搅拌功率及熔池深度的关系为：Δｈ＝０．８１５．Ｗ＾０．６６４．ｈ＾－０．６５９。     

EAF steelmaking process with increasing hot metal charging ratio and improving slagging regime

A new electric arc furnace (EAF) steelmaking process with increasing hot metal charging ratio and improving slagging regime simultaneously was developed and applied in a 50 t electric arc furnace for more than a year at No. 1 Steelmaking Plant of Shanxi Taigang Stainless Corporation Limited. The essential fact of the new EAF steelmaking process was to charge hot metal in two portions or steps: firstly, 35wt%-40wt% hot metal was pretreated by blowing oxygen in a specially designed reactor for decar burization and improving hot metal temperature and melting premelted slag; secondly, 30wt% hot metal was charged into EAF with high basicity refining slags from ladle furnace (LF)-vacuum degassing furnace (VD) refining process. The results show that the hot metal charging ratio can reach to about 65wt%-70wt% for the new EAF steelrnaking process; meanwhile, the tap-to-tap time of a 50 t EAF can shorten by 5-10 min, the electricity consumption can decrease by 35-50 kW·h/t, the lime consumption can reduce by 10.5 kg/t of molten steel, and the content of harmful heavy metals in molten steel can be easily controlled to less than the upper limits of aimed steel specification or grade compared with the traditional EAF steelmaking process. In addition, the dephosphorization ability shows a slight strengthening, however, a small degree of lessening for desulphurization ability is observed for the new EAF steelmaking process, but the weakness of desulphurization ability cannot become an obstacle to its further application since a stronger desulphurization ability can be achieved during secondary refining of LF coupled with VD after EAF steelmaking process.     

铁酸锌气体还原的热力学分析

根据热力学原理,计算并分析了含锌冶金粉尘中的重要成分ZnFe2 O4在CO- CO2气体还原过程中的热力学行为. ZnFe2 O4的气体还原遵循逐级还原规律,且ZnFe2 O4很容易被CO还原到ZnO和Fe3 O4.较高温度条件下,ZnO的气体还原易于FeO的还原.随着反应温度升高,锌完全反应和挥发所需要的CO含量不断降低,当反应温度从1100 K升高到1400 K时所需的CO体积分数由0.4降低到0.01以下.要达到还原分离金属锌的目的,不必将铁氧化物还原到金属铁,而只需将铁氧化物还原到Fe3 O4或FeO,同时满足锌的还原条件即可.在高炉炉身中上部,由于发生锌的还原反应和内部循环,给高炉生产带来危害,因此应减少和控制高炉的锌负荷.     

A novel hydrothermal method for zinc extraction and separation from zinc ferrite and electric arc furnace dust

A novel hydrothermal process was developed to extract zinc from pure zinc ferrite (ZnFe₂O₄) nanopowder and zinc-containing electric arc furnace (EAF) dust using hexahydrated ferric chloride (FeCl₃·6H₂O) as a decomposing agent. The effects of solid FeCl₃·6H₂O to ZnFe₂O₄ ratio by mass (R_F/Z), hydrothermal reaction temperature, and time on zinc extraction were systematically investigated. In the results, when the hydrothermal reaction is conducted at 150℃ for 2 h with R_F/Z of 15:20, the efficiency of zinc extraction from ZnFe₂O₄ reaches 97.2%, and the concentration of ferric ions (Fe3+) in the leaching solution is nearly zero, indicating a high selectivity for zinc. In addition, the zinc extraction efficiency from the EAF dust reaches 94.5% in the case of the hydrothermal reaction performed at 200℃ for 10 h with the solid FeCl₃·6H₂O to EAF dust ratio by mass (R_{F/EAF dust}) of 15:10. Zinc and iron separation is achieved by adjusting the pH value of the leaching solution according to the different precipitation pH values of metal hydroxides.