MoS_2-CaO-O_2系热力学分析及应用

通过热力学计算得出温度为800,900 K时,不同Mo S2,Ca O,O2初始物质量条件下对应Mo S2-Ca O-O2体系的热力学平衡,确定辉钼矿石灰焙烧的反应机制。热力学分析表明,800 K时体系初始摩尔量Mo S2∶Ca O=1∶3时,随着氧用量的增加Mo(VI)优先与石灰、氧气结合生成CaMoO_4,然后S(II)被氧化生成CaSO_4,体系氧化最终热力学平衡产物为CaSO_4,CaMoO_4;800 K时体系初始摩尔量Mo S2∶Ca O=1∶2时,随着氧用量的增加,约70%的Mo S2首先生成CaMoO_4,Ca S,然后Ca S氧化为CaSO_4,最终CaMoO_4作为固硫剂与残余的Mo S2反应生成Mo O3和CaSO_4,最终对应热力学平衡产物为CaSO_4,Mo O3。理论上证明可以实现辉钼矿选择性钙化焙烧;温度从800 K提高至900 K时,不影响全钙化焙烧过程;对于选择钙化焙烧高温不利于CaMoO_4固硫,而富氧益于固硫。验证试验采用100 g辉钼矿与55 g氧化钙混匀,在温度为800 K的马弗炉中焙烧2 h,焙砂钼、硫固定率分别为98.36%,91.44%,X射线衍射(XRD)分析表明钼硫分别以Mo O3,CaSO_4存在,与热力学分析结论一致。     

钙盐沉钒的热力学研究

根据同时平衡原理以及质量守恒定律,绘制了在不同的游离总钙浓度下Ca-V(Ⅴ)-H2O体系25℃时的热力学平衡图,并进行了热力学分析。结果表明,随着溶液pH值的增大,体系中依次出现V2O5、Ca(VO3)2、Ca2V2O7、Ca3(VO4)2、Ca3(VO4)2+Ca(OH)2、Ca(OH)2六个沉淀稳定区。当沉钒反应平衡后液游离总钙浓度为0.01mol/L时,在pH=5.1~9.8范围内,钒以Ca(VO3)2形式沉淀,钒浓度最低可降至2.2×10-3 mol/L;在pH=9.8~10.3范围内,钒以Ca2V2O7形式沉淀,钒浓度最低可降至1.2×10-2 mol/L;在pH=10.3~12.6范围内,钒以Ca3(VO4)2形式沉淀,钒浓度最低可降至2.4×10-4 mol/L,沉钒效果最佳。当游离总钙浓度为0.01~1.0mol/L时,理论最佳沉钒pH值基本维持在11.0~12.6。     

固态下SiO2对二元铁酸钙形成过程的影响

 铁酸钙作为高碱度烧结矿黏结相的主要组成,其形成受SiO2的影响,但到目前为止,其影响机理尚不是十分明确。通过XRD和矿相显微镜观察,并结合Rietveld法定量分析,研究了SiO2对二元铁酸钙形成过程的影响。结果表明：Fe2O3与CaO反应,700 ℃时形成Ca2Fe2O5,在800 ℃时出现CaFe2O4,随着温度升高,Ca2Fe2O5逐渐向CaFe2O4转变。SiO2存在时,在铁酸钙形成过程中有Ca2SiO4生成,温度低于900 ℃时,受动力学条件的影响,反应速率较低,Ca2SiO4的量相对较少,另外,SiO2的阻碍作用随其质量分数的增加而增强,进而导致已形成的Ca2Fe2O5与Fe2O3未能继续反应形成CaFe2O4而使其质量分数逐渐增多;高于900 ℃时,随着温度的升高,动力学条件改善,离子扩散能力增强,其中,Fe3+通过CaFe2O4层比Ca2+通过Ca2Fe2O5层更容易,进而促进了CaFe2O4形成反应的进行,Ca2Fe2O5向CaFe2O4转变,但随着SiO2质量分数增加,Ca2SiO4的生成量增多,CaO与Fe2O3的接触面积减小,抑制了CaFe2O4的生成。     

宜春锂云母压煮溶出新工艺研究

采用熟石灰、纯碱联合压煮法新工艺处理宜春锂云母 ,考察了压煮溶出过程中熟石灰用量、纯碱用量、反应温度和反应时间对锂、钾、铝、硅、氟等元素溶出行为的影响。结果表明 ,在最佳工艺条件下 (焙料 :Ca(OH) 2 ∶Na2 CO3=10∶9∶2 ,140℃ ,3h) ,Li2 O的溶出率在 92 %以上 ,K2 O的溶出率达 80 % ,杂质元素Al2 O3、SiO2 和F少量溶出     

高铁铝土矿直接还原回收粒铁和氧化铝

 采用煤基直接还原熔分技术和氧化铝溶出的方法,研究了直接还原工艺对粒铁尺寸和粒铁收得率的影响,以及钙铝比[(w(CaO)/w(Al2O3))] 对渣相组成和渣中氧化铝的溶出影响。结果表明,当[(w(CaO)/w(Al2O3))]为1.7、[w(C)/w(O)]为1.4、还原熔分温度为1 450 ℃,还原熔分时间为20 min时,还原熔分过程中的粒铁尺寸最大,粒铁收得率也最高,粒铁尺寸和收得率分别为11.5 mm和93%。当[(w(CaO)/w(Al2O3))]为1.0时,渣相组成主要以钙铝黄长石(Ca2Al(Al,Si)2O7)为主,当[(w(CaO)/w(Al2O3))]为1.5时,渣相组成主要以钙铝黄长石(Ca2Al(Al,Si)2O7)、硅酸二钙(Ca2SiO4)和七铝十二钙(Ca12Al14O33)为主,当[(w(CaO)/w(Al2O3))]为1.7～1.9时,渣相组成主要以七铝十二钙(Ca12Al14O33)和硅酸二钙(Ca2SiO4)为主。当[(w(CaO)/w(Al2O3))]为1.7时,溶出时间为2.0 h时,氧化铝的溶出率最高,溶出率为87.5%,溶出率较0.5 h时提高了9.4%。因此,当渣系组成以七铝十二钙(Ca12Al14O33)和硅酸二钙(Ca2SiO4)为主时,更有利于氧化铝的溶出。     

12 CaO·7 Al2 O3晶体结构及其氧化铝浸出性能

使用分析纯试剂配料,在1350℃保温1 h的条件下合成了A/S=5(Al2O3与Si O2质量比)的铝酸钙熟料.研究了钙铝比C/A(除去与Si O2结合的Ca O后Ca O与Al2O3的摩尔比)对熟料中12Ca O·7Al2O3晶体结构及其氧化铝浸出性能的影响,并通过X射线衍射和X射线荧光等分析手段对其作用机理进行了探讨.结果表明:由于12Ca O·7Al2O3量的增加,C/A=1.0~1.4时,石灰烧结法熟料溶出率随着C/A的提高而提高;在C/A=1.4时,熟料溶出率最高可达93.30%,此时Ca O的缺失形成了有缺陷的12Ca O·7Al2O3,且其中Ca O的物质的量小于11.3 mol;钙铝比提高到1.7时熟料溶出率又出现了下降趋势,这是由于Ca O的饱和导致12Ca O·7Al2O3晶体择优生长取向发生变化,由(211)面开始向(420)晶面转变.     

高钙镁钛精矿沸腾氯化制备TiCl4的热力学及动力学

针对高钙镁钛精矿难以满足沸腾氯化制备四氯化钛工艺问题,从热力学和动力学角度对高钙镁钛原料碳热还原—沸腾氯化制备TiCl4工艺进行了深入研究。结果表明：钛精矿高温碳热还原历程为：FeTiO3 → TiO2+Fe → TinO2n-1(n=4~9)+Fe → Ti3O5+Fe → Ti2O3+Fe → TiCxO1-x+Fe,碳氧钛生成的温度必须高于1 400 ℃,此时钛精矿中的Ca、Mg、Al、Si、Mn等杂质元素在1 800 ℃以内都不会被还原为对应的碳化物;高钙镁钛铁矿精矿碳热还原制备碳氧钛过程中,失重率随温度升高呈现4阶段上升,其中阶段1和3分别为受扩散控制生成金属Fe和碳氧钛的快速失重段,而阶段2和4分别为金属Fe和碳氧钛形核长大的缓慢失重阶段,4个阶段的表观活化能分别为49.84、—2.24、12.82、—2.53 kJ/mol。沸腾氯化过程还原产物中的Fe、MgO和CaO均会优先被氯气氯化,但当存在TiO2时,SiO2和Al2O3则不易被氯化,碳氧钛较适宜沸腾氯化的温度为300~650 ℃,沸腾氯化前5 min为还原产物中碳氧钛的快速氯化阶段,主要受表面化学反应的控制,而后5~20 min为Ti2O3的缓慢氯化阶段,主要受颗粒内部扩散控制的影响。     

低碳铝镇静钢中(CaO)_x(Al_2O_3)_y及CaS的形成与控制

生产低碳铝镇静钢过程中,为了控制夹杂物形态,一般要对其进行钙处理。如何使钙处理过程中生成液态的钙铝酸盐夹杂是生产控制的难点和重点。通过理论计算得出在一定条件下[Ca]-[Al]、[S]-[Al]关系图,以某低碳铝镇静钢为例,当w([Al])为0.03%时,控制w([Ca])为(9~15.8)×10-6,可以生成成分接近(CaO)12(Al2O3)7的液相夹杂。钢中w([S])为30×10-6,w([Al])为0.03%~0.04%,温度降低到1 723 K以下时,在(CaO)12(Al2O3)7上会析出CaS。     

提升钛精矿品级的研究

利用氧化热处理和酸浸工艺提升钛精矿的质量等级,研究了氧化处理对钛精矿球磨前后晶体结构的影响及酸浸工艺提高钛精矿品级的效果。结果表明,经750~800℃氧化退火,钛精矿中物相转变较充分,生成假金红石(Fe2Ti3O9)、Fe2O3和金红石型Ti O2相,钛精矿球磨后颗粒细化,物相转变从更低的温度开始,同样温度条件下物相的转变也更充分;对球磨后的钛精矿进行800℃退火和105℃酸浸后,Ca O和Mg O的含量分别降低到0.089%和0.888%,除去率为88.7%和51.8%,而Ti O2含量从44.12%提高到53.64%,能够显著提高钛精矿的质量等级。     

高强度船板钢钙处理热力学计算分析-夹杂物变质研究和应用

通过钙处理过程中Fe-Al-Ca-O-S体系的热力学平衡计算,得出在1 873 K时各种平衡态下的[Al]-[O]、[Al]-[Ca]、[Al]-[S]平衡曲线图,并系统分析了各组元对夹杂物变质的影响。研究发现F-级高强度船板钢[Al]为0.02%~0.03%时,为保证夹杂物充分变质,钢中[O]控制在25×10~(-6)以下;钢液中生成12CaO·7Al_2O_3的[Ca]为15.24×10~(-6)~19.97×10~(-6),生成3CaO·Al_2O_3的[Ca]为70.87×10~(-6)~92.88×10~(-6);适当低的钢液温度有利于生成CaS,抑制MnS的聚集析出。120 t BOF-LF-VD-板坯连铸流程生产F-级高强度船板钢DNV F40(/%:0.092C,0.41Si,1.56Mn,0.015P,0.002S,0.032A1,0.035Nb,0.035Ni,0.010Ti,0.080V)的结果表明,当LF精炼渣组成/%:24.9Al_2O_3,55.6CaO,7.7MgO,8.0SiO_2,1.24TFe,加钙前钢中铝含量0.03%,氧含量0.0010%时,每炉钢水喂纯钙线150 m(0.21 kg/m),钢中夹杂物由加钙前Al_2O_3变质为球形钙铝酸盐夹杂物。     

China's Major Non-ferrous Metals Imports & Exports

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Zinc Production by Province in 2014

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80% of Chinese Firms Purchasing Overseas Mines Ended up in the Red

<正>Minmetals Resources acquired the world’s largest copper mine under construction for USD5.85 billion.One after another,listed companies Jien Nickle,China Molybdenum and Chihong Zinc and Germanium raised money to get involved in overseas mining projects…SOEs and private enterprises are engaged in a frenzy of overseas mine purchasing.A reporter with Economic     

Copper Processing Profit Dropped Sharply,Copper Consumption Will Face Impact in the Second Half of the Year

正Judging from China’s copper consumption field,the biggest consumption unit is electric power,which accounts for 47%of total consumption;it is followed by light industry sector,including household electrical appliance,machinery,durable goods and hardware etc,which accounts for 22%of total consumption;followed by transportation field,     

Central Geological Prospecting Fund Newly Added 16.47 Million Tonnes of Bauxite in 2013

正In 2013,the Central Geological Prospecting Fund(CGPF)Project newly discovered 15 ore fields,including 3 large above ore fields,and 5medium sized ore fields.The reporter learned from the recently published"Annual Report of Central Geological Prospecting Fund Project(2013)"that,from 2006 to 2013 the CGPF     

Manufacturers of Copper Tube for Central Air Conditioner Use Face Mounting Pressure in the Final Quarter of the Year

正This year,the investment growth rate of real estate industry continued to slow down,sold area of commercial housing also dropped significantly,which brought huge pressure to the domestic air conditioning manufactures.In the first half of the year,by relying on high growth in national financial expenditure,along with investment in public infrastructure     

Xinjiang Ranks No.1 in Production of Primary Aluminum in China

正Kang Yi,Honorary Chairman of China Nonferrous Metals Industry Association,said recently at the Forum on Development of the Non-ferrous Metals Industry in Central and Western China held in Zhengzhou that,as more and more electrolytic aluminum factories in Xinjiang came into operation,the electrolytic aluminum output of Xinjiang had reached2,275,000 tons in the first 7 months this year,     

Shenhuo Coal Industry and Electricity Power Completed800,000 t/a Aluminum Project in Xinjiang

正"Xinjiang project has been completed according to schedule,but total completion and total start of production are two different concepts,after completion it still needs a gradual process of reaching production target."On the morning of November 3,Shenhuo Coal Industry and Electricity Power told investors the above statement on the investor interaction platform.     

Guangdong Metal Transaction Center has Become the Second Largest Precious Metal Transaction Platform Nationwide

正The reporter learned from Guangdong Province Precious Metal Transaction Center that in 2013the Center maintained healthy development momentum,and had become the second largest precious metal transaction platform in China in terms of market size;currently Guangdong is quickening steps of financial innovation for the Center,aiming to build a transaction center with international core competitiveness.     

Seven Rare Earth Projects Involving Close to 3 Billion Yuan Investment Landed In the HighTech Zone

正On May 22,Baotou Rare Earth Industry Cooperation Consultation MeetingProject Agreement-signing Ceremony was held in Ningbo,nearly 40 enterprises from Ningbo,Guangdong,Hunan,and Shanxi participated in project consultation.After multi-lateral communication,agreements were signed for a total of 7 rare earth projects successfully.