硫化钠对硅镁型红土镍矿气基还原焙烧的影响

镍是一种重要的战略金属,随着优质硫化镍矿日益匮乏,资源丰富的红土镍矿成为重要的提镍原料。本文以红土镍矿为研究对象,甲烷为还原剂,硫化钠为添加剂,考察了还原温度、甲烷浓度、还原时间及添加剂用量对镍、铁金属化率的影响,并通过扫描电子显微镜与能量色散光谱(SEM-EDS)分析对还原产物中镍铁的聚集情况进行了研究。结果表明：在还原温度900℃、还原时间60min、甲烷浓度20％、硫化钠添加量10％的条件下,还原产物中的镍、铁金属化率可分别达到89.05％、5.10％。硫化钠的加入促进了镍铁颗粒的聚集长大,有利于镍铁颗粒与杂质的分离,同时生成的FeS抑制了铁的深度还原,实现了镍的选择性还原。     

钒铅锌矿硫酸浸出提取钒锌

钒铅锌矿含有多种有价金属,V品位高,具有较高的经济价值。本工作采用硫酸浸出法从该矿中提取钒锌,对浸出过程热力学进行分析,通过条件实验研究硫酸浓度、液固比、浸出时间、搅拌速率、浸出温度等条件对钒、铅、锌等主要有价金属浸出率的影响。结果表明,在较高pH值及较高温度下,浸出液中V会出现水解,含V的水解产物留在浸出渣中影响V浸出率。得到最优浸出条件为：硫酸浓度200 g/L,液固比3:1,浸出时间30 min,搅拌速率200 r/min,浸出温度为30℃。最优条件下V浸出率可达97.90%,Zn浸出率为97.11%,Fe浸出率<1%,Pb浸出率<0.01%。动力学分析结果表明,浸出过程的反应速率受扩散过程控制。酸浸过程使V和Zn进入浸出液,Pb和Fe留在浸出渣中,所得浸出液可使用离子交换或萃取法分离V和Zn。浸出渣中含钒0.41wt%、锌0.61wt%、铁15.50wt%、铅47.70wt%,主要成分为PbSO₄和FeO(OH),可返回火法炼铅系统。     

高含H2S深层天然气藏长井段射孔技术

普光气田具有井深、射孔井段长、高含H2S等特点。介绍了射孔枪及射孔参数选择、抗硫材料选取、油管保护、起爆及传爆可靠性设计等方面开展的研究。通过对普光气田9口深井长井段射孔施工结果分析,证实采用防硫114射孔器并进行变孔密等技术设计能满足普光气田射孔后的酸压改造要求。复合射孔管柱、分段延时射孔、纵向和径向减震器的组合使用等技术措施可有效地保护油管,且可以满足长井段射孔可靠传爆的要求。     

Ce-Fe-O mixed oxide as oxygen carrier for the direct partial oxidation of methane to syngas

The Ce-Fe-O mixed oxide with a ratio of Ce/Fe=7:3, which was prepared by coprecipitation method and employed as oxygen carrier, for direct partial oxidation of methane to syngas in the absence of gaseous oxygen was explored. The mixed oxide was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), and the catalytic performances were studied in a fixed-bed quartz reactor and a thermogravimetric reactor, respectively. Approximately 99.4% H2 se...     

非等温条件下氢气还原Fe_2O_3-NiO制备镍铁合金的反应动力学EI北大核心CSCD

主要研究不同质量比的Fe_2O_3-NiO在氢气气氛下还原过程的非等温动力学。根据热分析动力学研究方法,结合样品的质量损失曲线,获得了样品在非等温还原过程中的动力学曲线,并确定Fe_2O_3-NiO体系在氢气气氛下还原过程的最佳机理函数(G(α)=[-ln(1-α)]~4),过程受随机成核和随后生长机理控制。结果表明:当样品中Fe_2O_3-NiO质量比从1:2变化到2:1时,还原反应过程的活化能从249.821 kJ/mol增加至390.074 kJ/mol;随着体系中NiO含量增加,还原反应开始的温度逐渐降低,还原产物物相由铁纹石相(Fe,Ni)和镍纹石相(Fe,Ni)逐渐转变为镍铁合金相(FeNi_3),产物微观颗粒尺寸变得不均匀。通过建立数学模型,验证了反应过程中反应分数的模型计算值与实验测量值具有良好的相关性。     

氯化钙作用下镁质贫镍红土矿选择性富集镍的研究

采用还原焙烧-磁选工艺, 对氯化钙作用下镁质贫镍红土矿选择性富集镍进行了研究, 考察了还原温度、还原时间、还原剂用量和氯化钙用量对富集镍的影响。结果表明, 在还原温度1 200 ℃、还原时间40 min、还原剂和氯化钙用量均为8%的条件下, 可获得镍品位8.67%、回收率92.01%的镍铁精矿; 相比于直接还原焙烧-磁选, 加入8%氯化钙后使镍的富集比由3增加到11, 显著提高了镍的富集效果。磁选产品物相分析显示, 镍主要以铁纹石形式存在于精矿中, 通过磁选实现了对镍铁精矿与脉石的有效分离。     

红土镍矿的固相还原动力学

采用非等温热分析法对红土镍矿固相还原动力学进行了研究,由热失重曲线确定了红土镍矿固相还原的反应机理函数f(a),在此基础上求解出动力学参数,并对建立的动力学模型进行了验证,分析了红土镍矿固相还原机理. 结果表明,红土镍矿失重率与加热温度密切相关,而升温速率对其影响很小;模型计算值与实测值具有良好的相关性;固相还原过程可分为473~773和773~1223 K两个阶段,反应活化能分别为171.91和52.75 kJ/mol,与挥发分的析出和镍、铁氧化物的还原对应;反应属随机成核和随后生长型机理函数,其微分形式为f(a)=1/4(1-a)[-ln(1-a)]-3,反应速率主要由碳气化反应控制.     

铜渣中铜的回收工艺及新技术

综述了几种铜渣贫化技术。基于铜渣的物相结构,分析了铜渣火法贫化、湿法提取及缓冷选矿3种方法的贫化机理,并讨论了各方法的贫化效果。结合氯化法在处理复杂物料中的优势,为实现渣中铜的高效提取,提出了一种铜渣氯化焙烧-烟气捕集回收铜的研究思路。     

Chemical interaction of Ce-Fe mixed oxides for methane selective oxidation

Chemical interaction of Ce-Fe mixed oxides was investigated in methane selective oxidation via methane temperature programmed reduction and methane isothermal reaction tests over Ce-Fe oxygen carriers. In methane temperature programmed reduction test, Ce-Fe oxide behaved complete oxidation at the lower temperature and selective oxidation at higher temperatures. Ce-Fe mixed oxides with the Fe content in the range of 0.1–0.5 was able to produce syngas with high selectivity in high-temperature range(800–900 °C), and a higher Fe amount over 0.5 seemed to depress the CO formation. In isothermal reaction, complete oxidation occurred at beginning following with selective oxidation later. Ce1–xFexO2–δ oxygen carriers(x≤0.5) were proved to be suitable for the selective oxidation of methane. Ce-Fe mixed oxides had the well-pleasing reducibility with high oxygen releasing rate and CO selectivity due to the interaction between Ce and Fe species. Strong chemical interaction of Ce-Fe mixed oxides originated from both Fe*activated CeO2 and Ce3+ activated iron oxides(FeOm), and those chemical interaction greatly enhanced the oxygen mobility and selectivity.     

Characteristic of macroporous CeO2-ZrO2 oxygen carrier for chemical-looping steam methane reforming

Chemical-looping steam methane reforming （CL-SMR） is a novel process towards the production of pure hydrogen and syngas, consisting ofa syngas production reaction and a hydrogen production reaction. Macroporous CeQ-ZrO2 oxygen carders with different pore sizes prepared by colloidal crystal templating method and characterized by techniques of scalming electron microscopy （SEM）, transmission electron microscopy （TEM）, Brunauer-Emmett-Teller （BET）, X-ray diffraction （XRD） and temperature pro- grammed reduction （H2-TPR） were tested in CL-SMR process. For comparison, nonporous CeO2-ZrO2 oxygen carrier prepared by precipitation method was also investigated. It was found that macroporous CeO2-ZrO2 oxygen carriers owned higher reducibility and reactivity in CL-SMR process than nonporous samples. For the macroporous CeO2-ZrO2 sample, the decline of pore size could im- prove the reducibility and reactivity. The macroporous sample with a pore size of 100 nm （labeled as Ce-Zr-100） showed the highest performance for the co-production of syngas and hydrogen during the successive CL-SMR redox cycles. After 10 redox cycles, it still retained good porous structure and reducibility. It was found that the porous structure could accelerate the oxygen release from bulk to surface, leading to a good mobility of oxygen and higher reducibility. In addition, it was also favorable for diffusion and penetration of methane and water steam into the sample particles to accelerate the reaction rate.