钒渣微波升温特性及氯化的研究

为了研究微波熔盐氯化钒渣的可行性,在2.45 GHz频率下采用谐振腔微扰法测量钒渣的介电特性,并考察了不同物料的升温特性,研究了不同熔盐对钒渣氯化的影响。结果表明:常温下,粒径小于75μm的钒渣具有良好的吸波性能,而氯化物的吸波性能较差;钒渣升温速率与粒径大小呈负相关,而钒渣质量增加,升温速率会先增大后减小;AlCl_3-NaCl-KCl熔盐对钒渣的氯化效果最强,强化氯化的机理可以描述为微波与熔盐的耦合更容易使矿相裂解,增加反应面积,增强氯化作用。     

从钒渣中浸出钒的宏观动力学研究

针对攀枝花某企业产出的钒渣,以碳酸氢铵水溶液为浸出剂,研究了从钒渣中浸出钒的宏观动力学,考察了搅拌速度、反应温度、浸出剂质量浓度和颗粒粒度对钒浸出率的影响。结果表明:钒浸出过程遵循"未反应收缩核模型",反应主要受固体产物层扩散控制;钒浸出率随液固体积质量比增大、搅拌速度增大、反应温度升高及浸出剂质量浓度增大、颗粒粒度减小而提高。根据试验数据,建立了宏观动力学模型,求得反应表观活化能E=18.0kJ/mol,指前因子A=0.713,确立了宏观动力学方程。     

亚熔盐法钒渣高效清洁提钒技术

针对目前钒渣焙烧提钒工艺钒资源利用率低、铬无法同步提取、"三废"环境污染严重等问题,基于亚熔盐非常规介质优异的物理化学性能,通过反应分离耦合工艺设计,提出了亚熔盐法高效清洁提钒新技术。亚熔盐新技术可将钒渣分解温度由传统工艺的850℃降至200～400℃,钒一次转化率可达95%以上,铬回收率提高到80%以上,可望突破传统钒渣提钒方法的资源环境制约。     

石煤脱硅渣中钒浸出动力学

以石煤熔融水淬后碱浸脱硅渣为原料,采用液固多相反应的缩芯模型研究了石煤脱硅渣中钒的浸出动力学,考察了浸出温度、初始硫酸浓度对钒浸出率的影响。结果表明,脱硅渣的浸出分为两个阶段:反应刚开始时的快速浸出阶段和2min之后的缓慢浸出阶段,这两个阶段均受固膜扩散控制,反应活化能为13.88kJ/mol。     

氯化焙烧提取浸钒渣中的镓

用多相多组元化学平衡的热力学理论模型对氯化焙烧过程进行了预测,找出影响镓的提取率的关键因素,利用通用旋转组合设计的方法得出了镓的提取率与温度、CaCl_2的加入量、C的加入量、焙烧时间及气氛的非线性模型。由非线性优化得到了最优的工艺条件及镓的最佳提取率。     

提钒弃渣回用对钒渣焙烧的影响

以钒渣和弃渣为原料,碳酸钠和氯化钠为钠化剂,进行焙烧试验。不仅降低钒资源的损失,而且能减轻环境污染。通过硫酸亚铁铵滴定法,考察了焙烧温度、保温时间、碱比、碱盐比对不同钒含量样品钒浸出率的影响。结果表明:钒渣中适量的弃渣加入能促进钒转化率的提高;弃渣掺杂量16.376%时,最佳煅烧温度为800℃,保温时间为60 min,碱比1.5,碱盐比3.5,钒浸出率98.43%。     

微波碳热还原法制备氮化钒的研究和实践

利用微波高温炉常压碳热还原渗氮法制备了氮化钒，并进行了试生产。实验结果表明微波加热法可以采用V2O5为原料一步反应制得氮化钒，配碳量和温度是影响产物成分的重要因素。试生产结果表明，产品理化指标满足炼钢的要求。与传统加热方式相比，微波加热缩短了反应时间，简化了工艺，因而大幅度地降低了成本。     

Kinetics of chlorination and carbochlorination of vanadium pentoxide

Kinetics of chlorination of V₂O₅ with Cl₂-air, C1₂-N₂, and C1₂-CO-N₂ gas mixtures have been studied by nonisothermal and isothermal thermogravimetric measurements. In the temperature range of 500 °C to 570 °C, the chlorination of V₂O₅ with C1₂-N₂ gas mixture is characterized by an apparent activation energy of about 235 kJ/mole. This could be attributed to chemical reaction. Between 570°C and 650 °C, the apparent activation energy is equal to 77 kJ/mole, indicating that the overall reaction rate is controlled by chemical reaction and pore diffusion. The reaction order with respect to chlorine is 0.78. The apparent activation energy of the carbochlorination of V₂O₅ by C1₂-CO-N₂ gas mixture is about 100 kJ/mole in the temperature range of 400 °C to 620 °C. In this case, the chemical reaction is the limiting step. At temperatures higher than 620 °C, an anomaly is observed in the Arrhenius plot, probably due to thermal decomposition of COC1₂ formedin situ and/or transformation of the vanadium oxide physical state. The maximum reaction rate is obtained by using a C1₂-CO-N₂ gas mixture having a C1₂/CO volume ratio equal to about 1. Formerly Graduate Student, Mineral Processing and Environmental Engineering Team. Formerly Graduate Student, Mineral Processing and Engineering Team, Institut National Polytechnique de Lorraine, Vandoeuvre, France.     

Kinetics of low-temperature chlorination of vanadium pentoxide by carbon tetrachloride vapor

Low-temperature chlorination of vanadium pentoxide by carbon tetrachloride vapor in dilution with nitrogen has been carried out. The effect of time, particle size, partial pressure of CCl₄ vapor (0.1 to 0.6 atm), and temperature (553 to 788 K) on the extent of chlorination of V₂O₅ has been investigated. The extent of chlorination of the oxide is found to increase with a decrease in its particle size. In all cases, the reaction followed a topochemical reaction model, obeying the following relationship:

X射线荧光光谱法测定钒渣、钒渣熟料和提钒尾渣中主次组分

以四硼酸锂-碳酸锂为熔剂,碘化铵做脱模剂,熔融法制备样品,建立了X射线荧光光谱法(XRF)测定钒渣、钒渣熟料、提钒尾渣中二氧化硅、三氧化二铝、氧化钙、氧化镁、氧化锰、五氧化二钒、氧化铬、磷、二氧化钛和全铁的分析方法。试验表明,在试样量为0.25 g、稀释比(m_样品∶m_熔剂)为1∶20、脱模剂用量为20 mg时熔样效果最佳。采用经验系数法对基体效应进行校正及谱线重叠干扰校正,测定钒渣样品各组分的相对标准偏差(RSD,n=10)在0.10%~1.9%之间,检出限在35~460 μg/g之间。用标准物质和实际样品验证,测定结果与标准物质认定值和实际样品湿法测定值相符,能够满足日常分析的要求。     

X射线光电子能谱分析钒渣熟料中钒的价态

将转炉钒渣和碳酸钠混合, 在800 ℃下通过控制空气氧化时间制备一系列氧化程度不同的钒渣熟料, 对这些熟料进行水浸试验与X射线衍射(XRD)物相分析, 并使用X射线光电子能谱(XPS)分析法, 对钒渣熟料中钒元素的价态进行了定量研究。试验结果表明, XPS全谱得到的钒渣熟料元素与原始成分基本相符。窄扫图谱拟合过程得到了熟料各价态V 2p_3/2的结合能与半峰高宽的数据, 钒价态拟合结果显示随着氧化时间的增加, 熟料中V和V含量分别增加和减少, V含量先升高后降低, 结果与熟料的水浸结果以及XRD分析结果相符。     

Kinetics of chlorination of niobium pentoxide by carbon tetrachloride

Kinetics of the chlorination of Nb₂O₅ powder by CCl₄ vapor in mixture with N₂ in a static bed in the temperature range of 698 to 853 K were carried out at different partial pressures of CCl₄ (p _{CCl 4}), varying from 0.10 to 0.75 atm. The fraction of Nb₂O₅ chlorinated R at p _{CCl 4} of 0.6 atm in the temperature range of 698 to 773 K was found to be proportional to time t, and the activation energy E is calculated to be 112 kJ/mole. Results on the effect of p _{CCl 4} (0.4, 0.6, and 0.75 atm) at 723 K suggest that the rate v (R/min) is proportional to p _{CCl 4} ^1.5. However, at p _{CCl 4} of 0.2 atm, R is not linear with t, rather, R ^1/2 is linear with t. Based on these results, two mechanisms, one at low p _{CCl 4} (0.2 atm) and another at higher p _{CCl 4} values, in the temperature range of 698 to 773 K have been suggested. Similar studies in the higher temperature range (793 to 853 K), where p _{CCl 4} used to decompose to elemental chlorine and carbon, were also carried out. At all temperatures and p _{CCl 4} values, R is found to be directly proportional to t. At two higher p _{CCl 4} (0.4 and 0.6 atm), v is proportional to p _{CCl 4} ^1.5, whereas at two lower p _{CCl 4} (0.1 and 0.2 atm) it is proportional to p _{CCl 4} ^1.5. The E values obtained in the temperature range of 793 to 853 K at p _{CCl 4} of 0.6 and 0.2 atm are found to be 57 and 115 kJ/mole, respectively. In this higher temperature range, two different reaction mechanisms have been proposed.     

提钒转炉溅渣护炉试验研究

溅渣是提高转炉炉龄最有效的技术,但由于钒渣与钢渣成分差异较大,溅渣护炉技术尚未在提钒转炉上得到应用.为解决提钒转炉炉衬侵蚀严重的问题,对改性钒渣溅渣进行了研究.结果表明,通过改性可以达到调整钒渣状态的目的.改性后的钒渣具有良好的溅渣性能,溅渣后炉厚增加10 mm以上.改性钒渣中w(CaO)可控制在3％ 以下,对钒渣和半...     

Experimental study on slag splashing with modified vanadium slag

Slag splashing is the most effective technology to improve the furnace campaign of converter; however, due to the great difference of composition between the vanadium slag and the steel slag, the technology has not been applied in the vanadium extraction converter. To solve the serious problem of lining erosion in the vanadium extraction converter, in this paper, slag splashing with modified vanadium slag was studied. The results showed that the purpose of adjusting the state of vanadium slag can be achieved through the modification. The modified slag had good slag splashing performance. After slag splashing, the thickness of the furnace was increased by more than 10?mm. The content of CaO in the modified vanadium slag can be controlled less than 3%, and the quality of vanadium slag and semi-steel was not obviously affected. The metallic iron content in the slag was greatly reduced, which was beneficial to reduce the iron loss in the vanadium extraction process.     

含钒钢渣添加SiO2后的钒富集相与钒富集行为

为含钒钢渣设计富钒相,使钢渣中的钒主要富集于所设计的富钒相中.中国马钢的钢渣和瑞典SSAB的钢渣是本研究使用的样本.尽管炉渣的来源和化学组成各不相同,但是可以发现其矿物组成大致相似,而且无法仅仅通过对炉渣的热处理来实现钒的富集.本文根据钒和炉渣的基本物理化学性质设计了两种适合于作为富钒相的矿物:溶有w(Si)＜3%的3CaO·V2O5和3CaO·P2O5的固溶体以及另外一种w(Si)约10%的由3CaO·2SiO2,3CaO·V2O5和3CaO·P2O5的组成的矿物.通过添加SiO2对炉渣的化学成分进行调整,在炉渣中得到了所设计的富钒相,且炉渣中超过2/3的钒富集于其中.本研究为钢渣中的钒提出了一种新的回收利用途径.     

钒渣中有价元素的富集

目前钒渣只能提取钒,造成了大量的铁、铬的损失.本文对高铬钒渣进行综合利用,基于铁的还原,通过对还原焙烧时煤粉的加入量和煅烧温度不同的研究,磁选富集铁、钒和铬元素.通过XRD,XRF,SEM/EDS等表征手段对样品进行了研究.结果表明,添加煤粉煅烧可分别回收72. 36%的钒,79. 32%的铬和98. 61%的铁.