A novel method for extracting vanadium by low temperature sodium roasting from converter vanadium slag

Long-term high temperature in conventional vanadium extraction process would cause particles to be sintered and wrapped, thus reducing extraction efficiency of vanadium. Based on the purpose of directional conversion and process intensification, this work proposed a combination of low temperature sodium roasting and high efficiency selective oxidation leaching in vanadium extraction. The investigation of the reaction mechanism suggested that the structure of vanadium slag was changed by roasting, which also caused the fracture of spinel. The addition of MnO₂ promoted the directional oxidation of low-valent vanadium into high valence. It also found that Na₂S₂O₈ could oxidize low-valent vanadium effectively in leaching. The leaching efficiency of vanadium reached 87.74% under the optimum conditions, including a roasting temperature of 650 °C, a roasting time of 2.0 h, a molar ratio of sodium-to-vanadium of 0.6, a MnO₂ (roasting additive) dosage of 5 wt% and a Na₂S₂O₈ (leaching oxidant) dosage of 5 wt%. This percentage is 7.18% higher than that of direct roasting-and-leaching under the same conditions.     

钠化焙烧转炉钒渣粉体分形生长的演化行为

转炉钒渣焙烧提钒技术效率低,过程涉及化学反应、传递及相变过程,蕴含物相分形生长的动力学行为。对钒渣分形变化规律的研究有助于促进钒的定向转化,进而对工业提钒具有指导意义。根据金相电镜图,使用“周长-面积法”对不同焙烧条件下钒渣粉体分形维数进行计算,得到分形维数变化与物相转化的规律。结果表明,焙烧前硅相、钒相紧密包裹,分形维数数值为1.60~2.00;加入碳酸钠焙烧后尖晶石破坏,钒相逐渐分离,使分形维数小于1.20;随着钠盐加入量的增加,物相分形维数逐渐下降;二次焙烧后,稳定的钒酸钠生成,体系趋于稳定,使得分形维数进一步下降为1.10~1.20。     

Two-stage cyclic ammonium sulfate roasting and leaching of extracting vanadium and titanium from vanadium slag

Compared with traditional sodium or calcification roasting process for vanadium extraction from raw vanadium slag (V-slag), ammonium sulfate (AS) roasting could reduce about 470℃ roasting temperature and avoid Cl₂, HCl, sodium-containing waste-water and waste gypsum discharging. To reduce the amount of AS added in vanadium extraction process, an efficient AS two-stage cyclic roasting and acid leaching process was proposed. The result of TG analysis indicates V-slag could be decomposed in 275-380℃ using AS roasting process. Using 2.03:1 total mass ratio of AS to V-slag, 90.86% V and 80.54% Ti could be extracted after 380℃ roasting for 30 min and 8% initial concentration of H₂SO₄ leaching at 70℃ for 100 min. XRD analysis indicates V-containing spinel phase in the 1st stage leaching residue would be efficiently decomposed by the cyclic two-stage roasting and leaching process. Furthermore, the valence of V(III) in raw V-slag was not changed after the 1st AS roasting stage, but a part of V(III) in the 1st leaching residue was oxidized to V(V) after 2nd roasting process.     

空气强化转炉钒渣湿法浸出行为

钒渣钠化焙烧过程低价钒氧化不充分,不能被浸出,降低了钒渣的浸出率。实验采用蒽醌磺酸钠（ADA）和栲胶作载氧体实现氧的传递,强化低价钒的氧化行为。通过X射线衍射、扫描电镜、紫外光谱以及紫外可见漫反射光谱等检测方法,分析了转炉钒渣浸出反应前后物相变化行为,探索了反应过程机理,证实了其可行性。结果表明,采用ADA和栲胶作载氧体,能将转炉钒渣中的低价钒氧化成可溶的高价钒,实现空气催化氧化高效浸钒。此时,钒浸出率由89.47%分别提高到92.84%和93.64%,且催化剂对体系后续工艺没有不良影响,转炉钒渣中的尾渣含钒量由1.1%分别降至0.52%和0.47%。     

转炉钒渣提钒技术研究现状及展望

如何低成本绿色高效回收转炉冶炼钒渣中的钒资源是保证我国钒产业可持续发展的重要举措。本文在分析转炉钒渣成分及物相特征的基础上,系统总结了国内外主要钒制品生产企业提钒工艺研究现状,以钠化焙烧-水浸、钙化焙烧-酸浸等现行工艺和微波焙烧、超重力选择性分离、微生物冶金等新型工艺为例,阐述了不同工艺提钒过程的原理、优点及存在的问题。文章指出：随着全球碳中和目标的推进,未来转炉钒渣提钒新工艺的开发应更加注重解决现行技术存在的资源环境问题,如含盐废水产生量大、含铵芒硝难处理、提钒尾渣钠高难利用等问题;同时,提钒新技术的开发也应加大基础热力学数据库和有价金属微观迁移动力学模型的建立,充分结合微波、超重力、超声波等非常规冶金技术的优点,实现污染的源头削减,兼顾提钒废液和尾渣中其他有价金属的循环高值利用,促进转炉钒渣提钒新工艺朝着绿色化、低成本、短流程、高收率的方向发展。     

A novel method to extract vanadium and chromium from vanadium slag using molten NaOH‐NaNO3 binary system

A new method using NaOH‐NaNO₃ binary melts to treat vanadium slag is proposed. Vanadium and chromium can be simultaneously extracted in the leaching processes. Under the optimum reaction conditions, the recovery of vanadium and chromium can reach 93.7% and 88.2% in 6 h, respectively. The kinetics investigation indicates that the decomposition of vanadium slag is controlled by mass transfer in product layer. During the reaction, NaOH is believed to provide basic media and facilitate the dissolution of acidic oxides. NaNO₃ decomposes to produce a large amount of active oxygen species, such as O, , and O^2?. NaOH intensifies the decomposition of NaNO₃ to NaNO₂, but inhibits further decomposition of NaNO₂. NaNO₃ can be regenerated by oxidation of NaNO₂ using oxygen at high temperature. The apparent activation energy of NaNO₂ oxidation in the temperature ranging from 350 to 450°C is 105.5 kJ/mol. © 2012 American Institute of Chemical Engineers AIChE J, 59: 541–552, 2013     

利用正交试验确定钒渣焙烧的最佳工艺条件

介绍了钒分厂利用正交试验法进行试验方案的设计及试验结果的直观分析，确定出钒渣烙烧的最佳工艺条件是：钒渣粒径小于0．12mm，烙烧气中氧气体积分数大于10％，焙烧温度850℃，烙烧时间60min，碱比(碱与钒渣质量比)16％，盐比(盐与钒渣质量比)5％，从而改变了以往在生产和转渣时组织生产的被动局面，为公司创造了可观的经济与社会效益。     

绢云母的焙烧提钾实验研究

以CaCl2、CaSO4、CaCO3、NaCl和NaOH为助熔剂对四川地区的绢云母矿进行了焙烧提钾试验,结果表明:助剂CaCl2、NaCl及NaOH用量与绢云母矿质量比为0.3∶1时,钾的浸出率分别高达45.46％、54.51％和66.70％;以CaCl2为助剂,进一步研究焙烧温度、添加剂用量、焙烧时间以及矿粉粒度等条件对提钾效果的影响,并通过正交实验确定了最佳提钾条件:绢云母矿粉与助剂质量比为1∶1.2,焙烧温度为900℃,焙烧时间为40 min.在最佳条件下焙烧后,熟料经过水浸,钾的浸出率为81.86％.通过对焙烧前后样品及水浸后的不溶物的XRD分析,初步确定了焙烧过程中的主要物相变化及反应机理.     

高硅水镁石钠化焙烧法除硅工艺研究

以高硅水镁石为原料、氢氧化钠为钠化剂,研究了高硅水镁石钠化焙烧除硅过程中氢氧化钠用量、焙烧温度、焙烧时间等对焙烧水洗产物中硅含量的影响,对不同温度条件下的焙烧产物和焙烧后水洗产物的结构和谱学特征进行分析和表征,以揭示高硅水镁石钠化焙烧除硅机理。结果表明：在焙烧温度为650 ℃、氢氧化钠用量为理论量3倍、焙烧时间为3 h的最优条件下,钠化焙烧过程中Na⁺会与蛇纹石热分解产物Mg₂SiO₄中的Mg²⁺发生置换反应,最终形成可溶性盐Na₄SiO₄,从而水洗除去,水洗产物中硅质量分数为1.89%,硅提取率达90.1%。     

钒渣钠化焙烧熟料浸出液除磷工艺研究

以钒渣钠化焙烧熟料浸出后得到的含钒溶液为原料,分析了二水硫酸钙在碱性条件下对含钒溶液中磷的去除机制,研究了二水硫酸钙用量、溶液pH、反应时间、反应温度等因素对磷去除率、钒损失率以及溶液中五氧化二钒与磷质量浓度比的影响。研究结果表明：在弱碱性条件下,二水硫酸钙可有效去除含钒溶液中的磷,磷去除率达到70%以上、钒损失率小于1%、五氧化二钒与磷质量浓度比大于2 300,满足后续沉钒的要求。确定的除磷工艺条件：二水硫酸钙与磷物质的量比为5.3,溶液pH为9.0,反应时间为30 min,反应温度为25 ℃。除磷后的含钒溶液经沉钒、洗涤、煅烧得到五氧化二钒产品,沉钒率大于99%,五氧化二钒产品质量满足YB/T 5304—2011《五氧化二钒》中99级的要求。     

Microwave-aided roasting for extraction of vanadium from stone coal

Low recovery rate,high energy consumption and serious pollution are existed in traditional processes of vanadium extraction.To seek a new process with high recovery rate,low energy consumption and less pollution discharge is of great significance.Microwave-aided roasting for vanadium extraction is an environmentally-friendly technology.Non-pollution roasting processes with additives following sodium carbonate and potassium carbonate,under microwave irradiation were investigated with stone coal.The valence variation of vanadium in oxidation roasting of the vanadium bearing stone coal was studied.The results showed that the oxidation process of vanadium was a stepwise process following V(Ⅲ)→V(Ⅳ)→V(Ⅴ).The roasted stone coal was characterized by XRD,SEM.Factors associated with extraction rate were investigated following roasting temperature,roasting time,microwave power,and amount of roasting additive.Comparing with conventional roasting process,the recovery rate was higher without air pollution.     

改性电炉钛渣矿相解构法制备富钛料新工艺研究

以氧化后的钛精矿电炉冶炼渣为研究对象,采用一段氟化氢铵浸出-二段盐酸浸出的新工艺制备可用于沸腾氯化生产的富钛料原料,从浸出反应热力学和改性钛渣浸出行为两方面进行了系统的研究。氟化氢铵浸出热力学研究表明,氟化氢铵浸出可分解硅酸盐和部分黑钛石,并形成CaMg2Al2F12, CaF2和AlF3沉淀,浸出后杂质元素硅主要以(NH4)2SiF6的形式进入到浸出液中。氟化氢铵浸出实验表明,在氟化氢铵浓度为15wt%、液固比为10:1、温度20℃、浸出时间2 h的条件下,Si, Al, Ti, Fe, Ca和Mg元素的浸出率分别为93.55wt%, 28.03wt%, 3.88wt%, 20.50wt%, 3.40wt%和2.45wt%。浸出渣中主要的物相为金红石、黑钛石和钙镁氟化盐。氟化浸出残渣的盐酸浸出热力学表明,CaMg2Al2F12, CaF2, AlF3沉淀和剩余的黑钛石可溶解于盐酸溶液中。盐酸浸出实验表明,在盐酸浓度为20wt%、液固比为8:1、温度120℃、浸出时间2 h的条件下,Ca, Al, Mg, Ti, Si和Fe的浸出率分别为86.78wt%, 62.33wt%, 92.31wt%, 18.08wt%, 40.23wt%和75.36wt%。盐酸浸出后浸出渣主要物相为金红石,TiO2品位95.20wt%、CaO含量为0.49wt%、MgO含量为0.48wt%,满足沸腾氯化法对原料成分的要求。     

从钒渣中提取钒的新方法

提出了从废催化剂中分离镍、铝后得到的钒渣中回收钒的方法,重点分析了电解分离法的可行性.     

A novel catalyst for CO oxidation at low temperature

Supported catalysts of palladium over ceria–titania mixed oxides (Pd/CeO₂–TiO₂) were prepared and tested for carbon monoxide oxidation. The catalysts exhibited high catalytic activity at room temperature. The Pd/CeO₂–TiO₂ catalyst was more active than Pd/CeO₂, Pd/SnO₂–TiO₂, Pd/ZrO₂–TiO₂, Pd/Al₂O₂–TiO₂ and Pd/TiO₂ catalysts under the same conditions examined. The effects of preparation methods of the support, the mole ratio of ceria and titania in mixed supports as well as Pd loading upon the catalytic activity of CO oxidation were investigated. Among the Pd/CeO₂–TiO₂ catalysts, the best one corresponds to the Pd loading of 1.0 wt% or above, and the mole ratio of ceria and titania ranging from 1 : 7 to 1 : 5. The steady-state catalytic performance of such catalyst was recorded without any deactivation over 8 h time-on-stream in the present study. This revised version was published online in July 2006 with corrections to the Cover Date.     

低冰镍转炉渣中钴的氧压酸浸行为及其动力学

研究了转炉渣中钴氧压硫酸体系选择性浸出过程的行为及其动力学。通过改变搅拌速度、反应温度、硫酸浓度、氧分压、物料粒度以及反应时间等浸出条件,考察钴浸出率的变化及影响,获得转炉渣中钴的浸出动力学规律。结果表明,钴的浸出率随着温度、酸度、氧分压的增加而增加;硫酸质量浓度大于0.4 mol·L^-1会导致铁大量溶出;浸出过程符合未反应芯收缩核模型,前期受化学反应控制,然后转变为混合控制,后期受固体产物层扩散控制。化学反应控制和固体产物层扩散控制过程的活化能分别为43.19 kJ·mol^-1 和10.49 kJ·mol^-1。化学反应控制过程对硫酸浓度、氧分压及粒度的反应级数分别为0.79、0.85和 -0.95。     

惰性气氛下电解锰渣高温还原焙烧脱硫

电解锰渣的化学成分与水泥的组成符合,但高含硫量限制了其在水泥生产中的掺量。本研究采用高温还原焙烧法脱除电解锰渣中的硫,以焦炭为还原剂,在氮气气氛中以不同条件对电解锰渣进行热分解生成SO₂。用扫描电镜（SEM）和X射线衍射（XRD）分析固体产物,气体分析仪分析SO₂的释放,高温还原焙烧法脱除电解锰渣中的硫,探究焙烧温度和焦炭添加量对焙烧产物的物相和硫含量的影响。实验结果表明,生成SO₂的最佳条件为焦炭添加量4％、分解温度1000℃。在最佳条件下,SO₂的最大浓度为3513mg/m³,可用于生产硫酸。焙烧固体产物在温度为900℃、焦炭添加量为4%添加时,SO₃含量可以降低到2.17％。根据GB175—2007《通用硅酸盐水泥》中规定,满足水泥中SO₃含量须低于3.5%的要求,电解锰渣还原焙烧产品可以作为水泥原料,为电解锰渣的资源化综合利用提供理论依据和技术参考。     

微波辅助碱溶法从高岭土尾矿中提取氧化铝的研究

本文以高岭土和氢氧化钠为主要原料,在微波辅助下用碱溶法提取氧化铝。研究了微波辅助碱溶法的溶出工艺和溶出性能,并系统讨论了反应阶段反应的微波时间、焙烧温度、微波功率、反应温度、氢氧化钠质量分数以及液固质量比对氧化铝溶出率的影响。通过试验研究,优化出最佳溶出工艺条件为：微波时间120min,焙烧温度450℃,微波功率600w,反应温度85℃,氢氧化钠质量分数为50％,液固质量比为30：1。该条件下氧化铝的溶出率为61．17％。     

硫铁矿炼磺渣选铁还原焙烧磁选还原剂试验研究

根据炼磺渣的性质,采用预选抛尾的方法预选了试样,在此基础上,分别进行了预选粗精矿还原焙烧的还原剂种类、还原剂用量、还原剂粒度、磁选磁场强度试验。试验表明:预选粗精矿焙烧时间在20 min,温度在850℃时,还原剂种类以焦炭、还原剂用量以5%、还原剂粒度以-1mm、磁场强度以0.29 T为宜,得到的铁品位为51.71%,铁回收率为77.20%。     

PVDF/CB composites prepared by novel solvent casting method for low voltage PTC temperature regulation applications

A novel solvent casting preparation technique utilizing three variants of poly(vinylidene fluoride) (PVDF) to achieve a thermal cut off and a self regulation effect at a low applied voltage is reported in this study. The positive temperature coefficient (PTC) composites were prepared by dissolving PVDF in 1‐methyl‐2‐pyrrolidone (NMP) solvent, blending with Vulcan® XC72 carbon black (CB) filler, crosslinking with vinyl trimethoxysilane (VTMOS) and quenching in water. All composites displayed a highly macrovoidal structure that promoted a PTC effect when subjected to a thermal expansion effect via an electrical current. Subsequently the current was cut off and self regulation behavior was exhibited. Kynar® 761A PVDF resulted in the strongest PTC effect, and displayed temperature regulation at around 100°C which may be attributed to the highly semi crystalline nature and the larger molecular weight of this polymer in comparison with the other PVDF composites studied. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

氟化物为助浸剂时石煤提钒的碱浸工艺研究

用空白焙烧-碱浸法从石煤钒矿中提取钒,氟化物为助浸剂,考察NaOH浓度、浸出温度及时间、固液比、NaF/石煤质量比对浸出效果的影响。结果表明,加入助浸剂NaF有助于提高钒的浸出率,最佳浸出条件为:NaOH浓度40.00 g/dm,浸出温度85.0℃,浸出时间3.0 h,液固比4∶1(m L/g),NaF/石煤质量比0.15∶1。对浸出机制做出了初步探讨。