常压下从含钒石煤中浸取钒的新技术研究
|
摘要
世界上的两大钒矿资源：钒钛磁铁矿和含钒石煤。前者的储量很大,主要分布于独联体、美国、南非、中国、挪威、瑞典、荷兰、加拿大和澳大利亚,在我国主要分布于攀枝花地区；后者广泛分布在我国南方缺煤的数省,储量大、层位稳定、含钒品位高,主要特性为灰份高、密度大、发热量低、结构致密、着火点高、不易燃烧且难以完全燃烧、较硬、难磨,且主要赋存于下寒武纪的地层中。
石煤不仅是一种含碳氢少、发热量低、灰分高的劣质煤,同时又是一种低品位的多金属矿石,具有很高的综合利用价值。按石煤中主要有价元素不同,石煤可分为含钒、钒钼、钒镍、钒镓、钒铀、钒硒、钒银等类型,解决好发热量低的石煤利用问题,有着十分重要的战略意义。
钒是一种重要的战略物资,具有高熔点、易变形加工等特性,其用途非常广泛,主要应用于钢铁工业、国防尖端技术、化学工业以及轻纺工业等领域。随着汽车工业、建材工业等应用低合金高强度钢的数量不断增多,钒的用量将会急剧增加。贵州铜仁地区有大量的含钒石煤资源,且含钒品位各异,本文对该地不同品位石煤原矿进行了大量的检测分析,提出了H2S04和R1按比例混合,反应过程加入R2的常压酸浸方法。
通过多元素化学分析、差热-热重分析、电子探针分析、扫描电镜分析等手段,查明本文研究的石煤矿中钒主要赋存于云母类矿物中,少量以类质同相形式取代Fe3-进入氧化铁及粘土矿等氧化矿物,极少量以类质同相形式取代A13+进入难溶硅铝酸盐相中；其中四价、五价钒含量之和在50%以上,均属易浸出矿石。
在此基础上,考察了反应时间、反应温度、H2SO4用量、反应液固比、R1用量、R2用量、R2加入时间等参数对钒浸出率的影响。当硫酸用量为35%、浸出温度92-93℃、恒温时间6h、R1用量4%-6%、R2用量0.4%、R2加入时间为恒温后3小时加入、液固比2：1时,含钒0.314%、0.78%、1.97%的三种石煤矿钒的浸出率分别可以达到89%、87%、91%。
同时比较了不同含钒品位石煤矿浸出各参数对钒浸出率影响的规律性。结果表明：不同品位石煤浸出各参数对钒浸出率的影响规律基本一致。为了进一步验证浸出的稳定性,选择最佳工艺参数进行了六公斤级扩大实验,钒的浸出率均不低于85%,与小试基本吻合。该工艺具有操作简单、适应性强、应用范围广、设备投资少、工艺流程短、成本较低等优点。
China is rich in two vanadium mineral resources:vanadic-titanomagnetite and stone coal vanadium mine. The former have a great reserves, mainly in the Commonwealth of Independent States、the United States、South Africa、China、Norway、Sweden、the Netherlands、Canada and Australia.in China, which are mainly distributed in the Pan zhihua region. The latter is widely distributed in several provinces which lack of coal in the South of China. Large reserves、a stable horizon、with high-grade vanadium, the main characteristics such as high content of ash、high density、low heat、compact structure、high point of ignition、difficult to combustion and difficult to completely Burning、much hard and hard grind. At the same time, the stone coal main occurrence in the Cambrian strata.
Stone coal is not only a low hydrocarbon and carbon but also low-calorie, low quality coal with high ash content, at the same time, it is a low-grade multi-metal ore contain a high utilization value. According to different Stone coal contain different main elements, stone coal can be divided into such types as vanadium、vanadium molybdenum、vanadium nickel、vanadium gallium、uranium vanadium、selenium vanadium and silver vanadium, solving the problem about use of low-heat stone coal has a very important strategic significance.
Vanadium is an important strategic material with a high melting point and easy processing characteristics of deformation, and its have a widespread use, mainly used in iron and steel industry、cutting-edge defense technologies、chemical industry、textile industry and other fields. With high-strength low-alloy steel increasing applications in the auto industry and building material industry, the amount of vanadium will be increased dramatically. Tongren Prefecture of Guizhou have a lot of stone coal resources with different grade of vanadium. A great deal of analysis are used to study the different grade of stone coal ore. a direct pressure acid leaching methods method H2SO4 and R1 mixed pro-rata and reaction process to join the regular R2 is used.
Through of such means that the multi-element chemical analysis、DTA-TGA、electron microprobe analysis and scanning electron microscopy analysis, we know that the stone coals in this paper about vanadium main occurrence in mica, a small amount compared to the same type of quality in the form of To replace the iron oxide and Fe3+ into the clay mineral ore, such as oxidation, and a very small amount compared to the same type of quality in the form of Al3+ to replace the insoluble into the silicon aluminate phase. At the same time, four of five price and the price of vanadium content in more than 50% of this study are easy to extract stone coal ore.
On this basis, the vanadium leaching rate is effect by parameters such as reaction time、reaction temperature、amount of H2SO、liquid-solid、amount of R1、amount of R2、time of accession R2 and etc. When the amount of sulfuric acid 35%, extraction temperature 92～93℃, temperature time 6h, the amount of hydrofluoric acid 4% to 6% and 0.4% the amount of sodium hypochlorite, sodium hypochlorite accession to the time of 3 hours after the temperature by adding liquid Solid than 2 to 1,the vanadium leaching rate can reach 89%,87%,91%.
At the same time, comparison of different grade of coal extraction parameters of vanadium extraction rate of regularity. The results show that the stone to a different grade of coal extraction parameters of vanadium extraction rate of the laws are basically the same. In order to further verify the stability of the leaching, to choose the best technical parameters for a six kintal category to expand the experiment, the vanadium leaching rate not lower than 85%,which have a same test results as small experiments. The process is simple、adaptable、application of a wide range、low equipment investment、short process and low cost advantages.
石煤不仅是一种含碳氢少、发热量低、灰分高的劣质煤,同时又是一种低品位的多金属矿石,具有很高的综合利用价值。按石煤中主要有价元素不同,石煤可分为含钒、钒钼、钒镍、钒镓、钒铀、钒硒、钒银等类型,解决好发热量低的石煤利用问题,有着十分重要的战略意义。
钒是一种重要的战略物资,具有高熔点、易变形加工等特性,其用途非常广泛,主要应用于钢铁工业、国防尖端技术、化学工业以及轻纺工业等领域。随着汽车工业、建材工业等应用低合金高强度钢的数量不断增多,钒的用量将会急剧增加。贵州铜仁地区有大量的含钒石煤资源,且含钒品位各异,本文对该地不同品位石煤原矿进行了大量的检测分析,提出了H2S04和R1按比例混合,反应过程加入R2的常压酸浸方法。
通过多元素化学分析、差热-热重分析、电子探针分析、扫描电镜分析等手段,查明本文研究的石煤矿中钒主要赋存于云母类矿物中,少量以类质同相形式取代Fe3-进入氧化铁及粘土矿等氧化矿物,极少量以类质同相形式取代A13+进入难溶硅铝酸盐相中；其中四价、五价钒含量之和在50%以上,均属易浸出矿石。
在此基础上,考察了反应时间、反应温度、H2SO4用量、反应液固比、R1用量、R2用量、R2加入时间等参数对钒浸出率的影响。当硫酸用量为35%、浸出温度92-93℃、恒温时间6h、R1用量4%-6%、R2用量0.4%、R2加入时间为恒温后3小时加入、液固比2：1时,含钒0.314%、0.78%、1.97%的三种石煤矿钒的浸出率分别可以达到89%、87%、91%。
同时比较了不同含钒品位石煤矿浸出各参数对钒浸出率影响的规律性。结果表明：不同品位石煤浸出各参数对钒浸出率的影响规律基本一致。为了进一步验证浸出的稳定性,选择最佳工艺参数进行了六公斤级扩大实验,钒的浸出率均不低于85%,与小试基本吻合。该工艺具有操作简单、适应性强、应用范围广、设备投资少、工艺流程短、成本较低等优点。
China is rich in two vanadium mineral resources:vanadic-titanomagnetite and stone coal vanadium mine. The former have a great reserves, mainly in the Commonwealth of Independent States、the United States、South Africa、China、Norway、Sweden、the Netherlands、Canada and Australia.in China, which are mainly distributed in the Pan zhihua region. The latter is widely distributed in several provinces which lack of coal in the South of China. Large reserves、a stable horizon、with high-grade vanadium, the main characteristics such as high content of ash、high density、low heat、compact structure、high point of ignition、difficult to combustion and difficult to completely Burning、much hard and hard grind. At the same time, the stone coal main occurrence in the Cambrian strata.
Stone coal is not only a low hydrocarbon and carbon but also low-calorie, low quality coal with high ash content, at the same time, it is a low-grade multi-metal ore contain a high utilization value. According to different Stone coal contain different main elements, stone coal can be divided into such types as vanadium、vanadium molybdenum、vanadium nickel、vanadium gallium、uranium vanadium、selenium vanadium and silver vanadium, solving the problem about use of low-heat stone coal has a very important strategic significance.
Vanadium is an important strategic material with a high melting point and easy processing characteristics of deformation, and its have a widespread use, mainly used in iron and steel industry、cutting-edge defense technologies、chemical industry、textile industry and other fields. With high-strength low-alloy steel increasing applications in the auto industry and building material industry, the amount of vanadium will be increased dramatically. Tongren Prefecture of Guizhou have a lot of stone coal resources with different grade of vanadium. A great deal of analysis are used to study the different grade of stone coal ore. a direct pressure acid leaching methods method H2SO4 and R1 mixed pro-rata and reaction process to join the regular R2 is used.
Through of such means that the multi-element chemical analysis、DTA-TGA、electron microprobe analysis and scanning electron microscopy analysis, we know that the stone coals in this paper about vanadium main occurrence in mica, a small amount compared to the same type of quality in the form of To replace the iron oxide and Fe3+ into the clay mineral ore, such as oxidation, and a very small amount compared to the same type of quality in the form of Al3+ to replace the insoluble into the silicon aluminate phase. At the same time, four of five price and the price of vanadium content in more than 50% of this study are easy to extract stone coal ore.
On this basis, the vanadium leaching rate is effect by parameters such as reaction time、reaction temperature、amount of H2SO、liquid-solid、amount of R1、amount of R2、time of accession R2 and etc. When the amount of sulfuric acid 35%, extraction temperature 92～93℃, temperature time 6h, the amount of hydrofluoric acid 4% to 6% and 0.4% the amount of sodium hypochlorite, sodium hypochlorite accession to the time of 3 hours after the temperature by adding liquid Solid than 2 to 1,the vanadium leaching rate can reach 89%,87%,91%.
At the same time, comparison of different grade of coal extraction parameters of vanadium extraction rate of regularity. The results show that the stone to a different grade of coal extraction parameters of vanadium extraction rate of the laws are basically the same. In order to further verify the stability of the leaching, to choose the best technical parameters for a six kintal category to expand the experiment, the vanadium leaching rate not lower than 85%,which have a same test results as small experiments. The process is simple、adaptable、application of a wide range、low equipment investment、short process and low cost advantages.
引文
[1]王忠,王军.国内外五氧化二钒市场状况与分析.矿冶,2007,16(2)：47-51
[2]肖松文,梁经冬.钠化焙烧提钒机理研究的新进展.矿冶工程,1994,14(2)：53-55
[3]邹晓勇,欧阳玉祝,彭清静等.含钒石煤无盐焙烧酸浸生产五氧化二钒工艺的研究.化学世界,2001,(3)：117-119
[4]邓庆云,刘松英.石煤钠化焙烧、酸浸、离子交换提钒新工艺的试验研究.稀有金属与硬质合金,1993,(115)：27-33
[5]Oriol Font,Xavier Querol,Roberto Juan,etal.Recovery of gallium and vanadium from gasification fly ash. Journal of Hazardous Material A,2007,(139):413-423
[6]林海玲,范必威.方口山石煤提钒焙烧相变机理的研究.稀有金属,2001,25(4)：273—277
[7]沈喜恩.上饶八都石煤直接酸浸提钒工艺研究.江西煤炭科技,1997,(3)：57-59.
[8]曹建兵,欧阳玉祝,李志平等.石煤矿渣中钒浸取工艺条件研究.湖南城市学院学报,2005,14(4)：54-56
[9]许国镇,陈波珍,韩晓梅等.黄山石煤中钒价态及提钒技术研究.有色金属冶炼部分,1994(1)：32-35,41
[10]漆明鉴.从石煤中提钒现状及前景.湿法冶金,1999,(4)：1-10
[11]文喆.国内外钒资源与钒产品的市场前景分析.世界有色金属,2001,(11)：7-8
[12]LAN Yaozhong, LIU Jin. Review of vanadium processing inChina. Engineer Sciences,2005,3(3):58-62
[13]刘世友.钒的应用与展望.稀有金属与硬质合金,2000,(141)：58-61
[14]Russell J H, D C Collins, Rule A R. Vanadium roast-leach dissolution from western phosphate tailings.BuMines RI 8695,1982:19
[15]R.R. Moskalyk,A.M. Alfantazi.Processing of vanadium:a review.Minerals Engineering,2003,16:793-805
[16]蔡晋强,巴陵.石煤提钒的几种新工艺.矿产保护与利用,1993,(5)：30-33
[17]顾坚.石煤的综合利用和石煤提钒.能源政策研究通讯,1989,(3)：32-36
[18]段炼,田庆华,郭学益.我国钒资源的生产及应用研究进展.湖南有色金属,2006,22(6)：17-20
[19]刘世森.石煤提钒工艺评述.工程设计与研究,1993,(90)：12-16
[20]王永双,李国良.我国石煤提钒及综合利用综述.钒钛,1993,(4)：21-31
[21]赵天从,傅崇说,何福煦等.有色金属提取冶金手册稀有高熔点金属下.北京：冶金工业出版社,1999
[22]屈启龙,谢建宏,王冠甫.高碳钒矿综合回收石墨试验研究.矿业快报,2007,(4)：35-37
[23]Holloway P C, Etsell T H. Process for the complete utilization of oil sands fly ash.Canadian Metallurgical Quarterly,2005,45(1):25-32
[24]Perrine Chaurand,Jerome Rose,Jeremie Domas,etal.Speciation of Cr and V within BOF steel slag reused in road constructions.Journal of Geochemical Exploration,2006,(88):10-14
[25]孙玉宝,张金水.霍邱县石煤矿床地质特征及其开发利用前景初探.矿产保护与利用,2007,(2)：24-27
[26]黄道鑫.提钒炼钢.北京：冶金工业出版社,2000
[27]宾智勇.钒矿石无盐焙烧提取五氧化二钒试验.钢铁钒钛,2006,27(1)：21-26
[28]Ricardo E S,Marcos A B, Aline S F,etal. Non-volatile vanadium determination in petroleum condensate,diesel and gasoline prepared as detergent emulsions using GF AAS. Fuel,2008,(87):1617-1622
[29]WANG Mingyu,XIANG Xiaoyan,ZHANG Liping,etal. Effect of vanadium occurrence state on the choice of extracting vanadium technology from stone coal. Rare Metals,2008,27(2):112-115
[30]K.Muthu Karuppasamy,A.Subrahmanyam. The electrochromic and photocatalytic properties of electron beamevaporated vanadium-doped tungsten oxide thin films.Solar Energy Materials & Solar Cells,2008,(92):1322-1326
[31]彭声歉,侯兰杰,刘福生.四川广旺石煤提钒焙烧过程中钒价态的变化.中国矿业,1999,8(1)：69-72
[32]范必威,林海玲.方山口石煤提钒焙烧工艺研究. 湿法冶金,2001,20(2)：79-83
[33]蔡世民,彭声歉,侯兰杰.四川广旺地区石煤资源开发利用研究.矿产综合利用,1998,(4)：44-47
[34]范德廉.中国的黑色页岩及其有关矿床.北京：科学出版社,2004
[35]陈友善.钒钛矿冶金化学物相分析.成都：四川人民出版社,1982
[36]唐修义,黄文辉等著.煤中微量元素.北京：商务印书馆,2004
[37]刘飞燕,朱志敏,沈冰.我国煤中微量元素的赋存及开发利用.资源开发与市场,2006,22(5)：467-468
[38]张爱云,翁成敏.黑色页岩型钒矿提钒的主导矿物.地球科学-中国地质大学学报,1989,14(4)：391-397
[39]董建华,杨芝兰,冯冀燕.石煤钒矿提精五氧化二钒的研究.西安冶金建筑学院学报,1993,25(3)：105-110
[40]江嘉济,许国镇,黄文英.含钒石煤的穆斯堡尔谱研究.现代地质,1991,5(2)：192—200
[41]任世觉.工业矿产资源开发利用手册.武汉：武汉工业大学出版社,1993：63.
[42]郑祥明,田学达,张小云等.湿法提取石煤中钒的新工艺研究.湘潭大学自然科学学报,2003,25(1)：43-45
[43]潘勇,于吉顺,吴红丹.石煤提钒的工艺评价.矿业快报,2007,(4)：10-13
[44]许国镇,王锐兵.八都、浙川石煤烧结、包裹与钒转化的研究.稀有金属,1994,18(6)：422-427
[45]Babu M N,Sahu K K, Pandey B D.Zinc recovery fromsphalerite concentrate by direct oxidative leaching with ammonium,sodium and potassium persulphates.Hydrometallurgy,2002,64(2):119-129
[46]Masud A,Abdel-latif. Recovery of vanadium and nickel from petroleum flyash. Minerals Engineering,2002,(15):953-961
[47]杨显万、邱定番.湿法冶金.北京：冶金工业出版社,1998：158-159
[48]Be.,RMGS,汪镜亮.加压浸出的工业现状.四川有色金属,1992,(1)：21-23
[49]Dreis., D,汪镜亮.加压湿法冶金的研究和发展前景.四川有色金属,1992,(1)：19-20
[50]李旻廷,魏昶,樊刚.石煤氧压酸浸提钒探索试验研究.稀有金属,2007(31)：28-31
[51]魏昶,樊刚,李曼廷.含钒石煤氧压酸浸中影响钒浸出率的主要因素研究.稀有金属,2007,(31)：98-101
[52]黄可龙.无机化学.北京：科学出版社,2007
[53]申泮文等.无机化学丛书第八卷：钛分族、钒分族、铬分族.科学出版社,1998.9
[54]刘英俊等.元素地球化学.北京：科学出版社,1984
[55]Justyna Poledniok, Franciszek Buhl.Speciation of Vanadium in soil. Talanta, 59 (2003):1-8
[56]许国镇.石煤中钒的价态及物质组成对提钒工艺的指导作用.煤炭加工与综合利用,1989,(5)：5-8
[57]鲍超.石煤发电烟尘沸腾钠化焙烧提钒过程的分析.矿冶工程,1990,10(3)：40-44
[58]Gomez-Bueno C O, Spink D R, Rempel G L. Extraction of vanadium from Athabasca tar sands fly ash. Metallurgical Transactions B.1981,12(2):341-352
[59]Godard J B. Salt roasting of vanadium ores. Extra Metal Met Proc Symp. 1981,127:45
[60]Habib Shelwit, Moussa Alibrahim. Extraction of sulfur and vanadium from petroleum coke by means of salt-roasting treatment. Fuel,2006,85:878-880
[61]许国镇,张秀荣,尹光衡.江西玉山石煤烧结包裹与钒转化的研究.现代地质,1993,7(1)：109-117
[62]彭声歉,许国镇.石煤提钒中钠盐的作用.西南工学院学报,1998,13(1)：9-12
[63]马荣骏.湿法冶金原理.北京：冶金工业出版社,2007
[64]杨显万,何蔼平,袁宝州.高温水溶液热力学数据计算手册.北京：冶金工业出版社,1983
[65]李洪桂.湿法冶金学.长沙：中南大学出版社,2002
[66]林海玲,范必威,庾化龙等.石煤中影响钒转浸率的主要因素研究.成都理工学院学报,1999,26(3)：317-320
[67]Karen M S.The production of ultra clean coal by sequential leaching with R1 followed by HNO3.Fuel,2003,82(15/17):1917-1920
[68]A.Bhatnagar,Ashwani Kumar Minocha,Deepak Pudasainee,etal.Vanadium removal from water by waste metal sludge and cement immobilization.Chemical Engineering Journal,2008:1-8
[69]鲁兆伶.用酸法从石煤中提取五氧化二钒的试验研究与工业实践.湿法冶金,2002,21(4)：175-183
[70]Lucid M.F, Robertson W J, Bowerman P D. Simultaneous extraction and recovery of uranium and vanadium from wet process acid. USA,4,212,849. 1976-09-07
[71]罗彩英.石煤提钒新工艺研究.湖南冶金,1995,(4)：5-8
[72]Ramani Venugopalan,D.Sathiyamoorthy.Investigation through factorial design on novel method of preparing vanadium carbide using carbon during aluminothermic reduction. Journal of Materials Processing Technology,2006,(176):133-139
[73]向小艳,王明玉,肖连生等.石煤酸浸提钒工艺研究.稀有金属与硬质合金,2007,35(3)：10-13
[74]冯其明,何东升,张国范等.石煤提钒过程中钒氧化和转化对钒浸出的影响.中国有色金属学报,2007,17(8)：1348-1352
[75]Dongsheng He, Qiming Feng, Guofan Zhang,etal. An environmentally-friendly technology of vanadium extraction from stone coal. Minerals Engineering,2007,(20):1184-1186
[76]林建明,林松柏,吴季怀等.聚丙烯酸盐/绢云母超吸水性复合材料的表征.矿物学报,2003,23(1)：7-11
[77]印万忠,刘杰,韩跃新.富钾页岩提钾及机理研究.金属矿山,2007,(4)：34-38
[78]苏英,周永恒,黄武等.石英玻璃与R1酸反应动力学的研究.硅酸盐学报,2004,32(3)：287-293
[79]刘杰,印万忠,韩跃新.硫一氟混酸作用下富钾页岩提钾的机理研究.矿冶,2007,16(4)：17-21
[80]叶大伦.无机物热力学数据手册.北京：科学出版社,1985
[81]肖文丁.广西上林石煤的矿物学和湿法提钒研究.有色金属,2007,8(3)：85-90
[2]肖松文,梁经冬.钠化焙烧提钒机理研究的新进展.矿冶工程,1994,14(2)：53-55
[3]邹晓勇,欧阳玉祝,彭清静等.含钒石煤无盐焙烧酸浸生产五氧化二钒工艺的研究.化学世界,2001,(3)：117-119
[4]邓庆云,刘松英.石煤钠化焙烧、酸浸、离子交换提钒新工艺的试验研究.稀有金属与硬质合金,1993,(115)：27-33
[5]Oriol Font,Xavier Querol,Roberto Juan,etal.Recovery of gallium and vanadium from gasification fly ash. Journal of Hazardous Material A,2007,(139):413-423
[6]林海玲,范必威.方口山石煤提钒焙烧相变机理的研究.稀有金属,2001,25(4)：273—277
[7]沈喜恩.上饶八都石煤直接酸浸提钒工艺研究.江西煤炭科技,1997,(3)：57-59.
[8]曹建兵,欧阳玉祝,李志平等.石煤矿渣中钒浸取工艺条件研究.湖南城市学院学报,2005,14(4)：54-56
[9]许国镇,陈波珍,韩晓梅等.黄山石煤中钒价态及提钒技术研究.有色金属冶炼部分,1994(1)：32-35,41
[10]漆明鉴.从石煤中提钒现状及前景.湿法冶金,1999,(4)：1-10
[11]文喆.国内外钒资源与钒产品的市场前景分析.世界有色金属,2001,(11)：7-8
[12]LAN Yaozhong, LIU Jin. Review of vanadium processing inChina. Engineer Sciences,2005,3(3):58-62
[13]刘世友.钒的应用与展望.稀有金属与硬质合金,2000,(141)：58-61
[14]Russell J H, D C Collins, Rule A R. Vanadium roast-leach dissolution from western phosphate tailings.BuMines RI 8695,1982:19
[15]R.R. Moskalyk,A.M. Alfantazi.Processing of vanadium:a review.Minerals Engineering,2003,16:793-805
[16]蔡晋强,巴陵.石煤提钒的几种新工艺.矿产保护与利用,1993,(5)：30-33
[17]顾坚.石煤的综合利用和石煤提钒.能源政策研究通讯,1989,(3)：32-36
[18]段炼,田庆华,郭学益.我国钒资源的生产及应用研究进展.湖南有色金属,2006,22(6)：17-20
[19]刘世森.石煤提钒工艺评述.工程设计与研究,1993,(90)：12-16
[20]王永双,李国良.我国石煤提钒及综合利用综述.钒钛,1993,(4)：21-31
[21]赵天从,傅崇说,何福煦等.有色金属提取冶金手册稀有高熔点金属下.北京：冶金工业出版社,1999
[22]屈启龙,谢建宏,王冠甫.高碳钒矿综合回收石墨试验研究.矿业快报,2007,(4)：35-37
[23]Holloway P C, Etsell T H. Process for the complete utilization of oil sands fly ash.Canadian Metallurgical Quarterly,2005,45(1):25-32
[24]Perrine Chaurand,Jerome Rose,Jeremie Domas,etal.Speciation of Cr and V within BOF steel slag reused in road constructions.Journal of Geochemical Exploration,2006,(88):10-14
[25]孙玉宝,张金水.霍邱县石煤矿床地质特征及其开发利用前景初探.矿产保护与利用,2007,(2)：24-27
[26]黄道鑫.提钒炼钢.北京：冶金工业出版社,2000
[27]宾智勇.钒矿石无盐焙烧提取五氧化二钒试验.钢铁钒钛,2006,27(1)：21-26
[28]Ricardo E S,Marcos A B, Aline S F,etal. Non-volatile vanadium determination in petroleum condensate,diesel and gasoline prepared as detergent emulsions using GF AAS. Fuel,2008,(87):1617-1622
[29]WANG Mingyu,XIANG Xiaoyan,ZHANG Liping,etal. Effect of vanadium occurrence state on the choice of extracting vanadium technology from stone coal. Rare Metals,2008,27(2):112-115
[30]K.Muthu Karuppasamy,A.Subrahmanyam. The electrochromic and photocatalytic properties of electron beamevaporated vanadium-doped tungsten oxide thin films.Solar Energy Materials & Solar Cells,2008,(92):1322-1326
[31]彭声歉,侯兰杰,刘福生.四川广旺石煤提钒焙烧过程中钒价态的变化.中国矿业,1999,8(1)：69-72
[32]范必威,林海玲.方山口石煤提钒焙烧工艺研究. 湿法冶金,2001,20(2)：79-83
[33]蔡世民,彭声歉,侯兰杰.四川广旺地区石煤资源开发利用研究.矿产综合利用,1998,(4)：44-47
[34]范德廉.中国的黑色页岩及其有关矿床.北京：科学出版社,2004
[35]陈友善.钒钛矿冶金化学物相分析.成都：四川人民出版社,1982
[36]唐修义,黄文辉等著.煤中微量元素.北京：商务印书馆,2004
[37]刘飞燕,朱志敏,沈冰.我国煤中微量元素的赋存及开发利用.资源开发与市场,2006,22(5)：467-468
[38]张爱云,翁成敏.黑色页岩型钒矿提钒的主导矿物.地球科学-中国地质大学学报,1989,14(4)：391-397
[39]董建华,杨芝兰,冯冀燕.石煤钒矿提精五氧化二钒的研究.西安冶金建筑学院学报,1993,25(3)：105-110
[40]江嘉济,许国镇,黄文英.含钒石煤的穆斯堡尔谱研究.现代地质,1991,5(2)：192—200
[41]任世觉.工业矿产资源开发利用手册.武汉：武汉工业大学出版社,1993：63.
[42]郑祥明,田学达,张小云等.湿法提取石煤中钒的新工艺研究.湘潭大学自然科学学报,2003,25(1)：43-45
[43]潘勇,于吉顺,吴红丹.石煤提钒的工艺评价.矿业快报,2007,(4)：10-13
[44]许国镇,王锐兵.八都、浙川石煤烧结、包裹与钒转化的研究.稀有金属,1994,18(6)：422-427
[45]Babu M N,Sahu K K, Pandey B D.Zinc recovery fromsphalerite concentrate by direct oxidative leaching with ammonium,sodium and potassium persulphates.Hydrometallurgy,2002,64(2):119-129
[46]Masud A,Abdel-latif. Recovery of vanadium and nickel from petroleum flyash. Minerals Engineering,2002,(15):953-961
[47]杨显万、邱定番.湿法冶金.北京：冶金工业出版社,1998：158-159
[48]Be.,RMGS,汪镜亮.加压浸出的工业现状.四川有色金属,1992,(1)：21-23
[49]Dreis., D,汪镜亮.加压湿法冶金的研究和发展前景.四川有色金属,1992,(1)：19-20
[50]李旻廷,魏昶,樊刚.石煤氧压酸浸提钒探索试验研究.稀有金属,2007(31)：28-31
[51]魏昶,樊刚,李曼廷.含钒石煤氧压酸浸中影响钒浸出率的主要因素研究.稀有金属,2007,(31)：98-101
[52]黄可龙.无机化学.北京：科学出版社,2007
[53]申泮文等.无机化学丛书第八卷：钛分族、钒分族、铬分族.科学出版社,1998.9
[54]刘英俊等.元素地球化学.北京：科学出版社,1984
[55]Justyna Poledniok, Franciszek Buhl.Speciation of Vanadium in soil. Talanta, 59 (2003):1-8
[56]许国镇.石煤中钒的价态及物质组成对提钒工艺的指导作用.煤炭加工与综合利用,1989,(5)：5-8
[57]鲍超.石煤发电烟尘沸腾钠化焙烧提钒过程的分析.矿冶工程,1990,10(3)：40-44
[58]Gomez-Bueno C O, Spink D R, Rempel G L. Extraction of vanadium from Athabasca tar sands fly ash. Metallurgical Transactions B.1981,12(2):341-352
[59]Godard J B. Salt roasting of vanadium ores. Extra Metal Met Proc Symp. 1981,127:45
[60]Habib Shelwit, Moussa Alibrahim. Extraction of sulfur and vanadium from petroleum coke by means of salt-roasting treatment. Fuel,2006,85:878-880
[61]许国镇,张秀荣,尹光衡.江西玉山石煤烧结包裹与钒转化的研究.现代地质,1993,7(1)：109-117
[62]彭声歉,许国镇.石煤提钒中钠盐的作用.西南工学院学报,1998,13(1)：9-12
[63]马荣骏.湿法冶金原理.北京：冶金工业出版社,2007
[64]杨显万,何蔼平,袁宝州.高温水溶液热力学数据计算手册.北京：冶金工业出版社,1983
[65]李洪桂.湿法冶金学.长沙：中南大学出版社,2002
[66]林海玲,范必威,庾化龙等.石煤中影响钒转浸率的主要因素研究.成都理工学院学报,1999,26(3)：317-320
[67]Karen M S.The production of ultra clean coal by sequential leaching with R1 followed by HNO3.Fuel,2003,82(15/17):1917-1920
[68]A.Bhatnagar,Ashwani Kumar Minocha,Deepak Pudasainee,etal.Vanadium removal from water by waste metal sludge and cement immobilization.Chemical Engineering Journal,2008:1-8
[69]鲁兆伶.用酸法从石煤中提取五氧化二钒的试验研究与工业实践.湿法冶金,2002,21(4)：175-183
[70]Lucid M.F, Robertson W J, Bowerman P D. Simultaneous extraction and recovery of uranium and vanadium from wet process acid. USA,4,212,849. 1976-09-07
[71]罗彩英.石煤提钒新工艺研究.湖南冶金,1995,(4)：5-8
[72]Ramani Venugopalan,D.Sathiyamoorthy.Investigation through factorial design on novel method of preparing vanadium carbide using carbon during aluminothermic reduction. Journal of Materials Processing Technology,2006,(176):133-139
[73]向小艳,王明玉,肖连生等.石煤酸浸提钒工艺研究.稀有金属与硬质合金,2007,35(3)：10-13
[74]冯其明,何东升,张国范等.石煤提钒过程中钒氧化和转化对钒浸出的影响.中国有色金属学报,2007,17(8)：1348-1352
[75]Dongsheng He, Qiming Feng, Guofan Zhang,etal. An environmentally-friendly technology of vanadium extraction from stone coal. Minerals Engineering,2007,(20):1184-1186
[76]林建明,林松柏,吴季怀等.聚丙烯酸盐/绢云母超吸水性复合材料的表征.矿物学报,2003,23(1)：7-11
[77]印万忠,刘杰,韩跃新.富钾页岩提钾及机理研究.金属矿山,2007,(4)：34-38
[78]苏英,周永恒,黄武等.石英玻璃与R1酸反应动力学的研究.硅酸盐学报,2004,32(3)：287-293
[79]刘杰,印万忠,韩跃新.硫一氟混酸作用下富钾页岩提钾的机理研究.矿冶,2007,16(4)：17-21
[80]叶大伦.无机物热力学数据手册.北京：科学出版社,1985
[81]肖文丁.广西上林石煤的矿物学和湿法提钒研究.有色金属,2007,8(3)：85-90