页岩焙烧提钒过程中钾物相转化研究
|
摘要
针对含钒页岩中钾元素利用率较低的问题,分析并研究钠盐焙烧提钒时钾物相转化过程及钒钾同步提取特征。研究结果表明:焙烧时含钒页岩中白云母及伊利石相转化为多元素熔融态颗粒;NaCl和Na2SO4与其中钾离子交换,使部分钾参与生成水溶性钾盐,部分随钠长石自颗粒中析出;Na_2CO_3使矿物颗粒与石英共熔,钾钠间离子交换受抑制,钾长石相析出,抑制水溶性钾盐生成;在750～800℃范围内焙烧,钠离子与钾离子和钒离子的交换及结合反应同步进行,钒钾共同提取过程效率较高;使用NaCl作为焙烧添加剂时,钒酸盐生成速率大于水溶性钾盐生成速率,当NaCl质量分数大于8%时,钾盐生成速率快速增大;在Na_2SO_4作用下钾盐生成速率略高于钒酸盐生成速率,两反应速率差随Na2SO4质量分数提高逐渐增大;当Na2CO3质量分数低于6%时,促进钒酸盐生成但影响钾浸出效果,若Na_2CO_3质量分数增加(高于6%),则阻碍矿石中离子交换过程,并不利于钒钾的共同提取。
In view of the problem of low utilization of potassium in vanadium-containing siliceous shale, the feature of simultaneous extraction of potassium and vanadium and the process of phase transformation of potassium were analyzed.The results show that the mica of siliceous shale containing vanadium transforms into the molten particle containing different elements. NaCl and Na2 SO4 promote the generation of soluble potassium salt and the crystallization of albite from the molten particle. Na2 CO3 inhibits the ion exchange between potassium and sodium, and the production of soluble potassium salt. At 750-800 ℃, reactions of sodium ions with potassium ions and vanadium ions carry on simultaneously,and the efficiency of co-extraction process of vanadium and potassium is higher. When the additive is NaCl, the generation rate of vanadate is higher than that of the soluble potassium salt. When the mass fraction of NaCl is more than8%, the quantity of soluble potassium salt begins to increase rapidly. The increase rate of potassium salt is slightly higher than the rate of vanadate generation, and the difference between the two rates increases with the increase of mass fraction of Na2 SO4.Na2 CO3 is not suitable for co-extraction of vanadium and potassium because of its obstruction to the ion exchange process when the mass fraction of dosage is more than 6%.
In view of the problem of low utilization of potassium in vanadium-containing siliceous shale, the feature of simultaneous extraction of potassium and vanadium and the process of phase transformation of potassium were analyzed.The results show that the mica of siliceous shale containing vanadium transforms into the molten particle containing different elements. NaCl and Na2 SO4 promote the generation of soluble potassium salt and the crystallization of albite from the molten particle. Na2 CO3 inhibits the ion exchange between potassium and sodium, and the production of soluble potassium salt. At 750-800 ℃, reactions of sodium ions with potassium ions and vanadium ions carry on simultaneously,and the efficiency of co-extraction process of vanadium and potassium is higher. When the additive is NaCl, the generation rate of vanadate is higher than that of the soluble potassium salt. When the mass fraction of NaCl is more than8%, the quantity of soluble potassium salt begins to increase rapidly. The increase rate of potassium salt is slightly higher than the rate of vanadate generation, and the difference between the two rates increases with the increase of mass fraction of Na2 SO4.Na2 CO3 is not suitable for co-extraction of vanadium and potassium because of its obstruction to the ion exchange process when the mass fraction of dosage is more than 6%.
引文
[1]陈明辉,胡祥昭,孙际茂,等.湖南省寒武系黑色岩系页岩型钒矿概论[J].地质找矿论丛,2012,27(4):410-420.CHEN Minghui,HU Xiangzhao,SUN Jimao,et al.Overview on the Cambrian black shale-hosted vanadium deposit in Hunan[J].Contributions to Geology and Mineral Resources Research,2012,27(4):410-420.
[2]LIU Chun,ZHANG Yimin,BAO Shenxu.Vanadium recovery from stone coal through roasting and flotation[J].Transactions of Nonferrous Metals Society of China,2017,27(1):197-203.
[3]叶国华,张爽,何伟,等.石煤的工艺矿物学特性及其与提钒的关系[J].稀有金属,2014,38(1):146-157.YE Guohua,ZHANG Shuang,HE Wei,et al.Process mineralogy characteristics of stone coal and its relationship to vanadium extraction[J].Chinese Journal of Rare Metals,2014,38(1):146-157.
[4]WANG Li,SUN Wei,ZHANG Qingpeng.Recovery of vanadium and carbon from low-grade stone coal by flotation[J].Transactions of Nonferrous Metals Society of China,2015,25(11):3767-3773.
[5]匡洪生,颜文斌,华骏,等.利用石煤提钒酸浸渣烧制硅酸盐水泥熟料的研究[J].硅酸盐通报,2015,34(4):1078-1083.KUANG Hongsheng,YAN Wenbin,HUA Jun,et al.Study on calcination of cement clinker by stone coal acid-leaching vanadium slag[J].Bulletin of the Chinese Ceramic Society,2015,34(4):1078-1083.
[6]张国范,闫继武,刘琨,等.石煤烧渣中硅、钒的高效分步提取[J].煤炭学报,2013,38(1):150-155.ZHANG Guofan,YAN Jiwu,LIU Kun,et al.Efficient step-by-step extraction of vanadium and silicon from stone coal cinder[J].Journal of China Coal Society,2013,38(1):150-155.
[7]MA Yiqian,WANG Xuewen,WANG Mingyu,et al.Separation of V(Ⅳ)and Fe(Ⅲ)from the acid leach solution of stone coal by D2EHPA/TBP[J].Hydrometallurgy,2015,153(3):38-45.
[8]印万忠,刘杰,韩跃新.富钾页岩提钾及机理研究[J].金属矿山,2007,37(4):34-38.YIN Wanzhong,LIU Jie,HAN Yuexin.Research of extracting potassium from potassium-rich shale and its mechanisms[J].Metal Mine,2007,37(4):34-38.
[9]JENA S K,DHAWAN N,RATH S S,et al.Investigation of microwave roasting for potash extraction from nepheline syenite[J].Separation and Purification Technology,2016,161(3):104-111.
[10]李紫谦,黄志良,孟鹏,等.氧化法从水云母中提钾及其机理[J].武汉工程大学学报,2015,37(9):40-44.LI Ziqian,HUANG Zhiliang,MENG Peng,et al.Extracting potassium from hydro-mica by oxidation method and its mechanism[J].Journal of Wuhan Institute of Technology,2015,37(9):40-44.
[11]蒋谋锋,张一敏,包申旭,等.含钒石煤钒钾镁硫酸浸出相关性研究[J].有色金属(冶炼部分),2014(11):34-38.JIANG Moufeng,ZHANG Yimin,BAO Shenxu,et al.Relevant research on sulfuric acid leaching of V,K and Mg from vanadium-bearing stone coal[J].Nonferrous Metals(Extractive Metallurgy),2014(11):34-38.
[12]KRZYSZTOF M.Recovery of vanadium,potassium and iron from a spent vanadium catalyst by oxalic acid solution leaching,precipitation and ion exchange processes[J].Hydrometallurgy,2013,134/135(3):26-31.
[13]陈亮.从钒浸出液中沉淀结晶型钒酸铁试验研究[J].湿法冶金,2010,29(3):171-175.CHEN Liang.Study on precipitation of crystal-forming fervanite from vanadium leaching solution[J].Hydrometallurgy of China,2010,29(3):171-175.
[14]阳亚玲,颜文斌,华骏,等.含钒浸出液除硅试验研究[J].非金属矿,2015,38(2):8-10.YANG Yaling,YAN Wenbin,HUA Jun,et al.Silicon removal from vanadium leaching solution[J].Non-Metallic Mines,2015,38(2):8-10.
[15]ZHAO Yunliang,ZHANG Yimin,BAO Shenxu,et al.Calculation of mineral phase and liquid phase formation temperature during roasting of vanadium-bearing stone coal using FactSage software[J].International Journal of Mineral Processing,2013,124(11):150-153.
[16]HAN Yuexin,LIU Jie,YIN Wanzhong.Research on the mechanism of the dissociation of potassium shale during roasting[J].Advanced Materials Research,2009,58(1):155-162.
[17]MENG Peng,HUANG Zhiliang,LI Ziqian,et al.Conditions and mechanism for extracting potassium from muscovite in potassium-bearing shale by the barium ion-exchange method[J].International Journal of Mineral Processing,2015,142(12):107-112.
[18]MIECZYS L T,KATARZYNA B L,KRZYSZTOF M.Investigations on the synthesis of KVO3 and Cl2 from KCl and V2O5 in the presence of oxygen[J].Chemical Engineering Science,2004,59(6):1241-1246.
[19]ZHANG Yimin,ZHU Xiaobo,LIU Tao,et al.Effect of colloidal potassium alum formation on vanadium recovery from acid leach solutions of stone coal[J].Hydrometallurgy,2013,138(6):54-58.
[20]HU Yangjia,ZHANG Yimin,BAO Shenxu,et al.Effects of the mineral phase and valence of vanadium on vanadium extraction from stone coal[J].International Journal of Minerals,Metallurgy and Materials,2012,19(10):893-898.
[21]林利,安莲英,刘世容.绢云母的焙烧提钾实验研究[J].化工矿物与加工,2012,41(2):12-15.LIN Li,AN Lianying,LIU Shirong.Study on extracting potassium from sericite by roasting[J].Industrial Minerals and Processing,2012,41(2):12-15.
[22]YAN Qunxuan,LI Xinhai,WANG Zhixing,et al.Extraction of lithium from lepidolite using chlorination roasting-water leaching process[J].Transactions of Nonferrous Metals Society of China,2012,22(7):1753-1759.
[23]颜群轩.锂云母中有价金属的高效提取研究[D].长沙:中南大学冶金科学与工程学院,2012:64-69.YAN Qunxuan.Extraction of valuable metals from lepidolite[D].Changsha:Central South University.School of Metalluragy Science and Engineering,2012:64-69.
[24]JI Yilong,SHEN Shaobo,LIU Jianhua,et al.Cleaner and effective process for extracting vanadium from vanadium slag by using an innovative three-phase roasting reaction[J].Journal of Cleaner Production,2017,149(8):1068-1078.
[25]陆岷,张一敏,刘涛,等.石煤提钒钠化焙烧中烧结现象的研究[J].稀有金属,2009,33(6):894-897.LU Min,ZHANG Yimin,LIU Tao,et al.Sintering action of NaCl calcination during extracting vanadium from stone coal[J].Chinese Journal of Rare Metals,2009,33(6):894-897.
[2]LIU Chun,ZHANG Yimin,BAO Shenxu.Vanadium recovery from stone coal through roasting and flotation[J].Transactions of Nonferrous Metals Society of China,2017,27(1):197-203.
[3]叶国华,张爽,何伟,等.石煤的工艺矿物学特性及其与提钒的关系[J].稀有金属,2014,38(1):146-157.YE Guohua,ZHANG Shuang,HE Wei,et al.Process mineralogy characteristics of stone coal and its relationship to vanadium extraction[J].Chinese Journal of Rare Metals,2014,38(1):146-157.
[4]WANG Li,SUN Wei,ZHANG Qingpeng.Recovery of vanadium and carbon from low-grade stone coal by flotation[J].Transactions of Nonferrous Metals Society of China,2015,25(11):3767-3773.
[5]匡洪生,颜文斌,华骏,等.利用石煤提钒酸浸渣烧制硅酸盐水泥熟料的研究[J].硅酸盐通报,2015,34(4):1078-1083.KUANG Hongsheng,YAN Wenbin,HUA Jun,et al.Study on calcination of cement clinker by stone coal acid-leaching vanadium slag[J].Bulletin of the Chinese Ceramic Society,2015,34(4):1078-1083.
[6]张国范,闫继武,刘琨,等.石煤烧渣中硅、钒的高效分步提取[J].煤炭学报,2013,38(1):150-155.ZHANG Guofan,YAN Jiwu,LIU Kun,et al.Efficient step-by-step extraction of vanadium and silicon from stone coal cinder[J].Journal of China Coal Society,2013,38(1):150-155.
[7]MA Yiqian,WANG Xuewen,WANG Mingyu,et al.Separation of V(Ⅳ)and Fe(Ⅲ)from the acid leach solution of stone coal by D2EHPA/TBP[J].Hydrometallurgy,2015,153(3):38-45.
[8]印万忠,刘杰,韩跃新.富钾页岩提钾及机理研究[J].金属矿山,2007,37(4):34-38.YIN Wanzhong,LIU Jie,HAN Yuexin.Research of extracting potassium from potassium-rich shale and its mechanisms[J].Metal Mine,2007,37(4):34-38.
[9]JENA S K,DHAWAN N,RATH S S,et al.Investigation of microwave roasting for potash extraction from nepheline syenite[J].Separation and Purification Technology,2016,161(3):104-111.
[10]李紫谦,黄志良,孟鹏,等.氧化法从水云母中提钾及其机理[J].武汉工程大学学报,2015,37(9):40-44.LI Ziqian,HUANG Zhiliang,MENG Peng,et al.Extracting potassium from hydro-mica by oxidation method and its mechanism[J].Journal of Wuhan Institute of Technology,2015,37(9):40-44.
[11]蒋谋锋,张一敏,包申旭,等.含钒石煤钒钾镁硫酸浸出相关性研究[J].有色金属(冶炼部分),2014(11):34-38.JIANG Moufeng,ZHANG Yimin,BAO Shenxu,et al.Relevant research on sulfuric acid leaching of V,K and Mg from vanadium-bearing stone coal[J].Nonferrous Metals(Extractive Metallurgy),2014(11):34-38.
[12]KRZYSZTOF M.Recovery of vanadium,potassium and iron from a spent vanadium catalyst by oxalic acid solution leaching,precipitation and ion exchange processes[J].Hydrometallurgy,2013,134/135(3):26-31.
[13]陈亮.从钒浸出液中沉淀结晶型钒酸铁试验研究[J].湿法冶金,2010,29(3):171-175.CHEN Liang.Study on precipitation of crystal-forming fervanite from vanadium leaching solution[J].Hydrometallurgy of China,2010,29(3):171-175.
[14]阳亚玲,颜文斌,华骏,等.含钒浸出液除硅试验研究[J].非金属矿,2015,38(2):8-10.YANG Yaling,YAN Wenbin,HUA Jun,et al.Silicon removal from vanadium leaching solution[J].Non-Metallic Mines,2015,38(2):8-10.
[15]ZHAO Yunliang,ZHANG Yimin,BAO Shenxu,et al.Calculation of mineral phase and liquid phase formation temperature during roasting of vanadium-bearing stone coal using FactSage software[J].International Journal of Mineral Processing,2013,124(11):150-153.
[16]HAN Yuexin,LIU Jie,YIN Wanzhong.Research on the mechanism of the dissociation of potassium shale during roasting[J].Advanced Materials Research,2009,58(1):155-162.
[17]MENG Peng,HUANG Zhiliang,LI Ziqian,et al.Conditions and mechanism for extracting potassium from muscovite in potassium-bearing shale by the barium ion-exchange method[J].International Journal of Mineral Processing,2015,142(12):107-112.
[18]MIECZYS L T,KATARZYNA B L,KRZYSZTOF M.Investigations on the synthesis of KVO3 and Cl2 from KCl and V2O5 in the presence of oxygen[J].Chemical Engineering Science,2004,59(6):1241-1246.
[19]ZHANG Yimin,ZHU Xiaobo,LIU Tao,et al.Effect of colloidal potassium alum formation on vanadium recovery from acid leach solutions of stone coal[J].Hydrometallurgy,2013,138(6):54-58.
[20]HU Yangjia,ZHANG Yimin,BAO Shenxu,et al.Effects of the mineral phase and valence of vanadium on vanadium extraction from stone coal[J].International Journal of Minerals,Metallurgy and Materials,2012,19(10):893-898.
[21]林利,安莲英,刘世容.绢云母的焙烧提钾实验研究[J].化工矿物与加工,2012,41(2):12-15.LIN Li,AN Lianying,LIU Shirong.Study on extracting potassium from sericite by roasting[J].Industrial Minerals and Processing,2012,41(2):12-15.
[22]YAN Qunxuan,LI Xinhai,WANG Zhixing,et al.Extraction of lithium from lepidolite using chlorination roasting-water leaching process[J].Transactions of Nonferrous Metals Society of China,2012,22(7):1753-1759.
[23]颜群轩.锂云母中有价金属的高效提取研究[D].长沙:中南大学冶金科学与工程学院,2012:64-69.YAN Qunxuan.Extraction of valuable metals from lepidolite[D].Changsha:Central South University.School of Metalluragy Science and Engineering,2012:64-69.
[24]JI Yilong,SHEN Shaobo,LIU Jianhua,et al.Cleaner and effective process for extracting vanadium from vanadium slag by using an innovative three-phase roasting reaction[J].Journal of Cleaner Production,2017,149(8):1068-1078.
[25]陆岷,张一敏,刘涛,等.石煤提钒钠化焙烧中烧结现象的研究[J].稀有金属,2009,33(6):894-897.LU Min,ZHANG Yimin,LIU Tao,et al.Sintering action of NaCl calcination during extracting vanadium from stone coal[J].Chinese Journal of Rare Metals,2009,33(6):894-897.