青海昆特依盐湖杂卤石矿焙烧过程的矿物学特征研究
|
摘要
以柴达木盆地昆特依盐湖大盐滩矿区杂卤石矿为原料,在300℃~500℃温区内进行杂卤石的焙烧,利用XRD表征焙烧前后矿物特征。结果表明:(1)杂卤石矿样焙烧后重量损失约0.41g,与杂卤石中两个结构水重量0.43g相当,表明在此温区内杂卤石结构破坏而使结构水脱除所致;(2)杂卤石矿样焙烧后,杂卤石中CaSO_4组分主要以硬石膏形式存在,K_2SO_4和MgSO_4组分以无水钾镁矾形式存在,两种矿物XRD特征峰非常明显;(3)随着焙烧温度的增加,焙烧产物中硬石膏和无水钾镁矾XRD特征峰强度随之变强,说明两种矿物含量增加,尤其在450℃和500℃时无水钾镁矾XRD特征峰最强;(4)杂卤石矿样中石英、云母、钠长石等硅酸盐矿物XRD特征峰强度不变,说明它们对杂卤石的热解无影响。经90℃热水浸取焙烧产物后发现,350℃~500℃温区内杂卤石矿样焙烧热浸后K收率皆大于95%,K离子含量皆大于43g/L,且随着焙烧温度的增加,溶浸液中K,Mg,SO_4离子含量和K收率随之增加,与无水钾镁矾XRD特征峰变化趋势一致,表明从杂卤石中提取价值元素K,Mg,SO_4等时,杂卤石结构破坏是非常重要的环节。
Mineralogy of the calcination processes of polyhalite ore from Kunteyi salt lake in Qinghai was studied by X-ray diffraction in order to investigate its thermal behavior,with a calcination experiment of at 300 ℃to 500 ℃.The obtained XRD data after roasting showed that(1)the weight changes after and before roasting raw polyhalite ore is about 0.41 g,equal to the weight of two structural water in polyhalite,indicating that the structure water is removed due to structural damage of polyhalite;(2)the component of CaSO_4 in polyhalite is in the form of anhydrite,the components of K_2 SO_4 and MgSO_4 in polyhalite are in the form of langbeinite,with obvious X-ray diffraction intensity;(3)the contents of anhydrite and langbeinite in roasting products increases with increase of calcination temperature,and its X-ray diffraction intensity increase with temperature(especially at 450 ℃ and 500 ℃),indicating serious destruction of structure;(4)the X-ray diffraction intensity of quartz,muscovite and albite in roasting products is invariable,indication of its invalid for thermal decomposition of polyhalite.After calcination,the calcinated products were leached by 90 ℃ hot water,and the result showed that(1)the K,Mg,SO_4 concentrations increase with the increase of calcination temperature(K concentration > 43 g/L);(2)K yield of leaching liquor increases with the increase of calcination temperature,and K yield exceeds95%;(3)the changes of K,Mg,SO_4 concentrations are consistent with above mentioned X-ray diffraction data of langbeinite;(4)the structural damage of polyhalite is very important to extract its value elements of K,Mg and SO_4.
Mineralogy of the calcination processes of polyhalite ore from Kunteyi salt lake in Qinghai was studied by X-ray diffraction in order to investigate its thermal behavior,with a calcination experiment of at 300 ℃to 500 ℃.The obtained XRD data after roasting showed that(1)the weight changes after and before roasting raw polyhalite ore is about 0.41 g,equal to the weight of two structural water in polyhalite,indicating that the structure water is removed due to structural damage of polyhalite;(2)the component of CaSO_4 in polyhalite is in the form of anhydrite,the components of K_2 SO_4 and MgSO_4 in polyhalite are in the form of langbeinite,with obvious X-ray diffraction intensity;(3)the contents of anhydrite and langbeinite in roasting products increases with increase of calcination temperature,and its X-ray diffraction intensity increase with temperature(especially at 450 ℃ and 500 ℃),indicating serious destruction of structure;(4)the X-ray diffraction intensity of quartz,muscovite and albite in roasting products is invariable,indication of its invalid for thermal decomposition of polyhalite.After calcination,the calcinated products were leached by 90 ℃ hot water,and the result showed that(1)the K,Mg,SO_4 concentrations increase with the increase of calcination temperature(K concentration > 43 g/L);(2)K yield of leaching liquor increases with the increase of calcination temperature,and K yield exceeds95%;(3)the changes of K,Mg,SO_4 concentrations are consistent with above mentioned X-ray diffraction data of langbeinite;(4)the structural damage of polyhalite is very important to extract its value elements of K,Mg and SO_4.
引文
[1]黎春阁,安连英,汪本高.杂卤石生产硫酸钾工艺研究[J].化工矿物与加工,2013,(7):4-7.
[2]高文远,冯文平,汤建良,等.杂卤石综合利用研究进展[J].盐业与化工,2016,45(5):9-13.
[3]Philippe F W,Eunja K,Carlos F,et al.First-principles study of anhydrite,polyhalite and carnallite[J].Chemical Physic Letters,2014,594:1-5.
[4]Guo X,Xu H.Enthalpies of formation of polyhalite:a mineal relevant to salt repositoty[J].The Journal of Chemical Thermodynamics,2017,114:44-47.
[5]Schoch E P.Ptassium sulfate from polyhalite[J].Industrial and Engineering Chemistry,1935,27(4):467-473.
[6]Yavorskii V T,Blazhivskii K I,Perekupko T V,et al.Acid decomposition of difficulty soluble potassium ores with the use of organic solvents[J].Russian Journal of Applied Chemistry,2009,82(5):767-771.
[7]金锋.国外杂卤石资源开发利用对我国的启示[J].化工矿山技术,1989,18(3):31-34.
[8]安连英,刘宁,殷辉安,等.杂卤石矿地浸模拟实验研究[J].矿物岩石,2007,27(2):112-115.
[9]刘晓元,安连英,冯振华.杂卤石制备硫酸钾工艺研究[J].当代化工,2011,40(12):1 221-1 223.
[10]郝丽芳,安连英,王永刚,等.杂卤石矿石可浸性试验研究[J].矿冶工程,2005,25(4):16-19.
[11]安莲英,殷辉安,唐明林.溶浸开采深埋藏杂卤石可行性及溶浸动力学模拟[J].地质学报,2010,84(11):1 690-1 696.
[12]唐明林,汪蓉.我国深部杂卤石中钾的利用途径研究[J].矿产综合利用,1997,(3):31-34.
[13]郝丽芳,安连英,殷辉安,等.用生物浸矿技术从杂卤石矿中提取钾的可行性分析[J].湿法冶金,2003,22(1):19-21.
[14]刘仲敏,曹友声.钾细菌及其在农业生产上的应用[J].河南农业科学,1993,(5):22-23.
[15]刘成林,王弭力,焦鹏程,等.世界主要古代钾盐找矿实践与中国找钾对策[J].化工矿产地质,2006,28(1):1-8.
[16]陈静.印度从杂卤石中提取钾盐[J].化工矿山技术,1997,26(1):11,52.
[17]王弭力.Q凹陷杂卤石的地质意义[J].地质论评,1982,28(1):28-37.
[18]黄宣镇.中国首例杂卤石矿床[J].云南地质,1996,15(1):52-60.
[19]张志宏,马艳芳,付振海,等.从杂卤石矿中静态溶浸提取钾及制备硫酸钾的方法[P].CN103397201A.
[20]都永生,高东林,山发寿,等.杂卤石开采方法[P].CN104847358A.
[21]刘铸,高东林,李斌凯,等.柴达木盆地昆特依盐湖大盐滩矿区杂卤石沉积特征及成因浅论[J].盐湖研究,2015,23(1):30-37.
[22]朱洪发,刘翠章,林付律.四川盆地中下三叠系含盐系岩石类型的成因和沉积相特征[J].矿物岩石,1986,6(3):76-86.
[23]廖林志,黄馥华,刘铅超,等.川东农乐石膏-硬石膏矿床中的杂卤石[J].矿物岩石,1984,(1):94-100.
[24]杨笃春,尹玲,马强,等.杂卤石(钾盐)粉体的制备及稳定性研究[J].济宁学院学报,2015,36(3):58-60.
[25]Fischer S,Voigt W,K9hnke K.The thermal decomposition of polyhalite[J].Crystal Research and Technology,1996,31:87-92.
[26]Jordan A B,Boukhalfa H,Caporuscio F A,et al.Hydrous Mineral Dehydration Around Heat-Generating Nuclear Waste in Bedded Salt Formations[J].Environmental Science and Technology,2015,49(11):6 783-6 790.
[27]Nathans M W.The Dehydration of polyhalite[J].The Journal of Physical Chemistry,1963,67(6):1 248-1 249.
[28]Bindi L.Reinvestigation of polyhalite,K2Ca2Mg(SO4)4·2H2O[J].Acta Crystallographica Section E,2005,61(8):i135-i136.
[29]Wollmann G,Freyer D,Voigt W.Polyhalite and its analogous triple salts[J].Monatshefte für Chemie,2008,139:739-745.
[30]Xu H,Guo X,Bai J.Thermal behavior of polyhalite:a high-temperature synchrotron XRD study[J].Physics and Chemistry of Minerals,2017,44:125-135.
[31]安连英,殷辉安,唐明林,等.杂卤石溶解性能的测定[J].矿物岩石,2004,24(4):108-110.
[2]高文远,冯文平,汤建良,等.杂卤石综合利用研究进展[J].盐业与化工,2016,45(5):9-13.
[3]Philippe F W,Eunja K,Carlos F,et al.First-principles study of anhydrite,polyhalite and carnallite[J].Chemical Physic Letters,2014,594:1-5.
[4]Guo X,Xu H.Enthalpies of formation of polyhalite:a mineal relevant to salt repositoty[J].The Journal of Chemical Thermodynamics,2017,114:44-47.
[5]Schoch E P.Ptassium sulfate from polyhalite[J].Industrial and Engineering Chemistry,1935,27(4):467-473.
[6]Yavorskii V T,Blazhivskii K I,Perekupko T V,et al.Acid decomposition of difficulty soluble potassium ores with the use of organic solvents[J].Russian Journal of Applied Chemistry,2009,82(5):767-771.
[7]金锋.国外杂卤石资源开发利用对我国的启示[J].化工矿山技术,1989,18(3):31-34.
[8]安连英,刘宁,殷辉安,等.杂卤石矿地浸模拟实验研究[J].矿物岩石,2007,27(2):112-115.
[9]刘晓元,安连英,冯振华.杂卤石制备硫酸钾工艺研究[J].当代化工,2011,40(12):1 221-1 223.
[10]郝丽芳,安连英,王永刚,等.杂卤石矿石可浸性试验研究[J].矿冶工程,2005,25(4):16-19.
[11]安莲英,殷辉安,唐明林.溶浸开采深埋藏杂卤石可行性及溶浸动力学模拟[J].地质学报,2010,84(11):1 690-1 696.
[12]唐明林,汪蓉.我国深部杂卤石中钾的利用途径研究[J].矿产综合利用,1997,(3):31-34.
[13]郝丽芳,安连英,殷辉安,等.用生物浸矿技术从杂卤石矿中提取钾的可行性分析[J].湿法冶金,2003,22(1):19-21.
[14]刘仲敏,曹友声.钾细菌及其在农业生产上的应用[J].河南农业科学,1993,(5):22-23.
[15]刘成林,王弭力,焦鹏程,等.世界主要古代钾盐找矿实践与中国找钾对策[J].化工矿产地质,2006,28(1):1-8.
[16]陈静.印度从杂卤石中提取钾盐[J].化工矿山技术,1997,26(1):11,52.
[17]王弭力.Q凹陷杂卤石的地质意义[J].地质论评,1982,28(1):28-37.
[18]黄宣镇.中国首例杂卤石矿床[J].云南地质,1996,15(1):52-60.
[19]张志宏,马艳芳,付振海,等.从杂卤石矿中静态溶浸提取钾及制备硫酸钾的方法[P].CN103397201A.
[20]都永生,高东林,山发寿,等.杂卤石开采方法[P].CN104847358A.
[21]刘铸,高东林,李斌凯,等.柴达木盆地昆特依盐湖大盐滩矿区杂卤石沉积特征及成因浅论[J].盐湖研究,2015,23(1):30-37.
[22]朱洪发,刘翠章,林付律.四川盆地中下三叠系含盐系岩石类型的成因和沉积相特征[J].矿物岩石,1986,6(3):76-86.
[23]廖林志,黄馥华,刘铅超,等.川东农乐石膏-硬石膏矿床中的杂卤石[J].矿物岩石,1984,(1):94-100.
[24]杨笃春,尹玲,马强,等.杂卤石(钾盐)粉体的制备及稳定性研究[J].济宁学院学报,2015,36(3):58-60.
[25]Fischer S,Voigt W,K9hnke K.The thermal decomposition of polyhalite[J].Crystal Research and Technology,1996,31:87-92.
[26]Jordan A B,Boukhalfa H,Caporuscio F A,et al.Hydrous Mineral Dehydration Around Heat-Generating Nuclear Waste in Bedded Salt Formations[J].Environmental Science and Technology,2015,49(11):6 783-6 790.
[27]Nathans M W.The Dehydration of polyhalite[J].The Journal of Physical Chemistry,1963,67(6):1 248-1 249.
[28]Bindi L.Reinvestigation of polyhalite,K2Ca2Mg(SO4)4·2H2O[J].Acta Crystallographica Section E,2005,61(8):i135-i136.
[29]Wollmann G,Freyer D,Voigt W.Polyhalite and its analogous triple salts[J].Monatshefte für Chemie,2008,139:739-745.
[30]Xu H,Guo X,Bai J.Thermal behavior of polyhalite:a high-temperature synchrotron XRD study[J].Physics and Chemistry of Minerals,2017,44:125-135.
[31]安连英,殷辉安,唐明林,等.杂卤石溶解性能的测定[J].矿物岩石,2004,24(4):108-110.