Preparation of potassium chloride from K-feldspar with calcium chloride as additive agent: a review

doi:10.16085/j.issn.1000-6613.2016.12.031

Abstract

Abstract: The research history and current situations of preparation of potassium chloride from K-feldspar with calcium chloride as additive agent is reviewed in this paper. Utilizing the K-feldspar derived from Baoxing county of Sichuan province as raw material,we evaluated and compared two processes of high temperature activation K-feldspar to fix carbon and hydrothermal alkaline decomposition K-feldspar from the perspectives of reaction principle,resource consumption,energy consumption,environmental compatibility and products. The results showed that both processes are feasible in principle,but the resource consumption,energy consumption and CO₂ emission by calcination K-feldspar for carbon fixation process is 1.59 times,2.45 times and 4.10 times of those by hydrothermal alkaline method,respectively. The calcination K-feldspar for carbon fixation process produces KCl products as well as a large amount of hydrochloric acid and solid waste,while the hydrothermal alkaline method could completely transform the K₂O,Al₂O₃ and SiO₂ in K-feldspar of the ores into valuable products and thus maximize the utilization of K-feldspar resources,and minimize the consumption of relevant mineral resources. What's more,the calcination K-feldspar for carbon fixation process has low efficiency of carbon fixation,and the fixed carbon is even less than that discharged due to the energy consumption for fix carbon. Therefore,the calcination K-feldspar for carbon fixation process is still far from the practical engineering application.

Key words: calcium chloride, K-feldspar, potassium chloride, calcination K-feldspar for carbon fixation process, hydrothermal alkaline method

摘要： 概述了国内外以CaCl₂为助剂分解钾长石制备氯化钾的研究历史及现状。以四川宝兴钾长石资源为例，从工艺过程的反应原理、资源消耗、能量消耗、环境相容性和产品方案等方面，对比分析了CaCl₂高温活化钾长石矿化CO₂联产氯化钾工艺（高温固碳法）与水热碱法分解钾长石制取硫酸钾工艺（水热碱法）。结果表明，两种工艺分解钾长石在原理上均可行，但高温固碳法的资源消耗、能量消耗和CO₂排放量分别为水热碱法的1.59倍、2.45倍和4.10倍；高温固碳法除产品氯化钾外，需排放大量含氯化氢气体的有毒尾气及固碳尾渣，而水热碱法的副产品均为高附加值产品，三废排放接近于零。高温固碳法的固碳效率低，所固化CO₂仅相当于因固碳而消耗能量所排放CO₂总量的11.9%。因此，高温固碳技术距实际工程应用尚十分遥远。

关键词: 氯化钙, 钾长石, 氯化钾, 高温固碳法, 水热碱法

CLC Number:

TQ443.5

CHEN Jian, MA Hongwen, ZHANG Pan, LIU Meitang. Preparation of potassium chloride from K-feldspar with calcium chloride as additive agent: a review[J]. Chemical Industry and Engineering Progree, 2016, 35(12): 3954-3963.

陈建, 马鸿文, 张盼, 刘梅堂. 氯化钙助剂分解钾长石制备氯化钾研究评述[J]. 化工进展, 2016, 35(12): 3954-3963.

References

[1] 中国人民共和国国土资源部编.中国矿产资源报告-2015[M].北京:地质出版社,2015:4-7.
[2] U.S.Department of the Interior,U.S.Geological Survey.Mineral commodity summaries 2015[R].Washington D C,2015:122-123.
[3] 马鸿文,杨静,苏双青,等.富钾岩石制取钾盐研究20年:回顾与展望[J].地学前缘,2014,21:1-19.
[4] 顾汉念,王宁,杨永琼,等.不溶性含钾岩石制备钾肥研究现状与评述[J].化工进展,2011,30(11):2450-2553.
[5] BICKELL C.Process of treating feldspar for a manure:US16111[P].1856-10-25.
[6] CUSHMAN A S,COGGESHALL G W.The production of available potash from the natural silicates[J].The Journal of Industrial and Engineering Chemistry,2002.DOI:10.1021/ie50047a010.
[7] AUDEN C.Extracting of potassium salts from potassium-bearing minerals:US1334940[P].1920-03-23.
[8] 薛彦辉,宋超,杜树涛,等.氟化物在低温烧结钾长石中行为的研究[J].中国非金属矿工业导刊,2002(1):29-30.
[9] 沈礼善.钾长石、磷矿石联产KPO₃和白水泥[J].化工进展,1993,12(6):57.
[10] 柯亮,石林,耿曼.脱硫灰渣与钾长石混合焙烧制钾复合肥的研究[J].化工矿物与加工,2007(7):17-20.
[11] 石林.钾长石-石膏-石灰石热分解体系研究[J].矿物岩石,2007,27(4):1-7.
[12] 刘浩.假白榴正长岩-碳酸钠体系中温烧结反应及水热浸出实验[D].北京:中国地质大学,2008:1-62.
[13] 赵晶星,赵建海,孟娇,等.低温条件下微波对钾长石溶出性能影响的微观机理分析[J].化工进展,2016,35(1):34-39.
[14] BLACKMORE H S.Process of making alkali salts:US513001[P].1894-02-16.
[15] ROSS W H.The extraction of potash from silicate rocks I[R].United States Department of Agriculture,1912:1-10.
[16] ROSS W H.The extraction of potash from silicate rocks Ⅱ[J].The Journal of Industrial and Engineering Chemistry,1917:467-472.DOI:10.1021/ie50089a012.
[17] RODY J A.Treatment of feldspar,leucite and the like:US1151533[P].1915-08-24.
[18] GRAUEL A.Process for recovering potassium from potassium bearing silicates:US1289736[P].1918-12-31.
[19] GLAESER W.Method of treating potash bearing silicates:US1379914[P].1921-05-31.
[20] 国外从钾长石中提取钾盐和制造钾肥的研究概况[J].化工矿山技术,1973(s1):1-82.
[21] JENA S K,DHAWAN N,RAO D S,et al.Studies on extraction of potassium values from nepheline syenite[J].International Journal of Mineral Processing,2014,133:13-22.
[22] 张雪梅,姚日生,邓胜松.不同添加剂对钾长石晶体结构及钾熔出率的影响研究[J].非金属矿,2001,24(6):13-16.
[23] 韩效钊,姚卫棠,胡波,等.离子交换法从钾长石提钾[J].应用化学,2003,20(4):373-375.
[24] 彭清静,彭良斌,邹晓勇,等.氯化钙熔浸钾长石提钾过程的研究[J].高校化学工程学报,2003,17(2):185-189.
[25] 刘旻.阴离子对熔盐浸取法从钾长石中提钾的影响[J].矿产保护与利用,2005(4):36-37.
[26] 白云起,吕一波,白青子.熔盐浸取法从钾长石中提取钾的影响[J].中国矿业,2006(15):11-13.
[27] 刘文秋.从钾长石中提取钾的研究[J].长春师范学院学报(自然科学版),2007,26(1):52-55.
[28] 周蔚,孙晓华,赵玉卿.青海省非可溶性钾矿提钾工艺初步研究[J].青海大学学报(自然科学版),2010,28(5):27-29,41.
[29] 胡天喜,于建国.CaCl₂-NaCl混合助剂分解钾长石提取钾的实验研究[J].过程工程学报,2010,10(4):701-705.
[30] 胡天喜,于建国.氯化钙和氯化钠分解钾长石提钾的动力学实验[J].化学矿物与加工,2011(1):11-13.
[31] 谢和平,王昱飞,鞠杨,等.地球自然钾长石矿化CO₂联产可溶性钾盐[J].科学通报,2012,57(26):2501-2506.
[32] YE L P,YUE H R,WANG Y F,et al.CO₂ mineralization of activated K-feldspar+CaCl₂ slag to fix carbon and produce soluble potash salt[J].Industrial&Engineering Chemistry Research,2014,53:10557-10565.
[33] YUAN B,LI C,LIANG B,et al.Extraction of potassium from K-feldspar via the CaCl₂ calcination route[J].Chinese Journal of Chemical Engineering,2015,23:1557-1564.
[34] 马鸿文,苏双青,杨静,等.钾长石水热碱法制取硫酸钾反应原理与过程评价[J].化工学报,2014,65(6):2363-2371.
[35] 马玺,马鸿文,杨静,等.钾长石-石膏-碳酸钙体系高温烧结法制取硫酸钾研究评述[J].化工矿物与加工,2015(4):55-61.
[36] 苏双青,马鸿文,杨静,等.利用钾长石粉体水热合成六方钾霞石的方法:ZL201010543249.9[P].2010-11-11.
[37] 苏双青,蔡比亚,马鸿文,等.一种利用钾霞石粉体制取农用硫酸钾的工艺:ZL201110064828.X[P].2012-12-31.
[38] 姚文贵,苏双青,马鸿文.利用钾长石提钾剩余铝硅滤饼制备煅烧高岭土的方法:ZL 201210038064.1[P].2014-01-22.
[39] 苏双青,马鸿文,蔡比亚.一种利用钾长石提钾铝硅尾渣合成4A型分子筛的方法:201210036829.8[P].2012-02-17.
[40] 蔡比亚,苏双青,马鸿文.利用钾长石提钾剩余铝硅滤饼制取工业硫酸铝的方法:ZL 201210036826.4[P].2014-12-03.
[41] WU H,YANG J, MA H W,et al.Preparation of acicular wollastonite using hydrothermal and calcining methods[J].Integrated Ferroelectrics,2013,146:144-153.
[42] HOLLAND T J B,POWELL R.An improved and extended internally consistent thermodynamic dataset for phases of petrological interest,involving a new equation of state for solids[J].Journal of Metamorphic Geology,2011,29:333-383.
[43] BINNEWIES M,MILKE E.Thermochemical data of elements and compounds[M].2nd edition,Wiley-VCH,Weinheim,2002.
[44] 马鸿文,苏双青,王芳,等.钾长石分解反应热力学与过程评价[J].现代地质,2007,21(2):426-434.
[45] 毕诗文,于海燕,杨毅宏,等.拜耳法生产氧化铝[M].北京:冶金工业出版社,2007,137-139:252.
[46] 马鸿文,杨静,刘贺,等.硅酸盐体系的化学平衡:(1)物质平衡原理[J].现代地质,2006,20(2):329-339.
[47] 石油化工设计能量消耗计算方法[S].中华人民共和国行业标准,SH/T 3110-2001.
[48] 综合能耗计算通则[S].中华人民共和国国家标准,GB/T 2589-2008.
[49] BABUSHKIN V I,MATVEYEV G M,MCHEDLOV-PETROSSYAN O P.Thermodynamics of Silicates[M].Berlin Heidelberg:Springer-Verlag,1985:251-280.