光卤石原矿品位对其冷分解结晶氯化钾过程影响浅析
收稿日期: 2023-10-30
网络出版日期: 2024-09-26
基金资助
国家重点研发计划项目(2022YFC2904000);国家自然科学基金项目(22178272)
Analysis of effect of carnallite raw ore grade on its cold decomposition and crystallization of potassium chloride
Received date: 2023-10-30
Online published: 2024-09-26
光卤石冷分解结晶是国内生产氯化钾的主要工艺,但随着光卤石原矿品位的下降,原有技术生产的氯化钾产品出现了粒度变小、易聚结、纯度差且收率低等问题,已成为困扰氯化钾行业发展的难题。对比了不同地区钾盐原矿品质,结合Na+、K+、Mg2+//Cl--H2O四元体系及其子体系的热力学相平衡规律,概述了原矿品质对分解结晶过程析盐规律的影响,从分解-结晶耦合过程动力学角度,总结了不同品位光卤石冷分解结晶制备氯化钾过程的产品粒度及形貌调控关键因素及其作用机理。结合产品现行标准,提出低钠光卤石、含钠光卤石和高钠光卤石的新分类方法和对应的工艺选择策略,并对不同品位光卤石原矿的冷分解结晶新工艺进行展望,以期为行业健康发展提供理论指导与参考。
郭凯花 , 范雨薪 , 杨静 , 赵文立 , 贾原媛 , 王彦飞 . 光卤石原矿品位对其冷分解结晶氯化钾过程影响浅析[J]. 无机盐工业, 2024 , 56(8) : 9 -18 . DOI: 10.19964/j.issn.1006-4990.2023-0516
Cold decomposition of carnallite is the main process of producing potassium chloride in China.However,the declining grade of carnallite ore has posed a challenge to the industrial development of potassium chloride.The resulting process produces potassium chloride with issues such as smaller particle size,increased tendency to aggregate,lower purity,and reduced yield.In this review,the quality of potassium ore in different regions was compared at first.The effect of raw ore quality on the salt precipitation order of the decomposition process was overviewed based on the thermodynamic phase equilibrium of the quaternary system(Na+,K+,Mg2+//Cl--H2O) and its sub⁃systems.From the kinetic perspective of the decomposition⁃crystallization coupling process,the crucial factors and underlying mechanisms for regulating the particle size and morphologies of potassium chloride crystals during the cold decomposition⁃crystallization process(CDCP) of different grades of carnallite raw ore were summarized.In addition,combined with the current product standards,a novel classification method and corresponding process⁃selection strategy for low⁃sodium carnallite,sodium⁃containing carnallite,and high⁃sodium carnallite were proposed.And the new CDCP for different grades of carnallite raw ore was prospected,in the hope of providing theoretical guidance and references for the sustainable development of the industry.
| 1 | 唐远,朱奥妮,陈琲琲,等.我国战略性非金属矿产分离技术进展[J].化工矿物与加工,2022,51(11):19-31,37. |
| TANG Yuan, ZHU Aoni, CHEN Beibei,et al.Research and development of technologies for separating strategic non?metallic minerals in China[J].Industrial Minerals & Processing,2022,51(11):19-31,37. | |
| 2 | 熊增华,王石军.中国钾资源开发利用技术及产业发展综述[J].矿产保护与利用,2020,40(6):1-7. |
| XIONG Zenghua, WANG Shijun.Overview of potassium resources exploitation & utilization technology and potash industry development[J].Conservation and Utilization of Mineral Resources,2020,40(6):1-7. | |
| 3 | 谭慧婷,孙伟,崔玉照,等.钾矿资源现状与杂卤石的开发应用分析[J].无机盐工业,2022,54(6):23-30. |
| TAN Huiting, SUN Wei, CUI Yuzhao,et al.Present situation of potash resources and analysis of development and application of polyhalite[J].Inorganic Chemicals Industry,2022,54(6):23-30. | |
| 4 | 王石军,王兴富,王罗海,等.浅议我国钾肥工业可持续发展与境外钾肥基地建设[J].化工矿物与加工,2019,48(1):66-69. |
| WANG Shijun, WANG Xingfu, WANG Luohai,et al.Discussion on sustainable development of China′s potash industry and construction of overseas potash base[J].Industrial Minerals & Processing,2019,48(1):66-69. | |
| 5 | 王凡,邓小林,郑绵平,等.新疆库车坳陷西段膏盐层沉积、地球化学特征及找钾方向[J].地球科学,2022,47(1):56-71. |
| WANG Fan, DENG Xiaolin, ZHENG Mianping,et al.Sedimentary?geochemical characteristics and potash?prospecting potential of gy? | |
| psum?salt layer in western Kuqa depression[J].Earth Science,2022,47(1):56-71. | |
| 6 | 程怀德,马海州,张志宏.高镁溶液对光卤石分解影响的初步研究[J].无机盐工业,2013,45(1):21-23. |
| CHENG Huaide, MA Haizhou, ZHANG Zhihong.Preliminary study on effect of high?magnesium solution on carnallite decomposition[J].Inorganic Chemicals Industry,2013,45(1):21-23. | |
| 7 | 亓昭英,屈小荣,杜双江,等.2019年我国钾肥行业运行情况及未来5年发展趋势分析[J].磷肥与复肥,2020,35(4):1-5. |
| QI Zhaoying, QU Xiaorong, DU Shuangjiang,et al.Analysis on the operation of potash fertilizer industry in 2019 and its development trend in the next five years[J].Phosphate & Compound Fertilizer,2020,35(4):1-5. | |
| 8 | QIN Zhanjie, LI Qingkuan, FAN Qishun,et al.Origin of underground brine in potassium?bearing strata in Khammouane,central Laos[J].Geochemistry International,2019,57(12):1327-1338. |
| 9 | 洪磊.老挝钾盐矿生产氯化钾试验研究及工艺优化[D].昆明:昆明理工大学,2020. |
| HONG Lei.Experimental study and process optimization of potassium chloride production from potash mine in Laos[D].Kunming:Kunming University of Science and Technology,2020. | |
| 10 | 邓天龙,周桓,陈侠.水盐体系相图及应用[M].北京:化学工业出版社,2020. |
| 11 | 王石军.光卤石矿类型对冷分解—浮选法生产氯化钾工艺的影响[J].海湖盐与化工,2000,29(5):1-4. |
| WANG Shijun.Influence of carnallite types on the production process of potassium chloride by cold decomposition?flotation[J].Sea-Lake Salt and Chemical Industry,2000,29(5):1-4. | |
| 12 | 赵静.杂盐对氯化钾浮选生产过程中的影响研究[D].太原:山西大学,2011. |
| ZHAO Jing.Effect of abraum salts on KC1 flotation process[D].Taiyuan:Shanxi University,2011. | |
| 13 | 蔡生吉,马国华,屈亚林.用盐湖卤水生产氯化钾反浮选冷结晶工艺流程[J].无机盐工业,2005,37(5):10-11. |
| CAI Shengji, MA Guohua, QU Yalin.The production of KCl from salt lake brine by anti?floatation?cold crystallization method[J].Inorganic Chemicals Industry,2005,37(5):10-11. | |
| 14 | 张秀春,庞旭岩,李承宝.冷结晶控制技术改进及节能降耗效果分析[J].化工矿物与加工,2009,38(7):30-32. |
| ZHANG Xiuchun, PANG Xuyan, LI Chengbao.Improvement on cold crystallization control technology and analysis of effect of its energy conservation and consumption reduction[J].Industrial Minerals & Processing,2009,38(7):30-32. | |
| 15 | CHEN Mingyang, WU Songgu, XU Shijie,et al.Caking of crystals:Characterization,mechanisms and prevention[J].Powder Technology,2018,337:51-67. |
| 16 | 周玲,沙作良,唐娜,等.光卤石分解制取氯化钾结晶过程的研究[J].盐业与化工,2009,38(4):13-18. |
| ZHOU Ling, SHA Zuoliang, TANG Na,et al.Study on the crystallization process of producing potassium chloride from carnallite decomposition method[J].Journal of Salt and Chemical Industry,2009,38(4):13-18. | |
| 17 | LIU Chang, JI Yuanhui, BAI Yang,et al.Formation of porous crystals by coupling of dissolution and nucleation process in fractional crystallization[J].Fluid Phase Equilibria,2007,261(1/2):300-305. |
| 18 | 张开勇,唐娜,廉颖.光卤石分解制备氯化钾结晶过程分解液浓度特性研究[J].盐业与化工,2010,39(1):3-6. |
| ZHANG Kaiyong, TANG Na, LIAN Ying.Study on the decomposition liquid concentration characteristics in the crystallizer of potassium chloride production by carnallite cold?decomposition method[J].Journal of Salt and Chemical Industry,2010,39(1):3-6. | |
| 19 | 洪显兰,夏树屏,高世扬.钾光卤石溶解过程研究[J].盐湖研究,1994,2(2):44-48. |
| HONG Xianlan, XIA Shuping, GAO Shiyang.Study on dissolution process of potassium carnallite[J].Journal of Salt Lake Research,1994,2(2):44-48. | |
| 20 | 韩冰,唐娜,沙作良,等.光卤石分解制氯化钾结晶机理研究[J].盐业与化工,2008,37(2):13-16. |
| HAN Bing, TANG Na, SHA Zuoliang,et al.Study on crystallization mechanism of producing potassium chloride by dissolving carnallite[J].Journal of Salt and Chemical Industry,2008,37(2):13-16. | |
| 21 | 张开勇.光卤石分解过程分解液浓度特性及动力学研究[D].天津:天津科技大学,2010. |
| ZHANG Kaiyong.Study on the decomposition liquid characteristics and dynamics in carnallite cold?decomposition process[D].Tianjin:Tianjin University of Science & Technology,2010. | |
| 22 | WANG Xiaobo, HOU Yuansheng, LI Huilin.Use of online electrical conductivity meter to monitor cold decomposition of carnalli? |
| te[J].Journal of Measurement Science and Instrumentation,2015,6(2):185-189. | |
| 23 | 张世春,付振海,唐海英,等.一种细粒高钠光卤石生产高品位农用氯化钾的方法:中国,113956079A[P].2022-01-21. |
| 24 | FENG Shanshan, YAO Menghui, GUO Shilin,et al.Morphology and microstructure regulation of inorganic salts in an additive?free water system via the self?organization of hierarchical crystal clusters:Mechanism,model,and applications[J].Chemical Engineering Science,2022,262:118053. |
| 25 | JIN Shasha, CHEN Mingyang, LI Zhenfang,et al.Design and mechanism of the formation of spherical KCl particles using cooling crystallization without additives[J].Powder Technology,2018,329:455-462. |
| 26 | 杨红梅.生产氯化钾的几种工艺分析[J].海湖盐与化工,2004,33(2):4-7. |
| YANG Hongmei.Analysis of the producing technology of potassium chloride[J].Sea-Lake Salt and Chemical Industry,2004,33(2):4-7. | |
| 27 | 朱晓东,郑秀洁.利用盐湖高钙含钾卤水制取氯化钾工艺试验研究[J].盐业与化工,2011,40(5):10-12. |
| ZHU Xiaodong, ZHENG Xiujie.Study and test of process of production of potassium chloride from high calcium potassium bearing brine in salt lake[J].Journal of Salt and Chemical Industry,2011,40(5):10-12. | |
| 28 | 吴礼定,曾波.我国氯化钾生产工艺概述[J].磷肥与复肥,2012,27(5):52-55. |
| WU Liding, ZENG Bo.Summary of production process for potassium chloride in China[J].Phosphate & Compound Fertilizer,2012,27(5):52-55. | |
| 29 | HANS S.Crystallization of potassium chloride from carnallite decomposition:US,3644102[P].1972-02-22. |
| 30 | 唐海英,俞学山,李成宝,等.细粒高钠光卤石分解结晶分解液浓度特性及动力学研究[J].化工矿物与加工,2023,52(7):15-20. |
| TANG Haiying, YU Xueshan, LI Chengbao,et al.Kinetics study on characteristics and concentration of decomposition solution from high?sodium carnallite with fine particle size[J].Industrial Minerals & Processing,2023,52(7):15-20. | |
| 31 | 乐有贵,曾波,罗康碧,等.老挝钾盐矿热溶结晶生产大颗粒氯化钾研究[J].化工矿物与加工,2013,42(4):15-19. |
| LE Yougui, ZENG Bo, LUO Kangbi,et al.Study on production of large particles of potassium chloride from Laotian potassium salt ore by thermal dissolution crystallization[J].Industrial Miner? | |
| als & Processing,2013,42(4):15-19. | |
| 32 | 周玲.NaCl碰撞成核规律与KCl结晶过程的研究[D].天津:天津科技大学,2009. |
| ZHOU Ling.Research on collision nucleation rule of NaCl and crystallization process of KCl[D].Tianjin:Tianjin University of Science & Technology,2009. | |
| 33 | NEUENDORF L, H?VING S, BENNEMANN L,et al.Detecting crystals in suspensions:Convolutional neural networks vs.gravity?based approach for size distribution detection[J].Chemie Ingenieur Technik,2023,95(7):1146-1153. |
| 34 | 任红伟,田红斌,袁建平,等.一种结晶器:中国,110025973B[P].2021-03-23. |
| 35 | 甘顺鹏,丁定,孙成高,等.地下原生高钠光卤石矿冷分解结晶工艺研究[J].无机盐工业,2024,56(1):67-72. |
| GAN Shunpeng, DING Ding, SUN Chenggao,et al.Study on cold decomposition crystallization process of underground primary high?sodium carnallite ore[J].Inorganic Chemicals Industry,2024,56(1):67-72. | |
| 36 | 唐娜,赵思俭,何永平,等.高钠钾盐矿的冷分解结晶及浮选 |
| 方法制备大颗粒氯化钾的系统及工艺:中国,103265055A[P]. 2013-08-28. | |
| 37 | 时历杰,王敏.一种利用高钠光卤石制取低钠光卤石及氯化钾的方法:中国,111362730B[P].2021-11-02. |
| 38 | 齐美玲,王刚,张莉媛,等.光卤石中氯化钾溶解度、介穏区、诱导期测定[J].无机盐工业,2020,52(5):45-49. |
| QI Meiling, WANG Gang, ZHANG Liyuan,et al.Determination of KCl solubility,interfacial region and induction period in carnallite[J].Inorganic Chemicals Industry,2020,52(5):45-49. | |
| 39 | 杜景灵,董伟兵,切知加,等.柠檬酸三钠对低钠光卤石分解制备氯化钾晶体粒度影响研究[J].无机盐工业,2022,54(4):112-118. |
| DU Jingling, DONG Weibing, Zhijia QIE,et al.Study on effect of trisodium citrate on particle size of potassium chloride crystal prepared by decomposition of low sodium carnallite[J].Inorganic Chemicals Industry,2022,54(4):112-118. | |
| 40 | GUO Xiaofu, YUAN Junsheng, JI Zhiyong,et al.Influences of additives on the crystal habit of potassium chloride[J].Frontiers of Chemical Engineering in China,2010,4(1):78-81. |
| 41 | 张世春,俞学山,唐海英,等.细粒氯化钠对光卤石分解结晶过程的影响研究[J].盐湖研究,2023,31(4):93-100. |
| ZHANG Shichun, YU Xueshan, TANG Haiying,et al.Effects of fine-NaCl on decomposition?crystallization process of carnallite with high content of fine-NaCl[J].Journal of Salt Lake Research,2023,31(4):93-100. | |
| 42 | COOPER J, BORNE L, COQUEREL G.Antisolvent addition:An effective method of controlled fluid inclusion formation in RDX crystals[J].Crystal Growth & Design,2020,20(11):7120-7128. |
| 43 | 齐美玲.低钠光卤石制备氯化钾结晶过程研究[D].西宁:青海民族大学,2020. |
| QI Meiling.Study on crystallization process of potassium chloride prepared from low sodium carnallite[D].Xining:Qinghai Minzu University,2020. | |
| 44 | 陈许龙,董伟兵,万俊峰,等.球形氯化钾结晶过程与聚结机理研究[J].无机盐工业,2021,53(7):53-57. |
| CHEN Xulong, DONG Weibing, WAN Junfeng,et al.Study on the crystallization process and agglomeration mechanism of spherical KCl[J].Inorganic Chemicals Industry,2021,53(7):53-57. | |
| 45 | 保英莲,张志强.光卤石分解制取KCl结晶过饱和度影响的研究[J].盐业与化工,2014,43(9):15-18. |
| BAO Yinglian, ZHANG Zhiqiang.Effect of supersaturation on preparation of potassium chloride by decomposition of carnalli? | |
| te[J].Journal of Salt and Chemical Industry,2014,43(9):15-18. | |
| 46 | 胡勇,卢志斌,杨三妹.青海某盐湖光卤石浮选尾盐综合回收钾钠资源试验研究[J].纯碱工业,2022(2):16-19. |
| HU Yong, LU Zhibin, YANG Sanmei.Experimental study on comprehensive recovery of potassium and sodium resources from carnallite flotation tail salt of a salt lake in Qinghai[J].Soda Industry,2022(2):16-19. | |
| 47 | 赵悦年,牛小慧.光卤石分解制备氯化钾的工艺条件优化试验研究[J].当代化工,2019,48(8):1707-1710. |
| ZHAO Yuenian, NIU Xiaohui.Study on preparation of potassium chloride from carnallite by thermal decomposition[J].Contemporary Chemical Industry,2019,48(8):1707-1710. | |
| 48 | 陈侠,邹艳爽,么佳,等.光卤石热分解生产氯化钾联产氯化镁实验研究[J].无机盐工业,2015,47(10):19-22. |
| CHEN Xia, ZOU Yanshuang, YAO Jia,et al.Research on production of potassium chloride and coproduction of magnesium chloride by thermal decomposition of carnallite[J].Inorganic Chemicals Industry,2015,47(10):19-22. | |
| 49 | 汪贵元.反浮选—冷结晶生产氯化钾工艺控制的探讨[J].海湖盐与化工,2002,31(3):27-29. |
| WANG Guiyuan.Research of process control of potassium chloride production by reverse?flotation and cold?crystallization met? | |
| hod[J].Sea-Lake Salt and Chemical Industry,2002,31(3):27-29. | |
| 50 | 张生富.光卤石分解母液相对密度对工艺控制的影响[J].盐业与化工,2012,41(11):29-32. |
| ZHANG Shengfu.Effect of relative density of carnallite decomposition mother liquor on technology control[J].Journal of Salt and Chemical Industry,2012,41(11):29-32. | |
| 51 | 靳莹皓.反浮选法制备氯化钾工艺原理及关键控制[J].盐业与化工,2013,42(4):31-32. |
| JIN Yinghao.Technology principle and key control of KCl preparation with reverse flotation?cooling crystallization method[J].Journal of Salt and Chemical Industry,2013,42(4):31-32. | |
| 52 | 程芳琴,张洪满,严霞,等.分解光卤石的分解液量对钾收率的影响研究[J].无机盐工业,2008,40(8):19-22. |
| CHENG Fangqin, ZHANG Hongman, YAN Xia,et al.Study on effect of the quantity of decomposition liquid on KCl recovery in process of carnallite cold?decomposition[J].Inorganic Chemicals Industry,2008,40(8):19-22. | |
| 53 | 方勤升,王庆生,钱晓杨,等.反浮选—冷结晶生产氯化钾工艺过程的优化[J].无机盐工业,2001,33(5):32-33,2. |
| FANG Qinsheng, WANG Qingsheng, QIAN Xiaoyang,et al.The optimization of process for the production of KCl by counter?floatation?cool crystallization[J].Inorganic Chemicals Industry,2001,33(5):32-33,2. | |
| 54 | 王石军.青海察尔汉盐湖深水盐田光卤石矿物化特性研究总结报告[J].盐湖研究,1997,5(1):7-20. |
| WANG Shijun.Summary research report of physical and chemical characters of carnallite for ChaErHan salt lake deep warter solar ponds[J].Journal of Salt Lake Research,1997,5(1):7-20. | |
| 55 | 切知加,马生奎,杜景灵,等.响应面法优化提高低钠光卤石制备KCl收率研究[J].盐科学与化工,2022,51(3):25-30. |
| Zhijia QIE, MA Shengkui, DU Jingling,et al.Optimization of KCl yield from low sodium carnallite by response surface methodolo? | |
| gy[J].Journal of Salt Science and Chemical Industry,2022,51(3):25-30. | |
| 56 | 李建国,黄姗姗,杨明山.“冷分解—正浮选—洗涤” 法生产氯化钾物料衡算[J].盐业与化工,2011,40(6):35-37. |
| LI Jianguo, HUANG Shanshan, YANG Mingshan.Materials balance of potassium chloride production in room?temperature decomposing and direct flotation and scrub method[J].Journal of Salt and Chemical Industry,2011,40(6):35-37. | |
| 57 | 朱孔金.氯化钾结晶粒度控制试验研究[J].化工矿物与加工,2016,45(11):24-25,37. |
| ZHU Kongjin.Test on control of potassium chloride crystal size control[J].Industrial Minerals & Processing,2016,45(11):24-25,37. | |
| 58 | CHENG Huaide, MA Haizhou, Qingyu HAI,et al.Model for the decomposition of carnallite in aqueous solution[J].International Journal of Mineral Processing,2015,139:36-42. |
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