沸石法卤水/苦卤钾富集工艺
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摘要
采用离子交换技术,研究了以硝酸钠为洗脱剂,富集生产硝酸钾的新工艺。主要研究了沸石法富集卤水/苦卤中钾离子的过程工艺参数,考察了洗脱剂浓度和洗脱温度对洗脱效果的影响。结果表明:在原料为卤水、采用硝酸钠溶液作为洗脱剂的洗脱实验中,高温、高浓度的洗脱剂有利于沸石柱的洗脱,当温度为80℃、硝酸钠溶液质量分数为46%时,富集后的钾离子浓度由原料浓度的0.84g/L提高到15.95g/L;改变原料的浓度,在原料为苦卤、硝酸钠溶液作为洗脱剂的洗脱过程中,高温同样有利于沸石柱的洗脱,当温度为80℃、硝酸钠溶液质量分数为46%时,富集后的钾离子浓度由原料的8.93g/L提高到23.34g/L;表明该方法适用于低钾卤水和高钾苦卤,且原料中钾离子浓度越高,饱和吸附量越高,所得富钾卤水中钾离子浓度越高。该研究为未来硝酸钾的生产工业化提供了新思路。
Thenewprocessofproducingpotassiumnitratewasinvestigated via ionexchangetechnology.In theprocess,sodiumnitratewasregardedaseluent,andtheprocessparametersofextractingpotassiumwere studied. The influence of eluent concentration and temperature on elution effect were explored. The results showedthathightemperatureandconcentrationoftheeluent(sodiumnitrate)werebeneficialforadsorption.When the raw material was brine and the temperature was 80℃ and the mass percent of sodium nitrate was46%,thepotassiumionconcentrationafterenrichmentincreasedfrom0.84 g/Lto15.95 g/L.Meanwhile,when the raw material was exchanged for bittern, high temperature was also beneficial for adsorption effect, the potassium ion concentration after enrichment increased from 8.93 g/L to 23.34 g/L under the same elution condition. It showed that the method was suitable for low potassium brine and high potassium bittern. The higher potassium concentration is, the higher saturated adsorption capacity and concentration of potassium can be obtained in the potassium-enrichment brine. This study provides the new way for potassium nitrate production industrialization in the future.
Thenewprocessofproducingpotassiumnitratewasinvestigated via ionexchangetechnology.In theprocess,sodiumnitratewasregardedaseluent,andtheprocessparametersofextractingpotassiumwere studied. The influence of eluent concentration and temperature on elution effect were explored. The results showedthathightemperatureandconcentrationoftheeluent(sodiumnitrate)werebeneficialforadsorption.When the raw material was brine and the temperature was 80℃ and the mass percent of sodium nitrate was46%,thepotassiumionconcentrationafterenrichmentincreasedfrom0.84 g/Lto15.95 g/L.Meanwhile,when the raw material was exchanged for bittern, high temperature was also beneficial for adsorption effect, the potassium ion concentration after enrichment increased from 8.93 g/L to 23.34 g/L under the same elution condition. It showed that the method was suitable for low potassium brine and high potassium bittern. The higher potassium concentration is, the higher saturated adsorption capacity and concentration of potassium can be obtained in the potassium-enrichment brine. This study provides the new way for potassium nitrate production industrialization in the future.
引文
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[4]CPHILLIPS R C.Potassium and cesium recovery process:FR1556475[P].1969-02-07.
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[13]王光华,董发勤,张宝述.沸石离子交换的研究现状及发展趋势[J].中国非金属矿工业导刊,2007(2):18-21.WANG Guanghua,DONG Faqin,ZHANG Baoshu.Present research state and perspective of ion-exchanging in clinoptilolite[J].China Nonmetallic Minerals Industry,2007(2):18-21.
[14]朱孔秀,袁俊生,于占花,等.国产天然斜发沸石的物性及离子交换性能研究[J].化工矿物与加工,2009,38(7):19-23.ZHU Kongxiu,YUAN Junsheng,YU Zhanhua,et al.Study on the physical properties and ion exchange performance of the domestic clinoptilolite[J].Industrial Minerals&Processing,2009,38(7):19-23.
[15]张国磊.超万吨海水苦卤提取硫酸钾及综合利用工程经济性分析研究[D].青岛:中国海洋大学,2009.ZHANG Guolei.Economic analysis research of project of ultra-tenthousand tons of seawater extraction bittern comprehensive utilization of potassium sulfate[D].Qingdao:Ocean University of China,2009.
[16]袁俊生,韩慧茹.海水提钾技术研究进展[J].河北工业大学学报,2004,33(2):140-147.YUAN Junsheng,HAN Huiru.Evolution and development trend of technologies of extracting potassium from seawater[J].Journal of Hebei University of Technology,2004,33(2):140-147.
[17]袁俊生,纪志永.沸石离子筛法海水提钾技术进展[J].中国科技成果,2010,11(14):9-11.YUAN Junsheng,JI Zhiyong.Development trend of technologies of extracting potassium from seawater using zeolite ion-sieve[J].China Science and Technology Achievements,2010,11(14):9-11.
[18]李雅芙,刘素芹.硝酸钾生产工艺综述[J].盐业与化工,2005,34(3):27-30.LI Yafu,LIU Suqin.Summarization of potassium nitrate production process[J].Journal of Salt Science and Chemical Industry,2005,34(3):27-30.
[19]闫会征.新型钾离子筛法海水提取硫酸钾新工艺的研究[D].天津:河北工业大学,2008.YAN Huizheng.Studies on the new technology for extracting potassium sulfate from seawater using novel ion-sieve[D].Tianjin:Hebei University of technology,2008.
[20]烟伟,黄西平,张琦,等.我国海水提钾的产业化前景[J].盐业与化工,2004,33(4):13-17.YAN Wei,HUANG Xiping,ZHANG Qi,et al.Prospects of industrialization on extracting potassium from seawater in China[J].Journal of Salt and Chemical Industry,2004,33(4):13-17.
[21]袁俊生,杨树娥,邓会宁.连续离子交换技术及其在海水提钾的应用[J].盐业与化工,2007,36(3):27-30.YUAN Junsheng,YANG Shue,DENG Huining.The technology of continuous ionic exchange and its application in extracting potassium from seawater[J].Journal of Salt and Chemical Industry,2007,36(3):27-30.
[22]袁俊生,王静康.钠型斜发沸石Na+-K+离子交换特性研究(Ⅰ)--离子交换过程热力学特性[J].离子交换与吸附,2004,20(6):541-547.YUAN Junsheng,WANG Jingkang.Research on Na+-K+ion exchange characteristiconNa-clinoptilolite(Ⅰ)-thermodynamicscharacteristicof the process[J].Ion Exchange and Adsorption,2004,20(6):541-547.
[23]袁俊生,王静康.钠型斜发沸石Na+-K+离子交换特性研究(Ⅱ)--过程传质模型及动力学特性研究[J].离子交换与吸附,2005,21(2):127-136.YUAN Junsheng,WANG Jingkang.Research on Na+-K+ion exchange characteristic on Na-clinoptilolite(Ⅱ)-mass transfer model and kinetic characteristics[J].Ion Exchange and Adsorption,2005,21(2):127-136.
[24]王德华,费维扬.钠改型天然斜发沸石的铵离子交换平衡[J].离子交换与吸附,2002,18(4):343-348.WANG Dehua,FEI Weiyang.Study on characterization of ammonium exchange on natural zeolite[J].Ion Exchange and Adsorption,2002,18(4):343-348.
[2]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):2450-2455.GU Hannian,WANG Ning,YANG Yongqiong,et al.Research progress of preparing potash fertilizer with potassium-bearing minerals[J].Chemical Industry and Engineering Progress,2011,30(11):2450-2455.
[3]KIELLAND J.Process for the recovery of potassium salts from solutions:DE691366[P].1940-05-24.
[4]CPHILLIPS R C.Potassium and cesium recovery process:FR1556475[P].1969-02-07.
[5]TAKEDA Y,YASUI A,MORITA M,et al.Extraction of sodium and potassium perchiorates with benzo-18-crown-6 into various organic solvents,quan titative elucidation of anion effects on the extractionability and selectivity for Na+and K+[J].Talanta,2002,56(3):505-513.
[6]GOODENOUH R D.Recovery of potassium chloride from aqueous solutions:US3212863[P].1965-10-19.
[7]TANAKA Y.Technology for removing potassium from concentrated seawater by electrodialysis and solar salt dissolved in brine[J].Separation Science and Technology,1993,28(11):2023-2034.
[8]TANAKA Y.Method for ion exchange and separation of sodium and potassium:JP 06198163[P].1994-07-19.
[9]韩立路.CDAH-2树脂的制取及其对钾离子的富集性能[J].化工进展,2009,28(6):1014-1018.HAN Lilu.Synthesis of CDAH-2 resin and its enrichment behavior for potassium ion[J].Chemical Industry and Engineering Progress,2009,28(6):1014-1018.
[10]袁俊生,张林栋,刘燕兰,等.我国海水钾资源开发利用技术现状与发展趋势[J].海湖盐与化工,2002,31(2):1-6.YUAN Junsheng,ZHANG Lindong,LIU Yanlan,et al.Present status and prospect of the technology of development and utilization of seawater potassium resources in China[J].Sea-Lake Salt and Chemical Industry,2002,31(2):1-6.
[11]YUAN Junsheng,ZHAO Yingying,LI Qinghui,et al.Preparation of potassium ionic sieve membrane and its application on extracting potash from seawater[J].Separation&Purification Technology,2012,99:55-60.
[12]袁俊生.离子交换法海水提钾技术的应用基础研究[D].天津:天津大学,2005.YUAN Junsheng.Research on fundamentals in the technology of extracting potash from seawater by ion exchange method[D].Tianjin:Tianjin University,2005.
[13]王光华,董发勤,张宝述.沸石离子交换的研究现状及发展趋势[J].中国非金属矿工业导刊,2007(2):18-21.WANG Guanghua,DONG Faqin,ZHANG Baoshu.Present research state and perspective of ion-exchanging in clinoptilolite[J].China Nonmetallic Minerals Industry,2007(2):18-21.
[14]朱孔秀,袁俊生,于占花,等.国产天然斜发沸石的物性及离子交换性能研究[J].化工矿物与加工,2009,38(7):19-23.ZHU Kongxiu,YUAN Junsheng,YU Zhanhua,et al.Study on the physical properties and ion exchange performance of the domestic clinoptilolite[J].Industrial Minerals&Processing,2009,38(7):19-23.
[15]张国磊.超万吨海水苦卤提取硫酸钾及综合利用工程经济性分析研究[D].青岛:中国海洋大学,2009.ZHANG Guolei.Economic analysis research of project of ultra-tenthousand tons of seawater extraction bittern comprehensive utilization of potassium sulfate[D].Qingdao:Ocean University of China,2009.
[16]袁俊生,韩慧茹.海水提钾技术研究进展[J].河北工业大学学报,2004,33(2):140-147.YUAN Junsheng,HAN Huiru.Evolution and development trend of technologies of extracting potassium from seawater[J].Journal of Hebei University of Technology,2004,33(2):140-147.
[17]袁俊生,纪志永.沸石离子筛法海水提钾技术进展[J].中国科技成果,2010,11(14):9-11.YUAN Junsheng,JI Zhiyong.Development trend of technologies of extracting potassium from seawater using zeolite ion-sieve[J].China Science and Technology Achievements,2010,11(14):9-11.
[18]李雅芙,刘素芹.硝酸钾生产工艺综述[J].盐业与化工,2005,34(3):27-30.LI Yafu,LIU Suqin.Summarization of potassium nitrate production process[J].Journal of Salt Science and Chemical Industry,2005,34(3):27-30.
[19]闫会征.新型钾离子筛法海水提取硫酸钾新工艺的研究[D].天津:河北工业大学,2008.YAN Huizheng.Studies on the new technology for extracting potassium sulfate from seawater using novel ion-sieve[D].Tianjin:Hebei University of technology,2008.
[20]烟伟,黄西平,张琦,等.我国海水提钾的产业化前景[J].盐业与化工,2004,33(4):13-17.YAN Wei,HUANG Xiping,ZHANG Qi,et al.Prospects of industrialization on extracting potassium from seawater in China[J].Journal of Salt and Chemical Industry,2004,33(4):13-17.
[21]袁俊生,杨树娥,邓会宁.连续离子交换技术及其在海水提钾的应用[J].盐业与化工,2007,36(3):27-30.YUAN Junsheng,YANG Shue,DENG Huining.The technology of continuous ionic exchange and its application in extracting potassium from seawater[J].Journal of Salt and Chemical Industry,2007,36(3):27-30.
[22]袁俊生,王静康.钠型斜发沸石Na+-K+离子交换特性研究(Ⅰ)--离子交换过程热力学特性[J].离子交换与吸附,2004,20(6):541-547.YUAN Junsheng,WANG Jingkang.Research on Na+-K+ion exchange characteristiconNa-clinoptilolite(Ⅰ)-thermodynamicscharacteristicof the process[J].Ion Exchange and Adsorption,2004,20(6):541-547.
[23]袁俊生,王静康.钠型斜发沸石Na+-K+离子交换特性研究(Ⅱ)--过程传质模型及动力学特性研究[J].离子交换与吸附,2005,21(2):127-136.YUAN Junsheng,WANG Jingkang.Research on Na+-K+ion exchange characteristic on Na-clinoptilolite(Ⅱ)-mass transfer model and kinetic characteristics[J].Ion Exchange and Adsorption,2005,21(2):127-136.
[24]王德华,费维扬.钠改型天然斜发沸石的铵离子交换平衡[J].离子交换与吸附,2002,18(4):343-348.WANG Dehua,FEI Weiyang.Study on characterization of ammonium exchange on natural zeolite[J].Ion Exchange and Adsorption,2002,18(4):343-348.