沸石法卤水/苦卤钾富集工艺

doi:10.16085/j.issn.1000-6613.2018-1112

化工进展 ›› 2019, Vol. 38 ›› Issue (03): 1190-1196.DOI: 10.16085/j.issn.1000-6613.2018-1112

沸石法卤水/苦卤钾富集工艺

赵颖颖^1,^2,^3,⁴(),李丹¹,王军^1,^2,³(),王宗瑞⁴,刘建路⁴,袁俊生^1,^2,³()

1. 河北工业大学化工学院，天津 300130
2. 海水资源高效利用化工技术教育部工程研究中心，天津 300130
3. 河北省现代海洋化工协同创新中心，天津300130
4. 山东海化集团有限公司，山东潍坊 262737

收稿日期:2018-05-29 修回日期:2018-07-23 出版日期:2019-03-05 发布日期:2019-03-05
通讯作者: 王军,袁俊生
作者简介:赵颖颖（1985—），女，副教授，博士，主要从事海水资源利用和工业结晶。E-mail：luckyzhaoyy@126.com。|王军，高级工程师，研究方向海水及卤水综合利用。E-mail：240561145@qq.com|袁俊生，教授，研究方向海水资源利用与保护。E-mail：jsyuan2012@126.com
基金资助:
河北省科技计划(17273101D);中国博士后基金面上项目(2017M611142);山东海化集团有限公司科技项目(SDHH-KJXM 201701JSYFZX)

Process of potassium enrichment from brine/bittern using zeolite

Yingying ZHAO^1,^2,^3,⁴(),Dan LI¹,Jun WANG^1,^2,³(),Zongrui WANG⁴,Jianlu LIU⁴,Junsheng YUAN^1,^2,³()

1. School of Chemical Engineering, Hebei University of Technology, Tianjin 300130, China
2. Engineering Research Center of Seawater Utilization Technology, Ministry of Education, Tianjin 300130, China
3. Modern Marine Chemical Collaborative Innovation Center in Hebei Province, Tianjin 300130, China
4. Shandong Haihua Group Co., Ltd., Weifang 262737, Shandong, China

Received:2018-05-29 Revised:2018-07-23 Online:2019-03-05 Published:2019-03-05
Contact: Jun WANG,Junsheng YUAN

摘要/Abstract

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。

关键词: 沸石, 卤水, 离子交换, 钾富集

Abstract:

The new process of producing potassium nitrate was investigated via ion exchange technology. In the process, sodium nitrate was regarded as eluent, and the process parameters of extracting potassium were studied. The influence of eluent concentration and temperature on elution effect were explored. The results showed that high temperature and concentration of the eluent (sodium nitrate) were beneficial for adsorption. When the raw material was brine and the temperature was 80℃ and the mass percent of sodium nitrate was 46%, the potassium ion concentration after enrichment increased from 0.84g/L to 15.95g/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 8.93g/L to 23.34g/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.

Key words: zeolite, brine, ion-exchange, potassium-enrichment

中图分类号:

TQ443.9

赵颖颖,李丹,王军,王宗瑞,刘建路,袁俊生. 沸石法卤水/苦卤钾富集工艺[J]. 化工进展, 2019, 38(03): 1190-1196.

Yingying ZHAO,Dan LI,Jun WANG,Zongrui WANG,Jianlu LIU,Junsheng YUAN. Process of potassium enrichment from brine/bittern using zeolite[J]. Chemical Industry and Engineering Progress, 2019, 38(03): 1190-1196.

图/表 15

图1 硝酸钾富集生产流程图

表1 沸石的性质

名称

化学组成/%

比表面积

/m²?g^-1

粒度

/mm

孔体积

/cm3?g^-1

Al₂O₃

SiO₂

图2 钾富集吸附和洗脱实验流程图

图3 卤水吸附曲线

图4 洗脱液浓度对洗脱效果的影响

表2 洗脱液浓度对富钾卤水中K+影响

洗脱液质量分数

/％

富钾卤水中K⁺平均浓度

/g?L^-1

富钾卤水体积

12.97

0.84

11.09

±

0.2

0.60

±

0.03

5.73

—

表2 洗脱液浓度对富钾卤水中K+影响

洗脱液质量分数

/％

富钾卤水中K⁺平均浓度

/g?L^-1

富钾卤水体积

12.97

0.84

11.09

±

0.2

0.60

±

0.03

5.73

—

图5 不同温度对洗脱效果的影响

表3 洗脱液温度对富钾卤水中K+影响

温度/℃	富钾卤水中K⁺平均浓度/g?L^-1	富钾卤水体积/L
65	11.52	0.66
70	12.07 $±$ 0.10	0.66 $±$ 0.01
80	12.98	0.84

表3 洗脱液温度对富钾卤水中K+影响

温度/℃	富钾卤水中K⁺平均浓度/g?L^-1	富钾卤水体积/L
65	11.52	0.66
70	12.07 $±$ 0.10	0.66 $±$ 0.01
80	12.98	0.84

表4 原料的主要成分

原料	Mg²⁺/g?L^-1	K⁺/g?L^-1	Cl^-/g?L^-1	SO₄ ^2-/g?L^-1	Na⁺/g?L^-1
卤水	5.42	0.84	86.77	6.29	48.34
苦卤	51.62	8.93	183.57	71.11	48.80

图6 苦卤吸附曲线

图7 不同温度对洗脱效果的影响

表5 洗脱液温度对富钾卤水中K+影响

温度/℃	富钾卤水中K⁺平均浓度/g?L^-1	富钾卤水体积/L
60	17.03	0.75
70	17.23 $±$ 0.10	1.25 $±$ 0.01
80	17.72	1.75

表5 洗脱液温度对富钾卤水中K+影响

温度/℃	富钾卤水中K⁺平均浓度/g?L^-1	富钾卤水体积/L
60	17.03	0.75
70	17.23 $±$ 0.10	1.25 $±$ 0.01
80	17.72	1.75

图8 不同吸附原料的沸石柱洗脱曲线对比图

表6 不同原料对富集的影响

原料	富钾卤水中K⁺平均浓度/g?L^-1	富钾卤水体积/L
苦卤	17.72	1.75
卤水	12.98	0.84

图9 苦卤与卤水吸附曲线对比图

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沸石法卤水/苦卤钾富集工艺

Process of potassium enrichment from brine/bittern using zeolite

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