铝酸钙飞灰中钾的回收利用工艺研究

doi:10.19964/j.issn.1006-4990.2022-0692

Abstract

Abstract:

Potassium is one of the plant nutrient elements.China is a large agricultural country，meanwhile，China is deficient in potassium.Every year，a large amount of potassium fertilizer（mainly potassium chloride） are imported to meet the needs of agriculture.A solid waste-fly ash is produced in the course of production of calcium aluminate by calcination.The fly ash contains potassium chloride，aphthitalite，syngenite，anhydrite，etc.Among these minerals，potassium chloride and aphthitalite are water-soluble.The content of soluble potassium in the fly ash is as high as about 23.52%，so it′s necessary to recycle the potassium.The results of its mineral characterization and theoretical analysis based on phase-diagram data showed that it was suitable for recycling of potassium to adopt process of thermal dissolution-evaporation-cold crystallization process.Potassium sulfate and potassium chloride could be produced.The investigation of the process condition and optimization were done.The optimal conditions were as follows：the temperature of thermal dissolution and cold crystallization，the liquid-solid ratio，dissolving time were 90 ℃ and 25 ℃，3.4:1，1 h，respectively.After continuous dissolving of 6 times，about 95% of potassium was dissolved.According to composition of the leaching liquid，the amount of water evaporation was as same as the theoretical analysis.And 81.3% of potassium was crystallized under the conditions.The results showed that it was available to recycle the potassium from the fly ash by dissolution-crystallization process to produce potassium sulfate and potassium chloride.

Key words: calcium aluminate, fly ash, soluble potassium, potassium sulfate, potassium chloride

CLC Number:

TQ131.13

YANG Hongjun, WANG Min, GE Haiwen, QIAO Youmin, QIAO Ziyang. Study on recycling process of potassium from calcium aluminate fly ash[J]. Inorganic Chemicals Industry, 2023, 55(10): 121-127.

Figures/Tables 13

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References 18

1	杨卉芃，曹飞.世界钾资源研究系列之一：资源概况及供需分析［J］.矿产保护与利用，2015（1）：75-78.
	YANG Huipeng， CAO Fei.Series study on potassium resources in world：General situation and analysis of supply and demand［J］.Conservation and Utilization of Mineral Resources，2015（1）：75-78.
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	王鑫，李恩泽，程芳琴.国内外钾资源及钾肥生产现状［J］.广州化工，2018，46（14）：9-10.
	WANG Xin， LI Enze， CHENG Fangqin.Present situation of domestic and abroad potassium resources and potash production［J］.Guangzhou Chemical Industry，2018，46（14）：9-10.
4	郭占成，彭翠，张福利，等.利用钢铁企业烧结电除尘灰生产氯化钾的方法：中国，200810101269.3［P］.2010-06-02.
5	闫新平，蒋宝华，刘竹焕.综合处理工业废弃物的方法：中国，201110040653.9［P］.2013-01-30.
6	王笑，吕扬，仪垂杰，等.烧结机头电除尘灰的资源化应用现状［J］.科技创新与应用，2022，12（10）：50-53，58.
	WANG Xiao， Yang LÜ， YI Chuijie，et al.Present situation of resource application of electrostatic precipitator dust in sintering machine head［J］.Technology Innovation and Application，2022，12（10）：50-53，58.
7	郭占成，詹光.一种利用水泥窑灰生产氯化钾及联产碳酸钙的方法：中国，201410074515.6［P］.2016-05-11.
8	张向南.关于利用水泥窑灰生产钾肥的分析［J］.化工管理，2016（29）：271.
9	周建国，张曙光，李萍，等.城市生活垃圾焚烧飞灰水洗脱氯实验研究［J］.天津城建大学学报，2015，21（6）：417-422.
	ZHOU Jianguo， ZHANG Shuguang， LI Ping，et al.Experimental study of removal of soluble chlorides by water-washing pretreatment of municipal solid waste incineration fly ash［J］.Journal of Tianjin Chengjian University，2015，21（6）：417-422.
10	郭煜诚.MSWI飞灰脱盐及固化重金属性能研究［D］.徐州：中国矿业大学，2021.
	GUO Yucheng.Research on granulation desalination of MSWI （municipal solid waste incineration） fly ash and solidification of heavy metals［D］.Xuzhou：China University of Mining and Technology，2021.
11	常威.生活垃圾焚烧飞灰的水洗及资源化研究［D］.杭州：浙江大学，2016.
	CHANG Wei.Study on the washing process and recycling of MSWI fly ash［D］.Hangzhou：Zhejiang University，2016.
12	张晓樵.生活垃圾焚烧飞灰毒性浸出规律及水洗预处理废水资源化处理探索［D］.上海：上海大学，2015.
	ZHANG Xiaoqiao.Leaching characteristics of heavy metals in MSWI fly ash and resource recovery from wastewater during pre-treatment process［D］.Shanghai：Shanghai University，2015.
13	王月香，邵兰燕，徐天男，等.垃圾焚烧飞灰中氯元素存在形态及深度脱氯的研究［J］.无机盐工业，2021，53（5）：78-83.
	WANG Yuexiang， SHAO Lanyan， XU Tiannan，et al.Study on existing speciation and deep dechlorination of chlorine in waste incineration fly ash［J］.Inorganic Chemicals Industry，2021，53（5）：78-83.
14	常威，刘宏辉，蒋旭光.垃圾焚烧飞灰水洗脱氯及重金属浸出特性研究［J］.无机盐工业，2022，54（3）：113-118.
	CHANG Wei， LIU Honghui， JIANG Xuguang.Study on dechlorination and heavy metal leaching characteristics of MSWI fly ash during water-washing［J］.Inorganic Chemicals Industry，2022，54（3）：113-118.
15	潘明亮，戚丽娜，王军堂，等.利用烧结法熟料窑窑灰生产氯化钾的方法：中国，200710015645.2［P］.2007-11-07.
16	梁保民.水盐体系相图原理及运用［M］.北京：轻工业出版社，1986.
17	牛自得，程芳琴.水盐体系相图及其应用［M］.天津：天津大学出版社，2002.
18	中国科学院青海盐湖研究所分析室.卤水和盐的分析方法［M］.2版.北京：科学出版社，1988.

温度/ ℃	液相组成/%			固相
温度/ ℃	J（Na₂²⁺）	J（SO₄^2-）	J（H₂O）	固相
25	100.0	19.9	1 590	NaCl+Na₂SO₄
	85.2	20.9	1 460	NaCl+Na₂SO₄+Gla
	80.0	13.6	1 460	NaCl+Gla
	75.0	9.4	1 465	NaCl+Gla
	70.5	6.5	1 465	NaCl+Gla+KCl
	70.0	0.0	1 525	NaCl+KCl
	86.2	30.0	1 540	Na₂SO₄+Gla
	87.5	50.0	1 650	Na₂SO₄+Gla
	87.8	57.0	1 660	Na₂SO₄+S₁₀+Gla
	100.0	46.5	1 730	Na₂SO₄+S₁₀
	87.3	60.0	1 690	S₁₀+Gla
	84.4	80.0	1 880	S₁₀+Gla
	81.3	100.0	2 070	S₁₀+Gla
	60.0	6.2	1 600	Gla+KCl
	40.0	5.5	1 855	Gla+KCl
	32.5	5.4	1 940	Gla+KCl+K₂SO₄
	34.0	20.0	2 930	Gla+K₂SO₄
	35.7	40.0	3 740	Gla+K₂SO₄
	37.6	60.0	4 160	Gla+K₂SO₄
	38.8	80.0	4 370	Gla+K₂SO₄
	39.1	100.0	4 445	Gla+K₂SO₄
	20.0	4.6	2 085	Gla+K₂SO₄
	0.0	3.5	2 285	Gla+K₂SO₄
100	100.0	12.2	1 530	NaCl+Na₂SO₄
	80.0	13.7	1 370	NaCl+Na₂SO₄
	70.0	14.4	1 290	NaCl+Na₂SO₄+Gla
	60.0	8.9	1 215	NaCl+Gla
	49.5	5.4	1 145	NaCl+Gla+KCl
	49.7	0.0	1 180	NaCl+KCl
	71.5	20.0	1 355	Na₂SO₄+Gla
	74.5	40.0	1 535	Na₂SO₄+Gla
	76.3	60.0	1 605	Na₂SO₄+Gla
	77.6	80.0	1 555	Na₂SO₄+Gla
	78.7	100.0	1 470	Na₂SO₄+Gla
	40.0	5.3	1 225	Gla+KCl
	30.0	5.1	1 300	Gla+KCl
	19.8	4.8	1 375	Gla+KCl+K₂SO₄
	21.0	20.0	2 100	Gla+K₂SO₄
	22.7	40.0	2 530	Gla+K₂SO₄
	24.4	60.0	2 725	Gla+K₂SO₄
	25.7	80.0	2 820	Gla+K₂SO₄
	26.8	100.0	2 850	Gla+K₂SO₄
	10.0	4.3	1 420	KCl+K₂SO₄
	0.0	3.9	1 450	KCl+K₂SO₄

序号	淡水量/ g	水量为理论值的倍数	浸取液中K⁺质量分数/%	K⁺溶出率/ %
1	466.0	1.1	7.54	43.0
2	512.0	1.3	7.17	53.5
3	680.0	2.0	6.78	64.7
4	920.0	3.0	4.86	78.7

序号	时间/h	溶出液中K⁺质量分数/%	K⁺的溶出率/%
1	6	7.51	47.2
2	4	6.78	64.7
3	2	5.50	70.4
4	1	5.31	75.0

序号	溶浸次数	溶出液中K⁺质量分数/%	K⁺的溶出率/%
1	4	7.95	78.2
2	5	9.62	81.2
3	6	12.60	95.2

阶段	名称		质量/g	质量分数/%
阶段	名称		质量/g	K⁺	Cl^-	SO₄^2-	Na⁺
Ⅰ	入料	浸取液	500.0	12.60	11.46	2.45	1.20
	出料	母液1	401.6	12.99	13.07	0.92	1.52
		固相1	18.2	43.23	4.36	48.47	0.62
		水	56.0	—	—	—	—
Ⅱ	入料	母液1	385.2	12.99	13.07	0.92	1.52
	出料	母液2	95.6	6.32	14.74	1.27	6.73
		固相2	92.1	47.10	43.55	2.56	2.59
		水	189.5	—	—	—	—

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on recycling process of potassium from calcium aluminate fly ash

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