磷石膏中磷的浸出行为及其动力学研究

doi:10.19964/j.issn.1006-4990.2024-0184

Abstract

Abstract:

It boasts an immense reserve of phosphogypsum with a low utilization rate in China，requiring large-scale stockpiling.In order to reduce the problem of phosphorus pollution caused by phosphogypsum storage process in China，a leaching technology which was widely used due to its simple process and high efficiency was adopted.The effects of nitric acid concentration，solid-liquid mass-to-volume ratio，stirring speed，temperature and reaction time on the leaching efficiency of phosphorus were investigated.The results showed that the phosphorus leaching efficiency was increased with the increase of nitric acid concentration，stirring speed，temperature and reaction time，and decreased with the increase of solid-liquid mass-to-volume ratio，in which the nitric acid concentration，solid-liquid mass-to-volume ratio and stirring speed had a significant effect on phosphorus leaching efficiency，while the temperature had a small effect on phosphorus leaching efficiency.A comparative analysis of the physicochemical properties of phosphogypsum，utilizing advanced characterization techniques such as XRD，XPS，and SEM，revealed a notable reduction in phosphorus content post-leaching.Through the response surface methodology，the optimal reaction conditions were obtained.Under the conditions of nitric acid concentration of 0.50 mol/L，solid-liquid mass-to-volume ratio of 1:14，stirring speed of 200 r/min and temperature of 30 ℃，the phosphorus leaching efficiency reached 97.23% in 120 min.Moreover，the phosphorus leaching kinetics in phosphogypsum was studied.It was proved that the reaction process was belonged to the diffusion control of solid product layer，and the activation energy of the reaction was 11.65 kJ/mol.The study provided a theoretical guidance which had important theoretical and practical significance for the efficient leaching of phosphorus，and offered alternative solutions to the phosphorus pollution issues that existed in the storage process of phosphogypsum in China.

Key words: phosphogypsum, phosphorus pollution, nitric acid, leaching, kinetic

CLC Number:

TQ177.3

TAN Shanyi, WEN Huizi, HE Shuyu, ZHANG Liwen, CHEN Shaohua, XI Benjun. Study on leaching behavior and kinetics of phosphorus from phosphogypsum[J]. Inorganic Chemicals Industry, 2025, 57(2): 105-112.

Figures/Tables 11

Fig.1

Fig.2

Table 1

Fig.3

Table 2

Fig.4

Table 3

Fig.5

Fig.6

Fig.7

Fig.8

References 19

1	王方舟.污泥中磷的释出效率与回收技术研究［D］.北京：中国地质大学（北京），2020.
	WANG Fangzhou.Study on phosphorus release efficiency and recovery technology in sludge［D］.Beijing：China University of Geosciences，2020.
2	刘怡心，夏琼霞，李卫华.从污泥中回收蓝铁矿的研究进展［J］.环境科学与技术，2023，46（9）：129-137.
	LIU Yixin， XIA Qiongxia， LI Weihua.Research progress in recovery of vianite from wastewater sludge［J］.Environmental Science & Technology，2023，46（9）：129-137.
3	张家豪，李继，王应席，等.磷石膏作为路用材料的研究进展［J］.化肥设计，2023，61（4）：1-5，26.
	ZHANG Jiahao， LI Ji， WANG Yingxi，et al.Research progress of phospho-gypsum as a road material［J］.Chemical Fertilizer Design，2023，61（4）：1-5，26.
4	LU Dinghui， CHEN Qianlin， LI Cuiqin，et al.Effect of potassium feldspar on the decomposition rate of phosphogypsum［J］.Journal of Chemical Technology & Biotechnology，2021，96（2）：374-383.
5	欧志兵，杨文娟，何宾宾.国内外磷石膏综合利用现状［J］.云南化工，2021，48（11）：6-9.
	Zhibing OU， YANG Wenjuan， HE Binbin.The general introduction of phosphogypsum comprehensive utilization technology in China［J］.Yunnan Chemical Technology，2021，48（11）：6-9.
6	徐怒潮，刘记来，张宗文，等.钟祥市某磷石膏渣场地下水中氨氮和砷的运移模拟研究［J］.环境污染与防治，2021，43（7）：819-821，828.
	XU Nuchao， LIU Jilai， ZHANG Zongwen，et al.Simulation study on ammonia nitrogen and arsenic transfer in the groundwater of a phosphogypsum slag site in Zhongxiang City［J］.Environmental Pollution & Control，2021，43（7）：819-821，828.
7	尹兆波，高利坤，饶兵，等.磷石膏湿法浸出稀土研究进展［J］.磷肥与复肥，2023，38（6）：37-43.
	YIN Zhaobo， GAO Likun， RAO Bing，et al.Research progress in wet leaching of rare earth from phosphogypsum［J］.Phosphate & Compound Fertilizer，2023，38（6）：37-43.
8	曹汐，景慧，王晶.环境水样中总磷检测方法的改进［J］.化工安全与环境，2024，37（3）：39-41，45.
	CAO Xi， JING Hui， WANG Jing.Improvement of detection method of total phosphorus in environmental water samples［J］.Chemical Safety & Environment，2024，37（3）：39-41，45.
9	王浩森，任柄臣，许德华，等.硝酸分解磷钾矿的浸出工艺及动力学［J］.无机盐工业，2023，55（5）：45-51.
	WANG Haosen， REN Bingchen， XU Dehua，et al.Leaching process and kinetics of phosphorus-potassium ore decomposition by nitric acid［J］.Inorganic Chemicals Industry，2023，55（5）：45-51.
10	XIAN Pengfei， ZHOU Shengfan， WANG Mingyu，et al.Extraction of molybdenum and nickel from roasted Ni-Mo ore by hydrochloric acid leaching，sulphation roasting and water leaching［J］.Transactions of Nonferrous Metals Society of China，2017，27（1）：220-226.
11	ZHU Xinrui， LIU Xuheng， ZHAO Zhongwei.Leaching kinetics of scheelite with sodium phytate［J］.Hydrometallurgy，2019，186：83-90.
12	刘佳兴，姜丽帅，冷红光，等.氧压水浸黄铁矿及其动力学研究［J］.湿法冶金，2023，42（5）：485-490.
	LIU Jiaxing， JIANG Lishuai， LENG Hongguang，et al.Oxygen pressure water leaching of pyrite and its kinetics［J］.Hydrometallurgy of China，2023，42（5）：485-490.
13	ZHOU Junfeng， ZHAO Junhua， YANG Fan，et al.Leaching kinetics of potassium and aluminum from phosphorus-potassium associated ore in HCl-CaF₂ system［J］.Separation and Purification Technology，2020，253：117528.
14	陈慧方，吴建，吕宁宁，等.钢渣中磷在盐酸中的浸出动力学研究［J］.金属材料与冶金工程，2022，50（5）：44-49.
	CHEN Huifang， WU Jian， Ningning LÜ，et al.Study on kinetics of dephosphorization process of steel slag［J］.Metal Materials and Metallurgy Engineering，2022，50（5）：44-49.
15	周佳琦，陈葵，武斌，等.磷尾矿煅烧及酸浸过程动力学研究［J］.无机盐工业，2022，54（1）：77-82，108.
	ZHOU Jiaqi， CHEN Kui， WU Bin，et al.Study on kinetics of phosphate tailings calcination and acid leaching process［J］.Inorganic Chemicals Industry，2022，54（1）：77-82，108.
16	孙宁宁，陈喜平，张雅琪.电解锰渣中锰的浸出行为与动力学分析［J］.湿法冶金，2024，43（1）：39-46.
	SUN Ningning， CHEN Xiping， ZHANG Yaqi.Analysis of leaching behavior and kinetics of manganese in electrolytic manganese residue［J］.Hydrometallurgy of China，2024，43（1）：39-46.
17	MADAKKARUPPAN V， PIUS A，T S，et al.Influence of microwaves on the leaching kinetics of uraninite from a low grade ore in dilute sulfuric acid［J］.Journal of Hazardous Materials，2016，313：9-17.
18	LI Chao， WANG Shizhao， WANG Yunshan，et al.Study on synergistic leaching of potassium and phosphorus from potassium feldspar and solid waste phosphogypsum via coupling reactions［J］.Chinese Journal of Chemical Engineering，2024，65：117-129.
19	罗征，杨静，马鸿文，等.氟化物助剂分解钾长石制取硫酸钾研究评述［J］.化工矿物与加工，2018，47（8）：65-70.
	LUO Zheng， YANG Jing， MA Hongwen，et al.Research review of preparation of potassium sulfate from K-feldspar with fluoride as additive agent［J］.Industrial Minerals & Processing，2018，47（8）：65-70.

来源	自由度	F值	P值	显著水平
模型	9	106.93	0.000 1	极显著
A	1	28.91	0.001 0	极显著
B	1	304.66	<0.000 1	极显著
C	1	463.72	<0.000 1	极显著
AB	1	6.67	0.036 3	显著
AC	1	1.95	0.205 1	不显著
BC	1	0.21	0.663 4	不显著

参数		液膜扩散控制	表面化学反应控制	固体产物层扩散控制
		x=Kt	1-（1-x）^1/3= Kt	1-2/3x- （1-x）^2/3=Kt
		R²	R²	R²
浓度/ （mol·L^-1）	0.05	0.693	0.801	0.952
	0.10	0.681	0.805	0.943
	0.30	0.670	0.843	0.954
	0.50	0.653	0.872	0.957
	0.70	0.636	0.890	0.944
	1.00	0.711	0.920	0.974
	1.20	0.689	0.914	0.956
	1.50	0.675	0.895	0.954
	2.00	0.663	0.888	0.940
固液比	1:5	0.677	0.757	0.942
	1:10	0.684	0.824	0.951
	1:15	0.653	0.872	0.957
	1:20	0.672	0.898	0.952
	1:25	0.671	0.901	0.943
搅拌速率/ （r·min^-1）	0	0.695	0.789	0.945
	100	0.661	0.782	0.933
	150	0.661	0.823	0.952
	200	0.653	0.872	0.957
	250	0.616	0.867	0.934
温度/ ℃	25	0.663	0.835	0.942
	30	0.653	0.872	0.957
	40	0.619	0.873	0.921

[1]	LENG Manxi, ZHU Yu, YAN Jikang, XIE Ke, ZOU Yongjie. Study on crystallization characteristics and mineral flotation performance of industrial waste phosphogypsum [J]. Inorganic Chemicals Industry, 2025, 57(3): 108-115.
[2]	TANG Kaijing, LIU Chuanbei, LI Yingding, JIANG Yong, WU Junnan, ZHANG Tao. Research on preparation and mechanism of superhydrophobic phosphogypsum products [J]. Inorganic Chemicals Industry, 2025, 57(1): 97-102.
[3]	ZHENG Kexin, WANG Haifeng, WANG Jiawei, ZHOU Xingjie, PEI Zhengqing, LU Ju, MA Dehua. Study on leaching and kinetics of rhododengite in Jingxi area of Guangxi [J]. Inorganic Chemicals Industry, 2025, 57(1): 51-57.
[4]	YAN Xin, LIU Hailu, LIU Baolin, LIU Yi, LIU Yanyang. Research on key technologies and mechanisms of green nano calcium carbonate production [J]. Inorganic Chemicals Industry, 2025, 57(1): 71-76.
[5]	ZENG Yijun, JIANG Ziwen, JIAN Chengzong, QUAN Xuejun. Study on deep extraction of chromium from calcium-free roasting slag of chromite ore [J]. Inorganic Chemicals Industry, 2025, 57(1): 90-96.
[6]	MA Shuqing, LI Changwen, SHI Chenglong, QIN Yaru. Kinetic study of lithium extraction from solution with iron-based ionic liquid system [J]. Inorganic Chemicals Industry, 2024, 56(9): 60-66.
[7]	TANG Dongwu, YE Changwen, DENG Jie, AO Fang. Study on leaching rate of calcium and magnesium from phosphorus tailings based on thermodynamic analysis and response surface method [J]. Inorganic Chemicals Industry, 2024, 56(9): 98-106.
[8]	FANG Fan, YAO Benlin, XIAO Yiqun, JIA Yanhong, CHEN Hui, LI Bin, HE Hui. Research progress on dissolution behavior and mechanism of uranium dioxide in nitric acid [J]. Inorganic Chemicals Industry, 2024, 56(9): 34-43.
[9]	ZOU Yang, LU Zhiyan, HU Zhilin, SUN Ze. Study on metastable zone width and primary nucleation kinetics for cooling crystallization of KNO₃ [J]. Inorganic Chemicals Industry, 2024, 56(9): 67-74.
[10]	TANG Xuemei, WANG Meibo, XU Li, ZHANG Xujie, TAI Shijun, YI Xianmei, LIU Hongjuan, PAN Linyi. Study on whitening of phosphogypsum by low⁃temperature calcination [J]. Inorganic Chemicals Industry, 2024, 56(8): 110-115.
[11]	SUN Lan, CHEN Shiying, YANG Liuxu, NIU Yiming, ZHAO Aonan. Basic study on fixing soluble phosphorus in phosphogypsum with magnesium slag [J]. Inorganic Chemicals Industry, 2024, 56(8): 92-98.
[12]	HU Cheng, LIU Meng, XIANG Weiheng, CHEN Ping, WANG Neng, LU Guanju, ZHOU Jinlan. Preparation of α-hemihydrous gypsum from CaCl₂ and MgCl₂ and their composite solution [J]. Inorganic Chemicals Industry, 2024, 56(7): 112-117.
[13]	CHENG Ziyang, CHEN Guofu. Early hydration kinetics research of nano-SiO₂ and cement composite cementitious materials [J]. Inorganic Chemicals Industry, 2024, 56(7): 80-87.
[14]	HU Dian, GUO Ze, ZHANG Hanquan, LU Manman. Research on effects of roasting process and typical impurities on reduction and decomposition process of phosphogypsum [J]. Inorganic Chemicals Industry, 2024, 56(7): 88-95.
[15]	XU Zijian, WANG Yu, LIU Jingyong, ZHU Chuanghai, CHEN Zhibin, HUANG Shengzheng, XIE Wuming, SUN Shuiyu. Study on defluorination process of secondary aluminum ash wet process and conversion behavior of fluoride [J]. Inorganic Chemicals Industry, 2024, 56(6): 109-118.

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on leaching behavior and kinetics of phosphorus from phosphogypsum

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 11

References 19

Related Articles 15

Metrics

Comments

Recommended 0