湿法磷酸浸出强化及有机质去除研究

doi:10.11949/0438-1157.20200672

摘要/Abstract

摘要：

在湿法磷酸浸出过程中由于部分有机物碳化不彻底，使产品磷酸呈现黑色。本文提出了一种新型的催化氧化湿法磷酸净化技术，即在湿法磷酸浸出过程中引入氧化剂（H₂O₂）及催化剂（MnO₂），基于转化过程中形成的 $· O H$ 和 $H O 2 ·$ 等过氧化物实现对有机物的去除与浸出过程的强化。重点考察不同反应条件对湿法磷酸浸出率及有机质去除的影响。结果表明，浸出时间为40 min、反应温度为80℃、H₂O₂用量为0.08 ml/g、催化剂与磷矿的质量比为0.04时，磷矿浸出率可达96.9%；同时测定得到的TOC去除率达到79%。分析机理可得，H₂O₂会与溶液中的H₃PO₄形成H₃PO₄·H₂O₂过氧化物，MnO₂与之发生类Fenton反应，产生大量 $· O H$ ，进而将黑色有机物充分氧化为CO₂和H₂O，打破有机物对磷矿颗粒表面的“包裹”，促进磷酸的浸出和有机物的去除。

关键词: 湿法磷酸, 黑色有机物, 催化氧化

Abstract:

In the process of wet-process phosphoric acid leaching, the product phosphoric acid appears black due to the incomplete carbonization of some organic matter. A novel type of catalytic oxidation wet-process phosphoric acid purification technology was proposed in this work. During the leaching process, the oxidant (H₂O₂) and catalyst (MnO₂) was added to form the peroxides such as ·OH and HO₂· in the transformation process, which can enhance the removal rate of organic matter and strengthen the leaching rate of phosphate rock. The different reaction conditions that affected the leaching rate of wet-phosphoric acid and the removal of organic matter were investigated. The results indicated that 96.9% of phosphate rock were leached under the optimum conditions of H₂O₂ dosage 0.08 ml/g, MnO₂/P mass ratio of 0.04, 80℃ and for 40 min. At the same time, the TOC remove rate reached 79%. The analysis mechanism showed that H₂O₂will form H₃PO₄· H₂O₂ peroxide with H₃PO₄in the solution, and MnO₂will react with it like Fenton to generate a large amount of ·OH, and then fully oxidized the black organic matter into CO₂ and H₂O. Organic matter “wrapped” on the surface of the phosphate rock is broken by ·OH, which promoted the leaching of phosphoric acid and enhanced the removal of organic matter.

Key words: wet-process phosphoric acid, black organic matter, catalytic oxidation

中图分类号:

TQ 126.3

陶长元, 王秀秀, 刘作华, 刘仁龙, 栾进华. 湿法磷酸浸出强化及有机质去除研究[J]. 化工学报, 2020, 71(10): 4792-4799.

Changyuan TAO, Xiuxiu WANG, Zuohua LIU, Renlong LIU, Jinhua LUAN. Research on leaching rate enhancement and organic matter removal in wet-process phosphoric acid[J]. CIESC Journal, 2020, 71(10): 4792-4799.

图/表 11

图1 磷矿石的XRD谱图

Fig.1 XRD pattern of phosphate rock

表1 磷矿石的成分

Table1 Composition of phosphate rock

成分	含量/%（mass）
Ca	60.98
P	20.36
Si	7.19
F	4.29
Mg	2.83
Fe	2.01
Al	0.78
K	0.43
S	0.37

图2 实验流程简图

Fig.2 Schematic diagram of experimental process

图3 反应时间对磷矿浸出率的影响

Fig.3 Effect of leaching time on leaching rate

图4 温度对浸出率的影响

Fig.4 Effect of the leaching temperature on leaching rate

图5 H2O2用量对磷矿浸出率的影响

Fig.5 Effect of mass of H2O2 on phosphorite leaching

图6 MnO2用量对磷矿浸出率的影响

Fig.6 Effect of mass of MnO2 on phosphorite leaching

图7 TOC去除率变化规律

Fig.7 Change rule of TOC removal rate

图8 不同浸出条件下磷矿XRD谱图

Fig.8 XRD patterns of phosphate rock under different extraction conditions a—original phosphate rock; b—direct acid extraction; c—H2O2 extraction; d—MnO2 extraction; e—H2O2with MnO2 extraction

图9 浸出前后磷矿的SEM图（a）原磷矿；（b）直接酸浸；（c） MnO2强化浸出；（d） H2O2强化浸出；（e） H2O2与MnO2协同浸出

Fig.9 SEM images of phosphate rock under different extraction conditions

图10 催化氧化法去除有机质机理图

Fig.10 Mechanism of organic matter removal by catalytic oxidation

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