湿法磷酸浸出强化及有机质去除研究

陶长元; 王秀秀; 刘作华; 刘仁龙; 栾进华

doi:10.11949/0438-1157.20200672

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湿法磷酸浸出强化及有机质去除研究

能源和环境工程 | 更新时间：2025-11-25

- 湿法磷酸浸出强化及有机质去除研究
- Research on leaching rate enhancement and organic matter removal in wet-process phosphoric acid
- 化工学报 2020年71卷第10期页码：4792-4799
- 作者机构：
  
  1.重庆大学化学化工学院，重庆 400044
  2.重庆大学煤矿灾害动力学与控制国家重点实验室，重庆 400044
  3.重庆地质矿产研究院，重庆 400044
- 作者简介：
  
  陶长元（1963—），男，博士，教授，taocy@cqu.edu.cn
- 基金信息：
  
  国家重点研发计划项目(2019YFC1905802);重庆市教委科学技术研究计划项目(KJZD-M201900101);重庆市规划和自然资源局科技项目(KJ-2019036)
- DOI：10.11949/0438-1157.20200672
  中图分类号： TQ 126.3
- 收稿：2020-06-03，
  
  修回：2020-07-14，
  
  纸质出版：2020-10-05
- 稿件说明：
移动端阅览
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

TAO Changyuan, WANG Xiuxiu, LIU Zuohua, LIU Renlong, LUAN Jinhua. Research on leaching rate enhancement and organic matter removal in wet-process phosphoric acid[J]. CIESC Journal, 2020, 71(10): 4792-4799
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 DOI： 10.11949/0438-1157.20200672.

TAO Changyuan, WANG Xiuxiu, LIU Zuohua, LIU Renlong, LUAN Jinhua. Research on leaching rate enhancement and organic matter removal in wet-process phosphoric acid[J]. CIESC Journal, 2020, 71(10): 4792-4799 DOI： 10.11949/0438-1157.20200672.

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（H

）及催化剂（MnO

），基于转化过程中形成的

http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=5545984&type=

http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=5545975&type=

6.01133347

2.28600001

和

http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=5546000&type=

http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=5545993&type=

6.94266701

3.21733332

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℃、H

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，H

会与溶液中的H

形成H

·H

过氧化物，MnO

与之发生类Fenton反应，产生大量

http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=5546022&type=

http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=5546011&type=

6.01133347

2.28600001

，进而将黑色有机物充分氧化为CO

和H

O，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。

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 (H

) and catalyst (MnO

) was added to form the peroxides such as ·OH and HO

· 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 H

dosage 0.08 ml/g

MnO

/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 H

will form H

· H

peroxide with H

in the solution

and MnO

will react with it like Fenton to generate a large amount of ·OH

and then fully oxidized the black organic matter into CO

and H

O. 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.

关键词

Keywords

references

Arisht S N , Abdul P M , Liu C M , et al . Biotoxicity assessment and lignocellulosic structural changes of phosphoric acid pre-treated young coconut husk hydrolysate for biohydrogen production [J]. International Journal of Hydrogen Energy , 2019 , 44 ( 1 ): 5830 - 5843 .

Matta S , Stephan K , Stephan J , et al . Phosphoric acid production by attacking phosphate rock with recycled hexafluosilicic acid [J]. International Journal of Mineral Processing , 2017 , 161 ( 10 ): 21 - 27 .

Ma H , Feng X , Zeng B . Self-anticorrosion for the combustion tower of heat recovered thermal process phosphoric acid production [J]. Process Safety and Environmental Protection , 2018 , 118 ( 8 ): 330 - 347 .

孟详东 , 黄群星 , 严建华 , 等 . 磷在污泥热解过程中的迁移转化 [J]. 化工学报 , 2018 , 69 ( 7 ): 3208 - 3215 .

Meng X D , Huang Q X , Yan J H , et al . Migration and transformation of phosphorus during pyrolysis process of sewage sludge [J]. CIESC Journal , 2018 , 69 ( 7 ): 3208 - 3215 .

张海燕 , 邹密 , 杨劲 , 等 . 中低品位磷矿直接制湿法磷酸技术研究 [J]. 化工矿物与加工 , 2015 , 44 ( 1 ): 17 - 20 .

Zhang H Y , Zhou M , Yang J , et al . Study on the direct preparation of wet phosphoric acid from medium and low grade phosphate [J]. Industrial Minerals and Processing , 2015 , 44 ( 1 ): 17 - 20 .

Han Y , Cui X , Lv X , et al . Preparation and characterization of geopolymers based on a phosphoric-acid-activated electrolytic manganese dioxide residue [J]. Journal of Cleaner Production , 2018 , 205 ( 20 ): 488 - 498 .

Li G , Zhou Q , Zhu Z , et al . Selective leaching of nickel and cobalt from limonitic laterite using phosphoric acid: an alternative for value-added processing of laterite [J]. Journal of Cleaner Production , 2018 , 189 ( 10 ): 620 - 626 .

Chen H , Li W , Wang J , et al . Adsorption of cadmium and lead ions by phosphoric acid-modified biochar generated from chicken feather: selective adsorption and influence of dissolved organic matter [J]. Bioresource Technology , 2019 , 292 : 12 - 19 .

Khoualdia B , Loungou M , Elaloui E . Adsorption of organic matter from industrial phosphoric acid (H 3 PO 4 ) onto activated bentonite [J]. Arabian Journal of Chemistry , 2017 , 10 : S1073 - S1080 .

Zermane S , Meniai A H . Experimental study of competitive adsorption of heavy metals and organic matter for the phosphoric acid purification [J]. Energy Procedia , 2012 , 18 : 888 - 895 .

李天祥 , 李白玉 , 刘飞 , 等 . 湿法磷酸中有机物的脱除方法 [J]. 无机盐工业 , 2008 , 40 ( 12 ): 44 - 46 .

Li T X , Li B Y , Liu F , et al . Method for removal of organic matter from wet phosphoric acid [J]. Inorganic Chemicals Industry , 2008 , 40 ( 12 ): 44 - 46 .

李燕凤 , 李军 , 任永胜 , 等 . 预分散溶剂萃取用于浓缩湿法磷酸脱色 [J]. 无机盐工业 , 2007 , 5 ( 7 ): 33 - 35 .

Li Y F , Li J , Ren Y S , et al . Predispersed solvent extraction is used to concentrate wet phosphoric acid for decolorization [J]. Inorganic Chemicals Industry , 2007 , 5 ( 7 ): 33 - 35 .

林倩 , 耿建铭 , 江燕斌 , 等 . 超纯过氧化氢制备中有机杂质的吸附净化技术进展 [J]. 化工进展 , 2006 , 67 ( 9 ): 1031 - 1035 .

Lin Q , Geng J M , Jiang Y B , et al . Advances in the adsorption and purification of organic impurities in the preparation of ultrapure hydrogen peroxide [J]. Chemical industry and Engineering Progress , 2006 , 67 ( 9 ): 1031 - 1035 .

Ulu F , Gengec E , Kobya M . Removal of natural organic matter from Lake Terkos by EC process: studying on removal mechanism by floc size and zeta potential measurement and characterization by HPSEC method [J]. Journal of Water Process Engineering , 2019 , 17 : 31 - 35 .

Särkkä H , Vepsäläinen M , Sillanpää M . Natural organic matter (NOM) removal by electrochemical methods — a review [J]. Journal of Electroanalytical Chemistry , 2015 , 755 ( 1 ): 100 - 108 .

Vepsäläinen M , Ghiasvand M , Selin J , et al . Investigations of the effects of temperature and initial sample pH on natural organic matter (NOM) removal with electrocoagulation using response surface method (RSM) [J]. Separation and Purification Technology , 2009 , 69 ( 15 ): 255 - 261 .

Ma L , He M , Fu P , et al . Adsorption of volatile organic compounds on modified spherical activated carbon in a new cyclonic fluidized bed [J]. Separation and Purification Technology , 2020 , 235 : 116146 .

李兵 , 杨义 , 刘作华 , 等 . 湿法磷酸固-液体系混沌混合与浸出强化行为 [J]. 化工学报 , 2019 , 70 ( 5 ): 1742 - 1749 .

Li B , Yang Y , Liu Z H , et al . Olid-liquid chaotic mixing and leaching enhancement performance in phosphoric acid leaching process [J]. CIESC Journal , 2019 , 70 ( 5 ): 1742 - 1749 .

Guillossou R , Le Roux J , Mailler R , et al . Influence of dissolved organic matter on the removal of 12 organic micropollutants from wastewater effluent by powdered activated carbon adsorption [J]. Water Research , 2020 , 172 : 115487 .

陈亮 , 李军 , 钟本和 . 浓缩湿法磷酸脱色研究 [J]. 无机盐工业 , 2005 , 37 ( 7 ): 21 - 22 .

Chen L , Li J , Zhong B H . Study on decolorization of concentrated wet phosphoric acid [J]. Inorganic Chemicals Industry , 2005 , 37 ( 7 ): 21 - 22 .

Ike I A , Karanfil T , Cho J , et al . Oxidation byproducts from the degradation of dissolved organic matter by advanced oxidation processes — a critical review [J]. Water Research , 2019 , 164 : 114929 .

Wang H , Quan B , Bo G , et al . Advanced oxidation treatment of dissolved organic matter from wastewater treatment plant secondary effluent using scattering electrical reactor [J]. Journal of Cleaner Production , 2020 , 267 : 122258 .

Fu L , Wu C , Zhou Y , et al . Ozonation reactivity characteristics of dissolved organic matter in secondary petrochemical wastewater by single ozone, ozone/H 2 O 2 , and ozone/catalyst [J]. Chemosphere , 2019 , 233 : 34 - 43 .

Razaviarani V , Zazo J A , Casas J A , et al . Coupled fenton-denitrification process for the removal of organic matter and total nitrogen from coke plant wastewater [J]. Chemosphere , 2019 , 224 : 653 - 657 .

Zhang Y , Liu H , Dai X , et al . The release of organic matter, nitrogen, phosphorus and heavy metals from erythromycin fermentation residue under heat-activated persulfate oxidation conditioning [J]. Science of the Total Environment , 2020 , 724 : 138349 .

Ernst M , Lurot F , Schrotter J C . Catalytic ozonation of refractory organic model compounds in aqueous solution by aluminum oxide [J]. Applied Catalysis B: Environmental , 2004 , 47 ( 8 ): 15 - 25 .

Tang Y , Zheng S , Xu Y , et al . Advanced batteries based on manganese dioxide and its composites [J]. Energy Storage Materials , 2018 , 12 : 284 - 309 .

国家技术监督局 , 化工部化工矿山设计研究院 . 磷矿石和磷精矿中五氧化二磷含量的测定磷钼酸喹啉重量法和容量法 : GB/T 1871.1—1995[S]. 北京 : 中国标准出版社 , 1995 .

The State Bureau of Quality and Technical Supervision, Chemical Mine Design and Research Institute, Ministry of Chemical Industry, Standardization Administration of The People's Republic of China . Phosphate rock and concentrate—determination of phosphrous pentoxide content—quinoline phosphomolybdate gravimetric and volumetric methods : GB/T 1871.1—1995[S]. Beijing : Standards Press of China , 1995 .

中华人民共和国国家质量监督检验检疫总局 , 中国国家标准化管理委员会 . 循环冷却水中总有机碳(TOC)的测定 : GB/T 32116—2015[S]. 北京 : 中国标准出版社 , 2015 .

General Administration of Quality Supervision , Inspection and Quarantine of the People's Republic of China , Standardization Administration of the People's Republic of China . Determination of total organic carbon (TOC) in industrial circulating cooling water : GB/T 32116-2015 [S]. Beijing : Standards Press of China , 2015 .

Shu J , Liu R , Liu Z , et al . Enhanced extraction of manganese from electrolytic manganese residue by electrochemical [J]. Journal of Electroanalytical Chemistry , 2016 , 780 ( 1 ): 32 - 37 .

Vega E , Valdés H . New evidence of the effect of the chemical structure of activated carbon on the activity to promote radical generation in an advanced oxidation process using hydrogen peroxide [J]. Microporous and Mesoporous Materials , 2018 , 259 ( 15 ): 1 - 8 .

Hao Z , Wang J , Yin Y , et al . Abiotic formation of organoiodine compounds by manganese dioxide induced iodination of dissolved organic matter [J]. Environment Pollution , 2018 , 236 : 672 - 679 .

Shu J , Liu R , Liu Z , et al . Manganese recovery and ammonia nitrogen removal from simulation wastewater by pulse electrolysis [J]. Separation and Purification Technology , 2016 , 168 ( 10 ): 107 - 113 .

Zhang X , Wang J , Dong X X , et al . Functionalized metal-organic frameworks for photocatalytic degradation of organic pollutants in environment [J]. Chemosphere , 2019 , 242 : 125144 .

Filipovic M R , Koppenol W H . The Haber-Weiss reaction — the latest revival [J]. Free Radical Biology Medicine , 2019 , 145 : 221 - 222 .

Baldikova E , Pospiskova K , Safarikova M , et al . Non-woven fabric supported manganese dioxide microparticles as a low-cost, easily recoverable catalyst for hydrogen peroxide decomposition [J]. Materials Chemistry and Physics , 2018 , 203 ( 1 ): 280 - 283 .

Zhang Y , Wang F , Ou P , et al . High efficiency and rapid degradation of bisphenol A by the synergy between adsorption and oxidization on the MnO 2 @nano hollow carbon sphere [J]. Journal of Hazardous Materials , 2018 , 360 ( 15 ): 223 - 232 .

Qu F , Yan Z , Liu W , et al . Effects of manganese dioxides on the ultrafiltration membrane fouling by algal extracellular organic matter [J]. Separation and Purification Technology , 2015 , 153 ( 16 ): 29 - 36 .

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