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从磷石膏浸出液中高效回收磷和氟:选择性沉淀和吸附。

Highly efficient recovery of phosphate and fluoride from phosphogypsum leachate: Selective precipitation and adsorption.

机构信息

Key Laboratory of Novel Biomass-Based Environmental and Energy Materials in Petroleum and Chemical Industry, Hubei Novel Reactor & Green Chemical Technology Key Laboratory, Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemistry and Environmental Engineering, Wuhan Institute of Technology, Wuhan, China.

Key Laboratory of Novel Biomass-Based Environmental and Energy Materials in Petroleum and Chemical Industry, Hubei Novel Reactor & Green Chemical Technology Key Laboratory, Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemistry and Environmental Engineering, Wuhan Institute of Technology, Wuhan, China.

出版信息

J Environ Manage. 2024 Sep;367:122064. doi: 10.1016/j.jenvman.2024.122064. Epub 2024 Aug 3.

Abstract

Phosphogypsum, a typical by-product in the phosphorus chemical industry, could generate a large amount of leachate containing phosphate and fluoride in the process of rainfall and long-term stacking, which not only causes serious environmental pollution, but also leads to a waste of resources. In this study, a united treatment of calcium hydroxide precipitation and lanthanum zeolite (La-ZFA) adsorption was proposed to achieve the recovery of phosphate and fluoride from phosphogypsum leachate. In phosphogypsum, most phosphorus could be leached except P in the residual occurrence form, while for fluoride, only water-soluble F could be effectively leached. The optimum leaching amounts of phosphate and fluoride were 22.59 and 4.64 mg/g, respectively, at liquid-solid ratio of 400:1, leaching time of 120 min, pH of 6.0, particle size of >200 mesh (<0.075 mm), and leaching temperature of 25°C. Using Ca(OH) as the precipitant, the phosphate could be precipitated selectively from phosphogypsum leachate by controlling pH and time, and the concentrations of it decreased significantly to 0.29 mg/L at pH 10.0, with a removal efficiency of 99.48%. XRD, SEM and Visual MINTEQ software analysis proved that the main component of the precipitate was hydroxyapatite (Ca(PO)(OH)). After P precipitation, a series of sorbents for fluoride were investigated, and La-ZFA sorbent was chosen and utilized to recover the fluoride from the leachate through a cyclic fixed-bed column. The efficiency of La-ZFA was basically not affected by the high concentration sulfate, and it can selectively adsorb fluoride from phosphogypsum leachate, leading to a final fluoride concentration of 0.29 mg/L in the effluent. The characterization demonstrated that fluoride might be adsorbed onto the La-ZFA via ligand exchange with hydroxy groups. The proposed method in this study is expected to sequentially recover phosphate and fluorine from the leachate of phosphogypsum, and it has great guiding significance for resource utilization and management of phosphogypsum.

摘要

磷石膏是磷化工生产过程中的一种典型副产物,在降雨和长期堆积过程中会产生大量含有磷酸盐和氟化物的浸出液,不仅造成严重的环境污染,而且导致资源浪费。本研究提出了一种联合处理方法,即采用氢氧化钙沉淀和镧沸石(La-ZFA)吸附,从磷石膏浸出液中回收磷酸盐和氟化物。在磷石膏中,除了残余赋存形式的磷外,大部分磷都可以浸出,而对于氟化物,只有水溶性氟可以有效浸出。在液固比为 400:1、浸出时间为 120 min、pH 值为 6.0、粒径大于 200 目(<0.075 mm)和浸出温度为 25°C 的条件下,磷酸盐和氟化物的最佳浸出量分别为 22.59 和 4.64 mg/g。使用 Ca(OH)2作为沉淀剂,可以通过控制 pH 值和时间从磷石膏浸出液中选择性沉淀磷酸盐,其浓度显著降低至 0.29 mg/L,去除率为 99.48%。XRD、SEM 和 Visual MINTEQ 软件分析证明,沉淀的主要成分是羟基磷灰石(Ca(PO)(OH))。磷沉淀后,考察了一系列用于氟化物的吸附剂,选择并利用 La-ZFA 吸附剂通过循环固定床柱从浸出液中回收氟化物。La-ZFA 的效率基本不受高浓度硫酸盐的影响,可以从磷石膏浸出液中选择性吸附氟化物,导致流出液中氟化物浓度最终达到 0.29 mg/L。表征表明,氟化物可能通过与羟基的配体交换吸附在 La-ZFA 上。本研究提出的方法有望从磷石膏浸出液中顺序回收磷酸盐和氟,对磷石膏的资源利用和管理具有重要的指导意义。

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