酸浸猪粪磷形态转变及强化蓝铁矿回收的研究  

Phosphorus Transformation and Vivianite Recovery Enhancement from Acid Leaching Pig Manure

作　　者：张雷 梁嘉林 李城坚 麦志宏 徐智敏 李月桂 刘晖[1] ZHANG Lei;LIANG Jia-lin;LI Cheng-jian;MAI Zhi-hong;XU Zhi-min;LI Yue-gui;LIU Hui(College of Resource and Environment,Zhongkai University of Agriculture and Engineering,Guangzhou 510225,China;Yongning Street Ecological Environmental Protection and Water Integrated Service Center of Zengcheng District,Guangzhou Municipality,Guangzhou 511358,China)

机构地区：[1]仲恺农业工程学院资源与环境学院,广东广州510225 [2]广州市增城区永宁街生态环境保护和水务综合服务中心,广东广州511358

出　　处：《生态与农村环境学报》2024年第9期1239-1250,共12页Journal of Ecology and Rural Environment

基　　金：广东省重点领域研发计划项目(2023B0202060001,2020B0202080002);广东省基础与应用基础研究基金(2022A1515110629);2023年度广东省农业面源污染监测点项目(0835-230Z52802722);2023年仲恺农业工程学院大学生创新基金(2023CX24)。

摘　　要：猪粪因其磷含量高而成为具有前景的磷回收原料。为了提高猪粪中磷的回收效果,考察了硫酸(H_(2) SO_(4))、盐酸(HCl)、草酸(H_(2) C_(2) O_(4))和抗坏血酸(C_(6)H_(8)O_(6))4种浸提剂的酸浸浓度、酸浸时间以及液固比对猪粪释磷效果的影响,以及对砷(As)、铬(Cr)、铜(Cu)和锌(Zn)等重金属元素浸出行为的影响;通过C-J连续提取法对比分析4种酸处理前后的磷形态,探明猪粪中磷形态转化规律;最后探讨了二价铁(Fe^(2+))诱导结晶生成蓝铁矿的可行性。结果表明,H_(2) C_(2) O_(4)酸浸释磷性能优于H_(2) SO_(4)和HCl,显著优于C_(6)H_(8)O_(6)。猪粪样品经4种提取液酸浸后,重金属元素释出量大小为Zn>Cu>As>Cr;与H_(2) SO_(4)和HCl相比,H_(2) C_(2) O_(4)对重金属元素的浸出量更低。H_(2) SO_(4)、HCl、H_(2) C_(2) O_(4)和C_(6)H_(8)O_(6)对固相磷中铝结合态磷(Al-P)和钙结合态磷(Ca-P)均具有较优的转化效果,转化率>80%;而对于固相磷中的交换态磷(Ex-P)、液相磷中的颗粒态磷(PP)和溶解性还原磷(RDP),与其他3种酸相比,H_(2) C_(2) O_(4)对其具有更高的转化效率。经综合比选,明确H_(2) C_(2) O_(4)为猪粪磷的最佳浸提剂。在H_(2) C_(2) O_(4)浓度为0.10 mol·L^(-1)、酸浸时间为60 min和液固比为50 mL·g^(-1)条件下处理猪粪,液相中可溶性正磷酸盐(Ortho-P)含量从188 mg·L^(-1)提高到882 mg·L^(-1),释磷量从9.42 mg·g^(-1)提升到44.1 mg·g^(-1),效率提升369%。采用Fe^(2+)诱导结晶生成蓝铁矿回收上清液中的磷,通过X射线衍射仪(XRD)、X射线光电子能谱(XPS)和扫描电镜(SEM)等表征手段得出,反应合成的磷回收产物为纯度较高的蓝铁矿。研究成果可为猪粪中磷回收率和回收产物价值的提升提供依据。Pig manure has been recognized as a potent source for phosphorus recovery due to its substantial phosphorus content.To optimize the efficiency of phosphorus extraction,the effects of various acid types(sulfuric acid-H_(2) SO_(4),hydrochloric acid-HCl,oxalic acid-H_(2) C_(2) O_(4),and ascorbic acid-C_(6)H_(8)O_(6)),concentration of acids,duration of leaching,and the liquid-to-solid ratio were thoroughly examined.Additionally,the leaching process was monitored for the release behavior of heavy metals such as As,Cr,Cu,and Zn.The transformation mechanisms of phosphorus speciation before and after treatment were analyzed using the C-J extraction method.The potential of Fe^(2+)-induced crystallization to produce vivianite,a phosphorus recovery method,was also explored.Results indicate that H_(2) C_(2) O_(4) was superior in phosphorus release efficiency compared to H_(2) SO_(4),HCl,and C_(6)H_(8)O_(6).The sequence of heavy metal release during the acid leaching was Zn>Cu>As>Cr,with the H_(2) C_(2) O_(4) group showing a significantly lower heavy metal release rate than the H_(2) SO_(4) and HCl groups.In terms of phosphorus conversion in solid forms(Al-P and Ca-P),all acid treatments achieved over 80%conversion efficiency.Notably,the H_(2) C_(2) O_(4) treatment showed enhanced conversion rates for Ex-P in solid phosphorus,as well as for particulate phosphorus(PP)and readily dispersible phosphorus(RDP)in the liquid phase.The optimal conditions for phosphorus extraction using H_(2) C_(2) O_(4) were determined to be a concentration of 0.10 mol·L^(-1),a leaching duration of 60 minutes,and a liquid-to-solid ratio of 50 mL·g^(-1).Under these conditions,the soluble orthophosphate(Ortho-P)concentration in the liquid phase soared from 188 mg·L^(-1) to 882 mg·L^(-1),while the phosphorus release content dramatically increased from 9.42 mg·g^(-1) to 44.1 mg·g^(-1),marking a 369%enhancement in phosphorus release efficiency.The method of employing Fe^(2+)-induced crystallization to recover phosphorus from the leachate treated wit

关 键 词：猪粪 磷回收 磷形态 酸浸 蓝铁矿 

分 类 号：X713[环境科学与工程—环境工程]