Study on Adsorption Removal of Pb(Ⅱ) by Xanthated Eggshell Membrane

ZOU Xue; GONG Zheng-jun

doi:10.13718/j.cnki.xdzk.2020.11.016

A novel xanthate-modified eggshell membrane (XESM) was synthesized, and used as an efficient adsorbent for the removal of lead ions from aqueous solutions. The structure of the adsorbent was analyzed by SEM and FTIR analysis. Batch biosorption experiments were carried out to evaluate the influences of pH, contact time, initial Pb(Ⅱ) concentration and coexisting substances on the biosorption capacity. The experimental data of the Pb(Ⅱ) removal fitted well with the Langmuir adsorption equation and the pseudo-second-order rate equation. The maximal equilibrium adsorption capacity of XESM to Pb(Ⅱ) was 33.11 mg/g, which was about 13.5-fold higher than that of ESM.

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对人体而言，铅是多系统、多亲和性的毒物，是不可生物降解的累积毒物，可在肾脏、肝脏、骨骼和大脑等多个身体器官中缓慢积累，即使长期低水平铅暴露也会对人类健康造成极大的伤害^[1-2].铅离子主要来源于金属回收(再生铅)，锡箔加工、冶炼和蓄电池制造等工业活动中.为了治理重金属污染，人们采用了很多方法，如化学沉淀、离子交换、超滤、反渗透和电渗析等^[3].由于技术或经济上的限制，传统的水处理程序通常不适合从地表水中有效去除低水平的重金属.而对于某些类型的生物质，即使是非常稀的水溶液，也能够结合和浓缩金属，因此生物吸附法从水溶液中去除和回收重金属越来越受到重视.

蛋壳膜表面含有大量的氨基以及羟基、羧基、二硫键胱氨酸残基、酰胺基等多种官能团，已用于多种污染物的去除，但吸附量较低，功能化可有效提高其吸附性能.目前已有采用氨基化^[4-5]、酸处理^[6]、巯基化^[7-8]和磺酸化^[9]等多种化学改性方法来提高其吸附能力.黄原酸酯是一种含极性基团和非极性基团的阴离子捕收剂，易于制备和金属配合物的高稳定性(低溶解性)产物，在捕收剂中得到广泛应用，加入蛋壳膜可提高蛋壳膜的硫基含量^[10-11].本研究旨在通过黄原酸功能化蛋壳膜，并研究其去除水溶液中Pb(Ⅱ)的性能.

1. 实验部分

1.1. 仪器与试剂

电感耦合等离子体原子发射光谱仪(ICP-2060T，江苏天瑞仪器股份有限公司)，扫描电镜(KYKY-3200，北京中科科仪技术发展有限公司)，傅立叶变换红外光谱仪(以KBr压片测定).超纯水仪(LD-50G-E，重庆利迪实验仪器设备有限公司)，恒温振荡培养箱.

蛋壳膜(eggshell membrane，ESM)：用自来水冲洗后剥下ESM，用超纯水洗净，放入0.5 mol/L HCl溶液中浸泡去除表面残存钙质，用超纯水洗至中性，煮沸30 min，再用超纯水洗净后于80 ℃烘干，剪碎即得. Pb标准储备溶液的质量浓度为1 000 mg/L.其余试剂均采用分析纯.

1.2. 材料制备及表征

将1 g ESM浸入50 mL 3.5 mol/L的氢氧化钠中，室温下搅拌3 h，加入2 mL二硫化碳溶液，搅拌3 h，用超纯水洗至中性后，再用V(乙醇):V(水)为70:30的溶液洗涤3次，最后再用无水乙醇洗涤1次，在室温下干燥24 h，得到黄原酸功能化蛋壳膜(xanthate-modified eggshell membrane，XESM).合成机理如化学反应方程式(1)，其中R代表蛋壳膜基体.

为了研究黄原酸功能化前后ESM的表面结构及官能团的变化，分别用扫描电镜和红外光谱仪对ESM和XESM进行表征.

1.3. 吸附实验

准确移取50 mL一定pH值的Pb(Ⅱ)溶液至100 mL具塞锥形瓶中，加入50 mg XESM后，置于一定温度下的恒温摇床中，振摇一段时间后(转速为180 r/min)，测定上清液中Pb(Ⅱ)的质量浓度，计算XESM对Pb(Ⅱ)的吸附量.实验考察了pH值、吸附时间、共存物质对XESM去除Pb(Ⅱ)的影响.所有实验均进行3次平行实验，结果取其平均值，误差线表示标准差. Pb(Ⅱ)的吸附量q的计算公式为：

式中，q为吸附量(mg/g)，V为溶液体积(L)，C₀为吸附前溶液中Pb(Ⅱ)质量浓度(mg/L)，C_e为吸附平衡后溶液中Pb(Ⅱ)质量浓度(mg/L)，m为吸附剂的质量(g).

Pb(Ⅱ)浓度采用电感耦合等离子体原子发射光谱仪测定，仪器工作参数如下：高频发生器功率，900 W；等离子气流量，12 L/min；辅助气流量，0.6 L/min；载气流速，0.6 L/min；泵速，1.5 mL/min；积分时间，3 s；读数延迟，30 s.

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Study on Adsorption Removal of Pb(Ⅱ) by Xanthated Eggshell Membrane

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Study on Adsorption Removal of Pb(Ⅱ) by Xanthated Eggshell Membrane