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六偏磷酸钠改性沸石处理矿井水中氨氮

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我国部分矿区矿井水中氨氮(NH4+—N)存在超标问题,且去除矿井水中的NH4+—N要求越来越高,为了实现矿井水中NH4+—N的高效去除,对天然沸石(NZ)进行六偏磷酸钠(SHMP)浸渍改性,增强其对矿井水中NH4+—N的去除效果.结果表明:天然沸石经过 0.1 mol/L SHMP溶液浸渍 3h制备出了六偏磷酸钠改性沸石(SHMP-NZ),在初始NH4+—N质量浓度 5 mg/L、投加量 2 g/L的条件下振荡吸附 2h后NH4+—N去除率可达到 95.7%,相较于未改性天然沸石提高了 39.9%.扫描电镜和比表面积测定显示改性后沸石孔隙变大,表面变得光滑松散,比表面积增加,微孔体积减小,介孔、大孔和平均孔径增加.X射线衍射和傅里叶红外光谱分析表明改性后沸石的基本骨架无明显变化.弱酸性或中性环境有利于SHMP-NZ吸附去除水中的NH4+—N,共存阳离子的影响由大到小排序为K+>Na+>Ca2+>Mg2+.拟一级动力学、拟二级动力学和Elovich动力学非线性拟合表明,天然沸石和SHMP-NZ吸附NH4+—N更加符合拟二级动力学模型,对NH4+—N的吸附属于化学吸附(离子交换)过程,颗粒内扩散模型表明 2种材料对NH4+—N的吸附涉及外扩散、内扩散和反应平衡 3个阶段;Freundlich等温线模型表明,SHMP-NZ较天然沸石更易于吸附NH4+—N,Langmuir等温线模型可以较好地描述天然沸石及SHMP-NZ吸附NH4+—N的过程,相关系数R2 分别为 0.963 6和 0.982 8,SHMP-NZ最大NH4+—N吸附量为 11.03 mg/g,较天然沸石提升了 88.23%;吸附热力学表明各试验温度下吉布斯自由能变(ΔG)均小于 0,焓变(ΔH)和熵变(ΔS)大于 0,是一个熵增反应,有利于NH4+—N的去除.SHMP-NZ吸附-解吸循环 5次后,对NH4+—N的去除效率仍有 89.7%.实际矿井水中低浓度NH4+—N的处理,改性沸石在投加量1 g/L,25℃条件下振荡吸附1h后,出水满足《地表水环境质量标准》Ⅲ类水质中氨氮的要求.
Treatment of mine water containing ammonia nitrogen by sodium hexametaphosphate modified zeolite
The ammonium nitrogen(NH4+—N)exceeding standard in mine waters is a widespread issue in certain mining regions of our country.As the demand for its removal escalates,a strategy involving the modification of natural zeolite(NZ)with sodium hexametaphos-phate(SHMP)immersion was employed to enhance its removal efficiency.The results demonstrated that after 3 h of immersion in a 0.1 mol/L SHMP solution,SHMP-modified zeolite(SHMP-NZ)was prepared.Under conditions with an initial NH4+—N concentration of 5 mg/L and a dosage of 2 g/L,an oscillatory adsorption of 2 h led to a NH4+—N removal efficiency of 95.7%,representing a 39.9%en-hancement compared to the unmodified natural zeolite.Scanning electron microscopy and surface area measurements revealed that upon modification,the zeolite exhibited enlarged pores,a smoother and more loosely structured surface,increased specific surface area,de-creased micropore volume,and an augmentation in mesopore,macropore,and average pore diameter.Analyses using X-ray diffraction and Fourier-transform infrared spectroscopy indicated no significant alteration in the fundamental framework of the modified zeolite.The ad-sorption of NH4+—N by SHMP-NZ was optimal under weakly acidic or neutral conditions.The impact of coexisting cations on the ad-sorption followed the order K+>Na+>Ca2+>Mg2+.Pseudo-first-order,pseudo-second-order,and Elovich kinetic nonlinear fitting sugges-ted that both natural zeolite and SHMP-NZ adsorption of NH4+—N is better aligned with the pseudo-second-order kinetic model.The ad-sorption process was identified as chemisorption(ion exchange),and particle inner diffusion models revealed that the NH4+—N adsorption by both materials involves three stages:external diffusion,internal diffusion,and reaction equilibrium.The Freundlich isotherm model re-vealed that SHMP-NZ is more conducive to NH4+—N adsorption compared to NZ.The Langmuir isotherm model aptly described the NH4+—N adsorption process by both natural zeolite and SHMP-NZ,with correlation coefficients R2 being 0.9636 and 0.9828,respect-ively.The maximum NH4+—N adsorption capacity of SHMP-NZ was 11.03 mg/g,an 88.23%improvement compared to NZ.Adsorption thermodynamics showed that the Gibbs free energy(ΔG)values at each test temperature were less than 0,while the enthalpy change(ΔH)and entropy change(ΔS)were greater than 0.This indicates that the adsorption process is constituting an entropy-increasing reaction which is favorable for the removal of NH4+—N.After five regenerations,SHMP-NZ still maintains an ammonia nitrogen removal efficiency of 89.7%.Research on treating low-concentration ammonia nitrogen in actual mine water with SHMP-NZ shows that after 1 h of oscillating adsorption at a dosage of 1 g/L and at 25℃,the effluent meets the ammonia nitrogen requirements of category III as per the environment-al quality standards for surface water.

mine waterlow concentrationammonia nitrogensodium hexametaphosphatemodified zeoliteadsorption

章丽萍、虎翔、王伟伟、雷文波、李蕙彤、孙华冉、战永祺、连泽谕

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中国矿业大学(北京)化学与环境工程学院,北京 100083

矿井水 低浓度 氨氮 六偏磷酸钠 改性沸石 吸附

2024

煤炭科学技术
煤炭科学研究总院

煤炭科学技术

CSTPCD北大核心
影响因子:2.095
ISSN:0253-2336
年,卷(期):2024.52(12)