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骨炭对印染废水离子型有机物的吸附行为规律

Adsorption behavior regularity of bone char for ionic organic compounds in printing and dyeing wastewater

  • 摘要: 以合成染料为代表的离子型有机物结构多样,导致骨炭吸附行为规律不明,难以推广应用。该研究以牛骨为原料热解制备骨炭,采用现代表征技术明确理化特性后,对比分析基于炭投加量、溶液初始pH值、溶液初始浓度、接触时间、溶液温度等环境条件下骨炭对离子型有机物的吸附行为规律;根据吸附前后骨炭表面元素质量分数、化学基团与晶体结构变化分析作用机制,并考察二元共存体系中骨炭的吸附性能。结果表明,骨炭介孔结构丰富,比表面积增大1 709倍;灰分含量、电导率、pH值和阳离子交换量分别提高61.8%、79.3%、53.2%和71.8%,化学基团特征峰增强,晶体结构完整。骨炭投加量增多,离子型有机物去除率分别呈对数、线性或幂函数趋势增长;中性或碱性pH值利于吸附阳离子型有机物,三苯甲烷类去除率高达99.8%,阴离子型有机物则在酸性pH值范围去除效果较佳;吸附后三苯甲烷类在骨炭表面呈单层均匀分布,Langmuir吸附常数KL分别为0.025和0.022,具有极强的稳定性;杂环、偶氮和蒽醌类为多层堆叠,Freundlich吸附常数1/n小于0.5,表现出易于吸附的特征;吸附以化学作用为主且均可自发进行;除阴离子型三苯甲烷外,吸附均为吸热、熵增反应。骨炭吸附机制主要包括孔隙填充、静电吸引、阳离子-π键、π-π相互作用、离子交换和矿物络合;二元共存体系中离子型有机物相互协同,骨炭吸附性能提升。该研究结果可为骨炭实际处理印染废水环境条件选择提供基础理论依据。

     

    Abstract: Ionic organic compounds represented by synthetic dyes are structurally diverse. Existing studies mostly focus on individual, newly selected target pollutants under different test conditions, and rarely conduct comparative investigations of different ionic organics using bone char (BC) within a unified experimental framework. This makes it difficult to clarify the general adsorption rules of BC for printing and dyeing wastewater. In this study, slaughterhouse bone waste from livestock and poultry was pyrolyzed at 700 ℃ under N2 to prepare BC, which was then subjected to detailed physicochemical characterization. On this basis, the adsorption behavior of BC towards typical ionic organic compounds with different types and structures was systematically compared under various environmental conditions, including cationic dyes (Malachite Green, triphenylmethane; Methylene Blue, heterocyclic thiazine; Rhodamine B, heterocyclic xanthene) and anionic dyes (Sunset Yellow, azo; Reactive Blue 19, anthraquinone; Acid Fuchsin, triphenylmethane). The prepared BC showed a well-developed mesoporous structure, with a specific surface area about 1709 times that of raw bone meal. After pyrolysis, the ash content, electrical conductivity, pH value and cation exchange capacity related to inorganic mineral components increased by 61.8%, 79.3%, 53.2% and 71.8%, respectively; characteristic peaks of surface functional groups were enhanced and the crystal structure became more ordered. These features indicate that the BC is a suitable adsorbent for ionic organic pollutants. With increasing BC dosage, both the removal efficiency and the equilibrium adsorption capacity increased, and the variation could be described by logarithmic, linear or power-function relationships depending on the pollutant. For cationic organics, the removal efficiency increased or remained nearly constant with increasing initial dye pH value, and the maximum removal of triphenylmethane cations reached 99.8%. Anionic dyes were more effectively removed under acidic conditions. Increases in initial dye concentration and contact time led to a rapid rise in adsorption capacity, followed by a gradual approach to equilibrium. Adsorption of triphenylmethane dyes conformed to the Langmuir isotherm model, indicating predominantly monolayer adsorption on relatively uniform sites, whereas adsorption of heterocyclic, azo and anthraquinone dyes followed the Freundlich isotherm model, indicating multilayer adsorption on heterogeneous surfaces. For all target compounds, the adsorption kinetics fitted the pseudo-second-order model, suggesting that chemisorption plays a dominant role. The Gibbs free energy change of adsorption was negative, indicating that the processes occurred spontaneously. Except for anionic triphenylmethane dyes, the adsorption processes were endothermic and accompanied by an increase in entropy. Malachite Green, which showed the highest adsorption performance among the tested compounds, was selected as a model pollutant to analyse the adsorption mechanism. According to the proportion of surface element content, functional groups and crystal structure of BC before and after adsorption indicate that pore filling, electrostatic attraction, cation-π interaction, π-π interaction, ion exchange and complexation with mineral components jointly contribute to the adsorption process. In the two-component system, ionic organics exhibited a certain degree of synergistic interaction, and the adsorption capacity of BC for each component was simultaneously enhanced. These results help to clarify the adsorption behavior and mechanism of BC towards ionic organic pollutants in printing and dyeing wastewater, and provide theoretical support for its engineering application in wastewater treatment.

     

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