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β-环糊精对蓝湿革中三氯苯酚的洗脱机理研究

Study on the Elution Effect of Trichlorophenol in Wet Blue based on β-Cyclodextrin Inclusion Complexation

  • 摘要:
    目的 开发高效、环保的氯酚脱除技术,提升皮革制品生态安全性,实现行业可持续发展。
    方法 以β-环糊精(β-CD)为洗脱剂,含2,4,5-三氯苯酚(TCP)的蓝湿革为研究对象,系统考察表面活性剂的种类及浓度、NaCl浓度、β-CD用量、pH、时间、温度、次数等因素对蓝湿革中TCP去除效果的影响。
    结果 研究结果表明,当非离子表面活性剂DW质量浓度为0.1 g/L、β-CD质量浓度为7 g/L、洗脱温度为298.15 K、洗脱时间为60 min、洗脱pH为5、蓝湿革中初始TCP含量为55.42 mg/kg时,经4次β-CD洗脱后蓝湿革中TCP含量可降低至4.83 mg/kg,去除率达到91.3%。
    结论 最后对洗脱前后蓝湿革的性能进行检测,发现β-CD洗脱操作不仅可有效降低TCP含量,还有利于蓝湿革后续的制革工艺。

     

    Abstract:
    Objective Wet blue is an indispensable intermediate product in leather manufacture. However, wet blue is prone to mildew due to its high moisture content, causing widespread use of chlorophenol-based antifungal agents. Chlorophenols are strictly regulated internationally due to their high toxicity, thereby their residues in leather could significantly influence the quality of finished leather. Thus, developing efficient and eco-friendly methods for the removal of chlorophenols is crucial for enhancing ecological safety of leather products and promoting sustainable development in leather industry.
    Methods In this research, we developed a novel eluting system via utilizing β-cyclodextrin (β-CD) as primary eluting agent and 2,4,5-trichlorophenol (TCP) as target pollutant to systematically investigate the removal mechanism of TCP from wet blue. The key parameters were optimized, including the type and concentration of surfactants, NaCl concentration, β-CD dosage, pH, elution time, temperature, and number of elution cycles.
    Results The best TCP removal rate was achieved at 0.1 g/L of surfactant DW, 7 g/L of β-CD, 298.15 K, 60 min of elution, and pH 5, resulting in a substantial elimination of TCP from 55.42 mg/kg to 4.83 mg/kg in wet blue with a removal efficiency of 91.3%, which meets the ecological standard of leather. Mechanistic investigation results revealed that the surfactant DW significantly reduced the surface tension of the β-CD solution and improved its wettability and penetration into the hydrophobic leather surface, thereby promoting the inclusion interaction between β-CD and TCP molecules. Afterwards, β-CD formed stable inclusion complexes with TCP via its hydrophobic cavity, realizing the efficient elution of TCP. During the elution process, the TCP removal rate was increased first and then inhibited with the increase of β-CD concentration, which may be attributed to the β-CD self-aggregation at excessive content. Moreover, it was found that the TCP removal efficiency could be improved by multiple elution cycles, particularly effective in processing wet blue with low or moderate TCP contamination. In addition, the physicochemical properties of wet blue before and after treatment were analyzed. The minimal release of chromium and hydroxyproline indicated the treatment barely influenced collagen fiber structure. Physical property tests proved that tensile strength, elongation at break, and tear strength remained unchanged. Microstructure analysis further confirmed that micropores and mesopores in wet blue were slightly increased after treatment, which benefited the deep penetration and binding of chemicals in wet-end process.
    Conclusions In this work, an efficient and eco-friendly treatment of TCP elimination was established via β-CD elution system, and the synergistic mechanism between β-CD and surfactant was revealed at micro level. These excellent findings are promising for practical application and provide new insights into pollutant control in leather manufacture.

     

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