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第 10 期                   林   壮,等: β-环糊精交联树脂的合成及其对双酚酸的吸附                                 ·1723·


            水作用控制着吸附速率。pH≥4.3 时 β-CDP 吸附性                      响,控制着整个反应的速率。β-CDP 再生性能优异,
            能下降进一步证实了这一点,因为 pH 过高加剧了                           使用甲醇进行解吸具有约 90%的解吸能力。虽然
            DPA 的电离程度,破坏了吸附过程中氢键的形成。                           β-CDP 对 DPA 具有良好的吸附性能,但再生过程中

                                                               过滤分离存在过滤速度慢的问题。如果将磁性材料
                                                               与 β-CDP 复合,制备具有磁性的吸附材料,使用磁
                                                               场分离技术则会使再生过程效率得以提高。采用磁
                                                               场将吸附剂悬浮在固定床中使吸附和再生过程更加
                                                               高效,会使 β-CDP 在实际应用中更加具有潜力。

                                                               参考文献:
                                                               [1]   Zhang R, Moore J  A. Synthesis, characterization and  properties of

                                                                   polycarbonate containing carboxyl side groups[J]. Macromol Symp,
                       图 4   β-CDP 吸附 DPA 的机理                      2003, 199(1): 375-390.
                Fig. 4    Adsorption mechanism of DPA onto β-CDP   [2]   Wang Y Q, Zhang H M. Exploration of binding of bisphenol A and
                                                                   its analogues with  calf thymus DNA  by optical spectroscopic and
            2.8    再生性能测定                                          molecular docking methods[J]. J Photochem Photobiol B Biol, 2015,
                                                                   149: 9-20.
                 再生性能是评价吸附剂性能的重要指标。通过                          [3]   Daiem M M A, Rivera-Utrilla J, Ocampo-Pérez R, et al. Treatment
                                                                   of water contaminated with diphenolic acid by gamma radiation in the
            β-CDP 吸附-解吸循环实验,在 β-CDP 与 DPA 的质                       presence of different compounds[J]. Chem Eng J, 2013, 219(3): 371-379.
            量比为 12.5、pH 为 4.3,吸附平衡时间为 150 min                  [4]   Repousi V, Petala A, Frontistis Z, et al. Photocatalytic degradation of
                                                                   Bisphenol A over Rh/TiO 2 suspensions in different water matrices[J].
            的条件下,以再生次数为横坐标,吸附量为纵坐标                                 Catal Today, 2016, 284: 59-66.
                                                               [5]   Zhang X, Wu L, Zhou J,  et al. A new ratiometric electrochemical
            作图,结果见图 5。由图可见,经过 5 次吸附-解吸                             sensor for sensitive detection of Bisphenol A based on poly-β-
            循环后,β-CDP 对 DPA 的吸附量从 66.2 mg/g 下降                     cyclodextrin/electroreduced graphene modified glassy carbon
                                                                   electrode[J]. J Electroanal Chem, 2015, 742: 97-103.
            到 47.5 mg/g,每次解吸循环后均能还原 β-CDP  约                   [6]   Valladares L  R, Yangali-Quintanilla V, Li Z,  et al. Rejection of
            90%的吸附能力,说明 β-CDP 再生性能良好。                              micropollutants by clean and fouled forward osmosis membrane[J].
                                                                   Water Res, 2011, 45(20): 6737-6744.

                                                               [7]   Yang Xinjie (杨欣洁), Chen Jianyu (谌建宇), Yu Jian (余健), et al.
                                                                   Adsorption features and kinetic of  bisphenol A onto magnetic
                                                                   composite organic sepiolite[J]. Chinese Journal of Environmental
                                                                   Engineering (环境工程学报), 2016, 10(7): 3597-3602.
                                                               [8]   Morin-Crini N, Crini G. Environmental applications  of water-
                                                                   insoluble  β-cyclodextrin–epichlorohydrin polymers[J]. Prog Polym
                                                                   Sci, 2013, 38(2): 344-368.
                                                               [9]   Zhang Y, Causserand C, Aimar P, et al. Removal of bisphenol A by a
                                                                   nanofiltration membrane in view of drinking water production[J].
                                                                   Water Res, 2006, 40(20): 3793-3799.
                                                               [10]  Szejtli J. Introduction and  general overview of cyclodextrin
                                                                   chemistry[J]. Chem Rev, 1998, 98(5): 1743-1754.
                                                               [11]  García-Zubiri Í X, González-Gaitano G, Isasi J R. Thermal stability
                                                                   of  solid dispersions of  naphthalene derivatives  with β-cyclodextrin and
                                                                   β-cyclodextrin polymers[J]. Thermochim Acta, 2006, 444(1): 57-64.
                                                               [12]  Alsbaiee A, Smith B J,  Xiao L,  et al. Rapid removal of organic
              图 5  经过 5 次循环再生后 β-CDP 吸附 DPA 的吸附量                   micropollutants from water by a porous β-cyclodextrin polymer[J].
            Fig. 5  Adsorption capacity of DPA by  β-CDP after five   Nature, 2016, 529(7585): 190-194.
                   regenerate cycles                           [13]  Ho Y S, Mckay G. Pseudo-second order model for sorption
                                                                   processes[J]. Process Biochem, 1999, 34(5): 451-465.
            3    结论                                            [14]  García-Zubiri I X, González-Gaitano G, Isasi J R. Sorption models in
                                                                   cyclodextrin  polymers: Langmuir, Freundlich, and a dual-mode
                                                                   approach[J]. J Colloid Interf Sci, 2009, 337(1): 11-18.
                 β-CDP 对 DPA 具有良好的吸附性能,当 β-CDP                 [15]  Wang Bo (王波),  He Shengfu (贺盛福), Zhang  Fan (张帆),  et al.
                                                                   Preparation of graphene oxide modified by dendritic polyamide-
            与 DPA 的质量比为 12.5∶1 时吸附性能最佳,此时                          amine and its adsorption thermodynamics and kinetics for Cu(Ⅱ)[J].
            β-CDP 的平衡吸附率和吸附量为 79.6%和 63.7 mg/g。                    Fine Chemicals (精细化工), 2014, 31(8):998-1004.
                                                               [16]  Yang Xiaoqiu (杨小秋), Qiu Haiou (邱海鸥). Synthesis, structure
            使用 NaOH 调节 pH 大于 DPA 水溶液自身 pH(>4.3)                    and properties study of  β-cyclodextrin cross-linking  polymer[J].
                                                                   Journal of Molecular Science (分子科学学报), 2012, 28(6):516-520.
            后,β-CDP 对 DPA 的吸附性能急剧下降,说明 DPA                     [17] He Qiuxing (何秋星), Wang Xuewen (王学文), Chen Wenting (陈文
            的电离程度增大,弱化了吸附过程中氢键的形成。                                 婷). Preparation and adsorption properties  of a noval chitosam/
                                                                   β-cyclodextrin magnetic  microspheres[J]. Fine Chemicals(精细化
            吸附动力学满足准二级动力学模型,吸附等温模型                                 工), 2012, 29(3): 280-284.
                                                               [18]  Von Oepen B, Kördel W, Klein W. Sorption of nonpolar and polar
            同时满足 Langmuir 和 Freundlich 两种;热力学结果
                                                                   compounds to soils: processes, measurements and experience with
            表明,β-CDP 吸附 DPA 为自发且放热的反应。β-CDP                        the applicability of the modified OECD-Guideline 106[J]. Chemosphere,
                                                                   1991, 22(3/4): 285-304.
            吸附 DPA 机理表明,吸附过程主要分为膜扩散阶段、                         [19]  Valle E M M D. Cyclodextrins and their uses: a review[J]. Process
            层间扩散阶段及动态平衡阶段。膜扩散阶段形成氢                                 Biochem, 2004, 39(9): 1033-1046.
                                                               [20]  Chen M, Diao G  W, Zhang E  R. Study of inclusion complex of
            键,反应迅速,层间扩散速率缓慢,受疏水作用影                                 β-cyclodextrin and nitrobenzene[J]. Chemosphere, 2006, 63: 522-529.
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