Preparation of cellulose-sodium alginate-sepiolite porous bead and its application in adsorption of methylene blue
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摘要: 以微晶纤维素(Microcrystalline cellulose,MCC)和海藻酸钠(Sodium alginate,SA)为网络框架,海泡石(Sepiolite,SEP)为功能单元,采用悬浮液滴法构建纤维素-海藻酸钠-海泡石(MCC-SA-SEP)双网络多孔复合微球。通过SEM和TG对复合微球结构和热稳定性能进行表征,并研究该微球对亚甲基蓝(Methylene blue,MB)水溶液的吸附性能。结果表明,MCC-SA-SEP复合微球呈现三维网络多孔结构,且随着SEP含量的增加热稳定性逐渐提高。吸附结果显示MCC-SA-SEP符合准二级动力学模型和Langmuir等温线,对MB的饱和吸附容量高达333.3 mg/g。经过五次再生循环后,对MB吸附能力仍能维持85.4%,表明该多孔复合微球可以作为一种高效可再生的有机-无机复合吸附剂用于染料废水处理。Abstract: Double network composite beads (MCC-SA-SEP) were synthesized by a floating droplet method, in which microcrystalline cellulose (MCC) and sodium alginate (SA) worked as the network frameworks, and sepiolite (SEP) was a functional component. The microstructure and thermal properties of the as-prepared MCC-SA-SEP beads were characterized by SEM and TG, respectively, and the adsorption performance for methylene blue (MB) aqueous solution was studied. The results present that the MCC-SA-SEP beads have three-dimensional porous structures, and the thermal stability increases gradually with the increasing of SEP contents. The adsorption process of MCC-SA-SEP follows the pseudo-second-order kinetic model and Langmuir isotherm, with the maximum adsorption capacity of 333.3 mg/g for MB. After five regeneration cycles, the adsorption capacity could still retain 85.4% of the initial adsorption amount, demonstrating a novel organic-inorganic hybrid adsorbent for dye waste water treatment.
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Key words:
- microcrystalline cellulose /
- sodium alginate /
- sepiolite /
- beads /
- methylene blue /
- adsorption
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表 1 不同SEP含量制备的微晶纤维素-海藻酸钠-海泡石(MCC-SA-SEP)复合微球
Table 1. Microcrystalline cellulose-sodium alginate-sepiolite (MCC-SA-SEP) composite beads prepared with various SEP contents
MCC-SA content/g SEP content/g Composite bead 2 0 MCC-SA-SEP-0 2 0.5 MCC-SA-SEP-41 2 1 MCC-SA-SEP-21 2 2 MCC-SA-SEP-11 表 2 MCC-SA-SEP-21多孔复合微球吸附MB的动力学模型拟合参数
Table 2. Parameters of kinetic adsorption models for MB onto MCC-SA-SEP-21 beads
Adsorbate Qe(exp)/(mg·g−1) Pseudo-first-order model Pseudo-second-order model Q1e(cal)/(mg·g−1) k1/(min−1) R2 Q2e(cal)/(mg·g−1) k2/(g·mg−1·min−1) R2 MB 306.7 199.3 1.06×10−2 0.9855 322.6 9.1×10−5 0.9967 Notes: k1, k2—Pseudo-first-order kinetic and Pseudo-second-order kinetic constants, respectively; Qe(cal)—Calculation amount of MB removed per unit mass of adsorbent; Qe(exp)—Experimental amount of MB removed per unit mass of adsorbent. 表 3 MCC-SA-SEP-21复合微球对MB的吸附等温拟合结果
Table 3. Isothermal parameters for the adsorption of MB onto MCC-SA-SEP-21 beads
Adsorbate Langmuir Freundlich Qmax/(mg·g−1) kL/(L·mg−1) R2 kF/(L·mg−1) n R2 MB 333.3 0.147 0.9985 112 5 0.8949 Notes: Qmax—Langmuir adsorption maximum; kL—Langmuir coefficient of distribution of the adsorption; kF—Freundlich coefficient of distribution of the adsorption; n—Freundlich constants related to adsorption strength. 表 4 同类纤维素复合微球吸附剂对MB的吸附容量对比
Table 4. Adsorption capacity ratio of similar cellulose composite beads adsorbents to MB
Adsorbent Adsorption capacity/(mg·g−1) Reference SA/cellulose hydrogel beads 163.36 [26] Cellulose/diatomite composite aerogel beads 71.9424 [27] MCDBs 117.65 [14] CMC-AlG/GO hydrogels beads 78.5 [28] CNC-ALG 255.5 [29] CNC/MnO2/ALG beads 136.7 [30] MCC-SA-SEP 333.3 This work Notes: GO—Graphene oxide; MCDBs—Modified cellulose/diatomite beads; CMC—Carboxymethyl cellulose; CNC—Cellulose nanocrystal; ALG—Alginate. 表 5 MCC-SA-SEP-21复合微球对MB的吸附热力学参数
Table 5. Thermodynamic parameters for the adsorption of MB onto MCC-SA-SEP-21 beads
T/K ΔGo/(kJ·mol−1) ΔHo/(kJ·mol−1) ΔSo/(J·mol−1·K−1) 303 −2.1 −22 −66.1 308 −1.6 − − 313 −1.2 − − 318 −1 − − 323 −0.7 − − Notes: ΔGo—Gibbs free energy variation of the adsorption process; ΔHo—Enthalpy change of the adsorption process; ΔSo—Entropy change of the adsorption process. -
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