纤维素-海藻酸钠-海泡石多孔微球的制备及其对亚甲基蓝吸附性能

李婷婷; 李瑞雪; 马政; 杨安廷; 焦晨璐; 王健

doi:10.13801/j.cnki.fhclxb.20210310.002

纤维素-海藻酸钠-海泡石多孔微球的制备及其对亚甲基蓝吸附性能

doi: 10.13801/j.cnki.fhclxb.20210310.002

安徽农业大学　轻纺工程与艺术学院，合肥 230036

基金项目: 国家自然科学基金青年基金(51803004)；安徽省高校自然科学研究项目(KJ2017A144)；安徽农业大学人才项目(yj2018-18)

详细信息

通讯作者:
王健，硕士，副教授，硕士生导师，研究方向为生物质基复合材料　E-mail：silkwj@ahau.edu.cn

中图分类号: TQ340.1
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出版历程
- 收稿日期: 2020-12-16
- 录用日期: 2021-02-22
- 网络出版日期: 2021-03-10
- 刊出日期: 2021-12-01

Preparation of cellulose-sodium alginate-sepiolite porous bead and its application in adsorption of methylene blue

School of Textile Engineering and Academy of Art, Anhui Agricultural University, Hefei 230036, China

摘要

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。
- 微晶纤维素 /
- 海藻酸钠 /
- 海泡石 /
- 微球 /
- 亚甲基蓝 /
- 吸附
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.
- microcrystalline cellulose /
- sodium alginate /
- sepiolite /
- beads /
- methylene blue /
- adsorption

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图 1 不同SEP含量的MCC-SA-SEP复合微球的SEM图像

Figure 1. SEM images of MCC-SA-SEP beads with different SEP contents

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图 2 MCC、SA、SEP及MCC-SA-SEP复合微球的TG曲线

Figure 2. TG curves of MCC, SA, SEP and MCC-SA-SEP beads

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图 3 MCC-SA-SEP-21微球投入量和溶液pH对吸附性能的影响

Figure 3. Effect of MCC-SA-SEP-21 beads dosage and pH on the adsorption properties

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图 4 吸附时间对MCC-SA-SEP-21复合微球吸性能的影响

Figure 4. Effect of time on the adsorption performance of MCC-SA-SEP-21 beads

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图 5 MCC-SA-SEP-21复合微球吸附亚甲基蓝(MB)的动力学模型拟合曲线

Figure 5. Kinetic fitting curves of adsorption data of methylene blue (MB) onto MCC-SA-SEP-21 beads

Q_e—Equilibrium adsorption on MB; Q_t—Adsorption time t corresponds to the adsorption capacity of MB

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图 6 不同初始浓度的MB对MCC-SA-SEP-21复合微球吸附性能的影响

Figure 6. Effect of initial concentrations of MB on the adsorption capacities of MCC-SA-SEP-21 beads

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图 7 MCC-SA-SEP-21复合微球的Langmuir等温吸附 (a) 和Freundlich等温吸附拟合曲线 (b)

Figure 7. Langmuir model fitting curve (a) and Freundlich model fitting curve (b) for MCC-SA-SEP-21 beads

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图 8 MCC-SA-SEP-21复合微对MB的吸附热力学拟合曲线

Figure 8. Thermodynamic fitting curve of MB onto MCC-SA-SEP-21 beads

K_c—Adsorption equilibrium constant

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图 9 MCC-SA-SEP-21复合微球的再生性

Figure 9. Regeneration property of MCC-SA-SEP-21 beads

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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

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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	Q_e(exp)/(mg·g⁻¹)	Pseudo-first-order model			Pseudo-second-order model
Adsorbate	Q_e(exp)/(mg·g⁻¹)	Q_1e(cal)/(mg·g⁻¹)	k₁/(min⁻¹)	R²	Q_2e(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; Q_e(cal)—Calculation amount of MB removed per unit mass of adsorbent; Q_e(exp)—Experimental amount of MB removed per unit mass of adsorbent.

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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
Adsorbate	Q_max/(mg·g⁻¹)	k_L/(L·mg⁻¹)	R²	k_F/(L·mg⁻¹)	n	R²
MB	333.3	0.147	0.9985	112	5	0.8949
Notes: Q_max—Langmuir adsorption maximum; k_L—Langmuir coefficient of distribution of the adsorption; k_F—Freundlich coefficient of distribution of the adsorption; n—Freundlich constants related to adsorption strength.

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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.

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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	ΔG^o/(kJ·mol⁻¹)	ΔH^o/(kJ·mol⁻¹)	ΔS^o/(J·mol⁻¹·K⁻¹)
303	−2.1	−22	−66.1
308	−1.6	−	−
313	−1.2	−	−
318	−1	−	−
323	−0.7	−	−
Notes: ΔG^o—Gibbs free energy variation of the adsorption process; ΔH^o—Enthalpy change of the adsorption process; ΔS^o—Entropy change of the adsorption process.

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