Adsorption of low-concentration phosphorus after cross-linked modification of bamboo-based cellulose nanofibrils

doi:10.16085/j.issn.1000-6613.2021-2371

Abstract

Abstract:

In this study, by optimizing the preparation conditions, the bamboo-based cellulose nanofibrils was cross-linked with polyamide-epichlorohydrin resin (PAE), and then loaded with Fe(OH)₃ to obtain a new composite material, CNFs-PAE-Fe, to remove low concentrations of phosphorus from wastewater. Compared to other crosslinkers, bamboo-based cellulose nanofibrils crosslinked with PAE and loaded iron showed better mechanical strength and adsorption properties. BET specific surface area measurement, thermogravimetric analysis, FTIR and scanning electron microscopy were used to characterize the materials, and the pore size, surface morphology, thermal stability and elemental composition of the materials before and after crosslinking and loading Fe(OH)₃ were investigated. The adsorption of phosphorus by CNFs-PAE-Fe conformed to the quasi-second-order kinetic model and the Langmuir isotherm adsorption model, which indicated that the adsorption process of phosphorus by the modified material was a monolayer adsorption based on chemical adsorption. CNFs-PAE-Fe maintained good adsorption performance for low concentrations of phosphorus in a wide pH range. The highest adsorption capacity of the prepared adsorbent could reach 9.11mg/g at pH 4.0. The regeneration of the modified material with saturated adsorption was studied, and the regeneration effect was best when the ratio of eluent V (NaCl):V (NaOH) was 3∶2. The desorbed material was freeze-dried and reused 5 times, and still maintained good strength and complete morphology.

Key words: cellulose nanofibrils, crosslinking, load, waste water, adsorption, regeneration, low concentration of phosphorus

摘要：

通过优化制备条件，将竹基纤维素纳米纤丝（cellulose nanofibrils，CNFs）与聚酰胺环氧氯丙烷树脂（polyamide epichlorohydrin resin，PAE）进行交联，随后负载Fe(OH)₃，得到了吸附废水中低浓度磷的新型复合材料CNFs-PAE-Fe。与其他交联剂相比，竹基纤维素纳米纤丝与PAE交联并负载后展现出更好的机械强度和吸附性能。通过BET比表面积测量、热重分析、FTIR、扫描电镜、XPS能谱分析，探究了交联负载Fe(OH)₃前后材料的孔径、热稳定性、表面形貌、元素组成等。CNFs-PAE-Fe对磷的吸附符合准二级动力学模型和Langmuir等温吸附模型，这表明改性材料对磷的吸附过程是以化学吸附为主的单分子层吸附。CNFs-PAE-Fe在较宽的pH范围下对低浓度磷都保持着较好的吸附性能，当pH=4.0时吸附容量最高，达到9.11mg/g。对吸附饱和的改性材料进行再生研究，洗脱液V(NaCl)∶V(NaOH)配比为3∶2时再生效果最好。解吸后的材料经冷冻干燥，重复利用5次，仍保持较好的强度和完整的形貌。

关键词: 纤维素纳米纤丝, 交联, 负载, 废水, 吸附, 再生, 低浓度磷

CLC Number:

X703.1

YANG Chengyu, LIU Min, YUAN Lin, HU Xuan, CHEN Ying. Adsorption of low-concentration phosphorus after cross-linked modification of bamboo-based cellulose nanofibrils[J]. Chemical Industry and Engineering Progress, 2022, 41(9): 5074-5084.

杨程嵛, 刘敏, 袁林, 胡璇, 陈滢. 竹基纤维素纳米纤丝交联改性后对水体中低浓度磷的吸附[J]. 化工进展, 2022, 41(9): 5074-5084.

Figures/Tables 17

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准一级				准二级				Elovich
q₁	k₁	R²		q₂	k₂	R²		a	b	R²
7.97	0.005	0.989		9.70	5.589	0.995		0.11	0.47	0.993

准一级				准二级				Elovich
q₁	k₁	R²		q₂	k₂	R²		a	b	R²
7.97	0.005	0.989		9.70	5.589	0.995		0.11	0.47	0.993

第一阶段			第二阶段			第三阶段
k₁	R²		k₂	R²		k₃	R²
0.534	0.977		0.241	0.995		0.017	0.726

第一阶段			第二阶段			第三阶段
k₁	R²		k₂	R²		k₃	R²
0.534	0.977		0.241	0.995		0.017	0.726

Langmuir	Freundlich	Temkin	Toth
q_m=15.90	K_f=6.22	K_T =7.33	T=0.92
K_L=1.00	1/n_f=0.36	b_T =682.21	b_T =0.77
R²=0.998	R²=0.961	R²=0.978	R²=0.983