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

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

摘要/Abstract

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

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

中图分类号:

X703.1

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.

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.

图/表 17

图1 CNFs-PAE-Fe制备及吸附磷示意图

图2 CNFs改性交联剂的选择及交联负载顺序对其吸附性能的影响

图3 CNFs改性前后的SEM图

图4 CNFs与CNFs-PAE-Fe热重分析图

图5 CNFs-PAE-Fe吸附磷前后FTIR图

图6 CNFs-PAE-Fe吸附磷前后的XPS能谱图

图7 准一级、准二级和Elovich动力学模型拟合曲线

表1 准一级、准二级与Elovich模型拟合参数

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

图8 颗粒内扩散模型拟合曲线

表2 颗粒内扩散模型拟合参数

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

图9 CNFs-PAE-Fe吸附磷的四种吸附等温线

表3 等温吸附模型拟合参数

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

图10 不同pH对CNFs-PAE-Fe吸附性能的影响

表4 不同改性吸附材料在溶液pH=6.0~9.0时对磷的吸附容量

吸附材料	C₀/mg·L^-1	q_e/mg·g^-1	参考文献
Al₂O₃/PVA改性材料	2.5	0.54~0.56	［3］
Al₂O₃/CA改性材料	2.5	2.00~2.40	［3］
Fe/Mn改性生物炭	0.5	0.91~0.94	［38］
FeZr改性生物炭	10.0	7.50~10.00	［39］
改性煤矸石	50.0	6.00~17.00	［40］
CNFs-PAE-Fe	1.0 10.0 50.0	5.59~8.68 14.76~15.83 32.36~47.20	本研究

图11 CNFs-PAE-Fe的zeta电位

图12 饱和CNFs-PAE-Fe解吸液配比探究

图13 CNFs-PAE-Fe再生探究

参考文献 41

1	马鑫雨, 杨盼, 张曼, 等. 湖泊沉积物磷钝化材料的研究进展[J]. 湖泊科学, 2022, 34(1): 1-17.
	MA Xinyu, YANG Pan, ZHANG Man, et al. Advances in researches on phosphorous inactivation materials in lake sediment[J]. Journal of Lake Sciences, 2022, 34(1): 1-17.
2	WU Baile, FANG Liping, FORTNER John D, et al. Highly efficient and selective phosphate removal from wastewater by magnetically recoverable La(OH)₃/Fe₃O₄ nanocomposites[J]. Water Research, 2017, 126: 179-188.
3	胡晓雅. 开发去除水体中低浓度磷的复合吸附材料[D]. 泉州: 华侨大学, 2018.
	HU Xiaoya. Development of composite adsorbents to remove low concentration of phosphorus in water[D]. Quanzhou: Huaqiao University, 2018.
4	YAN Yubo, SUN Xiuyun, MA Fangbian, et al. Removal of phosphate from wastewater using alkaline residue[J]. Journal of Environmental Sciences, 2014, 26(5): 970-980.
5	刘宁, 陈小光, 崔彦召, 等. 化学除磷工艺研究进展[J]. 化工进展, 2012, 31(7): 1597-1603.
	LIU Ning, CHEN Xiaoguang, CUI Yanzhao, et al. Research progress of chemical dephosphorization process[J]. Chemical Industry and Engineering Progress, 2012, 31(7): 1597-1603.
6	王文超, 张华, 张欣. 化学除磷在城市污水处理中的应用[J]. 水科学与工程技术, 2008(1): 14-16.
	WANG Wenchao, ZHANG Hua, ZHANG Xin. Chemical phosphorus removal in municipal wastewater[J]. Water Sciences and Engineering Technology, 2008(1): 14-16.
7	徐丰果, 罗建中, 凌定勋. 废水化学除磷的现状与进展[J]. 工业水处理, 2003, 23(5): 18-20.
	XU Fengguo, LUO Jianzhong, LING Dingxun. Present and prospects of the removal of phosphorus from wastewater chemically[J]. Industrial Water Treatment, 2003, 23(5): 18-20.
8	SEO Byung Soo, PARK Chong Min, SONG Unsook, et al. Nitrate and phosphate removal potentials of three willow species and a bald cypress from eutrophic aquatic environment[J]. Landscape and Ecological Engineering, 2010, 6(2): 211-217.
9	SHI Jing, PODOLA Björn, MELKONIAN Michael. Removal of nitrogen and phosphorus from wastewater using microalgae immobilized on twin layers: an experimental study[J]. Journal of Applied Phycology, 2007, 19(5): 417-423.
10	李小林. La(OH)₃负载的磁性阳离子水凝胶对水中低浓度磷的吸附特征及其放大制备研究[D]. 北京: 北京林业大学,2020 .
	LI Xiaolin. Study on the low concentration phosphate adsorption in aqueous solution by La(OH)₃ loaded magnetic cationic hydrogel: performance, mechanism and adsorbent scale-up preparation[D]. Beijing: Beijing Forestry University, 2020 .
11	GENZ Arne, Anja KORNMÜLLER, JEKEL Martin. Advanced phosphorus removal from membrane filtrates by adsorption on activated aluminium oxide and granulated ferric hydroxide[J]. Water Research, 2004, 38(16): 3523-3530.
12	王秀云. 废水除磷技术的研究进展[J]. 安徽农学通报, 2009, 15(16): 92-93, 129.
	WANG Xiuyun. Study progress of phosphorus removal from wastewater[J]. Anhui Agricultural Science Bulletin, 2009, 15(16): 92-93, 129.
13	戴晓婧, 覃柳琪, 张杉杉, 等. 竹基纳米纤维素晶体稳定的Pickering乳液制备及其形态和稳定性研究[J]. 纤维素科学与技术, 2018, 26(4): 52-59.
	DAI Xiaojing, QIN Liuqi, ZHANG Shanshan, et al. Investigation of the morphology and stability of Pickering emulsion stabilized by bamboo cellulose nanocrystal[J]. Journal of Cellulose Science and Technology, 2018, 26(4): 52-59.
14	王汉坤. 竹基纳米纤维素的制备、表征及应用[D]. 北京: 中国林业科学研究院, 2013.
	WANG Hankun. Preparation, characterization and application of nano cellulose fibrils from bamboo[D]. Beijing: Chinese Academy of Forestry, 2013.
15	覃发梅, 邱学青, 孙川, 等. 纳米纤维素去除水体系重金属离子的研究进展[J]. 化工进展, 2019, 38(7): 3390-3401.
	QIN Famei, QIU Xueqing, SUN Chuan, et al. Research progress in nanocellulose for the removal of heavy metal ions in water[J]. Chemical Industry and Engineering Progress, 2019, 38(7): 3390-3401.
16	TANG Juntao, SONG Yang, ZHAO Feiping, et al. Compressible cellulose nanofibril (CNF) based aerogels produced via a bio-inspired strategy for heavy metal ion and dye removal[J]. Carbohydrate Polymers, 2019, 208: 404-412.
17	CUI Guirong, LIU Min, CHEN Ying, et al. Synthesis of a ferric hydroxide-coated cellulose nanofiber hybrid for effective removal of phosphate from wastewater[J]. Carbohydrate Polymers, 2016, 154: 40-47.
18	王婷庭, 刘敏, 崔桂榕, 等. 五种改性纳米纤维素吸附剂的制备及除磷性能比较[J]. 化工进展, 2017, 36(11): 4279-4285.
	WANG Tingting, LIU Min, CUI Guirong, et al. Preparation of several modified cellulose nanofiber hybrid adsorbents and performance comparison of phosphate removals[J]. Chemical Industry and Engineering Progress, 2017, 36(11): 4279-4285.
19	LUO Ying, LIU Min, CHEN Ying, et al. Preparation and regeneration of iron-modified nanofibres for low-concentration phosphorus-containing wastewater treatment[J]. Royal Society Open Science, 2019, 6(9): 190764.
20	董凤霞, 戴磊. 纤维素纳米纤丝基水凝胶及其在废水处理中的应用进展[J]. 中国造纸, 2020, 39(5): 63-69.
	DONG Fengxia, DAI Lei. Research progress on cellulose nanofibrils-based hydrogel and its application in wastewater treatment[J]. China Pulp & Paper, 2020, 39(5): 63-69.
21	ZHANG Wei, ZHANG Yaan, LU Canhui, et al. Aerogels from crosslinked cellulose nano/micro-fibrils and their fast shape recovery property in water[J]. Journal of Materials Chemistry, 2012, 22(23): 11642-11650.
22	XU Zhaoyang, JIANG Xiangdong, ZHOU Huan, et al. Preparation of magnetic hydrophobic polyvinyl alcohol (PVA)-cellulose nanofiber (CNF) aerogels as effective oil absorbents[J]. Cellulose, 2018, 25(2): 1217-1227.
23	宋飞宇, 魏琪, 马浩, 等. 羧甲基半纤维素的制备及其与湿强剂PAE的联用[J]. 中国造纸, 2019, 38(3): 9-15.
	SONG Feiyu, WEI Qi, MA Hao, et al. Preparation of carboxymethyl hemicellulose and its application with polyamide epichlorohydrin resin as wet strength additive[J]. China Pulp & Paper, 2019, 38(3): 9-15.
24	关莹. 竹材半纤维素基软材料的制备及性能研究[D]. 北京: 北京林业大学, 2015.
	GUAN Ying. Preparation and properties of bamboo hemicellulose-based soft materials[D]. Beijing: Beijing Forestry University, 2015.
25	LU Lanxin, LIU Min, CHEN Ying, et al. Effective removal of tetracycline antibiotics from wastewater using practically applicable iron(Ⅲ)-loaded cellulose nanofibres[J]. Royal Society Open Science, 2021, 8(8): 210336.
26	ZHANG Xiaofang, LU Zhixing, ZHAO Jiangqi, et al. Exfoliation/dispersion of low-temperature expandable graphite in nanocellulose matrix by wet co-milling[J]. Carbohydrate Polymers, 2017, 157: 1434-1441.
27	LI Qingye, XUE Zhouhang, ZHAO Jiangqi, et al. Mass production of high thermal conductive boron nitride/nanofibrillated cellulose composite membranes[J]. Chemical Engineering Journal, 2020, 383: 123101.
28	ZHANG Xiaofang, ZHAO Jiangqi, HE Xu, et al. Mechanically robust and highly compressible electrochemical supercapacitors from nitrogen-doped carbon aerogels[J]. Carbon, 2018, 127: 236-244.
29	宋飞宇. 羧甲基半纤维素的制备及其与PAE湿强剂联用作用机制研究[D]. 广州: 华南理工大学, 2019.
	SONG Feiyu. Study on the preparation of carboxymethyl hemicellulose and the mechanism of its combination with PAE agent[D]. Guangzhou: South China University of Technology, 2019.
30	AFRIDI Muhammad Naveed, LEE Won Hee, KIM Jong Oh. Application of synthesized bovine serum albumin-magnetic iron oxide for phosphate recovery[J]. Journal of Industrial and Engineering Chemistry, 2020, 86: 113-122.
31	MAHMOUD Esawy, BAROUDY Ahmed EL, Nehal ALI, et al. Spectroscopic studies on the phosphorus adsorption in salt-affected soils with or without nano-biochar additions[J]. Environmental Research, 2020, 184: 109277.
32	KIM Ju Hyeong, PARK Gi Dae, YANG Su Hyun, et al. Uniquely structured iron hydroxide-carbon nanospheres with yolk-shell and hollow structures and their excellent lithium-ion storage performances[J]. Applied Surface Science, 2021, 542: 148637.
33	LIU Fuyang, LI Junjia, LI Qiliang, et al. High pressure synthesis, structure, and multiferroic properties of two perovskite compounds Y₂FeMnO₆ and Y₂CrMnO₆ [J]. Dalton Transactions, 2014, 43(4): 1691-1698.
34	XIA Wenjing, GUO Lixin, YU Linqian, et al. Phosphorus removal from diluted wastewaters using a La/C nanocomposite-doped membrane with adsorption-filtration dual functions[J]. Chemical Engineering Journal, 2021, 405: 126924.
35	DENG Shubo, LIU Han, ZHOU Wei, et al. Mn-Ce oxide as a high-capacity adsorbent for fluoride removal from water[J]. Journal of Hazardous Materials, 2011, 186(2/3): 1360-1366.
36	JANG Hyun Min, YOO Seunghyun, CHOI Yong Keun, et al. Adsorption isotherm, kinetic modeling and mechanism of tetracycline on Pinus taeda-derived activated biochar[J]. Bioresource Technology, 2018, 259: 24-31.
37	仇付国, 陈丽霞, 孙瑶, 等. 含铝活性炭污泥对磷的吸附特性研究[J]. 环境污染与防治, 2016, 38(5): 1-5, 11.
	QIU Fuguo, CHEN Lixia, SUN Yao, et al. Study of adsorption characteristics of phosphorus by aluminium-containing activated carbon sludge[J]. Environmental Pollution & Control, 2016, 38(5): 1-5, 11.
38	孙婷婷, 高菲, 林莉, 等. 复合金属改性生物炭对水体中低浓度磷的吸附性能[J]. 环境科学, 2020, 41(2): 784-791.
	SUN Tingting, GAO Fei, LIN Li, et al. Adsorption of low-concentration phosphorus from water by composite metal modified biochar[J]. Environmental Science, 2020, 41(2): 784-791.
39	郑宁捷, 唐登勇, 胡洁丽, 等. 混合改性芦苇生物炭对水中磷酸盐的吸附特性研究[J]. 中国农村水利水电, 2018(6): 97-101, 107.
	ZHENG Ningjie, TANG Dengyong, HU Jieli, et al. Study on the adsorption characteristics of mixed modified reed biochar on phosphate in water[J]. China Rural Water and Hydropower, 2018(6): 97-101, 107.
40	张梦瑶. 改性煤矸石吸附剂的制备及其去除水中磷的研究[D]. 成都: 西南交通大学, 2020.
	ZHANG Mengyao. Preparation of modified coal gangue adsorbent and study on phosphorus removal in water[D]. Chengdu: Southwest Jiaotong University,2020 .
41	NING Ping, BART Hans Jörg, LI Bing, et al. Phosphate removal from wastewater by model-La(‍Ⅲ) zeolite adsorbents[J]. Journal of Environmental Sciences, 2008, 20(6): 670-674.

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