两性纤维素多孔凝胶球的制备及其动态吸附性能

doi:10.13475/j.fzxb.20230402301

摘要/Abstract

摘要：

用于废水处理的多孔凝胶球存在制备工艺繁琐,吸附种类单一,吸附效率低等不足;为提高多孔凝胶球的性能,采用滴入相分离、酯化反应引入羧基及希夫碱反应引入氨基的化学改性方法,制备得到兼具高孔隙率、高力学性能和羧基/氨基活性基团的两性纤维素多孔凝胶球(ACM),并构建动态吸附柱装置以探究不同条件下ACM对染料的动态吸附性能。结果表明:通过降低染料初始质量浓度,增加填料高度和减慢进液流速的方式可有效提高吸附柱的动态吸附效率;0.8 g的ACM可处理7.5 L含染料的废水;对ACM的动态吸附过程进行动态模型拟合,其与Thomas和Yoon-Nelson模型的拟合程度高,表明吸附是均匀表面的单分子层吸附,动态吸附过程中存在2个或多个速率控制步骤,内部扩散和外部扩散均不是吸附过程中的限速步骤。基于ACM优异的分级孔结构、丰富的活性位点和低传质阻力等优势,认为ACM展现出良好的动态吸附性能,在印染废水处理方面有较大应用潜力。

关键词: 纤维素, 两性凝胶球, 吸附分离, 阴阳离子染料, 动态吸附性能, 印染废水, 废水处理

Abstract:

Objective Cellulose porous hydrogel spheres are increasingly used as adsorption fillers by virtue of their combined properties, which have become a current research focus. However, the preparation of these spheres is currently cumbersome and they exhibit limited adsorption efficiency and single adsorption species, restricting their applications. Therefore, it is important to develop a simple and efficient biomass adsorbent with both adsorption and separation capacity for ionic dyes.

Method In this paper, amphoteric cellulose porous microsphere (ACM) was developed by a two-step chemical modification method of esterification and Schiff base reaction. The surface morphology, pore structure and mechanical properties of the hydrogel spheres were characterized and analyzed using field emission scanning electron microscopy, specific surface area and pore size distribution instrument and universal testing machine, respectively. The adsorption column device was constructed to investigate the adsorption properties of ACM.

Results The specific surface area, pore size distribution and porosity of ACM with abundant pore structure on the surface and inside were 123.97 m²/g, 0.633 cm³/g and 89.22%, respectively. The compressive strength of ACM was found to be 591.9 kPa at 30% compression deformation, and the mechanical properties were about 63% of the initial value after 40 cycles of compression. ACM showed good compressive strength as well as structural stability because the carboxylation reaction took place at a high temperature, which increased the skeletal density and strength of the hydrogel spheres. Cross-linking occurred during the two-step reaction, producing three-dimensional network structure that enhanced the mechanical properties. It was found that the dynamic adsorption efficiency of the adsorption column wase improved by reducing the initial concentration, increasing the loading height, and slowing down the feed rate. With 0.8 g hydrogel spheres it was possible to treat almost 7.5 L of dye containing wastewater. The hydrogel spheres were chemically modified in two steps to combine high porosity, high mechanical properties, and abundance of carboxyl/amino active groups. 80% separation of mixed dyes was achieved by ACM, which possesses both carboxyl and amino active groups and has different adsorption properties under different acid and base conditions.

Conclusion The influence of different device parameters on the dynamic adsorption of ACM was investigated, and it was found that the dynamic adsorption efficiency of the column could be improved by decreasing the initial concentration, increasing the loading height, and slowing down the feed rate. The final device parameters were determined as 50 mg/L inlet concentration, 12 cm filling height and 4 mL/min inlet speed. 0.8 g of hydrogel spheres could treat about 7.5 L of wastewater containing dye MeB at the optimum device parameters, demonstrating the good adsorption and separation performance of the ACM.

Key words: cellulose, amphoteric hydrogel sphere, adsorption separation, anionic and cationic dye, dynamic adsorption property, printing and dyeing wastewater, wastewater treatment

中图分类号:

X703.1

郑康, 龚文丽, 鲍杰, 刘琳. 两性纤维素多孔凝胶球的制备及其动态吸附性能[J]. 纺织学报, 2024, 45(05): 102-112.

ZHENG Kang, GONG Wenli, BAO Jie, LIU Lin. Preparation and dynamic adsorption properties of amphoteric cellulose porous hydrogel spheres[J]. Journal of Textile Research, 2024, 45(05): 102-112.

导出引用管理器 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20230402301

http://www.fzxb.org.cn/CN/Y2024/V45/I05/102

图/表 20

图1

图2

图3

图4

图5

图6

图7

图8

表1

图9

表2

图10

表3

图11

表4

图12

表5

图13

表6

图14

参考文献 20

[1]	GONG W L, ZHENG K, ZHANG C Y, et al. Simultaneous and efficient removal of heavy metal ions and organophosphorus by amino-functionalized cellulose from complex aqueous media[J]. Journal of Cleaner Production, 2022. DOI: 10.1016/j.jclepro.2022.133040.
[2]	孙慧萍, 吕文洲. 膨润土负载锌-钴催化臭氧处理模拟染料废水[J]. 纺织学报, 2019, 43(2): 118-124.
	SUN Huiping, LÜ Wenzho. Bentonite supported Zn-Co ozone catalyst for treatment of simulated dye waste-water[J]. Journal of Textile Research, 2019, 43(2): 118-124.
[3]	LANGBEHN R K, MICHELS C, SOARES H M. Antibiotics in wastewater: From its occurrence to the biological removal by environmentally conscious technologies[J]. Environmental Pollution, 2021. DOI: 10.1016/j.envpol.2021.116603.
[4]	CHENG H, LI L J, WANG B J, et al. Multifaceted applications of cellulosic porous materials in environment, energy, and health[J]. Progress in Polymer Science, 2020. DOI: 10.1016/j.progpolymsci.2020.101253.
[5]	YAO T, GUO S, ZENG C, et al. Investigation on efficient adsorption of cationic dyes on porous magnetic polyacrylamide microspheres[J]. Journal of Hazardous Materials, 2015, 292: 90-97. doi: 10.1016/j.jhazmat.2015.03.014 pmid: 25797927
[6]	HAQUE A N M A, REMADEVI R, NAEBE M. A review on cotton gin trash: sustainable commodity for material fabrication[J]. Journal of Cleaner Production, 2021. DOI: 10.1016/j.jclepro.2020.125300.
[7]	魏娜娜, 刘碟, 马政, 等. 纤维素/壳聚糖磁性气凝胶的冻融法制备及其对染料吸附性能[J]. 纺织学报, 2022, 43(2): 53-60.
	WEI Nana, LIU Die, MA Zheng, et al. Adsorption perfor-mance of cellulose/chitosan magnetic aerogel prepared by freeze-thawing method[J]. Journal of Textile Research, 2022, 43(2): 53-60.
[8]	SHI W, CHING Y C, CHUAH C H. Preparation of aerogel beads and microspheres based on chitosan and cellulose for drug delivery: a review[J]. International Journal of Biological Macromolecules, 2021, 170: 751-767. doi: 10.1016/j.ijbiomac.2020.12.214 pmid: 33412201
[9]	LI J L, ZHOU L J, SONG Y K, et al. Green fabrication of porous microspheres containing cellulose nanocrystal/MnO₂ nanohybrid for efficient dye removal[J]. Carbohydrate Polymers, 2021. DOI: 10.1016/j.carbpol.2021.118340.
[10]	DING Y H, SONG C H, GONG W L, et al. Robust, sustainable, hierarchical multi-porous cellulose beads via pre-crosslinking strategy for efficient dye adsorption[J]. Cellulose, 2021, 28(11): 7227-7241.
[11]	CHEN C, CHEN Z L, SHEN J M, et al. Dynamic adsorption models and artificial neural network prediction of mercury adsorption by a dendrimer-grafted polyacrylonitrile fiber in fixed-bed column[J]. Journal of Cleaner Production, 2021. DOI: 10.1016/j.jclepro.2021.127511.
[12]	XU L H, WANG S D, ZHOU J W, et al. Column adsorption of 2-naphthol from aqueous solution using carbon nanotube-based composite adsorbent[J]. Chemical Engineering Journal, 2018, 335: 450-457.
[13]	YIN Y, XU G Y, XU Y X, et al. Adsorption of inorganic and organic phosphorus onto polypyrrole modified red mud: evidence from batch and column experiments[J]. Chemosphere, 2022. DOI: 10.1016/j.chemosphere.2021.131862.
[14]	BO S, LUO J, AN Q, et al. Efficiently selective adsorption of Pb(II) with functionalized alginate-based adsorbent in batch/column systems: mechanism and application simulation[J]. Journal of Cleaner Production, 2020. DOI: 10.1016/j.jclepro.2019.119585.
[15]	LI T F, WANG X Q, JIAO J, et al. Catalytic transesterification of pistacia chinensis seed oil using hpw immobilized on magnetic composite graphene oxide/cellulose microspheres[J]. Renewable Energy, 2018, 127: 1017-1025.
[16]	ROCHA I, HATTORI Y, DINIZ M, et al. Spectroscopic and physicochemical characterization of sulfonated cladophora cellulose beads[J]. Langmuir, 2018, 34(37): 11121-11125. doi: 10.1021/acs.langmuir.8b01704 pmid: 30169040
[17]	DU K F, LIU X H, LI S K, et al. Synthesis of Cu²⁺ chelated cellulose/magnetic hydroxyapatite particles hybrid beads and their potential for high specific adsorption of histidine-rich proteins[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(9): 11578-11586.
[18]	RUAN C Q, STROMME M, LINDH J. Preparation of porous 2,3-dialdehyde cellulose beads crosslinked with chitosan and their application in adsorption of Congo red dye[J]. Carbohydrate Polymers, 2018, 181: 200-207.
[19]	OONA K, TATIANA B. All-cellulose composite aerogels and cryogels[J]. Composites Part A, 2020. DOI: 10.1016/j.compositesa.2020.106027.
[20]	PAN Y F, XIE H L, LIU H Y, et al. Novel cellulose/montmorillonite mesoporous composite beads for dye removal in single and binary systems[J]. Bioresource Technology, 2019. DOI: 10.1016/j.biortech.2019.121366.

Metrics

Viewed

Full text

Abstract

Cited

Shared

Discussed

样品	t_b/min	R_b/%	t_s/min	R_s/%	Q_e/(mg·g^-1)	H_MTZ/cm
C25	21	0.79	3 308	0.520	215.11	11.923
C50	42	0.81	1 870	0.467	218.71	11.744
C100	10	0.73	870	0.505	219.84	11.862

样品	t_b/min	R_b/%	t_s/min	R_s/%	Q_e/(mg·g^-1)	H_MTZ/cm
H12	42.0	0.81	1870	0.467	218.71	11.74
H10	55.0	0.81	1480	0.456	202.56	9.62
H8	6.3	0.69	1091	0.389	159.01	7.95

样品	t_b/min	R_b/%	t_s/min	R_s/%	Q_e/(mg·g^-1)	H_MTZ/cm
V4	42	0.81	1 870	0.467	218.71	11.74
V6	63	0.82	1 342	0.421	212.37	11.43
V8	19	0.78	896	0.329	147.75	11.74

样品	实验数据	Thomas模型
样品	Q_e/ (mg·g^-1)	k_Th/ (mL·min^-1·mg^-1)	Q₀/ (mg·g^-1)	R²
C25	215.11	0.031 5	218.242	0.933 9
C50	218.71	0.030 8	218.541	0.953 3
C100	219.84	0.029 1	220.010	0.974 8
H12	218.71	0.030 8	218.541	0.953 3
H10	202.56	0.035 0	197.171	0.820 7
H8	159.01	0.041 0	124.958	0.802 0
V4	218.71	0.030 8	218.541	0.953 3
V6	212.37	0.045 6	212.261	0.920 6
V8	147.75	0.060 2	115.794	0.725 5

样品	实验数据			Yoon-Nelson模型
样品	t_0.5/min	Q_0.5/mg	R_0.5/%	k_YN/min^-1	τ_0.5/min	R²
C25	2 008	131.612	0.655 43	0.000 79	1 745.939	0.933 9
C50	721	96.624	0.670 06	0.001 54	874.162	0.953 3
C100	477	119.501	0.626 31	0.002 91	440.021	0.974 8
H12	721	96.624	0.670 06	0.001 54	874.162	0.953 3
H10	397	53.108	0.668 86	0.001 75	657.566	0.820 7
H8	184	22.368	0.607 82	0.002 05	333.639	0.802 0
V4	721	96.624	0.670 06	0.001 54	874.162	0.953 3
V6	451	87.006	0.643 06	0.002 28	566.031	0.920 6
V8	135	35.448	0.653 54	0.003 01	231.588	0.725 5