再生角蛋白凝胶对纺织退浆废水中浆料分子的吸附性能

doi:10.13475/j.fzxb.20230706401

纺织学报 ›› 2024, Vol. 45 ›› Issue (02): 142-152.doi: 10.13475/j.fzxb.20230706401

再生角蛋白凝胶对纺织退浆废水中浆料分子的吸附性能

杨美慧¹^,², 李博¹^,²^,³, 沈艳琴¹^,²(), 武海良¹^,²

1.西安工程大学纺织科学与工程学院, 陕西西安 710048
2.西安工程大学功能性纺织材料及制品教育部重点实验室, 陕西西安 710048
3.苏州大学纺织行业丝绸功能材料与技术重点实验室, 江苏苏州 215123

收稿日期:2023-07-26 修回日期:2023-11-01 出版日期:2024-02-15 发布日期:2024-03-29
通讯作者: 沈艳琴(1963—),女,教授,硕士。主要研究方向为新材料的开发与应用。E-mail:shenyanqin1208@126.com。
作者简介:杨美慧(1998—),女,硕士生。主要研究方向为再生生物质材料研发与应用。
基金资助:
陕西省自然科学基础研究计划项目(2023-JC-QN-0423);中国纺织工业联合会应用基础研究项目(J202203);纺织行业丝绸功能材料与技术重点实验室开放课题项目(SDHY2235);陕西省教育厅科研计划项目(23JY031)

Sorption properties of regenerated keratin gels to size macromolecules in textile desizing wastewater

YANG Meihui¹^,², LI Bo¹^,²^,³, SHEN Yanqin¹^,²(), WU Hailiang¹^,²

1. School of Textile Science and Engineering, Xi'an Polytechnic University, Xi'an, Shaanxi 710048, China
2. Key Laboratory of Functional Textile Material and Product, Ministry of Education, Xi'an Polytechnic University, Xi'an, Shaanxi 710048, China
3. China National Textile and Apparel Council Key Laboratory for Silk Functional Materials and Technology, Soochow University, Suzhou, Jiangsu 215123, China

Received:2023-07-26 Revised:2023-11-01 Published:2024-02-15 Online:2024-03-29

摘要/Abstract

摘要：

为实现废弃角蛋白纤维资源的高值化循环利用,在采用“还原预处理-甲酸”溶解法获取角蛋白多肽并引入α-硫辛酸进行化学改性基础上,制备再生凝胶材料用于纺织退浆废水中浆料分子的吸附处理。借助扫描电子显微镜、傅里叶红外光谱等测试技术对角蛋白凝胶的结构和性能进行表征。针对聚乙烯醇(PVA)和淀粉2种浆料,探究凝胶对不同浆料分子的吸附规律及机制。结果表明:角蛋白凝胶具有均匀的三维孔隙结构,其化学组成和官能团结构与原纤维基本一致,且结晶程度较高;该凝胶对溶液体系中PVA分子的吸附量和去除率分别为 16.278 mg/g 和30.013%,对淀粉浆料则可达到133.234 mg/g和28.868%;此外,吸附动力学和热力学研究显示,角蛋白凝胶对2种浆料的吸附规律均符合准二级动力学模型,其中对PVA分子主要为物理吸附作用,而对淀粉则可能存在化学吸附效果。

关键词: 角蛋白凝胶, 天然生物质, 生物吸附剂, 纺织退浆废水, 染料, 吸附动力学

Abstract:

Objective The effective recycling of waste protein fiber resources is one of the important aspects to achieve green and sustainable development of textile industry. In this study, regenerated keratin gels were prepared from waste wool fibers and applied to the sorption treatment of textile desizing wastewater. By exploring the sorption performance and mechanism of keratin gels to two common types of sizes, the research foundation is provided for promoting the industrialized application of this method.

Method On the basis of the preliminary study, the keratin polypeptides were extracted by ″reducing agent-formic acid method″, and then the polypeptides were modified by α-lipoic acid. These modified keratin polypeptides were prepared for creating regenerated gel materials by dialysis and freeze-drying. The sorption properties of the keratin gels to polyvinyl alcohol (PVA) size and starch size were studied, and the sorption mechanism was discussed by using the sorption kinetics and sorption isotherm model.

Results The experiment was based on the "reduction pretreatment-formic acid dissolution method", by adding the modifier α-lipoic acid for grafting modification, and then by "dialysis-freezing" method to prepare the keratin gel material. The photograph of the gel structure illustrated that the keratin gel was relatively fluffy and dense, and the microscopic morphology presented the characteristics of uniform pores with the pore size of about 3-4 μm. In comparison with the chemical structures of wool, the keratin gel material retained the basic chemical structure of keratin molecule, in which the keratin amide II band was blueshifted due to the transformation of the aggregation state of polypeptide molecules in the gel. Compared with the sulfur content on the surface of wool and keratin gel, the keratin gel was located at 169.58 eV and 170.68 eV. The results indicated that α-lipoic acid was effectively grafted to the sulfhydryl group on the keratin polypeptide macromolecular chain. In addition, the peak intensity of the gel at 21° increased significantly than those of the peak crystallinity of wool, and the test results exhibited that the molecular structure of the polypeptide modified by α-lipoic acid was optimized to a certain extent. The adsorption capacity and removal rate of keratin gel on PVA reached 16.278 mg/g and 30.013%, respectively, and the adsorption capacity and removal rate of starch slurry are 133.234 mg/g and 28.868%. Moreover, the kinetic model study showed that the adsorption of PVA and starch by keratin gel was in accordance with the quasi-secondary kinetic model, and the fit was close to 1. Thermodynamic model analysis presented that the adsorption of keratin for PVA was consistent with Langmuir model, and that starch was more suitable for the Freundlich model.

Conclusion The keratin gel prepared in this study has uniform physical morphology and abundant pore structure, and its chemical properties are basically consistent with wool. The keratin gels have good sorption performance to PVA and starch size. Among them, the action mode of gels to PVA is mainly physical adsorption, while there may be chemical effects on starch.

Key words: keratin gel, natural biomass, biosorbent, textile desizing wastewater, dye, sorption kinetics

中图分类号:

TS199

杨美慧, 李博, 沈艳琴, 武海良. 再生角蛋白凝胶对纺织退浆废水中浆料分子的吸附性能[J]. 纺织学报, 2024, 45(02): 142-152.

YANG Meihui, LI Bo, SHEN Yanqin, WU Hailiang. Sorption properties of regenerated keratin gels to size macromolecules in textile desizing wastewater[J]. Journal of Textile Research, 2024, 45(02): 142-152.

图/表 14

图1

图2

图3

图4

图5

图6

图7

图8

图9

图10

表1

对PVA及淀粉吸附动力学参数拟合结果"

吸附浆料种类	准一级动力学参数			准二级动力学参数
吸附浆料种类	K₁	q₁	$R 1 2$	K₂	q₂	$R 2 2$
PVA	-0.143 200	0.826 894	0.295 75	-0.183 25	11.252 40	0.999 88
淀粉	0.004 145	33.385 660	0.978 01	0.000 88	63.171 19	0.995 46

表1

图11

图12

表2

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吸附浆料种类	Langmuir				Freundlich
吸附浆料种类	q_m	K_L	R²	R_MSE/10^-2	n	K_F	R²	R_MSE/10^-3
PVA	21.753	0.245 0	0.954 19	1.178	3.298 5	6.671 1	0.910 62	4.14
淀粉	-6.740	-0.123 6	0.529 18	0.144	0.877 1	0.455 2	0.995 12	9.967

再生角蛋白凝胶对纺织退浆废水中浆料分子的吸附性能

Sorption properties of regenerated keratin gels to size macromolecules in textile desizing wastewater

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