胶原纤维固化黑荆树单宁对硼同位素的分离

doi:10.16085/j.issn.1000-6613.2022-1282

化工进展 ›› 2023, Vol. 42 ›› Issue (5): 2616-2625.DOI: 10.16085/j.issn.1000-6613.2022-1282

胶原纤维固化黑荆树单宁对硼同位素的分离

庞楠炯¹(), 王晓玲¹^,², 廖学品¹^,²^,³(), 石碧¹^,²^,³

^1.四川大学生物质与皮革工程系，四川成都 610065
^2.四川大学皮革化学与工程教育部重点实验室，四川成都 610065
^3.四川大学制革清洁技术国家工程研究中心，四川成都 610065

收稿日期:2022-07-08 修回日期:2022-08-31 出版日期:2023-05-10 发布日期:2023-06-02
通讯作者: 廖学品
作者简介:庞楠炯（1998—），男，硕士研究生，研究方向为生物质功能材料。E-mail：pangnanjiong@qq.com。
基金资助:
国家自然科学基金(22108181);反应堆燃料及材料重点实验室基金(6142A06190601)

Separation of boron isotopes by collagen fibers-immobilized black wattle tannin

PANG Nanjiong¹(), WANG Xiaoling¹^,², LIAO Xuepin¹^,²^,³(), SHI Bi¹^,²^,³

^1.Department of Biomass and Leather Engineering, Sichuan University, Chengdu 610065, Sichuan, China
^2.Key Laboratory of Leather Chemistry and Engineer of Ministry of Education, Sichuan University, Chengdu 610065, Sichuan, China
^3.National Engineering Research Center of Clean Technology in Leather Industry, Sichuan University, Chengdu 610065, Sichuan, China

Received:2022-07-08 Revised:2022-08-31 Online:2023-05-10 Published:2023-06-02
Contact: LIAO Xuepin

摘要/Abstract

摘要：

使用戊二醛为交联剂，将黑荆树单宁（BWT）固化在胶原纤维（CF）表面，得到新型硼同位素分离树脂 CF-BWT。通过FTIR、XPS、SEM、¹¹B MAS NMR分析，探究了CF-BWT吸附硼前后表面元素组成、形貌结构以及吸附机理等。研究结果表明，当pH为8.0，硼初始浓度为110mg/L时，CF-BWT的平衡吸附量可达1.9mg/g。吸附平衡符合Langmuir模型，平衡吸附量随温度升高而增加。吸附动力学可用准二级动力学模型描述，由模型计算得到的平衡吸附量与实验值接近。进一步研究发现，CF-BWT表面固化的黑荆树单宁与硼形成硼-单宁活性交换界面，促使¹⁰B和¹¹B发生同位素交换反应，从而将¹⁰B富集于CF-BWT表面，实现¹⁰B和¹¹B的分离。当pH为7.0时，CF-BWT对¹⁰B和¹¹B的单级分离因子可达1.17。当初始硼同位素丰度比（¹⁰B/¹¹B）为0.2180时，以CF-BWT为填料的固定床对¹⁰B和¹¹B进行分离，发现穿透段硼同位素丰度比（¹⁰B/¹¹B）为0.2149，而在洗脱段则达到0.2234。

关键词: 胶原纤维, 黑荆树单宁, 吸附作用, 硼同位素分离, 分离因子, 固定床

Abstract:

Glutaraldehyde was used as a cross-linking agent to immobilize black wattle tannin (BWT) on the surface of collagen fibers (CF) to obtain a new type of boron isotope separation resin (CF-BWT). Using FTIR, XPS, SEM and ¹¹B MAS NMR, the elemental composition, morphology, structure and adsorption mechanism of CF-BWT to boron were explored. The results showed that the equilibrium adsorption capacity of CF-BWT could reach 1.9mg/g when the pH was 8.0 and the initial concentration of boron was 110mg/L. The adsorption isotherms of CF-BWT to boron could be described by the Langmuir equation and the adsorption capacity increased with the increase of temperature. The adsorption kinetics could also be described by the pseudo-second-order kinetic model, and the equilibrium adsorption capacities calculated by the model were close to the experimental value. Furthermore, the boron-tannin active exchange interface formed by the tannin immobilized on the surface of CF-BWT promoted the isotope exchange reaction of ¹⁰B and ¹¹B, thereby enriching ¹⁰B on the surface of CF-BWT and realizing the separation of ¹⁰B and ¹¹B. The corresponding single stage separation factor could reach 1.17 at pH=7.0. When the initial boron isotope ratio (¹⁰B/¹¹B) was 0.2180, the column of CF-BWT was used for the separation of ¹⁰B and ¹¹B. The results showed that the boron isotope ratio (¹⁰B/¹¹B) was 0.2149 at the penetration section and high up to 0.2234 at the elution section, suggesting effective separation of ¹⁰B and ¹¹B.

Key words: collagen fibers, black wattle tannin, adsorption, boron isotope separation, separation factor, fixed bed

中图分类号:

庞楠炯, 王晓玲, 廖学品, 石碧. 胶原纤维固化黑荆树单宁对硼同位素的分离[J]. 化工进展, 2023, 42(5): 2616-2625.

PANG Nanjiong, WANG Xiaoling, LIAO Xuepin, SHI Bi. Separation of boron isotopes by collagen fibers-immobilized black wattle tannin[J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2616-2625.

图/表 8

图1 CF-BWT吸附分离硼同位素示意图

图2 CF、CF-BWT、CF-BWT-B的结构表征图

图3 pH对CF-BWT吸附性能的影响及其吸附动力学曲线和吸附等温线

表1 CF-BWT吸附硼动力学模型拟合参数

准一级动力学模型				准二级动力学模型
k₁/min^-1	q_e/mg·g^-1	R²		k₂/g·mg^-1·min^-1	q_e/mg·g^-1	R²
0.0235	2.3533	0.9860		0.0141	2.5011	0.9996

表2 CF-BWT对B的Langmuir和Freundlich吸附等温线参数

T/K	Langmuir			Freundlich
T/K	k_L/L·mg^-1	q_m/mg·g^-1	R²	k_F	1/n	R²
293	0.0208	2.4678	0.9882	0.2241	0.4078	0.9313
303	0.0238	2.6082	0.9846	0.2746	0.3863	0.9314
313	0.0239	2.8503	0.9911	0.2983	0.3878	0.9412

图4 CF-BWT-B和B(OH)3（0.5mol/L）的11B MAS NMR图、刺槐亭醇结构及其分别与10B(OH)3、11B(OH)3形成双螯合配合物的结构和结合能（1kcal/mol=4.18kJ/mol）

表3 11B MAS NMR中化学位移的信号峰面积相对积分

pH	化学位移2.6/%	化学位移7.8/%	化学位移13.9/%	化学位移17.7/%
6.0	—	25.7	73.5	—
7.0	5.9	34.9	59.2	—
8.0	3.9	43.0	49.5	3.6

图5 静态分离硼同位素实验流程、不同pH条件下CF-BWT的硼同位素分离因子和CF-BWT-B上同位素丰度、CF-BWT分离硼同位素的固定床实验装置和穿透与洗脱曲线

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胶原纤维固化黑荆树单宁对硼同位素的分离

Separation of boron isotopes by collagen fibers-immobilized black wattle tannin

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