苯硼酸基吸附树脂的制备及其在生物基1，3-丙二醇分离中的应用

doi:10.11949/0438-1157.20250533

摘要/Abstract

摘要：

生物基1,3-丙二醇的分离是其产业化的瓶颈，传统吸附树脂的吸附容量低，洗脱液用量大，目标产物回收能耗高。为此，本文利用1,3-丙二醇与硼酸存在亲和作用的特点，首先将苯硼酸固定化到多孔氯甲基聚苯乙烯树脂上，制备了PS-APBA和PS-CPBA两种功能性亲和树脂，并通过理化性质表征手段确认了苯硼酸基团的成功嫁接及树脂的热稳定性；其次考察了pH对树脂吸附容量的影响，确定了两种树脂在pH为13时的最大吸附量分别为226.4和192.6 mg/g；再次通过吸附动力学、吸附等温线、动态吸附、双组分竞争吸附实验考察了树脂的吸附特性，表明吸附过程符合准二级动力学，Langmuir模型拟合的最大吸附量分别为328.1和314.9 mg/g，Thomas模型拟合的最大动态吸附量为202.4和196.3 mg/g，树脂对1,3-丙二醇的吸附具有选择性；最后将两种树脂应用于浓缩发酵液中1,3-丙二醇的吸附分离，发现树脂经5次吸附-解吸后仍保留了较高的吸附量，1,3-丙二醇脱附率达到96%以上。本文的研究结果为生物基1,3-丙二醇的高效分离提供了新的技术方案。

关键词: 聚苯乙烯, 苯硼酸, 亲和树脂, 1,3-丙二醇, 吸附

Abstract:

The separation of bio-based 1,3-propanediol is the bottleneck in its industrialization. Conventional adsorption resins have low adsorption capacity, require large amounts of eluent, and consume high energy consumption for target product recovery. To overcome this problem, the advantage of the affinity between 1,3-propanediol and boric acid was utilized in this study by immobilizing phenylboronic acid onto porous chloromethyl polystyrene resin to prepare two functional affinity resins, i.e. PS-APBA and PS-CPBA. Physico-chemical characterization was first conducted to confirm the successful grafting of phenylboronic acid groups and the thermal stability of the resins. The effect of pH on adsorption capacities of two resins was then investigated to determine the maximum adsorption capacities of 226.4 mg/g and 192.6 mg/g at pH 13, respectively. Furthermore, the adsorption characteristics were explored by adsorption kinetics, isotherm, dynamic, and binary competitive adsorption experiments, respectively. The experimental results indicated that the adsorption process could be fitted by the pseudo-second-order kinetic model. The Langmuir model was used to fit adsorption isotherm and obtain the maximum adsorption capacities of 328.1 and 314.9 mg/g for the two resins, respectively. Dynamic adsorption experiments were fitted by Thomas model to calculate the theoretical maximum dynamic adsorption capacities of 202.4 mg/g and 196.3 mg/g, respectively. Binary competitive adsorption experiments demonstrated that the resins had good adsorption selectivity for 1,3-propanediol. Finally, two resins were applied for adsorption and separation of 1,3-propanediol in the concentrated fermentation broth, and exhibited higher adsorption capacities after five adsorption-desorption cycles with desorption rates of 1,3-propanediol exceeding 96%. The above research results provide a new technical proposal for the efficient separation of bio-based 1,3-propanediol.

Key words: polystyrene, phenylboronic acid, affinity resin, 1,3-propanediol, adsorption

中图分类号:

TQ 062⁺.1

黄路生, 肖志俊, 孙亚琴, 修志龙. 苯硼酸基吸附树脂的制备及其在生物基1，3-丙二醇分离中的应用[J]. 化工学报, 2025, 76(10): 5225-5235.

Lusheng HUANG, Zhijun XIAO, Yaqin SUN, Zhilong XIU. Preparation of phenylboronic acid-based adsorption resin and its application in the separation of bio-based 1,3-propanediol[J]. CIESC Journal, 2025, 76(10): 5225-5235.

图/表 15

图1 苯硼酸功能化改性树脂的合成路线

Fig.1 The synthesis of functional resins modified by phenylboronic acid

图2 苯硼酸基树脂的红外谱图

Fig.2 Infrared spectra of phenylboronic acid-based resins

图3 树脂改性前后的XPS全谱图和B 1s的精细谱图

Fig.3 XPS full spectra of resins before and after modification as well as fine spectrum of B 1s

图4 苯硼酸基树脂的N 1s和C 1s精细谱图

Fig.4 Fine spectra of N 1s and C 1s in phenylboronic acid-based resins

图5 苯硼酸基树脂的热重分析

Fig.5 Thermogravimetric analysis of phenylboronic acid-based resins

图6 体系pH对苯硼酸基树脂吸附容量的影响

Fig.6 Effect of pH on the adsorption capacities of phenylboronic acid-based resins

图7 两种苯硼酸基树脂对1,3-丙二醇的吸附曲线及动力学拟合

Fig.7 Adsorption curves and kinetic fitting of two phenylboronic acid-based resins for 1,3-propanediol

表1 吸附动力学拟合参数

Table 1 Fitting parameters of adsorption kinetics

树脂	拟一级动力学模型			拟二级动力学模型
树脂	Q_e/(mg/g)	k₁/min^-1	R²	Q_e/(mg/g)	k₂/(g/(mg·min))	R²
PS-APBA	247.9	0.09879	0.9702	268.6	5.264×10^-4	0.9881
PS-CPBA	229.5	0.08974	0.9300	250.9	4.893×10^-4	0.9731

图8 两种苯硼酸基树脂对1,3-丙二醇的吸附等温曲线及其拟合

Fig.8 Adsorption isothermal curves and their fitting of two phenylboronic acid-based resins for 1,3-propanediol

表2 Langmuir和Freundlich模型拟合树脂吸附等温线的参数

Table 2 The fitting parameters for the adsorption isothermal curves of two resins using Langmuir and Freundlich models

树脂	温度/K	Langmuir model			Freundlich model
树脂	温度/K	Q_m/ (mg/g)	K_L/(L/g)	R²	K_F	n	R²
PS-APBA	303	285.3	0.03206	0.9851	24.40	2.052	0.9496
	310	293.0	0.03585	0.9838	29.02	2.169	0.9502
	318	328.1	0.03451	0.9793	30.39	2.110	0.9305
PS-CPBA	303	296.0	0.02146	0.9445	15.20	1.743	0.9335
	310	303.4	0.02492	0.9526	18.99	1.848	0.9402
	318	314.9	0.02741	0.9825	21.97	1.910	0.9626

表3 树脂吸附1，3-丙二醇的热力学参数

Table 3 Thermodynamic parameters of two resins for the adsorption of 1，3-propanediol

树脂	T/K	∆H/(kJ/mol)	∆S/(J/mol/K)	∆G/(kJ/mol)
PS-APBA	303	30.46	114.50	-6.62
	310			-6.72
	318			-5.76
PS-CPBA	303	11.15	56.45	-5.88
	310			-5.21
	318			-4.16

图9 苯硼酸基树脂对甘油和1,3-丙二醇双组分的竞争吸附

Fig.9 Two-component competitive adsorption of two phenylboronic acid-based resins

图10 苯硼酸基树脂吸附1,3-丙二醇浓缩发酵液的穿透曲线

Fig.10 Breakthrough curve of phenylboronic acid-based resins for the concentrated fermentation broth of 1,3-propanediol

表4 Yoon-Nelson和Thomas模型的拟合参数

Table 4 The fitting parameters of Yoon-Nelson and Thomas models

树脂	Yoon-Nelson model			Thomas model
树脂	k_YN/min^-1	τ/min	R²	k_Th/(L/(mg·min))	Q_m/(mg/g)	R²
PS-APBA	0.1104	30.91	0.9858	2.024×10^-3	202.4	0.9769
PS-CPBA	0.1231	30.52	0.9936	1.887×10^-3	196.3	0.9837

图11 苯硼酸基树脂对1,3-丙二醇吸附和脱附循环使用性能

Fig.11 The adsorption and desorption cyclic performance of 1,3-propanediol by phenylboronic acid-based resins

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