磁性氢氧化铬硼吸附剂的制备及性能研究

doi:10.11949/0438-1157.20251251

摘要/Abstract

摘要：

首先构建了硼物种分布三维图，系统阐明了不同初始浓度与pH协同作用下各硼形态的分布规律。在此基础上，成功合成一种磁性氢氧化铬基硼吸附材料。通过FT-IR和XPS等表征手段确认Cr–OH为关键活性位点。此外，结合Raman光谱技术，揭示了该材料对B（OH）₃和B（OH） $4 -$ 具有选择性吸附行为。通过DFT计算与吸附动力学模型相结合，进一步定量分析了多种硼物种（B（OH）₃、B（OH） $4 -$ 、B₃O₃（OH） $4 -$ 、B₃O₃（OH） $5 2 -$ 、B₄O₅（OH） $4 2 -$ 和B₅O₆（OH） $4 -$ ）的水合离子直径，并与BET孔隙结构数据进行对比，结果表明：该吸附过程的速率控制步骤主要由吸附剂颗粒内部的内扩散阻力决定。离子竞争实验显示，常见共存离子（如Li⁺、Na⁺、K⁺、NO $3 -$ 和SO $4 2 -$ ）对硼吸附性能具有轻微促进作用，而CO $3 2 -$ 和HCO $3 -$ 则表现出显著抑制作用，分别归因于盐效应促进硼酸解离以及强配体与活性位点之间的竞争性吸附。结合磁分离技术，该吸附剂在10次吸脱附循环中溶损率仅为3%，在真实卤水中开展连续20次吸附实验结果表明，脱硼效率高达90%。因此，本研究为金属氧化物与氢氧化物类硼吸附剂的功能化官能团设计及高效分离策略提供了新思路。

关键词: 吸附剂, 分离, 解吸, 氢氧化铬, 磁性硼吸附, 活性位点, 吸附机理

Abstract:

Three-Dimensional distribution mapping of boron species was developed to analyze boron species distribution under varying initial concentrations and pH levels. Based on this, a magnetic chromium hydroxide-based adsorbent was synthesized. FT-IR and XPS confirmed Cr–OH as the key active site, while Raman spectroscopy showed selective adsorption of B(OH)₃ and B(OH) $4 -$ . Combining DFT calculations with kinetic models, hydrated diameters of six boron species were analyzed and compared with BET pore data, revealing that internal diffusion resistance controls the adsorption rate. Ion competition tests showed that common ions (Li⁺, Na⁺, K⁺, NO $3 -$ , SO $4 2 -$ ) slightly enhance boron uptake, whereas CO $3 2 -$ and HCO $3 -$ significantly inhibit it due to promoted boric acid dissociation and competitive ligand adsorption, respectively. In real brine, 20-cycle magnetic separation experiments achieved 90% deboronation efficiency with only 3% adsorbent loss. This study offers new insights into designing functional groups and efficient separation strategies for metal oxide/hydroxide-based boron adsorbents.

Key words: adsorbents, separation, desorption, chromium hydroxide, magnetic boron adsorption, active sites, adsorption mechanism

中图分类号:

TQ110.2

刚洁, 唐竟耀, 张成勇, 陈彩霞, 关云山, 吕红梅, 张卫东. 磁性氢氧化铬硼吸附剂的制备及性能研究[J]. 化工学报, DOI: 10.11949/0438-1157.20251251.

Jie GANG, Jingyao TANG, Chengyong ZHANG, Caixia CHEN, Yunshan GUAN, Hongmei LV, Weidong ZHANG. Preparation and Performance Study of Magnetic Chromium hydroxide Boron Adsorbent[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251251.

图/表 12

表1 金属氧化物和氢氧化物吸附硼的性能比较

Table 1 Comparison of the performance of metal oxides and hydroxides in adsorbing boron

吸附剂	pH	Q_e/(mmol·g^-1)	c₀/(mol·L^-1)	脱附再生条件	参考文献
氧化镁	9	4.23	0.019	350 ℃煅烧	^[23]
	8	3.98
	5	3.7
氢氧化镍	9	2.04	0.019	0.05 mol·L^-1NaOH	^[26]
	8	1.85
	5	1.67
E-氢氧化镍	9	2.92	0.019	0.05 mol·L^-1 NaOH	^[26]
氢氧化锆	9	1.79	0.019	0.5 mol·L^-1 NaOH	^[27]
	8	0.93
	5	0.60
氢氧化铬	8	1.94	0.08	pH=12 水溶液	本文
	5	0.7	0.08	pH=12 水溶液
	8	0.65	0.019	pH=12 水溶液

图1 Cr(OH)x吸附剂的(a)PXRD；(b)氮气吸附-脱附等温线；(c)孔径分布图；(d)TGA；(e)磁滞回线；(f)磁性吸附体系实物图；(g)扫描电镜图片及其元素组成注:Cr (OH)x adsorbents

Fig. 1 (a) PXRD; (b) Nitrogen adsorption-desorption isotherms; (c) Pore size distribution diagram; (d) TGA; (e) Hysteresis loop; (f) Physical diagram of the magnetic adsorption system; and (g) SEM images and EDS-mapping of as-prepared

图2 (a-f) B(OH)₃、B(OH)4-、B₃O₃(OH)4-、B₃O₃(OH)52-、B₄O₅(OH)42-和B₅O₆(OH)4-分布含量图；(g) pH对吸附性能的影响；(h)浓度对吸附性能的影响；(i) 0.08 mol·L-1硼酸溶液中硼物种的含量积分

Fig. 2 (a-f) Distribution of B(OH)₃, B(OH)4-, B₃O₃(OH)4-, B₃O₃(OH)52-, B₄O₅(OH)42-, and B₅O₆(OH)4-; (g) pH effect on adsorption; (h) Concentration effect on adsorption; (i) integral of boron content in 0.08 mol·L-1 boric acid solution

图3 (a)温度与浓度对吸附性能的影响；(b) Henry模型；(c) Langmuir模型及(d) Freundlich模型对吸附等温线拟合结果

Fig. 3 (a) Effect of temperature and concentration on adsorption performance; (b) Henry; (c) Langmuir; and (d) Freundlich model fitting results for adsorption isotherms.

表2 Henry、Langmuir和Freundlich模型对吸附等温线的拟合参数

Table 2 Fitting parameters of Henry， Langmuir， and Freundlich adsorption isotherm models

Model and parameter	Henry		Langmuir			Freundlich
T(℃)	K_H/(mL·g^-1)	R²	K_L/(L·mol^-1)	Q_m/(mmol·g^-1)	R²	K_F	1/n	R²
25	19.5	0.976	30.5	2.23	0.903	7.10	0.561	0.985
35	24.4	0.951	39.3	2.59	0.967	8.94	0.548	0.984
45	24.1	0.972	46.3	2.56	0.953	7.61	0.486	0.992

图4 (a)吸附时间对吸附性能的影响；(b)氢氧化铬对硼的颗粒内扩散模型拟合；(c)准一级吸附动力学模型拟合；(d) 准二级吸附动力学模型拟合；(e) B(OH)₃、B(OH)4-、B₃O₃(OH)4-、B₃O₃(OH)52-、B₄O₅(OH)42-和B₅O₆(OH)4-的水合直径

Fig. 4 (a) Effect of adsorption time on performance; (b) Intraparticle diffusion model fitting for boron adsorption by chromium hydroxide; (c) Pseudo-first-order kinetic model fitting; (d) Pseudo-second-order kinetic model fitting; (e) The hydrated diameters of B(OH)₃, B(OH)4-, B₃O₃(OH)4-, B₃O₃(OH)52-, B₄O₅(OH)42-, and B₅O₆(OH)4-

表3 吸附动力学模型拟合参数

Table 3 Kinetic model parameters for boron adsorption

Model and parameter		Intraparticle diffusion model
	k_i/(mmol·g^-1·h^-0.5)	Q₁/(mmol·g^-1)	R²	k_i/(mmol·g^-1·h^-0.5)	Q₂/(mmol·g^-1)	R²
Value	0.299	0.761	0.954	0.105	1.445	0.679
Model and parameter	Quasi-first-order kinetic model			Quasi-second-order kinetic model
	k₁/h^-1	Q_e/(mmol·g^-1)	R²	k₂/(g·mmol^-1·h^-1)	Q_e/(mmol·g^-1)	R²
Value	0.324	1.263	0.829	0.629	1.857	0.983

图5 吸附剂吸附前后(a)红外光谱的对比图；(b)拉曼光谱的对比图；(c) XPS总谱图；(d) O 1s分峰拟合谱图

Fig. 5 Comparison of (a) infrared spectra; (b) Raman spectra; (c) XPS survey spectrum; and (d) O 1s peak-fitting spectrum of the adsorbent before and after adsorption

图6 (a)共存盐对吸附性能的影响；不同浓度(b) LiCl；(c) NaCl；(d) KCl对吸附性能的影响；(e)体系pH对吸附性能的影响；(f) zeta电位

Fig. 6 (a) Influence of coexisting salts on adsorption performance; Influence of different concentrations of (b) LiCl; (c) NaCl; and (d) KCl on adsorption performance; (e) The influence of system pH on adsorption performance; and (f) zeta potential

图7 吸附剂的再生性能：(a)洗脱液pH值对洗脱率的影响；(b洗脱液温度对洗脱率的影响；(c)洗脱时间对洗脱率的影响；(d)连续10次循环的吸附性能；(e)真实卤水20次循环吸附

Fig. 7 Regeneration performance of the adsorbent: (a) Influence of the pH value; (b) temperature of the eluent; (c) elution time on the elution rate; (d) Adsorption performance over 10 consecutive cycles; (e) 20 cycles of adsorption in real brine

表4 XX锂业有限公司高锂合格液经硼吸附剂处理前后的组成分析

Table 4 Compositional analysis of high lithium solution from XX Lithium Industry Co.， Ltd. Before and after boron adsorbent treatment

样品	Cl^-(mol·L^-1)	Na⁺ (mol·L^-1)	B (mol·L^-1)	Li⁺ (mol·L^-1)	Ca²⁺ (mol·L^-1)	Mg²⁺ (mol·L^-1)
吸附前	4.46	1.9	0.1	0.8	0.0002	ND
吸附后	4.38	2.4	0.01	0.8	0.00008	ND

图8 吸附机理示意图

Fig. 8 Schematic Diagram of Adsorption Mechanism

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