弱酸性蓝AS染料排放的废盐制碳基吸附剂及利用

doi:10.11949/0438-1157.20240048

化工学报 ›› 2024, Vol. 75 ›› Issue (3): 890-899.DOI: 10.11949/0438-1157.20240048

弱酸性蓝AS染料排放的废盐制碳基吸附剂及利用

张天永¹^,²(), 张晶怡¹, 姜爽¹^,²(), 李彬¹^,²(), 吕东军³, 陈都民⁴, 陈雪⁴

^1.天津大学化工学院，天津市应用催化科学与工程重点实验室，天津 300354
^2.天津市功能精细化学品技术工程中心，天津 300354
^3.德州学院化学化工学院，山东德州 253023
^4.宇虹颜料股份有限公司，山东德州 253000

收稿日期:2024-01-10 修回日期:2024-01-29 出版日期:2024-03-25 发布日期:2024-05-11
通讯作者: 姜爽,李彬
作者简介:张天永（1966—），男，博士，教授，tyzhang@tju.edu.cn；
基金资助:
泰山产业领军人才工程项目(tscx202211094);德州市重大科技创新工程项目

Preparation and utilization of carbon-based adsorbent from organic pollutants in waste salt during acidic blue AS dye production

Tianyong ZHANG¹^,²(), Jingyi ZHANG¹, Shuang JIANG¹^,²(), Bin LI¹^,²(), Dongjun LYU³, Dumin CHEN⁴, Xue CHEN⁴

^1.Tianjin Key Laboratory of Applied Catalysis Science and Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300354, China
^2.Tianjin Engineering Research Center of Functional Fine Chemicals, Tianjin 300354, China
^3.College of Chemistry and Chemical Engineering, Dezhou University, Dezhou 253023, Shandong, China
^4.Yuhong Pigment Co. , Ltd. , Dezhou 253000, Shandong, China

Received:2024-01-10 Revised:2024-01-29 Online:2024-03-25 Published:2024-05-11
Contact: Shuang JIANG, Bin LI

摘要/Abstract

摘要：

将染料弱酸性蓝AS(AS)生产排放的含盐废水喷雾干燥后制成废盐，再将其有机污染物煅烧制备成类活性炭吸附剂(LAC)，用于AS染料生产过程中产生的洗涤废水的吸附脱色净化，同时回收粗盐NaCl可循环用于AS工业生产的盐析过程。对LAC进行吸附过程动力学、热力学研究，并研究AS染料废水溶液初始浓度、温度及pH对吸附性能的影响。在40 mg/L的AS染料废水中，温度为318 K的条件下，平衡吸附量为29.22 mg/g。在酸性及温度较高时吸附能力较强。Langmuir等温线方程能更好拟合吸附实验结果。另外，采用一锅混合法，添加四水合乙酸镁对LAC进行改性，改性后的吸附剂LACMg0.75比表面积较LAC提升了近5倍，饱和吸附量能够达到550.02 mg/g，较LAC提升了接近20倍。

关键词: 弱酸性蓝AS, 废水处理, 吸附剂, 回收, 活性炭, 以废治废

Abstract:

The salt-containing wastewater discharged from the production of the dye weak acid blue AS (AS) is spray-dried to make waste salt, and then the organic pollutants are calcined to prepare a quasi-activated carbon adsorbent (LAC). It was utilized for the adsorption and decolorization of wash wastewater from AS dye production. Additionally, the crude salt (NaCl) recovery from the above calcination technology could be reused in the salting-out process in AS industrial production. This research was conducted to determine the optimal temperature for calcining LAC, and calcination in a muffle furnace at 450℃ yielded the best results. Furthermore, the impact of initial dye wastewater concentration, temperature, and pH on the adsorption performance of LAC was investigated. The findings revealed that, in AS dye wastewater with an initial concentration of 40 mg/L, the adsorption at 318 K was more effective than at 298 K and 278 K. At 318 K, the equilibrium adsorption capacity was 29.22 mg/g, and acidic conditions favored the adsorption process. The adsorption kinetics study on LAC indicated that the pseudo-second-order kinetic model better fitted the adsorption results. Thermodynamic analysis revealed that the Langmuir isotherm equation provided a better fit for the adsorption experimental results.Moreover, investigations into the cyclic regeneration performance of LAC demonstrated its good regenerative capabilities, and could be reused several times. Even after four cycles, the adsorption rate for AS dye remained above 80%. Additionally, a modification using a one-pot mixed approach with addition of magnesium acetate tetrahydrate improved the surface area of adsorbent LACMg0.75 by nearly 5 times compared to LAC, achieving a saturation adsorption capacity of 550.02 mg/g, nearly 20 times higher than that of LAC.

Key words: acidic blue AS, wastewater treatment, adsorbent, recycle, activated carbon, treating waste with waste

中图分类号:

TQ 09

张天永, 张晶怡, 姜爽, 李彬, 吕东军, 陈都民, 陈雪. 弱酸性蓝AS染料排放的废盐制碳基吸附剂及利用[J]. 化工学报, 2024, 75(3): 890-899.

Tianyong ZHANG, Jingyi ZHANG, Shuang JIANG, Bin LI, Dongjun LYU, Dumin CHEN, Xue CHEN. Preparation and utilization of carbon-based adsorbent from organic pollutants in waste salt during acidic blue AS dye production[J]. CIESC Journal, 2024, 75(3): 890-899.

图/表 16

图1 AS染料的分子结构

Fig.1 Molecular structure of dye AS

图2 制备的吸附剂的SEM图

Fig.2 SEM images of the prepared adsorbents

图3 未煅烧废盐及LAC的FTIR图

Fig.3 FTIR spectra of uncalcined waste salt and LAC

图4 LAC及LACMg样品的BET测试结果

Fig.4 BET test results of LAC and LACMg samples

表1 吸附剂的比表面积及孔容

Table 1 Specific surface area and pore volume of the adsorbent

样品	比表面积/ (m²/g)	孔容/(cm³/g)
样品	比表面积/ (m²/g)	微孔	介孔	总孔容
LACMg0.75	638.4	0.10	1.82	1.91
LACMg0.5	542.3	0.07	1.37	1.43
LACMg1	597.5	0.07	1.46	1.53
LACMg1.25	592.8	0.05	1.13	1.18
LAC	133.2	0.04	0.10	0.15

表2 不同温度煅烧废盐得到的固体质量及LAC收率

Table 2 Solid mass and LAC recovery from waste salt calcined at different temperatures

煅烧温度/℃	煅烧后剩余固体质量/g	LAC收率/%
300	4.91	有易分散在水中的物质难以洗净
350	4.82	有易分散在水中的物质难以洗净
400	4.73	57.1
450	4.69	49.2
500	4.64	40.9
550	4.59	有易分散在水中的物质难以洗净

图5 AS初始浓度对LAC的吸附性能的影响

Fig.5 Effect of AS initial concentration on LAC adsorption performance

图6 不同温度对LAC的吸附性能的影响

Fig.6 Effects of different temperatures on LAC adsorption properties

图7 pH对LAC吸附性能及Zeta电位的影响

Fig.7 Effect of pH on LAC adsorption properties and Zeta potential

图8 LAC吸附动力学曲线

Fig.8 Adsorption kinetics curves of LAC

表3 AS吸附动力学参数

Table 3 Adsorption kinetic parameters of AS

模型	参数	278 K	298 K	318 K
准一级动力学模型	k₁/min^-1	0.0152	0.0199	0.0182
	q₁/(mg/g)	8.8852	12.0109	11.0777
	R²	0.9760	0.9265	0.9915
准二级动力学模型	k₂/(g/(mg·min))	0.0052	0.0042	0.0046
	q₂/(mg/g)	25.0878	29.3944	29.9670
	R²	0.9991	0.9988	0.9993

图9 吸附热力学曲线

Fig.9 Thermodynamic curves of adsorption

表4 不同等温方程模拟吸附相关参数

Table 4 Relevant parameters of different isothermal equation simulation

模型	参数	278 K	298 K	318 K
Langmuir	q_m/(mg/g)	29.6033	30.5343	31.3676
	K_L/(L/mg)	0.8551	1.9705	2.9711
	R²	0.9987	0.9998	0.9999
Freundlich	1/n	0.1031	0.0585	0.0489
	K_F/(mg $1 - 1 n$ ·L $1 n$ /g)	19.5602	24.3214	25.9670
	R²	0.9194	0.9215	0.9037

表4 不同等温方程模拟吸附相关参数

Table 4 Relevant parameters of different isothermal equation simulation

模型	参数	278 K	298 K	318 K
Langmuir	q_m/(mg/g)	29.6033	30.5343	31.3676
	K_L/(L/mg)	0.8551	1.9705	2.9711
	R²	0.9987	0.9998	0.9999
Freundlich	1/n	0.1031	0.0585	0.0489
	K_F/(mg $1 - 1 n$ ·L $1 n$ /g)	19.5602	24.3214	25.9670
	R²	0.9194	0.9215	0.9037

图10 LAC循环利用性能实验结果

Fig.10 The results of LAC cycle performance test

图11 LAC与改性后吸附剂吸附性能比较

Fig.11 Comparison of adsorption properties of LAC and modified adsorbent

图12 LACMg0.75广谱吸附实验结果

Fig.12 Universal adsorption experimental results of LACMg0.75

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弱酸性蓝AS染料排放的废盐制碳基吸附剂及利用

Preparation and utilization of carbon-based adsorbent from organic pollutants in waste salt during acidic blue AS dye production

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