煤气化细渣简单制备吸附剂吸附亚甲基蓝及其回收燃烧性能研究

doi:10.19965/j.cnki.iwt.2024-0829

摘要/Abstract

摘要：

分别采用稀盐酸和稀氢氧化钠溶液对煤气化细渣（CGFS）进行简单活化处理，考察处理前后其对水中亚甲基蓝（MB）的吸附性能和其作为燃料回收利用的燃烧性能。结果表明，稀盐酸活化使CGFS中钙铁辉石（CaFeSi₂O₆）溶解消失，增大了细渣的孔径，而稀碱活化使CGFS的Si—O—Si键断裂，并伴随着大量微孔的产生，提高了CGFS的比表面积和孔体积。以上活化过程均使得CGFS对MB的去除率明显提高，尤其是碱活化后CGFS对水中质量浓度为160 mg/L的MB去除率高达99.99%。活化前后，CGFS对MB的吸附等温线均符合Langmuir等温吸附模型，吸附过程符合准二级反应动力学模型，以单分子层化学吸附为主，且是自发的吸热过程。此外，颗粒内扩散模型拟合结果表明边界层扩散和颗粒内扩散在MB的吸附过程中起到重要作用，同时吸附MB增加了改性CGFS的平均燃烧速率、最大燃烧速率和综合燃烧指数，一定程度上提升了CGFS的燃烧性能，使得吸附MB后的灰渣可作为燃料回收利用。

关键词: 煤气化细渣, 活化, 亚甲基蓝, 吸附, 燃烧

Abstract:

Dilute hydrochloric acid and dilute sodium hydroxide solution were used to activate coal gasification fine slag(CGFS) to prepare adsorbent respectively. Its adsorption performance of methylene blue(MB) in water and its combustion characteristics as fuel for recycling and utilization before and after treatment were explored. The results showed that dilute acid activation resulted to the dissolution and disappearance of calcium-iron pyroxene(CaFeSi₂O₆) in CGFS, and the increase of pore size of the fine slag. The Si—O—Si bond of mineral phase was broken by the activation of dilute alkali, and a large number of micropores were generated, which increased the specific surface area and pore volume of the CGFS. The above features all significantly improved the removal rate of MB by CGFS, especially after alkaline activation, the removal rate of MB in water with 160 mg/L MB reached 99.99%. The adsorption isotherms for MB by CGFS before and after activation were consistent with the Langmuir isothermal adsorption model, and the adsorption processes were consistent with quasi-secondary kinetics, which were dominated by chemisorption in a single molecular layer and were spontaneous heat-trapping processes. In addition, the fitting results of the intraparticle diffusion model showed that boundary layer diffusion and intraparticle diffusion played important roles in the adsorption process of MB. It was found that the adsorption of MB increased the average combustion rate, maximum combustion rate and comprehensive combustion index of modified CGFS, and improved the combustibility of CGFS. The activated CGFS after adsorption of MB could be recycled as fuel.

Key words: coal gasification fine slag, activation, methylene blue, adsorption, combustion

中图分类号:

X703.1

于希豪, 刘祺, 张杰, 张钊, 马晓贝, 孙领民, 田志强, 刘伟, 庄淑娟, 王志刚. 煤气化细渣简单制备吸附剂吸附亚甲基蓝及其回收燃烧性能研究[J]. 工业水处理, 2025, 45(10): 130-140.

Xihao YU, Qi LIU, Jie ZHANG, Zhao ZHANG, Xiaobei MA, Lingmin SUN, Zhiqiang TIAN, Wei LIU, Shujuan ZHUANG, Zhigang WANG. Simple preparation of adsorbent from coal gasification fine slag for methylene blue adsorption and its combustion characteristics for recycling[J]. Industrial Water Treatment, 2025, 45(10): 130-140.

https://www.iwt.cn/CN/Y2025/V45/I10/130

图/表 21

表1 CGFS工业分析结果

Table 1 Industrial analysis results of CGFS

项目	水分	灰分	挥发分	固定C
质量分数/%	6.32	46.98	3.76	42.94

表2 CGFS的灰分

Table 2 The ash composition of CGFS

项目	K₂O	SiO₂	SO₃	Al₂O₃	CaO	Fe₂O₃	MgO	P₂O₅	TiO₂	Na₂O
质量分数/%	1.05	41.52	2.10	19.76	18.70	10.40	1.88	0.40	0.82	3.37

图1 CGFS-1、CGFS-2和CGFS-3的XRD

Fig.1 XRD of the CGFS-1，CGFS-2， and CGFS-3

图2 CGFS-1、CGFS-2和CGFS-3的N₂吸附-脱附等温线（a~c）和孔径分布（d~f）

Fig.2 The N₂ adsorption-desorption isotherms（a-c）and the pore size distribution curves （d-f）of CGFS-1，CGFS-2，and CGFS-3

表3 CGFS-1、CGFS-2和CGFS-3的比表面积和孔结构参数

Table 3 Specific surface area and pore structure parameters of CGFS-1， CGFS-2， and CGFS-3

项目	比表面积/（m²·g^-1）	平均孔径/nm	总孔体积/（cm³·g^-1）
CGFS-1	250.119	0.718	0.256
CGFS-2	242.975	1.410	0.290
CGFS-3	343.078	0.718	0.351

图3 CGFS-1（a，b）、CGFS-2（c）和CGFS-3（d）的SEM

Fig.3 SEM of CGFS-1（a，b），CGFS-2（c）， and CGFS-3（d）

图4 CGFS-1、CGFS-2和CGFS-3的FT-IR

Fig.4 FT-IR of the CGFS-1，CGFS-2， and CGFS-3

图5 吸附剂投加量对其吸附效果的影响

Fig.5 Influence of adsorbent dosage on its adsorption effect

图6 MB去除率随吸附时间的变化

Fig.6 The variation of MB removal rate with adsorption time

图7 MB去除率随反应温度的变化

Fig.7 The variation of MB removal rate with reaction temperature

图8 准一级（a）和准二级（b）反应动力学模型拟合曲线

Fig.8 Fitting curves of pseudo-first-order（a）and pseudo-second-order（b） reaction kinetics models

表4 准一级和准二级反应动力学模型拟合参数

Table 4 The fitting parameters of pseudo-first-order and pseudo-second-order reaction kinetics models

吸附剂	q _实测/（mg·g^-1）	准一级反应动力学模型			准二级反应动力学模型
吸附剂	q _实测/（mg·g^-1）	q _e，1/（mg·g^-1）	k ₁/min^-1	R ₁ ²	q _e，2/（mg·g^-1）	k ₂/（g·mg^-1·min^-1）	R ₂ ²
CGFS-1	153.49	13.81	0.026 93	0.942	157.73	0.208	0.999
CGFS-2	158.45	9.17	0.031 64	0.861	158.98	0.557	0.999
CGFS-3	159.93	7.26	0.057 33	0.961	160.26	0.121	0.999

图9 颗粒内扩散模型拟合曲线

Fig.9 Intra-particle diffusion model fitting curves

表5 颗粒内扩散模型拟合参数

Table 5 The fitting parameters of intraparticle diffusion model

吸附剂	k _d，1	C ₁/（mg·g^-1）	R ²	k _d，2	C ₂/（mg·g^-1）	R ²	k _d，3	C ₃/（mg·g^-1）	R ²
CGFS-1	2.03	86.37	0.886	0.35	93.19	0.999	0.89	89.04	0.999
CGFS-2	2.18	87.94	0.915	0.71	93.35	0.954	0.045	98.68	0.999
CGFS-3	1.52	91.94	0.973	0.41	96.93	0.895	0.012	99.86	0.999

图10 Langmuir（a）和Freundlich（b）模型拟合吸附等温线

Fig.10 Langmuir （a） and Freundlich（b） models fitting adsorption isotherms

表6 吸附等温线拟合参数

Table 6 The fitting parameters of adsorption isotherms

吸附剂	Langmuir 模型			Freundlich 模型
吸附剂	R ²	q _m/（mg·g^-1）	K _L/（L·mg^-1）	R ²	K _F/（mg^1-1/ ⁿ ·L^1/ ⁿ ·g^-1）	n
CGFS-1	0.979	248.75	0.29	0.741	144.55	8.53
CGFS-2	0.941	253.16	0.45	0.815	146.35	8.62
CGFS-3	0.996	258.39	0.92	0.849	160.92	9.05

表7 吸附过程的热力学参数

Table 7 The thermodynamic parameters of adsorption process

吸附剂	ΔH ⁰/（kJ·mol^-1）	ΔS ⁰/（kJ·mol^-1）	ΔG ⁰/（kJ·mol^-1）
吸附剂	ΔH ⁰/（kJ·mol^-1）	ΔS ⁰/（kJ·mol^-1）	303 K	313 K	323 K
CGFS-1	3.819	0.029	-5.07	-5.46	-5.63
CGFS-2	19.87	0.084	-5.94	-6.41	-7.65
CGFS-3	85.45	0.308	-8.21	-10.72	-14.39

图11 某样品燃烧的TG-DTG曲线

Fig.11 TG-DTG curves of a certain sample

图12 CGFS-1、CGFS-2和CGFS-3的TG（a）及DTG（b）曲线

Fig.12 TG（a） and DTG（b） curves of CGFS-1，CGFS-2 and CGFS-3

表8 燃烧曲线特征参数

Table 8 Characteristic parameters of combustion curve

材料	t _a/℃	t _c/℃	t _d/℃	W _max/（%·min^-1）	W _mean/（%·min^-1）	S/（% ²·min^-2·℃^-3）
CGFS-1	578.84	506.47	716.08	1.92	0.55	5.48×10^-9
CGFS-2	613.50	484.83	705.00	2.64	0.42	6.69×10^-9
CGFS-3	576.65	487.91	721.00	1.84	0.55	5.89×10^-9
CGFS-1-MB	597.26	528.57	700.34	2.22	0.88	9.98×10^-9
CGFS-2-MB	612.41	485.30	701.00	2.72	0.48	7.91×10^-9
CGFS-3-MB	584.41	504.00	713.00	2.11	0.71	8.27×10^-9

图13 吸附MB后CGFS-1（a）、CGFS-2（b）和CGFS-3（c）的DTG曲线

Fig.13 DTG curves of CGFS-1（a），CGFS-2（b），and CGFS-3（c） after MB adsorption

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