KOH改性电石渣脱除羰基硫的性能研究

doi:10.11949/0438-1157.20230296

摘要/Abstract

摘要：

以电石渣为原料，采用过体积浸渍法制备KOH改性电石渣，考察了不同制备条件及工艺条件对脱除羰基硫（COS）的影响，并通过N₂-BET、SEM-EDS、XPS、FTIR等方法进行表征，初步探究了改性电石渣的脱硫性能及反应过程，发现KOH改性电石渣脱除COS的过程中主要发生催化水解、氧化反应及酸碱吸附。结果表明，最佳制备条件为焙烧温度800℃、焙烧时间6 h，KOH最适添加量为25%；在此条件下，当入口浓度、反应温度和空速分别为600 mg/m³、25℃和5733 h^-1时，KOH改性电石渣脱除COS效果最佳，穿透吸附量为43.70 mg/g。

关键词: 电石渣, 羰基硫, 制备, 多相反应, 固定床, 性能

Abstract:

In this paper, KOH modified carbide slag was prepared by excessive impregnation using carbide slag as raw material, and the effects of different KOH content (10%—30%), calcination temperature (700—900℃), calcination time (5—7 h), carbonyl sulfide (COS) inlet concentration (200—1000 mg/m³), space velocity (5733—11404 h^-1), and reaction temperature (25—75℃) on the removal of COS were investigated. The desulfurization performance and reaction process of KOH modified carbide slag were preliminarily studied by N₂-BET, SEM-EDS, XPS, XRD and FTIR, and it was found that catalytic hydrolysis, oxidation reaction and acid-base adsorption mainly occurred in the process of COS removal with KOH modified carbide slag. The results showed that the optimal preparation conditions were the calcination temperature of 800℃, the calcination time of 6 h, and the KOH content of 25%. Under this condition, the best effect of COS removal from KOH modified carbide slag was achieved when the inlet concentration, reaction temperature and space velocity was 600 mg/m³, 25℃ and 5733 h^-1, respectively, and COS breakthrough adsorption amount was 43.70 mg/g at this time.

Key words: carbide slag, carbonyl sulfide, preparation, multiphase reaction, fixed-bed, performance

中图分类号:

X 511

朱风, 陈凯琳, 黄小凤, 鲍银珠, 李文斌, 刘嘉鑫, 吴玮强, 高王伟. KOH改性电石渣脱除羰基硫的性能研究[J]. 化工学报, 2023, 74(6): 2668-2679.

Feng ZHU, Kailin CHEN, Xiaofeng HUANG, Yinzhu BAO, Wenbin LI, Jiaxin LIU, Weiqiang WU, Wangwei GAO. Performance study of KOH modified carbide slag for removal of carbonyl sulfide[J]. CIESC Journal, 2023, 74(6): 2668-2679.

图/表 20

表1 电石渣化学组成

Table 1 Chemical composition of carbide slag

化学组成/%（质量）
CaO	SiO₂	Al₂O₃	Fe₂O₃	MgO	Na₂O	Cl	SO₃
93.278	3.006	1.864	0.245	0.093	0.38	0.093	0.502

图1 实验装置图

Fig.1 Diagram of experimental device

图2 不同KOH添加量改性电石渣脱除COS穿透曲线

Fig.2 COS breakthrough curves of carbide slag modified by different KOH addition levels

图3 不同焙烧温度下KOH改性电石渣脱除COS穿透曲线

Fig.3 COS breakthrough curves of KOH modified carbide slag under different roasting temperatures

图4 电石渣TG-DTA曲线

Fig.4 TG-DTA curves of carbide slag

图5 电石渣800℃焙烧前后XRD谱图

Fig.5 XRD patterns of carbide slag before and after roasting at 800℃

图6 不同焙烧时间下KOH改性电石渣脱除COS穿透曲线

Fig.6 COS breakthrough curves of KOH modified carbide slag under different roasting time

图7 不同浓度下KOH改性电石渣脱除COS穿透曲线

Fig.7 COS breakthrough curves of KOH modified carbide slag under different COS concentrations

图8 不同空速下KOH改性电石渣脱除穿透曲线

Fig.8 COS breakthrough curves of KOH modified carbide slag under different space velocity

图9 不同温度下KOH改性电石渣脱除COS穿透曲线

Fig.9 COS breakthrough curves of KOH modified carbide slag under different temperatures

表2 800-6-CS、800-6-25%KOH-CS、800-6-25%KOH-CS-COS的孔结构特征

Table 2 Pore structure characteristics of 800-6-CS， 800-6-25%KOH-CS， and 800-6-25%KOH-CS-COS

样品	比表面积/(m²/g)	总孔体积/(cm³/g)	平均孔径/nm
800-6-CS	1.8618	0.007424	7.8737
800-6-25%KOH-CS	7.5073	0.042714	25.6445
800-6-25%KOH-CS-COS	5.5664	0.043636	19.3113

图10 800-6-CS、800-6-25%KOH-CS、800-6-25%KOH-CS-COS的吸附-脱附等温线

Fig.10 Nitrogen adsorption-desorption isotherms of 800-6-CS, 800-6-25%KOH-CS, and 800-6-25%KOH-CS-COS

图11 800-6-CS、800-6-25%KOH-CS、800-6-25%KOH-CS-COS的孔径分布曲线

Fig.11 Pore size distribution of 800-6-CS, 800-6-25%KOH-CS, and 800-6-25%KOH-CS-COS

图12 CS、800-6-CS、800-6-25%KOH-CS、800-6-25%KOH-CS-COS的XRD谱图

Fig.12 XRD patterns of CS, 800-6-CS, 800-6-25%KOH-CS, and 800-6-25%KOH-CS-COS

图13 800-6-CS、800-6-25%KOH-CS、800-6-25%KOH-CS-COS的EDS能谱分析

Fig.13 EDS spectra analysis of 800-6-CS, 800-6-25%KOH-CS, and 800-6-25%KOH-CS-COS

图14 800-6-CS、800-6-25%KOH-CS、800-6-25%KOH-CS-COS的EDS面扫图

Fig.14 EDS mapping of 800-6-CS, 800-6-25%KOH-CS, and 800-6-25%KOH-CS-COS

表3 800-6-CS、800-6-25%KOH-CS、800-6-25%KOH-CS-COS的EDS元素分析

Table 3 EDS elemental analysis of 800-6-CS， 800-6-25%KOH-CS， and 800-6-25%KOH-CS-COS

样品	质量分数/%							原子分数/%
样品	C	O	Ca	Al	Si	K	S	C	O	Ca	Al	Si	K	S
800-6-CS	2.73	33.23	60.17	0.99	2.11	0.03	0.07	5.77	52.66	38.21	0.93	1.90	0.04	0.06
800-6-25%KOH-CS	7.50	39.00	43.70	1.00	1.40	7.06	0	14.00	55.10	24.70	0.80	1.10	4.10	0.03
800-6-25%KOH-CS-COS	9.30	40.60	41.60	0.80	1.00	5.10	1.60	16.80	55.30	22.60	0.70	0.70	2.80	1.20

图15 800-6-CS、800-6-25%KOH-CS、800-6-25%KOH-CS-COS红外光谱图

Fig.15 FTIR spectra of 800-6-CS, 800-6-25%KOH-CS, and 800-6-25%KOH-CS-COS

图16 800-6-25%KOH-CS脱除COS前后XPS光谱图(K 2p、O 1s、S 2p)

Fig.16 XPS spectra of 800-6-25%KOH-CS before and afrer COS removal (K 2p, O 1s, S 2p)

图17 COS在KOH改性电石渣上的反应过程

Fig.17 The reaction process of COS on KOH modified carbide slag

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