Performance study of KOH modified carbide slag for removal of carbonyl sulfide

doi:10.11949/0438-1157.20230296

Abstract

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

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

CLC Number:

X 511

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.

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.

Figures/Tables 20

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

Fig.1 Diagram of experimental device

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

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

Fig.4 TG-DTA curves of carbide slag

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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