Effect of preparation conditions on low-temperature co-removal of COS and CS2 from modified calcium carbide slag

doi:10.11949/0438-1157.20241329

Abstract

Abstract:

Carbonyl sulfide (COS) and carbon disulfide (CS₂) often coexist in sulfur-containing pollutants in the iron and steel industry, and their joint removal is of great significance to the development of the industry and environmental protection. Different metal-and alkali-modified calcium carbide slags were prepared by ultrasound-assisted impregnation for the simultaneous removal of COS and CS₂ at low temperatures. The effects of different active components, calcination temperatures, and the content of the active components on the simultaneous removal of COS and CS₂ from the modified calcium carbide slag were investigated. The slags were characterized by XRD, N₂-BET, XPS, FTIR and TG-DTA to explore their removal mechanism. The results showed that the modified carbide slag prepared at a roasting temperature of 750℃ and an active component of 6.25%(mass) KOH has the best catalytic hydrolysis effect, and the total sulfur capacity reaches 180.68 mg/g. In the process of the modified calcium carbide slag in the co-degradation of COS and CS₂, the loaded KOH provided the —OH group for the catalytic hydrolysis, and a portion of the hydrolysis product, part of the hydrolysis product hydrogen sulfide (H₂S) further undergoes oxidation reaction, and part of it combines with metal ions and eventually generates sulfate and metal sulfide to achieve sulfur fixation. In summary, this study provides theoretical support for the high value-added resource utilization of calcium carbide slag and the development of efficient catalytic hydrolysis agents for COS and CS₂.

Key words: preparation, carbide slag, carbonyl sulfide, carbon disulfide, catalysis, hydrolysis

摘要：

羰基硫（COS）和二硫化碳（CS₂）常共存于钢铁行业的含硫污染物中。通过超声辅助浸渍法制备不同改性电石渣用于低温下共脱除COS和CS₂，研究不同活性组分、组分含量及煅烧温度对改性电石渣共脱除COS和CS₂的影响，借助XRD、N₂-BET、XPS、FTIR和TG-DTA等方法进行表征，以探究其脱除机理。结果表明，当焙烧温度为750℃、活性组分为6.25%（质量分数）KOH时制备的改性电石渣催化水解效果最佳，总硫容达到180.68 mg/g；在共脱除COS和CS₂的过程中，负载的KOH为催化水解提供—OH基团，水解产物硫化氢（H₂S）一部分进一步发生氧化反应，一部分与金属离子结合，并最终生成硫酸盐和金属硫化物达到固硫作用。本文可为电石渣的高附加值资源化利用、COS和CS₂高效催化水解剂的开发提供理论支撑。

关键词: 制备, 电石渣, 羰基硫, 二硫化碳, 催化, 水解

CLC Number:

X 781.2

Yinxiang TANG, Feng ZHU, Yingying FAN, Yuxin LONG, Yong DAI, Chunling DENG, Xiaofeng HUANG. Effect of preparation conditions on low-temperature co-removal of COS and CS₂ from modified calcium carbide slag[J]. CIESC Journal, 2025, 76(7): 3639-3650.

唐银香, 朱风, 范莹莹, 龙雨欣, 代雍, 邓春玲, 黄小凤. 制备条件对改性电石渣低温共脱除COS和CS₂的影响[J]. 化工学报, 2025, 76(7): 3639-3650.

Figures/Tables 19

Fig.1 Main flow of modified calcium carbide slag preparation

Fig.2 Flow chart of the experimental setup

Table 1 Chemical composition of calcium carbide slag

化学组成	质量分数/%
CaO	84.825
SiO₂	3.079
Al₂O₃	1.904
Cl^-	0.655
SO₃	0.567
Na₂O	0.142
Fe₂O₃	0.130

Fig.3 XRD pattern of calcium carbide slag

Fig.4 SEM-EDS surface scanning analysis of calcium carbide slag

Fig.5 TG-DTA curve of calcium carbide slag

Fig.6 XRD patterns of calcium carbide slag at different roasting temperatures

Fig.7 Simultaneous removal of COS and CS2 by KOH-modified roasted and unroasted calcium carbide slag

Table 2 Penetration time and penetration sulfur capacity of modified calcium carbide slag for simultaneous removal of COS and CS2

样品	COS穿透时间/min	CS₂穿透时间/min	COS穿透硫容/(mg/g)	CS₂穿透硫容/(mg/g)	总硫容/(mg/g)
改性未焙烧电石渣	636	31	41.96	0.19	42.15
改性焙烧电石渣	1744	56	180.18	0.50	180.68

Fig.8 Simultaneous removal of COS and CS2 and H2S export from modified calcium carbide slag with different metal species

Fig.9 Simultaneous removal of COS and CS2 by NaOH and KOH modified calcium carbide slag

Table 3 Penetration time and penetration sulfur capacity of NaOH and KOH modified calcium carbide slag for simultaneous removal of COS and CS2

样品	COS穿透时间/min	CS₂穿透时间/min	COS穿透硫容/(mg/g)	CS₂穿透硫容/(mg/g)	总硫容/(mg/g)
NaOH改性电石渣	60	12	6.44	0.12	6.56
KOH改性电石渣	1744	56	180.18	0.50	180.68

Fig.10 Infrared spectra of calcium carbide slag, roasted calcium carbide slag, and modified calcium carbide slag

Fig.11 Simultaneous removal of COS and CS2 by modified calcium carbide slag with different KOH contents

Table 4 Penetration time and penetration sulfur capacity for simultaneous removal of COS and CS2 from modified calcium carbide slag with different KOH contents

KOH含量/%（质量分数）	COS穿透时间/min	CS₂穿透时间/min	COS穿透硫容/(mg/g)	CS₂穿透硫容/(mg/g)
0	2	5	0.10	0.02
2.50	540	25	70.51	0.33
3.75	600	26	80.53	0.34
6.25	1744	56	180.18	0.50
8.75	640	151	89.21	2.07

Fig.12 Effect of KOH content on sulfur capacity

Table 5 Specific surface area of modified calcium carbide slag with different KOH content

KOH含量/%（质量分数）	比表面积/(m²/g)
0	1.68
2.50	4.87
3.75	4.53
6.25	4.27
8.75	3.19

Fig.13 Nitrogen adsorption isotherms and pore size distribution curves for roasted and modified calcium carbide slag

Fig.14 K 2p, O 1s and S 2p spectra of modified calcium carbide slag before and after its use for desulfurization

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Effect of preparation conditions on low-temperature co-removal of COS and CS₂ from modified calcium carbide slag

制备条件对改性电石渣低温共脱除COS和CS₂的影响

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