制备条件对改性电石渣低温共脱除COS和CS2的影响

doi:10.11949/0438-1157.20241329

摘要/Abstract

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

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

中图分类号:

X 781.2

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.

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.

图/表 19

图1 改性电石渣制备的主要流程

Fig.1 Main flow of modified calcium carbide slag preparation

图2 实验装置流程图

Fig.2 Flow chart of the experimental setup

表1 电石渣化学组成

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

图3 电石渣XRD谱图

Fig.3 XRD pattern of calcium carbide slag

图4 电石渣的SEM-EDS面扫描分析

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

图5 电石渣TG-DTA曲线

Fig.5 TG-DTA curve of calcium carbide slag

图6 电石渣在不同焙烧温度下的XRD谱图

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

图7 KOH改性焙烧与未焙烧电石渣对COS和CS2的同时脱除

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

表2 改性电石渣对COS和CS2的同时脱除的穿透时间与穿透硫容

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

图8 不同金属种类改性电石渣对COS和CS2的同时脱除及H2S出口情况

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

图9 NaOH、KOH改性电石渣对COS和CS2的同时脱除

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

表3 NaOH、KOH改性电石渣同时脱除COS和CS2的穿透时间与穿透硫容

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

图10 电石渣、焙烧电石渣以及改性电石渣的红外光谱

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

图11 不同KOH含量改性电石渣对COS和CS2的同时脱除

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

表4 不同KOH含量改性电石渣同时脱除COS和CS2的穿透时间与穿透硫容

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

图12 KOH含量对硫容的影响

Fig.12 Effect of KOH content on sulfur capacity

表5 不同KOH含量改性电石渣的比表面积

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

图13 焙烧电石渣和改性电石渣的氮气吸附等温线和孔径分布曲线

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

图14 改性电石渣用于脱硫前后的K 2p、O 1s和S 2p光谱图

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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制备条件对改性电石渣低温共脱除COS和CS₂的影响

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

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