湿法脱硫中多硫离子分离方法的建立

doi:10.16085/j.issn.1000-6613.2023-0689

摘要/Abstract

摘要：

多硫离子 $S x 2 -$ 是湿式催化氧化脱硫技术中H₂S向单质硫转化的中间产物，在脱硫环境中，析硫反应和副盐反应存在平行竞争关系， $S x 2 -$ 的存在形态及浓度是评价两个竞争反应程度的前提条件。本文通过紫外-可见分光光度法（UV-vis）、液相色谱-质谱仪（LC-MS）和高效液相色谱（HPLC）方法可实现对 $S x 2 -$ 的存在形态及各形态浓度定量测定的目标。结果表明：UV-vis法可测定出S _x^2-的总浓度；甲基化法可将 $S x 2 -$ 的各个形态进行捕捉，LC-MS和HPLC法可将各形态的甲基化多硫化物分离，且 $S x 2 -$ 的硫原子数（2—10）越大保留时间越长；结合UV-vis建立的标准曲线和HPLC上各个形态 $S x 2 -$ 出峰的相对强度，推算出溶液中各形态 $S x 2 -$ 的绝对浓度；多硫化钠溶液主要以 $S 4 2 -$ 、 $S 5 2 -$ 、 $S 6 2 -$ 、 $S 10 2 -$ 为主，其中浓度和pH对 $S x 2 -$ 的影响较小，而温度过高不利于 $S x 2 -$ 的生成，从而不利于单质硫的生成。这一项工作为进一步从源头上研究副盐成因及加快析硫反应的研究奠定了基础。

关键词: 多硫离子, 湿法脱硫, 硫化钠

Abstract:

Polysulfide ion $S x 2 -$ is an intermediate product of the conversion of H₂S to elemental sulfur in wet catalytic oxidation desulfurization technology. In the desulfurization environment, there is a parallel competition between the sulfur evolution reaction and parasite reaction, and the existing form and concentration of $S x 2 -$ are the prerequisite for evaluating the degree of the two competitive reactions. In this paper, UV-vis, LC-MS, and HPLC methods were used to determine the existence and concentration of $S x 2 -$ . The results showed that the total concentration of $S x 2 -$ could be determined by the UV-vis method. The methylation method could capture each form of $S x 2 -$ , LC-MS and HPLC methods could separate each form of methylated polysulfide, and the larger the number of sulfur atoms (2—10) of $S x 2 -$ , the longer the retention time. Combined with the standard curve established by UV-vis and the relative intensity of each form of $S x 2 -$ on HPLC, the absolute concentration of each form of $S x 2 -$ in solution was calculated. $S 4 2 -$ , $S 5 2 -$ , $S 6 2 -$ and $S 10 2 -$ were the main types of sodium polysulfide solution, in which the concentration and pH had little effect on $S x 2 -$ , and the high temperature was not conducive to the formation of $S x 2 -$ , thus not conducive to the formation of elemental sulfur. This work laid a foundation for further research on the origin of parasites and the acceleration of sulfur evolution.

Key words: polysulfide ions, wet desulfurization, sodium sulfide

中图分类号:

TQ536

高康, 张弦, 陈帅军, 武喜明, 申峻, 王玉高, 牛艳霞. 湿法脱硫中多硫离子分离方法的建立[J]. 化工进展, 2024, 43(4): 2210-2218.

GAO Kang, ZHANG Xian, CHEN Shuaijun, WU Ximing, SHEN Jun, WANG Yugao, NIU Yanxia. Establishment of separation method for polysulfide ions in wet desulfurization[J]. Chemical Industry and Engineering Progress, 2024, 43(4): 2210-2218.

图/表 21

图1 湿式催化氧化脱硫工艺存在问题

图2 湿式催化氧化脱硫体系中硫元素的物质流分析

图3 不同浓度Na2S x 溶液的UV-vis光谱图

图4 Na2S x 溶液浓度与吸光度的关系

图5 不同温度Na2S x 溶液的UV-vis光谱图

图6 不同pH Na2S x 溶液的UV-vis光谱图

图7 Na2S x 在碳酸盐溶液中随浓度变化的UV-vis光谱图

图8 Na2S x 在碳酸盐缓冲溶液中浓度与吸光度的关系

图9 Na2S x 在碳酸盐缓冲溶液中温度与吸光度的关系

图10 (CH3)2S x 溶液的总离子流图

表1 总离子流图中(CH3)2S x 的存在形态及相应信息

化合物形态	RT/min	Mass	Abound	Formula	Tgt Mass	Diff /ug·g^-1
CH₃S₅CH₃	1.189	189.9082	79507	C₂H₆S₅	189.9073	4.47
CH₃S₆CH₃	1.945	221.8824	15744	C₂H₆S₆	221.8794	13.5
CH₃S₇CH₃	3.815	253.8561	11901	C₂H₆S₇	253.8514	18.18
CH₃S₈CH₃	5.576	285.824	15889	C₂H₆S₈	285.8235	1.61
CH₃S₉CH₃	6.905	317.7957	9168	C₂H₆S₉	317.7956	0.4
CH₃S₁₀CH₃	7.885	349.7675	4533	C₂H₆S₁₀	349.7677	-0.34

图11 CH3SCH3、CH3S2CH3、CH3S3CH3的HPLC图

图12 Na2S x 溶液甲基化后的HPLC图

表2 不同形态多疏离子的保留时间(min)

S^2-	$S 2 2 -$	$S 3 2 -$	$S 4 2 -$	$S 5 2 -$	$S 6 2 -$	$S 7 2 -$	$S 8 2 -$	$S 9 2 -$	$S 10 2 -$
5.532	6.377	7.410	8.486	10.363	12.925	16.758	22.197	30.261	31.617

表2 不同形态多疏离子的保留时间(min)

S^2-	$S 2 2 -$	$S 3 2 -$	$S 4 2 -$	$S 5 2 -$	$S 6 2 -$	$S 7 2 -$	$S 8 2 -$	$S 9 2 -$	$S 10 2 -$
5.532	6.377	7.410	8.486	10.363	12.925	16.758	22.197	30.261	31.617

图13 保留时间对数In（Rt）与硫原子个数x的关系

图14 不同浓度Na2S x 溶液甲基化后HPLC图A—0.20mol/L；B—0.10mol/L；C—0.05mol/L；D—0.025mol/L；E—0.02mol/L

表3 不同形态Sx2-（x=2~10）面积百分比随Na2S x 溶液浓度的变化

浓度 /mol·L^-1	$S x 2 -$ (x=2~10)所占面积百分比%
浓度 /mol·L^-1	$S 2 2 -$	$S 3 2 -$	$S 4 2 -$	$S 5 2 -$	$S 6 2 -$	$S 7 2 -$	$S 8 2 -$	$S 9 2 -$	$S 10 2 -$	总计
0.2	0.168	9.864	21.999	31.190	12.042	3.975	1.384	0.581	7.325	88.528
0.1	0.093	5.319	17.715	22.932	15.888	8.240	3.444	1.309	15.397	90.337
0.05	1.636	0.932	12.527	16.762	13.835	7.212	3.157	1.127	22.497	79.685
0.025	0	2.294	14.357	9.167	10.025	7.247	2.310	0	38.249	83.649
0.02	0	1.653	9.159	17.070	16.264	8.248	3.270	0	30.789	86.453

表3 不同形态Sx2-（x=2~10）面积百分比随Na2S x 溶液浓度的变化

浓度 /mol·L^-1	$S x 2 -$ (x=2~10)所占面积百分比%
浓度 /mol·L^-1	$S 2 2 -$	$S 3 2 -$	$S 4 2 -$	$S 5 2 -$	$S 6 2 -$	$S 7 2 -$	$S 8 2 -$	$S 9 2 -$	$S 10 2 -$	总计
0.2	0.168	9.864	21.999	31.190	12.042	3.975	1.384	0.581	7.325	88.528
0.1	0.093	5.319	17.715	22.932	15.888	8.240	3.444	1.309	15.397	90.337
0.05	1.636	0.932	12.527	16.762	13.835	7.212	3.157	1.127	22.497	79.685
0.025	0	2.294	14.357	9.167	10.025	7.247	2.310	0	38.249	83.649
0.02	0	1.653	9.159	17.070	16.264	8.248	3.270	0	30.789	86.453

图15 不同形态Sx2-（x=2~10）面积百分比随Na2S x 溶液浓度的变化

图16 不同温度Na2Sx溶液甲基化后的HPLC图A—30℃；B—40℃；C—50℃；D—70℃；E—80℃

表4 不同形态Sx2-（x=2~10）面积百分比随Na2S x 溶液温度的变化

温度/℃	$S x 2 -$ (x=2~10)所占面积百分比/%
温度/℃	$S 2 2 -$	$S 3 2 -$	$S 4 2 -$	$S 5 2 -$	$S 6 2 -$	$S 7 2 -$	$S 8 2 -$	$S 9 2 -$	$S 10 2 -$	总计
30	0.221	6.58	19.428	20.842	14.654	7.723	3.284	1.226	12.497	86.455
40	0.110	5.220	18.012	19.845	13.354	6.575	2.873	1.016	14.397	81.402
50	0.195	5.523	15.59	18.511	14.240	7.021	2.919	1.048	12.457	77.504
70	0.180	4.625	14.243	16.577	10.489	4.684	2.064	0.573	13.222	66.657
80	0.234	3.148	9.863	11.143	5.788	2.731	1.044	0	17.080	51.031

表4 不同形态Sx2-（x=2~10）面积百分比随Na2S x 溶液温度的变化

温度/℃	$S x 2 -$ (x=2~10)所占面积百分比/%
温度/℃	$S 2 2 -$	$S 3 2 -$	$S 4 2 -$	$S 5 2 -$	$S 6 2 -$	$S 7 2 -$	$S 8 2 -$	$S 9 2 -$	$S 10 2 -$	总计
30	0.221	6.58	19.428	20.842	14.654	7.723	3.284	1.226	12.497	86.455
40	0.110	5.220	18.012	19.845	13.354	6.575	2.873	1.016	14.397	81.402
50	0.195	5.523	15.59	18.511	14.240	7.021	2.919	1.048	12.457	77.504
70	0.180	4.625	14.243	16.577	10.489	4.684	2.064	0.573	13.222	66.657
80	0.234	3.148	9.863	11.143	5.788	2.731	1.044	0	17.080	51.031

图17 不同形态S x2-（x=2~10）面积百分比随Na2S x 溶液温度的变化

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