Study on release and inhibition behavior of COS during high-temperature gas desulfurization process using Zn-based oxide derived from hydrotalcite

doi:10.11949/0438-1157.20221524

Abstract

Abstract:

High-temperature coal gas desulfurization is one of the key technologies for coal clean conversion process. Previous studies have shown that Zn-based oxide derived from Zn-Al hydrotalcite (ZnAl-HTO) can efficiently remove H₂S from high-temperature gas. However, there is a lack of qualitative and quantitative studies on the law of COS release during the desulfurization process. In this study, the possible pathways of COS release in the desulfurization process of ZnAl-HTO were investigated, the thermodynamic analysis and experimental study were also carried out. A nickel doping strategy was proposed to inhibit the formation of COS during the desulfurization process. It was shown that the main way to generate COS when zinc-aluminum hydrotalcite-based oxides to remove CO₂ from gas is the gas-solid phase catalytic reaction between H₂S and CO₂, and the amount of COS released by this way accounts for 78% of the total release. The doping of a small amount of nickel additives into the ZnAl-HTO results in no significant change in the morphology. It also effectively inhibits the COS release during desulfurization process. Under the optimal molar ratio of Zn/Ni (30), the overall desulfurization performance of ZnAl-HTO is significantly improved. Compared to sorbents without Ni-doping, the amount of COS released before H₂S-breakthrough reduced by 88%, while the corresponding sulfur capacity declined by only 1.5%.

Key words: hot coal gas, hydrotalcite-like compounds, hydrogen sulfide, carbonyl sulfide, catalysis, desulfurization

摘要：

高温煤气脱硫是煤炭清洁转化过程中的关键技术之一。前期研究表明，锌铝类水滑石基衍生氧化物可高效脱除高温煤气中的H₂S，但其脱硫过程中COS释放规律缺乏定性定量研究。探讨了类水滑石衍生锌基氧化物脱硫过程COS释放的可能途径，包括反应热力学分析及实验研究，提出采用镍掺杂策略以抑制脱硫剂脱硫过程中生成COS。研究表明，锌铝类水滑石基衍生氧化物脱除煤气中H₂S时产生COS的主要途径是H₂S与CO₂间的气固相催化反应，该途径所释放COS量占总释放量的78%。通过镍助剂的掺杂使得锌铝类水滑石基衍生氧化物既保持了原有结构形貌，也有效抑制了其脱硫过程中COS的释放；其中最佳镍掺杂量(Zn/Ni摩尔比为30)脱硫剂穿透前的COS释放量减少88%，而硫容仅降低1.5%。

关键词: 热煤气, 类水滑石, 硫化氢, 羰基硫, 催化, 脱硫

CLC Number:

TQ 546.5

Tianhao BAI, Xiaowen WANG, Mengzi YANG, Xinwei DUAN, Jie MI, Mengmeng WU. Study on release and inhibition behavior of COS during high-temperature gas desulfurization process using Zn-based oxide derived from hydrotalcite[J]. CIESC Journal, 2023, 74(4): 1772-1780.

白天昊, 王晓雯, 杨梦滋, 段新伟, 米杰, 武蒙蒙. 类水滑石衍生锌基氧化物高温煤气脱硫过程中COS释放行为及其抑制研究[J]. 化工学报, 2023, 74(4): 1772-1780.

Figures/Tables 12

Fig.1 Desulfurization performance test device

Fig.2 Breakthrough curve of ZnAl-HTO under simulated gas atmosphere and simple atmosphere (a), and sulfur capacity and COS release amount under simulated gas atmosphere (b)

Table 1 Possible COS formation pathways and corresponding thermodynamic parameters

反应编号	反应方程式	ΔH/ （kJ/mol）	K^Ө	X/%
1	H₂S+CO $\overset{}{̿}$ COS+H₂	-2.6	3.3×10^-2	79
2	H₂S+CO₂ $\overset{}{̿}$ COS+H₂O	34.6	6.6×10^-3	33
3	H₂S $\overset{}{̿}$ S+H₂	34.1	8.6×10^-4	0.008
4	S+CO $\overset{}{̿}$ COS	-36.7	38.4	99.6
5	2S+2CO₂ $\overset{}{̿}$ COS+SO₂+CO	222.8	4.5×10^-8	69.2
6	ZnS+CO $\overset{}{̿}$ COS+Zn	181.1	1.0×10^-11	7.2×10^-7
7	ZnS+CO₂ $\overset{}{̿}$ COS+ZnO	108.0	7.3×10^-8	7.2×10^-5

Table 1 Possible COS formation pathways and corresponding thermodynamic parameters

反应编号	反应方程式	ΔH/ （kJ/mol）	K^Ө	X/%
1	H₂S+CO $\overset{}{̿}$ COS+H₂	-2.6	3.3×10^-2	79
2	H₂S+CO₂ $\overset{}{̿}$ COS+H₂O	34.6	6.6×10^-3	33
3	H₂S $\overset{}{̿}$ S+H₂	34.1	8.6×10^-4	0.008
4	S+CO $\overset{}{̿}$ COS	-36.7	38.4	99.6
5	2S+2CO₂ $\overset{}{̿}$ COS+SO₂+CO	222.8	4.5×10^-8	69.2
6	ZnS+CO $\overset{}{̿}$ COS+Zn	181.1	1.0×10^-11	7.2×10^-7
7	ZnS+CO₂ $\overset{}{̿}$ COS+ZnO	108.0	7.3×10^-8	7.2×10^-5

Fig.3 Breakthrough curve (a) and COS release amount (b) of ZnAl-HTO under CO/CO2+H2S+N2 atmosphere

Fig.4 XRD patterns of the Ni-doped ZnAl-HTLCs (a) and its oxide ZnAl-HTO (b)

Fig.5 Isothermal adsorption-desorption curve (a) and pore size distribution curve (b) of Ni-doped desulfurizer

Table 2 Structural parameters of desulfurizer holes before and after nickel doping

样品	比表面积/（m²/g）	孔容/（cm³/g）
ZnAl-HTO	31	0.09
Zn30Ni1Al-HTO	37	0.22
Zn20Ni1Al-HTO	41	0.20
Zn10Ni1Al-HTO	43	0.27

Fig.6 SEM images of ZnAl-HTO (a), Zn30Ni1Al-HTO (b), Zn20Ni1Al-HTO (c), and Zn10Ni1Al-HTO (d)

Fig.7 The outlet H2S / COS curve (a) corresponding to ZnNiAl-HTO and the corresponding saturated sulfur capacity and COS release amount (b) during sulfur absorption saturation

Fig.8 Breakthrough curve before ZnNiAl-HTO breakthrough (a) and breakthrough capacity and COS release amount (b)

Fig.9 Ni 2p XPS profile of Zn30Ni1Al-HTO

Fig.10 Zn 2p3/2 and O 1s XPS profiles of ZnAl-HTO and Zn30Ni1Al-HTO

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