硫化氢深度吸附材料的研究进展

doi:10.11949/0438-1157.20201063

摘要/Abstract

摘要：

目前硫化氢（H₂S）日益成为制约工业化发展的一个重要因素，即使在较低的浓度下仍会破坏环境、腐蚀设备。如何能将含硫气体清洁、高效、深度脱除已成为国内外学者的研究重点。吸附法脱硫以其脱硫程度高、高效环保、操作简单和吸附剂可重复利用等优点具有良好的发展前景。研制一种选择性好、吸附容量大、性能稳定、再生性好的吸附剂是吸附法脱硫的关键。本文以深度脱除H₂S为目标，综述了碳基材料、多孔金属氧化物、沸石分子筛、金属有机框架（MOFs）等几种不同吸附材料的研究进展，总结深度脱硫今后的发展方向，旨在为后续的研究提供借鉴。

关键词: 脱硫, H₂S, 吸附剂, 吸附, 气体净化, 分离

Abstract:

At present, hydrogen sulfide (H₂S) has increasingly become an important factor restricting the development of industrialization. Even at a low concentration, it will still damage the environment and corrode equipment. The deep purification of sulfur-containing gas by using an environmental and efficient method has gained the attention of researchers on domestic and overseas. Adsorption desulfurization has a good prospective because of its deep removal, high efficiency, environmental-friendly performance and good regeneration. The key of adsorption desulfurization is to develop an adsorbent with good selectivity, large adsorption capacity, stable performance and good reproducibility. This paper summarizes the recent advances in several adsorbent materials such as carbon-based materials, porous metal oxides, zeolite and metal-organic frameworks (MOFs), making a comment on the future development directions of deep removal of H₂S, aiming at providing a reference for further research.

Key words: desulfurization, H₂S, adsorbent, adsorption, gas purification, separation

中图分类号:

TQ 028.2

于涛, 王运东, 刘作华, 马建修, 靖宇. 硫化氢深度吸附材料的研究进展[J]. 化工学报, 2021, 72(2): 748-760.

YU Tao, WANG Yundong, LIU Zuohua, MA Jianxiu, JING Yu. Research progress of hydrogen sulfide deep adsorption materials[J]. CIESC Journal, 2021, 72(2): 748-760.

图/表 10

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材料	比表面积/(m²/g)	孔体积/ (cm³/g)	平均孔径/nm	气体组成	操作温度/℃	穿透容量^①/(mg/g)	文献
WSC	860	0.40	0.7	50% H₂, 15% CO₂, 9% CO, 2% N₂, 24% H₂O, 10^-3 H₂S 50% H₂, 15% CO₂, 9% CO, 2% N₂, 24% H₂O, 10^-3 H₂S	150 150	71(0.2)	[11]
WSCU	945	0.43	0.8		150 150	133(0.2)	[11]
S208C	898	0.48	—	60% CH₄, 40% CO₂, 10^-3 H₂S, 70% H₂O预加湿	—	27.2(ND)	[13]
S-A	905	0.48	—	60% CH₄, 40% CO₂, 10^-3 H₂S, 70% H₂O预加湿	—	26.4(ND)	[13]
S-AU	640	0.34	—	60% CH₄, 40% CO₂, 10^-3 H₂S, 70% H₂O预加湿	—	34.0(ND)	[13]
S-AM	37	0.02	—	60% CH₄, 40% CO₂, 10^-3 H₂S, 70% H₂O预加湿	—	0.4(-)	[13]
S-B	882	0.47	—	60% CH₄, 40% CO₂, 10^-3 H₂S, 70% H₂O预加湿	—	17.6(ND)	[13]
S-BU	808	0.43	—	60% CH₄, 40% CO₂, 10^-3 H₂S, 70% H₂O预加湿	—	54.1(ND)	[13]
S-BM	732	0.39	—	60% CH₄, 40% CO₂, 10^-3 H₂S, 70% H₂O预加湿	—	71.9(ND)	[13]
AC-KOH/KI	1042	0.42	—	2% O₂, 10^-4 H₂S, 90%相对湿度, N₂平衡	45 45	65.6(0.2)	[14]
AC-KOH/KI	1042	0.42	—	10^-4 H₂S, 90%相对湿度, N₂平衡	45 45	34.9(0.2)	[14]
RB₂-NaOH₅₀	758	0.25	1.56	2.5×10^-4 H₂S, N₂平衡	25	43.5(ND)	[15]
AC-NaOH	—	—	—	3×10^-3 H₂S, He平衡	30	0.4(10)	[16]
AC-KI	—	—	—	3×10^-3 H₂S, He平衡	30	1.56(<10)	[16]
AC-Na₂CO₃	—	—	—	3×10^-3 H₂S, He平衡	30	1.58(<10)	[16]
AC-KOH	—	—	—	3×10^-3 H₂S, He平衡	30	1.58(<10)	[16]
GAC	1678±41	0.75±0.03	0.89±0.16	80% H₂O, 1% H₂S, 空气 80% H₂O, 1% H₂S, 空气	25 25	53(N)	[17]
MgO-GAC	1358±39	0.60±0.01	0.88±0.23	80% H₂O, 1% H₂S, 空气 80% H₂O, 1% H₂S, 空气	25 25	275(N)	[17]
Cu_0.5Zn_0.5/AC	570	0.76	—	10^-4 H₂S, 2.5×10^-3 O₂, 50%相对湿度, N₂平衡	30	25.0(ND)	[18]
NORIT	978	0.30	—	5×10^-5 H₂S, N₂平衡	—	- (<0.5)	[19]

材料	比表面积/(m²/g)	孔体积/ (cm³/g)	平均孔径/nm	气体组成	操作温度/℃	穿透容量^①/(mg/g)	文献
WSC	860	0.40	0.7	50% H₂, 15% CO₂, 9% CO, 2% N₂, 24% H₂O, 10^-3 H₂S 50% H₂, 15% CO₂, 9% CO, 2% N₂, 24% H₂O, 10^-3 H₂S	150 150	71(0.2)	[11]
WSCU	945	0.43	0.8		150 150	133(0.2)	[11]
S208C	898	0.48	—	60% CH₄, 40% CO₂, 10^-3 H₂S, 70% H₂O预加湿	—	27.2(ND)	[13]
S-A	905	0.48	—	60% CH₄, 40% CO₂, 10^-3 H₂S, 70% H₂O预加湿	—	26.4(ND)	[13]
S-AU	640	0.34	—	60% CH₄, 40% CO₂, 10^-3 H₂S, 70% H₂O预加湿	—	34.0(ND)	[13]
S-AM	37	0.02	—	60% CH₄, 40% CO₂, 10^-3 H₂S, 70% H₂O预加湿	—	0.4(-)	[13]
S-B	882	0.47	—	60% CH₄, 40% CO₂, 10^-3 H₂S, 70% H₂O预加湿	—	17.6(ND)	[13]
S-BU	808	0.43	—	60% CH₄, 40% CO₂, 10^-3 H₂S, 70% H₂O预加湿	—	54.1(ND)	[13]
S-BM	732	0.39	—	60% CH₄, 40% CO₂, 10^-3 H₂S, 70% H₂O预加湿	—	71.9(ND)	[13]
AC-KOH/KI	1042	0.42	—	2% O₂, 10^-4 H₂S, 90%相对湿度, N₂平衡	45 45	65.6(0.2)	[14]
AC-KOH/KI	1042	0.42	—	10^-4 H₂S, 90%相对湿度, N₂平衡	45 45	34.9(0.2)	[14]
RB₂-NaOH₅₀	758	0.25	1.56	2.5×10^-4 H₂S, N₂平衡	25	43.5(ND)	[15]
AC-NaOH	—	—	—	3×10^-3 H₂S, He平衡	30	0.4(10)	[16]
AC-KI	—	—	—	3×10^-3 H₂S, He平衡	30	1.56(<10)	[16]
AC-Na₂CO₃	—	—	—	3×10^-3 H₂S, He平衡	30	1.58(<10)	[16]
AC-KOH	—	—	—	3×10^-3 H₂S, He平衡	30	1.58(<10)	[16]
GAC	1678±41	0.75±0.03	0.89±0.16	80% H₂O, 1% H₂S, 空气 80% H₂O, 1% H₂S, 空气	25 25	53(N)	[17]
MgO-GAC	1358±39	0.60±0.01	0.88±0.23	80% H₂O, 1% H₂S, 空气 80% H₂O, 1% H₂S, 空气	25 25	275(N)	[17]
Cu_0.5Zn_0.5/AC	570	0.76	—	10^-4 H₂S, 2.5×10^-3 O₂, 50%相对湿度, N₂平衡	30	25.0(ND)	[18]
NORIT	978	0.30	—	5×10^-5 H₂S, N₂平衡	—	- (<0.5)	[19]

材料	比表面积/(m²/g)	孔体积/(cm³/g)	平均孔径/nm	气体组成	操作温度/℃	饱和容量^①/(mg/g)	穿透容量^①/(mg/g)	文献
3DOM-Fe₂O₃	16~44	—	20~33	5% H₂, 3×10^-4 H₂S, N₂平衡 5% H₂, 3×10^-4 H₂S, N₂平衡	350 350	—	37.18(<0.2)	[25]
3DOM-Fe₂O₃/SiO₂	80~220	—	6~17	5% H₂, 3×10^-4 H₂S, N₂平衡 5% H₂, 3×10^-4 H₂S, N₂平衡	350 350	—	38.92(<0.2)	[25]
MFT	—	—	—	39.8% H₂, 32.6% CO₂, 2.5×10^-3 H₂S, N₂平衡	400	216(N)	—	[26]
Engelhard ZnO	53.13	0.28	—	8×10^-6 H₂S, 34.4% H₂, 20% H₂O, N₂平衡	300	—	28.1(0.02)	[27]
ZSCo-0	151.3	0.42	7.40	8×10^-4 H₂S, 混合气体(N₂, H₂O)	30	174.6	117.8(ND)	[28]
ZSCo-0.05	188.7	0.58	7.82	8×10^-4 H₂S, 混合气体(N₂, H₂O)	30	195.2	146.4(ND)	[28]
ZSCo-0.15	206.4	0.63	9.58	8×10^-4 H₂S, 混合气体(N₂, H₂O)	30	208.4	169.8(ND)	[28]
ZSCo-0.3	192.1	0.55	9.24	8×10^-4 H₂S, 混合气体(N₂, H₂O)	30	230.5	188.4(ND)	[28]
ZSCo-0.50	161.5	0.46	7.53	8×10^-4 H₂S, 混合气体(N₂, H₂O)	30	194.1	143.4(ND)	[28]
Extruded-Fe₂O₃	60.6	13.90	99.0	6×10^-4 H₂S, 混合气体	30 ± 2	22.4	16.0(N)	[32]
Fe-Cu-Al-O	96.7	—	—	10^-3 H₂S, CO₂	40	—	113.9(ND)	[33]
ZnO	10.2	0.029	介-大孔	51% H₂, 30% He, 10% H₂O, 4×10^-4 H₂S	400	457.3(2)	—	[34]
Ni-ZnO	6.8	0.025	介-大孔	51% H₂, 30% He, 10% H₂O, 4×10^-4 H₂S	400	730.0(2)	—	[34]
HZn20SC	272.59	0.17	—	33% CO, 39% H₂, 5% H₂O,3×10^-4 H₂S, N₂平衡	450	—	44.6(ND)	[35]
Z20M4C6SC	207.33	0.03	—	33% CO, 39% H₂, 5×10^-4 H₂S, N₂平衡	500	—	138.4(ND)	[36]
ZnO	—	—	—	54% H₂, 21%CO₂, 2.5×10^-5 H₂S, He 平衡	150	—	131(<0.1)	[37]
ZnO	—	—	—	54% H₂, 21%CO₂, 2.5×10^-5 H₂S, He 平衡	200	—	110(<0.1)	[37]
3DOM-ZnFe₂O₄/SiO₂	213.10	0.39	7.40	5% H₂, 3% H₂O, 0.1% H₂S, N₂平衡	500	—	92(<0.5)	[38]
3DOM-ZnO/SiO₂	336	0.244	1.436	3% H₂O, 500 mg/m³ H₂S, N₂平衡	室温	—	135(<0.72)	[40]

材料	比表面积/(m²/g)	孔体积/(cm³/g)	平均孔径/nm	气体组成	操作温度/℃	饱和容量^①/(mg/g)	穿透容量^①/(mg/g)	文献
3DOM-Fe₂O₃	16~44	—	20~33	5% H₂, 3×10^-4 H₂S, N₂平衡 5% H₂, 3×10^-4 H₂S, N₂平衡	350 350	—	37.18(<0.2)	[25]
3DOM-Fe₂O₃/SiO₂	80~220	—	6~17	5% H₂, 3×10^-4 H₂S, N₂平衡 5% H₂, 3×10^-4 H₂S, N₂平衡	350 350	—	38.92(<0.2)	[25]
MFT	—	—	—	39.8% H₂, 32.6% CO₂, 2.5×10^-3 H₂S, N₂平衡	400	216(N)	—	[26]
Engelhard ZnO	53.13	0.28	—	8×10^-6 H₂S, 34.4% H₂, 20% H₂O, N₂平衡	300	—	28.1(0.02)	[27]
ZSCo-0	151.3	0.42	7.40	8×10^-4 H₂S, 混合气体(N₂, H₂O)	30	174.6	117.8(ND)	[28]
ZSCo-0.05	188.7	0.58	7.82	8×10^-4 H₂S, 混合气体(N₂, H₂O)	30	195.2	146.4(ND)	[28]
ZSCo-0.15	206.4	0.63	9.58	8×10^-4 H₂S, 混合气体(N₂, H₂O)	30	208.4	169.8(ND)	[28]
ZSCo-0.3	192.1	0.55	9.24	8×10^-4 H₂S, 混合气体(N₂, H₂O)	30	230.5	188.4(ND)	[28]
ZSCo-0.50	161.5	0.46	7.53	8×10^-4 H₂S, 混合气体(N₂, H₂O)	30	194.1	143.4(ND)	[28]
Extruded-Fe₂O₃	60.6	13.90	99.0	6×10^-4 H₂S, 混合气体	30 ± 2	22.4	16.0(N)	[32]
Fe-Cu-Al-O	96.7	—	—	10^-3 H₂S, CO₂	40	—	113.9(ND)	[33]
ZnO	10.2	0.029	介-大孔	51% H₂, 30% He, 10% H₂O, 4×10^-4 H₂S	400	457.3(2)	—	[34]
Ni-ZnO	6.8	0.025	介-大孔	51% H₂, 30% He, 10% H₂O, 4×10^-4 H₂S	400	730.0(2)	—	[34]
HZn20SC	272.59	0.17	—	33% CO, 39% H₂, 5% H₂O,3×10^-4 H₂S, N₂平衡	450	—	44.6(ND)	[35]
Z20M4C6SC	207.33	0.03	—	33% CO, 39% H₂, 5×10^-4 H₂S, N₂平衡	500	—	138.4(ND)	[36]
ZnO	—	—	—	54% H₂, 21%CO₂, 2.5×10^-5 H₂S, He 平衡	150	—	131(<0.1)	[37]
ZnO	—	—	—	54% H₂, 21%CO₂, 2.5×10^-5 H₂S, He 平衡	200	—	110(<0.1)	[37]
3DOM-ZnFe₂O₄/SiO₂	213.10	0.39	7.40	5% H₂, 3% H₂O, 0.1% H₂S, N₂平衡	500	—	92(<0.5)	[38]
3DOM-ZnO/SiO₂	336	0.244	1.436	3% H₂O, 500 mg/m³ H₂S, N₂平衡	室温	—	135(<0.72)	[40]

材料	比表面积/(m²/g)	孔体积/(cm³/g)	平均孔径/nm	气体组成	操作温度/℃	饱和容量/(mg/g)	穿透容量^①/ (mg/g)	文献
天然斜发沸石	34.2	0.12	17.9	59.95% CH₄, 39.95% CO₂, 0.1% H₂S	25	—	1.4(<3)	[44]
4A	49.5	—	—	10^-3 H₂S, N₂平衡	50	—	8.36(~0)	[45]
13X	567	0.34	—	2×10^-2 H₂S, 10^-2 SO₂, 15% H₂O, N₂平衡	150	—	179.7(ND)	[46]
NaX	503	0.255	—	63% N₂, 35% CO₂, 2% H₂S, 2×10^-4 COS	25	24.96	21.44(ND)	[47]
ZnX	538	0.307	—	63% N₂, 35% CO₂, 2% H₂S, 2×10^-4 COS	25	48.96	45.44(ND)	[47]
CoX	511	0.288	—	63% N₂, 35% CO₂, 2% H₂S, 2×10^-4 COS	25	44.16	41.28(ND)	[47]
AgX	333	0.169	—	63% N₂, 35% CO₂, 2% H₂S, 2×10^-4 COS	25	51.84	48.96(ND)	[47]
13X Ex-Cu	239	—	—	2×10^-4 H₂S, N₂平衡	120	—	40.12±0.6(ND)	[48]
13X-Ex-Cu (2.3mmol/g Cu)	370	—	—	8×10^-6 H₂S, He平衡	40	—	39.8(0)	[49]
5-TiO₂/zeolite	93.42±0.06	0.59±0.06	—	65% CH₄, 35% N₂, 0.1% H₂S	25	—	4.43(ND)	[50]
20Zn/NaA zeolite	7.99	—	2.43	2×10^-4 H₂S, N₂平衡	28	—	15.75(0)	[51]