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摘要: 采用水热合成法制备介孔分子筛SBA-15，用（CH3COO）2Co对其进行超声浸渍改性，并用硅烷偶联剂APTS将氨基引入SBA-15分子筛中，制备出Co-NH2-SBA-15吸附剂，考察了常温条件下H2S的吸附性能。通过SEM、XRD、FT-IR、BET、XPS等表征手段对吸附剂进行表征。结果表明，氨基与金属同时负载在分子筛表面，氨基与硅物质的量比为0.20，Co负载质量分数为8%的SBA-15吸附效果最好，当原料气H2S体积分数为227 μL/L，温度25 ℃，气体流量75 mL/min时，穿透硫容和饱和硫容达0.151和0.190 mmol/g，且吸附剂可再生利用。SBA-15表面嫁接氨基并浸渍金属改性的手段不仅提高了吸附容量，同时提高了分子筛的稳定性。Abstract: The mesoporous molecular sieve SBA-15 was prepared by hydrothermal synthesis, modified with the ultrasonic immersion by (CH3COO)2Co and with the introduction of the amino group into it with APTS as silane coupling agent, and characterized by SEM, XRD, FT-IR, BET and XPS. The prepared Co-NH2-SBA-15 was used for adsorption of H2S at normal temperature. The results show that both amino group and metal have been introduced into the molecular sieve. When the molar ratio of amino group to silicon is 0.20 and the Co loading is 8%, the adsorption capacity of SBA-15 is the highest. Under the conditions of the volume fraction of hydrogen sulfide of 227 μL/L, the temperature of 25 ℃ and the gas flow rate of 75 mL/min, the capacities of breakthrough sulfur and saturated sulfur come to 0.151 and 0.190 mmol/g, respectively. Moreover, the adsorbent can be regenerated for recycle. Under the assistance of molecular sieve surface being grafted by amino group and impregnated by metal, the adsorption capacity can be improved and the stability of molecular sieve can be enhanced.
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Key words:
- SBA-15 /
- modified /
- APTS /
- H2S adsorption
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图 1 SBA-15与Co-NH2-SBA-15样品的小角XRD谱图
Figure 1 Small angle XRD patterns of SBA-15 and Co-NH2-SBA-15
(a): different-NH2 payload; (b): different Co payload
图 2 不同Co负载量Co-NH2-SBA-15的XRD谱图
Figure 2 XRD patterns of Co-NH2-SBA-15 with different Co loadings
图 3 SBA-15及8%Co-0.20NH2-SBA-15的SEM照片
Figure 3 SEM images of SBA-15 and 8%Co-0.20NH2-SBA-15
图 5 SBA-15及Co-NH2-SBA-15的N2吸附-脱附曲线和孔径分布
Figure 5 N2 adsorption/desorption isothems and pore size distributions of SBA-15 and Co-NH2-SBA-15
(a): N2 adsorption/desorption isothems; (b): pore size distributions a: SBA-15; b: 4%Co-0.20NH2-SBA-15; c: 8%Co-0.20NH2-SBA-15
图 7 不同负载量Co-NH2-SBA-15的H2S吸附穿透曲线
Figure 7 Breakthrough curves of H2S adsorption over Co-NH2-SBA-15 with different loadings
a: SBA-15; b: 0.15NH2-SBA-15; c: 4%Co-0.20NH2-SBA-15; d: 6%Co-0.15NH2-SBA-15; e: 6%Co-0.20NH2-SBA-15; f: 8%Co-0.25NH2-SBA-15; g: 8%Co-0.20NH2-SBA-15; h: 10%Co-0.20NH2-SBA-15
图 8 不同湿度下8%Co-0.20NH2-SBA-15的H2S吸附穿透曲线
Figure 8 Breakthrough curves of H2S adsorption over 8%Co-0.20NH2-SBA-15 at different levels of humidity
a: water-free; b: the volume fraction of water is 100 μL/L
图 9 再生次数与吸附剂穿透硫容关系
Figure 9 Relationship between regenerated times and the sulfur capacity of the adsorbent
(a): 8%Co-0.20NH2-SBA-15; (b): 8%Co-SBA-15
表 1 SBA-15及改性后样品的BET表征
Table 1 BET data of SBA-15 and its modified samples
Sample Surface area A/(m2·g-1) Pore volume v/(cm3·g-1) Pore diameter d/nm SBA-15 796.6 0.9579 7.6 4%Co-0.20NH2-SBA-15 551.4 0.8377 6.4 8%Co-0.20NH2-SBA-15 292.4 0.3488 5.2 
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表 2 不同负载量Co-NH2-SBA-15的吸附性能
Table 2 H2S adsorption performance of Co-NH2-SBA-15 with different Co loadings
Adsorbent Breakthrough time t/min Saturation time t/min Cap(BT)/(mmol·g-1) Cap(S)/(mmol·g-1) SBA-15 2.4 6.6 0.002 0.007 0.15NH2-SBA-15 36.2 46.2 0.037 0.047 4%Co-0.20NH2-SBA-15 49.8 62.8 0.042 0.064 6%Co-0.15NH2-SBA-15 70.2 88.2 0.072 0.090 6%Co-0.20NH2-SBA-15 84.6 98.6 0.086 0.101 8%Co-0.25NH2-SBA-15 106.2 150.2 0.108 0.153 8%Co-0.20NH2-SBA-15 148.1 186.1 0.151 0.190 10%Co-0.20NH2-SBA-15 134.8 199.8 0.137 0.204
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