Preparation of coal derived nitrogen-doped mesoporous carbon for the catalytic oxidation of H2S at room temperature
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摘要: 采用纳米二氧化硅模板辅助的共炭化方法，以煤转化副产物煤焦油的蒽油馏分为碳源、三聚氰胺为氮源，制备出高氮元素掺杂、发达介孔结构的氮掺杂介孔炭（NMCs）。结合元素分析、扫描/透射电镜观察、低温氮气吸附-脱附及X射线光电子能谱测试分析，对比考察了不同合成条件对所得样品的组成、结构及其室温催化脱硫性能的影响。结果表明，控制合适的模板剂用量、碳/氮源比例和炭化温度（700℃），所制备的样品具有适宜的氮元素掺杂量及丰富的吡啶/吡咯氮构型、较大比表面积、介孔孔径和孔容，在室温下对H2S的氧化脱除显示出高效催化性能。Abstract: Nitrogen-doped mesoporous carbon (NMCs) with high N doping level and developed mesoporous structure were prepared by a nanoscale-size SiO2 template-assisted blend carbonization process, using anthracene oil (AO), one of distillates of coal tar, as carbon source and melamine (M) as nitrogen source. With the assistance of elemental analysis, FESEM/TEM, N2 adsorption-desorption and XPS characterizations, the effects of various synthesis parameters on the chemical composition, pore structure and the catalytic performance of NMCs in H2S oxidation at room temperature were investigated. The results show that NMC sample with suitable nitrogen doping level, abundant pyridinic/pyrrolic configurations, uniform large mesopore size, as well as high pore volume and specific surface area can be prepared by using appropriate amount of template agent, carbon/nitrogen source ratio and carbonization temperature (700℃), which exhibits high efficiency in the removal of H2S through catalytic oxidation at room temperature.
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Key words:
- mesoporous carbon /
- coal tar /
- nitrogen-doping /
- hydrogen sulfide /
- catalytic oxidation
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图 2 不同系列NMCs样品的低温N2吸附-脱附等温线及孔径分布曲线
Figure 2 N2 adsorption-desorption isotherms (a), (b), (c) and corresponding pore size distributions (d), (e), (f) of different NMCs samples
图 3 NMC-1-700-x样品在全谱范围内XPS谱图及N 1s高分辨谱图
Figure 3 XPS survey (a) and N 1s spectra (b) of NMC-1-700-x samples
图 4 NMC-1-700-1/2样品的FESEM照片、元素组成扫描照片和TEM照片
Figure 4 FESEM images ((a), (b)), element mapping (c) and TEM image (d) of NMC-1-700-1/2 sample
图 5 NMCs催化剂上H2S催化氧化脱硫穿透曲线
Figure 5 Breakthrough curves for the removal of H2S through catalytic oxidation over NMC-x-t-y
(a): NMC-x-700-1/2; —■—: NMC-0.5-700-1/2; —●—: NMC-1-700-1/2; —▲—: NMC-2-700-1/2; —▼—: NMC-4-700-1/2; (b): NMC-1-t-1/2; —■—: NMC-1-600-1/2; —●—: NMC-1-700-1/2; —▲—: NMC-1-800-1/2; (c): NMC-1-700-y; —■—: NMC-1-700-2; —●—: NMC-1-700-1; —▲—: NMC-1-700-1/2; —▼—: NMC-1-700-1/4
图 6 NMC-1-700-1/2及其脱硫后催化剂NMC-1-700-1/2-S的XRD谱图和脱硫后催化剂的FESEM元素组成扫描照片
Figure 6 XRD patterns of the original NMC-1-700-1/2 and spent NMC-1-700-1/2-S catalyst (a) and FESEM element mapping of the spent NMC-1-700-1/2-S catalyst (b)
表 1 不同条件下合成NMCs样品的氮含量、比表面积、孔结构参数及其硫容
Table 1 Doped-nitrogen content, surface area, pore parameters and sulfur capacity of various NMCs samples
Series Sample Element N/% content C/N ABET /(m2·g-1) vtotal /(cm3·g-1) Sulfur capacity /(gH2S·gcat-1) Ⅰ NMC-0.5-700-1/2 13.2 0.18 473 1.23 4.25 NMC-1-700-1/2 19.1 0.29 468 1.34 4.74 NMC-2-700-1/2 12.0 0.21 572 0.85 0.60 NMC-4-700-1/2 6.5 0.09 796 0.88 0.76 Ⅱ NMC-1-600-1/2 28.0 0.49 275 0.79 2.88 NMC-1-800-1/2 16.4 0.24 579 1.37 3.72 Ⅲ NMC-1-700-2 4.6 0.06 663 1.66 4.40 NMC-1-700-1 12.6 0.18 570 1.49 4.55 NMC-1-700-1/4 24.1 0.40 343 0.85 2.51 a: mass ratio of C/N 
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