TEPA负载复合氧化活性炭吸附烟气中的CO2性能

doi:10.11949/0438-1157.20191178

摘要/Abstract

摘要：

以商业煤基活性炭为原料，经低浓度氧气焙烧、H₂O₂氧化改性，并以四乙烯五胺（TEPA）浸渍，得到胺负载复合氧化活性炭，用于模拟烟道气[(15%(体积)CO₂+85%(体积)N₂）+10%(体积)H₂O]中CO₂吸附。低浓度氧气焙烧后，活性炭的最大比表面积和孔体积分别为1421.82 m²/g、0.83 cm³/g。经复合氧化改性后，活性炭的介孔体积增大，表面含氧官能团增加，使得TEPA负载复合氧化活性炭的CO₂吸附性能提高。焙烧时间为4 h，H₂O₂氧化、负载40%TEPA的样品COAC-4-40TEPA，在60℃时CO₂饱和吸附量最高为2.45 mmol/g，是TEPA负载未改性活性炭AC-40TEPA的2.02倍。经过十次吸附循环后，COAC-4-40TEPA的 CO₂饱和吸附量可维持在92.24%，而TEPA的浸出量仅有0.67%。失活模型研究表明，COAC-4-40TEPA的初始吸附速率常数是AC-40TEPA的1.64倍，且失活速率常数低于AC-40TEPA。

关键词: 活性炭, 氧化, 二氧化碳, 吸附, 四乙烯五胺, 再生

Abstract:

Commercial coal-based activated carbon was used as raw material, roasted with low concentration of oxygen, oxidized and modified with H₂O₂, and impregnated with tetraethylenepentamine (TEPA) to obtain an amine-loaded composite oxidized activated carbon, which was used to simulate flue gas [(15%(vol) CO₂ + 85%(vol) N₂) +10%(vol) H₂O] adsorption of CO₂. After low concentration oxygen modification, activated carbon showed highest specific surface area of 1421.82 m²/g and highest pore volume of 0.83 cm³/g. The content of oxygen-containing groups on the activated carbon surface and mesoporous volume increased through composited oxidation, resulting higher CO₂ adsorption performance on TEPA-impregnated composited oxidized activated carbon. Compared different adsorbents, the sample COAC-4-40TEPA prepared through 4 h oxidation, H₂O₂ oxidation and 40% TEPA impregnation, showed highest CO₂ adsorption capacity of 2.45 mmol/g, which is 2.02 times of AC-40TEPA. Moreover, the CO₂ adsorption capacity could maintain 92.24% after ten adsorption cycles. The deactivation model analysis showed that initial adsorption rate of COAC-4-40TEPA was 1.64 times of AC-40TEPA, and the deactivation rate was lower.

Key words: activated carbon, oxidation, carbon dioxide, adsorption, TEPA, regeneration

中图分类号:

TQ 424

王燕霞, 胡修德, 郝健, 郭庆杰. TEPA负载复合氧化活性炭吸附烟气中的CO₂性能[J]. 化工学报, 2020, 71(5): 2333-2343.

Yanxia WANG, Xiude HU, Jian HAO, Qingjie GUO. The CO₂ adsorption performance under flue gas for TEPA-impregnated composited oxidized activated carbon[J]. CIESC Journal, 2020, 71(5): 2333-2343.

图/表 15

图1 CO2穿透吸附装置1—氮气；2—混合气（15%(体积)CO2/85%(体积)N2）；3—质量流量计；4—混合器； 5—水浴锅； 6—鼓泡发生器； 7—加热带；8—吸附反应器；9—固定床；10—温度控制器；11—气相色谱仪；12—数据记录

Fig.1 Schematic diagram of CO2 adsorption setup

图2 扫描电镜图和COAC-4-40TEPA的碳、氧、氮元素的能量分布图

Fig.2 SEM images of samples and mapping images of C, O, N element of COAC-4-40TEPA

图3 氮气吸/脱附等温线及孔径分布曲线

Fig.3 N2 adsorption/desorption isotherms and pore size distribution of samples

表1 不同吸附剂的孔结构参数与氧含量

Table 1 Textural properties and oxygen content of adsorbents

样品名称	比表面积/ (m²/g)	孔体积/ (cm³/g)	微孔体积/ (cm³/g)	氧含量/ %(质量)
AC	1256.69	0.70	0.38	6.39
OAC-4	1360.80	0.81	0.28	10.54
COAC-4	1228.59	0.76	0.24	16.91
COAC-4-20TEPA	543.39	0.35	0.12	—
COAC-4-30TEPA	69.44	0.09	0	—
COAC-4-40TEPA	23.15	0.04	0	—
COAC-4-50TEPA	16.21	0.02	0	—

图4 不同吸附剂的红外光谱图

Fig.4 FT-IR spectra of adsorbents

图5 热失重曲线

Fig.5 TGA profiles of samples

图6 不同焙烧时间制备吸附剂的饱和吸附量对比

Fig.6 Comparison of saturated adsorption capacity for different adsorbents

表2 不同焙烧时间得到活性炭的孔结构参数

Table 2 Textural properties of activated carbons

样品名称	比表面积/(m²/g)	孔体积/ (cm³/g)	微孔体积/(cm³/g)	介孔体积/(cm³/g)
AC	1256.70	0.70	0.38	0.32
OAC-2	1421.82	0.83	0.39	0.44
OAC-4	1360.80	0.81	0.28	0.51
OAC-8	1071.78	0.69	0.21	0.48

图7 不同吸附剂在模拟烟气下的穿透吸附曲线

Fig.7 Breakthrough adsorption curves under simulated flue gas of adsorbents

表3 不同样品的CO2吸附量和胺效率

Table 3 CO2 adsorption capacity and amine efficiency of samples

样品名称	穿透时间/ min	穿透吸附量/ （mmol/g）	饱和吸附量/ （mmol/g）	胺效率/ (mmol CO₂/(g TEPA))
COAC-4-20TEPA	4	0.62	1.40	8.31
COAC-4-30TEPA	6	0.93	1.83	7.12
COAC-4-40TEPA	10	1.55	2.45	6.66
COAC-4-50TEPA	6	0.93	2.20	4.49

图8 不同吸附温度下COAC-4-40TEPA的穿透吸附曲线及吸附量随温度的变化曲线

Fig.8 Breakthrough adsorption curves and adsorption capacities under different temperatures

图9 对比样品AC、AC-40TEPA、COAC-4-40TEPA的穿透吸附曲线

Fig.9 Breakthrough adsorption curves of controlled samples

图10 样品COAC-4-40TEPA的循环性能及热稳定性

Fig.10 Ten cycled CO2 adsorption capacity of COAC-4-40TEPA and TGA profiles before and after ten cycles

图11 失活模型对样品AC、AC-40TEPA、COAC-4-40TEPA穿透吸附曲线的拟合

Fig.11 Fitting of deactivation model to breakthrough adsorption curves of samples

表4 对比样品AC、AC-40TEPA、COAC-4-40TEPA的失活模型参数

Table 4 Parameters of deactivation model for fitting controlled samples

样品名称	k₀/(ml/(min·g))	k_d/(1/min)	R²
AC	66.0498	2.0001	0.9996
AC-40TEPA	43.6547	0.4577	0.9793
COAC-4-40TEPA	71.8006	0.3943	0.9775

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TEPA负载复合氧化活性炭吸附烟气中的CO₂性能

The CO₂ adsorption performance under flue gas for TEPA-impregnated composited oxidized activated carbon

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