Wet ball-milling method to prepare nanocrystalline Li4SiO4 materials for CO2 capture at high temperatures
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摘要: 采用不同硅源、锂源以湿磨法结合高温焙烧制备了纳米Li4SiO4材料,利用X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)表征了合成材料的结构和表面形貌,利用热重分析仪(TG)研究了Li4SiO4材料高温下的CO2吸收性能和循环使用稳定性。结果表明,湿磨法制备的Li4SiO4材料在550℃、2.5×104 Pa下,10 min可达吸收平衡,平衡吸收量为27.9%(质量分数),经五次吸收-解吸后仍保持初始吸收性能,显示了良好的循环稳定性。将25%CO2-25%N2-50%He混合气通过Li4SiO4材料床层,发现在550℃下,CO2能被高效捕集,在相对湿度为10%的水汽存在下,Li4SiO4捕集CO2的性能没有明显下降。Abstract: A wet ball-milling method followed by calcination was adopted to prepare nanocrystalline Li4SiO4 materials by using different silicon and lithium sources. X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM) were applied to characterize the structure and morphology of the as-prepared Li4SiO4 materials. CO2 uptakes and recycle stability of the prepared Li4SiO4 materials were investigated on a thermogravity (TG) analyzer. Absorption equilibrium of 27.9% was achieved within 10 min at 550℃ and CO2 partial pressure of 2.5×104 Pa. The prepared nanocrystalline Li4SiO4 material kept the original absorption properties after 5 capture-regeneration cycles, indicating the good cycle stability. A mixture of 25% CO2-25% N2-50% He was introduced through the Li4SiO4 absorption bed, showing that CO2 can be efficiently captured at 550℃. The adsorption capacity showed no significant decrease in the presence of 10% humidity.
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Key words:
- Li4SiO4 /
- wet ball-milling /
- CO2 capture /
- high temperature /
- moisture
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表 1 不同硅源、锂源制备的Li4SiO4材料及其CO2吸收性能
Table 1 Li4SiO4 materials prepared by various silicon and lithium sources and their CO2 absorption properties
Sample Lithium source Silicon source Absorption
equilibrium w/%1 LiOH·H2O silica sol 19.9 2 LiOH·H2O fumed silica 2.3 3 LiOH·H2O silicic acid 25.6 4 LiOH·H2O TEOS 27.9 5 Li2CO3 TEOS no absorption 6 LiNO3 TEOS - -: the precursor is in paste form and cannot produce the solid precursor 表 2 湿磨法制备的Li4SiO4材料与文献中报道的锂基类吸收剂的CO2吸收性能比较
Table 2 Comparison of the CO2 capture properties of the Li4SiO4 sorbent prepared using the wet ball-milling method and lithium based sorbents reported in references
Sorbent CO2 capture conditions Maximum of
CO2 capture rate
/(%·min-1)aEquilibrium
sorption amount
w/%Time required
to equilibrium
t/minReference temp
t/ ℃CO2
pressure
p/Patotal feed
flow
q/(mL·min-1)Li4SiO4 550 2.5×104 40 6.4 27.8 ~10 this work Li2ZrO3 550 2.5×104 40 0.5 5.20 ~20 [14] K-Li2ZrO3 550 2.5×104 40 1.9 22.0 < 20 [16] Li4SiO4 550 2.5×104 40 3.1 23.9 >60 [19] Li4SiO4 550 2.5×104 40 3.2 24.5 >60 [20] Fe0.15Li3.45SiO4 550 2.5×104 40 3.4 26.0 ~25 [20] Li4SiO4 550 2.5×104 40 5.5 29.8 ~7.5 [21] Li4SiO4 680 1.0×105 - 2.0 27.5 ~40 [18] Li4SiO4 620 5×104 100 2.7 28.62 80 [17] a: differential values of the uptake curves -
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