Preparation of rod-like γ-alumina/volcanic rock porous material and preliminary study on the adsorption property of Congo red
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摘要: 以火山岩为基体材料，硝酸铝、碳酸氢铵为原料，采用原位生长技术，成功制备火山岩孔道中交织生长棒状γ-氧化铝的火山岩基多孔材料，应用XRD、SEM、N2吸附-脱附、TG-DSC等技术表征该材料的结构与性质，并研究其对刚果红的吸附性能。研究表明，硝酸铝溶液通过扩散吸附填充到火山岩基体材料孔道中，焙烧后形成无定型相氧化铝。水热处理及焙烧时，形成的氧化铝依次转变为碱式碳酸铝铵和γ-氧化铝。制备棒状γ-氧化铝/火山岩基多孔材料的最佳反应条件为碳酸氢铵溶液浓度0.8 mol/L，反应温度140 ℃，反应时间4 h。火山岩孔道中堆积的棒状γ-氧化铝晶粒直径为50−150 nm，长度3−10 μm，该多孔材料孔容为0.1 mL/g，比表面积为47 m2/g。当刚果红溶液浓度为500 mg/L，多孔材料投加量为2 g/L时，刚果红脱除率达96%，吸附量为243 mg/g。Abstract: The porous materials of rod-like γ-alumina interlaced in pores of volcanic rock were prepared by in-situ growth using volcanic rock as matrix material, aluminum nitrate and ammonium bicarbonate as raw materials. The structure and properties of the materials were characterized by XRD, SEM, N2 adsorption-desorption and TG-DSC technology. The adsorption performance of Congo red was also studied. It was found that the aluminum nitrate solution filled the pores of volcanic matrix materials by diffusion and adsorption, and amorphous alumina was formed after calcination. During hydrothermal treatment and calcination, the formed alumina was transformed into ammonium aluminum carbonate hydroxide and γ-alumina. The optimal reaction conditions for the preparation of rod-like γ-alumina/volcanic rock porous materials were as following: the concentration of ammonium bicarbonate solution was 0.8 mol/L, the reaction temperature was 140 ℃, and the reaction time was 4 h. The rod-like γ-alumina stacked in the channels of volcanic rock with a diameter of 50−150 nm and length of 3−10 μm. The specific surface area and pore volume of the porous material was 0.1 mL/g and 47 m2/g, respectively. When the concentration of Congo red solution was 500 mg/L and the dosage of porous material was 2 g/L, the removal rate was 96% with the adsorption amount of 243 mg/g.
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Key words:
- rod-like /
- γ-alumina /
- volcanic rock /
- porous material /
- Congo red /
- adsorption
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图 1 不同碳酸氢铵浓度条件下样品的SEM照片
Figure 1 SEM images of samples prepared with different concentrations of ammonium bicarbonate
(a): volcanic rock material; (b): volcanic rock impregnated with aluminum nitrate and calcination; (c): 0.1 mol/L; (d): 0.4 mol/L; (e): 0.8 mol/L; (f): 1.2 mol/L
图 2 不同反应温度条件下样品的SEM照片
Figure 2 SEM images of samples prepared by different reaction temperature
(a): 80 ℃; (b): 100 ℃; (c): 120 ℃; (d): 140 ℃; (e): 160 ℃; (f): 180 ℃
图 3 不同反应时间条件下样品的SEM照片
Figure 3 SEM images of samples prepared with different reaction time
(a): 1 h; (b): 2 h; (c): 4 h; (d): 6 h
图 4 样品的XRD谱图
Figure 4 XRD patterns of the samples
a: volcanic rock material A; b: volcanic rock load alumina B; c: hydrothermal treatment material; d: rod-like γ-alumina/volcanic rock porous material D
图 6 水热处理干燥未焙烧样品的XRD谱图
Figure 6 XRD patterns of samples prepared by hydrothermal treatment, dry but not calcination
a: 1 h; b: 2 h; c: 4 h; d: 6 h; e: 8 h
图 7 水热处理干燥未焙烧样品的SEM照片
Figure 7 SEM images of samples prepared by hydrothermal treatment, dry but not calcination
(a): 1 h; (b): 2 h; (c): 4 h; (d): 6 h; (e): 8 h
图 8 棒状γ-氧化铝/火山岩基多孔材料形成示意图
Figure 8 Formation of rod-like γ-alumina/volcanic rock porous material
图 9 棒状γ-氧化铝/火山岩基多孔材刚果红吸附性能
Figure 9 Congo red adsorption performance of rod-like γ-alumina/volcanic rock porous material
(a): effect of adsorption time on the removal rate; (b): effect of adsorbent dosage on the removal rate and adsorption capacity
表 1 火山岩基体材料及棒状γ-氧化铝/火山岩基多孔材料的孔结构
Table 1 Pore structure of volcanic rock material and rod-like γ-alumina/volcanic rock porous material
Sample Specific surface area /（m2·g−1） pore volume /（mL·g−1） Volcanic rock 5 0.005 Rod-like γ-alumina/volcanic Rock porous material 47 0.10 
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表 2 不同反应时间条件下棒状γ-氧化铝/火山岩基多孔材料的孔结构
Table 2 Pore structure of rod-like γ-alumina/volcanic rock porous materials prepared by different reaction time
Sample Specific surface area /（m2·g−1） Pore volume /（mL·g−1） Volcanic rock 5 0.005 Volcanic rock load with alumina 11 0.01 1 h 17 0.03 2 h 21 0.04 4 h 47 0.10 6 h 51 0.10 8 h 52 0.11
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表 3 粒子内扩散方程线性分析参数
Table 3 Intra-particle diffusion model kinetic constants
kt1/（mg·g−1·min1/2） kt2/（mg·g−1·min1/2） kt3/（mg·g−1·min1/2） I1 I2 I3 $R^{2}_{1} $ $ R^{2}_{2} $ $ R^{2}_{3} $ 55.2 10.2 2.3 49.4 156.2 223.3 0.984 0.850 0.993
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