化工学报 ›› 2021, Vol. 72 ›› Issue (6): 3380-3389.DOI: 10.11949/0438-1157.20201653
梁兴唐(),李凤枝,钟书明,张瑞瑞,焦淑菲,汪双双,尹艳镇()
收稿日期:
2020-11-16
修回日期:
2020-12-30
出版日期:
2021-06-05
发布日期:
2021-06-05
通讯作者:
尹艳镇
作者简介:
梁兴唐(1982—),男,博士,副教授,基金资助:
LIANG Xingtang(),LI Fengzhi,ZHONG Shuming,ZHANG Ruirui,JIAO Shufei,WANG Shuangshuang,YIN Yanzhen()
Received:
2020-11-16
Revised:
2020-12-30
Online:
2021-06-05
Published:
2021-06-05
Contact:
YIN Yanzhen
摘要:
为了制备具有胺基利用率高、结构稳定、使用方便的Cr(Ⅵ)吸附材料,以聚乙烯亚胺(PEI)为胺基改性剂,具有类海绵多孔结构的灯芯草(JC)为支撑基材,将吸入JC的PEI通过环氧氯丙烷原位接枝于其纤维表面,获得可整块使用的多孔吸附材料(PEI-JC)。采用元素分析、SEM、FT-IR、XPS表征PEI-JC的组成与结构,分析PEI-JC对Cr(Ⅵ)的吸附机理。考察PEI浓度、溶液的pH、Cr(Ⅵ)浓度与共存化合物等因素对吸附的影响。结果表明,质量分数为10.0%的PEI所制备的PEI10.0-JC,在30℃与pH为2.0的条件下,其Langmuir模型的最大吸附量为474.6 mg·g-1;PEI10.0-JC可将含各种共存化合物溶液中的Cr(Ⅵ)从10 mg·L-1降至排放标准(0.5 mg·L-1)以下;PEI10.0-JC可重复使用,其结构在吸附过程中未发生明显变化;吸附与还原作用是PEI-JC去除水溶液中Cr(Ⅵ)的主要机制。
中图分类号:
梁兴唐, 李凤枝, 钟书明, 张瑞瑞, 焦淑菲, 汪双双, 尹艳镇. 聚乙烯亚胺原位改性多孔灯芯草高效吸附废水中的Cr(Ⅵ)[J]. 化工学报, 2021, 72(6): 3380-3389.
LIANG Xingtang, LI Fengzhi, ZHONG Shuming, ZHANG Ruirui, JIAO Shufei, WANG Shuangshuang, YIN Yanzhen. In-situ modification of porous juncus with polyethyleneimine for efficient capture of Cr(Ⅵ) from wastewater[J]. CIESC Journal, 2021, 72(6): 3380-3389.
图1 JC (a)、PEI5.0-JC (b)、PEI10.0-JC (c)与PEI15.0-JC (d)的SEM照片;PEI10.0-JC吸附Cr(Ⅵ)后的SEM照片(插图)及Cr面扫描能谱 (e);吸附-脱附5次后PEI10.0-JC的SEM照片(f)
Fig.1 SEM images of JC (a), PEI5.0-JC (b), PEI10.0-JC (c) and PEI15.0-JC (d); SEM image(inset) and Cr mapping of PEI10.0-JC after adsorbing Cr(Ⅵ) (e); SEM image of PEI10.0-JC after 5 cycles of adsorption-desorption (f)
图2 JC (a)、PEI10.0-JC (b)、吸附Cr(Ⅵ)后PEI10.0-JC (c)以及吸附-洗脱5次后PEI10.0-JC (d)的FT-IR谱图
Fig.2 FT-IR spectra of JC (a), PEI10.0-JC (b), PEI10.0-JC after the adsorption of Cr(Ⅵ) (c) and the PEI10.0-JC after 5 cycles of adsorption-desorption (d)
C0 /(mg·L–1) | k /(g·mg–1·min–1) | QE/(mg·g–1) | R2 |
---|---|---|---|
100 | 3.74×10-4 | 106.3 | 0.999 |
200 | 1.69×10-4 | 196.1 | 0.998 |
表1 PEI10.0-JC对Cr(Ⅵ)吸附的准二级动力学参数
Table 1 Kinetic parameters of PEI10.0-JC toward Cr(Ⅵ) removal fitted with pseudo-second-order model
C0 /(mg·L–1) | k /(g·mg–1·min–1) | QE/(mg·g–1) | R2 |
---|---|---|---|
100 | 3.74×10-4 | 106.3 | 0.999 |
200 | 1.69×10-4 | 196.1 | 0.998 |
T/℃ | Langmuir | Freundlich | Tempkin | ||||||
---|---|---|---|---|---|---|---|---|---|
Qm | KL | R2 | KF | n | R2 | KT | b | R2 | |
30 | 474.6 | 0.038 | 0.977 | 59.0 | 2.78 | 0.960 | 1.87 | 41.3 | 0.885 |
40 | 519.7 | 0.043 | 0.983 | 70.3 | 2.82 | 0.951 | 2.50 | 39.9 | 0.856 |
50 | 550.0 | 0.045 | 0.984 | 76.5 | 2.85 | 0.924 | 1.01 | 28.5 | 0.965 |
表2 PEI10.0-JC在不同温度下等温吸附模型的拟合参数
Table 2 Isotherms parameters for the adsorption of PEI10.0-JC toward Cr(Ⅵ) at various temperatures
T/℃ | Langmuir | Freundlich | Tempkin | ||||||
---|---|---|---|---|---|---|---|---|---|
Qm | KL | R2 | KF | n | R2 | KT | b | R2 | |
30 | 474.6 | 0.038 | 0.977 | 59.0 | 2.78 | 0.960 | 1.87 | 41.3 | 0.885 |
40 | 519.7 | 0.043 | 0.983 | 70.3 | 2.82 | 0.951 | 2.50 | 39.9 | 0.856 |
50 | 550.0 | 0.045 | 0.984 | 76.5 | 2.85 | 0.924 | 1.01 | 28.5 | 0.965 |
Sample | pH | T/℃ | Qm/(mg·g-1) | Ref. |
---|---|---|---|---|
PEI/氧化石墨 | 2.0 | 35 | 50.3 | [ |
PEI/纤维素 | 2.0 | 25 | 119.4 | [ |
PEI/甲壳素 | 2.0 | 25 | 330.4 | [ |
PEI/boehmite | 3.0 | 25 | 51.1 | [ |
PEI/pineapple leaf fiber | 2.0 | 30 | 222.4 | [ |
PEI/PVA | 4.0 | 23 | 150.0 | [ |
PEI/carbon nanotube | 2.0 | 25 | 40.3 | [ |
PEI/chitosan | 3.0 | 30 | 331.3 | [ |
PEI/graphene oxide | 2.0 | 30 | 436.2 | [ |
PEI10.0-JC | 2.0 | 30 | 474.6 | 本研究 |
表3 基于PEI改性吸附剂的性能比较
Table 2 Comparison of the performance for the PEI modified adsorbents
Sample | pH | T/℃ | Qm/(mg·g-1) | Ref. |
---|---|---|---|---|
PEI/氧化石墨 | 2.0 | 35 | 50.3 | [ |
PEI/纤维素 | 2.0 | 25 | 119.4 | [ |
PEI/甲壳素 | 2.0 | 25 | 330.4 | [ |
PEI/boehmite | 3.0 | 25 | 51.1 | [ |
PEI/pineapple leaf fiber | 2.0 | 30 | 222.4 | [ |
PEI/PVA | 4.0 | 23 | 150.0 | [ |
PEI/carbon nanotube | 2.0 | 25 | 40.3 | [ |
PEI/chitosan | 3.0 | 30 | 331.3 | [ |
PEI/graphene oxide | 2.0 | 30 | 436.2 | [ |
PEI10.0-JC | 2.0 | 30 | 474.6 | 本研究 |
T/K | ΔG/(kJ·mol-1) | ΔS/(kJ·(mol·K)-1) | ΔH/(kJ·mol-1) |
---|---|---|---|
303 | -19.11 | ||
313 | -20.05 | 0.086 | 6.91 |
323 | -20.83 |
表4 PEI10.0-JC对Cr(Ⅵ)的吸附的热力学参数
Table 4 Thermodynamic parameters for the adsorption of Cr(Ⅵ) by PEI10.0-JC
T/K | ΔG/(kJ·mol-1) | ΔS/(kJ·(mol·K)-1) | ΔH/(kJ·mol-1) |
---|---|---|---|
303 | -19.11 | ||
313 | -20.05 | 0.086 | 6.91 |
323 | -20.83 |
图10 Cr(Ⅵ)吸附前、后PEI10.0-JC的全范围(a)、Cr 2p (b)和N 1s[(c)、(d)]的XPS谱图
Fig.10 Full range (a), Cr 2p (b) and N 1s [(c),(d)] XPS spectra of PEI10.0-JC before and after Cr(Ⅵ) adsorption
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