活性炭去除游离氯的失效机制及热再生研究

doi:10.11949/0438-1157.20190924

摘要/Abstract

摘要：

研究了初始游离氯浓度以及活性炭粒径和投加量等对游离氯去除的影响，并通过Boehm滴定、傅里叶转换红外光谱仪、比表面积分析仪、扫描电子显微镜、光电子能谱等手段分析了反应前后的活性炭，发现活性炭的失效主要是由于其表面还原性官能团的消耗及表面结构的氧化破坏所带来的孔结构和比表面积变化。将失效活性炭在不同气氛(氮气、氢气、氨气)条件下进行热再生，均可使其游离氯去除能力得到恢复，且氨气条件最好，这主要得益于孔结构的提升及还原性官能团的再生。将再生后活性炭进行连续流柱实验，证实其能够长时间有效运行。

关键词: 游离氯, 活性炭, 失活, 再生, 去除

Abstract:

The effects of initial free chlorine concentration, activated carbon particle size and dosage on free chlorine removal by activated carbon were studied. The activated carbon before and after the reaction was analyzed by means of Boehm titration, Fourier transform infrared spectrometer, specific surface area analyzer, scanning electron microscope, and photoelectron spectroscopy. It is found that the failure of the activated carbon was mainly due to the consumption of reductive functional groups on the surface and the oxidative destruction of the surface structure, causing the loss of pore structure and specific surface. The thermal regeneration of the spent activated carbon under different atmospheres (nitrogen, hydrogen and ammonia) can recover the removal ability on free chlorine; and the ammonia gas regeneration is the best, which is mainly due to the improvement of pore structure and the regeneration of the reductive functional groups. The performance of regenerated activated carbon in continuous flow column test was evaluated, and it was confirmed that the regenerated one can achieve an effective and long-time operation.

Key words: free chlorine, activated carbon, failure, regeneration, removal

中图分类号:

TU 991.2

刘小艳, 蔡万欣, 赵立坤, 曾香, 毛旭辉. 活性炭去除游离氯的失效机制及热再生研究[J]. 化工学报, 2020, 71(4): 1781-1790.

Xiaoyan LIU, Wanxin CAI, Likun ZHAO, Xiang ZENG, Xuhui MAO. Failure mechanism and thermal regeneration of activated carbon for free chlorine removal[J]. CIESC Journal, 2020, 71(4): 1781-1790.

图/表 12

图1 活性炭去除游离氯的影响因素

Fig.1 Influencing factors for removal of free chlorine by activated carbon

图3 失效及再生前后活性炭的氮气吸脱附曲线(a)及孔径分布(b)

Fig.3 Nitrogen absorption and desorption curves (a) and pore size distribution (b) of activated carbon and the ones after failure and regeneration

图2 游离氯去除中活性炭的失效行为

Fig.2 Failure behavior of activated carbon for free chlorine removal

表1 活性炭表面结构特性

Table 1 Surface structure characteristics of activated carbon

样品	比表面积/ (m²?g^-1)	孔容/(cm³?g^-1)	微孔/(cm³?g^-1)	中孔/(cm³?g^-1)	平均粒径/nm	元素分析/%
样品	比表面积/ (m²?g^-1)	孔容/(cm³?g^-1)	微孔/(cm³?g^-1)	中孔/(cm³?g^-1)	平均粒径/nm	C	H	N
B-AC	1512.2	0.7128	0.665	0.0478	1.8855	73.45	1.67	0.09
A-AC	999.1	0.4845	0.447	0.0375	1.9399	63.60	2.11	0.05
N_2-AC	1289.8	0.616	0.588	0.028	1.9102	66.76	2.66	0.10
H₂-AC	645.93	0.3168	0.3014	0.0154	1.9617	76.70	1.45	0.07
NH₃-AC	1186.9	0.5608	0.5355	0.0253	1.8899	67.88	1.98	1.35

图4 活性炭失效前后电镜扫描以及粒径分布

Fig.4 Electron microscopy and particle size distribution of activated carbon before and after failure

表2 活性炭表面官能团的测定结果

Table 2 Results of surface functional groups of activated carbon

样品	表面官能团/(mmol?g^-1)
样品	—OH	—COOR	—COOH	酸性官能团	碱性官能团
B-AC	0.07	0.22	0.07	0.36	0.55
A-AC	1.12	1.17	2.17	4.49	0.35
N₂-AC	0.37	0.07	—	0.44	0.45
H₂-AC	0.12	0.05	0.04	0.22	0.50
NH₃-AC	0.16	0.17	—	0.34	0.71

图5 活性炭失效及再生前后的XPS分析结果

Fig.5 XPS analysis of activated carbon before and after failure and regeneration

表3 XPS C 1s/O 1s区域拟合的结果（校正为总原子比）

Table 3 Deconvolution of XPS C1s/O1s region (corrected to total oxygen atomic percent)/%(atom)

		结合能/eV	B-AC	A-AC	N₂-AC	H₂-AC	NH₃-AC
C 1s	C—C	284.8	71.03	56.33	60.23	61.04	57.71
	C—O	286.0	16.23	14.42	17.60	8.89	11.23
	CO	287.4	0.22	1.31	0.07	3.21	6.89
	—O—CO	288.8	2.39	7.42	3.85	2.90	2.12
	总原子C/%		89.87	79.47	87.79	81.53	79.82
O 1s	CO	531.0~531.9	4.81	10.92	8.16	5.65	5.8
	C—O	533.0~533.4	4.89	7.42	7.26	4.34	6.33
	H₂O	535.2~535.4	0	1.51	2.50	1.73	2.18
	总原子O/%		9.70	19.86	17.92	11.73	14.31
O/C比			0.11	0.25	0.13	0.22	0.18

图6 活性炭失效及再生前后的FTIR谱图

Fig.6 FTIR spectra of activated carbon before and after failure and regeneration

图7 不同条件下活性炭的再生

Fig.7 Regeneration of activated carbon under different conditions

图8 柱实验结果 (插图为柱实验装置的示意图)

Fig.8 Results of column experiment (inset is schematic of column experimental setup)

表4 原始活性炭及热再生活性炭柱实验结果

Table 4 Column experimental results of original activated carbon and thermal-regenerated activated carbon

时间/d	游离氯/活性炭/ (mg?g^-1)	B-AC 出水游离氯/ (mg?L^-1)	N₂-AC出水游离氯/ (mg?L^-1)	NH₃-AC出水游离氯/(mg?L^-1)
0	0	0	0	0
3	172.8	0.6	0.2	0.4
6	345.2	1.4	0	0
7	403.2	0.4	2.4	0.2
10	576	0.4	2.8	0.4
11	633.6	0.2	4.2	1.2
14	806.4	0.6	6.8	2
15	864	8.6	—	—
17	979.2	29.2	6.7	2.8

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