活性炭纤维氧化改性后的脱硫性能

doi:10.16085/j.issn.1000-6613.2019-0305

摘要/Abstract

摘要：

为了将活性炭纤维（ACF）应用于空调领域实现新风的过滤优化以及提高吸附极性分子SO₂的效率，对ACF进行液相氧化改性制成了具有极性的折叠式复合体滤网，并进行了SEM、BET和FTIR分析；搭建了直流式系统实验台，选用甲醛吸收-副玫瑰苯胺分光光度法检测室外空气进入滤网前后SO₂的浓度，定量研究了在不同初始SO₂浓度下改性前后滤网的动态脱硫效率。结果表明：① ACF经HNO₃氧化改性处理后，表面微观结构有显著变化，比表面积、孔容、孔径分别由653.70m²/g、0.43cm³/g、2.64nm降低至488.84m²/g、0.32cm³/g、2.58nm，O—H和C—O的透射率分别由96%、95%降低至65.5%、75%，即表面酸性含氧官能团（羟基、羧基和醚基）含量增加；② 改性前后ACF对低浓度SO₂的平均动态脱硫效率分别为33%和75%，即改性后ACF的表面极性增强，滤网的动态脱硫效率提高了42%，应用于空调过滤网可有效改善室内空气品质。

关键词: 活性碳纤维, 液相氧化, 直流式系统, 吸附, 二氧化硫

Abstract:

In order to apply activated carbon fiber (ACF) to air conditioning field to optimize the filtration of fresh air and improve the adsorption efficiency of ACF on polar molecule SO₂, ACF was modified by liquid phase oxidation to make polar fold-type complex filter，which were characterized by SEM、BET and FTIR. A direct air system test bench was established. The formaldehyde absorption-pararosaniline spectrophotometric method was used to detect the concentration of SO₂before and after outdoor air enters the fold-type complex filter. The dynamic desulfurization efficiency of unmodified ACF and modified ACF with different initial SO₂ concentrations was studied quantitatively. The results showed that (1) after HNO₃ oxidation modification, the surface microstructure of ACF was significantly changed. The specific surface area, pore volume and pore diameter respectively decreased from 653.70m²/g, 0.43cm³/g and 2.64nm to 488.84m²/g, 0.32cm³/g and 2.58nm. The transmittance of O—H and C—O decreased from 96% and 95% to 65.5% and 75% respectively, namely the content of surface acidic oxygen-containing functional groups (hydroxyl, carboxyl and ether group) increased. (2) The average dynamic desulfurization efficiency of unmodified ACF and modified ACF at low SO₂concentration was 33% and 75%, respectively, i.e., due to the enhancement of ACF surface polarity, the dynamic desulfurization efficiency was increased by 42%, which can be used in air conditioning filter to improve indoor air quality effectively.

Key words: activated carbon fiber, liquid phase oxidation, direct air system, adsorption, sulfur dioxide

中图分类号:

TU834.8

张兴惠,杨姣姣,都亚茹. 活性炭纤维氧化改性后的脱硫性能[J]. 化工进展, 2019, 38(11): 5151-5157.

Xinghui ZHANG,Jiaojiao YANG,Yaru DU. Desulfurization performance of activated carbon fiber after oxidation modification[J]. Chemical Industry and Engineering Progress, 2019, 38(11): 5151-5157.

图/表 9

参考文献 22

1	HOLGATE S T . Every breath we take: the lifelong impact of air pollution — A call for action[J]. Clinical Medicine, 2017, 17 (1): 8-12.
2	NIKNADDAF S , ATKINSON J . D , SHARIATY P , et al . Heel formation during volatile organic compound desorption from activated carbon fiber cloth[J]. Carbon, 2016, 96: 131-138.
3	GAUR V , SHARMA A , VERMA N . Preparation and characterization of ACF for the adsorption of BTX and SO₂ [J]. Chemical Engineering and Processing, 2006, 45(1):1-13.
4	邹洋, 夏凌风, 王运东, 等 . 燃煤电厂烟气脱硫技术最新进展[J]. 化工进展, 2011, 30(s1): 702-708.
	ZOU Yang , XIA Lingfeng , WANG Yundong , et al . Recent advances in flue gas desulphurization in coal fired power plant[J]. Chemical Industry and Engineering Progress, 2011, 30 (s1): 702-708.
5	SHI Wenxiao , CHEN Lin , WEI Chen , et al . Environmental effect of current desulfurization technology on fly dust emission in China[J]. Renewable & Sustainable Energy Reviews, 2017, 72: 1-9.
6	王光培 . 探讨大气环境中影响甲醛法测定二氧化硫标准曲线斜率的因素[J]. 环境与发展, 2017, 29 (7): 135.
	WANG Guangpei . The factors influencing the slope of standard curve of sulfur dioxide influencing formaldehyde method in atmospheric environment were discussed[J]. Environment and Development, 2017, 29 (7): 135.
7	陆益民, 梁世强 . 活性炭纤维化学改性的研究现状与展望[J]. 合成纤维工业, 2004, 27 (5): 33-36.
	LU Yimin , LIANG Shiqiang . Research status and prospect of chemical modification of activated carbon fiber[J]. Synthetic Fiber Industry, 2004, 27 (5): 33-36.
8	袁艳梅, 陈长安, 张丽, 等 . 活性碳纤维改性技术研究进展[J]. 化工环保, 2009, 29 (4): 331-334.
	YUAN Yanmei , CHEN Chang’an , ZHANG Li , et al . Research progresses in modification of activated carbon fiber[J].Environmental Protection of Chemical Industry, 2009, 29 (4): 331-334.
9	张金萍, 李德生 . 活性炭纤维过滤器在室内空气净化中的试验研究[J]. 环境工程, 2000, 18 (5): 32-35.
	ZHANG Jinping , LI Desheng . Experimental study of activated carbon fiber filter in indoor air purification[J]. Environmental Engineering, 2000, 18 (5): 32-35.
10	梅凡民, 傅成诚, 杨青莉, 等 . 活性炭表面酸性含氧官能团对吸附甲醛的影响[J]. 环境污染与防治, 2010, 32 (3): 18-22.
	MEI Fanmin , FU Chengcheng , YANG Qingli , et al . The effect of acid functional groups of modified activated carbon on formaldehyde absorption[J]. Environmental Pollution & Control, 2010, 32(3):18-22.
11	黄华存 . 活性碳纤维低温选择性催化还原NO的机理研究进展[J]. 化工进展, 2011, 30 (7): 1478-1481.
	HUANG Huacun . Research advance in mechanism of low-temperature SCR of NO on carbon materials[J]. Chemical Industry and Engineering Progress, 2011, 30(7):1478-1477.
12	CLOIREC Pierre Le . Adsorption onto activated carbon fiber cloth and electrothermal desorption of volatile organic compound (VOCs): a specific review[J]. Chinese Journal of Chemical Engineering, 2012, 20 (3): 461-468.
13	孟冠华, 李爱民, 张全兴 . 活性炭的表面含氧官能团及其对吸附影响的研究进展[J]. 离子交换与吸附, 2007, 23 (1): 88-94.
	MENG Guanhua , LI Aimin , ZHANG Quanxing . Research progress on surface oxygen-containing functional groups of activated carbon and adsorption effects[J]. Ion Exchange and Adsorption, 2007, 23 (1): 88-94.
14	高首山, 邓景屹, 刘文川 . 活性碳纤维的化学改性[J]. 辽宁科技大学学报, 2000, 23 (6): 406-409.
	GAO Shoushan , DENG Jingyi , LIU Wenchuan . Chemical modification of activated carbon fiber[J]. Journal of Liaoning University of Science and Technology, 2000, 23 (6): 406-409.
15	许绿丝 . 改性处理活性炭纤维吸附氧化脱除SO₂/NO _x /Hg的研究[D]. 武汉: 华中科技大学, 2007.
	XU Lusi . Adsorption and oxidation of SO₂/NO _x /Hg by modified activated carbon fibers[D]. Wuhan: Huazhong University of Science and Technology, 2007.
16	宋华, 王璐, 张娇静, 等 . 氧化铁改性活性炭的制备及其吸附脱硫性能[J]. 化工进展, 2013, 32 (3): 639-644.
	SONG Hua , WANG Lu , ZHANG Jiaojing , et al . Adsorption of H₂S by iron oxide modified activate carbon[J]. Chemical Industry and Engineering Progress, 2013, 32 (3): 639-644.
17	师杰, 赵志伟, 崔福义, 等 . 化学改性强化活性炭纤维吸附重金属离子[J]. 哈尔滨工业大学学报, 2016, 48 (8):102-107.
	SHI Jie , ZHAO Zhiwei , CUI Fuyi , et al . Enhancement of heavy metals adsorption on activated carbon fibers by chemically modification[J]. Journal of Harbin Institute of Technology, 2016，48 (8): 102-107.
18	冒爱琴, 王华, 谈玲华, 等 . 活性炭表面官能团表征进展[J]. 应用化工, 2011, 40 (7): 1266-1270.
	MAO Aiqin , WANG Hua , TAN Linghua , et al . Research progess in characterization of functional groups on activated carbon[J]. Applied Chemistry, 2011, 40 (7): 1266-1270.
19	李娜, 朱健, 查庆芳 . 活性炭表面基团的定性和定量分析[J]. 高等学校化学学报, 2012, 33 (3): 548-554.
	LI Na , ZHU Jian , ZHA Qingfang . Qualitative and quantitative analysis of surface groups of activated carbon[J]. Chemistry Journal of Chinese Universities, 2012, 33 (3): 548-554.
20	SHIN S , JANG J , YOON S H , et al . A study on the effect of heat treatment on functional groups of pitch based activated carbon fiber using FTIR[J]. Carbon, 1997, 35 (12): 1739-1743.
21	谢捷鸿, 彭晓峰 . 活性碳纤维的SO₂和NO脱除特性[J]. 东莞理工学院学报, 2006, 13 (4): 117-124.
	XIE Jiehong , PENG Xiaofeng . Removal characteristics of SO₂ and NO in activated carbon fiber[J]. Journal of Dongguan University of Technology, 2006, 13 (4): 117-124.
22	环境保护部 . 环境空气二氧化硫的测定甲醛吸收-副玫瑰苯胺分光光度法: HJ482—2009[S]. 北京: 中国环境科学出版社，2009．
	Ministry of Environmental Protection . Ambient air Determination of sulfur dioxide Formaldehyde absorption-Pararosaniline spectrophotometric method: HJ482—2009[S]. Beijing: China Environmental Science Press, 2009.

序号	波数/cm^-1	引起吸收的主要基团	官能团	ACF透射率/%	mACF透射率/%
1	3418	O—H伸缩振动	酚羟基，羧基	96	65.5
2	1632	CC伸缩振动	烯烃，苯环	99	88
3	1000～1250	CH₂—O—CH₂中的C—O伸缩振动	醚基	95	75
4	867	C—H面外弯曲振动	烯烃	100	95
5	500～650	C—C伸缩振动	芳香氢	95	84

序号	波数/cm^-1	引起吸收的主要基团	官能团	ACF透射率/%	mACF透射率/%
1	3418	O—H伸缩振动	酚羟基，羧基	96	65.5
2	1632	CC伸缩振动	烯烃，苯环	99	88
3	1000～1250	CH₂—O—CH₂中的C—O伸缩振动	醚基	95	75
4	867	C—H面外弯曲振动	烯烃	100	95
5	500～650	C—C伸缩振动	芳香氢	95	84

序号	采样点	空气平均温度/℃	A	A ₀	实测ρ(SO₂)/μg·m^-3	温度校正ρ(SO₂)/μg·m^-3	η/%
1	q	7.5	0.0563	0.0282	118.38	131.53	35.58
	h	15.7	0.0459	0.0282	80.50	84.73
2	q	6.2	0.0432	0.0247	82.20	91.33	32.72
	h	12.8	0.0366	0.0247	58.38	61.45
3	q	7.5	0.0583	0.0250	138.66	154.06	30.08
	h	14.3	0.0483	0.0250	102.33	107.71
4	q	6.8	0.0317	0.0224	56.07	62.30	30.57
	h	14.5	0.0271	0.0224	35.77	37.65
5	q	7.8	0.0514	0.0261	107.16	119.07	35.12
	h	16.5	0.0421	0.0261	73.39	77.25
6	q	8.2	0.0354	0.0256	48.33	53.70	32.85
	h	17.9	0.0315	0.0256	34.26	36.06
7	q	7.4	0.0576	0.0275	125.50	139.44	33.69
	h	16.7	0.0472	0.0275	87.85	92.47

序号	采样点	空气平均温度/℃	A	A ₀	实测ρ(SO₂)/μg·m^-3	温度校正ρ(SO₂)/μg·m^-3	η/%
1	q	7.5	0.0563	0.0282	118.38	131.53	35.58
	h	15.7	0.0459	0.0282	80.50	84.73
2	q	6.2	0.0432	0.0247	82.20	91.33	32.72
	h	12.8	0.0366	0.0247	58.38	61.45
3	q	7.5	0.0583	0.0250	138.66	154.06	30.08
	h	14.3	0.0483	0.0250	102.33	107.71
4	q	6.8	0.0317	0.0224	56.07	62.30	30.57
	h	14.5	0.0271	0.0224	35.77	37.65
5	q	7.8	0.0514	0.0261	107.16	119.07	35.12
	h	16.5	0.0421	0.0261	73.39	77.25
6	q	8.2	0.0354	0.0256	48.33	53.70	32.85
	h	17.9	0.0315	0.0256	34.26	36.06
7	q	7.4	0.0576	0.0275	125.50	139.44	33.69
	h	16.7	0.0472	0.0275	87.85	92.47

序号	采样点	空气平均温度/℃	A	A ₀	实测ρ(SO₂)/μg·m^-3	温度校正ρ(SO₂)/μg·m^-3	η/%
1	q	6.3	0.0484	0.0280	88.47	98.30	70.11
1	h	12.7	0.0323	0.0280	27.91	29.38
2	q	6.7	0.0344	0.0241	50.23	55.82	75.77
2	h	13.1	0.0245	0.0241	12.85	13.52
3	q	6.5	0.0526	0.0290	100.78	111.97	78.11
3	h	12.3	0.0321	0.0290	23.29	24.52
4	q	7.3	0.0553	0.0254	125.24	139.16	70.96
4	h	13.5	0.0324	0.0254	38.40	40.42
5	q	8.5	0.0602	0.0280	134.89	149.88	73.71
5	h	17.5	0.0346	0.0280	37.43	39.40
6	q	7.8	0.0403	0.0247	70.93	78.82	71.52
6	h	14.6	0.0273	0.0247	21.33	22.45
7	q	8.4	0.0327	0.0224	60.67	67.41	80.57
7	h	12.7	0.0221	0.0224	12.44	13.10