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随着社会经济的发展, 大气中氮氧化物(NOx)的浓度逐年上升, 成为空气污染的主要来源之一, 对生态系统和人类的日常生活造成了严重影响[1-2]。同时, NOx还是光化学污染、酸雨和臭氧层破坏的主要因素[3]。因此, 对NOx吸附效果的探讨已经成为近些年来研究者们深入研究的重要课题之一[4-5]。本研究主要目的是实现新风通过空调系统进入室内之前对室外空气进行过滤优化。这对于降低室内NOx浓度, 提高空气品质非常有意义[6]。
活性碳纤维较大的比表面积和丰富的微孔结构使其对空气中的污染物具有很强的吸附能力[7]。活性碳纤维的应用已经体现在电子工业、医疗、水处理、气体处理等各个方面, 尤其是对大气中污染气体的吸附处理方面已经成为科学研究的热点[8-9]。同时, 有研究[10-11]发现将活性碳纤维表面进行改性之后, 其吸附能力将大幅度提高。因此, 研究者们逐渐将研究方向转为改性活性碳纤维的应用, 尤其在污水处理和气体净化方面。有研究[12]发现, 经改性后活性碳纤维处理过的水中苯类化合物质量浓度完全可以达到国家一级排放标准; 活性碳纤维经硫酸亚铁溶液改性后对磷的去除能力大大提高, 从而能够处理高质量的含磷废水[13]; 将活性碳纤维表面用热处理法进行改性后, 对二氧化硫的脱除效率明显升高; 用浸渍硝酸铜的方法对活性碳纤维改性发现其脱氮效率明显提高, 从而可以将其应用到汽车尾气处理中[14]。
目前针对定量研究改性活性碳纤维对氮氧化物的吸附效果研究相对较少。本研究主要涉及定量研究室外NOx初始浓度, 过滤器处风速和温度等影响因素对改性前后活性碳纤维吸附效率的影响。此外, 进行了扫描电子显微镜(SEM), 傅里叶变换红外光谱(FT-IR), X射线光电子能谱(XPS)和比表面积及孔隙度自动分析(BET)性质表征, 分析了改性前后活性碳纤维的表面结构和表面性质变化。
浸渍改性活性碳纤维吸附氮氧化物性能
NOx adsorptive performance by impregnated activated carbon fibers
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摘要: 为实现新风在通过空调进入室内前已被优化的目的, 搭建了一套开式循环系统。通过对活性碳纤维进行浸渍改性, 采用比表面测定、SEM观察、XPS分析、傅里叶变换红外谱图分析对改性前后活性碳纤维进行了表征; 定量研究了室外氮氧化物初始浓度、温度和风速等环境因素对改性前后活性碳纤维吸附氮氧化物效率的影响。结果表明, 改性对活性碳纤维表面活性官能团种类、含氧官能团数量、表面微观结构及比表面积等特性均有显著影响, 提高了其对氮氧化物的吸附效率; 室外初始浓度、风速、温度对改性前后活性碳纤维吸附氮氧化物效率的变化趋势基本一致; 改性前后活性碳纤维对氮氧化物的吸附率随初始浓度的升高而逐渐降低, 随过滤器处风速增大先升高后降低, 随过滤器处温度的升高先升高后降低。改性后活性碳纤维对空气中氮氧化物的吸附率明显提高, 可以将其应用于空调系统中。Abstract: In order to realize the optimization of fresh air before it enters the room through the air conditioning, an open circulation system was set up. Modified activated carbon fibers were prepared by impregnation method, and BET, SEM, XPS and FT-IR were used to characterize the pristine and modified fibers. The effects of outdoor initial NOx concentration, wind speed and temperature at the core filter on NOx adsorption effect were quantitatively studied. The results show that the modification had significant effects on the surface functional group, the number of oxygen-containing functional groups, the surface microstructure and specific surface area of the activated carbon fibers, and improves its removal efficiency of NOx. The initial NOx concentration, wind speed and temperature presented the same effect trend in NOx adsorption efficiency on activated carbon fibers before and after modification. NOx removal rate by pristine and impregnated activated carbon fiber decreased with the increase of initial NOx concentration, and increased first and then decreased with the increase of wind speed or temperature at the filter. The maximum NOx removal rate by modified activated carbon fiber was 60%. Thus it can be applied to an air conditioning system.
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表 1 活性碳纤维改性前后孔结构分布
Table 1. Pore structure distribution of ACF and N-ACF
样品 比表面积/(m2·g-1) 孔容/(cm3·g-1) 平均孔径/nm N-ACF 488.84 0.32 3.34 ACF 110.52 0.06 4.51 表 2 活性碳纤维改性前后表面C1s、O1s和N1s含量
Table 2. C1s, O1s and N1s content on ACF and N-ACF surface
% 样品 O1s元素含量 C1s元素含量 N1s元素含量 531.26 eV 531.58 eV 284.16 eV 283.95 eV 400.25 eV 401.24 eV N-ACF 26.81 0.79 50.69 12.19 2.06 0.70 ACF 14.00 0.39 60.27 20.46 1.31 0.45 -
[1] KUBIE L, PARKINSON B A. Photosensitization of single-crystal oxide substrates with quantum confined semiconductors[EB/OL]. [2018-08-27]. https://pubs.acs.org.ccindes.cn/doi/10.1021/acs.langmuir.8b00720. [2] MOCHIDA I, KORAI Y, SHIRAHAMA M, et al. Removal of SOx and NOx over activated carbon fibers[J]. Carbon, 2000, 38(2): 227-239. doi: 10.1016/S0008-6223(99)00179-7 [3] FU Y, ZHANG Y, LI G, et al. NO removal activity and surface characterization of activated carbon with oxidation modification[J]. Journal of the Energy Institute, 2016, 34(37): 183-194. [4] GUO J X, LIANG J, CHU Y H, et al. Desulfurization activity of nickel supported on acid-treated activated carbons[J]. Applied Catalysis A: General, 2012, 421-422(15): 142-147. [5] WANG M, LIU H, HUANG Z H, et al. Activated carbon fibers loaded with MnO2 for removing NO at room temperature[J]. Chemical Engineering Journal, 2014, 256(6): 101-106. [6] 刘鹤年, 黄正宏, 王明玺, 等.常温下沥青基活性炭纤维对NO的催化氧化性能[J].化工学报, 2011, 62(2): 369-373. [7] SVETLANA B, BANDOSZ T J. The effects of urea modification and heat treatment on the process of NO2 removal by wood-based activated carbon[J]. Journal of Colloid and Interface Science, 2009, 333(1): 97-103. doi: 10.1016/j.jcis.2009.01.052 [8] WANG Y, GE C Z, ZHAN L, et al. MnOxCeO2/ activated carbon honeycomb catalyst for selective catalytic reduction of NO with NH3 at low temperatures [J]. Industrial & Engineering Chemistry Research, 2012, 51(36): 11667-11673. [9] BOYANO A, G LVEZ M E, L ZARO M J, et al. Characterization and kinetic study of carbon-based briquettes for the reduction of NO[J]. Carbon, 2006, 44(12): 2399-2403. doi: 10.1016/j.carbon.2006.05.032 [10] 李国亭, 冯艳敏, 柴晓琪, 等.镧改性活性炭纤维高效吸附去除对苯醌[J].环境工程学报, 2016, 10(4): 1638-1644. [11] 王秀丽, 盛义平.活性炭纤维的改性及对Cu2+吸附性能影响的研究[J].环境科学与管理, 2012, 37(5): 94-96. doi: 10.3969/j.issn.1673-1212.2012.05.026 [12] 赵谦, 李春香, 王晓红, 等.改性活性炭纤维及处理硝基苯废水的应用[J].江苏大学学报(自然科学版), 2005, 26(1):76-79. doi: 10.3969/j.issn.1671-7775.2005.01.019 [13] 杨晶, 岳钦艳, 李颖, 等.改性活性碳纤维在含磷废水中的应用[J].山东大学学报(工学版), 2008, 38(1): 92-95. [14] 岳彩霞.表面改性的活性炭纤维在气体净化中的应用[J].当代化工研究, 2017(2): 24-25. doi: 10.3969/j.issn.1672-8114.2017.02.014 [15] 国家环境保护局.环境空气氮氧化物(一氧化氮和二氧化氮)的测定盐酸萘乙二胺分光光度法: HJ 479-2009[S].北京: 中国环境科学出版社, 2009. [16] 贾民选.活性炭纤维的应用与开发[J].图书情报导刊, 2004, 14(11): 205-206. doi: 10.3969/j.issn.1005-6033.2004.11.124 [17] 牟军, 马艳, 袁媛.盐酸萘乙二胺法测定大气中氮氧化物影响因素分析[J].低碳世界, 2017(7): 18-19. [18] 吴美玲.活性炭纤维的吸附性能研究与应用[J].广州化工, 2015, 43(9): 39-40. doi: 10.3969/j.issn.1001-9677.2015.09.016 [19] 张金萍.活性炭纤维净化装置对室内污染气体去除效果的研究[J].建筑科学, 2016, 32(12): 119-126. [20] 刘义, 曹子栋, 唐强, 等.有效脱附在活性炭法烟气脱硫中的作用[J].西安交通大学学报, 2003, 37(1): 98-101. [21] 许绿丝.改性处理活性炭纤维吸附氧化脱除SO2/NOx/Hg的研究[D].武汉: 华中科技大学, 2007. http://cdmd.cnki.com.cn/Article/CDMD-10487-2009033812.htm [22] 王启芬.聚丙烯腈纤维结构及其形成过程的研究[D].济南: 山东大学, 2010. http://cdmd.cnki.com.cn/Article/CDMD-10422-2010100356.htm [23] 胡晓敏, 刘华章.活性炭纤维及其在催化中的应用[J].工业催化, 2005, 13(1): 1-4. doi: 10.3969/j.issn.1008-1143.2005.01.001 [24] 丁春生, 彭芳, 黄燕, 等.硝酸改性活性炭的制备及其对Cu2+的吸附性能[J].金属矿山, 2011, 40(10): 135-138. [25] 李善评, 李冲, 连军锋, 等.活性炭纤维的改性及其表面特性对挂膜启动的影响[J].水处理技术, 2009, 35(8): 80-83. [26] 任建莉, 陈俊杰, 罗誉娅, 等.活性炭纤维脱除烟气中气态汞的试验研究[J].中国电机工程学报, 2010, 30(5): 28-34. [27] 章冬冬, 蒋新, 郭森, 等.硝酸改性活性炭纤维负载TiO2及其催化降解甲苯性能[J].化学反应工程与工艺, 2013, 29(2):125-133. [28] LSZL K, TOMB C Z E, JOSEPOVITS K. Effect of activation on the surface chemistry of carbons from polymer precursors[J]. Carbon, 2001, 39(8): 1217-1228. doi: 10.1016/S0008-6223(00)00245-1 [29] BINIAK S, SZYMAŃSKI G, SIEDLEWSKI J, et al. The characterization of activated carbons with oxygen and nitrogen surface groups[J]. Carbon, 1997, 35(12): 1799-1810. doi: 10.1016/S0008-6223(97)00096-1 [30] JANSEN R J J, BEKKUM H V. XPS of nitrogen-containing functional groups on activated carbon[J]. Carbon, 1995, 33(8):1021-1027. doi: 10.1016/0008-6223(95)00030-H [31] HUANG M C, TENG H. Nitrogen-containing carbons from phenol-formaldehyde resins and their catalytic activity in NO reduction with NH[J]. Carbon, 2003, 41(5): 951-957. doi: 10.1016/S0008-6223(02)00436-0 [32] JU S, CHUN-HU L I, MIAO M Q, et al. Surface characterization and SO2 removal activity of activated semi-coke with heat treatment[J]. New Carbon Materials, 2008, 23(1): 37-43. doi: 10.1016/S1872-5805(08)60011-6 [33] HONTORIA-LUCAS C, LPEZ-PEINADO A J, LPEZ-GONZ LEZ J D D, et al. Study of oxygen-containing groups in a series of graphite oxides: Physical and chemical characterization[J]. Carbon, 1995, 33(11): 1585-1592. doi: 10.1016/0008-6223(95)00120-3 [34] BOEHM H P. Surface oxides on carbon and their analysis: a critical assessment[J]. Carbon, 2002, 40(2): 145-149. doi: 10.1016/S0008-6223(01)00165-8 [35] 庞成勇, 李玉平.用活性炭吸附法脱除氮氧化物的研究[J].能源环境保护, 2006, 20(6): 38-41. doi: 10.3969/j.issn.1006-8759.2006.06.012