摘要
活性炭是一种应用广泛的吸附剂,具有发达的空隙结构和巨大的比表面积,在环境污染处理方面,尤其是去除废水及废气中有机物方面,具有广泛的应用。随着应用范围的进一步扩大,对活性炭性能的要求也越来越高,活性炭的改性工作也在被越来越多的学者研究。
在通常的活性炭活化过程中,活性炭表面会产生一些亲水性的基团,亲水性基团和水分子在活性炭表面上的竞争性反应大大降低了活性炭对废水中有机物的吸附能力,因此具有一个合适的憎水性对于增加活性炭的应用范围具有十分重要的意义。本文从此方面着手,通过表面改性,赋予了活性炭表面一个合适的憎水性,从而增强了其在废水中吸附有机物的能力。实验表明:相比原始活性炭,改性活性炭的孔容形状和孔大小并没有显著改变。本课题研究了憎水性活性炭对亚甲基蓝的吸附能力以评估其对印染废水的吸附性能,结果表明:相比原始活性炭,改性活性炭对亚甲基蓝吸附量增加约22%。同时研究了改性活性炭对目前广泛存在的污染物-甲醛的吸附能力,结果表明:相比原始活性炭,改性活性炭在甲醛吸附过程中提高了约24%的效率。表明了通过憎水性能的改变,活性炭增强了对有机物的吸附效率。
与此同时,由于吸附过程中的放热,同时散热不及时,活性炭在空气存在的条件下容易引起燃烧,其较低的抗氧化性能限制了其在工
Active carbon (AC) is a widely used catalyst and adsorption material, boasting a developed interspaces structure and a huge surface area, having an extensive application in the aspects of environment pollution treatment,especially adsorbing the organ compounds in the waste water and the waste gas. The expanding application of AC has generated research effort on modified AC to meet some special purpose.
Previous research has show that there are many hydrophilic groups produced in the activation process on the active carbon surface. The adsorption efficiency of AC decreases because of a competitive adsorption between the water and the organic pollutes to the active sites on the active carbon surface. It is therefore clear that for efficient adsorption of an organic compound in the waste water, active carbon must be imparted with an appropriate degree of hydrophobicity. For that purpose, a surface hydrophobic active carbon is produced through a surface modification process. The modified AC shows a good hydrophobic in the adsorption of
引文
[1] 舒俭民等编,全球环境问题,贵阳,贵州科技出版社,2001,9,174-178
[2] 张春山,邵曼君,活性炭材料改性及其在环境治理中的应用,过程工程学报,2005,5(2):223-227
[3] Pavan, P. C.,Crepaldi, E. L.,Valim, J. B.,Sorption of anionic surfactants on layered double hydroxides, Colloid Interface Sci,2000,9(15)346-352
[4] Hoeft, C. E.,Zollars, R. L.,Adsorption of single anionic surfactants on hydrophobic surfaces, Colloid Interface Sci. 1996,177(1): 171-178
[5] Lin, S. H.,Chen, Y. W., Huang, J. K.,Hydrochlorofluoro carbon adsorption by granular and extruded activated carbons,Adsorption Science and Technology,1996(13):187-195
[6] 立本英机(日),安部郁夫(日)主编,高尚愚译编,活性炭的应用,南京:东南大学出版社,2002:167
[7] 张世润,东北林区活性炭工业的现状与发展前景,1996 年全国活性炭学术交流会论文集,1996:377.
[8] 贺近悟,李启基等,林产化学工业全书,北京:中国林业出版社,1997:919-1068
[9] 张义颖,张文辉,张学军等,活性炭研究与新产品开发现状,洁净煤技术,1999(5):24-26
[10] 王同华,朱英华,徐敏等,废植物炭制活性炭的研究,大连理工大学学报,1999,39(1):73-76
[11] 立木英机(日),安部郁夫(日)主编,高尚愚译编,活性炭的应用技术:其维持管理及存在问题,2002(7):17-125
[12] 马建标,李晨曦,功能高分子材料,化学工业出版社,2000:70-87
[13] 孙家跃,杜海燕,无机材料的制造与应用,化学工业出版社,2001:67-80
[14] 乔文明,刘朗,高比表而积活性炭的研究与应用,新型碳材料,1996,11(1):25-31
[15] 黄律先,木材热解工艺学,北京:中国林业出版社,1995
[16] 方智利,陈木梁,章江洪等,国内外活性炭制备发展动态,云南化工,2001,28(5):23-26
[17] JANA S et al. Effect of time and temperature of activation of coconut shell char on the surface area and bulk density of the activated carbon developed,India J,Cryog,1995,20(2):10-11
[18] K. J. Huttinger,R. Minges,Catalytic water vapor gasification of carbon:importance of melting and wetting behavior of the "catalyst" ,Fuel,1985,64(4): 491-494
[19] 乔文明等,KOH 活化动力学及活化机理初探,炭素技术,1994(1): 10-12.
[20] F. Caturla,M. Molina-Sabio,F. Rodriguez-Reinoso,Preparation of activated carbon by chemical activation with ZnCl2,Carbon,1991,29(7):999-1007
[21] 刘海燕等,高比表面积活性炭的制备及其吸附性能的初步研究,新型炭材料,1999(2):21-23
[22] 张晓听等,高表面活性炭的制备,材料科学与工程,1999,14(4):34-36
[23] Daulan C,Lyubchik S B,Rouzaud J N,et al,Infuence of Anthracite Pretreatment in The Preparation of Activated Carbons,Fuel,1998,77(6):495-502
[24] 魏娜,赵乃勤,贾威,活性炭的制备及应用研究进展,材料科学与工程学报,2003,21(5):777-780
[25] 郑经堂,张引枝,王茂章,多孔炭材料的研究进展及前景,化学进展,1996 8(3):241-251
[26] 贾金平,何翊,黄骏雄,固相微萃取技术与环境样品前处理,化学进展,1998,10(1):74-85
[27] 冯雪,贾金平,王亚林等,固相微萃取技术的研究与应用现状,化工环保,2002,22(03):146-150
[28] 贾金平,何翊,新型固相微萃取萃取纤维的研制及性能研究,化学世界,1998,04:14-21
[29] Figueriedo J L,Moulijn J A,Carbon and Coal Gasification Science and Technology,Dordreceht: Martinus Nijhoff Publishers,1986:560-582
[30] Rouzaud J N, Structure Micro texture and Optical Properties of Anthracite and Saccharine-based Carbons,Carbon,1989,27(4):517-529
[31] Stoeckli H F,Microporous Carbons and Their Characterization:The State of The Art,Carbon,1990,28(1):1-6.
[32] Walker P L,Chemistry and Phisics of Carbon,London:Edward Arnold,1966:51
[33] Smisek M,Cerny S,Active Carbon Manufacture Properties and Application,Elsevier Pub. Co.:Amsterdam,1970
[34] 齐龙,国内活性炭应用的发展趋势,吉林林业科技,2002,31(2):30-33.
[35] 曹玉登,煤制活性炭及污染治理,北京:中国环境科学出版社,1995
[36] Boehm H P,Some Aspects of the Surface Chemistry of Carbon Blacks and Other Carbons ,Carbon,1994,32(5):759-769
[37] Kienle H,Bader E,活性炭材料及其工业应用,魏同成译,北京:中国环境科学出版社,1990:7-13
[38] 杨永岗,贺福,王茂章等,炭纤维表面结构和性质的评价,炭素,1997(1):17-23
[39] 范延臻,王宝贞,活性炭表面化学,煤炭转化,2000,23(4):26-30
[40] 刘振宇,郑经堂,王茂章,活性炭纤维孔结构控制和表面改性,离子交换与吸附,1997,13(4):353-358
[41] 傅献彩,沈文霞,姚天扬编,物理化学,高等教育出版社,1990,(5),949-951
[42] Kutics K,Suzuki M, Adsorption of organics on surface treated activated carbon fibers,Hungarian Journal of Industrial Chemistry,1993,21(2):93-99
[43] 谢裕坛,活性炭吸附治理多组分有机废气的研究,浙江大学硕士学位论文,2002
[44] 兰文艺,邵刚,实用环境工程手册(水处理材料与药剂),北京,化学工业出版社,2002:18-33
[45] American Water Works Association Society of Civil Engineers,Water Treatment Plant Design,1998
[46] 汪琼,高建平,宁平等,活性炭在环境工程中的应用,云南环境科学,1999,18(1):33-35.
[47] 王宝庆,陈亚雄,宁平,活性炭水处理技术应用,云南环境科学,2002,19(3):46-48
[48] 赵启涛,陈雯,活性炭的应用与研究进展,昆明理工大学学报,2000,25(5):8-12
[49] 江琼,高建培等,活性炭在环境工程中的应用,云南环境科学,1999,18(1):33-35
[50] 郊其庚,活性炭的应用,上海,化东理工大学出版社,2002,144-148
[51] 赵雪娜,迟文澎,池金志,负载活性炭催化氧化技术及其进展,城市管理与科技,2004,6(3):111-115
[52] 傅建秀,叶平,王连生等,催化氧化法处理对硝基酚钠生产废水的研究,城市环境与城市生态,2001,14(4):40-41
[53] 蒋小平,袁先友,张敏等,活性炭负载磷钨酸催化合成烷基溴,化学试剂 2004,26(1):41-44
[54] MANUEL FERNANDO R,PEREIRA,SAMANTA F,SOAIRES,et al,Adsorption of dyes on activated Carbons; influence of surface chemical groups ,Carbon,2003,41(4):811-821
[55] Chiang Hunglung,Huang C P,Chiang P C,Effect of Metal Additives on the Physical-chemical Characteristics of Activated Carbon Exemplified by Benzene and Acetic Acid. Carbon,1999,37:1919-1928
[56] 闫联生,孟昭富,活性炭纤维的制备及性能表征,炭素,1994(4):27-30
[57] 詹亮,李开喜,朱星明等,正交实验法在超级活性炭研制中的应用,煤炭转化,2001,24(4):71-75
[58] 邢伟,张明杰,阎子峰,超级活性炭的合成及活化反应机理,物理化学学报,2002,18(4):340-345
[59] Caturla F.,Molina- Sabio M.,Rodriguez-noso F,Preparation of activated carbon by chemical activation with ZnCl2,Carbon,1991,29(7):999-1007
[60] Molina-Sabio M.,Rodriguez-Reinoso F.,Caturla F.,et al,Development of porosity in combined acid carbon dioxide activation. Carbon,1996,34(4):457-462
[61] Vinke P,van Verbree M,Voskamp A F,et al,Modification of the Surfaces of Gas-Activated Carbon and a Chemically Activated Carbon with HNO3,Carbon,1994,32(4):675-686
[62] S HAYDAR,M A FERRO-GARCIA,J RIVERA-UTRILLA,et al. Adsorption of p-nitrophenol on an activated carbon with different oxidations [J].Carbon,2003,41(3):387-395
[63] Parkand S J,Kin K D,Adsorption Behaviors Of CO2 and NH3 on Chemical Surface-treated Activated Carbons,J Colloid and Interface Science,1999,221:186-189
[64] 唐乃红等.乌柏籽壳活性炭的改性及其应用的研究.信阳师范学院学报(自然科学版),1997,10(1):78-83
[65] 王重庆,刘晓勤,姚虎卿,表面改性活性炭对 CO2 的吸附性能,南京化工大学学报,2002,22(2):63-65
[66] 白树林,赵桂英,付希贤,改性活性炭对水溶液中 Cr3+吸附的研究,化学研究与应用,2001,13(6):670-672
[67] 范顺利,孙剑辉,李红星等,改性活性炭的吸附性能变异探讨,河南师范大学学报(自然科学版),1995,23(4):48-50
[68] Menendez J.A.,Phillips J.,Xia B.,et al,On the modification of chemical surface properties of active carbon:in the search of carbon with stable basic properties.Langmuir,1996,12:4404-4410
[69] 高尚愚,安部郁夫,表面改性活性炭材料对苯酚及苯磺酸吸附的研究,林产化学与工业,1994,24(3):29-34
[70] 万福成等,活性炭富集溶液中 An(III)的研究,信阳农业高等专科学校学报,1999,9(2):39-43
[71] LOTH MONSER,NAFAA ADHOUM,Modified activated carbon for the removal of copper,zinc,chromium and cyanide from wastewater,Separation and Purification Technology,2002,26(2-3):137-146
[72] KLINIK J,GRZYBEK T,The influence of cobalt,nickl,manfanese and vanadium to active carbons on their efficiency in SO2 removal from stack gases,Fuel,1992,71(11):1303
[73] 刘慧英等,以果物核壳为原料制备活性炭及其改性研究,宁夏大学学报(自然科学版),1996,17(2):32-35
[74] 杨全红,郑经堂,刘平光等,处理气氛对 FeS04 -ACF 结构及吸附性能的影响,炭素技术,1997(3):4-7
[75] Hu ZH,Srinivasan MP,Ni YM,Novel activation process for preparing highly microporous and mesoporous activated carbons,CARBON,2001,39(6):877-886
[76] Frederick S. Baker,Wando S.C,Production of highly microporous activated carbon products,US patent,5416056,1995,5(16)
[77] 章燕豪,吸附作用,上海:上海科学技术文献出版社,1989
[78] 扬骏,黄止而,王定珠,高比表面活性炭的制备及表征,炭素技术 1994,(6):5-9
[79] 宋燕,李开喜,杨常玲等,石油焦制备高比表面积活性炭的研究,石油化工,2002,31(6):431-435
[80] 廖乾初,蓝芬兰,扫描电镜原理及应用技术,北京:冶金土业出版社,1990
[81] 德·凯利·巴德著,魏同成译,活性炭及其工业应用,北京:中国环境科学出版社,1990:43-49
[82] Kortum, G.,Vogel, W.,Andrussow, K.,Dissociation Constants of Organic Acids in Aqueous Solutions., Butterworths,London,1961
[83] Boehm, H. P.,Surface oxides on carbon and their analysis:a critical assessment,Carbon,2002,40(2):145-149
[84] 裘著革主编,杨旭,徐东群副主编,室内空气污染与健康,北京:化学工业出版社,2003:74-76
[85] 古可隆,活性炭的应用,林产化工通讯,1999,33(4):37-40