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高氟废水除氟实验研究
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摘要
氟是人体必需的微量元素之一,饮用水适宜的氟浓度为0.5~1mg/L。水中氟含量超过1ppm。能够使居民患“斑状齿”。如浓度达4~6ppm,小儿将全部都患“斑状齿”,浓度再高还能导致严重的佝偻病,甚至导致氟中毒。我国氟化工行业产生的高氟废水的处理技术还不成熟,主要存在基建投资大、运行费用高、处理效果不稳定的缺点。本课题针对有机氟化工行业产生的酸性高浓度含氟废水,研究了石灰沉降法和吸附法除氟,为高氟废水的治理提供新的治理方法。
     论文在钙盐混凝沉降法除氟研究中,通过一系列试验,确定了最佳运行工艺参数及操作条件,探明了同离子效应,回流污泥等影响因素的作用,建立了氟去除化学动力学方程。西安金珠近代公司是一家有机氟化工公司,该公司在生产中产生大量的强酸性高氟废水,废水中[F~-]=3000mg/L左右,pH=0.8。该公司在应用本部分实验结果替代其原设计方案后,处理运行效果好,出水水质稳定在10mg/L以下,大大减少其基建投资费,且操作简单。
     同时在对活性氧化铝吸附除氟研究中,探索了活性氧化铝活化与再生条件,明确了影响活性氧化铝除氟的因素及影响程度,确定了连续处理的工艺控制条件,研究了活性氧化铝除氟的吸附等温线和吸附速度。
     论文还对流化床诱导结晶法除氟进行了研究。在流化床诱导结晶法除氟研究中,确定了以磷灰石为结晶核的氟化钙结晶过程中的最佳工艺参数。
     实验研究表明,采用钙盐混凝沉降法处理强酸陸高氟废水,在钙离子投加量为0.25mol/L,即钙离子与原水中氟离子摩尔浓度比[Ca~(2+)]/[F~-]为1.75,硫酸铝投加量为400~600mg/L,聚丙烯酰胺的投加量为2mg/L,pH控制在9左右条件下,出水完全能够达到《污水综合排放标准》GB8978—96中一级排放标准10mg/L以下,去除率为99.8%;回流氟化钙污泥对处理氟浓度高达3000mg/L左右的废水没有效果,但对于40mg/L以下的低浓度含氟废水非常有效;除氟反应中,氟浓度衰减速率符合三级动力学方程。采用流化床诱导结晶法处理强酸性高氟废水,当pH=7~9、进水[Ca~(2+)]/[F~-]摩尔浓度比控制在1~1.3、进水[F~-]负荷控制在2kg[F~-]/m~2·h、水力负荷35~50m/h条件下,出水[F~-]稳定在5mg/L以下。采用活性氧化铝吸附法处理低浓度含氟废水,
    
    活性氧化铝在25OC时的吸附等温线符合Lan脚lulr吸附等温式q。二
    1 .035C
    l+0 .246C
    活性氧化铝
    的吸附量随活性氧化铝粒径的减小而显著增加,在pH值今~9的范围内,吸附量随着PH值的
    增大而略有减小;连续运行的停留时间对处理效果起决定性作用,吸附曲线的推移速度与水流
    流速、原水浓度有关。
The fluorine is one of necessary nutritional trace element for human health. Drinking water with 0.5~1mg/L concentration of fluoride is fit. But when excess fluorine is absorbed by body it can lead to "Dental Fluorosis" When the fluoride concentration reached 4~6ppm, even caused fluorosis. In our country, the technology of fluoride removal from high fluoride-containing wastewater in the chemical combination industry has not grown up. The main disadvantage of the technology is high equipment charge, high running fee and disposal effect instability. In this paper, studying on fluoride removal by lime and alumina , to provide a new method for fluoride removal from high fluoride-containing wastewater.
    In the research of removing fluoride by lime sedimentation method, by arranging a series experiment, confirm the optimal process parameter and manipulating conditions, establish chemical kinetics equation on the fluoride removal, study the effect of reflux CaF2 sludge. Xi'an Jinzhu jindai is a fluoride chemical combination company, during the produce process , which send out a lot of acidic and containing high fluoride wastewater, the wastewater containing fluoride 3000mg/L and pH0.8. After the company applying the result of this part experiment, the fluoride containing reduced to below 10mg/L.
    In the research on the use of activated alumina removal fluoride, explore the parameter of activated alumina activation and regeneration. Definitude the effect factor that influence activated alumina removal fluoride, get the consecutive diposal process dominating factor, study the adsorption isotherm of activated alumina and the rate of the adsorption.
    Fluoride can be removal from wastewater by growing crystals in a fluidized-bed reactor.Optimal conditions for crystallizing have been investigated on a laboratory scale pellet reactor initially seeded with phosphorite.
    In this paper, the study of using calcium salt coagulant and precipitation method disposal high
    
    
    acidic and high furoride-containing wastewater state that when the [Ca2+]=10g/Lm, that is afflux [Ca2+]/[F]=1.75, adding A12(SO4)3 400~600mg/L and PAM 2mg/L, pH controlled at 9, the fluoride in the wastewater can be reduced to below 10mg/L,which fit the regulate let out concentration hi the "Generalized Sewage let out Criterion" (GB8979-96). Reflux CaF2 sludge is inefficient to the fluoride concentration at 3000mg/L, but to the fluoride concentration at 40mg/L is useful. The results indicated that rate of fluoride removal with the kinetics equation of third order reaction in precipitation reaction. The study of fluoride removal by growing crystals in a fluidized-bed indicate that with an effluent-pH of 7-9, a [Ca2+]/[F~] feeding ratio of l~1.3mol/mol,an fluoride-load of less 2kg F per square meter reactor cross-section per hour and a hydraulic load of 35~50m/h,the effluent fluoride concentration was below 5mg/L. The study on fluoride removal by activated alumina state that there are many factors influencing
    the adsorption capacity. The adsorption isotherm of activated alumina conforms to Langmuir adsorption equation as qe = 1.035Ce/l + 0.246Ce in 25 C. The adsorption capacity decreases with pH, as pH varies from 4 to 9. In the continuous-flow column experiment,the contact-time is a very important factor, the pull-down speed of adsorption curve in the continuous-flow column is related to the concentration and flow rate of the raw water.
引文
[1] 张自杰主编,张忠祥,龙腾锐等:废水处理理论与设计,中国建筑工业出版社,284—286,2003.2;
    [2] J.W.帕特森(美):工业废水处理技术手册,化学工业出版社,145—148,1985;
    [3] Machoy Mokrzynska: A. Fuorine in toxicology, medicine, and environment protection, Fluorine Vol. 32, No. 4 248~250, 1999;
    [4] 王聪玲:地方性氟病,农村生态环境学报,Vol.11,No.3,3—5,1995;
    [5] 任何江:氟与人体健康[J],化学世界,Vol.39,No.8,7—9,1998;
    [6] Pathasarathy N, Buffle J,et al. Conbined use of calcium sails wastewater. Water Research, Vol.29, No. 4 443~448,1996;
    [7] 唐锦涛等:萤石矿高氟废水处理,环境化学,Vol.9,No.3,20~24,1990;
    [8] 李雪玲,刘俊峰,李培元:石灰沉淀法除氟的应用,水处理技术,Vol.26, No.6,2000;
    [9] 武丽敏,钱振华:含F~-工业废水处理的一种新方法,工业水处理Vol.15 No.3,20~22,1995;
    [10] 阎秀芝:CaCl_2磷酸盐法处理含氟废水的探讨,环境保护科学,Vol.24 No.2,12~24,1998;
    [11] 王凤鸣,王东:含氟饮用矿泉水中氟的净化工艺,水处理技术,Vol.22,NO.4,223~226,1996;
    [12] 马艳然等:粉煤灰处理含氟废水,水处理技术,Vol.19,No.6,355~359,1993;
    [13] 刘士荣、杨爱云:硫酸铝混凝处理磷肥厂高氟废水数学模型,水处理技术,Vol.18,No.2,96~101,1992;
    [14] Bose O, Kemnitz, et al. XPS analysis of AIF_3 phaseith Al successively substituted by Mg to used for heterogeneously catalyzed Cl/F exchange reactional Appl Surf Sci, Vol. 120, No. 10, 181~190, 1997;
    [15] 卢建杭:铝盐混凝剂水解聚合形态分析及混凝机理研究,杭州,浙江大学博士学位论文,1999;
    [16] 卢建杭、刘维屏、郑巍:铝盐混凝去除氟离子的作用机理探讨,环境科学学报,Vol.20,No.6,709—713,2000;
    [17] 李茂松等,含镍电镀废水处理及回用技术,给水与废水处理国际会议论文集,488—494,1994,7;
    
    
    [18] 唐维学等:铝型材厂含氟废水的除氟工艺研究[J],工业水处理,Vol.20,N0.10,19~20,2000;
    [19] 周琪:含氟废水治理研究进展,给水排水Vol.28,No.12,2002:
    [20] 石荣,王承智:含高氟废水处理方法的研究,辽宁师专学报Vol.3,No.3,2001;
    [21] Mooney. G.A. Nogueira. and D. Cope:Two-stage Lime Treatment in practice, Eviron. Prog, 1274~280,1982;
    [22] 谢祖芳,周能,陈渊:含氟废水处理研究与应用,玉林师范学院(自然科学),Vol.23,No.3,66_69,2002;
    [23] 卢建杭等:铝盐混凝法去除氟离子的一般作用规律,化工环保,Vol.20,No.6,7—11,2000;
    [24] 凌波:铝盐混凝沉淀除氟[J],水处理技术,Vol.16,No.6,418—42l,1993;
    [25] 白卯娟,娄性义,王珂:含氟水治理方法的分析,青岛建筑工程学院学报,Vol.23,No.1,85—88,2002:
    [26] Etoh. Y, and T. Takadoi: "Treatment of Waste Water Containing Fluoride and Boron Compounds", Chem, Abstr, 87(1987);341;
    [27] ParthasarathyN, BuffleJ, et al:Study of Interaction of Polymeric Aluminum Hydroxide with Fluoride[J], Can. J. Cham., VOL. 64, NO.1,24—30,1986;
    [28] Toyoa A Trata T. New method for treatmenting fluorine waste water to reduce sludge and running costs. IEEE transaction on semiconductor manufacturing, Vol. 13, No. 3 305~309,2000;
    [29] 周钰明,余春香:吸附法处理含氟废水的研究进展,离子交换与吸附,Vol.17,No.5,369—376,2001;
    [30] 石荣,刘海英:含氟废水处理方法的研究,环境保护科学Vol.28 No.109,2002
    [31] 金刺博康:含氟废水的深度处理法,PPM,1979;
    [32] 鲁春锋:含氟废水处理的实验研究,西安建筑科技大学硕士论文;
    [33] 姜利群,季民,顾平:化学混凝法处理高浓度含氟废水试验研究[J],城市环境与城市生态,VOL.11,N0.4,7—9,1998;
    [34] D.F.劳勒等(美):现代水处理技术,中国环境科学出版社,1989;
    [35] 刘易斯(英):国外水处理新技术,上海科学技术出版社,1989;
    [36] W.W.埃肯费尔德(美)著:工业水污染控制,中国建工出版社,1992
    
    
    [37] 张希衡:水污染控制工程,冶金工业出版社,1994;
    [38] 陈豪立:石灰沉降法处理含氟废水,贵州化工,1998,4;
    [39] 仇付国:王晓昌,王云波,活性氧化铝和骨炭除氟技术,西安建筑科技大学学报Vol.33 No.1 Mar.2001;
    [40] ALMAYEHU MEKONEN, PRADEEP KUMAR and ARVIND KUMAR: INTEGRATED BIOLOGICAL AND PHYSIOCHEMICAL TREATMENT PROCESS FOR NITRATE AND FLUORIDE, War. Res, Vol. 35, No. 13, 3127-3136, 2001;
    [41] S. SAHA: TREATMENT OF AQUEOUS EFFLUENT FOR FLUORIDE REMOVAL, Wat. Res, Vol. 27, No. 8, pp. 1347-1350,1993;
    [42] Wilms D. Buldeo Rai P. Van Dijk J.C. and Scholler M.:RECOVERY OF NICKEL BY CRYSTALLIZATION OF NICKEL CARBONATE IN A FLUIDIZED-BED REACTOR. In Water Pollution Control In Asia, pp. 449-456. Pergamon Press, Oxford, 1988;
    [43] 张焕祯等:石灰—CaCl_2絮凝法处理酸性高氟废水的试验研究,环境工程,Vol.13,No.1,Feb.1995;
    [44] 纪兰:石灰—聚合硫酸铁法处理含氟废水,湖南有色金属,Vol.13,No.1, Jan.1997;
    [45] 李永明:新型氟离子吸附剂的研究,工业水处理,Vol.17,No.6,Jan.1997;
    [46] 高锡珍,靳宏志:水洗在活性氧化铝氟解吸过程中的作用,湿法冶金,Vol.19,No.4,1—5,2000;
    [47] 彭天杰等:工业污染治理技术手册,四川科学技术出版社,1985;
    [48] 许保玖,严煦世等:水和废水技术研究,中国建筑工业出版社,1997;
    [49] 金奇庭:水质控制的物化法原理,西安建筑科技大学,11~50,2000;
    [50] 许保玖:给水处理理论,中国建筑工业出版社,118~168,2000;
    [51] W.斯塔姆(瑞士),J.J.摩尔根(美):水化学,科学出版社,188~220,1987;
    [52] C.N.Sawyer P.L.McCarty:环境工程化学,原子能出版社,1988
    [53] 北京轻工业学院编:基础化学实验,中国标准出版社,1999;
    [54] 华东师范大学无机化学教研室:南京师范大学无机化学教研室编著,无机化学,65—125,华东师范大学出版社,1992;
    [55] 王九思等:水处理化学,化学工业出版社,85~155,2002;
    [56] 常青:水处理絮凝学,化学工业出版社,50~160,2002;

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