摘要
以城市污水厂生化活性污泥及剩余污泥和石化污水厂剩余污泥为原料，采用化学活化法制备了用于污水处理的吸附剂，并对其进行了物化性质表征。结果表明活化剂ZnCl_2与H_2SO_4浓度均为5mol·L~(-1)、固液比为1：2.5、热解温度和时间分别为550℃和2h的条件下，制备的吸附剂性能最好；在投加量为0.5％的条件下，活性污泥吸附剂对废水COD、总磷及色度的去除率分别为63.2％、98.3％和87.5％；流速为20mL·h~(-1)时动态吸附穿透时间为12h，加热法再生2次后穿透时间为10h；在投加量为0.05％的条件下，石化污泥吸附剂对含油废水含油去除率为94.3％；等温吸附过程可用Freundlich模型描述。
城市污水厂剩余污泥采用热解法制备了烟气脱硫吸附剂，并进行了物化性质表征。结果表明在原料粒径为0.1cm～0.5cm、N_2流量为30L·h~(-1)、热解温度和时间分别为550℃和1h的条件下，制备的吸附剂性能最好；在SO_2入口浓度2021.38mg·m~(-3)、O_2含量12％、气体流速和温度分别为4.25m·min~(-1)和40℃的模拟烟气条件下，污泥吸附剂的脱硫效率为75.3％，吸附容量为8.68mg·g~(-1)，水洗法再生2次后，脱硫效率下降至66.2％，吸附容量为6.25mg·g~(-1)；在SO_2入口浓度2021.38mg·m~(-3)、O_2含量12％、H_2O_((g))含量12％、气体流速4.25m·min~(-1)和温度60℃的条件下，脱硫效率为85.1％，吸附容量为12.20mg·g~(-1)，再生2次后，脱硫效率下降至76.2％，吸附容量为10.36mg·g~(-1)；干态下污泥吸附剂对SO_2吸附主要为物理吸附，水蒸气存在时以化学吸附为主，化学吸附效果好于物理吸附；固定床吸附模型的预测值与实验结果较好吻合。
对城市污水厂剩余污泥采用浸渍碳酸钠溶液或负载金属氧化物的方法进行改性制备烟气脱硫吸附剂。结果表明同时负载5％MnO_2和5％MgO的吸附剂性能最好；在SO_2入口浓度2021.38mg·m~(-3)、O_2含量12％、H_2O_((g))含量12％、气体流速2.13m·min~(-1)和温度60℃的条件下，污泥吸附剂的脱硫效率为93.7％，吸附容量为99.3mg·g~(-1)；水蒸气存在时，复合氧化物的协同作用促进了对SO_2的化学吸附；氨溶液再生2次后污泥吸附剂的脱硫效率为93.0％，吸附容量为84.4mg·g~(-1)。
对改性污泥吸附剂的制备进行了初步工艺设计，并核算了原材料成本，结果表明其具有较好的经济性和应用前景。
Adsorbents for wastewater treatment were prepared from biochemical and surplus sludge of sewage and surplus sludge of petrochemistry by chemical activation, and their physical and chemical properties were studied. The results show that the best performance of adsorbents are made by complex of ZnCl_2 and H_2SO_4, and the optimum preparation conditions are concentration of two activators 5 mol·L~(-1), ratio of solid to liquid 1:2.5, pyrolysis temperature 550 ℃, pyrolysis time 2 h. Under the condition that the concentration is 0.5%, the removal rates of adsorbent made from the biochemical sludge for COD, total phosphorus and the chromaticity color of sewage are 63.2%, 98.3% and 87.5% respectively. On the condition that the flow is 20 mL·h~(-1), the breakthrough time decreased from 12 h to 10 h by heating method for two times in dynamic adsorption experiment. Under the condition that the concentration is 0.05%, the oil removal rate of adsorbent made from the sludge of petrochemistry in the treatment of oil-bearing wastewater is 94.3%. The isothermal adsorption process can be described by Freundlich Model.
Adsorbent for flue gas desulfurization was prepared from surplus sludge of sewage by pyrolysis, and its physical and chemical properties was studied. The results show that the optimum preparation conditions are particle diameter of material 0.1 cm ～0.5 cm, the flow of N_2 30 L·h~(-1), pyrolysis temperature 550 ℃, pyrolysis time 1 h. Under the adsorption conditions of inlet concentration of SO_2 2021.38 mg·m~(-3), O_2 12%, flue gas velocity 4.25 m·min~(-1), temperature 40℃, the desulfurization efficiency and adsorption capacity of sludge-derived adsorbent for simulation flue gas are 75.3% and 8.68 mg·g~(-1) respectively, and those decrease to 66.2% and 6.25 mg·g~(-1) after renovation by washing with water for two times. Under the adsorption conditions of inlet concentration of SO_2 2021.38 mg·m~(-3), O_2 12%, H_2O (g) 12%, flue gas velocity 4.25 m·min~(-1), temperature 60 ℃, the desulfurization efficiency and adsorption capacity are 85.1% and 12.20 mg·g~(-1) respectively, and those decrease to 76.2% and 10.36 mg·g~(-1) after renovation for two times. If water vapour is present, the adsorption mechanism of SO_2 is mainly changed from physical adsorption to chemical adsorption, and the adsorption effect of chemical adsorption is better than physical adsorption. Predictable values by stationary adsorption bed model and experimental values are tallied preferably.
The adsorbents for flue gas desulfurization were prepared from surplus sludge of sewage by different modifation methods such as impregnation of Na_2CO_3 solution and
引文
1 尹军，谭学军．污水污泥处理处置与资源化利用．北京：化学工业出版社，2005
2 赵庆祥．污泥资源化技术．北京：化学工业出版杜，2002
3 半振明，高忠爱，祁梦兰．固体废物的处理与处置．北京：高等教育出版社，1992
4 顾夏生，黄铭荣，王占生，等．水处理工程．北京：清华大学出版社，1985
5 马那，陈玲，熊飞．我国城市污泥的处置与利用．生态环境，2003，12(1)：92～95
6 周少奇．城市污泥处理处置与资源化．广州：华南理工大学出版社，2002
7 何晶晶，顾国维，李笃中．城市污泥处理与利用．北京：科学出版社，2003
8 肖锦．城市污水处理及回用技术．北京：化学工业出版社，2002
9 周寿荣．草坪植被与人类环境．成都：四川科学技术出版社，1996
10 何晶晶，顾国维．污水厂污泥热化学转化制油关键技术研究．上海市环境保护科学技术发展基金报告．上海：同济大学，1998：80～82
11 魏先勋．环境工程设计手册．长沙：湖南科学技术出版社，2002
12 Raj A. Sludge disposal where next. W&WT, 1992, 35 (9): 135～142
13 Bjarne P, Kiell T N. Strategy for land application of sewage sludge in Norway. Water Science and Technology, 1997, 36 (11): 283～290
14 乔显亮，骆永明，吴胜春．污泥的土地利用及其环境影响．土壤，2000，(2)：79～85
15 Tay J H, Hong S Y, Show K Y. Reuse of sewage sludge as palletized aggregate. Journal of Environmental Engineering, 2000, 126 (3): 279～286
16 Hall J E. Sewage sludge production, treatment and disposal in the European Union. J Chartered Institution of Water and Environmental Management, 1995, 19 (8): 335～343
17 Hudson J A. Current technologies for sludge treatment and disposal. J CIWEM, 1996, 1 (2): 10
18 Hanbivlvardi K R. Sludge ash as fine aggregate for concrete mix. Journal of Environmental Engineering, 1995, 101 (9): 635～638
19 Okuno N, Takahashi S. Full scale application of manufacturing bricks from sewage. Water Science and Technology, 1997, 36 (11): 243～250
20 Endo H. Production of glass ceramics from sewage sludge. Water Science and Technology, 1997, 36 (11), 235～241
21 杨朝晖，杨霞．污水处理厂的污泥处置．环境科学与技术，1995，18(4)：40～42
22 Recale R J. Sludge reuses stratagies changing. Environmental Protection, 1981, 2(1): 20～25
23 EPA. Process design manual: Land application of municipal sludge. PB90-187048, Department of Commoner, Land Technical Information Service, 1983
24 Wang M J. Land application of sewage sludge in china. The Science of Total Environment, 1997, 197(1-3): 149～160
25 莫测辉，吴启堂，蔡全英，等．论城市污泥资源化与可持续发展．生态学报，2000，11(1)：157～160
26 史昕龙，陈绍伟．城市污水污泥的处置与利用．环境保护，2001，(3)：45～46
27 周立祥，胡蔼堂，戈乃汾，等．城市污泥土地利用研究．生态学报，1999，19(3)：185～193
28 Keefer R F. Metal-organic associations in two extracts from nice soils amends with three sewage sludge. Agriculture Ecosystem and Environment, 1994, 16 (55): 151～165
29 Hall J E. Soil ingestion of sewage sludge and animal slurries. Fertilizer, 1988, 22 (4): 63～68
30 郭妮兰，田若淘，上雁卿，等．城市污泥和污泥垃圾堆肥作为肥源对作物重金属积累的影响．农业环境保护，1995，14(2)：67～71
31 Mclaren R G, Taylor M, Hendy T, et al. Leaching of metals and nutrients from soils treated with metal-amended sewage sludge. In: Currie L Ded. Best Management Practices for Production. Palmereston North, New Zealand: Massey University, 1999
32 Kelly W D, Martens D C. Agriculture use of sewage sludge: A Literature Review Virginia Polytechnic Institute and State University, 1984
33 Okazawa K, Henmi M, Sota K. Energy Saving in sewage sludge incineration with indirect neat drying. In: Processing of 1986 National Waste Processing Conference. Denver, ASME, 1986: 177～191
34 Bayer B, Kutubuddin M. Temperature conversion of sludge and waste to oil from K J thome-Kozmiendsy, Eds. Processing of the International Recycling Congress. Berlin: E F Verlag 1978: 314～318
35 Campbell H W. Sewage sludge treatment and use: New development. London: Elsevier Applied Science, 1989
36 Bridle T R, Hammerton I, Hertle C K. Control of heavy metals and organchlorines using the oil from sewageprocess. Wat. Sci. Tech., 1990, 22(12): 249～258
37 Frost R C, Bruce A M. Alternative uses for sewage sludge. Oxford: Pergamon Press, 1991: 323～341
38 何晶晶，顾国维，邵立明，等．污水污泥低温热解处理技术研究．中国环境科学，1996，16(4)：254～257
39 欧国荣，陈奇洲．生活污水污泥油化试验研究．环境污染与防治，1996，18(4)：20～21
40 何晶晶，邵立明，陈正夫，等．污水厂污泥低温热化学转化过程机理研究．中国环境科学，1998，18(1)：39～42
41 胡光垠，洪云希．城市污泥合成燃料的应用研究．中国给水排水，1996，12(2)：13～15
42 汪恂．污泥热化学处理的试验研究．武汉理工大学学报，2002，24(6)：35～37
43 Shen L, Zhang D K. An experimental study of oil recovery sewage sludge by low temperature pyrolysis in a fluidized-bed. Fuel, 2003, 82 (4): 455～472
44 Dominguez A, Menendez J A, Inguanzo M, et al. Gas chromatographic-mass spectrometric study of the oil fractions produced by microwave-assisted pyrolysis of different sewage sludges. Journal of chromatography A, 2003, 1012 (2): 193～206
45 邵立明，何晶晶，李国建．污水厂污泥低温热解过程能量平衡分析．上海环境科学，1996，15(6)：19～21
46 何晶晶．城市污水处置厂污泥直接热化学液化处理技术．环境科学，1999，16(4)：75～80
47 Holliday J. The effect of surplus activated sludge on the sludge thickening strategy for a large sewage-treatment works. In European Conf. On Sludge and Organic Waste, University of Leeds, 1994: 4～12
48 刘英对，王峰．城市污泥的资源化与防治措施．资源保护，1998，14(6)：271～273
49 王敦球，谢庆林，李金城．城市污水污泥农用资源化研究．重庆环境科学，1999，21(6)：50～52
50 唐黎华，朱于彬，赵庆祥．活性污泥用作气化用型煤粘结剂．华东理工大学学报，1998，24(5)：506～509
51 唐黎华．活性污泥作为气化用型煤粘结剂的研究．环境科学学报，1999，19(1)：87～91
52 牛樱，李季华．剩余污泥处理技术进展．工业用水与废水，2000，31(5)：4～6
53 蔡文金．城市污泥的处理利用的探索．环境工程，1991，9(4)：22～23
54 Hudson J A. Treatment and disposal of sewage sludge in the mid-1990s. JCIWEN, 1995, 9(3): 93～99
55 Heart S. Protecting the environment from waste disposal: The cement kiln option. Environmental Protection Engineering, 1997, 23(1): 25～35
56 上海情报科技所．国外剩余污泥的处理与利用．上海：上海科技情报所，1975
57 朱小山，孟范平，赵希锦．城市污泥的处理技术及资源化展望．四川环境，2002，21(4)：8～12
58 Tay J H, Chen X G, Jeyaseelan S, et al. Optimising the preparation of activated carbon from digested sewage sludge and coconut husk. Chemosphere, 2001, 44: 45～51
59 张仲燕，卞华松，庞文静．生化污泥改性制含碳吸附剂及应用研究．上海环境科学，1996，15(9)：22～24
60 Chiang P C, You J H. Use of sewage sludge for manufacturing adsorbents. J. Chem. Eng. (Canada), 1987, 65 (3): 922～930
61 Chen X, Jeyaseelan S. Study of sewage sludge pyrolysis mechanism and mathematical modeling. Journal of Environmental Engineering, 2000, 126 (7): 585～592
62 Lu G Q, Low J F, Liu C Y, et al. Sufaee area development of sewage sludge during pyrolysis. Fuel, 1995, 74 (3): 244～348
63 Lu G Q, Lan D D. Characterization of sewage sludge-derived adsorbents for H_2S removal. Part 2: Surface and pore structural evaluation in chemical activation. Gas. Sep. Purif., 1996, 10 (2): 103～111
64 Jeyaseelan S, Lu G Q. Development of adsorbent/catalyst from municipal wastewater sludge. Wat. Sci. Tech., 1996, 34 (3-4): 499～505
65 Lu G Q. Preparation and evaluation of adsorbents from waste carbonaceous materials for SO_X and NO_X removal. Environmental Progress, 1995, 15 (1): 12～18
66 Tay J H, Chen X G, Jeyaseelan S, et al. A comparative study of anaerobically digested and undigested sewage sludges in preparation of activated carbon. Chemosphere, 2001, 44 (1): 53～57
67 Sutherland J. Preparation of activated carbonaceous materials from sewage and sulfuric acid. U. S. Patent3, 998, 757 (1976)
68 Lewis F M. Method of pyrolyzing sewage sludge to produce activated carbon. U. S. Patent 4, 122, 036 (1977)
69 马志毅，侯红娟，刘瑞强，等．污水厂污泥作为吸附剂的试验研究．中国给水排水，1997，13(4)：10～13
70 Kojima N, Mitomo A, Itaya Y, et al. Adsorption removal of pollutants by active cokes produced from sludge in the energy recycle process of wastes. Waste Management, 2002, 22: 399～404
71 Caballero J A, Front R, Marcilla A. Characterization of sewage sludges by primary and secondary pyrolysis. Journal of Analytical and Applied Pyrolysis, 1997, 40-41: 433～450
72 张德见，魏先勋，曾光明，等．化学活化法制取污泥衍生吸附剂的实验研究．安全与环境学报，2003，3(5)：44～46
73 Chiang H L, Chao C G, Shih Y C. The reuse of biosludge as an adsorbent from a petrochemical wastewater treatment plant. J. Air & Waste Manage Assoc., 2003, 53 (9): 1042～1051
74 Nasrin R K, Marta C. Production of micro and mesoporous activated carbon from paper mill sludge. Ⅰ. Effect of zinc chloride activation. Carbon, 2000, 38 (14): 1905～1915
75 吴健，乔华．利用污水污泥制取活性炭的试验研究．中国给水排水，1990，6(3)：19～23
76 万洪云．利用活性污泥制造活性炭的研究．干旱环境监测，2000，14(4)：220～225
77 胡华龙，韩梅，黄秉禾，等．利用石化污泥生产新型除油吸附剂的试验研究．交通环保，2001，22(4)：12～14
78 赵由才．环境工程化学．北京：化学工业出版社，2003
79 高廷耀，顾国维．水污染控制工程．北京：高等教育出版社，2000
80 谢锦辉，罗文连．活性炭在给水处理中的应用．冶金矿山设计与建设，2000，32(3)：34～37
81 马青兰，王增长，李敏敏，等．活性炭净化废水处理研究．新型碳材料，2002，17(1)：59～61
82 石太宏，方建章，王松平，等．活性炭吸附Zn~(2+)的热力学及其机理研究．水处理技术，1999，25(2)：103～107
83 Chiang P C, Chang E E. Comparison of chemical and thermal regeneration of aromatic compounds on exhausted activated carbon. Wat. Sci. Tech., 1997, 35 (7): 279～285
84 陶红，周仕林，高廷耀．13X分子筛处理含苯胺废水的实验研究．环境科学学报，2002，22(3)：408～411
85 张全兴，黄杰，裘兆蓉，等．树脂吸附法处理含苯胺工业废水的研究．离子交换与吸附，1991，7(6)：421～426
86 卞华松，张仲燕，刘芝玲．有机污泥改制含炭吸附剂工艺及应用．环境科学，1999，20(6)：56～59
87 Chen X, Jeyaseelan S, Graham N. Physical and chemical properties study of the activated carbon made from sewage sludge. Waste Management, 2002, 22(7): 755～760
88 Otero M, Rozada F, Calvo L F. Elimination of organic water pollutants using adsorbents obtained from sewage sludge. Dyes and Pigments, 2003, 57: 55～65
89 Rozada F, Calvo L F, Carcia A I. Dye adsorption by sewage sludge-based activated carbons in batch and fixed-bed systems. Bioresource Technology, 2003, 87 (3): 221～230
90 Maria J M, Adriana A, Dolors B M, et al. Activated carbons developed from surplus sewage sludge for the removal of dyes from dilute aqueous solutions. Chemical Engineering Journal, 2003, 94(3): 231～239
91 Otero M, Rozada F, Calvo L F, et al. Kinetic and equilibrum modeling of the methylene blue removal from solution by adsorbent materials produced from sewage sludge. Biochemical Engineering Journal, 2003, 15 (1): 59～68
92 Jain A K, Bhatnagar A. Methylphenols removal from water by low cost adsorbents. Journal of Colloid and Interface Science, 2002, 251 (1): 39～45
93 Graham N, Chen X G, Jeyaseelan S. The potential application of activated carbon from sewage sludge toprganicdyesremoval. Wat. Sci. Technol., 2001, 34 (2): 245～252
94 Calvo L F, Otero M, et al. Upgrading sewage sludges for adsorbent preparation by different treatments. Bioresource Technology, 2001, 80: 143～148
95 Netpradit S, Thiravetvan P, Towprayoon S. Application of 'waste' metal hydroxide sludge for adsorption of azo reactive dyes. Water Research, 2003, 37: 763～772
96 钟秦．燃煤烟气脱硫脱硝及工程实例．北京：化学工业出版社，2002
97 王小明．国内外烟气脱硫技术的发展与现状．电力环境保护，2000，16(1)：31～34
98 张会平，钟辉，叶李艺．不同化学方法再生活性炭的对比研究．化工进展，1999，(5)：31～34
99 [日] 炭素材料学会组编．高尚愚译．活性炭基础及应用．1975
100 朱世勇．环境与工业气体净化技术．北京：化学工业出版社，2001
101 张守玉．活性炭(焦)脱除烟道气中二氧化硫工艺．煤炭转化，1999，22(3)：28～34
102 张力，刘伟．活性炭吸附烟气脱硫的展望．辽宁化工，1996，15(5)：145～147
103 Slack A V著．上海轻工业设计院技术情报组译．废气脱硫．北京：中国建筑工业出版社，1977
104 Schotte W E. Experiment of desulfurization on activated carbon. AICHE 67th Annual Meeting, 1974, 3: 85
105 邹长武．活性炭纤维催化脱硫动力学研究．成都：四川大学出版社，2002
106 中科院大连物化所．活性炭催化剂用于消除和回收烟气中低浓度的二氧化硫．催化学报，1982，3(3)：198～203
107 刘义，曹子栋．活性炭法烟气脱硫工艺中硫酸转化条件的实验研究．西安交通大学学报，2002，36(1)：108～200
108 蔡光宇．消除及回收烟气中二氧化硫的糠醛渣活性炭研究．环境科学，1993，14(2)：2～6
109 刘中正．活性炭烟气脱硫技术研究新进展．四川环境，1993，12(4)：9～12
110 Lu D D. Development of adsorbent from waste materials for air pollution control[dissertation]. Singapore: Nanyang Technological University, 1994
111 Bagreev A, Bashkova S, Locke D C, et al. Sewage sludge-derived materials as efficient adsorbents for removal of hydrogen sulfide. Environ. Sci. Technol., 2001, 35 (17): 1537～1543
112 Andrey B, Teresa J. H_2S adsorbent/oxidation on materials obtained using sulfuric acid activation of sewage sludge-derived fertilizer. Journal of Colloid and Interface Science, 2002, 252 (1): 188～194
113 Bashkova S, Bagreev A, Locke D C, et al. Adsorption of SO_2 on sewage sludge-derived materials. Environ. Sci. Technol., 2001, 35 (15): 3263～3269
114 Yunbo Z. Effects of metallic derivatives in adsorbent derived from sewage sludge on adsorption of sulfur dioxide. J. Cent. South. Univ. Technol., 2004, 11(1): 55～58
115 刘平．活性炭及其在脱硫方面的应用．大众标准化，2002，(2)：40～41
116 张亚君，邓先和，徐国想．二氧化硫氧化过程的优化研究．化学工程，2001，29(2)：34～37
117 李怀珠，吉建斌，郭鉴，等．我国煤质活性炭工业的发展趋势．煤化工，1994，(2)：6～9
118 张守玉，向银花，赵建涛，等．活性炭质材料脱硫机理探讨．煤炭转化，2002，25(2)：29～34
119 李永祥，程振民，袁渭康．低浓度SO_2在部分润湿活性炭上的催化氧化．化工学报，2000，51(4)：485～488
120 Otake T, Tone S, Yokou Y, et al. Kinetics of sulfur dioxide oxidation over activated carbon. Chem. Eng. Japan, 1971, 4 (2): 155～159
121 Zawadzki J. Infrared studies of SO_2 on Carbon-1. The SO_2 species adsorbed on carbon films. Carbon, 1987, 25 (4): 495～502
122 Zawadzki J. Infrared studies of SO_2 on carbon-1. Interaction of SO_2 with carbon films. Carbon, 1987, 25 (3): 431～436
123 Rubio B, Izquierdo M T. Low cost adsorbents for low temperature cleaning of flue gases. Fuel, 1998, 77 (6): 631～637
124 Lizzio A A, Debarr J A. Mechanism of SO_2 removalbycarbon. Energy and Fuels, 1997, 7: 284～291
125 赵修松．消除烟道气中二氧化硫的活性炭催化剂-SO_2在催化剂上动态吸附研究．环境科学，1992，13(5)：67～70
126 程振民，蒋正兴，袁渭康．活性炭表面SO_2的催化氧化三相反应动力学．华东理工大学学报，1997，23(1)：7～13
127 蒋正兴，程振民，李永祥．活性炭-水-SO_2三相反应动力学及传质特性研究．华东理工大学学报，1996，22(4)：375～382
128 张小广，陈凡植，武秀文．低床层烟炱吸附法烟气脱硫试验研究及机理探讨．江苏化工，2003，31(1)：43～47
129 Yang R T 著．杨树森．曾美云，胡竟民译．吸附法气体分离．北京：化学工业出版社，1991
130 刘家祺．分离过程与技术．天津：天津大学出版社，2001
1 Tay T J, Chen X G, Jeyaseelan S, et al. Optimising the preparation of activated carbon from digested sewage sludge and coconut husk. Chemosphere, 2001, 44 (1): 45～51
2 Guo J, Lua A C. Textual and chemical characterizations of adsorbent prepared from palm shell by potassium hydroxide impregnation at different stages. Journal of Colloid and Interface Science, 2002, 254 (1): 227～233
3 Rozada F, Calvo L F, Garcia A I, et al. Dye adsorption by sewage sludge-based activated carbons in batch and fixed-bed systems. Bioresource Technology, 2003, 87 (3): 221～230
4 Caballero J A, Front R, Marcilla A. Characterization of sewage sludges by primary and secondary pyrolysis. Journal of Analytical and Applied Pyrolysis, 1997, 40-41: 433～450
5 Menendez J A, Inguanzo M, Pis L J. Microwave induced pyrolysis of sewage sludge. Water Research, 2002, 36 (9): 3261～3264
6 中华人民共和国标准．煤质颗粒活性炭试验方法．水分的测定．GB／T 7702．1-1997
7 中华人民共和国标准．煤质颗粒活性炭试验方法．灰分的测定．GB／T 7702．15-1997
8 中华人民共和国标准．煤质颗粒活性炭试验方法．碘吸附值的测定．GB／T7702．7-1997
9 魏复盛．水和废水监测分析方法指南(中册)．北京：中国环境科学出版社，1997
10 中华人民共和国标准．水质色度的测定．GB／11903-89
11 中华人民共和国标准．碎屑岩油藏注水水质推荐指标及分析方法．SY／T5329-94
12 Calve L F, Otero M, Moran A, et al. Upgrading sewage sludge for adsorbent preparation by different treatments. Bioresource Technology, 2001, 80 (2): 143～148
13 Martin M J, Balaguer M D, Rigolar M. Feasibility of activated carbon production from biological sludge by chemical activation with ZnCl_2 and H_2SO_4. Environ. Technol., 1996, 17 (4): 667～672
14 詹亮，李开喜，朱星明，等．高硫焦制备超级活性炭的正交实验研究．石油学报，2002，18(1)：89～92
15 Molina S M, Rodroguez R F, Caturla F, et al. Porosity in granular carbons activated with phosphoric acid. Carbon, 1995, 33 (8): 1105～1113
16 Wigmans T. Industrial aspects of production and use of activated carbon. Carbon, 1989, 27 (2): 13～22
17 Tsai W T, Chang C Y, Lin M C, et al. Adsorption of acid dye onto activated carbons prepared from agricultural waste bagasse by ZnCl_2 activation. Chemosphere, 2001, 42 (1): 51～58
18 Bevia F R. Activated carbon from almond shells: chemical activation, activateding reagent selection and variables influence. Ind. Eng. Chem. Prod. Res., 1984, 23 (2): 266～269
19 Catural F, Molina S M, Rodriguez R F. Preparation of activated carbon by chemical activation with zinc chloride. Carbon, 1991, 29(3): 999～1007
20 Lopez J D, Valenzuela C C, Navarreteguijosa A, et al. Carbonisation of olive wood: Evalution of surface area and porosity with treatment temperature. Adsorp. Sci. Tech., 1986, 4 (3): 41～48
21 Marc R, Stammbach B K. Pyrolysis of sewage sludge in a fluidized bed. Energy & Fuel, 1989, 3: 255～259
22 Junichi H, Atsuo K, Katsuhiko M, et al. Preparation of activated carbon from lignin by chemical activation. Carbon, 38 (13): 1873～1878
23 蒙哥马利著．汪仁官，陈荣昭译．实验设计与分析．北京：中国统计出版社，1998
24 顾惕人，李外郎，马季铭，等．表面化学．北京：科学出版社，1999
25 Duggan O, Allen S J. Study of the physical and chemical characteristics of a range chemically treated, lignite, based carbons. Wat. Sci. Tech., 1997, 35 (7): 21～27
26 陆婉珍，袁洪福，徐广通，等．现代近红外光谱分析技术．北京：中国石化出版社，2000
27 杨润昌，周书天．石油炼厂废水污泥硫酸催化炭化研究．环境科学，1996，17(4)：54～57
28 俞誉福，叶明吕，郑志坚．环境化学导论．上海：复旦大学出版社，1994
29 顾夏生，黄铭荣，王占生．水处理工程．北京：中国建筑工业出版社，1995
1 国家环保总局．中国环境质量公报，2003
2 污染源统一监测分析方法编写组．污染源统一监测分析方法．废气部分．北京：中国标准出版社，1983
3 王小明．国内外烟气脱硫技术的发展与现状．电力环境保护，2000，16(1)．31～34
4 叶振华．化工吸附分离过程．北京：中国石化出版社，1992
5 唐强，曹子栋，王盛，等．活性炭吸附法脱硫实验研究和工业性应用．现代化工，2003，23(3)：37～40
6 Bashkova S, Bagreev A, Locke D C, et al. Adsorption of SO_2 on sewage sludge-derived materials. Environ. Sci. Technol., 2001, 35 (15): 3263～3269
7 Daley M A, Mangun C L, Debarr J A, et al. Adsorption of SO_2 onto oxidized and heat-treated activated carbon fibers(ACFS). Carbon, 1997, 35 (3): 411～417
8 Rubio B, Izquierdo M T. Low cost adsorbents for low temperature cleaning of flue gases. Fuel, 1998, 77 (6): 631～637
9 Mangun C L, Daley M A, Braatz R D, et al. Effect of pore size on adsorption of hydrocarbons in phenolic-based activated carbon fibers. Carbon, 1998, 36 (1-2): 123～129
10 化学工程手册编写委员会．化学工程手册．北京：化学工业出版社，1989
11 Yang R T 著．杨树森，曾美云，胡竟民译．吸附法气体分离．北京：化学工业出版社，1991
12 Wang Y. FTIR study of adsorption and reaction of SO_2 and H_2S on Na/SiO_2. Applied Catalysis B: Environmental, 1998, 16: 27～29
13 郑玉婴，张汉辉．蔡伟龙，等．有机膨润土制备及性能表征．光谱学与光谱分析，2005，25(1)：62～64
14 蒋先明，何伟平．简明红外光谱识谱法．南宁：广西师范大学出版社，1992
15 冯治宇，金应培．活性炭吸附法脱除烟气中SO_2的实验研究．环境保护科学，1994，20(4)：37～39
16 Moreno C C, Carrasco M F. Effect of non-oxidant and oxidant acid treatments on the surface properties of an activated carbon with very low ash content. Fuel, 1997, 36 (2): 145～151
17 Paolo D. The effect of certain metallic derivatives on the adsorption of sulfur dioxide on activated carbon. Carbon, 2001, 39 (2): 419～424
18 张小广，陈凡植，武秀文．低床层烟炱吸附法烟气脱硫试验研究及机理探讨．江苏化工，2003，31(1)：43～47
19 程振民，蒋正兴，袁渭康．活性炭脱硫研究(Ⅱ)水蒸汽存在下SO_2的氧化反应机理．环境科学学报，1997，17(3)：273～277
20 程振民，蒋正兴．活性炭脱硫研究(Ⅰ)：SO_2-N_2-O_2体系中SO_2氧化反应机理．环境科学学报，1997，17(3)：268～272
21 Otake T, Tone S, Yokou Y, et al. Kinetics of sulfur dioxide oxidation over activated carbon. Chem. Eng. Japan, 1971, 4(2): 155～159
22 Zawadzki J. Infrared studies of SO_2 on Carbon-1. The SO_2 species adsorbed on carbon films. Carbon, 1987, 25 (4): 495～502
23 大连物化所八0二组．活性炭催化剂用于消除和回收烟气中的低浓度二氧化硫．催化学报，1982，3(2)：198～204
24 Ruhland F. The kinetics of the adsorption of sulfur dioxide in calcium in calcium hydroxide suspension. Chem. Eng. Sci., 1991, 46 (4): 939～947
25 Lizzie A A, Dcbarr J A. Mechanism of SO_2 removal by carbon. Energy and Fuels, 1997, 7: 284～291
26 赵振国．吸附作用应用原理．北京：化学工业出版社，2005
27 苏玉红，朱利中．苯蒸气在有机膨润土上的吸附性能及机理研究．中国环境科学，2001，21(3)：252～255
28 程振民，蒋正兴，袁渭康．SO_2在活性炭床层中的透过曲线．化工学报，1996，47(5)：515～521
1 冯玲，杨景玲，蔡树中．烟气脱硫技术的发展与应用现状．环境工程，1997，15(2)：19～24
2 陈笃慧，于腊佳．除SO_2、NO_X且副产工业硫酸的烟道气净化法．化工进展，1995，(4)：28～31
3 Norbert O. DeSNO_X proeess for flue gas cleaning. Catalysis Today, 1993, 16: 247～261
4 徐正中．SNO_X烟气双脱新工艺．环境工程，2000，11(6)：34～37
5 蒲恩奇．大气污染治理工程．北京：高等教育出版社，1999
6 Bashkova S, Bagreev A, Locke D C, et al. Adsorption of SO_2 on sewage sludge-derived materials. Environ. Sci. Technol., 2001, 35 (15): 3263～3269
7 Bekir Z U, Inci A, Hayrettin Y. Sorption of SO_2 on metal oxides in a fluidized bed. Ind. Eng. Chem. Res., 1988, 27: 434～439
8 时黎明，徐旭常．水合作用对钙基吸收剂脱硫特性的影响．环境工程，1999，16(2)：37～39
9 Ali S, Hitoki M, Masanobu H. Utilization of highly improved fly ash for SO_2 caprture. Journal of Chemical Engineering of Japan, 1995, 28(1): 53～58
10 Hiroaki T, Tomohiro I, Tsutomu U, et al. Highly active adsorbent for SO_2 removal prepared from coal fly. Ind. Eng. Chem. Rest, 1995, 34 (4): 1404～1411
11 Karel S, Weigang L, Jens H, et al. Low-temperature flue gas desulfurization by alumina-CaO regenerable sorbents. Fuel, 1994, 73 (7): 1144～1150
12 刘守军，刘振宇，牛宏贤，等．CuO／AC脱硫剂的制备．煅烧温度对脱硫活性的影响．环境科学，2000，21(1)：12～17
13 Benoit K, Benjamin K H. Temperature-programmed reduction and X-ray photoelectron spectroscopy of copper oxide on alumina following exposure to sulfur dioxide and oxygen. Ind. Eng. Chem. Res., 1991, 30 (9): 2105～2113
14 杨国华．硫化床CuO烟气脱硫实验研究．环境工程，1995，10(5)：19～22
15 吴菊贤，刘世斌，韩振海．氧化铁吸收SO_2的反应机理．硫酸工业，1992，(5)：18～23
16 张福国，韩振海．加钒氧化铁脱硫剂脱除SO_2的机理研究．太原工业大学学报，1993，24(4)：33～40
17 Jin S Y, Alak A B, Cecelia A R. DeSO_X catalyst: an XRD study of magnesium aluminate spinel and its solid. Ind. Eng. Chem. Res., 1991, 30 (7): 1444～1448
18 Bekiv Z U, Inci A, Hayrettin Y. Selective sulfur dioxide adsorbents prepared from designed dispersions of groups ⅠA and ⅡA metal oxides on alumina. Journal of catalysis, 1996, 163: 176～185
19 Yang R T, M S S. Calcium silicates: A new class of highly regenerative sorbents for hot gas desulfurization. AICHE Journal, 1979, 25:5
20 Przepiorski J, Oya A. K_2CO_3-loaded deodorizing activated carbon fiber against H_2S gas: Factors of influencing the deodorizing efficiency and the regeneration method. Journal of Materials Science Letters, 1998, 17: 679～682
21 Vissanu M, David L. Adsorption-reaction processes for the removal of hydrogen sulphide from gas streams. J. Chem. Tech. Biotechnol., 1997, 120 (68): 411～416
22 Polovina M, Babic B, Kaluderovic B, et al. Surfuce characterization of oxidized activated carbon cloth. Carbon, 1998, 35(8): 1047～1052
23 Martyniuk H, Wieckowska J. Adsorbents and catalysts from brown coal for flue gas desulfurization. Fuel, 1995, 74: 1716～1718
24 Davini P, Stoppato G. Desulfurization properties of active carbons obtained from petroleum pitch pyrolysis carbon. Carbon, 1999, 37(9): 1363～1371
25 [德]H 凯利，E 巴德著．魏同成译．活性炭及其应用．北京：中国环境科学出版社，1990
26 Akio N, Minoru K, Yoshimichi K, et al. New type of active carbon catalyst for simultaneous of SO_X and NO_X. Bull. Chem. Soc. Jpn., 1980, 53 (11): 3356～3360
27 刘守军，刘振宇，朱珍平，等．高活性炭载金属脱硫剂的制备与筛选．煤炭转化，2000，23(2)：53～58
28 Mignel A A, Francisco C M, Carlos M C. Adsorption of SO_2 from flowing air by alkaline-oxide-containing actived carbons. Applied catalysis B: Environmental, 1997, 13: 229～240
29 Grzybek T, Klinik J. Montmorillonites modified with carbonaceous deposits: 1. Formation mechanism and acidity. Journal of colloid and interface science, 2000, 227 (2): 291～301
30 王一萌．纳米孔材料的构筑与功能化．南京大学，博士论文，2005
31 Mangun C L, Debarr J A, Economy J. Adsorption of sulfur dioxide on ammonia-treated activated carbon fibers. Carbon, 2001, 39: 1689～1696
32 张力，刘伟．活性炭吸附烟气脱硫的展望．辽宁化工．1996，(5)：16～18
33 谭小耀，李秀贞，吴迪镛，等。改性活性炭低温催化氧化脱除H_2S的研究．石油化工，1995，4(10)：716～720
34 唐强，曹子栋，王盛，等．活性炭吸附法脱硫实验研究和工业性应用．现代化工，2003，23 (3)：37～40
35 谭小耀，吴迪镛，袁权．浸渍活性炭脱除低浓度H_2S的研究．化学工程，1996，24(6)：21～25，46
36 Madia G, Elsener M, Koebel M. Thermal stability of vanadia-tungsta-titania catalysts in the SCR process. Applied catalysis B: Environmental, 2002, 39: 181～190
37 罗津克诺普著．南京化王研究院译．从工业气体中回收二氧化硫．北京：化学王业出版社，1996
38 Abbruzzes C. Percolation leaching of manganses ore by aqueous sulfur dioxide. Hydrometallurgy, 1990, 25: 85～97
39 Conldin M H, Holimann M R. Metal iron sulfur(N) Chemistry. 2. Kinetic studies of the redox chemistry of copper(Ⅱ) sulfur(Ⅳ) complexes. Environmental Science & Technology, 1988, 22 (8): 891～898
40 Ziajka J, Bear F, Warneck P. Iron catalysed oxidation of a free radical chain mechanism. Atmospheric Environment, 1994, 28(15): 2549～2552
41 Conklin M H, Hoffmann M R. Metal iron sulfur(Ⅳ) Chemistry. 3. Thermodynamics and kinetic of transient iron(Ⅲ) sulfur(Ⅳ) complexes. Environmental Science & Technology, 1988, 22(8): 899～907
42 Hussjr A, Lim P K, Eckert C A. Oxidation of aqueous sulfur dioxide. 1. Homogeous manganese(Ⅱ) and iron(Ⅱ) catalysis at low pH. J. Phys. Chem., 1982, 86 (21): 4224～4228
43 Daley M A, Mangun C L, Debarr J A, et al. Adsorption of SO_2 onto oxidized and heat-treated activated carbon fibers(ACFS). Carbon, 1997, 35 (3): 411～417
44 Moreno C C, Carrasco M F, et al. Effect of non-oxidant and oxidant acid treatments on the surface properties of an activated carbon with very low ash content. Fuel, 1997, 36 (2): 145～151
45 Mangun C L, Daley M A, Braatz R D, et al. Effect of pore size on adsorption of hydrocarbons in phenolic-based activated carbon fibers. Carbon, 1998, 36 (1-2): 123～129
46 Christian B, Rudi V E. Transition metal catalysed oxidation of sulfur(Ⅳ) oxides, atmospheric relevant process and mechanism. Chemical Reviews, 1995, 95 (1): 119～190
47 Huss A J, Lim P K, Eckert C A. Oxidation of aqueous sulfur dioxide. 2. High pressure studies and proposed reaction mechanisms. J. Phys. Chem., 1982, 86 (21): 4229～4233
48 张立寨．中温条件下氧化铁对氧化钙脱硫的活化作用．化工学报，2003，54(1)：30～33
49 Abbruzzese C. Semi-industrial testing on leaching of manganeses ore by aqueous sulfur dioxide. Industries Minerals, 1987, 9: 109～112
50 Jan D, Miller, Rong Y W. Reaction kinetics of the leaning of MnO_2 by sulfur dioxide. Hydrometallurgy, 1983, 10: 219～242
51 黄研，王治军．软锰矿浆脱除烟气中SO_2的研究．环境工程，1998，16(4)：43～46
52 Meyer J, Schramm W, et al. A comprehensive treatise on theoretical and inorganic chemistry. New York, ⅩⅡ, 1983
53 张昭，刘立全．三氧化硫浸出软锰矿．化工冶金，2000，21(1)：103～107
54 Khalafalla S E, Pohlman J E. Selective extration of metals from pacific sea nodules with dissolved sulfur dioxide. Bureau ofMinesR. 1. 1981. 8518
55 钟秦．燃煤烟气脱硫脱硝及工程实例．北京：化学工业出版社，2002
56 Yunbo Z, Xianxun W, Guangming Z. Adsorbent prepared from sewage sludge by chemical activation and its application to sulfur dioxide adsorption. TNMSC, 2004, 14 (special 1): 122～126
1 赵庆祥．污泥资源化技术．北京：化学工业出版社，2002
2 魏先勋．环境工程设计手册．长沙：湖南科学技术出版社，2002
3 钟秦．燃煤烟气脱硫脱硝技术及工程实例．北京：化学工业出版社，2002
4 孙克勤，钟秦．火电厂烟气脱硫系统设计、建造及运行．北京：化学工业出版社，2005
5 尹军，谭学军．污水污泥处理处置与资源化利用．北京：化学工业出版社，2005