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生物滴滤床对 H2S 废气的去除效率研究 ＊ 章黎笋 1 俞 敏 2 沙昊雷 1 於建明 1 陶 佳 1 王家德 1 1.浙江工业大学生物与环境工程学院, 浙江 杭州 310032; 2.浙江医药股份有限公司新昌制药厂, 浙江 新昌 312500 摘要 本试验采用生物滴滤床 BTF 工艺净化制药厂污水站 H2S废气。 装置采用实验室分离纯化的菌种经现场培养 扩增后所得的高浓度混合菌菌液, 在8 d内迅速完成启动; 试验过程 H2S 气量为11. 3 m3 h, 平均浓度为385. 6 mg m3, 平 均空床停留时间 EBRT 为13. 5 s, H2S 的平均去除效率 96, 且去除率稳定。 随着污染物在 BTF 内 EBRT 的减少, 去除 率逐渐减小; H2S 去除负荷极限 ECmax为209. 6 g m3h, 且 80的去除负荷由填料床的下层承担; 增加液体喷淋量有 助于强化处理效果, 但液膜厚度对净化效率有着负面影响, 循环液中的 SO2- 4 累积浓度 28 g L时, 去除率低于 90。 试验结果表明, BTF 系统运行稳定, 适应性好, 应用于工业废气处理是可行的。 关键词 生物滴滤床 H2S 生物法 空气污染控制 ＊浙江省重大科技攻关项目 2003C13004 0 引言 H2S 是具有臭鸡蛋气味的刺激性气体, 其嗅阈值 为0. 5 10 -9 ～ 2. 5 10 -8 ,广泛存在于工业生产过程 中, 低剂量时对人体危害也很大 [ 1] 。目前 , 治理 H2S 常用的方法归纳起来有吸收法 、 吸附法 、 燃烧氧化法、 化学氧化法 、 冷凝法和生物脱除法等, 但存在能源消 耗大 ,投资运行费用高, 产生二次污染等缺陷。国外 一些研究和工业实践表明 ,采用生物法净化 H2S 恶臭 气体可以获得良好的净化效果, 且能消除上述缺陷, 是世界上工业废气净化研究的前沿热点研究课题 之一 [ 2-3] 。 近年来,许多学者开始研究生物反应器 如生物 滤塔和生物滴滤塔 对 H2S 的去除, 且主要研究低浓 度H2S 废气 [ 4-9] 。研究表明, H2S 能在生物滤塔和生 物滴滤塔中被有效转化, 且在欧美等国家已实现工业 化应用。而国内相关的工作主要处于实验室研究阶 段,工业化应用在近几年也有少量报道 [ 9-15] 。经废气 监测 ,浙江某制药厂污水站产生的高含硫恶臭废气主 要含有 H2S 。作者应用现场的实际废气进行了长达 3 个多月的废气生物处理中试试验 ,其目的是通过中 试试验应用于工业化, 使现场废气净化脱臭 、 污染物 达标排放 。 1 材料与方法 1. 1 试验装置 本试验以污水站气浮池、综合调节池和兼氧池收 集的废气作为试验气源, 废气主要成分为 H2S 。试验 装置为自主研制的生物滴滤床 BTF 废气净化装置, 其装置如图 1 所示。试验采用气液逆流操作, 循环水 罐的 pH 值测定和控制以及温度都由 PLC 控制系统 自动控制。反应器材质均采用有机玻璃 ,其设计参数 见表 1。 图 1 中试装置流程图 表 1 BTF工艺的设计参数 中试装置设计参数BTF 反应器尺寸 内径高度280 mm940 mm 填充填料以多孔聚合物为主的混合填料 填料高度620 mm pHPLC自控 喷淋水连续喷淋 9 . 75 m3 m2h 1. 2 测定项目及方法 H2S 浓度 ≥10 mg m 3 时, 用碘量法测定 ,H2S 浓 度28 g L时, 微生物降解菌活性被抑制 , 系统 H2S 的去除能力明显下降 , 去除率降到 90以下 , 需更换 营养液。这为工业化上更换循环液 、 提高去除效果提 供了理论依据, 能节省操作成本。 3 结论 本次试验所采用的 BTF 系统现场处理 H2S 工艺 技术性能良好、运行稳定 ,其推广应用可望取得巨大 的经济和环境效益 。试验为工业化设计提供了可靠 的依据,试验得到如下结果 1 采用实验室分离纯化的菌种经现场培养扩增 后所得的高浓度混合菌菌液 ,在8 d内迅速完成启动, 比同类型的废气处理装置提前 5～ 7 d [ 10] 。 2 污染物在 BTF 内的停留时间减少 ,去除率逐 渐减小, 但在同一停留时间 EBRT 下, 去除率比较 稳定 。 3 H2S 去除负荷极限 ECmax为 209. 6 g m 3h 。 从去除率和去除负荷的轴向分布看 ,H2S 近 80 的去 除负荷由填料床的下层承担。 4 增加液体喷淋量有助于强化处理效果 ,但液 膜厚度对净化效率有着负面影响, BTF 系统循环液中 的SO 2- 4累积浓度 28 g L时, 去除率降到90以下 。 参考文献 [ 1] 徐桂芹, 姜尔玺, 赵玉鑫, 等. 不同填料生物过滤去除 H2S 恶臭 影响研究. 哈尔滨商业大学学报 自然科学版 , 2003, 19 5 539 -542. [ 2] Otten L , Afzal M T , Mainville D M . Biofiltration of odours laboratory studies using butyric acid. Adv . Environ. Res. , 2004, 8 397-409 . [ 3] Cho K S, Ryu H W, Lee N Y. Biological deodorization of hydrogen sulfide using porous lava as a carrier of thiobacillus thiooxidans. J Biosci Bioeng . , 2000, 90 25 -31. [ 4] 黄兵, 李晓梅, 孙石, 等. 生物膜填料塔净化低浓度硫化氢恶 臭气体研究. 环境科学与技术,1999 4 17 -21 . [ 5] Shinabe K ,Oketani S, Ochi T ,et al. Characteristics of hydrogen sulfide removal in a carrier -packed biological deodorization system. Biochem. Eng . J. ,2000, 5 3 209 -217. [ 6] Hirai M ,Kamamoto M, Yani M, et al. Comparison of the biological H2S removal characteristics among four inorganic packing materials. J Biosci Bioeng . , 2001, 91 4 396 -402. [ 7] Malhautier L, Gracian C, Roux J C, et al. Biological treatment process of airloaded withanammoniaandhydrogensulfidemixture. Chemosphere , 2003, 50 1 145 -153. [ 8] Chung Y C, Lin Y Y,Tseng C P. Removal of high concentration of NH3 and coexistent H2S by biological activated carbon BAC biotrickling filter. Bioresour. Technol . ,2005, 96 16 1812 -1820 . [ 9] 郭兵兵, 刘丽, 王毓仁, 等. 生物法净化石化企业污水处理场恶 臭废气现场小型试验. 石油炼制与化工,2005, 36 2 52 -56 . [ 10] 麦穗海, 李菊, 白海梅, 等. 生物填料塔脱除 H2S 的现场试验. 中 国给水排水, 2002, 18 2 49-52. [ 11] 羌宁, 吴志超, 麦穗海. 生物法去除H2S 恶臭设备的现场工业化 试验研究. 同济大学学报 自然科学版 ,2005, 33 5 640 -643. [ 12] Chen J M, Jiang L Y,Sha H L. Removal efficiency of high -concentration H2S in a pilot-scale biotrickling filter. Environ. Technol. , 2006, 27 7 759 -766. [ 13] Oyarz n P, Arancibia F, Canales C, et al . Biofiltration of high concentration of hydrogen sulfide using Thiobacillus thioparus. Process Biochem. , 2003,39 2 165 -170 . [ 14] Cox H H J. Deshusses M A . Co-treatment of H2S and toluene in a biotrickling filter. Chem Eng J. , 2002, 87 1 101 -110 . [ 15] Lu Z J, Allen D G , Sologar V S. Biofiltration of concentrated mixtures of hydrogen sulfide and methanol. Environ. Prog . , 2003, 22 2 129 -136 . [ 16] BrunnerW,StaubD,LeisingerT .Bacterialdegrationof dichloromethane . Appl. Environ. Microbiol. , 1980, 40 5 950 -958. 作者通讯处 王家德 310032 浙江杭州朝晖六区 浙江工业大学 生物与环境工程学院 2007- 04-04 收稿 以清洁生产实现节能降耗 河南省舞钢市指导大型钢铁公司进行天然气置换项目 。2006 年对锅炉实施两次油改气改造, 使 22t 锅炉 热效率就提高 15 以上,年节约费用 1000 余万元 。用水煤气替代重油, 提高加热效率 10, 年节约重油 6000t 左右, 节约费用 2100 万元。炼钢系统采用双兑铁吹氧及废钢预热新工艺 , 能源吨钢成本可降低 135 元以上。 同时 ,通过实施避峰生产 ,2006 年节约电费 1000 多万元。2004 年把轧钢主电机控制系统改造为可控硅数子控 制系统,减少空转,降低电耗。 摘自“中国环境报” 63 环 境 工 程 2007年 12 月第 25卷第 6 期 INLETZhang Liqiang Ma Chunyuan Song Zhanlong et al 43 Abstract The gas and solid flows have been studied by using the CFD s. The RNG renormalization groupk -εturbulent model is employed for the single -phase, and the Lagrangian DPM model for the solid phase.The emphasis is focused on the flow field, the separating efficiency and the resistance pressure of the cyclone. The results show that the flow field in the cyclone changed obviously after adopting the louver concentrator inlet. The tangential velocity of gas and solid of the new type cyclone is larger than the common cyclone, which has the advantage of separating the large solids. The separating efficiency and the resistance of this cyclone with different types of louver concentrators are also studied. Which provides a basis for the engineering design. Keywords cyclone, louver concentrator inlet, flow field and numerical simulation RESEARCH ON THE REMOVAL OF ODOR SUBSTANCES BY LOW TEMPERATURE PLASM Ma Jingtao Zhou Zhefei Wu Zucheng et al 46 Abstract Using low temperature plasma to treat odor gas is a newly emerging technology. It was studied the removal of some typical odor substances i. e. hydrogen sulfide, ethyl mercaptan, benzene, and tolueneby low temperature plasma treatment. The results show using corona discharge plasma to treat odor gas is practicable;the longer the residence time and the higher the voltage, the better the removal effect; when the residence time is longer than 9 s and the voltage is higher than 20 kV, the odor removal efficiency is basically above 90; further increasing the residence time and the voltage won t dramatically increase the removal efficiency ; basically, the alkane background gaswith a low concentration has no effect on the odor removal efficiency ,while the alkane background gas with a high concentration will decrease the odor removal efficiency; besides, the presence of hydrogen with a higher concentration will also decrease the odor removal efficiency, while increasing the concentration of oxygen will remarkably increase the removal efficiency of hydrogen sulfide. Keywords plasma, waste gas treatment, odor, hydrogen sulfide, mercaptan, benzene and toluene ANALYSIS OF FACTORS INFLUENCING DESULPHURATION EFFICIENCY OF FUME BY WASTEWATER FROM CONVERTERLu Gang Xing Yi Song Cunyi 50 Abstract A series of single factor experimentswere carried out on desulfurization of fume by waste water from converter. Factors as pH and concentration of Fe2etc are studied to find out their impacts on desulfurization, hence some comparisonswere carried out. The result comes that, those factors have significant impacts and special rule on the desulfurization. Keywords waste water from converter, fume and desulfurization MEMBRANE -BASED GAS ABSORPTION COUPLING FOR CO2CAPTURE Lu Jiangang Wang Lianjun Zheng Youfei et al 53 Abstract During the last two decades there has been significant progress in the development of coupling technology of membrane -based gas absorption MGAfor CO2capture. This review focuses on technical process and characteristics of MGA . Mass transfer, kinetics and chemical enhancements with chemical reactions in MGA are emphatically analyzed.Recent advances of MGA for CO2capture are comprehensively summarized. Keywords membrane -based gas absorption, carbon dioxide, mass transfer kinetics and chemical enhancement factor STUDY ON REMOVAL EFFICIENCY OF PURIFYING HYDROGEN SULFIDE IN BIOTRICKLING FILTERZhang Lisun Yu Min Sha Haolei et al 60 Abstract A biotrickling filter is used to do a test of purifying H2S emissions from pharmaceuticalfactory . The outfit uses highly concentrated mix funguswhich is separated and purified in the laboratory and raise to extend in field-pilot, rapidly completesthe startup in8 days; The air flow of biotrickling filter BTFis 11. 3 m3 h, the average density is 385. 6mg m3, the average empty -bed residence time EBRTis 13. 5 s, the H2S removal efficiency REreached 96, and the RE is steady. With pollutant reducing the EBR T in BTF, RE is reduced gradually ; the ECmaxof BTF is 209. 6 g m3h, and about 80 is undertaken by the lower floor of packing . To increase liquid quantity is helpful to improve removal effect, but the thickness of fluid film has negative influence to the RE. When the SO2 - 4 density of BTF accumulate more than 28 g L, RE is less than 90. The results show that the BTF system runs steadily and adapts well, which is feasible to purify industrial waste gases. Keywords biotrickling filter, hydrogen sulfide, biological treatment and air pollution control APPLICATION OF DUAL -EDDY CURRENT INREMOVAL OF DUST AND SULFUR OF FLUE GAS FROM COAL -FIRED POWER PLANTZhu Li Sun Limi Wang Fucheng 64 Abstract It is given a brief introduction to the feature and working principle on dual-eddy current in removal of dust and sulfur of flue gas from coal -fired power plant. The efficientof removalof dust and sulfur of flue gas hasbeen analyzed through a practical project. The results show that the technology is quite effective in collecting and removing both submicron particulate matter and sulfur dioxide with flue gas desulfurization efficient of 77. 2 and dust removal efficient of 94. 8. Keywords dual-eddy current technology for purifying boiler gas, coal -fired power plant, removal of dust sulfur and application MICROBIAL RECYCLE OF WASTE NATURAL RUBBERWITHSACCHAROMYCES CEREVISIAE EXTRACTYu Xiumei Wang Yaqin Zhao Suhe et al 67 4 ENVIRONMENTAL ENGINEERING Vol. 25, No. 6, Dec . , 2007
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