镁基—海水法船舶烟气脱硫废水水质分析与处理
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摘要
随着航运事业的不断发展,因船舶烟气中二氧化硫排放造成的污染日益严重。为满足国际海事组织(IMO)对水上航运环境的严格要求,船舶烟气脱硫技术的研究倍受人们关注。而船舶脱硫废水的研究相对较少,对船舶烟气脱硫废水进行水质分析与处理研究亟待展开。
实验室在某集装箱船设计安装一套镁基-海水法湿式烟气脱硫系统,当船舶主机正常运行时,进行烟气脱硫处理。脱硫废水水样为脱硫率大于90%以上时取得,对《废气清洗系统导则(2009)》(MEPC.184(59)决议)中洗涤水排放标准要求的水质指标进行分析；并根据水质特点,采用预曝气,活性炭二级吸附作用的技术方法处理。
经实验分析得出船舶烟气脱硫水质主要特点为：废水颜色为黄色、略带刺激性气味、pH为8.87、亚硫酸根为10.21mg/L、悬浮物为1.471×104mg/L、浊度为50.2FTU、 CODOH-KI为224mg/L、PAHs为370.6μg/L、亚硝酸根为1.56mg/L,硝酸根为9.28mg/L。该类废水亚硫酸盐、氯离子含量较高、COD、悬浮物(SS)、多环芳烃(PAHs)、浊度超出海水污水排放标准及废气清洗系统(EGC)中洗涤水排放标准相关指标值。
废水经预曝气,活性碳二级吸附作用方法处理结果为：250mL废水,在曝气1.5h时,亚硫酸盐的转化率为29.6%,和曝气2h时的转化率29.7%相差仅为0.1%,从经济性角度考虑,曝气时间定位1.5h。曝气处理后的废水50mL,调节pH为7.5,加入1.5g活性炭,吸附1.5h,废水的CODOH-KI与PAHs分别降为110mg/L和52.5gg/L,亚硝酸根为1.43mg/L,硝酸根为9.50mg/L,出水pH为7.56,且各项指标都符合船舶污水排放标准和废气清洗系统中的洗涤水排放标准。其中活性炭对PAHs的饱和吸附量为44.851μg/g。
The pollution caused by sulfur dioxide discharged from shipborne flue gas increases with the development of shipping continuously. In order to meet the stringent requirements set down by the International Maritime Organization (IMO) on the shipping environment, more and more attention is paid to the research on shipborne flue gas desulfurization. However there has been relatively little research on shipborne desulfurization wastewater treatment. It is urgent to analyze and treat wastewater from shipborne flue gas desulfurization.
When the main engine of the ship is being the normal operation, a self-made wet-method flue gas desulfurization (FGD) equipment with MgO-seawater as desulfurizer was applied on a container ship. When the desulfurization efficiency is more than90%, the wastewater sample was taken and the relevant water quality indicators of 《Exhaust gas cleaning system guide (2009)》(MEPC.184(59) resolution) was analyzed. According to the characteristics of the wastewater, a method of pre-aeration and activated carbon adsorption was applied to treat the wastewater.
The main characteristics of the yellow and slightly pungent alkaline wastewater were obtained as follows:the value of pH was8.87, the turbidity was50.2FTU, the contents of sulfite, suspended solids(SS), CODOH-KI, polycyclic aromatic hydrocarbons (PAHs), nitrite and nitrate were10.21mg/L,1.471×104mg/L,224mg/L,370.6μg/L,1.56mg/L and9.28mg/L, respectively. The wastewater has high contents of sulfite and chloride, and the contents of COD, SS and PAHs are greater than the values in the seawater turbidity sewage discharge standard and the exhaust gas cleaning system (EGC) in the wash water discharge standards related indexes.
The results of wastewater treatment by pre-aeration and activated carbon adsorption were as follows:after the wastewater (250mL) aerated by1.5h and2h, the sulfite conversion efficiency was29.6%and29.7%respectively. The latter was only 0.1%greater than the former. From the economic point of view, the aeration time of1.5h is reasonable. The contents of CODOH-KI, PAHs, nitrite and nitrate were decreased to1lOmg/L,52.5μg/L,1.43mg/L and9.50mg/L respectively, and the value of pH was7.56, when1.5g activated carbon was used to treat the wastewater (50mL) in the aeration time of1.5h. The indicators meet all requirements of Exhaust Gas Cleaning System Guide (2009)(MEPC.184(59) resolution). The saturated adsorption capacity of PAHs/activated carbon is44.85μg/g.
实验室在某集装箱船设计安装一套镁基-海水法湿式烟气脱硫系统,当船舶主机正常运行时,进行烟气脱硫处理。脱硫废水水样为脱硫率大于90%以上时取得,对《废气清洗系统导则(2009)》(MEPC.184(59)决议)中洗涤水排放标准要求的水质指标进行分析；并根据水质特点,采用预曝气,活性炭二级吸附作用的技术方法处理。
经实验分析得出船舶烟气脱硫水质主要特点为：废水颜色为黄色、略带刺激性气味、pH为8.87、亚硫酸根为10.21mg/L、悬浮物为1.471×104mg/L、浊度为50.2FTU、 CODOH-KI为224mg/L、PAHs为370.6μg/L、亚硝酸根为1.56mg/L,硝酸根为9.28mg/L。该类废水亚硫酸盐、氯离子含量较高、COD、悬浮物(SS)、多环芳烃(PAHs)、浊度超出海水污水排放标准及废气清洗系统(EGC)中洗涤水排放标准相关指标值。
废水经预曝气,活性碳二级吸附作用方法处理结果为：250mL废水,在曝气1.5h时,亚硫酸盐的转化率为29.6%,和曝气2h时的转化率29.7%相差仅为0.1%,从经济性角度考虑,曝气时间定位1.5h。曝气处理后的废水50mL,调节pH为7.5,加入1.5g活性炭,吸附1.5h,废水的CODOH-KI与PAHs分别降为110mg/L和52.5gg/L,亚硝酸根为1.43mg/L,硝酸根为9.50mg/L,出水pH为7.56,且各项指标都符合船舶污水排放标准和废气清洗系统中的洗涤水排放标准。其中活性炭对PAHs的饱和吸附量为44.851μg/g。
The pollution caused by sulfur dioxide discharged from shipborne flue gas increases with the development of shipping continuously. In order to meet the stringent requirements set down by the International Maritime Organization (IMO) on the shipping environment, more and more attention is paid to the research on shipborne flue gas desulfurization. However there has been relatively little research on shipborne desulfurization wastewater treatment. It is urgent to analyze and treat wastewater from shipborne flue gas desulfurization.
When the main engine of the ship is being the normal operation, a self-made wet-method flue gas desulfurization (FGD) equipment with MgO-seawater as desulfurizer was applied on a container ship. When the desulfurization efficiency is more than90%, the wastewater sample was taken and the relevant water quality indicators of 《Exhaust gas cleaning system guide (2009)》(MEPC.184(59) resolution) was analyzed. According to the characteristics of the wastewater, a method of pre-aeration and activated carbon adsorption was applied to treat the wastewater.
The main characteristics of the yellow and slightly pungent alkaline wastewater were obtained as follows:the value of pH was8.87, the turbidity was50.2FTU, the contents of sulfite, suspended solids(SS), CODOH-KI, polycyclic aromatic hydrocarbons (PAHs), nitrite and nitrate were10.21mg/L,1.471×104mg/L,224mg/L,370.6μg/L,1.56mg/L and9.28mg/L, respectively. The wastewater has high contents of sulfite and chloride, and the contents of COD, SS and PAHs are greater than the values in the seawater turbidity sewage discharge standard and the exhaust gas cleaning system (EGC) in the wash water discharge standards related indexes.
The results of wastewater treatment by pre-aeration and activated carbon adsorption were as follows:after the wastewater (250mL) aerated by1.5h and2h, the sulfite conversion efficiency was29.6%and29.7%respectively. The latter was only 0.1%greater than the former. From the economic point of view, the aeration time of1.5h is reasonable. The contents of CODOH-KI, PAHs, nitrite and nitrate were decreased to1lOmg/L,52.5μg/L,1.43mg/L and9.50mg/L respectively, and the value of pH was7.56, when1.5g activated carbon was used to treat the wastewater (50mL) in the aeration time of1.5h. The indicators meet all requirements of Exhaust Gas Cleaning System Guide (2009)(MEPC.184(59) resolution). The saturated adsorption capacity of PAHs/activated carbon is44.85μg/g.
引文
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[2]Siagi ZO, Mbarawa M.Dissolution rate of South African calcium-based materials at constant-pH[J].J Hazard Mater,2009,163:678-682.
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[5]Hao Jin ming, Wang Shu xiao.Designation of Acide Rain and SO2 Control Zones and Control Policies in China[J],J Environ Sci Health, Part A,2000,35(10),1901-1914.
[6]任如山,黄学敏,石发恩等.湿法烟气脱硫技术研究进展[J].工业安全与环保,2010,36(6)：14-15.
[7]崔一尘,刘惠永,廖洪强,孙俊民,姚强.燃煤烟气脱硫技术发展及其应用前景[J].热电技术,2001,1：19-24.
[8]景启国,徐康富.氧化镁FGD脱硫过程的建模及其应用[J].环境污染治理技术及设备,2005,11(6)：32-38.
[9]徐宏建,张超,葛红花.镁法烟气脱硫工艺的实验窒模拟及其优化[J].上海电力学院学报,2010,4,26(2)：145-146.
[10]魏刚.氧化镁法脱硫废水处理系统设计.天津化工[A].2007,2(21)：55.
[11]郭东明.脱硫工程技术与设备[M].北京.化学工业出版社,2007.
[12]GB8978-1996污水综合排放标准.
[13]F ederal L aw G azette,BGBl.I ordinance o n Requirements for the Discharge of Waste Water into Waters [S].2004:1108.
[14]中国船级社.73/78公约[M].北京：人民交通出版社,2003.
[15]葛红花,华晶晶,曹雨欣.氧化镁脱硫废水处理絮凝剂研究[J].上海电力学院学报.2006,22(3)：239.
[16]王中原,王俩,宋宝华.氧化镁湿法烟气脱硫废水处理技术探讨[A].2010.
[17]应春华,刘柏辉,戴豪波,牛延军.脱硫废水排放的控制项目及标准探讨.热力发电,2005 (9).
[18]王中原,王俩,宋宝华.氧化镁湿法烟气脱硫废水处理技术探讨[A].2010.
[19]S V D.imirtova Meatl sorption on blast fnraceslga[J].WatRes.1996,30(1):228-232.
[20]S K Srivasatva.Removal of lead chromimu by activated slag-ablastufmacewaset[J].Jourmal of Enviormnental Engineering,1997(5):461-468.
[21]赵玉娥,徐克贤,高大明.悬浮物沉降与治理试验[J].黄金.1989,10(12)：4648.
[22]来勇.化学沉淀-絮凝法处理双碱法烟气脱硫废水[M].(硕十学位论文).杭州：浙江大学,2005.
[23]李彩亭,刘精今.炉渣处理烟气除尘脱硫废水[J].环境与开发.1996,11(4).
[24]Menzie C, A,Potoki B.B.Exposure to carcinogenic PAHs in the environment[J]. Enviro n Sci Technol,1992,26(7):1278-1284.
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