作者：韦聪1,2, 李磊1, 吕文英1, 刘国光1, 吴海珍3, 韦朝海2
作者单位：1. 广东工业大学环境科学与工程学院, 广东 广州 510006;
2. 华南理工大学环境与能源学院, 广东 广州 510006;
3. 华南理工大学生物科学与工程学院, 广东 广州 510006
关键词：化学需氧量;重铬酸钾法;微波消解技术;分析方法;干扰组分
摘要：
化学需氧量（chemical oxygen demand，COD）作为表征污水或废水污染程度的一个重要指标，在全球范围内被普遍采用。通过追踪COD方法发展的历史，以工业废水中最常用的重铬酸钾法为例，从氧化还原电位、催化作用等方面分析方法原理的特点、影响因素与适用范围，结合氧化剂的选择、定义的科学性、二次污染、COD成分的毒性以及干扰组分的存在5个方面讨论传统COD方法中存在的问题，指出方法创新和完善的方向；在方法原理基础上，论述微波消解技术、分光光度技术、库仑滴定技术等方面的COD技术化及其实际应用的动态，提出实现流程的标准化和样品的批量化可以提高效率的观点。通过对我国工业废水COD测定方法、技术应用的过程分析，指出COD方法及技术的创新性、可靠性、时效性对于我国未来的工业废水污染控制的稳定性与水环境管理的规范性将发挥重要的影响作用。
Analysis of the development of the industrial wastewater CODCr determination method and technology
WEI Cong1,2, LI Lei1, LÜ Wenying1, LIU Guoguang1, WU Haizhen3, WEI Chaohai2
1. School of Environment Science and Engineering, Guangdong University of Technology, Guangzhou 510006, China;
2. School of Environment and Energy, South China University of Technology, Guangzhou 510006, China;
3. School of Bioscience and Bioengineering, South China University of Technology, Guangzhou 510006, China
Abstract: Chemical oxygen demand (COD) as an important indicator of water quality has been widely used for characterizing the pollution extent of sewage or wastewater. By tracking the history of COD analysis and taking the commonly-used potassium dichromate approach as an example, here the authors carry out a thorough review on(i) the principle of COD detection method, the key factors and the scope of its application; and(ii) the important issues related to the traditional method including the selection of oxidants, the scientific meaning of definition, the second pollution, the toxic components and the interferential components. In addition, we discuss the development and current status of the microwave digestion technology, spectrophotometry technology and Coulomb titration technology, and propose the view of standardization and batch processing in order to improve the efficiency of COD determination. Lastly, we emphasize that the novelty, reliability, and timeliness of COD method/technology play significant roles in our country's industrial wastewater pollution control and water environment management.
Keywords: chemical oxygen demand;potassium dichromate method;microwave digestion technology;analytical method;interferential components
2017, 43(7): 1-9 收稿日期: 2016-01-20;收到修改稿日期: 2016-12-15
基金项目: 国家自然科学基金重点项目（51278199）；广东省应用型科技研发专项基金项目（2015B020235005）
作者简介: 韦聪(1990-),男,广西河池市人,硕士研究生,专业方向为环境工程。
参考文献
[1] SAWYER C N. Biological engineering in sewage treatment[J]. Sewage Works Journal,1944,16(5):925-935.
[2] BARNETT J, DUPRÉD J, HOLLOWAY B J, et al. Analogues of pantothenic acid. Part IV. Aryl derivatives of pantoyltaurine[J]. Journal of the Chemical Society(Resumed),1944,24(8):94-96.
[3] ADENEY W E, DAWSON B B. The estimation of organic matter in water by means of potassium bichromate and sulphuric acid[J]. Scientific Proceedings of the Royal Dublin Society,1926,18(1):199-202.
[4] MUERS M M. The biological purification of whey solutions[J]. Journal of the Society of Chemical Industry,1936,55(3):71-72.
[5] MOORE W A, KRONER R C, RUCHHOFT C C. Dichromate reflux method for determination of oxygen consumed[J]. Analytical Chemistry,1949,21(8):953-957.
[6] MOORE W A, LUDZACK F J, RUCHHOFT C C. Determination of oxygen-consumed values of organic wastes[J]. Analytical Chemistry,1951,23(9):1297-1300.
[7] DZYADZIO A M. The true oxygen consumption of sewage and a method for Its determination[J]. Vodosnabzheniei Sanit Tekh(USSR),1938,9(3):117-120.
[8] DOBBS R A, WILLIAMS R T. Elimination of chloride interference in the chemical oxygen demand test[J]. Analytical Chemistry,1963,35(8):1064-1067.
[9] 魏复盛,毕彤,齐文启. 水和废水检测分析方法[M]. 4版. 北京:中国环境科学出版社,2002:211-213.
[10] 沈叔平. 水和废水监测分析方法指南(上册)[M]. 北京:中国环境科学出版社,1990:231-232.
[11] 刘爱鹰. 影响COD测定精度因素初探[J]. 当代化工,2006, 35(4):295-298.
[12] SELVAPATHY P, STARLET J J. A new catalyst for COD determination[J]. Indian Journal of Environmental Health,1991,33(1):96-102.
[13] SUN J H, XIA S Q, SUN R X. Rapid determination of wastewater COD using Mn(H2PO4)2 as catalyst[J]. Journal of Environmental Sciences,1996,8(2):212-217.
[14] RAMON R, VALERO F, DEL VALLE M. Rapid determination of chemical oxygen demand using a focused microwave heating system featuring temperature control[J]. Analytica Chimica Acta,2003,491(1):99-109.
[15] DASGUPTA P K, PETERSEN K. Kinetic approach to the measurement of chemical oxygen demand with an automated micro batch analyzer[J]. Analytical Chemistry,1990,62(4):395-402.
[16] 沈澄英. 掩蔽剂硫酸汞用量对水样中CODCr测定的影响[J]. 安徽化工,2014,40(6):96-98.
[17] 李瑞祥,曾红梅,周向葛. 无机化学[M]. 北京:化学工业出版社,2013:100-101.
[18] ZHAO J L, YAN B, WEI C H, et al. Multispecies acute toxicity evaluation of wastewaters from different treatment stages in a coking wastewater-treatment plant[J]. Environmental Toxicology and Chemistry,2014,33(9):1967-1975.
[19] JARDIM W F, ROHWEDDER J J R. Chemical oxygen demand(COD) using micro-wave digestion[J]. Water Research,1989,23(8):1069-1071.
[20] DEL VALLE M, POCH M, ALONSO J, et al. Evaluation of microwave digestion for chemical oxygen demand determination[J]. Environmental Technology,1990,11(12):1087-1092.
[21] DOMINI C E, HIDALGO M, MARKEN F, et al. Comparison of three opimized digestion methods for rapid determination of chemical oxygen demand:Closed microwaves, open microwaves and ultrasound irradiation[J]. Analytica Chimica Acta,2006,561(1):210-217.
[22] NAKAMURA H, KOBAYASHI S, HIRATA Y, et al. A spectrophotometric biochemical oxygen demand determination method using 2, 6-dichlorophenolindophenol as the redox color indicator and the eukaryote Saccharomyces cerevisiae[J]. Analytical Biochemistry,2007,369(2):168-174.
[23] VYRIDES I, STUCKEY D C. A modified method for the determination of chemical oxygen demand(COD) for samples with high salinity and low organics[J]. Bioresource Technology,2009,100(2):979-982.
[24] 王方园,盛贻林,郑绍成. 高浓度氯离子化工废水中COD测定方法比较[J]. 工业水处理,2006,26(5):72-74.
[25] 黄荣富,周觅,俞建军,等. 高氯低COD废水COD测定方法研究[J]. 精细化工中间体,2014,44(1):61-63.
[26] 叶晓新,郭利群. COD测定中氯离子干扰消除方法的探讨[J]. 环境科学导刊,2011,30(5):95-97.
[27] VAIDYA B, WATSON S W, COLDIRON S J, et al. Reduction of chloride ion interference in chemical oxygen demand(COD) determinations using bismuth-based adsorbents[J]. Analytica Chimica Acta, 1997,357(1):167-175.
[28] 郭劲松,林佳琪,方芳,等. 屏蔽氯离子干扰高盐榨菜废水中COD的测定方法[J]. 重庆大学学报,2014,6(1):147-153.
[29] BELKIN S, BRENNER A, ABELIOVICH A. Effect of inorganic constituents on chemical oxygen demand-I. Bromides are unneutralizable by mercuric sulfate complexation[J]. Water Research,1992,26(12):1577-1581.
[30] 曹国民,盛梅,钟晨,等. 工业废水中溴离子对COD测定的影响[J]. 中国给水排水,2007,23(20):85-88.
[31] KANG Y W, CHO M J, HWANG K Y. Correction of hydrogen peroxide interference on standard chemical oxygen demand test[J]. Water Research,1999,33(5):1247-1251.
[32] 曹臣,韦朝海,杨清玉,等. 废水处理生物出水中COD构成的解析-以焦化废水为例[J]. 环境化学2012,31(10):1494-1501.
