张哲舟,赵立新,秦松岩,李雪,李爱玲,李海青,张瑞玲

• 1:天津理工大学环境科学与安全工程学院
• 2:天津市德信成环保科技有限公司

摘要(Abstract)：

工业危险废液的热值准确测定对于保障热解处置工艺的正常运行至关重要。多相低热值工业危险废液不易燃烧、多相共存、成分难辨,故难以用氧弹直接燃烧法准确反映热值。今基于工业危废液的特性,提出对工业危废液分相测定热值,即固相残余物直接燃烧结合含水馏出物间接估算的总思路。针对含水馏出物成分复杂难辨的特性,提出了基于气相色谱-质谱法对工业危险废液成分化学式及物质量相对比例的辨识,通过推导统一化学计量式计算热值的间接估算法。结果表明该方法估算热值误差小于6%,核算同分异构体对热值的影响误差较小。针对危废液热值的日常监控,可选用COD为热值关联表征参数。选取7种不同行业危废液的热值实测及计算,验证了方法的普适性。

关键词(KeyWords)： 工业危险废液;热值;色谱;化学计量式;间接估算法

Abstract:

Keywords:

基金项目(Foundation): 天津市自然科学基金重点项目(16JCZDJC39800)

作者(Author): 张哲舟,赵立新,秦松岩,李雪,李爱玲,李海青,张瑞玲

参考文献(References)：

• [1]中华人民共和国环境保护部,危险废物处置工程技术导则:HJ 2042-2014[S].北京:中国环境科学出版社,2014.Ministry of Environmental Protection of the People's Republic of China,General specifications of engineering and technology for hazardous waste disposal,Standardization:HJ 2042-2014[S].Beijing:Environmental Science Press of China,2014.
• [2]AMETA S C,AMETA R.Advanced oxidation processes for waste water treatment[M].Netherlands:Academic Press,2018:333-358.
• [3]ANIKEEV V,FAN M H.Supercritical fluid technology for energy and environmental applications[M].Netherlands:Elsevier,2014:181-190.
• [4]COCERO M J.Supercritical water processes:Future prospects[J].The Journal of Supercritical Fluids,2018,134:124-132.
• [5]GARCIA-RODRIGUEZ Y,MATO F A,MARTIN A,et al.Energy recovery from effluents of supercritical water oxidation reactors[J].The Journal of Supercritical Fluids,2015,104:1-9.
• [6]ABELLEIRA J,SANCHEZ-ONETO J,PORTELA J R,et al.Kinetics of supercritical water oxidation of isopropanol as an auxiliary fuel and co-fuel[J].Fuel,2013,111:574-583.
• [7]LAVRIC E D,WEYTEN W,RUYCK J D,et al.Supercritical water oxidation improvements chemical reactors energy integration[J].Applied Thermal Engineering,2006,23(13):1385-1392.
• [8]中华人民共和国国家质量监督检验检疫总局,煤的发热量测定方法:GB/T 213-2008[S].北京:中国标准出版社,2008.General Administration of Quality Supervision,Inspection and Quarantine of the People’s Republic of China,Determination of calorific value of coal,GB/T 213-2008[S].Beijing:Standards Press of China,2015.
• [9]SHIZAS I,BAGLEY B D.Experimental determination of energy content of unknown organics in municipal wastewater streams[J].Journal of Energy Engineering-ASCE,2004,130(2):45-53.
• [10]高旭,马蜀,郭劲松,等.城市污水厂污水污泥的热值测定分析方法研究[J].环境工程学报,2009,1(11):1938-1942.GAO X,MA S,GUO J S,et al.Determination of the calorific value of wastewater and sludge from a municipal wastewater treatment plant[J].Chinese journal of Environmental Engineering,2009,1(11):1938-1942.
• [11]周利,郭雪松,肖本益,等.城市污水处理厂剩余污泥热值测定方法优化研究[J].环境工程学报,2012,6(8):2805-2808.ZHOU L,GUO X S,XIAO B Y,et al.Optimization study on the caloric value determination of excess sludge from municipal wastewater treatment plants[J].Chinese journal of Environmental Engineering,2012,6(8):2805-2808.
• [12]马蜀,高旭,郭劲松,等.城市污水处理厂剩余污泥的元素含量分析[J].中国给水排水,2007,23(19):60-63.MA S,GAO X,GUO J S,et al.Element analysis of excess activated sludge in WWTP[J].China Water&WasteWater,2007,23(19):60-63.
• [13]金余其,严建华,池涌,等.中国城市生活垃圾燃烧的特性[J].环境科学,2002,23(3):107-110.JIN Y Q,YAN J H,CHI Y,et al.Combustion characteristics of municipal solid wastes in China[J].Environmental Science,2002,23(3):107-110.
• [14]MANCINI M,RINNAN A,PIZZI A,et al.Prediction of gross calorific value and ash content of woodchip samples by means of FT-NIR spectroscopy[J].Fuel Processing Technology,2018,169:77-83.
• [15]OZYUGURAN A,AKTURK A,YAMAN S.Optimal use of condensed parameters of ultimate analysis to predict the calorific value of biomass[J].Fuel,2018,214:640-646.
• [16]TELMO C,LOUSADA J,MOREIRA N.Proximate analysis,backwards stepwise regression between gross calorific value,ultimate and chemical analysis of wood[J].Bioresource Technology,2010,101(11):3808-3815.
• [17]JAIN S R,SUNDARARAJAN R.New method of calculating calorific values from elemental compositions of fossil fuels[J].Fuel,1981,60(11):1079-1082.
• [18]THIPKHUNTHOD P,MEEYOO V,RANGSUNVIGIT P.Predicting the heating value of sewage sludges in Thailand from proximate and ultimate analyses[J].Fuel,2005,84:849-857.
• [19]中华人民共和国环境保护部,水质硝基苯类化合物的测定气相色谱法:HJ/T 592-2010[S].北京:中国环境科学出版社,2010.Ministry of Environmental Protection of the People's Republic of China,Water quality Determination of nitrobenzene-compounds by Gas chromatography:HJ/T 592-2010[S].Beijing:Environmental Science Press of China,2014.
• [20]杜一平.现代仪器分析方法(第二版)[M].上海:华东理工大学出版社,2015:74.DU Y P.Modern instrumental analysis methods[M].Shanghai:East China University of Science and Technology,2015:74.
• [21]中华人民共和国环境保护部,水质化学需氧量的测定快速消解分光光度法:HJ/T 399-2007[S].北京:中国环境科学出版社,2007.Ministry of Environmental Protection of the People's Republic of China,Water quality Determination of the chemical oxygen demand:HJ/T 399-2007[S].Beijing:Environmental Science Press of China,2007.
• [22]FERGUSON L N.The modern structural theory of organic chemistry[M].New Delhi:Prentice-Hall of India,1969.
• [23]ALBAHRI T A.Accurate prediction of the standard net heat of combustion from molecular structure[J].Journal of Loss Prevention in the Process Industries,2014,32:377-386.
• [24]TURKER L.Contemplation on the heats of combustion of isomeric hydrocarbons[J].Journal of Molecular Structure,2004,680(1/2/3):29-31.
• [25]吴文渊,张子栋,杨励丹,等.高浓度有机废液焚烧特性参数的确定[J].哈尔滨工业大学学报,1994,26(6):14-17.WU W Y,ZHANG Z D,YANG L D,et al.Determination of characteristic parameters in incineration of organic waste liquid with high concentration[J].Journal of Harbin Institute of Technology,1994,26(6):14-17.
• [26]别如山,陆慧林,杨励丹,等.高浓度有机废液热值的探讨[J].上海环境科学,1998,17(4):35-37.BIE R S,LU H L,YANG L D,et al.Approach on heating value of high concentrated organic waste liquid[J].Shanghai Environmental Sciences,1998,17(4):35-37.
• [27]魏徽,余红伟,宴欣,等.喷气燃料热值实验室测定研究[J].实验技术与管理,2014,31(7):50-52.WEI Z,YU H W,YAN X,et al.Study on determination of jet fuel calorific value in laboratory[J].Experimental Technology and Management,2014,31(7):50-52.
• [28]YAWS C L.Handbook of chemical compound data for process safety[M].Netherlands:Gulf Professional Publishing,1997:109-135.
• [29]赵卫东,黄健泉,倪康,等.气-液两相放电加氢精制生物油的试验研究[J].石油与天然气化工,2014,46(3):1-6.ZHAO W D,HUANG J Q,NI K,et al.Experimental study of gas-liquid two-phase discharge hydrofining bio-oil[J].Chemical Engineering of Oil&Gas,2014,46(3):1-6.
• [30]HU J H,TAMURA K,MURAKAMI S.Excess thermodynamic properties of binary mixtures of ethyl formate with benzene,ethanol,and 2,2,2-trifluoroethan-1-ol at 298.15 K[J].Fluid Phase Equilibria,1997,131(1):197-212.