醇基燃料热值的影响因素与计算方法研究
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摘要
醇基燃料热值的准确与快速测试及计算,对醇基燃料应用发展具有重要意义。由于甲醇水混溶过程的特殊性,传统的热值测试方法和计算方法较为复杂并存在偏差。本文从影响醇基燃料发热值的诸多因素出发研究快速标定醇基燃料发热值的简易计算方法。
鉴于尚无醇基燃料热值研究资料可查的情况,在查阅国内外关于其它燃料测试研究和甲醇-水组合化学结构研究资料的基础上,通过实验测试、误差分析、假设模型模拟等方法对影响醇基燃料热值的浓度配比、密度变化、混溶过程的放热、高锰酸钾的稳定性等因素进行了深入研究,获得基于密度计算醇基燃料低发热值的公式。公式计算结果与研究修正的门捷列夫理论经验公式的计算值对比表明：两者热值误差范围为0.25%-4.94%；研究成果为醇基燃料热值的快速测量提供了理论基础。
It is significantly important for application and development of methanol-based fuel (MBF)that how the calorific value of MBF can be rapidly measured and accuratly calculated. And nowadays, Because of the special nature of the process of methanol dissolved in water. it have always been two focal issues of dispute that how to solve complex and deviation of traditional test means and calculation method. So the fundamental properties of MBF were investigated by means of theory and experiment in terms of simplified calculation methods of its calorific value.
In view of none of research data for MBF being checked,the formula of MBF calorific value based on its density affected by different concentrations,densities,exothermal phenomena and Stability of potassium permanganate in the process of being mixed have been acquired by means of further investigation of experimental test, error analysis and model simulation,on the basis of consulting similar research of other fuels and chemical structure of methanol-water group, and the calculation results in contrast with that of modified Mendeleev experience formulas show that:the average error scope is 0.25%-4.94%; The research results provides a theoretical basis for rapid test of calorific value.
鉴于尚无醇基燃料热值研究资料可查的情况,在查阅国内外关于其它燃料测试研究和甲醇-水组合化学结构研究资料的基础上,通过实验测试、误差分析、假设模型模拟等方法对影响醇基燃料热值的浓度配比、密度变化、混溶过程的放热、高锰酸钾的稳定性等因素进行了深入研究,获得基于密度计算醇基燃料低发热值的公式。公式计算结果与研究修正的门捷列夫理论经验公式的计算值对比表明：两者热值误差范围为0.25%-4.94%；研究成果为醇基燃料热值的快速测量提供了理论基础。
It is significantly important for application and development of methanol-based fuel (MBF)that how the calorific value of MBF can be rapidly measured and accuratly calculated. And nowadays, Because of the special nature of the process of methanol dissolved in water. it have always been two focal issues of dispute that how to solve complex and deviation of traditional test means and calculation method. So the fundamental properties of MBF were investigated by means of theory and experiment in terms of simplified calculation methods of its calorific value.
In view of none of research data for MBF being checked,the formula of MBF calorific value based on its density affected by different concentrations,densities,exothermal phenomena and Stability of potassium permanganate in the process of being mixed have been acquired by means of further investigation of experimental test, error analysis and model simulation,on the basis of consulting similar research of other fuels and chemical structure of methanol-water group, and the calculation results in contrast with that of modified Mendeleev experience formulas show that:the average error scope is 0.25%-4.94%; The research results provides a theoretical basis for rapid test of calorific value.
引文
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[2]BP.BP Statistical Review of World Energy 2008[OL].[2008-04].http: //www.bp.com/statisticalreview.
[3]王玉庆.中国环境科学学会2004年学术年会.2005-9-23.
[4]温家宝.第十届全国人民代表大会第三次会议政府工作报告.北京,2005-3-5.
[5]欧奋达.全球资源告急[J].福建环境,1999,06：11-12.
[6]政协”一号提案”锁定低碳[R].环境经济,2010(3)：10-13.
[7]George A. Olah, Alain Goeppert, GK. Surya Prakash, Beyond Oil and Gas:The Methanol Economy[J].Angewandte Chemie International Edition Volume 44, Issue 18, Pages 2636-2639,2005.
[8]张全,刘洋,赵军.醇基燃料热值的研究探讨[J].工业加热,2009,39(1)：17-19.
[9]房鼎业.甲醇生产技术及进展[M].上海：华东化工学院出版社,1990.
[10]凌斌,梁玮.甲醇生产与市场应用前景[J].天然气与石油,2008,26(3)：51-53.
[11]张蕊.我国甲醇行业现状与发展建议[J].中国科技财富,2008,(10)：160.
[12]衣宝廉.燃料电池——原理技术应用[M],化学工业出版社.2003.
[13]徐维正.国外甲醇燃料电池技术开发概况[J].精细与专用化学品.2006(14)：26-27.
[14]Heinzel A,Barragn V M.A review of the state-of-the-art of the methanol crossover in direct methanol fuel cells[J].Power Sources,1999,84:70-74.
[15]Hogarth M P,Hards G A,Direct methanol fuel cells technological advances and further requirements[J].Platinum Metals Rex,1996,40:150-159.
[16]方显忠,刘巽俊.直喷压燃式发动机用双喷射系统燃用柴油--甲醇的研究[J].内燃机学报.2003,21(6)：411-414.
[17]Huang Z H,Lu H B,Jiang D M,et al.Combustion behaviors of acompression ignition engine fuelled with dieseFmethanol blends under various fuel delivery advance angles[J].Bioresource Technology,2004,95(3):331-341.
[18]张全,刘洋,赵军.后石油时代的选择-醇基燃料[R].北京：2009年中国新能源及可再生能源科技发展论坛,中国能源学会,2009：269-277.
[19]R.L. Fyans. In:Thermal Analysis Application Study # 21[C].Perkin-Elmer Corp., Norwalk,CT(1977).
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[21]Peter H. Given, Diane Weldon, Jerome H. Zoeller. Calculation of calorific values of coals from ultimate analyses:theoretical basis and geochemical implications. l.1986,65(6):849-854.
[22]M.J. Munoz-Guillena, A. Linares-Solano,and C.Salinas-Martinez de Lecea. Determination of calorific values of coals by differential thermal analysis.[J].fuel. 1992,71(5):579-583.
[23]Ahmad Reza Shirazi, Olle Bortin, Lars Eklund,Oliver Lindqvist. The impact of mineral matter in coal on its combustion, and a new approach to the determination of the calorific value of coal. [J]. Fuel.1995,74(2):247-251.
[24]Jothi V. Kumar, Benjamin C. Pratt. Determination of calorific values of some renewable biofuels.[J]. Thermochimica acta.1996,279:111-120.
[25]L.B.M. van Kesse, A.R.J. Arendsen, G. Brem. On-line determination of the calorific value of solid fuels.[J]. Fuel.2004,83:59-71.
[26]杨丽,文科军,姚晓霞.城市生活垃圾、污泥和煤粉混合燃料热值的研究[J].环境工程学报,2008,9(2)：1239-1242.
[27]申玉春,郭慧,吴灶和.池塘悬浮物COD值与灼烧减重燃烧热值的定量关系[J].环境科学与技术,2010,33(1)：16-18.
[28]谢承利,陆继东,沈凯.基于焚烧运行参数的垃圾热值软测量模型[J].燃烧科学与技术,2007,13(1)：81-85.
[29]Skaf M S,Ladanyi B M.[J].Chem,1996,100:18258-18268.
[30]Ladanyi B M.Skaf M S.[J].Phys Chem.1996,100:1368-1380.
[31]Zhang G,Wu C.[J].Am Chem Soc.2001,123:1376-1380.
[32]胡宏纹.有机化学[M].北京：高等教育出版社,2006.
[33]克拉辛,毛钜凡译.磁化水[M].北京：计量出版社,1982,10.
[34]Thomas R. Dyke, Kenneth M. Mack, J. S. Muenter. The structure of water dimer from molecular beam electric resonance spectroscopy.[J].Chern.Phys.1997,66 (2):498-510.
[35]J. G.Loeser,M. J. Elrod.Dynamics of Structural Rearrangements in the Water Trimer.[J]. Am. Chem. Soc.1994,116:3507-3512.
[36]J. D.cruzan,L.B. Branly. Quantifying Hydrogen Bond Cooperativity in Water:VRT Spectroscopy of the Water Tetramer.[J].Science.1996,271(5245):59-62.
[37]S.S.Xantheas,T Hdunning.Jr,Ab initio studies of cyclic water clusters(H2O)n, n=1-6.i.optimal structures and vibrational spectra.[J].Chem.Phys.1993,99(11): 8774-8792.
[38]K.Liu,M.G.Brown, Carter C,Characterization of a Cage Form ofthe Water Hexamer, [J].Nature.1996,381:501-503.
[39]龚珍,李象远,李泽荣.水和甲醇混合溶剂氢键相互作用及对高分子链溶解能力 的理论研究[J].高等学校化学学报,2004,25(3)：539-542.
[40]A.Rahman, F.H.Stillinger, Hydrogen-Bond Patterns in Liquid Water, [J]. Am. Chem. Soc.1973,95:7943-7948.
[41]Wallqvist A,Mountain R D.Molecular models of water:Derivation and descdption[J].Reviews in Computational Chemistry,1999.13,183-247.
[42]Jaime L. Iosue, David M. Benoit, David C. Clary, Diffusion Monte Carlo simulations of methanol-waterclusters,[J].Chemical Physics Letters.1999,301:275-280.
[43]AbhishekMandal,Muthuramalingam Prakash,Ravva Mahesh Kumar,Ramakrishnan Parthasarathi,Venkatesan Subramanian. Ab Initio and DFT Studies on Methanol-Water Clusters.[J].Chern. Phys.2010,114:2250-2258.
[44]王林双,王榕树.水分子簇的研究进展[J].化学进展,2001,13(2)：81-86.
[45]赫斯洛普.高等无机化学[M].北京：人民教育出版社,1982.
[46]姜月顺,李铁津.光化学[M].北京：化学工业出版社,2005.
[47]Lee Eung Seok,Schwartz,Franklin W.Characteristics and applications of controlled-release KMnO4 for groundwater remediation[J].chemosphere 2007,66(11):2058-2066.
[48]Chen Jen Jeng.Yeh Hsuan Hsien. The mechanisms of potassium permanganate on algae removal[J]. Water Research.2005,39(18):4420-4428.
[49]杜清枝,杨继舜.物理化学[M].重庆：重庆大学出版社,1997.
[50]梅光贵,钟竹前.湿法冶金新工艺[M].长沙：中南工业大学出版社,1994.
[51]梁英教,车荫昌.无机物热力学数据手册[M].沈阳：东北大学出版社,1993.
[52]尚杰锋,李金利,荣中波.高锰酸钾标准溶液的稳定性及标定准确性探讨[J].大氮肥.2003,26(2)：106-108.
[53]A. R. Burkin.The Chemistry of Hydrometallurgical Process[M]London:Spon.1987.
[2]BP.BP Statistical Review of World Energy 2008[OL].[2008-04].http: //www.bp.com/statisticalreview.
[3]王玉庆.中国环境科学学会2004年学术年会.2005-9-23.
[4]温家宝.第十届全国人民代表大会第三次会议政府工作报告.北京,2005-3-5.
[5]欧奋达.全球资源告急[J].福建环境,1999,06：11-12.
[6]政协”一号提案”锁定低碳[R].环境经济,2010(3)：10-13.
[7]George A. Olah, Alain Goeppert, GK. Surya Prakash, Beyond Oil and Gas:The Methanol Economy[J].Angewandte Chemie International Edition Volume 44, Issue 18, Pages 2636-2639,2005.
[8]张全,刘洋,赵军.醇基燃料热值的研究探讨[J].工业加热,2009,39(1)：17-19.
[9]房鼎业.甲醇生产技术及进展[M].上海：华东化工学院出版社,1990.
[10]凌斌,梁玮.甲醇生产与市场应用前景[J].天然气与石油,2008,26(3)：51-53.
[11]张蕊.我国甲醇行业现状与发展建议[J].中国科技财富,2008,(10)：160.
[12]衣宝廉.燃料电池——原理技术应用[M],化学工业出版社.2003.
[13]徐维正.国外甲醇燃料电池技术开发概况[J].精细与专用化学品.2006(14)：26-27.
[14]Heinzel A,Barragn V M.A review of the state-of-the-art of the methanol crossover in direct methanol fuel cells[J].Power Sources,1999,84:70-74.
[15]Hogarth M P,Hards G A,Direct methanol fuel cells technological advances and further requirements[J].Platinum Metals Rex,1996,40:150-159.
[16]方显忠,刘巽俊.直喷压燃式发动机用双喷射系统燃用柴油--甲醇的研究[J].内燃机学报.2003,21(6)：411-414.
[17]Huang Z H,Lu H B,Jiang D M,et al.Combustion behaviors of acompression ignition engine fuelled with dieseFmethanol blends under various fuel delivery advance angles[J].Bioresource Technology,2004,95(3):331-341.
[18]张全,刘洋,赵军.后石油时代的选择-醇基燃料[R].北京：2009年中国新能源及可再生能源科技发展论坛,中国能源学会,2009：269-277.
[19]R.L. Fyans. In:Thermal Analysis Application Study # 21[C].Perkin-Elmer Corp., Norwalk,CT(1977).
[20]C.M. Earnest and R.L. Fyans. In:B. Miller, Editor, Thermal Analysis, Vol.Ⅱ, Proc. of the 7th ICTA[C] John Wiley and Sons, New York (1982):1260-1268.
[21]Peter H. Given, Diane Weldon, Jerome H. Zoeller. Calculation of calorific values of coals from ultimate analyses:theoretical basis and geochemical implications. l.1986,65(6):849-854.
[22]M.J. Munoz-Guillena, A. Linares-Solano,and C.Salinas-Martinez de Lecea. Determination of calorific values of coals by differential thermal analysis.[J].fuel. 1992,71(5):579-583.
[23]Ahmad Reza Shirazi, Olle Bortin, Lars Eklund,Oliver Lindqvist. The impact of mineral matter in coal on its combustion, and a new approach to the determination of the calorific value of coal. [J]. Fuel.1995,74(2):247-251.
[24]Jothi V. Kumar, Benjamin C. Pratt. Determination of calorific values of some renewable biofuels.[J]. Thermochimica acta.1996,279:111-120.
[25]L.B.M. van Kesse, A.R.J. Arendsen, G. Brem. On-line determination of the calorific value of solid fuels.[J]. Fuel.2004,83:59-71.
[26]杨丽,文科军,姚晓霞.城市生活垃圾、污泥和煤粉混合燃料热值的研究[J].环境工程学报,2008,9(2)：1239-1242.
[27]申玉春,郭慧,吴灶和.池塘悬浮物COD值与灼烧减重燃烧热值的定量关系[J].环境科学与技术,2010,33(1)：16-18.
[28]谢承利,陆继东,沈凯.基于焚烧运行参数的垃圾热值软测量模型[J].燃烧科学与技术,2007,13(1)：81-85.
[29]Skaf M S,Ladanyi B M.[J].Chem,1996,100:18258-18268.
[30]Ladanyi B M.Skaf M S.[J].Phys Chem.1996,100:1368-1380.
[31]Zhang G,Wu C.[J].Am Chem Soc.2001,123:1376-1380.
[32]胡宏纹.有机化学[M].北京：高等教育出版社,2006.
[33]克拉辛,毛钜凡译.磁化水[M].北京：计量出版社,1982,10.
[34]Thomas R. Dyke, Kenneth M. Mack, J. S. Muenter. The structure of water dimer from molecular beam electric resonance spectroscopy.[J].Chern.Phys.1997,66 (2):498-510.
[35]J. G.Loeser,M. J. Elrod.Dynamics of Structural Rearrangements in the Water Trimer.[J]. Am. Chem. Soc.1994,116:3507-3512.
[36]J. D.cruzan,L.B. Branly. Quantifying Hydrogen Bond Cooperativity in Water:VRT Spectroscopy of the Water Tetramer.[J].Science.1996,271(5245):59-62.
[37]S.S.Xantheas,T Hdunning.Jr,Ab initio studies of cyclic water clusters(H2O)n, n=1-6.i.optimal structures and vibrational spectra.[J].Chem.Phys.1993,99(11): 8774-8792.
[38]K.Liu,M.G.Brown, Carter C,Characterization of a Cage Form ofthe Water Hexamer, [J].Nature.1996,381:501-503.
[39]龚珍,李象远,李泽荣.水和甲醇混合溶剂氢键相互作用及对高分子链溶解能力 的理论研究[J].高等学校化学学报,2004,25(3)：539-542.
[40]A.Rahman, F.H.Stillinger, Hydrogen-Bond Patterns in Liquid Water, [J]. Am. Chem. Soc.1973,95:7943-7948.
[41]Wallqvist A,Mountain R D.Molecular models of water:Derivation and descdption[J].Reviews in Computational Chemistry,1999.13,183-247.
[42]Jaime L. Iosue, David M. Benoit, David C. Clary, Diffusion Monte Carlo simulations of methanol-waterclusters,[J].Chemical Physics Letters.1999,301:275-280.
[43]AbhishekMandal,Muthuramalingam Prakash,Ravva Mahesh Kumar,Ramakrishnan Parthasarathi,Venkatesan Subramanian. Ab Initio and DFT Studies on Methanol-Water Clusters.[J].Chern. Phys.2010,114:2250-2258.
[44]王林双,王榕树.水分子簇的研究进展[J].化学进展,2001,13(2)：81-86.
[45]赫斯洛普.高等无机化学[M].北京：人民教育出版社,1982.
[46]姜月顺,李铁津.光化学[M].北京：化学工业出版社,2005.
[47]Lee Eung Seok,Schwartz,Franklin W.Characteristics and applications of controlled-release KMnO4 for groundwater remediation[J].chemosphere 2007,66(11):2058-2066.
[48]Chen Jen Jeng.Yeh Hsuan Hsien. The mechanisms of potassium permanganate on algae removal[J]. Water Research.2005,39(18):4420-4428.
[49]杜清枝,杨继舜.物理化学[M].重庆：重庆大学出版社,1997.
[50]梅光贵,钟竹前.湿法冶金新工艺[M].长沙：中南工业大学出版社,1994.
[51]梁英教,车荫昌.无机物热力学数据手册[M].沈阳：东北大学出版社,1993.
[52]尚杰锋,李金利,荣中波.高锰酸钾标准溶液的稳定性及标定准确性探讨[J].大氮肥.2003,26(2)：106-108.
[53]A. R. Burkin.The Chemistry of Hydrometallurgical Process[M]London:Spon.1987.