部分加氢生物柴油改善柴油机的燃烧与排放
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摘要
部分加氢工艺可显著提升生物柴油的氧化安定性,同时改善燃料的着火性能,是提高生物柴油品质的有效途径。以Raney-Ni为催化剂,异丙醇为供氢体,在85℃的水环境下对大豆生物柴油进行催化转移加氢试验,得到部分加氢生物柴油,并以传统柴油作为参照,分别制备B20(80%传统柴油+20%生物柴油)和PHB20(80%传统柴油+20%加氢生物柴油),在186FA型柴油机上进行发动机性能试验,并使用燃烧分析仪、尾气分析仪和烟度计等仪器探究加氢生物柴油对柴油机燃烧过程及排放性能的影响。研究结果表明:柴油机燃用柴油、B20及PHB20的当量燃油消耗率基本相当;在标定工况下,尽管加氢生物柴油运动黏度略有升高而不利于燃油雾化,但其十六烷值较高更易于燃烧,在燃料特性的综合影响下,与柴油机燃用柴油相比,B20和PHB20的着火时刻依次提前了0.8°曲轴转角和1.4°曲轴转角,瞬时放热峰及最大爆发压力亦随之提前,但最大放热率和最大爆发压力依次略有降低;在标定工况下,与燃用柴油相比, B20的HC,CO和烟度排放分别下降了9.9%、9.3%和15.2%,NO_x排放上升了8.5%;而PHB20的HC,CO和烟度排放分别下降了12.4%、13.5%和17.1%,NO_x排放上升了6.7%;综合可见,PHB20改善柴油机燃烧及排放的效果优于B20。
The oxidation stability and ignitability of biodiesel can be significantly raised by partial hydrogenation, which is an effective approach to upgrade the biodiesel quality. With isopropanol as hydrogen donor, partial hydrogenation of soybean methyl ester(SME) was conducted by catalysis of Raney-Ni under water at the temperature of 85 ℃ to obtain partially hydrogenated soybean methyl ester(PHSME). To explore the effects of hydrogenated biodiesel on combustion and emissions, a comparative experiment of engine performance was conducted on a one-cylinder 186 FA diesel engine with equipments comprising a combustion analyzer, exhaust gas analyzer and smoke meter. The experiment was conducted when the engine was individually fueled with the reference diesel, B20(80% diesel+20% SME) and PHB20(80% diesel+20% PHSME). The results show that diesel, B20 and PHB20 roughly share identical equivalent fuel consumptions. Although an increase in the kinematic viscosity for the partially hydrogenated biodiesel may lead to weak atomization, however, the partially hydrogenated biodiesel can combust better owing to its higher cetane number. Compared with the reference diesel, at the rated power mode, the ignition timing was advanced by 0.8 ° crank angle and 1.4 ° crank angle respectively for B20 and PHB20; the pressure peaks and heat release peaks were advanced accordingly, while their values were slightly reduced successively. Compared with the reference diesel, the HC, CO and PM emissions of B20 were reduced by 9.9%, 9.3% and 15.2% individually, whereas the NO_x emission was increased by 8.5%; while the HC, CO and PM emissions of PHB20 were reduced by 12.4%, 13.5% and 17.1% respectively, and the NO_x emission was increased by 6.7%. As a total, PHB20 presents better combustion and emission performances than B20.
The oxidation stability and ignitability of biodiesel can be significantly raised by partial hydrogenation, which is an effective approach to upgrade the biodiesel quality. With isopropanol as hydrogen donor, partial hydrogenation of soybean methyl ester(SME) was conducted by catalysis of Raney-Ni under water at the temperature of 85 ℃ to obtain partially hydrogenated soybean methyl ester(PHSME). To explore the effects of hydrogenated biodiesel on combustion and emissions, a comparative experiment of engine performance was conducted on a one-cylinder 186 FA diesel engine with equipments comprising a combustion analyzer, exhaust gas analyzer and smoke meter. The experiment was conducted when the engine was individually fueled with the reference diesel, B20(80% diesel+20% SME) and PHB20(80% diesel+20% PHSME). The results show that diesel, B20 and PHB20 roughly share identical equivalent fuel consumptions. Although an increase in the kinematic viscosity for the partially hydrogenated biodiesel may lead to weak atomization, however, the partially hydrogenated biodiesel can combust better owing to its higher cetane number. Compared with the reference diesel, at the rated power mode, the ignition timing was advanced by 0.8 ° crank angle and 1.4 ° crank angle respectively for B20 and PHB20; the pressure peaks and heat release peaks were advanced accordingly, while their values were slightly reduced successively. Compared with the reference diesel, the HC, CO and PM emissions of B20 were reduced by 9.9%, 9.3% and 15.2% individually, whereas the NO_x emission was increased by 8.5%; while the HC, CO and PM emissions of PHB20 were reduced by 12.4%, 13.5% and 17.1% respectively, and the NO_x emission was increased by 6.7%. As a total, PHB20 presents better combustion and emission performances than B20.
引文
[1] TEIXEIRA G A A, MAIA A S, ROSENHAIM R, et al. Thermo-oxidative Decomposition of Biodiesel Samples Obtained from Mixtures of Beef Tallow, Soybean Oil, and Babassu Oil [J]. Journal of Thermal Analysis and Calorimetry, 2011, 106 (2): 569-574.
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[4] 陈秀,袁银男,来永斌,等.生物柴油组成与组分结构对其低温流动性的影响[J].石油学报:石油加工,2009,25(5):673-677. CHEN Xiu, YUAN Yin-nan, LAI Yong-bin, et al. Impact of Composition and Molecular Structure Upon the Cold Flow Properties for Biodiesel [J]. Acta Petrolei Sinica: Petroleum Processing Section, 2009, 25 (5): 673-677.
[5] GOPINATH A, PUHAN S, NAGARAJAN G. Effect of Biodiesel Structural Configuration on Its Ignition Quality [J]. International Journal of Energy & Environment, 2010, 1 (2): 295-306.
[6] PINZI S, ROUNCE P, HERREROS J M, et al. The Effect of Biodiesel Fatty Acid Composition on Combustion and Diesel Engine Exhaust Emissions [J]. Fuel, 2013, 104 (2): 170-182.
[7] 董芳,郑东前,张凤泉,等.生物柴油储存过程中其质量性能的变化 [J]. 石油学报:石油加工, 2011, 27 (5): 801-805. DONG Fang, ZHANG Dong-qian, ZHANG Feng-quan, et al. The Variation of Biodiesel Quality During Storage Period [J]. Acta Petrolei Sinica: Petroleum Processing Section, 2011, 27 (5): 801-805.
[8] SERRANO M, MARTíNEZ M, ARACIL J. Long Term Storage Stability of Biodiesel: Influence of Feedstock, Commercial Additives and Purification Step [J]. Fuel Processing Technology, 2013, 116 (6): 135-141.
[9] KNOTHE G. Some Aspects of Biodiesel Oxidative Stability [J]. Fuel Processing Technology, 2007, 88 (7): 669-677.
[10] MOSER B R, HAAS M J, WINKLER J K, et al. Evaluation of Partially Hydrogenated Methyl Esters of Soybean Oil as Biodiesel [J]. European Journal of Lipid Science and Technology, 2007, 109 (1): 17-24.
[11] SOUZA B S, PINHO D M M, LEOPOLDINO E C, et al. Selective Partial Biodiesel Hydrogenation Using Highly Active Supported Palladium Nanoparticles in Imidazolium-based Ionic Liquid [J]. Applied Catalysis A: General, 2012, 433-434 (16): 109-114.
[12] SHIN H Y, RYU J H, BAE S Y, et al. Biodiesel Production from Highly Unsaturated Feedstock Via Simultaneous Transesterification and Partial Hydrogenation in Supercritical Methanol [J]. The Journal of Supercritical Fluids, 2013, 82 (90): 251-255.
[13] YANG R, SU M, LI M, et al. One-pot Process Combining Transesterification and Selective Hydrogenation for Biodiesel Production from Starting Material of High Degree of Unsaturation [J]. Bioresource Technology, 2010, 101 (15): 5903-5909.
[14] ZACCHERIA F, PSARO R, RAVASIO N. Selective Hydrogenation of Alternative Oils: A Useful Tool for the Production of Biofuels [J]. Green Chemistry, 2009, 11 (4): 462-465.
[15] WADUMESTHRIGE K, SALLEY S O, NG K Y S. Effects of Partial Hydrogenation, Epoxidation, and Hydroxylation on the Fuel Properties of Fatty Acid Methyl Esters [J]. Fuel Processing Technology, 2009, 90 (10): 1292-1299.
[16] MCCORMICK R L, GRABOSKI M S, ALLEMAN T L, et al. Impact of Biodiesel Source Material and Chemical Structure on Emissions of Criteria Pollutants from a Heavy-duty Engine [J]. Environmental Science & Technology, 2001, 35 (9): 1742-1747.
[17] 武文涛,支国.碳碳双键催化加氢的研究进[J].化学研究,2011,22(2):84-87. WU Wen-tao, ZHI Guo. Research Progress in Catalytic Hydrogenation of C=C Bond [J]. Chemical Research, 2011, 22 (2): 84-87.
[18] 解振兵,卢义和,宫素芝,等.混合脂肪酸选择性加氢展望[J].河北工业科技,2006,23(3):190-192. XIE Zhen-bing, LU Yi-he, GONG Su-zhi, et al. Prospect of Mixed Fatty Acid Selectivity Hydrogenation [J]. Hebei Journal of Industrial Science and Technology, 2006, 23 (3): 190-192.
[19] MOSER B R, WILLIAMS A, HAAS M J, et al. Exhaust Emissions and Fuel Properties of Partially Hydrogenated Soybean Oil Methyl Esters Blended with Ultra Low Sulfur Diesel Fuel [J]. Fuel Processing Technology, 2009, 90 (9): 1122-1128.
[20] 袁银男,顾萌,戴鹏飞,等.生物柴油催化转移加氢改善其燃烧特[J].农业工程学报,2017,33(11):54-59. YUAN Yin-nan, GU Meng, DAI Peng-fei, et al. Biodiesel Modified by Catalytic Transfer Hydrogenation Improving Combustion Performance [J]. Transactions of the Chinese Society of Agricultural Engineering, 2017, 33 (11): 54-59.
[21] 戴晓雁,朱家骅,吴平.C18烯酸的等离子选择性加氢[J].四川大学学报:工程科学版,2000,32(4):50-52. DAI Xiao-yan, ZHU Jia-hua, WU Ping. Selective Hydrogenation of C18 Unsaturated Fatty Acid by H2 Plasma [J]. Journal of Sichuan University: Engineering Science Edition, 2000, 32 (4): 50-52.
[22] WANG X, HUANG Z, KUTI O A, et al. Experimental and Analytical Study on Biodiesel and Diesel Spray Characteristics Under Ultra-high Injection Pressure [J]. International Journal of Heat and Fluid Flow, 2010, 31 (4): 659-666.
[23] SUN J F, CATON J A, JACOBS T J. Oxides of Nitrogen Emissions from Biodiesel-fuelled Diesel Engines [J]. Progress in Energy and Combustion Science, 2010, 36 (6): 677-695.
[2] ATABANI A E, SILITONGA A S, BADRUDDIN I A, et al. A Comprehensive Review on Biodiesel as an Alternative Energy Resource and Its Characteristics [J]. Renewable & Sustainable Energy Reviews, 2012, 16 (4): 2070-2093.
[3] SINGH S, SHARMA S, MOHAPATRA S K, et al. Characterisation of Biodiesel Derived from Waste Cotton Seed Oil and Waste Mustard Oil [J]. Asian Journal of Engineering and Applied Technology, 2013, 2 (2): 73-77.
[4] 陈秀,袁银男,来永斌,等.生物柴油组成与组分结构对其低温流动性的影响[J].石油学报:石油加工,2009,25(5):673-677. CHEN Xiu, YUAN Yin-nan, LAI Yong-bin, et al. Impact of Composition and Molecular Structure Upon the Cold Flow Properties for Biodiesel [J]. Acta Petrolei Sinica: Petroleum Processing Section, 2009, 25 (5): 673-677.
[5] GOPINATH A, PUHAN S, NAGARAJAN G. Effect of Biodiesel Structural Configuration on Its Ignition Quality [J]. International Journal of Energy & Environment, 2010, 1 (2): 295-306.
[6] PINZI S, ROUNCE P, HERREROS J M, et al. The Effect of Biodiesel Fatty Acid Composition on Combustion and Diesel Engine Exhaust Emissions [J]. Fuel, 2013, 104 (2): 170-182.
[7] 董芳,郑东前,张凤泉,等.生物柴油储存过程中其质量性能的变化 [J]. 石油学报:石油加工, 2011, 27 (5): 801-805. DONG Fang, ZHANG Dong-qian, ZHANG Feng-quan, et al. The Variation of Biodiesel Quality During Storage Period [J]. Acta Petrolei Sinica: Petroleum Processing Section, 2011, 27 (5): 801-805.
[8] SERRANO M, MARTíNEZ M, ARACIL J. Long Term Storage Stability of Biodiesel: Influence of Feedstock, Commercial Additives and Purification Step [J]. Fuel Processing Technology, 2013, 116 (6): 135-141.
[9] KNOTHE G. Some Aspects of Biodiesel Oxidative Stability [J]. Fuel Processing Technology, 2007, 88 (7): 669-677.
[10] MOSER B R, HAAS M J, WINKLER J K, et al. Evaluation of Partially Hydrogenated Methyl Esters of Soybean Oil as Biodiesel [J]. European Journal of Lipid Science and Technology, 2007, 109 (1): 17-24.
[11] SOUZA B S, PINHO D M M, LEOPOLDINO E C, et al. Selective Partial Biodiesel Hydrogenation Using Highly Active Supported Palladium Nanoparticles in Imidazolium-based Ionic Liquid [J]. Applied Catalysis A: General, 2012, 433-434 (16): 109-114.
[12] SHIN H Y, RYU J H, BAE S Y, et al. Biodiesel Production from Highly Unsaturated Feedstock Via Simultaneous Transesterification and Partial Hydrogenation in Supercritical Methanol [J]. The Journal of Supercritical Fluids, 2013, 82 (90): 251-255.
[13] YANG R, SU M, LI M, et al. One-pot Process Combining Transesterification and Selective Hydrogenation for Biodiesel Production from Starting Material of High Degree of Unsaturation [J]. Bioresource Technology, 2010, 101 (15): 5903-5909.
[14] ZACCHERIA F, PSARO R, RAVASIO N. Selective Hydrogenation of Alternative Oils: A Useful Tool for the Production of Biofuels [J]. Green Chemistry, 2009, 11 (4): 462-465.
[15] WADUMESTHRIGE K, SALLEY S O, NG K Y S. Effects of Partial Hydrogenation, Epoxidation, and Hydroxylation on the Fuel Properties of Fatty Acid Methyl Esters [J]. Fuel Processing Technology, 2009, 90 (10): 1292-1299.
[16] MCCORMICK R L, GRABOSKI M S, ALLEMAN T L, et al. Impact of Biodiesel Source Material and Chemical Structure on Emissions of Criteria Pollutants from a Heavy-duty Engine [J]. Environmental Science & Technology, 2001, 35 (9): 1742-1747.
[17] 武文涛,支国.碳碳双键催化加氢的研究进[J].化学研究,2011,22(2):84-87. WU Wen-tao, ZHI Guo. Research Progress in Catalytic Hydrogenation of C=C Bond [J]. Chemical Research, 2011, 22 (2): 84-87.
[18] 解振兵,卢义和,宫素芝,等.混合脂肪酸选择性加氢展望[J].河北工业科技,2006,23(3):190-192. XIE Zhen-bing, LU Yi-he, GONG Su-zhi, et al. Prospect of Mixed Fatty Acid Selectivity Hydrogenation [J]. Hebei Journal of Industrial Science and Technology, 2006, 23 (3): 190-192.
[19] MOSER B R, WILLIAMS A, HAAS M J, et al. Exhaust Emissions and Fuel Properties of Partially Hydrogenated Soybean Oil Methyl Esters Blended with Ultra Low Sulfur Diesel Fuel [J]. Fuel Processing Technology, 2009, 90 (9): 1122-1128.
[20] 袁银男,顾萌,戴鹏飞,等.生物柴油催化转移加氢改善其燃烧特[J].农业工程学报,2017,33(11):54-59. YUAN Yin-nan, GU Meng, DAI Peng-fei, et al. Biodiesel Modified by Catalytic Transfer Hydrogenation Improving Combustion Performance [J]. Transactions of the Chinese Society of Agricultural Engineering, 2017, 33 (11): 54-59.
[21] 戴晓雁,朱家骅,吴平.C18烯酸的等离子选择性加氢[J].四川大学学报:工程科学版,2000,32(4):50-52. DAI Xiao-yan, ZHU Jia-hua, WU Ping. Selective Hydrogenation of C18 Unsaturated Fatty Acid by H2 Plasma [J]. Journal of Sichuan University: Engineering Science Edition, 2000, 32 (4): 50-52.
[22] WANG X, HUANG Z, KUTI O A, et al. Experimental and Analytical Study on Biodiesel and Diesel Spray Characteristics Under Ultra-high Injection Pressure [J]. International Journal of Heat and Fluid Flow, 2010, 31 (4): 659-666.
[23] SUN J F, CATON J A, JACOBS T J. Oxides of Nitrogen Emissions from Biodiesel-fuelled Diesel Engines [J]. Progress in Energy and Combustion Science, 2010, 36 (6): 677-695.
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