纳米稀土固溶氧化物改善高速柴油机重油有害排放的研究
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摘要
随着世界石油资源的不断开采,轻质燃油的产量逐渐减少,随之带来了汽柴油价格的不断上涨。对于开发劣质燃油的应用有着广阔的前景,从当今的石油炼制过程来看,重质燃油的产量相对较大,其价格也相对低廉。面对重质燃油在中高速发动机上燃用时所带来的排放恶化问题,本论文主要研究利用纳米级稀土氧化物颗粒作为添加剂,研究其对中高速柴油机燃用重油时改善有害排放的机理与效果。
稀土元素氧化物由于其晶体具有独特萤石结构,同时在稀土元素价态变化过程中表现出的与氧离子结合能力的变化使其表现出显著的储氧及释氧能力,对劣质燃油的燃烧过程有着积极的促进所用。并且由于其对发动机有害排放物的催化还原作用,有利于进一步降低废气排放中有害物的浓度。本实验通过化学方法合成纳米Ce02颗粒,并且对其进行多种金属氧化物的固溶以提高催化剂的热稳定性能。将催化剂按不同比例添加到重油中,在柴油机上进行负荷特性试验。利用相关测试设备来测试发动机各工况中的缸内燃烧情况,排气中CO、HC、NO及碳烟的排放浓度。通过对比重油在掺混添加剂前后在发动机上各参数的差别,分析添加剂对柴油机燃用重油的影响,验证添加剂对发动机有害排放物催还还原的效能。
通过实验数据的比对证明,纳米Ce0。与几种金属氧化逇固溶物添加剂无论对发动机缸内燃烧过程还是尾气排放中的有害成分都有显著的改善效果。掺混添加剂的重油样品与无添加剂重油相比,其发动机试验过程中的缸内压力明显提高,燃烧始点提前,燃油消耗率下降,证明了其改善燃油缸内燃烧质量的作用。同时发动机排气中碳烟、CO、HC与NO等有害排放物的浓度也相应降低,证明了其作为添加剂在重油应用中的积极作用。
As the continuously consumption of the resources of oil, the shortage of the product oil has caused more concerns than any time before, which should take responsibility for the increasing price of fuel product. It has a broad prospective of developing the crude oil's utilization. From the process of oil refining, we can find that the huge amount of production of heavy oil turns it to be a kind of cheap fuel. However, we must face the problems of heavier air pollutions when the high and middle speed diesel engines use this kind of fuel. This thesis is mainly discuss the effects of using the rare soil elements oxidize as fuel additives and research the function of the additive for reducing the harm pollutions exhausted by the diesel engine.
Now it is commonly known that the oxides of rare soil elements have sort of unique crystal lattice, meanwhile at the process of transition from Ce3+to Ce4+, the rare soil elements demonstrate a remarkable capability of storing and releasing oxygen element, which could help to promote the combustion process of the low quality fuel utilized in a diesel engine. Moreover, because of the fact that the rare soil elements also have significant characters of oxidize and reductive catalyst, the additives can help to reduce the density of the harm pollutant output by the diesel engines. The CeO2which was used in this experiment was composed through several chemical routes, after that, the compound of CeO2was made to the solid resolution of many other metal elements, which help to promote the CeO2solid resolution thermal steady significantly. The different samples of heavy oil with various fraction of catalyst joined into it were measured by the engine's load characteristic test. And monitor the cylinder combustion process and the density of NO, CO, HC, carbon soot with relevant equipments. Analyze the functions of which the additives reduce the harm exhaust by comparing the difference of the test data on the engine's running.
The additives of nanometer CeO2solid resolutions have proved to be very effective for optimizing the heavy oil's process of combustion in the cylinder and reducing the harm component of the exhaust gas. The heavy oil sample with additives on the engine test were observed for increasing the cylinder pressure, moving forward the fuel ignition moment, lowering the fuel consumption rate, which indicate that the additives bring some positive impact on combusting quality of heavy oil. Meanwhile, the exhaust gas test result also manifest that the density of carbon soot, NO, CO, HC were all dropped. According to the consequences of this experiment the additives good performance in heavy oil should be convinced.
稀土元素氧化物由于其晶体具有独特萤石结构,同时在稀土元素价态变化过程中表现出的与氧离子结合能力的变化使其表现出显著的储氧及释氧能力,对劣质燃油的燃烧过程有着积极的促进所用。并且由于其对发动机有害排放物的催化还原作用,有利于进一步降低废气排放中有害物的浓度。本实验通过化学方法合成纳米Ce02颗粒,并且对其进行多种金属氧化物的固溶以提高催化剂的热稳定性能。将催化剂按不同比例添加到重油中,在柴油机上进行负荷特性试验。利用相关测试设备来测试发动机各工况中的缸内燃烧情况,排气中CO、HC、NO及碳烟的排放浓度。通过对比重油在掺混添加剂前后在发动机上各参数的差别,分析添加剂对柴油机燃用重油的影响,验证添加剂对发动机有害排放物催还还原的效能。
通过实验数据的比对证明,纳米Ce0。与几种金属氧化逇固溶物添加剂无论对发动机缸内燃烧过程还是尾气排放中的有害成分都有显著的改善效果。掺混添加剂的重油样品与无添加剂重油相比,其发动机试验过程中的缸内压力明显提高,燃烧始点提前,燃油消耗率下降,证明了其改善燃油缸内燃烧质量的作用。同时发动机排气中碳烟、CO、HC与NO等有害排放物的浓度也相应降低,证明了其作为添加剂在重油应用中的积极作用。
As the continuously consumption of the resources of oil, the shortage of the product oil has caused more concerns than any time before, which should take responsibility for the increasing price of fuel product. It has a broad prospective of developing the crude oil's utilization. From the process of oil refining, we can find that the huge amount of production of heavy oil turns it to be a kind of cheap fuel. However, we must face the problems of heavier air pollutions when the high and middle speed diesel engines use this kind of fuel. This thesis is mainly discuss the effects of using the rare soil elements oxidize as fuel additives and research the function of the additive for reducing the harm pollutions exhausted by the diesel engine.
Now it is commonly known that the oxides of rare soil elements have sort of unique crystal lattice, meanwhile at the process of transition from Ce3+to Ce4+, the rare soil elements demonstrate a remarkable capability of storing and releasing oxygen element, which could help to promote the combustion process of the low quality fuel utilized in a diesel engine. Moreover, because of the fact that the rare soil elements also have significant characters of oxidize and reductive catalyst, the additives can help to reduce the density of the harm pollutant output by the diesel engines. The CeO2which was used in this experiment was composed through several chemical routes, after that, the compound of CeO2was made to the solid resolution of many other metal elements, which help to promote the CeO2solid resolution thermal steady significantly. The different samples of heavy oil with various fraction of catalyst joined into it were measured by the engine's load characteristic test. And monitor the cylinder combustion process and the density of NO, CO, HC, carbon soot with relevant equipments. Analyze the functions of which the additives reduce the harm exhaust by comparing the difference of the test data on the engine's running.
The additives of nanometer CeO2solid resolutions have proved to be very effective for optimizing the heavy oil's process of combustion in the cylinder and reducing the harm component of the exhaust gas. The heavy oil sample with additives on the engine test were observed for increasing the cylinder pressure, moving forward the fuel ignition moment, lowering the fuel consumption rate, which indicate that the additives bring some positive impact on combusting quality of heavy oil. Meanwhile, the exhaust gas test result also manifest that the density of carbon soot, NO, CO, HC were all dropped. According to the consequences of this experiment the additives good performance in heavy oil should be convinced.
引文
[1]周世光.有机纳米稀土金属复合物对原油及燃油变性影响的研究[D].济南：山东师范大学,2006.
[2]王攀.NPAC技术降低柴油机NOx和PM排放的机理分析及试验研究[D].镇江：江苏大学,2009.
[3]王贺武,周龙保.含氧燃料添加剂对柴油机性能和排放的影响[J].内燃机学报,2001(1)：1-4.
[4]毛小波,陈耀强,龚茂初.高能Ce0.35Zr0.55Y0.1O1.9稀土储氧材料的研究[J].无机化学学报,2006(8)：1521-1524.
[5]张明.MnOx-CeO2负荷氧化物用于催化氧化柴油车排气碳烟性能的研究[D].广州：华南理工大学,2011.
[6]周玲.重油纳米化及纳米催化剂对重油燃烧性能影响研究[D].广州：暨南大学,2007.
[7]韩祖豪,李明海,崔洪江.重柴油的应用研究[J].能源研究与信息,2006(2)：118-122.
[8]周玲,李玲.纳米CeO2对乳化重油燃烧性能的影响[J].稀土,2007(6)：92-94.
[9]杨曦,张昭良,王仲鹏.柴油车燃料添加型催化剂研究进展[J].环境科学与技术,2010(7)68-70.
[10]张立军,李信中,刘炽棠.利用余热改善柴油机燃用重油后的性能[J].小型内燃机,1997(5)：1-4.
[]1]郭存霞.高比表面积纳米CeO2及Au/CeO2的制备和催化性能研究[D].金华：浙江师范大学,2006.
[12]冯明志,罗远荣.柴油机燃油添加剂及其发展[J].小型内燃机,1994(23)：22-26.
[13]方萍,严新宇,王晓霞,罗孟飞.纳米CeO2基复合氧化物催化剂消除柴油机炭黑颗粒的催化燃烧研究[J].工业催化,2006(14)：357-361.
[14]张东恒,狄泽超,连玉双,于军.纳米CeO2柴油添加剂制备及改善内燃机节油与排放性能研究[J].石油炼制与化工,2011(6)：66-72.
[15]姚春德,卢艳彬.柴油机燃油添加剂研究发展综述[J].柴油机,2003(5)：12-15.
[16]林慧斌,蔡锐彬,王辉.柴油添加剂对改善发动机燃烧特性的实验研究[J].机电工程技术,2004(7)：71-73.
[17]徐海军.汽车尾气催化剂添加Ce-Zr-La复合氧化物和催化反应机理研究[D].成都：成都理工大学,2002.
[18]胡玉才,冯长根,王丽球,王亚军.新型储氧材料Ce0.6Tb0.1Zr0.3O2在三效催化剂中的应用研究[J].现代化工,2003(23)：173-175.
[19]何宏舟,吴德华.重油燃烧技术的夏装与展望[J].锅炉技术,2004(3)：40-44.
[20]网中俊,陈军.中高速船用柴油机燃用重油的应用[J].船海工程,2010(2)：74-77.
[21]郑育英,黄慧民,邓淑华,李大光,余双平.水热法制备高纯超细CeO2-ZrO2复合氧化物[J].无机化学学报,2005(8)：1227-1230.
[22]方萍,鲁继青,贾爱平,罗孟飞.纳米CeO2基固溶体催化柴油机碳颗粒物燃烧性能[J].物理化学学报,2007,23(8)：1275-1280.
[23]杨志强,毛东森,郭强胜,顾蕾.这被发放对CuO/CeO2-ZrO2催化CO低温氧化活性的影响[J].物理化学学报,2010,26(12)：3278-3284.
[24]宋晓岚,王海波,吴雪兰,邱冠周.纳米CeO2的制备技术及应用[J].稀土,2004(3)：55-61.
[25]燕萍,胡筱敏,孙旭东.尿素均相沉淀法制备纳米粉体Ce0.8Sm0.2O1.9的烧结性能[J].重油有色金属学报,2011(2)：425-429.
[26]孙淑敏,楚文玲,杨惟慎.高热稳定性的铈铝复合氧化物用于柴油机尾气中碳烟的消除[J].催化学报,2009(7)：685-689.
[27]王晓红,卢冠忠,郭耘,乔东升,张志刚,郭杨龙,李春忠.负载型CeO2-ZrO2固溶体的性能极其在加完燃烧Pd催化剂中的应用[J].催化学报,2008(10)：1043-1050.
[28]I. Atribak, A. Bueno-Lopez, A. Garcia-Garcia. Combined removal of diesel soot particulates and NOx over CeO2-ZrO2 mixed oxides[J]. Journal of Catalysis,2008(1):123-132.
[29]J. Kaspar, P. Fornasiero, G. Balducci, R. Di monte, N. Hickey, V. Sergo. Effect of ZrO2 content on textural and structural properties of CeO2-ZrO2 solid solutions made by citrate complexation route[J]. Inorganica Chimica Acta,2003,349:217-226.
[30]Meng-Fei Luo, Jing-Meng Ma, Ji-Qing Lu, Yu-Peng Song, Yue-Juan Wang. High-surface area CuO-CeO2 catalysts prepared by a surfactant-templated method for low-temperature CO oxidation[J]. Journal of Catalusis,2007,246:52-59.
[31]L. F. Chen, G. Gonzalez, J. A. Wang, L. E.Norena, A.Toledo, S.Castillo, M. Moran-Pineda. Surfactant-controlled synthesis of Pd/Ce0.6Zr0.4O2 catalyst for NO reduction by CO with excess oxygen[J]. Applied Surface Science,2005,243:319-328.
[32]Andrzej Adamaski, Barbara Gil, Zbihniew Sojka. Role of vanadium sites in NO and O2 adsorption process over VOx/CeO2-ZrO2 catalyst-EPR and IR studies [J]. Catalysis Today,2008,137:292-299.
[33]A. Martinez-Arias, M. Fernandez-Gar i a, A. Iglesias-Juez, A. B. Hungria, J.A.Anderson, J. C. Conesa, J. Soria. New Pd/CexZr1-xO2/Al2O3 three-way catalusts prepared by microemulsion:Part 2. In situ analysis of CO oxidation and NO reduction under stoichiometric CO+NO+O2[J]. Applied Catalysis B:Environmental,2001 (1):51-60.
[34]C. C. Pantazis, D.E. Petrakis, P.J. Pomonis. Simultaneous and/or separate SO2/NO reduction by CO over high surface area Cu/Ce containing mesoporous silica[J]. Applied Catalysis B:Environmental,2007(1-2):66-72.
[35]Bin Wen, Mingyuan He, Ethan Schrum, Can Li. NO reduction and CO oxidation over Cu/Ce/Mg/Al mixed oxide catalyst in FCC operation [J]. Journal of Molecular Catalysis A:Chemical,2002(1-2):187-192.
[2]王攀.NPAC技术降低柴油机NOx和PM排放的机理分析及试验研究[D].镇江：江苏大学,2009.
[3]王贺武,周龙保.含氧燃料添加剂对柴油机性能和排放的影响[J].内燃机学报,2001(1)：1-4.
[4]毛小波,陈耀强,龚茂初.高能Ce0.35Zr0.55Y0.1O1.9稀土储氧材料的研究[J].无机化学学报,2006(8)：1521-1524.
[5]张明.MnOx-CeO2负荷氧化物用于催化氧化柴油车排气碳烟性能的研究[D].广州：华南理工大学,2011.
[6]周玲.重油纳米化及纳米催化剂对重油燃烧性能影响研究[D].广州：暨南大学,2007.
[7]韩祖豪,李明海,崔洪江.重柴油的应用研究[J].能源研究与信息,2006(2)：118-122.
[8]周玲,李玲.纳米CeO2对乳化重油燃烧性能的影响[J].稀土,2007(6)：92-94.
[9]杨曦,张昭良,王仲鹏.柴油车燃料添加型催化剂研究进展[J].环境科学与技术,2010(7)68-70.
[10]张立军,李信中,刘炽棠.利用余热改善柴油机燃用重油后的性能[J].小型内燃机,1997(5)：1-4.
[]1]郭存霞.高比表面积纳米CeO2及Au/CeO2的制备和催化性能研究[D].金华：浙江师范大学,2006.
[12]冯明志,罗远荣.柴油机燃油添加剂及其发展[J].小型内燃机,1994(23)：22-26.
[13]方萍,严新宇,王晓霞,罗孟飞.纳米CeO2基复合氧化物催化剂消除柴油机炭黑颗粒的催化燃烧研究[J].工业催化,2006(14)：357-361.
[14]张东恒,狄泽超,连玉双,于军.纳米CeO2柴油添加剂制备及改善内燃机节油与排放性能研究[J].石油炼制与化工,2011(6)：66-72.
[15]姚春德,卢艳彬.柴油机燃油添加剂研究发展综述[J].柴油机,2003(5)：12-15.
[16]林慧斌,蔡锐彬,王辉.柴油添加剂对改善发动机燃烧特性的实验研究[J].机电工程技术,2004(7)：71-73.
[17]徐海军.汽车尾气催化剂添加Ce-Zr-La复合氧化物和催化反应机理研究[D].成都：成都理工大学,2002.
[18]胡玉才,冯长根,王丽球,王亚军.新型储氧材料Ce0.6Tb0.1Zr0.3O2在三效催化剂中的应用研究[J].现代化工,2003(23)：173-175.
[19]何宏舟,吴德华.重油燃烧技术的夏装与展望[J].锅炉技术,2004(3)：40-44.
[20]网中俊,陈军.中高速船用柴油机燃用重油的应用[J].船海工程,2010(2)：74-77.
[21]郑育英,黄慧民,邓淑华,李大光,余双平.水热法制备高纯超细CeO2-ZrO2复合氧化物[J].无机化学学报,2005(8)：1227-1230.
[22]方萍,鲁继青,贾爱平,罗孟飞.纳米CeO2基固溶体催化柴油机碳颗粒物燃烧性能[J].物理化学学报,2007,23(8)：1275-1280.
[23]杨志强,毛东森,郭强胜,顾蕾.这被发放对CuO/CeO2-ZrO2催化CO低温氧化活性的影响[J].物理化学学报,2010,26(12)：3278-3284.
[24]宋晓岚,王海波,吴雪兰,邱冠周.纳米CeO2的制备技术及应用[J].稀土,2004(3)：55-61.
[25]燕萍,胡筱敏,孙旭东.尿素均相沉淀法制备纳米粉体Ce0.8Sm0.2O1.9的烧结性能[J].重油有色金属学报,2011(2)：425-429.
[26]孙淑敏,楚文玲,杨惟慎.高热稳定性的铈铝复合氧化物用于柴油机尾气中碳烟的消除[J].催化学报,2009(7)：685-689.
[27]王晓红,卢冠忠,郭耘,乔东升,张志刚,郭杨龙,李春忠.负载型CeO2-ZrO2固溶体的性能极其在加完燃烧Pd催化剂中的应用[J].催化学报,2008(10)：1043-1050.
[28]I. Atribak, A. Bueno-Lopez, A. Garcia-Garcia. Combined removal of diesel soot particulates and NOx over CeO2-ZrO2 mixed oxides[J]. Journal of Catalysis,2008(1):123-132.
[29]J. Kaspar, P. Fornasiero, G. Balducci, R. Di monte, N. Hickey, V. Sergo. Effect of ZrO2 content on textural and structural properties of CeO2-ZrO2 solid solutions made by citrate complexation route[J]. Inorganica Chimica Acta,2003,349:217-226.
[30]Meng-Fei Luo, Jing-Meng Ma, Ji-Qing Lu, Yu-Peng Song, Yue-Juan Wang. High-surface area CuO-CeO2 catalysts prepared by a surfactant-templated method for low-temperature CO oxidation[J]. Journal of Catalusis,2007,246:52-59.
[31]L. F. Chen, G. Gonzalez, J. A. Wang, L. E.Norena, A.Toledo, S.Castillo, M. Moran-Pineda. Surfactant-controlled synthesis of Pd/Ce0.6Zr0.4O2 catalyst for NO reduction by CO with excess oxygen[J]. Applied Surface Science,2005,243:319-328.
[32]Andrzej Adamaski, Barbara Gil, Zbihniew Sojka. Role of vanadium sites in NO and O2 adsorption process over VOx/CeO2-ZrO2 catalyst-EPR and IR studies [J]. Catalysis Today,2008,137:292-299.
[33]A. Martinez-Arias, M. Fernandez-Gar i a, A. Iglesias-Juez, A. B. Hungria, J.A.Anderson, J. C. Conesa, J. Soria. New Pd/CexZr1-xO2/Al2O3 three-way catalusts prepared by microemulsion:Part 2. In situ analysis of CO oxidation and NO reduction under stoichiometric CO+NO+O2[J]. Applied Catalysis B:Environmental,2001 (1):51-60.
[34]C. C. Pantazis, D.E. Petrakis, P.J. Pomonis. Simultaneous and/or separate SO2/NO reduction by CO over high surface area Cu/Ce containing mesoporous silica[J]. Applied Catalysis B:Environmental,2007(1-2):66-72.
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