生物柴油催化剂——磁性纳米固体碱的制备及应用
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摘要
目前生物柴油生产与开发已成为世界各国解决能源短缺问题竞相研究的热点。生物柴油是一种典型的“绿色能源”,工业化生产生物柴油主要是化学催化法,其中催化剂工艺和原料来源、价格是生物柴油工业化生产的关键。
本文主要研究了碱土金属氧化物系列的负载型磁性催化剂(KF/MO-Fe_3O_4,M=Mg,Ca,Sr)的制备条件的优化和材料表征,并将系列催化剂中催化效率最高、制备最简单的催化剂用于乌桕梓油的酯交换反应制备生物柴油。主要研究内容如下:
(1)研究了磁性纳米固体碱催化剂KF/MgO-Fe_3O_4的最优制备条件,并采用透射电镜(TEM)、低温N_2吸附-脱附、X-射线粉末衍射(XRD)和Hammett指示剂等方法表征该催化剂的结构、形貌、成分和碱强度。
(2)研究了磁性纳米固体碱催化剂KF/CaO-Fe_3O_4的最优制备条件,并采用透射电镜(TEM)、低温N_2吸附-脱附、X-射线粉末衍射(XRD)、拉曼(Raman)、Hammett指示剂和振动样品磁强计(VSM)等方法表征该催化剂的结构、形貌、成分和碱强度。
(3)研究了磁性纳米固体碱催化剂KF/SrO-Fe_3O_4的最优制备条件,并采用透射电镜(TEM)、低温N_2吸附-脱附、拉曼(Raman)和Hammett指示剂等方法表征该催化剂的结构、形貌、成分和碱强度。
(4)经比较研究发现,在碱土金属氧化物系列的负载型磁性催化剂中,催化剂KF/CaO-Fe_3O_4的制备较简单,并且催化效率较高。因此,选择催化剂KF/CaO-Fe_3O_4以进一步研究该催化剂的最优酯交换反应条件、催化剂耐酸耐水性能和回收、重复利用及再生性能等。初步探讨了催化反应机理。
(5)设计了磁性纳米固体碱催化剂制备乌桕梓油生物柴油的生产工艺,并设计了一种有效的磁性分离管,用来辅助分离磁性催化剂。
Now biodiesel production and exploitation have been the hot spots in solving the worldwide problem of energy source shortage. The green fuel biodiesel is produced mostly by chemically catalyzed method in industry at home and abroad. Nowadays, catalyst preparation, source and cost of feedstocks are the keys in industrial production of biodiesel.
In this thesis, optimization of preparation conditions and characterization of composite catalyst of alkaline earth metals oxide group with magnetism (KF/MO-Fe_3O_4, M = Mg, Ca, Sr) have been studied, then the catalyst which has the highest catalytic efficiency and the easiest preparation method was used to produce biodiesel from stillingia oil by transesterification reactions. The main research contents are as follows:
(1) The optimum preparation conditions of magnetic nano-solid-base KF/MgO-Fe_3O_4 have been studied, and TEM, low temperature N_2 adsorption-desorption, XRD and Hammett indicator methods were adopted to characterize the structure, shape, component and basic strength.
(2) The optimum preparation conditions of magnetic nano-solid-base KF/CaO-Fe_3O_4 have been studied, and TEM, low temperature N_2 adsorption-desorption, XRD Raman, Hammett indicator and VSM methods were adopted to characterize the structure, shape, component and basic strength.
(3) The optimum preparation conditions of magnetic nano-solid-base KF/SrO-Fe_3O_4 have been studied, and TEM, low temperature N_2 adsorption-desorption, Raman and Hammett indicator methods were adopted to characterize the structure, shape, component and basic strength.
(4) Comparing with other composite catalyst of alkaline earth metals oxide with magnetism, KF/CaO-Fe_3O_4 has the advantages of easy preparation and high catalytic efficiency. So the catalyst KF/CaO-Fe_3O_4 was chose to investigate the optimum transesterification conditions, resistance to FFA and water, reclaimation, reuse and regeneration of the catalyst. The mechanism of the catalytic reaction was discussed.
(5) The preliminary production techniques of stillingia oil biodiesel catalized by magnetic nano-solid-base catalyst have been designed and an effective magnetic separator tube has been designed to separate the magnetic catalyst.
本文主要研究了碱土金属氧化物系列的负载型磁性催化剂(KF/MO-Fe_3O_4,M=Mg,Ca,Sr)的制备条件的优化和材料表征,并将系列催化剂中催化效率最高、制备最简单的催化剂用于乌桕梓油的酯交换反应制备生物柴油。主要研究内容如下:
(1)研究了磁性纳米固体碱催化剂KF/MgO-Fe_3O_4的最优制备条件,并采用透射电镜(TEM)、低温N_2吸附-脱附、X-射线粉末衍射(XRD)和Hammett指示剂等方法表征该催化剂的结构、形貌、成分和碱强度。
(2)研究了磁性纳米固体碱催化剂KF/CaO-Fe_3O_4的最优制备条件,并采用透射电镜(TEM)、低温N_2吸附-脱附、X-射线粉末衍射(XRD)、拉曼(Raman)、Hammett指示剂和振动样品磁强计(VSM)等方法表征该催化剂的结构、形貌、成分和碱强度。
(3)研究了磁性纳米固体碱催化剂KF/SrO-Fe_3O_4的最优制备条件,并采用透射电镜(TEM)、低温N_2吸附-脱附、拉曼(Raman)和Hammett指示剂等方法表征该催化剂的结构、形貌、成分和碱强度。
(4)经比较研究发现,在碱土金属氧化物系列的负载型磁性催化剂中,催化剂KF/CaO-Fe_3O_4的制备较简单,并且催化效率较高。因此,选择催化剂KF/CaO-Fe_3O_4以进一步研究该催化剂的最优酯交换反应条件、催化剂耐酸耐水性能和回收、重复利用及再生性能等。初步探讨了催化反应机理。
(5)设计了磁性纳米固体碱催化剂制备乌桕梓油生物柴油的生产工艺,并设计了一种有效的磁性分离管,用来辅助分离磁性催化剂。
Now biodiesel production and exploitation have been the hot spots in solving the worldwide problem of energy source shortage. The green fuel biodiesel is produced mostly by chemically catalyzed method in industry at home and abroad. Nowadays, catalyst preparation, source and cost of feedstocks are the keys in industrial production of biodiesel.
In this thesis, optimization of preparation conditions and characterization of composite catalyst of alkaline earth metals oxide group with magnetism (KF/MO-Fe_3O_4, M = Mg, Ca, Sr) have been studied, then the catalyst which has the highest catalytic efficiency and the easiest preparation method was used to produce biodiesel from stillingia oil by transesterification reactions. The main research contents are as follows:
(1) The optimum preparation conditions of magnetic nano-solid-base KF/MgO-Fe_3O_4 have been studied, and TEM, low temperature N_2 adsorption-desorption, XRD and Hammett indicator methods were adopted to characterize the structure, shape, component and basic strength.
(2) The optimum preparation conditions of magnetic nano-solid-base KF/CaO-Fe_3O_4 have been studied, and TEM, low temperature N_2 adsorption-desorption, XRD Raman, Hammett indicator and VSM methods were adopted to characterize the structure, shape, component and basic strength.
(3) The optimum preparation conditions of magnetic nano-solid-base KF/SrO-Fe_3O_4 have been studied, and TEM, low temperature N_2 adsorption-desorption, Raman and Hammett indicator methods were adopted to characterize the structure, shape, component and basic strength.
(4) Comparing with other composite catalyst of alkaline earth metals oxide with magnetism, KF/CaO-Fe_3O_4 has the advantages of easy preparation and high catalytic efficiency. So the catalyst KF/CaO-Fe_3O_4 was chose to investigate the optimum transesterification conditions, resistance to FFA and water, reclaimation, reuse and regeneration of the catalyst. The mechanism of the catalytic reaction was discussed.
(5) The preliminary production techniques of stillingia oil biodiesel catalized by magnetic nano-solid-base catalyst have been designed and an effective magnetic separator tube has been designed to separate the magnetic catalyst.
引文
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3.段炼.全球生物柴油产业的发展.日用化学品科学,2009,32(1):7-11
4.郭登峰,盛梅,罗士平.气相色谱法测定生物柴油中多种脂肪酸甲酯.中国油脂,2004,29(4):44-46
5.韩明汉,陈和,王金福,金涌.生物柴油制备技术的研究进展.石油化工,2006,35(12):1119-1124
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