催化法电石合成新工艺及其特征催化剂的研究
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摘要
电石—乙炔路线是重要的有机合成路线,但是工业上生产电石的电热法需要2200℃左右的高温,是一条高能耗、高污染的合成工艺路线。本论文主要是向现有的电石合成工艺中引入催化的概念,并开发出一种特征催化剂,利用催化反应降低电石合成的能耗、提高反应转化率。
基于对电石热合成反应的理论分析,本论文通过电热法将石灰和焦炭的混合物在1700℃、氩气气氛下反应1.5h制得了电石样品,所得电石样品与水反应尾气中乙炔含量较高,体积分数可达97%。本论文考察了碳源和钙源的活性对于电石合成的影响,结果表明活性炭作为碳源合成电石样品的发气量较高;预处理钙源有利于电石合成,但预处理碳源却不利于电石合成。本论文考察了粘结剂、助熔剂等助剂对电石合成反应的影响,结果表明在反应过程中液相的形成对于电石合成有促进作用。
在此基础上,本论文选取碳酸钾、氧化铁、磷酸三钙、硅酸钙等作为备选催化剂,通过X射线衍射技术(XRD)考察了备选催化剂的加入对合成的电石样品组成的影响,并将标准电石发气量测定装置测定的发气量结果作为评价备选催化剂催化效果的依据。实验结果表明,在所有备选催化剂中,磷酸三钙具有最好的催化效果,可将合成样品的发气量提高32%,故而本论文选取磷酸三钙作为电石催化合成工艺的特征催化剂。本论文同时考察了青海湖钾盐对于电石合成的影响,结果表明青海湖钾盐对于提高电石合成反应转化率的催化效果不明显。
本论文对以磷酸三钙为特征催化剂的电石催化合成工艺的工艺条件进行了优化,考察了原料的粒径及配比、催化剂加入量、反应时间对合成电石样品发气量的影响,得到了最优化的工艺条件。在最优化的工艺条件下,电石样品的发气量达到257.7L/kg,基本满足国家标准(GB10665-2004)中对合格电石产品发气量的要求。本论文通过在线反应、反应尾气检测、EDS能谱分析等技术手段考察了磷酸三钙的催化机理,认为在反应条件下磷酸三钙的熔化促进了碳原子的转移、改善了原料接触,同时,在反应过程中,磷酸三钙起到了离子传递媒介的作用。
The production of acetylene from calcium carbide is an important organic synthesis route. However, reaction temperature of the commercial production of calcium carbide through electrothermal method is approximately 2200℃, that is, the process is a high energy cost and serious polluting route. This paper focuses on the concept of catalytic process for the production of calcium carbide and tends to develop an effective catalyst which might reduce energy consumption and improve conversion efficiency.
Based on thermodynamics analysis of the synthesis reaction, calcium carbide is successfully synthesized from coke and lime at 1700℃for 1.5h under Ar atmosphere. The content of acetylene in gas emissions from reaction of calcium carbide and water is as high as 97 percent. Effects of different carbon sources and the activity of carbon sources and calcium source on synthesis of calcium carbide are also investigated. It is found that activated carbon as carbon source has a best performance in the process and the treated calcium source also has a positive performance, however, the treated carbon sources have a passive function. Investigations on effects of binder and fluxing agents on synthesis of calcium carbide are carried out and the results indicate that the formation of liquid phase is beneficial to the synthetic process.
Based on the above mentioned, potassium carbonate, ferric oxide, calcium phosphate, calcium silicate are chosen as catalyst candidates and effects of their addition on synthesis are observed by using X-ray diffraction. The gas output original data are detected on a standard device. The results suggest that calcium phosphate has a better effective function than all the other candidates, and the gas output of its product is increased by 32 percent. Therefore, calcium phosphate is chosen as specific catalyst. It is noticed that salts from Qinghai Lake have a disadvantageous influence on calcium carbide synthesis.
The reaction conditions of catalytic synthesis of calcium carbide, including particle size and mole ratio of raw materials, amount of catalyst, reaction time, are optimised by orthogonal experiments, and the optimum conditions are formulated. Output of sample synthesized under optimum conditions is 257.7L/kg, and by and large meets the demands of the national standard(GB10665-2004). Thermogravimetry(TG), Gas Chromatogram(GC), Energy Disperse Spectroscopy(EDS) are employed in the investigation of catalytic mechanism of calcium phosphate. It is believed that calcium carbide facilitates the transportation of coke, improves the interaction between raw materials, and above all, serves as a medium of ion transfer.
基于对电石热合成反应的理论分析,本论文通过电热法将石灰和焦炭的混合物在1700℃、氩气气氛下反应1.5h制得了电石样品,所得电石样品与水反应尾气中乙炔含量较高,体积分数可达97%。本论文考察了碳源和钙源的活性对于电石合成的影响,结果表明活性炭作为碳源合成电石样品的发气量较高;预处理钙源有利于电石合成,但预处理碳源却不利于电石合成。本论文考察了粘结剂、助熔剂等助剂对电石合成反应的影响,结果表明在反应过程中液相的形成对于电石合成有促进作用。
在此基础上,本论文选取碳酸钾、氧化铁、磷酸三钙、硅酸钙等作为备选催化剂,通过X射线衍射技术(XRD)考察了备选催化剂的加入对合成的电石样品组成的影响,并将标准电石发气量测定装置测定的发气量结果作为评价备选催化剂催化效果的依据。实验结果表明,在所有备选催化剂中,磷酸三钙具有最好的催化效果,可将合成样品的发气量提高32%,故而本论文选取磷酸三钙作为电石催化合成工艺的特征催化剂。本论文同时考察了青海湖钾盐对于电石合成的影响,结果表明青海湖钾盐对于提高电石合成反应转化率的催化效果不明显。
本论文对以磷酸三钙为特征催化剂的电石催化合成工艺的工艺条件进行了优化,考察了原料的粒径及配比、催化剂加入量、反应时间对合成电石样品发气量的影响,得到了最优化的工艺条件。在最优化的工艺条件下,电石样品的发气量达到257.7L/kg,基本满足国家标准(GB10665-2004)中对合格电石产品发气量的要求。本论文通过在线反应、反应尾气检测、EDS能谱分析等技术手段考察了磷酸三钙的催化机理,认为在反应条件下磷酸三钙的熔化促进了碳原子的转移、改善了原料接触,同时,在反应过程中,磷酸三钙起到了离子传递媒介的作用。
The production of acetylene from calcium carbide is an important organic synthesis route. However, reaction temperature of the commercial production of calcium carbide through electrothermal method is approximately 2200℃, that is, the process is a high energy cost and serious polluting route. This paper focuses on the concept of catalytic process for the production of calcium carbide and tends to develop an effective catalyst which might reduce energy consumption and improve conversion efficiency.
Based on thermodynamics analysis of the synthesis reaction, calcium carbide is successfully synthesized from coke and lime at 1700℃for 1.5h under Ar atmosphere. The content of acetylene in gas emissions from reaction of calcium carbide and water is as high as 97 percent. Effects of different carbon sources and the activity of carbon sources and calcium source on synthesis of calcium carbide are also investigated. It is found that activated carbon as carbon source has a best performance in the process and the treated calcium source also has a positive performance, however, the treated carbon sources have a passive function. Investigations on effects of binder and fluxing agents on synthesis of calcium carbide are carried out and the results indicate that the formation of liquid phase is beneficial to the synthetic process.
Based on the above mentioned, potassium carbonate, ferric oxide, calcium phosphate, calcium silicate are chosen as catalyst candidates and effects of their addition on synthesis are observed by using X-ray diffraction. The gas output original data are detected on a standard device. The results suggest that calcium phosphate has a better effective function than all the other candidates, and the gas output of its product is increased by 32 percent. Therefore, calcium phosphate is chosen as specific catalyst. It is noticed that salts from Qinghai Lake have a disadvantageous influence on calcium carbide synthesis.
The reaction conditions of catalytic synthesis of calcium carbide, including particle size and mole ratio of raw materials, amount of catalyst, reaction time, are optimised by orthogonal experiments, and the optimum conditions are formulated. Output of sample synthesized under optimum conditions is 257.7L/kg, and by and large meets the demands of the national standard(GB10665-2004). Thermogravimetry(TG), Gas Chromatogram(GC), Energy Disperse Spectroscopy(EDS) are employed in the investigation of catalytic mechanism of calcium phosphate. It is believed that calcium carbide facilitates the transportation of coke, improves the interaction between raw materials, and above all, serves as a medium of ion transfer.
引文
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