【作者】 肖艳；

【导师】 马海洪； 王安军；

【作者基本信息】 天津大学 ， 化学工程（专业学位）， 2016， 硕士

【摘要】 正戊醛是一种重要的化工中间体,经过加氢可制得附加值较高的正戊醇,经过氧化可生成正戊酸。此外,正戊醛经羟醛缩合和加氢反应可制成异癸醇,进而可用于生产新一代性能优良的增塑剂邻苯二甲酸二癸酯(DPHP)。戊醛的市场范围正在不断扩大,应用前景广阔。工业上普遍采用丁烯羰基合成法生产戊醛。世界上公开报道的已工业化的羰基合成制戊醛工艺多以1-丁烯为原料。以1-丁烯为原料的羰基合成戊醛工艺,其原料1-丁烯需要从混合丁烯中进行分离,增加了能耗的同时也提高了戊醛的生产成本。相比较而言,直接以混合丁烯为原料的羰基合成工艺在原料成本上更具优势。研究以混合丁烯为原料的戊醛生产工艺不仅可以提高我国C4烯烃的利用率,降低生产成本,还可以弥补戊醛需求量的缺口,为后续产品提供低价优质的原材料。因此,鉴于混合丁烯羰基合成生产戊醛已成为混合C4化工利用的一个发展方向,对其开展深入的试验研究,开发新工艺,具有重要意义。本文采用国内某研究单位提供的铑复合物催化剂及三齿膦化合物配体,以混合丁烯、合成气为原料,在实验室小型羰基合成装置中开展了羰基合成条件试验研究,主要考察了反应压力、反应温度、铑浓度和原料组分等工艺条件对反应过程和反应结果的影响,根据试验结果筛选出了较佳反应工艺条件。首先对混合丁烯中最难反应组分反-2-丁烯进行了条件试验研究,综合考虑反应速率、戊醛选择性及收率、产品正异比等因素,确定以反-2-丁烯为原料制备戊醛的较佳反应条件为:反应温度123~127℃、反应压力1.5MPaG、铑含量430~600ppm。选择在反应温度125℃、反应压力1.5MPaG、铑含量430ppm的条件下,以混合丁烯和合成气为原料进行羰基合成反应,得到丁烯转化率为90%,戊醛的选择性为83%,戊醛的正异比为13.5。在实验研究的基础上,采用化工流程模拟软件,对混合丁烯为原料的羰基合成戊醛工艺进行了模拟开发,建立了混合丁烯羰基合成戊醛生产工艺流程,完成了工艺过程计算。论文研究工作为混合丁烯羰基合成戊醛新工艺的开发及设计提供了基础数据。更多还原

【Abstract】 Valeraldehyde is an important chemical intermediate;it can be used for producing pentanol by hydrogenation and producing pentanoic acid by oxidation.Besides,by aldol condensation and hydrogenation,it can also be used for producing 2-n-propyl-1-heptanol(2-PH),which can be used in the production of a new generation of excellent performance of plasticizer-DHDP.Valeraldehyde market scope is expanding constantly and has a broad application prospect.Valeraldehyde is mainly produced by Oxo synthesis in industrial.1-Butene is the raw material of the most industrialized oxo synthesis process in the world.However,1-butene should be separate from butene mixture,which increased energy consumption and cost.In comparison,the process with butene mixture as the raw material has competitive advantage.Research of the process for producing valeraldehyde with butene mixture as the raw material can not only improve the utilization rate of butene mixture in China and reduce the production cost,but also fill up the gap of the demand of valeraldehyde,and provide low-cost and high-quality valeraldehyde product.Oxo synthesizing process of valeraldehyde with butene mixture as raw material has become a research focus of C4 resource chemical utilization,which is of great significance.In this thesis,the oxo synthesis of valeraldehyde with butene mixture and syngas as material,rhodium complex as catalyst and tridentate phosphine as ligand was studied in an intermittent experimental set-up.The effects of reaction temperature,pressure,catalyst content and different materials on the oxo synthesis were investigated,and then the more optimal reaction conditions were screened out.Firstly,trans-2-butene,which is the most difficultly reactive component in the butene mixture,has been studied.Considering the reaction rate,conversion of trans-2-butene and valeraldehyde yield,the mole ratio of n-valeraldehyde to 2-methyl butaldehyde in the products,we found out the more optimal reaction conditions of the oxo synthesis with trans-2-butene as raw material are those with the temperature at 123~127℃,the reaction pressure at 1.5MPaG,the rhodium concentration at 430~600ppm.Under the reaction conditions of reaction temperature 125℃,reaction pressure 1.5MPaG,rhodium content 430 ppm,the conversion of butene mixture,selectivity to valeraldehyde,and mole ratio of n-valeraldehyde to 2-methyl butaldehyde in the products reached 90%,83% and 13.5.The production process of oxo synthesizing valeraldehyde with butene mixture as raw material was developed on basis of the experimental research data and the process simulation was finished with the use of chemical process simulation software.The simulation result can be used basic data for the industrial plant design of this new valeraldehyde production process.更多还原