新型Cu基催化剂草酸二甲酯加氢合成乙二醇催化剂性能及安全性研究概要

沈阳化工大学（）本科毕业论文开题报告题目：新型Cu基催化剂草酸二甲酯加氢合成乙二醇催化剂性能及安全性研究院系：环境与安全工程学院专业：安全工程班级：0902学生姓名：张军琛指导教师：吴静(教授)提交日期：2013年3月18日沈阳化工大学本科毕业论文开题报告目录目录前言··················································································1第一章文献综述·····································································21.1乙二醇的性质和应用·························································21.1.1乙二醇的性质·····························································21.1.2乙二醇的应用·····························································31.2乙二醇生产原理及工艺·······················································41.2.1乙二醇的生产原理·······················································41.3国内外研究进展······························································51.3.1石化路线合成乙二醇···················································51.3.2碳酸乙烯酯(EC)法合成乙二醇········································61.3.3合成气合成乙二醇·······················································71.3.4以甲醛为原料的生产方法·············································91.3.5常压草酸二甲酯加氢合成乙二醇新工艺的开发··················111.3.6以合成气为原料生产乙二醇的新技术(非石化路线)···········121.3.7常压草酸二甲酯加氢合成乙二醇催化剂的研究进展···········131.4课题的选择及研究内容····················································161.4.1课题的选择·····························································161.4.2研究内容·································································17沈阳化工大学本科毕业论文开题报告目录第二章实验研究方法·····························································132.1实验原理及化学试剂·······················································132.1.1实验仪器及装置·······················································132.1.2实验药品·································································142.2催化剂的制备································································142.2.1溶胶-凝胶法······························································142.2.2共沉淀法································································142.3催化剂的性能评价方法····················································142.3.1稳态近似法·····························································142.3.2产物分析方法··························································152.4催化剂的表征································································172.4.1催化剂的织构表征·····················································172.4.2XRD表征·································································182.4.3催化剂的TPR表征·····················································18第三章进度安排···································································183.1.完成查阅文献、撰写开题报告的时间节点···························183.2.完成各研究内容的时间节点············································183.3.撰写毕业论文的时间节···················································18附录···················································································21沈阳化工大学本科毕业论文开题报告前言1前言乙二醇,俗名甘醇,是一种重要的有机化工原料。它不仅是生产聚对苯二甲酸乙二醇酯(PET,即聚酯树脂)、醇酸树脂、聚酯纤维和聚酯塑料的重要原料,而且是常用的高沸点溶剂。其60%的水溶液的凝固点为-40℃,可用作冬季汽车散热器的防冻剂和飞机发动机的致冷剂。此外乙二醇的二硝酸酯还可用作炸药,加热后产生的蒸汽可用作舞台烟幕,同时也是生产增塑剂、油漆、胶粘剂、表面活性剂、农药及电容器电解液不可缺少的成份。目前,工业上主要是由石油乙烯经环氧乙烷水合得到乙二醇。该工艺路线完全依赖于不可再生的石油资源，而基于煤化工和天然气的合成气法制取乙二醇的路线在与传统的乙烯路线竞争中，逐渐体现出它的原料来源广泛低廉、工艺流程短、技术经济性高等多种优势，成为研究的热点。合成气法合成乙二醇可分为直接法和间接法，其中直接法是指CO和H2在催化剂的作用下反应直接生成乙二醇，该方法符合原子经济性的要求，但由于合成压力过高（50MPa）以及高温下（230～260℃）催化剂活性和稳定性之间的矛盾等问题，还不适合工业化应用；间接法主要分为草酸酯合成法和甲醇甲醛合成法，其中草酸酯合成法不但可以得到乙二醇,而且可以通过转化CO等有毒气体来改善环境.从经济和环保角度来看都具有很高的实用价值,尤其是对于石油资源缺乏的中国来说,此领域的研究显得更加重要.均相催化剂,在7MPa,200℃下EG收率为95%。由于均相催化剂分离比较困难,研究者逐渐转向铜基非均相催化剂。尽管Cu-Cr催化剂能够获得较高的EG收率,但Cr元素具有毒性,环境不友好,限制了其应用,因此,研究者致力于开发无铬催化剂。作为一种新型的催化材料,非晶态合金具有长程无序而短程有序的结构,对某些反应具有高活性及选择性。而其中的化学还原法简单快捷,制得的非晶态合金由于其无定型非晶结构导致表面原子配位高度不饱和,因此,受到人们的广泛关注。草酸二甲酯加氢是串联反应，先加氢生成乙醇酸甲酯，乙醇酸甲酯再加氢生成乙二醇，过度加氢则能生成乙醇、1,2-丁二醇等副产物，因此需要制备一种活性选择性都很高的催化剂，其中最具代表性的是CuO/SiO2催化剂。第沈阳化工大学本科毕业论文开题报告第一章文献综述2第一章文献综述1.1乙二醇的性质和应用1.1.1乙二醇的性质（1）乙二醇的物理性质乙二醇(EthyleneGlycol)，俗称“甘醇”。无色有甜味稍稠的液体。易吸水，相对湿度为100%时，能吸两倍于自身质量的水。与水、甘油、乙酸、丙酮、吡啶及部分醛酮混溶，在乙醚中稍溶(1：200)．不溶于苯及其同系物、氯代烃、石油醚。分子式：C2H6O2，分子量62.07，熔点-13℃，沸点197.6℃，相对密度1.1274，折光率1.4317。乙二醇易发生去水缩合反应，得二缩、三缩和多缩缩水乙二醇。用途：用作汽车水箱防冻剂、抗凝剂、润湿剂、溶剂等。乙二醇是一种重要的基础有机原料，从消费结构看，乙二醇主要用于生产聚酯，进而制造聚酯纤维(涤纶)、聚酯瓶类容器、薄膜等，还有少量用于炸药、赛路玢等。在制革和制药工业中，分别用作水合剂和溶剂。（2）乙二醇的化学性质化学性质与乙醇相似，主要能与无机或有机酸反应生成酯，一般先只有一个羟基发生反应，经升高温度、增加酸用量等，可使两个羟基都形成酯。如与混有硫酸的硝酸反应，则形成二硝酸酯。酰氯或酸酐容易使两个羟基形成酯。乙二醇在催化剂（二氧化锰、氧化铝、氧化锌或硫酸）作用下加热，可发生分子内或分子间失水。乙二醇能与碱金属或碱土金属作用形成醇盐。通常将金属溶于二醇中，只得一元醇盐；如将此醇盐（例如乙二醇一钠）在氢气流中加热到180℃～200℃，可形成乙二醇二钠和乙二醇。此外用乙二醇与2摩尔甲醇钠一起加热，可得乙二醇二钠。乙二醇二钠与卤代烷反应，生成乙二醇单醚或双醚。乙二醇二钠与1，2－二溴乙烷反应，生成二氧六环。此外，乙二醇也容易被氧化，随所用氧化剂或反应条件的不同,可生成各种产物,如乙醇醛HOCH2CHO、乙二醛OHCCHO、乙醇酸HOCH2COOH、草酸HOOCCOOH及二氧化碳和水。乙二醇与其他二醇不同,经高碘酸氧化可发生碳链断裂。工业上由环氧乙烷用稀盐酸水解制得。实验室中可用水解二卤代烷或卤代乙醇的方法制备。应用乙二醇常可代替甘油使用。在制革和制药工业中，分别用作第沈阳化工大学本科毕业论文开题报告第一章文献综述3水合剂和溶剂。乙二醇的衍生物二硝酸酯是炸药。乙二醇的单甲醚或单乙醚是很好的溶剂，如甲溶纤剂HOCH2CH2OCH3可溶解纤维、树脂、油漆和其他许多有机物。乙二醇的溶解能力很强，但它容易代谢氧化，生成有毒的草酸，因而不能广泛用作溶剂。乙二醇是一个抗冻剂，60％的乙二醇水溶液在－40℃时结冰。1.1.2乙二醇的应用乙二醇的主要用途：主要用于制聚酯涤纶，聚酯树脂、吸湿剂，增塑剂，表面活性剂,合成纤维、化妆品和炸药，并用作染料/油墨等的溶剂、配制发动机的抗冻剂,气体脱水剂，制造树脂、也可用于玻璃纸、纤维、皮革、粘合剂的湿润剂。可生产合成树脂PET，纤维级PET即涤纶纤维，瓶片级PET用于制作矿泉水瓶等。还可生产醇酸树脂、乙二醛等也用作防冻剂。除用作汽车用防冻剂外，还用于工业冷量的输送，一般称呼为载冷剂乙二醇本身是相对活跃的物质容易聚合成高分子聚合物，进一步氧化成聚合物有机酸，通常所说的油泥。形成十分粘重的物质，沉积后容易结垢，另乙二醇与氧气反应生成微量的甲酸和乙酸主要用于生产聚酯树脂、醇酸树脂、增塑剂、防冻剂也用于化妆品和炸药;用作分析试剂、色谱分析试剂及电容介质;乙二醇是杀菌剂戊