【作者】 曹金朋；

【导师】 胡云峰；

【作者基本信息】 东北石油大学 ， 油气田化学工程， 2011， 硕士

【摘要】 乙腈是重要的石油化工产品,它在石油化工中常作为丁二烯、异戊二烯馏分的抽提剂;是重要的医药、农药、染料以及合成香料的原料或中间体,也可作为分析试剂用于高效液相色谱分析。目前工业上生产乙腈是从丙烯氨氧化合成丙烯腈的副产品中分离出来的,受各种条件的限制,已经不能满足当今的市场需求,因此,开发一种以乙腈为目的产物的生产工艺是解决市场对乙腈不断增长需求的关键。将Cu系催化剂应用于乙醇氨化合成乙腈反应中,采用气相色谱质谱联用和红外光谱对反应产物进行了系统定性分析,对催化剂中各组分的作用进行了研究。针对Cu/γ-Al₂O₃而言,Cu作为活性中心起脱氢作用,载体γ-Al₂O₃不仅起分散活性组分的作用而且还要发挥良好的脱水性能。在此基础上,本研究考察了CuO不同制备方法以及负载量、载体性质和助剂Zn元素的加入等因素对催化性能的影响,结合XRF、XRD、TPR、CO吸附等主要表征手段,实验结果表明,共沉淀法和浸渍法制备的Cu系催化剂,应用于乙醇氨化合成乙腈反应中都有着良好的催化性能,适宜的Cu负载量因制备方法不同,Cu物种也因负载量的变化而不同,但是在低Cu负载量情况下催化剂皆因稳定性问题而效果不佳;Zn元素助剂在催化剂中以尖晶石结构ZnAl2O4存在,它的添加起到了稳定活性中心Cu物种的作用,尤其是针对高负载量的Cu系催化剂作用更为突出;载体的酸碱性对产物分布有着直接的影响。通过共沉淀法制备出工业催化剂DYC-1,考察了反应温度、反应空速、氨醇摩尔比等条件对催化性能的影响,找到了适宜反应条件:在反应温度为290℃,反应空速为1.0h-1,氨醇摩尔比为7的条件下,乙醇转化率可达99.9%,乙腈收率为93.5%。更多还原

【Abstract】 Acetonitrile is an important petrochemical product. It is widely used as extraction solvents for butyldiene and isoprene in the petrochemical industry, an important raw material and intermediate for the synthesis of medicine, pesticide, dye and perfume, and is also used as analytical reagent in HPLC analysis. Acetonitrile is generally extracted from the byproduct of the acrylonitrile synthesis by propene ammoxidation and the process with various restrictions can not meet today’s industrial needs. Therefore, it is necessary to develop a new process to produce acetonitrile as objective product for the increasing demand.The products of acetonitrile synthesis on copper catalysts by ethanol ammoniation are determined by gas chromatography-mass spectrometry and IR, and the function of each component of catalysts is studied. As far as Cu/γ-Al₂O₃ is concerned, the results show that dehydrogenation of enthanol mainly takes place on copper, andγ-Al₂O₃ not only play the carrier of active components but also should have good dewatering properties.The effects of different preparation methods of CuO, CuO loading amount, properties of carrier and the addition of Zn element as aids on the catalytic properties are investigated. with the aid of the main charaterization methods such as XRF, XRD, TPR, CO absorption, it is found that the copper catalysts prepared with co-precipitation and impregnation have good catalytic properties for the reaction. The most suitable CuO loading amount is varied with the preparation methods, the type of Cu species is varied with CuO loading amount. But catalytic performances of catalysts with low CuO loading amount, no matter what preparation method, are not ideal becase of the stability of copper. The addition of Zn element with spinel structure （ZnAl2O4） improves the stability of catalyst by stabilising copper, it is more obvious for catalysts with high Cu loading amount. The acid-base properties of carrier are closely related to product distribution.Catalyst DYC-1 is commercially produced by co-precipitation method. On the basis of this, the effects of reaction temperature, ethanol WHSV, ammonia alcohol mole ratio on catalytic properties are investigated. The optimal reaction conditions are found: reaction temperature of 290℃, WHSV of 1.0h-1, ammonia alcohol mole ratio of 7:1, ethanol conversion and yield of acetonitrile are respectively 99.9%, 93.5% in the conditions.更多还原