【作者】 石磊；

【导师】 马正飞；

【作者基本信息】 南京工业大学 ， 化学工艺， 2002， 硕士

【摘要】 甲醇羰基合成醋酸较成熟的是Monsanto公司开发的均相催化合成工艺，催化剂为羰基铑-碘，该工艺存在设备腐蚀严重、产物与催化剂难分离、活性金属铑价格昂贵等问题，而甲醇气相羰基化在解决上述问题方面显示了很好的前景，并具有在低压下操作和生产效率高等优点，因而成为合成醋酸的新的研究领域。本文选取具有较高羰化活性、非贵金属镍（Ni）为主活性金属，比表面较大的活性炭（AC）为载体，在系统研究Ni/AC催化体系的基础上，对双金属和多金属负载催化剂进行了筛选和羰化工艺的考察，并对甲醇气相羰基化中其他因素的影响做了探索性的研究。具体内容如下：1. 采取浸渍法制备Ni/ AC催化剂，确定了合适的浸渍、干燥、活化处理方法。发现经适宜的热处理和还原有助于增加活性中心数目，提高羰化活性和收率，最佳热处理温度为400℃、还原温度为550℃。2. 在低压气-固相反应条件下，研究了Ni/AC负载型催化剂用于甲醇羰化反应的情况。按正交表L9(34)设计了正交试验，发现镍含量和反应温度是低压羰化活性的重要影响因素，增加镍含量会提高羰化活性，但也促使副反应的产生；温度的升高可大大增加反应收率，但温度过高会造成助剂碘甲烷的分解。3. 甲醇低压气相羰化反应最佳工艺条件：在温度300℃，压力1MPa，接触时间为10gcat·h/mol，n（CO/CH3OH/CH3I）为60/20/1，镍含量取8.5%（wt）的条件下，羰化产物的总选择性超过90%，甲醇转化率为92.85%，羰化收率为48.19%。与山西煤化所在280℃、1.5MPa、镍含量2.5%，经高温（930℃）活化处理的催化体系相比，醋酸收率提高了1.83%，副产物选择性减少了12.26%。4. 研究了双金属和三金属负载型催化剂的低压甲醇气相羰化反应。以Ni/AC催化剂为基础，对加入的第二种金属元素进行了简单筛选，发现Cu、Zn、Sn、La等作为第二种添加金属有助催化作用，Fe 、Mo、Pb等反而会使催化活性降低，副产物增多。5. 镍含量为5%，Cu、Zn不同负载配比的Ni-Zn-Cu/AC的三金属催化剂的羰化实验的考察表明：在压力为1MPa， 温度为300℃，n（CO/CH3OH/CH3I）为60/20/1，接触时间为10gcat·h/mol时，（5%Ni-5%Zn-5%Cu）/AC的配比组<WP=4>合催化活性最好，此时，甲醇的转化率为94.58%，醋酸的单程选择性为16.58%，羰基类化合物的总收率为51.26%。6．在其他因素对低压气相羰化活性影响的探索性研究中，发现稀土的添加能缩短反应的诱导期，氢气能抑制羰化活性，床层压力的提升对羰化性活影响不明显，而碘甲烷的助催化作用是羰化活性的关键。更多还原

【Abstract】 The carbonylation of methanol to synthesize acetic acid is a comparatively mature technique currently that developed by Monsanto, utilizes a homogeneous Rh-I based catalyst for implementing the reaction in the presence of methyl iodide. But the liquid homogeneous process has several disadvantages, such as corrosive attack to the reactors, difficult separation of products from the catalyst, limited supply of Rh, etc.. Recently, the studies of vapor phase carbonylation show good foreground in solving above-mentioned problems, and has virtue of good production efficiency and low on-stream pressure as well，so exploratory research on related fields are drawing more and more attention from both industrial and academic sectors. Since nickel is inexpensive with superior catalytic activity, active carbon has better specific area, in this paper, a series of nickel-loaded catalysts （Ni/AC ）were prepared and studied systematically, then bimetal catalysts were carefully examined and compared, technological conditions of tri-metals catalyst were observed, finally, exploratory researches were carried out on some possible influencing factors in the oxo process.The studies of this thesis mainly include the following aspects:1. Ni/AC catalysts were prepared by dip-molding, and appropriate ways of steep, desiccation, heat and activation treatment were ascertained .It is discovered that the optimal temperature of heat and H2 activation treatment, which turned out to be 400℃ and 550℃, conduced to increasing number of active centers and enhancing the yield of acetic acid .2.Under low pressure vapor phase and Ni/AC catalysts, orthogonal experiments L9(34) were utilized to inspect factors affecting the oxo process. According to the results, the content of Ni and reaction temperature are crucial in the carbonylation, the increase of both standards could impove catalytic activity and by-products .3. Under the optimal reaction conditions: n( CO/MeOH/CH3I)=60/20/1, 1MPa ,<WP=6>300℃, contact time is 10gcat·h/mol and the content of Ni is 8.5%(wt),a maximum activity is achieved. The total selectivity of carbonyl products is more than 90%,the conversion of methanol reaches 92.85% and the yield of carbonyl products is 48.19%.Compared with the results from Institute of Coal Chemistry, which reaction conditions are 1.5MPa,280℃, 2.5%,the yield of acetic acid in this paper is increased by 1.83%,while the selectivity of by-products is decreased by 12.26%.4. A series of Ni-based bimetallic catalysts were investigated under low pressure vapor-solid phase . It is revealed that the additive of Cu、Zn、Sn、La into Ni/AC facilitated the reaction while Fe 、Mo、Pb restrained it.5. The simultaneous addition of Cu and Zn to Ni/AC has better catalytic activity in the oxo process of methanol to acetic acid, the appropriate ratio of the three metals is 5%Ni:5%Zn:5%Cu(wt),under the optimal conditions, the conversion of methanol reaches 94.58%,and the total yield of carbonyl products is 51.26%.6. Exploratory researches on some possible influencing factors in the oxo process revealed that the addition of rare earth could shorten the induction period, hydrogen could suppress the catalytic activity, increasing of pressure contributed little to the oxo synthesis, and methyl iodide as a promoter was pivotal.更多还原