Vapor Phase Carbonylation of Methanol to Acetic Acid with Pressurized Fluidyzed Bed Reactor

发现了一个活性碳上的镍（Ni/A.C.）催化剂表现出对气相中甲醇到醋酸盐在中等压力下（5-30大气压）和加热（200-300 ° C）条件的高活性和选择性。2.5%Ni/A.C.催化剂释放; 100%的甲醇转化和97%的Acetic yield，在甲基碘化引发剂和过量的碳单氧化物中存在。反应路径是明确的：每个产品的yield作为时间因素的一个功能很好地模拟了每个单元反应的速率。Ni/A.C.催化剂在反应期间稳定，这表明了50天的半寿命。催化活性中的降解并不被用于将催化剂中镍的蒸发，而是将焦油材料沉积在催化剂上，导致催化剂中的微片插入。一种流化床反应堆中，有可能在气体循环条件下运行，并被建造并被提交给甲醇碳化物。一个引人注目的平板温度配置文件出现在反应期间，如果催化剂躺下，则得到了超过1公斤乙酸/公斤分类的结果。h具有99%碳酸盐产品的选择性。即使是固定的床反应，也是很高的，对工业化也是有帮助的。它也发现了饲料气体中的氢，在CO中常见的存在，并且可以明显地保证反应在产品选择中的微小变化。氢并不鼓励任何特定的反应，但鼓励所有反应在反应网络中。However，气体阶段中的小氢并没有在产品中增加，建议说，促销效果不是在直接的方式上，而是在间接的方式上。目前工艺的可行性研究建议，因为它对目前的操作工艺具有竞争力，哪些使用rhodium催化剂。

It was found that a nickel on active carbon (Ni/A.C.) catalyst exhibited a high activity and selectivity for the vapor phase carbonylation of methanol to acetic acid under moderately pressurized (5-30 atm) and heated (200-300 ゜C) conditions. The 2.5% Ni/A.C. catalyst gave ; 100% methanol conversion and 97% acetic acid yield, in the presence of methyl iodide promoter and excess carbon monoxide. The reaction path was clarified as follows: The yield of each product as a function of time factor was well simulated by calculating numerically the rate of each unit reaction. The Ni/A.C. catalyst was stable during the reaction, which exhibited a half life time of 50 days. The decrease in the catalytic activity was not attributed to the vaporization of nickel from the catalyst but to the deposition of tarry material on the catalyst, which caused the plugging of micro-pores in the catalyst.A fluidized bed reactor, which was able to be operated under pressurized conditions with a gas-recycle, was built and subjected to the methanol carbonylation. A remarkable flat temperature profile was attained in the catalyst bed during the reaction, which gave a result of more than 1 Kg-acetic acid/Kg-cat.h with a selectivity of 99% carbonylated products. The level is even superior to that of a fixed bed reaction and is sufficient for industrialization.It was also found that hydrogen in the feed gas, which commonly exist in CO, remarkably promotes the reaction with little change in the product selectivity. The hydrogen did not promote any particular reaction but promoted all reactions in the reaction network. However, little hydrogen in the gas phase was not incorporated in the product, suggesting that the promotional effect being not in the direct way but in the indirect way.The feasibility study of the present process suggests that it is competitive to a presently operating process which uses rhodium catalyst.