Snpecriecd fluid as a reaction media for solid catalyzed reaction

特定流体作为固体催化反应的反应介质

基本信息

批准号：
05453105
负责人：
ARAI Kunio
金额：
$ 4.74万
依托单位：
Tohoku Unibersity
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1993
资助国家：
日本
起止时间：
1993 至 1994
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05453105/
关键词：
Supesitical fluid catelyst pitch kinetics denitrogenation 溶媒和

项目摘要

There are some problems in a conventional process of hydroreforming of eforming hydrocarbons. One problem is coking on the solid catalyst. When a liquid solvent is employedt as a reaction media, slow mass transfer rate in a liquid phase sometimes limits the process performance while the wlbing probrem is solned. In a procese for denitrogenation from coal tar pitch through catalytic hydrogenation, there are such roblems, the reaction is in three phases (hydrogen gas phase, molten pitch phase and solid catalyst). Diffusion of hydrogen in a molten pitch onto the catalyst is very slow and coking on the catalyst is significant. We applied supercritical toluenetetralin as a reaction media for this process, expecting homogeneous reaction atmosphere and in-situ removal of coke from the catalyst surface. We found out that the reaction rate was enhanced and coke formation was suppressed in a supercritical phase. To elucidate the reason for this enhancement of the reaction, the effect of the particle size on the reaction rate was examined and the results were compared for supercritical phase (toluenel tetralin) and liquid phase reaction (1-methyl naphthalenel tetralin). Even under the control of chemical reaction, the reaction rate in supercritical phase is faster than that in liquid phase, especially for the base nitrogen compounds (carbazol, etc.), rather than for the neutral nitrogencompounds (benzo-quinoline etc.)For the elucidation of the machanism, carbazol was employed as a model compound for this reaction. The main reaction pathways were elucidated and the kinetics for the reaction was evaluated. With reducing pressure from 15 to 5 MPa, the reaction rate of enitrogenation was decreased to be half. This can be explained by both the variations of eauiriburium constant and that of elementary rate constants.

在传统的碳氢化合物的传统过程中，存在一些问题。一个问题是凝视固体催化剂。当用作反应介质的液体溶剂时，液相的质量转移速率缓慢有时会限制工艺性能，而在WLBING处溶液中。在一种从燃料焦油通过催化氢化的procese来硝化作用中，存在这样的棘突，反应分为三个相（氢气相，熔融螺距相和固体催化剂）。氢在熔融到催化剂上的扩散非常缓慢，并且在催化剂上凝视很重要。我们将超临界甲甲肾上腺素作为此过程的反应培养基，期望从催化剂表面从催化剂表面降解可乐。我们发现反应速率得到了提高，并且在超临界相中抑制了焦炭的形成。为了阐明这种反应增强的原因，检查了粒径对反应速率的影响，并比较了超临界相（甲氟苯甲酸甲酸酯）和液相反应（1-甲基萘苯甲烯烯）的结果。即使在化学反应的控制下，超临界相的反应速率也比液相的反应速率快，尤其是对于基础氮化合物（卡巴唑等），而不是用于中性氮（苯佐 - 奎诺氨酸等），用于阐明甲虫作为模型化合物的甲壳虫。阐明了主反应途径，并评估了反应的动力学。随着压力从15 MPa降低，启动的反应速率降低为一半。这可以通过Eauiriburium常数的变化和基本速率常数的变化来解释。