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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.

在常规的重整烃的加氢重整方法中存在一些问题。一个问题是固体催化剂上的焦化。当采用液体溶剂作为反应介质时，在液相中缓慢的传质速率有时限制了过程性能，同时解决了wlbing问题。在煤沥青催化加氢脱氮过程中，存在着这样的问题，即反应分为三个阶段（氢气相、熔融沥青相和固体催化剂相）。熔融沥青中的氢在催化剂上的扩散非常缓慢，并且催化剂上的焦化是显著的。我们采用超临界甲苯四氢萘作为反应介质，期望得到均匀的反应气氛和原位去除催化剂表面的焦炭。我们发现，在超临界相中，反应速率得到提高，焦炭的形成得到抑制。为了阐明这种增强的反应的原因，粒径对反应速率的影响进行了检查，并比较了超临界相（甲苯四氢化萘）和液相反应（1-甲基萘四氢化萘）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快，特别是对于碱性含氮化合物（咔唑等），而不是中性氮化合物（苯并喹啉等）。为了阐明反应机理，以咔唑为模型化合物。阐明了主要的反应途径，并对反应动力学进行了评价。当压力从15 MPa降至5 MPa时，脱氮反应速率降低一半。这可以用铕离子常数和基元速率常数的变化来解释。