石油炼制与化工 ›› 2016, Vol. 47 ›› Issue (5): 1-5.

• 基础研究 •    下一篇

待生剂上焦炭部分氧化制CO本征反应动力学

张书红,任磊,李延军,汪燮卿   

  1. 中国石化石油化工科学研究院
  • 收稿日期:2016-04-13 修回日期:2015-11-16 出版日期:2016-05-12 发布日期:2016-04-25
  • 通讯作者: 张书红 E-mail:zhangsh.ripp@sinopec.com
  • 基金资助:

    国家重点基础研究发展计划(973计划)项目

INTRINSIC REACTION KINETICS OF PARTIAL OXIDATION OF COKE TO CO ON SPENT CATALYST

  • Received:2016-04-13 Revised:2015-11-16 Online:2016-05-12 Published:2016-04-25

摘要:

制备了碳含量(w)为1.7%的待生剂作为焦炭反应的原料,在反应温度510~780 ℃区间内,开展了以制CO为目的的焦炭部分氧化本征反应动力学研究,获得了不同反应环境下碳转化速率的本征反应动力学参数。实验结果表明:在碳-水体系中,碳、水的反应级数为零级,碳气化反应的活化能和指前因子分别为161.23 kJ/mol和116.2 g/(g?s);在碳-氧-水体系中,当氧和水过量时,碳的反应级数为一级,氧、水的反应级数为零级,待生剂上碳含量(w)低于0.5%时,在510~665 ℃下碳气化反应的表观活化能和指前因子分别为38.22 kJ/mol和1.37 s-1;在碳-氧-水体系中,当碳和水过量时,氧的反应级数为一级,碳、水的反应级数为零级,碳气化反应的本征活化能和指前因子分别为79.74 kJ/mol和311 712 s-1;在反应温度低于800 ℃时,CO主要由碳和氧反应生成,待生剂上碳与氧反应初始生成CO与CO2的摩尔比λ与温度T的关系为:λ=8.31e-16 736/(RT)。

关键词: 焦炭, 部分氧化, Co, 本征反应动力学

Abstract:

Spent catalyst with 1.7% of carbon content was prepared as the material for kinetic study. The intrinsic reaction kinetics of partial oxidation of coke was investigated at the reaction temperatures ranging from 510℃ to 780℃. The kinetic parameters of carbon conversion were obtained for various reaction conditions. For the carbon-water system, when the gasification of carbon took place below 780℃ with present of excessive carbon, the gasification of coke followed zero-order reaction, with the activation energy and the frequency factor of 161.23 kJ/mol and 116.2 s-1, respectively. For the carbon-oxygen-water system, when oxygen and water were excessive, the coke gasification in the temperature range of 510-665 ℃ followed first-order reaction with the activation energy and the frequency factor of 38.22 kJ/mol and 1.37 s-1; when the carbon and water were excessive, the oxygen consumption followed first-order reaction, with the activation energy and frequency factor to be 79.74 kJ/mol and 311 712 s-1, respectively. Experimental results indicated that the formation of CO was mainly from the reaction of carbon and oxygen at the reaction temperatures below 800 ℃. The relationship between the value of λ and T is λ=8.31e-16 736/(RT)], where λ is the molar ratio of CO to CO2 from the primary reaction of carbon and oxygen.

Key words: coke, partial oxidation, CO, intrinsic reaction kinetics