钴钼耐硫变换催化剂的制备研究论文

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山东科技大学硕士学位论文
摘要
摘
要
在 CO 变换工艺中，传统工艺制备的钴-钼系耐硫变换催化剂因具有较高的催化活 性、较长的使用寿命、有突出的耐硫和抗毒性能、以及较好的选择性而备受青睐。然而 此类催化剂在制备过程中需要消耗大量的浓氨水，浓氨水的大量使用严重危害了操作工 人的人身安全，并且污染了周边环境。 本文研究了一种新型钴-钼系耐硫变换催化剂的制备工艺。新工艺下钴- 钼活性组分 分步负载，钼活性组分通过混捏法负载于催化剂载体，这与传统的浸渍法负载相比，避 免了传统工艺配制钴-钼浸渍溶液需要大量浓氨水助溶而污染环境的问题； 钴活性组分通 过浸渍法与催化剂载体负载。 在研究这种新工艺催化剂的活性过程中，采用常压微反装置，考察了不同活性组分 含量对催化剂变换活性的影响。得出最佳的活性组分含量为 CoO 1.0wt% 、MoO3 7.0~9.0 wt% 、K2 O 5.0~7.0 wt% 。同时考察了不同的工艺条件对催化剂变换活性的影响。得出最 佳工艺条件为：空速：3000h-1 ，水气比：0.8。实验表明研制的催化剂有较好的热稳定性 。 在相同工艺条件下与钴-钼工业催化剂进行 CO 转化率对比，新工艺催化剂在中温条 件下 CO 转化率能达到 90% 以上，活性优于工业催化剂。表明新工艺催化剂不仅解决了 制备过程中浓氨水污染环境的难题，而且具有较高的催化活性，工业应用前景很乐观。 关键词：新工艺；钴钼耐硫变换催化剂；活性表征；硫化；CO 变换
目 录
1 前言.................................................................................................................... 1
1.1 1.2 1.3 1.4 1.5 1.6 1.7 引言................................................................................................................................... 1 焦炉气的主要用途........................................................................................................... 2 变换反应机理................................................................................................................... 5 国内外研究现状及发展动态........................................................................................... 6 耐硫变换催化剂的特点、发展趋势............................................................................... 8 催化剂的制备方法........................................................................................................... 9 课题来源及研究主要内容............................................................................................. 17
声
明
本人呈交给山东科技大学的这篇硕士学位论文，除了所列参考文献和世所 公认的文献外，全部是本人在导师指导下的研究成果。该论文资料尚没有呈交 于其它任何学术机关作鉴定。
硕士生签名： 日 期：
AFFIRMATION
I declare that this dissertation, submitted in fulfillment of the requirements for the award of Master of Philosophy in Shandong University of Science and Technology, is wholly my own work unless referenced of acknowledge. The document has not been submitted for qualification at any other academic institute.
山东科技大学硕士学位论文
Abstract
Keywords: New technology; Co-Mo sulfur-resista nt shift catalyst; Activity character ization; Sulfuration; CO shift
山东科技大学硕士学位论文
目录
专业名称： 化学工艺 指导教师： 张 新 堂
论文提交日期：2011 年 6 月 7 日 论文答辩日期：2011 年 6 月 10 日 授予学位日期：
STUDY ON PREPARATION OF Co-Mo SULFURRESISTANT SHIFT CATALYST
A Dissertation submitted in fulfillment of the requirements of the degree of
山东科技大学硕士学位论文
Abstract
Abstract
In the CO shift technology, the Co-Mo sulfur-resista nt shift catalyst made by the traditiona l preparation gains popularity because of it’s high catalytic activity, long lifetime, outsta nding sulfur and poison resista nce, excellent selectivity. However, plenty of strong aqua ammonia will be consumed during the process of catalyst preparation, which does not only harm to the safety of workers, but also pollutes the surrounding environment. This paper studies the preparation technology of a new Co-Mo sulfur-resista nt shift catalyst. The active components of cobalt and molybdenum are loaded on the supports at two stags. The active component of molybdenum is loaded on the supports with the method of mixing and kneading. Compared with the traditiona l impregnating method to load the two active components, it settles the problem of environmental pollution which is caused by the plenty of strong aqua ammonia needed to promote the solution of cobalt and molybdenum in the traditiona l preparation of impregnating solution. The active component of cobalt is loaded on the supports with the impregnating method. In the process of studying the activity of this new technology catalyst, the atmosphere micro-reactor were adopted to study the effects of different active components contents on the shift activity of the catalyst and got the optimum active components content CoO 1.0 wt% 、 MoO3 7.0~9.0wt% 、 K2 O 5.0~7.0wt%. Simulta neously, it also studied the influences of different technologica l conditions on the shift activity of the catalyst and got the optimum technologica l condition as follows: space velocity is 3000h-1 ;water-gas ratio is 0.8. The exper iment shows that such catalyst has good ther mal stability. This research compared the CO conversion ratios of this new technology catalyst with that of industria l Co-Mo catalyst under the same process conditions . The CO conversion ratios of this new technology catalyst could reach to 90% or more at intermed iate temperate and it’s activity is super ior to industria l catalyst. It shows that the new technology catalyst not only solves the problem of strong aqua ammonia polluting environment during the preparation process, but also has high catalytic activity. So the prospects for industria l applications of such catalyst are optimistic.
MASTER OF PHILOSOPHY
Fra Baidu bibliotek
from
Shandong University of Science and Technology
by
Tian He
Supervisor: Professor Zhang Xintang
The College of Chemical and Environmental Engineering June 2011
分类号： TQ032 UD C ：
密
级： 公
开
单位代码： 10424
学 位 论 文
钴钼耐硫变换催化剂的制备研究
田 禾
申请学位级别：硕士学位 指导教师姓名：张 新 堂
专业名称：化学工艺 职 称：教 授
山 东 科 技 大 学
二零一一年六月
论文题目：
钴钼耐硫变换催化剂的制备研究
作者姓名： 田
禾
入学时间： 2008 年 9 月 研究方向： 精 细 化 工 职 称： 教 授