论文总字数：25151字

摘 要

甲基异丁基酮(MIBK)作为一种有机化工产品在工业生产中具有非常广泛的应用。近年来，随着MIBK在国内的需求量不断增加，因此研究MIBK的工业化生产技术已显得越来越重要。本文针对丙酮加氢一步法合成MIBK反应，研发了一系列双功能催化剂并在连续固定床反应器中评价了各体系催化剂的催化性能。本文制备了一系列Pd/HZSM-5和Pd/NKC-9树脂催化剂，应用催化剂表征手段分析了催化剂组成对其物化性质的调变，研究了丙酮在Pd/HZSM-5和Pd/NKC-9树脂催化剂上加氢一步法合成MIBK的催化性能。

本文采用浸渍法分别制备了不同Pd负载量的Pd/HZSM-5分子筛催化剂，并探讨了丙酮加氢一步法合成MIBK反应中Pd/HZSM-5分子筛催化剂中Pd负载量、反应温度、系统压力、床层空速及氢酮比对丙酮转化率和MIBK选择性的影响。实验结果表明：当Pd质量百分含量为0.5%时，该催化剂催化性能最好；在优化工艺条件下：温度140℃，系统压力1MPa，床层空速0.48g·h^-1·g_cat^-1，氢酮比1，丙酮转化率可达到45%，MIBK选择性达94%；积碳失活后的催化剂，经空气气氛下高温焙烧、氢气还原后，催化剂催化性能和失活前催化剂相当。

为解决丙酮加氢一步法生产MIBK工艺中分子筛催化剂在反应过程中积碳失活的问题，本文采用浸渍法分别制备了不同Pd负载量的Pd/NKC-9树脂催化剂，并研究丙酮加氢一步法合成MIBK反应中树脂载体催化剂中Pd负载量、反应温度、系统压力、床层空速及氢酮比对丙酮的转化率和MIBK选择性的影响。结果表明：当Pd质量百分含量为0.5%时，该催化剂催化性能最好；在优化工艺条件下：反应温度110℃，系统压力3MPa，床层空速0.48g·h^-1·g_cat^-1，氢酮比1，丙酮转化率可以达到60%，MIBK选择性达89%；丙酮加氢一步法生产MIBK仍具有稳定的催化性能连续反应1000h后，催化剂催化活性始终稳定在开始状态。因此，Pd负载树脂催化剂在工业上具有广阔的应用前景。

关键词：丙酮 加氢 催化 MIBK DIBK

Acetone hydrogenation catalyzed synthesis of methyl isobutyl ketone

Abstract

Methyl isobutyl ketone (MIBK) is one of important organic chemical product, which has an extremely widespread application. In recent years, the demand for MIBK is increasing in our country, so it is obviously necessary and urgent to study the synthesis technology of MIBK. To the reaction of one-step synthesis of MIBK from acetone and hydrogen, this paper has developed some effective catalysts of which catalytic performance was evaluated in the continuous fixed bed reactor. In this paper, a series of Pd/NKC-9 resin and Pd/HZSM-5 catalysts are prepared, which are researched by various characterization methods to study the effect of the catalyst composition to the physicochemical properties, then investigates the catalytic performance of the Pd/NKC-9 resin and Pd/HZSM-5 on the reaction of one-step synthesis of MIBK from acetone.

A series of Pd/HZSM-5 catalyst was prepared by impregnation method in this paper. The catalysts were applied to the reaction of one-step synthesis of MIBK from acetone, and investigated the effect of technological parameters (loading of Pd, reaction temperature, reaction pressure, the liquid phase space velocity and hydrogen ketone molar ratio) to the catalytic performance of the reaction one-step synthesis of MIBK from acetone on Pd/ HZSM-5 catalyst. The experimental results show that the catalyst activity reach the highest when the Pd load is 0.5wt%, Under optimized process conditions (reaction temperature 140℃, reaction pressure 1MPa, the liquid phase space velocity 0.48g·h^-1·g_cat^-1, hydrogen ketone molar ratio 1, the conversion of acetone can be 45%, and the selectivity of MIBK can reach 94%. The catalyst which is carbon deposited to inactivation, of which activity can reach the level of the fresh one again after high temperature calcinations and reduction.

To solve the problem about carbon deposition inactivation of supported zeolite catalyst in the reaction one-step synthesis of MIBK from acetone, a series of Pd/NKC-9 resin catalyst was prepared by impregnation method in this paper. The catalysts were applied to the reaction of one-step synthesis of MIBK from acetone, and investigated the effect of technological parameters (loading of Pd in resin catalysts, reaction temperature, reaction pressure, the liquid phase space velocity and hydrogen ketone molar ratio) to the catalytic performance of the reaction one-step synthesis of MIBK from acetone on Pd/NKC-9 resin catalyst. The results show that the catalyst activity reach the highest when Pd load was 0.5wt%, Under optimized process conditions (reaction temperature 110℃, reaction pressure of 3MPa, the liquid phase space velocity 0.48g·g_cat^-1·h^-1, hydrogen ketone molar ratio 1), the conversion of acetone can be 60%, and the selectivity of MIBK can reach 89%. After 1000 hour of continuous reaction for one-step synthesis of MIBK from acetone，it still has a stable catalytic activity, the supported resin catalyst has the same catalytic activity as before. In conclusion, the Pd supported resin catalyst has a great application in industrial prospect.

Key Words: acetone ; hydrogenation ; catalysis ; MIBK ; DIBK

目 录

摘 要 I

Abstract II

第一章 文献综述 1

1.1 研究背景 1

1.1.1 甲基异丁基酮的物理化学性质 1

1.1.2 国内外甲基异丁基酮生产与消费情况 1

1.2 丙酮制备MIBK的工艺路线 2

1.2.1 丙酮三步法 2

1.2.2 丙酮一步法 3

1.3 丙酮一步法合成MIBK的催化剂研究进展 4

1.3.1 Cu系催化剂 5

1.3.2 Ni系催化剂 5

1.3.3 Pd系催化剂 6

1.4 本课题研究的目的和意义 8

第二章 实验部分 9

2.1 实验试剂与仪器 9

2.1.1 实验试剂 9

2.1.2 实验仪器 9

2.2 催化剂制备 10

2.3 催化剂活性评价 10

2.3.1 催化剂活性评价装置 10

2.3.2 催化剂活性评价方法 12

第三章 Pd/HZSM-5催化剂表征及催化性能研究 14

3.1 丙酮加氢一步法合成MIBK反应的影响因素 14

3.1.1 Pd负载量对反应性能的影响 14

3.1.2 温度对反应性能的影响 15

3.1.3 氢酮摩尔比对反应性能的影响 15

3.1.4 质量空速对反应性能的影响 16

3.1.5 压力对反应性能的影响 17

3.2 催化剂稳定性评价 17

3.3 本章小结 18

第四章 Pd/NKC-9树脂催化剂表征及催化性能研究 19

4.1 丙酮加氢一步法合成MIBK反应的影响因素 19

4.1.1 Pd负载量对反应性能的影响 19

4.1.2 温度对反应性能的影响 20

4.1.3 氢酮摩尔比对反应性能的影响 21

4.1.4 质量空速对反应性能的影响 21

4.1.5 压力对反应性能的影响 22

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