论文总字数：17040字

摘 要

以生物质丁二酸二甲酯为原料，通过铜基催化剂加氢制备1,4-丁二醇、四氢呋喃以及γ-丁内酯三种重要产品。本论文采用Cu/SiO₂催化剂，在连续流固定床反应器中进行，考察了不同的反应压力、氢酯摩尔比、反应温度、液时空速对加氢反应的影响。较佳的工艺条件为：反应压力为5 Mpa，氢酯摩尔比为150，反应温度为215 ℃，丁二酸二甲酯的液时空速为0.4 h^-1。在这种条件下，丁二酸二甲酯的转化率高于90 %，1,4-丁二醇的选择性在70%以上。同时研究了丁二酸二甲酯气相加氢反应宏观动力学，建立了丁二酸二甲酯加氢体系的动力学模型，求取了动力学参数。模型验证结果表明：模型对实验数据的拟合是较好的。

关键词：丁二酸二甲酯 1,4-丁二醇 催化剂 加氢

Reaction kinetic of hydrogenation over dimethyl succinate

Abstract

With dimethyl succinate as raw materials,we used copper-based catalyst for the preparation of 1,4-butanediol, tetrahydrofuran and γ- butyrolactone three important products. In this study, Cu/SiO₂ catalyst in a continuous flow tubular reactor. Experimental effects of reaction pressure, hydrogen carbonate molar ratio, reaction temperature, liquid hourly space velocity of the hydrogenation reaction. Preferred conditions are: a reaction pressure of 5Mpa, ester molar ratio of 150 hydrogen, the reaction temperature was 215 ℃, dimethyl succinate LHSV 0.4h^-1. Under these conditions, dimethyl succinate conversion was greater than 90%, the selectivity of 1,4-butanediol is greater than 70% . Also studied the kinetic parameters of gas-phase hydrogenation of dimethyl succinate intrinsic kinetics, a dynamic model of dimethyl succinate hydrogenation system, the strike. Model validation results show that: the model fit the experimental data is valid

Key Words: Dimethyl succinate；1,4-Butanediol；Catalyst；Hydrogenation

目 录

摘要······························································I

ABSTRACT······················································II

第一章 文献综述················································ 1

1.1 前言·······················································1

1.2 加氢催化剂的研究进展·······································2

1.2.1 铜基催化剂············································2

1.2.2 钌基催化剂············································2

1.3 丁二酸酯及其加氢产物········································3

1.4 丁二酸酯加氢的反应设备······································4

1.4.1 釜式反应器············································5

1.4.2 固定床式反应器········································5

1.5 1,4-丁二醇的生产工艺········································6

1.5.1 Reppe法··············································6

1.5.2 丁二烯乙酰氧基化法····································6

1.5.3 环氧丙烷法············································7

1.5.4 顺酐法················································7

1.6 1,4-丁二醇生产现状·········································7

1.7 本课题的研究内容和意义······································8

1.7.1 研究内容··············································8

1.7.2 研究的意义············································8

第二章 实验部分·················································9

2.1 实验仪器、原料及试剂········································9

2.1.1 实验仪器··············································9

2.1.2 原料及试剂············································9

2.2 催化剂的制备···············································10

2.3 实验过程···················································10

2.3.1 实验原理·············································10

2.3.2 催化剂评价···········································10

2.3.3 气相分析条件·········································11

2.3.4 校正因子f的求算·····································12

第三章 结果与分析··············································14

3.1 反应压力的影响·············································14

3.2 氢酯比的影响···············································15

3.3 温度的影响·················································16

3.4 原料空速的影响·············································18

3.5 动力学模型的建立···········································19

3.5.1 动力学方程参数估算··································19

3.5.2 动力学模型验证·······································20

3.6 本章小结···················································21

第四章 结论与展望··············································22

参考文献···························································23

致谢·······························································25

第一章 文献综述

1.1 前言

近十年来，丁二醇及其下游产品构成的产业链是发展最快、产量增长最快、生产技术进步最快的行业之一，1,4-丁二醇的终端产品及衍生物的的需求大量增长推动着其不断发展。1,4-丁二醇的生产方法中，以生物质为原料的加氢生产工艺因其来源范围广、价格便宜、可再生的巨大优势成为主要研究方向。其中又以生物质丁二酸为主要研究材料之一。

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