齐齐哈尔大学化学工程与工艺专业毕业设计论文(20万吨甲醇羰基化法醋酸车间醋酸精馏工段)

摘要

甲醇羰基化法醋酸又名尼龙酸，是己二酸生产过程产生的副产物，仅国内己二酸生产企业每年就副产混合二元酸40-60万吨。由于其含杂质、水分多，颜色呈绿色或黄褐色，难以利用。国外一般将其送进污水处理装置作焚烧或填埋处理；国内有采用重结晶法回收，但回收率低于60％，废水量较大，不仅对环境造成污染，而且也造成资源的浪费。为了物尽其用，本文开展了应用基础研究以C4-C6混合二元酸为原料、对甲苯磺酸为催化剂，制备混合二元酸二甲酯，并利用减压精馏得到纯净的二甲酯。实验中考查了各种反应的影响因素，并利用制备的混合二甲酸二甲酯与异辛醇进行酯交换制备混合二元酸二异辛酯。

根据实验数据表明，通过酯化法分离混合二元酸的工艺路线是可行的。酯化的适宜反应条件为：反应时间5.0h，醇酸物质的量比6:1，催化剂用量1.0%混合酸，以此条件，二元酸二甲酯的收率可达89%。酯化所得粗酯可以在压力为40mmHg下进行减压精馏，截取95～105℃下的馏分，为丁二酸二甲酯，截取110～120℃下的馏分，为戊二酸二甲酯，截取145～155℃下的馏分，为己二酸二甲酯。利用精馏所得的二元酸二甲酯，通过酯交换法制得的二元酸二异辛酯的颜色很浅，说明通过酯化法可以有效地分离混合二元酸。

关键词：甲醇羰基化；醋酸；酯交换；混合二元酸二甲酯

Abstract

Mixed dibasic acid (DBA), also known as nylon acid, adipic acid production process by-products, only domestic producers of adipic acid by-product mixture in each of dicarboxylic acid 40-60 million tons. Because of its impurities, water content, the color green or brown, it is difficult to use. Foreign general to be sent to sewage treatment plant for incineration or landfilling; domestic use recrystallization recovery, but recovery was less than 60%, large amount of wastewater, not only pollute the environment, but also a waste of resources. In order to make the best use, this application of basic research carried out to C4-C6 dicarboxylic acid as raw material mixture, p-toluenesulfonic acid as catalyst, prepared by mixing two yuan acid ester, and the use of vacuum distillation to get pure dimethyl ester. Experiment examined the response of various factors, and use a mixture of dimethyl ester prepared with different octanol prepared by mixing two yuan for transesterification ethylhexyl sebacate.

According to the experimental data show that, by esterification of dicarboxylic acid mixture separation process route is feasible. Esterification of the appropriate reaction conditions: reaction time 5.0h, alkyd molar ratio of 6:1, 1.0% mixed acid catalyst, in this condition, binary acid ester yield of 89%. Esters derived from crude esterification can be carried out under the pressure of 40mmHg vacuum distillation, the interception of 95 ~ 105 ℃under the distillate, as dimethyl succinate, the interception of 110 ~ 120 ℃under the fractions for Dimethyl glutarate , the interception of 145 ~ 155 ℃under the distillate, is dimethyl adipate. The use of binary distillation from acid ester by transesterification of the binary system were acid-ethylhexyl the color is very light, indicating that by esterification can be effectively separated mixed dicarboxylic acid.

Key words: mixed dibasic acid; toluenesulfonate; transesterification; mixed two yuan Dimethyl

目录

摘要 .............................................. 错误！未定义书签。Abstract .......................................................... II

第1章绪论 (5)

1.1 课题的目的、意义 (5)

1.1.1 甲醇羰基化法醋酸的由来 (5)

1.1.2 甲醇羰基化法醋酸的利用 (6)

1.1.3 甲醇羰基化法醋酸的分离 (7)

1.1.4 甲醇羰基化法醋酸的用途 (10)

1.2 甲醇羰基化法醋酸制备的研究 (11)

1.2.1 固体酸H催化法 (11)

1.2.2 硫酸氢钠催化法 (12)

1.2.3 固载磷钨酸催化法 (12)

1.2.4 树脂催化法 ............................ 错误！未定义书签。

1.2.5 一水硫酸氢钠催化法 .................... 错误！未定义书签。

1.2.6 复合固体酸催化法 ...................... 错误！未定义书签。

1.2.7 杂多酸催化法 .......................... 错误！未定义书签。

1.3 本课题的研究内容........................... 错误！未定义书签。第2章实验部分 ................................... 错误！未定义书签。

2.1 实验原理................................... 错误！未定义书签。

2.1.1 酯化反应原理 ........................... 错误！未定义书签。

2.1.2 减压蒸馏原理 ........................... 错误！未定义书签。

2.1.3 酯交换反应原理 ......................... 错误！未定义书签。

2.2 实验仪器设备及试剂 ......................... 错误！未定义书签。

2.2.1 实验仪器设备 ........................... 错误！未定义书签。

2.2.2 实验试剂 ............................... 错误！未定义书签。

2.3 实验装置图 ................................. 错误！未定义书签。

2.4 实验步骤 ................................... 错误！未定义书签。

2.4.1 甲醇羰基化法醋酸的合成 ................... 错误！未定义书签。