论文总字数：23305字

摘 要

乙酸乙酯(Ethyl acetate，EA)作为一种重要的基础化工产品，广泛用于制药、涂料、粘合剂、油墨、香料添加剂等领域。随着市场上乙酸乙酯的高需求，装置产能也随之提高，在生产过程中产生大量高浓度有机废水，并且排量有逐年增大的趋势。目前对于乙酸乙酯废水的工业化处理方法主要采用汽提-焚烧法，但该法不仅能耗高、设备投资大，而且汽提后的废水仍需要通过生化处理净化，是一种极不经济的处理方法，因此在实现乙酸乙酯废水零排放的前提下尽可能地做到降低单位废水处理成本是亟需解决的难题。鉴于此，本文提出一种固定床反应器临氧裂解氧化净化的处理方法，处理后的废水和废气达标排放。此外，本文建立了乙酸乙酯废水临氧裂解氧化动力学模型，并模拟计算了反应器催化剂用量和床层体积。最后考察了乙酸乙酯废水临氧裂解氧化最佳的工艺条件。

在本文中，乙酸乙酯废水为1%乙酸乙酯和0.5%乙醇（wt%）的混合溶液，处理量25 t/h，COD=28615 mgO₂/L。乙酸乙酯废水和空气或者氧气混合进入固定床反应器临氧裂解氧化。在不同压缩比下，对比空气氧化和氧气氧化两种条件的工艺，得出空气氧化条件下单位废水的处理成本更低。以此确定实验方案，在常压下，有机物与氧气摩尔比=1:3，反应温度290~410°C，体积空速4220～33150h^-1，测得宏观动力学实验数据并建立了宏观动力学模型，借助MATLAB程序，用最小二乘法拟合模型参数。采用复相关系数、F统计以及残差分布分析对估值进行检验， F统计量远远大于10F_0.01（置信域=99.0%），结果表明模型是显著可信的。

本文采用固定床反应器实验装置进行乙酸乙酯废水临氧裂解氧化工艺考察实验。常压下、有机物与氧气摩尔比=1:3、废水的进料空速为3 L/（kg·h），反应温度为450 °C，装置出口冷凝液中的COD=0，排出固定床的气体中VOCs含量不超过80 mg/m³，均可以直接排放。

关键词：乙酸乙酯废水 固定床反应器 临氧裂解 宏观动力学

Study on Kinetics and Process of Oxidation of Ethyl Acetate Wastewater

ABSTRACT

Ethyl acetate (EA), as an important basic chemical product, is widely used in the fields of pharmacy, coating, adhesive, ink, spice additive and so on. With the high demand of ethyl acetate on the market, the capacity of the production increases, and the production process discharges a large amount of high concentration organic wastewater, and its emission has an increasing trend. At present, the industrialized treatment of ethyl acetate wastewater mainly adopts stripping-burning method, but the method not only has high energy consumption and large equipment investment, but also the wastewater need to be purified by biochemical treatment after stripping, which is a very uneconomical treatment method, Therefore, it is an urgent problem to reduce the cost of unit wastewater treatment as far as possible under the precondition of zero discharge of ethyl acetate wastewater. In view of this, this paper proposes a treatment method for oxygen oxidation and purification of fixed-bed reactors. The treated wastewater and waste gas meet the discharge standards.In addition, the apparent kinetic model of catalytic cracking oxidation of ethyl acetate wastewater was established, and the dosage of catalyst and the volume of bed were simulated. At last, the optimum technological conditions for catalytic cracking oxidation of ethyl acetate wastewater were investigated.

In this paper, ethyl acetate wastewater is 1% ethyl acetate and 0.5% ethanol (wt%) of the mixed solution, the treatment amount of 25 t/h, COD=28615 mgO₂/L. Ethyl acetate wastewater can be mixed with air or oxygen into a fixed-bed reactor for catalytic cracking oxidation. Compared with the two conditions of air oxidation and oxygen oxidation under different compression ratios, it is found that the treatment cost of unit wastewater is lower under the former. After confirming the experimental scheme, at atmospheric pressure, the organic and oxygen molar ratio is 1:3, the reaction temperature range is 290~410 °C, the volume airspeed range is 4220~33150 h^-1, the apparent kinetic experimental data are measured and the apparent dynamic model is established, with the help of MATLAB program, the model parameters are fitted with the least square method. By using multiple correlation coefficient, F statistic and residual distribution analysis to examine the valuation, multiple correlation coefficient , number of obs F(28,3) =21938.6gt;10F_0.01 (28,3), F statistic is much larger than 10F_0.01 (confidence interval=99.0%), the result shows that the model is significant and credible.

In this paper, the experimental equipment of fixed-bed reactor was used to investigate technology of ethyl acetate wastewater of catalytic cracking oxidation. Atmospheric pressure, organic and oxygen mole ratio = 1:3, wastewater feed space velocity of 3 L/(kg·h), the reaction temperature is 450 °C, the device outlet condensate COD=0, to reach the rain drainage standard, discharge fixed-bed of gas VOCs content not exceeding 80 mg/m³.

Key Words: ethyl acetate wastewater; fixed-bed reactor; catalytic cracking oxidation; apparent kinetic

目录

摘要 I

ABSTRACT II

第一章 文献综述 1

1.1 乙酸乙酯概述 1

1.2 乙酸乙酯生产工艺 2

1.2.1 乙醛缩合法 2

1.2.2 酯化法 3

1.2.3 酸烯加成法 3

1.2.4 乙醇脱氢法 3

1.3 乙酸乙酯废水特性及危害 4

1.4 酯化废水处理工艺 4

1.4.1 焚烧法 4

1.4.2 湿式催化氧化法 5

1.4.3 微波辐射法 6

1.4.4 膜处理法 6

1.5 论文的研究意义 7

1.6 论文的研究思路及研究内容 8

1.5.1 主要研究内容 8

1.5.2 拟采用的研究手段 8

第二章 实验部分 9

2.1 实验主要仪器 9

2.2 实验主要试剂 9

2.3 实验装置及流程 10

2.3.1 固定床反应综合实验装置 10

2.3.2 实验流程 11

2.3.3 催化剂的装填 11

2.4 产物的定性和定量分析方法 12

2.4.1 气相产物的定性、定量方法 12

2.4.2 液相产物的定性、定量分析方法 14

第三章 乙酸乙酯废水临氧裂解氧化的宏观动力学及反应器模拟计算 16

3.1 宏观动力学研究方法 16

3.2 宏观动力学实验装置 16

3.3 宏观动力学预备实验 17

3.3.1 床反应器的装填 17

3.3.2 反应器恒温区的测定 17

3.3.3 外扩散影响检验 17

3.4 宏观动力学实验数据的获取 18

3.4.1 宏观动力学实验条件 18

3.4.1 宏观动力学实验数据 18

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