碱减量废水残渣甲酯化反应动力学研究
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摘要
为实现碱减量废水残渣有效利用,对碱减量废水残渣甲酯化反应条件与反应动力学规律进行了系统考察。论文首先考虑洗涤干燥等预处理方法对碱减量废水残渣组成的影响,然后通过改变醇酸比、初始水分含量及反应温度条件,进行了碱减量废水残渣甲酯化反应动力学实验研究。结果表明,预处理可有效去除残渣中的无机盐杂质提高对苯二甲酸纯度,但预处理会明显降低后续残渣甲酯化产物对苯二甲酸二甲酯(DMT)的收率以及对苯二甲酸(TA)甲酯化反应的转化。TA甲酯化两步反应均对温度敏感,采用典型的可逆平衡反应模型对实验数据进行拟合,得到动力学模型参数,并在此基础上对动力学模型进行检验,结果表明所建立的动力学模型是可靠的,能很好的预测各组分的浓度。研究所得可为碱减量废水残渣甲酯化工艺放大与设计提供依据。
To achieve the effective utilization of alkali weight-reduction wastewater residue, the methyl esterification reaction conditions and the reaction kinetics were systematically investigated. The kinetics of methyl esterification reaction of alkali weight reduction wastewater residue was studied by firstly considering the effect of pretreatment such as washing and drying on the composition on the wastewater residue and followed by changing the alcohol-to-acid ratio, initial moisture content and reaction temperature. The results showed that the pretreatment could on one hand effectively remove the inorganic salt impurities in the residue to improve the purity of terephthalic acid(TA), but on the other hand it could significantly reduce the yield of dimethyl terephthalate(DMT) and the conversion of terephthalic acid(TA) methylation reaction. Two steps TA methyl esterification reactions were both temperature sensitive. The typical reversible equilibrium reaction model was used to fit the experimental data to obtain the kinetic model parameters, and on this basis, the kinetic model was tested. The results showed that the established kinetic model was reliable and can well predict the concentration of each component. The study can provide the basis for further scale-up and design of methyl esterification process for alkali weight reduction wastewater residue.
To achieve the effective utilization of alkali weight-reduction wastewater residue, the methyl esterification reaction conditions and the reaction kinetics were systematically investigated. The kinetics of methyl esterification reaction of alkali weight reduction wastewater residue was studied by firstly considering the effect of pretreatment such as washing and drying on the composition on the wastewater residue and followed by changing the alcohol-to-acid ratio, initial moisture content and reaction temperature. The results showed that the pretreatment could on one hand effectively remove the inorganic salt impurities in the residue to improve the purity of terephthalic acid(TA), but on the other hand it could significantly reduce the yield of dimethyl terephthalate(DMT) and the conversion of terephthalic acid(TA) methylation reaction. Two steps TA methyl esterification reactions were both temperature sensitive. The typical reversible equilibrium reaction model was used to fit the experimental data to obtain the kinetic model parameters, and on this basis, the kinetic model was tested. The results showed that the established kinetic model was reliable and can well predict the concentration of each component. The study can provide the basis for further scale-up and design of methyl esterification process for alkali weight reduction wastewater residue.
引文
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[2]舒新华.对苯二甲酸残渣生产对苯二甲酸二甲酯[J].江苏化工,1997,25(6):29-31.Shu Xinhua.Production of dimethyl terephthalate from terephthalic acid waste[J].Jiangsu Chemical Industry,1997,25(6):29-31.
[3]张敏,颜连学,丁龙福.由废对苯二甲酸生产对苯二甲酸二甲酯的新工艺[J].江苏化工,2001,29(4):32-34.Zhang Min,Yan Lianxue,Ding Longfu.New processes of DMT manufacture from waste PTA and Methanol[J].Jiangsu Chemical Industry,2001,29(4):32-34.
[4]韦建国.对苯二甲酸二异辛酯合成的反应机理及动力学研究[D].郑州:郑州大学,2004.
[5]戴李宗,沈俊杰,刘秀彩.对苯二甲酸二异辛酯的合成及动力学研究[J].精细石油化工,1996,2(1):1-3.Dai Lizong,Shen Junjie,Liu Xiucai.Synthesis of diisooctylterephthalate(DOTP)and research for kinetics[J].Speciality Chemicals,1996,2(1):1-3.
[6]张旭霞,汪少朋,杨立英.PTA直接酯化过程动力学的研究[J].合成纤维工业,2003,26(6):15-17.Zhang Xuxia,Wang Shaopeng,Yang Liying.Kinetic study on PTA direct esterification[J].China Synthetic Fiber Industry,2003,26(6):15-17.
[7]沈灜坪,赵玲.聚酯(PET)反应过程研究Ⅱ酯化反应过程动力学研究[J].化学反应工程与工艺,1997,13(2):179-183.Shen Yingping,Zhao Ling.The research process of poly ethylene terephthalateⅡThe study of esterification reaction kinetics between terephthalic acid and ethylene glycol[J].Chemical Reaction Engineering and Technology,1997,13(2):179-183.
[8]张雷,胡晓萍,吴嘉.硫酸催化合成邻苯二甲酸二甲酯的动力学[J].化学反应工程与工艺,2011,27(1):87-91.Zhang Lei,Hu Xiaoping,Wu Jia.Kinetics on synthesis of Dimethyl Phthalate Catalyzed with Sulfuric Acid[J].Chemical Reaction Engineering and Technology,2011,27(1):87-91.
[9]Shujauddin Changi,Tanawan Pinnarat,Phillip Savage.Modeling Hydrolysis and Esterification Kinetics for biofuel process[J].Industrial&Engineering Chemistry Research,2011,50(6):3026-3211.
[10]Shujauddin Changi,Tanawan Pinnarat,Phillip Savage.Mechanistic modeling of hydrolysis and esterification for biofuel process[J].Industrial&Engineering Chemistry Research,2011,50(22):12471-12478.
[11]Irving Roberts,Harold C.Urey.The mechanisms of acid catalyzed ester hydrolysis,esterification and oxygen exchange of carboxylic acids[J].J.Am.Chem.Soc,1939,61(10):2584-2587.
[12]韦建国,刘大壮,孙培勤.对苯二甲酸二异辛酯合成的反应机理和动力学[J].高校化学工程学报,2006,20(4):665-668.Wei Jianguo,Liu Dazhuang,Sun Peiqin.Mechanism and kinetics of diisooctyl terephthalate synthesis[J].Journal of Chemical Engineering of Chinese Universities,2006,20(4):665-668.