甲基异丙基甲酮-苯酚-对苯二酚-水的液液相平衡数据测定、模型关联及萃取过程模拟

doi:10.11949/j.issn.0438-1157.20170067

摘要/Abstract

摘要：

液液相平衡测定为溶剂萃取及回收的准确模拟、设计和过程开发提供基础数据。以甲基异丙基甲酮为萃取剂，在处理高浓煤化工含酚废水的三元液液相平衡萃取基础上，选定其中典型单元酚苯酚和多元酚对苯二酚为代表物，测定甲基异丙基甲酮-苯酚-对苯二酚-水在常压40℃下的液液相平衡数据。采用NRTL和UNIQUAC活度系数模型对实验数据进行热力学关联，回归得到该四元体系的二元交互作用参数。结果表明该模型可以很好地关联实验数据，两种模型的相对均方根偏差分别小于0.190%和0.266%。进一步将得到的二元交互参数导入流程模拟系统，对萃取单元模块进行计算。当萃取温度40℃、萃取级数5级、相比1：7.72时，甲基异丙基甲酮能将总酚12700 mg×L^-1，多元酚4250 mg×L^-1的含酚废水的酚浓度分别降低至300 mg×L^-1和299 mg×L^-1以下。

关键词: 甲基异丙基甲酮, 对苯二酚, 相平衡, 溶剂萃取, 模拟

Abstract:

Experimental determination of the liquid-liquid equilibrium system provides basic data for accurate simulation, design and process development of solvent extraction and recovery. In this work, methyl isopropyl ketone (MIPK) was chosen as the extraction agent and the liquid-liquid equilibrium of methyl isopropyl ketone-phenol-hydroquinone-water was studied since phenol and hydroquinone are typical monophenols and polyphenols in the coal chemical industry wastewater. The liquid-liquid equilibrium data were determined at 40℃ under atmospherics pressure. The experimental data were correlated with the NRTL and UNIQUAC models. The binary interaction parameters of the quaternary systems were obtained. The LLE results calculated by the NRTL and UNIQUAC models agreed quite well with the experimental data with root mean square deviations below 0.190% and 0.266% for these two models. Furthermore, the extraction process was simulated with binary interaction parameters calculated from the UNIQUAC model. According to these simulations, the total phenols and total polyphenols in the phenolic wastewater could respectively decrease from 12700 mg×L^-1 to 300 mg×L^-1 and from 4250 mg×L^-1 to 299 mg×L^-1 under the operation condition of extraction temperature 40℃, extraction stages 5 and solvent to wastewater ratio 1:7.72.

Key words: methyl isopropyl ketone, hydroquinone, phase equilibria, solvent extraction, simulation

中图分类号:

TQ028.3

陈赟, 吕冉, 熊康宁, 张涛, 李理波. 甲基异丙基甲酮-苯酚-对苯二酚-水的液液相平衡数据测定、模型关联及萃取过程模拟[J]. 化工学报, 2018, 69(4): 1299-1306.

CHEN Yun, LÜ Ran, XIONG Kangning, ZHANG Tao, LI Libo. Experimental determination,thermodynamic modeling and process simulation of methyl isopropyl ketone-phenol-hydroquinone-water quaternary systems[J]. CIESC Journal, 2018, 69(4): 1299-1306.

参考文献 30

[1]	姜忠义, 李玉平, 陈志强, 等. 煤化工废水近零排放与资源化关键技术研究与应用示范[J]. 化工进展, 2016, 35(12):4099-4100. JIANG Z Y, LI Y P, CHEN Z Q, et al. Key technologies study and application demonstration of near-zero-liquid-discharge and resource recovery of coal chemical industry wastewater[J]. Chemical Industry and Engineering Progress, 2016, 35(12):4099-4100.
[2]	张润楠, 范晓晨, 贺明睿, 等. 煤气化废水深度处理与回用研究进展[J]. 化工学报, 2015, 66(9):3341-3349. ZHANG R N, FAN X C, HE M R, et al. Research progress on deep treatment and reclamation of coal gasification wastewater[J]. CIESC Journal, 2015, 66(9):3341-3349.
[3]	庄海峰, 韩洪军, 单胜道, 等. 缺氧/好氧移动床生物膜反应器短程脱氮工艺深度处理煤化工废水性能[J]. 化工学报, 2016, 67(9):3919-3926. ZHUANG H F, HAN H J, SHAN S D, et al. Advanced treatment of coal chemical wastewater using a novel MBBR process with short-cut biological nitrogen removal[J]. CIESC Journal, 2016, 67(9):3919-3926.
[4]	ZHU H, HAN Y X, MA W C, et al. Removal of selected nitrogenous heterocyclic compounds in biologically pretreated coal gasification wastewater (BPCGW) using the catalytic ozonation process combined with the two-stage membrane bioreactor (MBR)[J]. Bioresource Technology, 2017, 245(Part A):786-793.
[5]	JI Q H, TABASSUM S, HENA S, et al. A review on the coal gasification wastewater treatment technologies:past, present and future outlook[J]. Journal of Cleaner Production, 2016, 126 (7):38-55.
[6]	钱宇, 周志远, 陈赟, 等. 煤气化废水酚氨分离回收系统的流程改造和工业实施[J]. 化工学报, 2010, 61(7):1821-1828. QIAN Y, ZHOU Z Y, CHEN Y, et al. Process retrofit and industrial implementation of phenol and ammonia recovery from coal-gasification wastewater[J]. CIESC Journal, 2010, 61(7):1821-1828.
[7]	陈赟, 余振江, 盖恒军, 等. 煤气化污水化工处理新流程[J]. 化工进展, 2009, 28(12):1895-1899. CHEN Y, YU Z J, GAI H J, et al. A novel chemical process for coal-gasification wastewater treatment[J]. Chemical Industry and Engineering Progress, 2009, 28(12):1895-1899.
[8]	陈赟, 王卓. 煤气化污水酚氨回收技术进展、流程优化及应用[J]. 煤化工, 2013, 41(4):44-48. CHEN Y, WANG Z. Application research status of the chemical process of ammonia/phenol recovery from coal-gasification wastewater[J]. Coal Chemical Industry, 2013, 41(4):44-48.
[9]	马东辉, 崔培哲, 杨思宇, 等. 煤气化高浓酚氨废水处理技术研究进展[J]. 化工进展, 2016, 35(6):1884-1893. MA D H, CUI P Z, YANG S Y, et al. Research advances in treatment of coal gasification wastewater with high phenol and ammonia[J]. Chemical Industry and Engineering Progress, 2016, 35(6):1884-1893.
[10]	王卓, 王慧敏, 刘东, 等. 煤化工高浓含酚废水萃取脱酚实验研究[J]. 化学工程, 2016, 44(2):7-11. WANG Z, WANG H M, LIU D, et al. Experimental study on removal of phenols from coal chemical wastewater[J]. Chemical Engineering (China), 2016, 44(2):7-11.
[11]	杨楚芬. 煤气化废水萃取脱酚流程及其液液相平衡关系的研究[D]. 广州:华南理工大学, 2007. YANG C F. Process study of solvent extraction and removal of phenols from coal-gasification wastewater and liquid-liquid equilibria research[D]. Guangzhou:South China University of Technology, 2007.
[12]	孔令启, 王渊朴, 曹婺, 等. 乙酸乙酯-间苯二酚-酸性盐水液液相平衡测定及关联[J]. 化工学报, 2016, 67(4):1098-1102. KONG L Q, WANG Y P, CAO W, et al. Measurement and correlation of liquid-liquid equilibrium data for acetic ether-resorcinol-acid brine system[J]. CIESC Journal, 2016, 67(4):1098-1102.
[13]	庄志海, 张建强, 刘殿华. 聚甲氧基二甲醚+水+正己烷三元体系的液液相平衡[J]. 化工学报, 2016, 67(9):3545-3551. ZHUANG Z H, ZHANG J Q, LIU D H. Liquid-liquid equilibria for ternary systems polyoxymethylene dimethyl ethers + water +n-hexane[J]. CIESC Journal, 2016, 67(9):3545-3551.
[14]	CHEN Y, ZHOU S M, WANG Y C, et al. Screening solvents to extract phenol from aqueous solutions by the COSMO-SAC model and extraction process simulation[J]. Fluid Phase Equilibria, 2017, 451:12-24.
[15]	CHEN Y, LÜ R, LI L B, et al. Measurement and thermodynamic modeling of ternary (liquid + liquid) equilibrium for extraction of o-cresol, m-cresol or p-cresol from aqueous solution with 2-pentanone[J]. Journal of Chemical Thermodynamics, 2017, 104:230-238.
[16]	XU G J, YANG D L, NING P G, et al. Measurements and correlation of liquid-liquid equilibrium data for the ternary (3-heptanone + phenol+ water) system[J]. Journal of Chemical Thermodynamics, 2017, 106:295-302.
[17]	杨楚芬, 钱宇, 章莉娟, 等. 甲基异丁基酮-水-苯酚三元物系液液相平衡数据的测定与关联[J]. 化工学报, 2007, 58(4):805-809. YANG C F, QIAN Y, ZHANG L J, et al. Measurement and correlation of liquid-liquid equilibrium data for methyl isobutyl ketone-water-phenol ternary system[J]. Journal of Chemical Industry and Engineering(China), 2007, 58(4):805-809.
[18]	CHEN Y, WANG H M, LÜ R, et al. Liquid-liquid equilibrium for ternary systems, methyl isobutyl ketone +(catechol, resorcinol and hydroquinone) + water at 333.15 K, 343.15 K and 353.15 K[J]. Fluid Phase Equilibria, 2017, 433:206-211.
[19]	YANG C F, YANG S Y, QIAN Y, et al. Simulation and operation cost estimate for phenol extraction and solvent recovery process of coal-gasification wastewater[J]. Industrial & Engineering Chemistry Research, 2013, 52(8):12018-12115.
[20]	余振江. 煤气化过程高浓度酚氨污水化工处理流程开发、模拟与工业实施[D]. 广州:华南理工大学, 2011. YU Z J. Process development, simulation, and industrial implementation of a new coal-gasification wastewater treatment installation to remove phenols and ammonia[D]. Guangzhou:South China University of Technology, 2011.
[21]	YU Z J, CHEN Y, FENG D C, et al. Process development, simulation and industrial implementation of new coal-gasification wastewater treatment installation for phenol and ammonia removal[J]. Industrial & Engineering Chemistry Research, 2010, 49(2):2874-2881.
[22]	程能林. 溶剂手册[M]. 北京:化学工业出版社, 2007. CHENG N L. Solvent Handbook[M]. Beijing:Chemical Industry Press, 2007.
[23]	CHEN Y, ZHOU S M, CHEN H, et al. Extraction of o-, m-and p-cresol from aqueous solution with methyl isopropyl ketone:equilibrium, correlations, and COSMO-RS predictions[J]. Journal of Chemical Thermodynamics, 2017, 115:180-190.
[24]	CHEN Y, LÜ R, WANG F R, et al. Determination and modeling of liquid-liquid equilibrium for ternary mixtures of methyl isopropyl ketone, cresol isomers and water[J]. Fluid Phase Equilibria, 2016, 429:107-112.
[25]	CHEN Y, LÜ R, WANG H M, et al. Ternary liquid-liquid equilibria for methyl isopropyl ketone +(resorcinol or hydroquinone) + water systems at different temperatures[J]. Fluid Phase Equilibria, 2016, 429:93-97.
[26]	LÜ R, LI L B, WANG H M, et al. Experimental determination and correction of liquid-liquid equilibria for methyl isopropyl ketone+ phenol+ water mixtures at 298.15, 313.15 and 323.15 K[J]. Journal of Chemical and Engineering Data, 2016, 61(7):2221-2225.
[27]	冯艺荣, 盖恒军, 郭凯, 等. 甲基戊烯酮-水-邻苯二酚三元物系液液相平衡数据的测定与关联[J]. 化工学报, 2017, 68(3):848-853. FENG Y R, GAI H J, GUO K, et al. Measurement and correlation of liquid-liquid equilibrium data for mesityl oxide-water-catechol ternary system[J]. CIESC Journal, 2017, 68(3):848-853.
[28]	盖恒军, 国洪跃, 宋红兵. 甲基戊烯酮-水-苯酚三元物系液液相平衡数据的测定与关联[J]. 高校化学工程学报, 2015, 29(6):1320-1324. GAI H J, GUO H Y, SONG H B. Measurement and correlation of liquid-liquid equilibrium data of mesityl oxide-water-phenol ternary systems[J]. Journal of Chemical Engineering of Chinese Universities, 2015, 29(6):1320-1324.
[29]	YANG C F, JIANG Y B, ZHANG L J, et al. Liquid-Liquid equilibria for the ternary system methyl isobutyl ketone + water + hydroquinone[J]. Journal of Chemical and Engineering Data, 2006, 51(11):2107-2109.
[30]	YANG C F, QIAN Y, JIANG Y B, et al. Liquid-liquid equilibria for the quaternary system methyl isobutyl ketone-water-phenol-hydroquinone[J]. Fluid Phase Equilibria, 2007, 258:73-77.