微通道反应器氯磷酸单丁酯与正丁醇酯化反应数值模拟

doi:10.16085/j.issn.1000-6613.2021-2526

摘要/Abstract

摘要：

基于微通道反应器内氯磷酸单丁酯（MCP）与正丁醇（n-BuOH）酯化反应的实验结果，确定了有限速率（finite-rate）模型所需的反应动力学参数（活化能和指前因子），进而通过此模型，采用数值模拟方法讨论了微通道几何尺寸及反应物进口流速对整个反应体系的影响。研究结果表明：在相同停留时间的前提下，管径减小使反应器出口位置的转化率升高，最高可达73%，并且反应器内物质分布的均匀性和一致性得到提升；在物料进口流速不变的条件下，随着反应器管长增加，出口位置反应物转化率有所提高，最高可达64%，但在实验条件的停留时间下，出口位置反应物转化率并没有达到峰值，峰值所在位置与出口位置相距约0.89m，存在一定的滞后现象；减小反应物进口流速会提高反应物的轴向转化率，但同时也会降低产品的质量流率。

关键词: 微通道反应器, 三氯氧磷, 有限速率模型, 数值模拟

Abstract:

Based on the experimental result of esterification between chlorophosphate and N-butyl alcohol in the microchannel reactor, the parameters of finite-rate kinetics (e.g. pre-exponential factor and activation energy) were determined in this paper, and the influence of microchannel geometry and inlet velocity on the reaction system was investigated by numerical simulation. The results indicated that with the decrease of diameter, the conversion rate of outlet rose with the same residence time and reached to 73%. The uniformity and consistency of material distribution was improved. Under the consistent condition of constant flow rate at the inlet of the reactor, the conversion rate at the outlet of the product increased up to 64% with the development of the reactor's length, but the conversion rate of reactant at the outlet did not reach the peak value with the residence time of experimental conditions. There was a hysteresis that peak position and export position were about 0.89m apart. In addition, reducing the inlet flow rate of reactants would increase the axial conversion rate, but the mass flow rate of product was reduced simultaneously.

Key words: microchannel reactor, phosphorus oxychloride, finite-rate kinetics, numerical simulation

中图分类号:

陈秋实, 郑辰, 张敏弟. 微通道反应器氯磷酸单丁酯与正丁醇酯化反应数值模拟[J]. 化工进展, 2022, 41(S1): 29-35.

CHEN Qiushi, ZHENG Chen, ZHANG Mindi. Numerical simulation of the esterification between chlorophosphate and n-butyl alcohol in microchannel reactor[J]. Chemical Industry and Engineering Progress, 2022, 41(S1): 29-35.

图/表 13

图1 平推流反应器示意图

图2 正丁醇（n-BuOH）和氯磷酸单丁酯（MCP）的酯化反应式[21]

图3 微通道反应器模型及网格示意图

图4 实验装置原理图[21]

图5 不同网格数量下的径向速度轮廓分布图

表1 出口位置MCP转化率验证

实验结果	数值模拟结果
约60%	58.6%

表2 各组分物性参数

物质名称	密度/kg·m^-3	相对分子质量/kg·mol^-1	比热容/J·mol^-1·K^-1	热导率/W·m^-1·K^-1	黏度/Pa·s
环己烷	791	84.16	156	1.23×10^-4	9.12×10^-4
正丁醇	810	74.12	176.67	1.54×10^-4	2.948×10^-3
MCP	1414.9	193	—	—	—
DCP	1159.1	229.5	—	—	—
氯化氢	1.477	36.5	—	—	—

表3 进口物料组分及比例

物质名称	摩尔分数
环己烷	0.59
正丁醇	0.34
MCP	0.035
氯化氢	0.035

图6 管径对微通道轴向转化率的影响

图7 不同管径下产物（DCP）摩尔分数云图

图8 管长对微通道轴向转化率的影响与对比[21]

表4 不同流速下出口处DCP质量流率

物料进口流速	DCP质量流率/kg·m^-1·s^-1
0.25u	0.00151
0.5u	0.00266
0.75u	0.00347
u	0.00443
1.5u	0.00582
2u	0.00687
3u	0.00867

图9 物料进口流速对轴向转化率的影响（中心位置）

参考文献 22

1	骆广生, 王凯，王玉军，等. 微化工系统的原理和应用[J]. 化工进展, 2011, 30(8): 1637.
	LUO Guangsheng， WANG Kai, WANG Yujun, et al. Principles and applications of micro-structured chemical system[J]. Chemical Industry and Engineering Progress, 2011, 30(8): 1637.
2	陈光文, 赵玉潮, 乐军, 等. 微化工过程中的传递现象[J]. 化工学报, 2013, 64(1): 63-75.
	CHEN Guangwen, ZHAO Yuchao, YUE Jun, et al. Transport phenomena in micro-chemical engineering[J]. CIESC Journal, 2013, 64(1): 63-75.
3	刘明艳, 徐向华, 梁新刚. 高热流密度下矩形微小通道对流换热的模拟与优化[J]. 工程热物理学报, 2010, 31(4): 633-636.
	LIU Mingyan, XU Xianghua, LIANG Xingang. Numerical simulation and optimization on convective heat transfer characteristic in rectangular macro channel by high heat flux[J]. Journal of Engineering Thermophysics, 2010, 31(4): 633-636.
4	SURYAWANSHI P L, GUMFEKAR S P, BHANVASE B A, et al. A review on microreactors: reactor fabrication, design, and cutting-edge applications[J]. Chemical Engineering Science, 2018, 189: 431-448.
5	YAO Xingjun, ZHANG Yan, DU Lingyun, et al. Review of the applications of microreactors[J]. Renewable and Sustainable Energy Reviews, 2015, 47: 519-539.
6	KUMAR V, PARASCHIVOIU M, NIGAM K D P. Single-phase fluid flow and mixing in microchannels[J]. Chemical Engineering Science, 2011, 66(7): 1329-1373.
7	REBROV E V, SCHOUTEN J C, DE CROON M H J M. Single-phase fluid flow distribution and heat transfer in microstructured reactors[J]. Chemical Engineering Science, 2011, 66(7): 1374-1393.
8	穆金霞, 殷学锋. 微通道反应器在合成反应中的应用[J]. 化学进展, 2008, 20(1): 60-75.
	MU Jinxia, YIN Xuefeng. Application of microfluidic reactors on synthesis reactions[J]. Progress in Chemistry, 2008, 20(1): 60-75.
9	BODLA V K, SEERUP R, KRÜHNE U, et al. Microreactors and CFD as tools for biocatalysis reactor design: A case study[J]. Chemical Engineering & Technology, 2013, 36(6): 1017-1026.
10	ENGLER M, KOCKMANN N, KIEFER T, et al. Numerical and experimental investigations on liquid mixing in static micromixers[J]. Chemical Engineering Journal, 2004, 101(1/2/3): 315-322.
11	SARKAR S, SINGH K K, SHANKAR V, et al. Numerical simulation of mixing at 1-1 and 1-2 microfluidic junctions[J]. Chemical Engineering and Processing: Process Intensification, 2014, 85: 227-240.
12	LIU Zhendong, LU Yangcheng, WANG Jiawei, et al. Mixing characterization and scaling-up analysis of asymmetrical T-shaped micromixer: experiment and CFD simulation[J]. Chemical Engineering Journal, 2012, 181/182: 597-606.
13	BAWORNRUTTANABOONYA K, DEVAHASTIN S, MUJUMDAR A S, et al. A computational fluid dynamic evaluation of a new microreactor design for catalytic partial oxidation of methane[J]. International Journal of Heat and Mass Transfer, 2017, 115: 174-185.
14	SOHN S, YOON S H. Numerical study of heat and mass transfer by reverse water-gas shift reaction in catalyst-coated microchannel reactor[J]. Journal of Mechanical Science and Technology, 2020, 34(5): 2207-2216.
15	CHENG Kunpeng, LIU Chunyu, GUO Tianyu, et al. CFD and experimental investigations on the micromixing performance of single countercurrent-flow microchannel reactor[J]. Chinese Journal of Chemical Engineering, 2019, 27(5): 1079-1088.
16	郭锴, 唐小恒, 周绪美. 化学反应工程[M]. 3版. 北京: 化学工业出版社, 2017.
	GUO Kai, TANG Xiaoheng, ZHOU Xumei. Chemical reaction engineering [M]. 3rd ed. Beijing: Chemical Industry Press, 2017.
17	曾少行, 孙勤. 三氯氧磷及其衍生产品的生产及应用综述[J]. 氯碱工业, 2002, 38(2): 28-32.
	ZENG Shaoxing, SUN Qin. Review on the production and application of phosphorus oxychloride and its derivatives[J]. Chlor-Alkali Industry, 2002, 38(2): 28-32.
18	ACHMATOWICZ M M, THIEL O R, COLYER J T, et al. Hydrolysis of phosphoryl trichloride (POCl₃): characterization, in situ detection, and safe quenching of energetic metastable intermediates[J]. Organic Process Research & Development, 2010, 14(6): 1490-1500.
19	高清伟. 磷酸三丁酯和磷酸三异辛酯的合成及其固定化研究[D]. 天津: 河北工业大学, 2015.
	GAO Qingwei. Study on preparation and immobilization of tributyl phosphate and triisooctyl phosphate[D]. Tianjin: Hebei University of Technology, 2015.
20	张辉. 连续法合成磷酸三丁酯的研究[D]. 天津: 河北工业大学, 2017.
	ZHANG Hui. Continuous synthesis of tributyl phosphate[D]. Tianjin: Hebei University of Technology, 2017.
21	ZHANG Yuqiang, LI Jun, JIN Yang, et al. Determination of kinetic parameters of homogenous continuous flow esterification of monobutyl chlorophosphate in a microreactor[J]. The Canadian Journal of Chemical Engineering, 2020, 98(5): 1139-1147.
22	ZHENG Chen, ZHANG Mindi, QIU Sicong, et al. Numerical simulation and experimental investigation of gas-liquid two-phase flow in a complex microchannel[J]. Chemical Engineering Science, 2021, 230: 116198.

[1]	郭强, 赵文凯, 肖永厚. 增强流体扰动强化变压吸附甲硫醚/氮气分离的数值模拟[J]. 化工进展, 2023, 42(S1): 64-72.
[2]	邵博识, 谭宏博. 锯齿波纹板对挥发性有机物低温脱除过程强化模拟分析[J]. 化工进展, 2023, 42(S1): 84-93.
[3]	王太, 苏硕, 李晟瑞, 马小龙, 刘春涛. 交流电场中贴壁气泡的动力学行为[J]. 化工进展, 2023, 42(S1): 133-141.
[4]	陈匡胤, 李蕊兰, 童杨, 沈建华. 质子交换膜燃料电池气体扩散层结构与设计研究进展[J]. 化工进展, 2023, 42(S1): 246-259.
[5]	刘炫麟, 王驿凯, 戴苏洲, 殷勇高. 热泵中氨基甲酸铵分解反应特性及反应器结构优化[J]. 化工进展, 2023, 42(9): 4522-4530.
[6]	赵曦, 马浩然, 李平, 黄爱玲. 错位碰撞型微混合器混合性能的模拟分析与优化设计[J]. 化工进展, 2023, 42(9): 4559-4572.
[7]	叶振东, 刘涵, 吕静, 张亚宁, 刘洪芝. 基于钙镁二元盐的热化学储能反应器的性能优化[J]. 化工进展, 2023, 42(8): 4307-4314.
[8]	俞俊楠, 俞建峰, 程洋, 齐一搏, 化春键, 蒋毅. 基于深度学习的变宽度浓度梯度芯片性能预测[J]. 化工进展, 2023, 42(7): 3383-3393.
[9]	单雪影, 张濛, 张家傅, 李玲玉, 宋艳, 李锦春. 阻燃型环氧树脂的燃烧数值模拟[J]. 化工进展, 2023, 42(7): 3413-3419.
[10]	王硕, 张亚新, 朱博韬. 基于灰色预测模型的水煤浆输送管道冲蚀磨损寿命预测[J]. 化工进展, 2023, 42(7): 3431-3442.
[11]	周龙大, 赵立新, 徐保蕊, 张爽, 刘琳. 电场-旋流耦合强化多相介质分离研究进展[J]. 化工进展, 2023, 42(7): 3443-3456.
[12]	卢兴福, 戴波, 杨世亮. 转鼓内圆柱形颗粒混合的超二次曲面离散单元法模拟[J]. 化工进展, 2023, 42(5): 2252-2261.
[13]	张晨宇, 王宁, 徐洪涛, 罗祝清. 纳米颗粒强化传热的多级潜热储热器性能评价[J]. 化工进展, 2023, 42(5): 2332-2342.
[14]	马润梅, 杨海超, 李正大, 李双喜, 赵祥, 章国庆. 表面强化镀层对高速轴承腔密封端面变形及摩擦磨损影响分析[J]. 化工进展, 2023, 42(4): 1688-1697.
[15]	张成松, 张静, 龚斌, 李明洋, 袁佳新, 李宏业. 自吸射流柔性搅拌桨振动特性[J]. 化工进展, 2023, 42(4): 1728-1738.