离子液体催化烷基化体系在微反应器内的流动和反应基础研究

doi:10.11949/0438-1157.20210935

摘要/Abstract

摘要：

离子液体催化剂可以显著提高烷基化反应速率，开发适用于该工艺的高效反应器具有重要意义。基于微反应器在过程强化方面的优势，设计了适用于烷基化反应的微反应器，考察了烷基化模拟体系的流动规律，在较大操作范围内实现了催化剂与产物的连续分相。以上述研究为基础，实现了C₄烷基化反应的微型化，分别考察了停留时间、反应温度、分散尺寸对反应性能的影响。研究结果表明，微反应器内的烷基化反应在2 s内完成。C₈选择性和TMPs（三甲基戊烷）/DMHs（二甲基己烷）分别最高可达70.90%与13.4，均高于相同反应条件下搅拌釜反应器内的反应结果，证明微反应器在优化烷基化反应性能方面拥有巨大潜力。

关键词: 微反应器, 烷基化, 流动, 分离, 反应

Abstract:

Ionic liquid catalysts can significantly increase the rate of alkylation reaction, and it is of great significance to develop high-efficiency reactors suitable for this process. Based on the advantages of microreactor in process intensification, microreactor used for alkylation reaction was designed in this paper. The flow behavior of simulated fluid system was investigated and the phase separation in a wide range of throughput was achieved continuously. According to the above study, the isobutane alkylation was realized in microreactor, and the effects of residence time, temperature and droplet size on the reaction performance were studied. This research finds that the reaction can be finished in 2 s; the maximum selectivity of C₈ and TMPs/DMHs are 70.90% and 13.4 respectively, which are both higher than that in stirred tank reactor. This survey indicates that the microreactor has great potential in optimizing the alkylation reaction performance.

Key words: microreactor, alkylation, flow, separation, reaction

中图分类号:

TQ 052.5

玄雪梅, 王苗, 蔡迪宗, 张睿, 兰文杰. 离子液体催化烷基化体系在微反应器内的流动和反应基础研究[J]. 化工学报, 2021, 72(11): 5582-5589.

Xuemei XUAN, Miao WANG, Dizong CAI, Rui ZHANG, Wenjie LAN. Fundamental study on flow and reaction performance of isobutane alkylation catalyzed by ionic liquid in microreactor[J]. CIESC Journal, 2021, 72(11): 5582-5589.

图/表 14

表1 混合烃原料组成

Table 1 Components of the feedstock

混合烃组分	摩尔分数/%
异丁烷	97.7540
正丁烷	0.0675
反-2-丁烯	0.0192
正-1-丁烯	0.0254
异丁烯	0.0201
顺-2-丁烯	2.1138

表2 两相流体的密度和黏度

Table 2 Density and viscosity of the fluid

试剂

分子式

密度/

(g/cm³)

黏度/

(mPa·s)

C₈H₁₈

Et₃NHCl-1.8AlCl₃-xCuCl

1.29

75.57

表3 两相流体界面张力

Table 3 Interfacial tension of two-phase fluid

序号	体系		界面张力/(mN/m)
序号	分散相	连续相	界面张力/(mN/m)
（W1）	正辛烷	基础离子液体	7.75
（W2）	正辛烷	复合离子液体	10.21

图1 微反应器结构

Fig.1 The schematic diagram of microreactor

图2 实验装置流程图

Fig.2 The schematic overview of the experimental setup

表4 平行实验结果

Table 4 Parallel experiments results

产物	产物分布/%(质量)			平均值	标准偏差/%(质量)	相对标准偏差/%
产物	1#	2#	3#	平均值	标准偏差/%(质量)	相对标准偏差/%
C₅	6.98	7.66	7.84	7.49	0.40	6.06
C₆	9.15	9.7	10.72	9.86	0.53	8.08
C₇	7.38	6.79	7.75	7.31	0.52	6.62
C₈	41.05	38.39	38.78	39.41	1.54	3.64
$C 9 +$	35.44	37.46	34.92	35.94	1.56	3.73
C₈组分
TMPs	35.16	33.2	33.34	33.9	1.13	3.23
DMHs	5.61	4.89	5.17	5.22	0.43	6.95

表4 平行实验结果

Table 4 Parallel experiments results

产物	产物分布/%(质量)			平均值	标准偏差/%(质量)	相对标准偏差/%
产物	1#	2#	3#	平均值	标准偏差/%(质量)	相对标准偏差/%
C₅	6.98	7.66	7.84	7.49	0.40	6.06
C₆	9.15	9.7	10.72	9.86	0.53	8.08
C₇	7.38	6.79	7.75	7.31	0.52	6.62
C₈	41.05	38.39	38.78	39.41	1.54	3.64
$C 9 +$	35.44	37.46	34.92	35.94	1.56	3.73
C₈组分
TMPs	35.16	33.2	33.34	33.9	1.13	3.23
DMHs	5.61	4.89	5.17	5.22	0.43	6.95

图3 流型和流型转换

Fig.3 Micrographs of flow regimes and flow patterns transition

图4 两相流速对液滴尺寸的影响

Fig.4 The effect of two-phase flow rates on the droplet size

图5 射流中两相流量比对有机相特征尺寸的影响

Fig.5 The effect of Qc/Qd on the characteristic size in jetting flow

图6 分相范围

Fig.6 Flow rates range of phase seperation

图7 烯烃转化率随停留时间的变化 (Qc = 40 μl/min，Qd = 20 μl/min, ddrop = 300 μm）

Fig.7 Variation of olefin conversion with residence time (Qc = 40 μl/min，Qd = 20 μl/min, ddrop = 300 μm）

图8 停留时间对反应性能的影响(Qc = 40 μl/min，Qd = 20 μl/min, ddrop = 300 μm, T = 10℃)

Fig.8 The effect of residence time on reaction performance(Qc = 40 μl/min，Qd = 20 μl/min, ddrop = 300 μm, T = 10℃)

图9 温度对反应性能的影响(Qc = 40 μl/min，Qd = 20 μl/min, ddrop = 300 μm, t = 2 s)

Fig.9 The effect of temperature on reaction performance(Qc = 40 μl/min，Qd = 20 μl/min, ddrop = 300 μm, t = 2 s)

表5 分散尺寸对烷基化产物分布的影响

Table 5 Effect of droplet size on yields

产物	产物分布（质量分数）/%
产物	100 μm^①	200 μm^②	500 μm^②	86 μm^③[13,31]
C₅	9.65	7.37	10.88	4.36
C₆	6.53	6.43	5.65	7.22
C₇	5.78	6.12	3.90	5.56
C₈	70.90	66.18	33.60	61.36
$C 9 +$	7.12	13.90	45.98	21.50
C₈分布
TMPs	66	59.89	29.11	56.63
DMHs	4.93	6.09	4.12	5.28
TMPs/DMHs	13.4	9.83	7.06	8.10
RON	95.3	94	83.7	92.11
烯烃转化率	94.96	99.65	99.34

表5 分散尺寸对烷基化产物分布的影响

Table 5 Effect of droplet size on yields

产物	产物分布（质量分数）/%
产物	100 μm^①	200 μm^②	500 μm^②	86 μm^③[13,31]
C₅	9.65	7.37	10.88	4.36
C₆	6.53	6.43	5.65	7.22
C₇	5.78	6.12	3.90	5.56
C₈	70.90	66.18	33.60	61.36
$C 9 +$	7.12	13.90	45.98	21.50
C₈分布
TMPs	66	59.89	29.11	56.63
DMHs	4.93	6.09	4.12	5.28
TMPs/DMHs	13.4	9.83	7.06	8.10
RON	95.3	94	83.7	92.11
烯烃转化率	94.96	99.65	99.34

参考文献 31

1	毕建国. 烷基化油生产技术的进展[J]. 化工进展, 2007, 26(7): 934-939.
	Bi J G. Advances in alkylate manufacture technology[J]. Chemical Industry and Engineering Progress, 2007, 26(7): 934-939.
2	Gan P X, Tang S W. Research progress in ionic liquids catalyzed isobutane/butene alkylation[J]. Chinese Journal of Chemical Engineering, 2016, 24(11): 1497-1504.
3	李迪, 孙伟振, 奚桢浩, 等. 混合丁烯/异丁烷硫酸烷基化反应动力学[J]. 化工学报, 2015, 66(2): 585-590.
	Li D, Sun W Z, Xi Z H, et al. Alkylation kinetics of mixed butenes/isobutane by sulfuric acid [J]. CIESC Journal, 2015, 66(2): 585-590.
4	Hommeltoft S I. Isobutane alkylation recent developments and future perspectives[J]. Applied Catalysis A: General, 2001, 221(1): 421-428.
5	Albright L F. Present and future alkylation processes in refineries[J]. Industrial & Engineering Chemistry Research, 2009, 48(3): 1409-1413.
6	Corma A, Martínez A. Chemistry, catalysts, and processes for isoparaffin-olefin alkylation: actual situation and future trends[J]. Catalysis Reviews, 1993, 35(4): 483-570.
7	Busca G. Acid catalysts in industrial hydrocarbon chemistry[J]. Chemical Reviews, 2007, 107(11): 5366-5410.
8	Olah G A, Mathew T, Goeppert A, et al. Ionic liquid and solid HF equivalent amine-poly(hydrogen fluoride) complexes effecting efficient environmentally friendly isobutane-isobutylene alkylation[J]. Journal of the American Chemical Society, 2005, 127(16): 5964-5969.
9	刘鹰, 刘植昌, 徐春明. 异丁烷与2-丁烯在含有抑制剂离子液体中的烷基化反应[J]. 化工学报, 2005, 56(11): 2119-2123.
	Liu Y, Liu Z C, Xu C M. Alkylation of isobutane and 2-butene in inhibited chloroaluminate ionic liquids[J]. Journal of Chemical Industry and Engineering (China), 2005, 56(11): 2119-2123.
10	Li L T, Zhang J S, Du C C, et al. Intensification of the sulfuric acid alkylation process with trifluoroacetic acid[J]. AIChE Journal, 2019, 65(1): 113-119.
11	Huang C P, Liu Z C, Xu C M, et al. Effects of additives on the properties of chloroaluminate ionic liquids catalyst for alkylation of isobutane and butene[J]. Applied Catalysis A: General, 2004, 277(1/2): 41-43.
12	Liu Y, Hu R S, Xu C M, et al. Alkylation of isobutene with 2-butene using composite ionic liquid catalysts[J]. Applied Catalysis A: General, 2008, 346(1/2): 189-193.
13	Liu Z C, Meng X H, Zhang R, et al. Reaction performance of isobutane alkylation catalyzed by a composite ionic liquid at a short contact time[J]. AIChE Journal, 2014, 60(6): 2244-2253.
14	Hu P C, Wang Y D, Meng X H, et al. Isobutane alkylation with 2-butene catalyzed by amide-AlCl₃-based ionic liquid analogues[J]. Fuel, 2017, 189: 203-209.
15	Wang H, Meng X Z, Zhao G Y, et al. Isobutane/butene alkylation catalyzed by ionic liquids: a more sustainable process for clean oil production[J]. Green Chemistry, 2017, 19(6): 1462-1489.
16	Hartman R L, McMullen J P, Jensen K F. Deciding whether to go with the flow: evaluating the merits of flow reactors for synthesis[J]. Angewandte Chemie International Edition, 2011, 50(33): 7502-7519.
17	Aschauer S J, Jess A. Effective and intrinsic kinetics of the two-phase alkylation of i-paraffins with olefins using chloroaluminate ionic liquids as catalyst[J]. Industrial & Engineering Chemistry Research, 2012, 51(50): 16288-16298.
18	Zhang J S, Wang K, Teixeira A R, et al. Design and scaling up of microchemical systems: a review[J]. Annual Review of Chemical and Biomolecular Engineering, 2017, 8(1): 285-305.
19	Günther A, Jensen K F. Multiphase microfluidics: from flow characteristics to chemical and materials synthesis[J]. Lab on a Chip, 2006, 6(12): 1487-1503.
20	Yoshida J I, Kim H, Nagaki A. Green and sustainable chemical synthesis using flow microreactors[J]. ChemSusChem, 2011, 4(3): 331-340.
21	Jensen K F. Flow chemistry—microreaction technology comes of age[J]. AIChE Journal, 2017, 63(3): 858-869.
22	Burns J R, Ramshaw C. Development of a microreactor for chemical production[J]. Chemical Engineering Research and Design, 1999, 77(3): 206-211.
23	Yao X J, Zhang Y, Du L Y, et al. Review of the applications of microreactors[J]. Renewable and Sustainable Energy Reviews, 2015, 47: 519-539.
24	Su Y H, Zhao Y C, Chen G W, et al. Liquid-liquid two-phase flow and mass transfer characteristics in packed microchannels[J]. Chemical Engineering Science, 2010, 65(13): 3947-3956.
25	Dummann G, Quittmann U, Gröschel L, et al. The capillary-microreactor: a new reactor concept for the intensification of heat and mass transfer in liquid-liquid reactions[J]. Catalysis Today, 2003, 79/80: 433-439.
26	Li L T, Zhang J S, Wang K, et al. Caprolactam as a new additive to enhance alkylation of isobutane and butene in H₂SO₄[J]. Industrial & Engineering Chemistry Research, 2016, 55(50): 12818-12824.
27	Li L T, Zhang J S, Du C C, et al. Kinetics study of sulfuric acid alkylation of isobutane and butene using a microstructured chemical system[J]. Industrial & Engineering Chemistry Research, 2019, 58(3): 1150-1158.
28	Li S W, Xu J H, Wang Y J, et al. Low-temperature bonding of poly-(methyl methacrylate) microfluidic devices under an ultrasonic field[J]. Journal of Micromechanics and Microengineering, 2009, 19(1): 015035.
29	Yao C Q, Zhao Y C, Ma H Y, et al. Two-phase flow and mass transfer in microchannels: a review from local mechanism to global models[J]. Chemical Engineering Science, 2021, 229: 116017.
30	Lan W J, Liu D, Guo X Q, et al. Study on liquid-liquid droplet flow separation in a T-shaped microseparator[J]. Industrial & Engineering Chemistry Research, 2020, 59(26): 12262-12269.
31	Qi L, Meng X H, Zhang R, et al. Droplet size distribution and droplet size correlation of chloroaluminate ionic liquid-heptane dispersion in a stirred vessel[J]. Chemical Engineering Journal, 2015, 268: 116-124.

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