基于磁力搅拌的微型CSTR流动特征及微观混合性能

doi:10.11949/0438-1157.20240457

摘要/Abstract

摘要：

微型连续搅拌反应器（CSTR）作为一种新型主动式强化微反应器，具有较强的处理涉固反应体系的能力。构建了一套基于磁力搅拌、总体积为3 ml且由16个微圆槽串联而成的微型CSTR，通过停留时间分布测量和Villermaux-Dushman快速平行竞争反应实验对其流动特征以及微观混合性能进行探究。研究结果显示，对于该微型CSTR，流速和转速对其返混程度只有较小的影响，Peclet数（Pe）整体维持在20~30之间，返混程度略高于传统管式微反应器，但仍属较低。微型CSTR微观混合效率优于管式微反应器，尤其是在低流速时，其混合效率远高于管式微反应器。进一步通过团聚模型计算获得该微型CSTR的特征混合时间，其值处于0.5~1.0 ms之间。

关键词: 微反应器, 混合, 停留时间分布, 微型CSTR, 微观混合

Abstract:

As a new type of actively enhanced microreactor, micro continuous stirred reactor (micro-CSTR), has a strong ability to handle solid-related reaction systems. In this paper, a micro-CSTR based on magnetic stirring with a total volume of 3 ml and consisting of 16 micro cylindrical grooves was constructed. Its flow characteristics and micromixing performance were investigated by residence time distribution measurement and Villermaux-Dushman fast parallel competitive reaction experiments. The results demonstrated that the flow rate and rotational speed exerted weak influence on the degree of backmixing in the micro-CSTR. The overall Peclet number (Pe) was maintained between 20 and 30, indicating that the degree of backmixing was slightly higher than that of tubular microreactors frequently applied. However, the degree of backmixing remained relatively low. The micromixing efficiency of the micro-CSTR was superior to that of the tubular microreactor, particularly at low flow rates. The characteristic mixing time of this micro-CSTR was further determined using the incorporation model, with a value falling within the range of 0.5 ms to 1.0 ms.

Key words: microreactor, mixing, residence time distribution, micro-CSTR, micromixing

中图分类号:

TQ 052

钟子豪, 刘塞尔, 商敏静, 苏远海. 基于磁力搅拌的微型CSTR流动特征及微观混合性能[J]. 化工学报, 2024, 75(11): 4217-4225.

Zihao ZHONG, Sai'er LIU, Minjing SHANG, Yuanhai SU. Flow characteristics and micromixing performance of micro-CSTR with magnetic stirring[J]. CIESC Journal, 2024, 75(11): 4217-4225.

图/表 8

图1 微型CSTR整体(a)、上盖板(b)、下盖板(c)示意图以及微型CSTR实物图(d)

Fig.1 Micro-CSTR overall (a), upper cover plate (b)， lower cover plate (c)， schematic diagram and physical diagram of micro-CSTR reactor (d)

图2 连续测定微型CSTR的RTD曲线装置示意图

Fig.2 Schematic diagram of a device for measuring RTD curve of a micro-CSTR reactor

表1 停留时间分布测定数据

Table 1 Residence time distribution measurement data

Entry	Reactor system	Rotary speed /(r/min)	Flow rate / (ml/min)	Mean residence time/s		$σ_{θ}^{2}$	Pe	N
Entry	Reactor system	Rotary speed /(r/min)	Flow rate / (ml/min)	Theoretical	Experimental	$σ_{θ}^{2}$	Pe	N
1	micro-CSTR	1000	0.8	240.00	222.80	0.0941	20.20	10.6
2		1000	1.2	160.00	167.68	0.0839	22.78	11.9
3		1000	1.6	120.00	123.10	0.0842	22.71	11.9
4		1000	2	96.00	106.13	0.0798	24.02	12.5
5		1000	2.4	80.00	86.56	0.0812	23.58	12.3
6		1000	2.8	68.00	69.83	0.0804	23.83	12.4
7		0	1.6	120.00	133.04	0.0694	27.79	14.4
8		200	1.6	120.00	138.43	0.0729	26.41	13.7
9		600	1.6	120.00	136.34	0.0820	23.33	12.2
10		800	1.6	120.00	134.60	0.0844	22.66	11.8
11	capillary microreactor	—	0.8	382.00	369.55	0.0238	82.93	—
12		—	1.6	191.00	192.04	0.0584	33.19	—
13		—	2.4	127.00	143.27	0.0804	23.84	—

表1 停留时间分布测定数据

Table 1 Residence time distribution measurement data

Entry	Reactor system	Rotary speed /(r/min)	Flow rate / (ml/min)	Mean residence time/s		$σ_{θ}^{2}$	Pe	N
Entry	Reactor system	Rotary speed /(r/min)	Flow rate / (ml/min)	Theoretical	Experimental	$σ_{θ}^{2}$	Pe	N
1	micro-CSTR	1000	0.8	240.00	222.80	0.0941	20.20	10.6
2		1000	1.2	160.00	167.68	0.0839	22.78	11.9
3		1000	1.6	120.00	123.10	0.0842	22.71	11.9
4		1000	2	96.00	106.13	0.0798	24.02	12.5
5		1000	2.4	80.00	86.56	0.0812	23.58	12.3
6		1000	2.8	68.00	69.83	0.0804	23.83	12.4
7		0	1.6	120.00	133.04	0.0694	27.79	14.4
8		200	1.6	120.00	138.43	0.0729	26.41	13.7
9		600	1.6	120.00	136.34	0.0820	23.33	12.2
10		800	1.6	120.00	134.60	0.0844	22.66	11.8
11	capillary microreactor	—	0.8	382.00	369.55	0.0238	82.93	—
12		—	1.6	191.00	192.04	0.0584	33.19	—
13		—	2.4	127.00	143.27	0.0804	23.84	—

图3 不同流速下微型CSTR(a)和管式微反应器(b)停留时间分布函数

Fig.3 Function of residence time distribution in different flow rate in micro-CSTR (a) and capillary microreactor (b)

图4 不同转速下微型CSTR停留时间分布函数

Fig.4 Function of residence time distribution in different rotor speed in micro-CSTR

图5 不同转速和流速对微型CSTR离集指数的影响

Fig.5 Influence for rotary speed and flow rate on Xs in micro-CSTR

图6 不同流速下微型CSTR和管式微反应器微观混合效率对比

Fig.6 Comparison of micro-mixing efficiencies of micro-CSTR and tubular microreactor at different flow rates

图7 微型CSTR反应器和传统管式微反应器内微观混合时间tm与离集指数Xs的关系

Fig.7 Relationship between microscopic mixing time tm and off-set index Xs in micro-CSTR reactors and conventional tubular reactors

参考文献 30

1	Jähnisch K, Hessel V, Löwe H, et al. Chemistry in microstructured reactors[J]. Angewandte Chemie (International Ed. in English), 2004, 43(4): 406-446.
2	Jas G, Kirschning A. Continuous flow techniques in organic synthesis[J]. Chemistry-A European Journal, 2003, 9(23): 5708-5723.
3	Malet-Sanz L, Susanne F. Continuous flow synthesis. A pharma perspective[J]. Journal of Medicinal Chemistry, 2012, 55(9): 4062-4098.
4	Hughes D L. Applications of flow chemistry in drug development: highlights of recent patent literature [J]. Organic Process Research & Development, 2018, 22(1): 13-20.
5	Stueckler C, Hermsen P, Ritzen B, et al. Development of a continuous flow process for a matteson reaction: from lab scale to full-scale production of a pharmaceutical intermediate [J]. Organic Process Research & Development, 2019, 23(5): 1069-1077.
6	Zong J, Yue J. Continuous solid particle flow in microreactors for efficient chemical conversion[J]. Industrial & Engineering Chemistry Research, 2022, 61(19): 6269-6291.
7	Henry C, Minier J P, Lefèvre G. Towards a description of particulate fouling: from single particle deposition to clogging [J]. Advances in Colloid and Interface Science, 2012, 185/186: 34-76.
8	Liedtke A K, Bornette F, Philippe R, et al. Gas-liquid-solid "slurry taylor" flow: experimental evaluation through the catalytic hydrogenation of 3-methyl-1-pentyn-3-ol[J]. Chemical Engineering Journal, 2013, 227: 174-181.
9	Zhao S N, Yao C Q, Dong Z Y, et al. Role of ultrasonic oscillation in chemical processes in microreactors: a mesoscale issue[J]. Particuology, 2020, 48: 88-99.
10	Bannock J H, Krishnadasan S H, Nightingale A M, et al. Continuous synthesis of device-grade semiconducting polymers in droplet-based microreactors[J]. Advanced Functional Materials, 2013, 23(17): 2123-2129.
11	Noël T, Naber J R, Hartman R L, et al. Palladium-catalyzed amination reactions in flow: overcoming the challenges of clogging via acoustic irradiation[J]. Chemical Science, 2011, 2(2): 287-290.
12	Hartman R L, Naber J R, Zaborenko N, et al. Overcoming the challenges of solid bridging and constriction during Pd-catalyzed C—N bond formation in microreactors [J]. Organic Process Research & Development, 2010, 14(6): 1347-1357.
13	Khan S A, Günther A, Schmidt M A, et al. Microfluidic synthesis of colloidal silica [J]. Langmuir, 2004, 20(20): 8604-8611.
14	Khan S A, Jensen K F. Microfluidic synthesis of titania shells on colloidal silica [J]. Advanced Materials, 2007, 19(18): 2556-2560.
15	董正亚, 陈光文, 赵帅南, 等. 声化学微反应器——超声和微反应器协同强化[J]. 化工学报, 2018, 69(1): 102-115.
	Dong Z Y, Chen G W, Zhao S N, et al. Sonochemical microreactor-synergistic intensification of ultrasound and microreactor[J]. CIESC Journal, 2018, 69(1): 102-115.
16	Mo Y M, Jensen K F. A miniature CSTR cascade for continuous flow of reactions containing solids[J]. Reaction Chemistry & Engineering, 2016, 1(5): 501-507.
17	Pomberger A, Mo Y M, Nandiwale K Y, et al. A continuous stirred-tank reactor (CSTR) cascade for handling solid-containing photochemical reactions[J]. Organic Process Research & Development, 2019, 23(12): 2699-2706.
18	Hopley A, Doyle B J, Roberge D M, et al. Residence time distribution in coil and plate micro-reactors[J]. Chemical Engineering Science, 2019, 207: 181-193.
19	陈光文, 袁权. 微化工技术[J]. 化工学报, 2003, 54(4): 427-439.
	Chen G W, Yuan Q. Micro-chemical technology[J]. Journal of Chemical Industry and Engineering (China), 2003, 54(4): 427-439.
20	Othman R, Vladisavljević G T, Hemaka Bandulasena H C, et al. Production of polymeric nanoparticles by micromixing in a co-flow microfluidic glass capillary device[J]. Chemical Engineering Journal, 2015, 280: 316-329.
21	Xu C, Zhong Y J, Zheng Y N, et al. Micromixing-assisted preparation of TiO₂ films from ammonium hexafluorotitanate and urea by liquid phase deposition based on simulation of mixing process in T-shaped micromixer[J]. Ceramics International, 2019, 45(9): 11325-11334.
22	Chang Y J, Mugdur P, Han S Y, et al. Nanocrystalline CdS MISFETs fabricated by a novel continuous flow microreactor [J]. Electrochemical and Solid State Letters, 2006, 9(5): 174.
23	Lobasov A S, Minakov A V, Kuznetsov V V, et al. Investigation of mixing efficiency and pressure drop in T-shaped micromixers [J]. Chemical Engineering and Processing-Process Intensification, 2018, 134: 105-114.
24	骆广生, 徐建鸿, 陈桂光, 等. 微结构设备内液-液均相混合性能研究进展[J]. 现代化工, 2005, 25(11): 19-23.
	Luo G S, Xu J H, Chen G G, et al. Advances in research of liquid-liquid homogeneous mixing performance in micro-structured devices[J]. Modern Chemical Industry, 2005, 25(11): 19-23.
25	Rahimi M, Aghel B, Hatamifar B, et al. CFD modeling of mixing intensification assisted with ultrasound wave in a T-type microreactor [J]. Chemical Engineering and Processing: Process Intensification, 2014, 86: 36-46.
26	Fournier M C, Falk L, Villermaux J. A new parallel competing reaction system for assessing micromixing efficiency—experimental approach[J]. Chemical Engineering Science, 1996, 51(22): 5053-5064.
27	Fournier M C, Falk L, Villermaux J. A new parallel competing reaction system for assessing micromixing efficiency—determination of micromixing time by a simple mixing model[J]. Chemical Engineering Science, 1996, 51(23): 5187-5192.
28	Reis M H, Varner T P, Leibfarth F A. The influence of residence time distribution on continuous-flow polymerization[J]. Macromolecules, 2019, 52(9): 3551-3557.
29	Wong S H, Ward M C L, Wharton C W. Micro T-mixer as a rapid mixing micromixer[J]. Sensors and Actuators B: Chemical, 2004, 100(3): 359-379.
30	Hoffmann M, Schlüter M, Räbiger N. Experimental investigation of liquid-liquid mixing in T-shaped micro-mixers using μ-LIF and μ-PIV[J]. Chemical Engineering Science, 2006, 61(9): 2968-2976.

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