DOI: 10.3724/SP.J.1095.2013.20617

Chinese Journal of Applied Chemistry (应用化学) 2013/30:12 PP.1375-1385

Application of Microreactor Technology in Synthetic Chemistry

Micro Reactor Technique(MRT), which shows great advantages in heat transfer, mass transfer and mixing, can enhance the mixing process and control the reaction temperature precisely. In addition, it can dramatically shorten the screening period and scale-up process. This review emphasized the application of the microreactor technology in liquid phase reaction, gas phase reaction and gas-liquid phase reaction in detail. Meanwhile, photochemistry and electrochemistry were introduced briefly. We also presented the existing problems in such technique.

Key words:microreactor,heat transfer,mass transfer,liquid phase microreaction,gas phase microreaction,gas-liquid phase microreaction

ReleaseDate:2015-06-08 13:47:11

[0] Nanoparticles[J]. Org Process Res Dev,2007,11(3):458-462.

[1] Ehrfeld W,Hessel V,Lowe H. Microreactor:New Technology for Modern Chemistry[M]. LUO Guangsheng,WANG Yujun,LU Yangcheng,Trans. Beijing:Chemical Industry Press,2004(in Chinese).艾菲尔德 W,海瑟奥 V,李卫 H. 微反应器:现代化学中的应用技术[M]. 骆广生,王玉军,吕阳成,译。 北京:化学工业出版社,2004.

[2] Dummann G,Quittmann U,Groschell L,et al. The Capillary-microreactor:A New Reactor Concept for the Intensification of Heat and Mass Transfer in Liquid-Liquid Reactions[J]. Catal Today,2003,79(1/4):433-439.

[3] Pennemann H,Hessel V,Lowe H. Chemical Microprocess Technology-form Laboratory-scale to Production[J]. Chem Eng Sci,2004,59(22/23):4789-4794.

[4] Lob P,Lowe H,Hessel V. Fluorinations, Chlorinations and Brominations of Organic Compounds in Micro Reactors[J]. J Fluorine Chem,2004,125(11):1677-1694.

[5] Chen G G,Luo G S,Li S W,et al. Experimental Approaches for Understanding Mixing Performance of a Minireactor[J]. AIChE J,2005,51(11):2923-2929.

[6] Xu J H,Luo G S,Chen G G,et al. Mass Transfer Performance and Two-phase Flow Characteristic in Membrane Dispersion Mini-Extractor[J]. J Membr Sci,2005,249(1/2):75-81.

[7] Kralj J G,Schmidt M A,Jensen K F. Surfactant-Enhanced Liquid-Liquid Extraction in Microfluidic Channel with Inline Electric-field Enhanced Coalescence[J]. Lab Chip,2005,5(5):531-535.

[8] Dendukuri D,Tsoi K,Hatton T A,et al. Controlled Synthesis of Nonspherical Microparticles Using Microfluidics[J]. Langmuir,2005,21(6):2113-2116.

[9] Rebrov E V,Duinkerke S A,Schouten J C,et al. Optimization of Heat Transfer Characteristics, Flow Distribution, and Reaction Processing for a Microstructured Reactor/Heat-exchanger for Optimal Performance in Platinum Catalyzed Ammonia Oxidation[J]. Chem Eng J,2003,93(3):201-216.

[10] Pohar A,Plazl I. Laminar to Turbulent Transition and Heat Transfer in a Microreactor:Mathematical Modeling and Experiments[J]. Ind Eng Chem Res,2008,47(19):7447-7455.

[11] Antes J,Boskovic D,Krause H,et al. Analysis and Improvement of Strong Exothermic Nitrations in Microreactors[J]. Chem Eng Res Des,2003,81(A7):760-765.

[12] Roberge D M,Ducry L,Bieler N,et al. Microreactor Technology:a Revolution for the Fine Chemical and Pharmaceutical Industries[J]. Chem Eng Technol,2005,28(3):318-323.

[13] Haswell S J,Middleton R J,O′Sullivan B,et al. The Application of Microreactors to Synthetic Chemistry[J]. Chem Commun,2001,(5):391-398.

[14] Nikbin N,Ladlow M,Ley S V. Continuous Flow Ligand-Free Heck Reactions Using Monolithic Pd

[15] SUN Feifei,ZHONG Shunhe. Chemisorption of Supported Au/TiO2 Catalyst in Direct Epoxidation of Propylene[J]. Chinese J Appl Chem,2003,20(9):849-852(in Chinese).孙菲菲,钟顺和。 丙烯在Au/TiO2催化剂上的化学吸附与临氢环氧化反应[J]. 应用化学,2003,20(9):849-852.

[16] Fortt R,Wootton R C R,de Mello A J. Continuous-Flow Generation of Anhydrous Diazonium Species:Monolithic Microfluidic Reactors for the Chemistry of Unstable Intermediates[J]. Org Process Res Dev,2003,7(5):762-768.

[17] Bou-Diab L,Fierz H,Gwerder C,et al. A New Multipurpose Microreactor for Process Safety Studies[J]. Org Process Res Dev,2003,7(6):1077-1078.

[18] Watts P,Haswell S J. Electrochemical Oxidation of Tertiary Amines to Form Iminium Ions Which Deprotonate to Form Enamines[P]:GB 2387171,2003-08-08.

[19] Antes J,Tuercke T,Marioth E,et al. Topical Conference Proceedings; IMRET 4, 4th International Conference on Microreaction Technology, AIChE Spring National Meeting, March 5-9, 2000,Atlanta, GA;New York:American Institute of Chemical Engineers,2000:194-200.

[20] Lobbecke S,Antes J,Turcke T,et al. In Proceedings of the 31st International Annual Conference ICT:Energetic Materials-Analysis, Diagnostics and Testing,June 27-30,2000,Karlsruhe,Germany.

[21] Burns J R,Ramshaw C. Development of a Microreactor for Chemical Production[J]. Chem Eng Res Des,1999,77(3):206-211.

[22] Burns J R,Ramshaw C. In Topical Conference Proceedings; IMRET 4, 4th International Conference on Microreaction Technology, AIChE Spring National Meeting, March 5-9, 2000, Atlanta, GA;New York:American Institute of Chemical Engineers,2000:133-140.

[23] Knapkiewicz P,Skowerski K,Jaskolska D E,et al. Nitration Under Continuous Flow Conditions:Convenient Synthesis of 2-Isopropoxy-5-nitrobenzaldehyde, an Important Building Block in the Preparation of Nitro-Substituted Hoveyda-Grubbs Metathesis Catalyst[J]. Org Process Res Dev,2012,16:1430-1435.

[24] Chen Y Z,Zhao Y C,Han M,et al. Safe, Efficient and Selective Synthesis of Dinitroherbicides via a Multifunctional Continuous-Flow Microreactor:One-step Dinitration with Nitric Acid as Agent[J]. Green Chem,2013,15:91-94.

[25] Wiles C,Watts P,Haswell S J,et al. Solution Phase Synthesis of Esters within a Microreactor[J]. Tetrahedron,2003,59(51):10173-10179.

[26] ZHANG Lixiong,JU Jingxi,XU Nanping. Method for Manufacturing Biological Diesel Oil with Microchannel Reactor[P]:CN,1861751A,2006-11-15(in Chinese).张利雄,鞠景喜,徐南平。 一种利用微通道反应器制备生物柴油的方法:中国,1861751A[P],2006-11-15.

[27] Madalina T,Diana M,Cristian T,et al. Biocatalytic Microreactor Incorporating HRP Anchored on Micro-/Nano-lithographic Patterns for Flow Oxidation of Phenols[J]. J Mol Catal B,2011,69:133-139.

[28] Maruyama T,Uchida J I,Ohkawa T,et al. Enzymatic Degradation of p-Chlorophenol in a Two-phase Flow Microchannel System[J]. Lab Chip,2003,3(4):308-312.

[29] Belder D,Ludwig M,Wang L,et al. Enantioselective Catalysis and Analysis on a Chip[J]. Angew Chem Int Ed,2006,45(15):2463-2466.

[30] Kanno K,Maeda H,Izumo S,et al. Rapid Enzymatic Transglycosylation and Oligosaccharide Synthesis in a Microchip Reactor[J]. Lab Chip,2002,2(1):15-18.

[31] Sasson Y,Neumann R,Eds. Handbook of Phase Transfer Catalysis;London:Blackie Academics and Professionals,1997.

[32] Fiamegos Y C,Stalikas C D. Phase-Transfer Catalysis in Analytical Chemistry[J]. Anal Chim Acta,2005,550(1/2):1-12.

[33] Hisamoto H,Saito T,Tokeshi M,et al. Fast and High Conversion Phase-Transfer Synthesis Exploiting the Liquid Liquid Interface Formed in a Microchannel Chip[J]. Chem Commun,2001,(24):2662-2663.

[34] Ahmed-Omer B,Barrow D,Wirth T. Effect of Segmented Fluid Flow, Sonication and Phase Transfer Catalysis on Biphasic Reactions in Capillary Microreactors[J]. Chem Eng J,2007,135(Suppl.1):S280-S283.

[35] Ueno M,Hisamoto H,Kitamori T,et al. Phase-Transfer Alkylation Reactions Using Microreactors[J]. Chem Commun,2003,(8):936.

[36] Nakashima T,Shimizu M,Kukizaki M. Membrane Emulsification by Microporous Glass[J]. Key Eng Mater,1992,(61/62):513-516.

[37] Bayer T,Pysall D,Wachsen O. In Topical Conference Proceedings; IMRET 3, 3rd International Conference on Microreaction Technology, AIChE Spring National Meeting;Ehrfeld W, Ed.;Berlin:Springer-Verlag,2000:165-170.

[38] Pysall D,Wachsen O,Bayer T,et al. Method and Device for Continuous Production of Polymers:DE 19816886 C1[P],1998-04-17.

[39] Honda T,Miyazaki M. Controllable Polymerization of N-Carboxy Anhydrides in a Microreaction System[J]. Lab Chip,2005,5(8):812-818.

[40] Kraut M,Nagel A,Schubert K. In Topical Conference Proceedings; IMRET 6, 6th International Conference on Microreaction Technology, AIChE Spring National Meeting, March 11-14,2002,New Orleans,LA; American Institute of Chemical Engineers:New York,2002:352-356.

[41] Kawaguchi T,Miyata H,Ataka K,et al.  Room-Temperature Swern Oxidations by Using a Microscale Flow System[J]. Angew Chem Int Ed,2005,44(16):2413-2416.

[42] Mikami K,Islam M N,Yamanaka M,et al. Nanoflow System for Perfect Regiocontrol in the Baeyer-Villiger Oxidation by Aqueous Hydrogen Peroxide Using Lowest Concentration of a Fluorous Lanthanide Catalyst[J]. Tetrahedron Lett,2004,45(18):3681-3683.

[43] Acke D R J,Stevens C V. Study of the Baylis-Hillman Reaction in a Microreactor Environment:First Continuous Production of Baylis-Hillman Adducts[J]. Org Process Res Dev,2006,10(3):417-422.

[44] WU Wei,ZHANG Jing,QIAN Gang,et al. Continuous Synthesis of Peracetic Acid in Micro-Channel Reactor[J]. Chem React Eng Technol,2009,25(2):180-183(in Chinese).吴巍,张晶,钱刚,等。 微通道内连续合成过氧乙酸[J]. 化学反应工程与工艺,2009,25(2):180-183.