mikroglas Technology and Products mikroglas chemtech GmbH Galileo-Galilei-Str. 28, 55129 Mainz Tel.: 06131/55550-0 Fax: 06131/55550-52 info@mikroglas.com www.mikroglas.com an Invenios company Available Micro Fluidic Modules Micro reactors are commercially available for different applications, e.g.: micro emulsifier micro mixer micro falling film reactor micro heat exchanger micro photo reactor micro reactor Different materials are available: glass, metal, ceramics, silicon, etc. Different designs for different applications are available. Handling of gases, liquids and particles are possible. an Invenios company Example for reactions in mikroglas mixer Synthesis of Benzaldehyd from Sulfuric acid and Benzal Chloride CHCl2 CHO H2SO4 Properties of the reaction liquidphase reaction: 2 phases, highly viscous, difficult to mix exothermic reaction: cooling to 0°C necessary conventional technology microreaction technology difficult mixing fast diffusion controlled mixing temperatur: 0°C temperature: +70°C yield: 65% yield 69% reaction time: several hours reaction time: 6 min an Invenios company Interdigital Micromixer for liquid mixing SEM of the mixing chamber - mixing of two liquid or gaseous media - 30 channels run parallel in a mixing chamber channels: width 65 µm depth 150 µm walls: width down to 30 µm depth 150 µm Developed in co-operation with Institut für Mikrotechnik Mainz GmbH an Invenios company Direct Nitration of Toluene Example out of EC funded project NEPUMUC Properties of the reaction - two-phase reaction - very exothermic (explosive !) 50 µm channels In usual interdigital micromixers: Within seconds the droplets agglomerate to large plugs ! an Invenios company Column micromixer free space between columns: 50 µm bubble size: < 40 µm stable emulsion emulsion after column micromixer plug flow coming from interdigital micromixer Column height: 100 µm 20,000 columns ! an Invenios company Cyclone Mixer for gas - liquid mixing homogeneous mixing within 2 s Mixing of O2 and water (isopropanol) dimension of the 16 nozzles: width 50 µm / height 150 µm mixing chamber: diameter 10 mm height 2,15 mm RESULTS: - homogeneous bubble size (~ 150µm) - dissolution: 35g/l (equilibrium: 45 g/l) Developed in cooperation with IMM an Invenios company Fluidic Chip for Electrochemistry Applying voltage Voltage Platinum electrodes: diameter 250 µm Liquid Flow Geometry: dimension of the feeding channels width 400 µm / height 400 µm dimension of the connecting channels width 150 µm / height 150 µm Developed in cooperation with the University of Hull an Invenios company Equipment for Electro Chemistry plant - with syrringe pumps - mfc for gas feed (e.g. O2, CO2, N2) membrane reactor for electro chemistry - with electrodes out of Au, Pt, or Cu - integrated electrical heater in co-operation with University of Stuttgart (Prof. Klemm) an Invenios company Micro Reactor for Photochemistry The synthesis of bioactive compounds by photodecarboxylative addition of carboxylates to phthalimides S. Gallagher, F. Hatoum, M. Oelgemöller and A. G. Griesbeck, Book of Abstracts, Central Europ. Conf. on Photochemistry (CECP 2008), Bad Hofgastein,Austria, February 2008, p. 69. results: - significant reduction of the reaction time - yield 97% - channel length: 1.4 m - flow: 0,08 ml/min - residence 21 min - exposure at 300 nm (Luzchem UB Panel) an Invenios company mikroglas photo reactor GEOMETRY: Reaction channel: outer dimensions: channel dimensions: exposure area: 1.4 ml internal Volume 118 mm x 73 mm x 6.0 mm 1.15 m x 2.0 mm x 0.5 mm 2300 mm² mikroglas photo reactor with XeCl excimer lamp (308 nm 10 W) (Heraeus Noblelight GmbH) integrated heat exchanger material: Foturan-Glass fluidic connection with teflon tubes Temperature range: -20°C up to 120°C flow: up to 30 ml/min. an Invenios company Local Plasma Deposition of Channels Y-mixer und Y-separator hydrophilic Channel geometry: separation: 150x200 µm² reaction: 300x200 µm² hydrophobic separation of: Toluol – red coloured water Test setup flows: 0,1 - 2 mL/min per liquid an Invenios company Gas - Liquid Separation triangular or arrow shaped separation modules chamber depth: 500 µm with surface modification hydrophilic hydrophobic an Invenios company Modification of Micro Settler Separation has been optimized by: - A "nose" breaks adhesion of liquid bubbles at upper wall. - Active pumping keeps liquid level in settler constant. - Surface modification holds liquid in lower half of settler. "nose" an Invenios company Upscaling an Invenios company New mikroglas reactor for high troughput Inlet Feed 2 1/8“ Inlet Feed 1 1/8“ Heat exchanger Inlet/Outlet ¼” Mixer/Reactor 5 parallel mixers: • á 96 mm x 0.5 mm x 0.5 mm • flowrate 9 l/h at 1.5 bar Heat exchanger 2 x 17 parallel channels: • á 75 mm x 2.0 mm x 0.5mm • flowrate 150 l/h at 0.3 bar Heat exchanger Inlet/Outlet ¼” Product Outlet 1/8“ mikroglas microreactor with redesigned heat exchanger for low pressure drop and integrated preheater for feed streams. an Invenios company New mikroglas reactor for high troughput Pressure loss depending on volume flow [Reactor] 1,80 Pressure loss [bar] 1,60 1,40 1,20 1,00 0,80 0,60 0,40 0,20 0,00 0,00 20,00 40,00 60,00 80,00 100,00 120,00 140,00 160,00 Volume flow [ml/min] an Invenios company New mikroglas reactor for high troughput Pressure loss depending on volume flow [Heat exchanger] Pressure loss [bar] 0,30 0,25 0,20 0,15 0,10 0,05 0,00 0,00 500,00 1000,00 1500,00 2000,00 2500,00 3000,00 Volume flow [ml/min] an Invenios company Production scale Number of reactors at 10 kg/h throughput per reactor Product Feed concentration in wt% 3 5 20 50 100 10 kg/day 2 1 1 1 1 100 kg/week 3 2 1 1 1 5 T/month 25 15 4 2 1 10 T/month 50 30 8 3 2 50 T/year 21 13 4 2 1 100 T/year 50 25 7 3 2 50 14 6 4 1000 T/year Day: 24h Week: 120 h Month: 667h Year 8000h an Invenios company Numbering up of Reactors Stack out of 4 mikroglas microreactors which can run in series or parallel. E.g. with this setup one can reach a production capacity of 50 T/year down to a feed concentration of 20 wt%! an Invenios company mikroSyn in Vitamin A production 8 heat parallel exchanger moduls • inlet temperature 70°C • outlet temperature < 60°C • inlet pressure from 2 up to 3 bar • outlet pressure 1 bar • flowrate 200 l/h Cooling water: • inlet temperature 25°C • outlet temperature < 40°C • inlet pressure 3 bar • outlet pressure 1 bar • flowrate 200 l/h Source: Roche AG an Invenios company Equipment an Invenios company Chemical Plant Set screw Inlet Outlet Outlet pressure relief valve microreactors Sensor block sensors control software fluidic connection equipment with pumps, heater/cooler, automation, analytics an Invenios company Connecting microreactors • teflon tubing • standard HPLC-Fittings • thermal insulation • maximum pressure: 20 bar an Invenios company Sensors for process control ATR-IR-sensor pH-sensor viscosity sensor sensorblock for press. & temp. with pressure reliefvalve an Invenios company Photo Cycloaddition Photo Cycloaddition of Benzaldehyde to 2,3-Dihydrofuran (one-step, liquid/liquid reaction, no catalyst) temperature -20°C – 120°C pressure 10 bar solvent ethanol residence time minutes to hours (conv: 14 hrs.) volume flow 0.1 ml/min - 10 ml/min production volume approx. 1 kg/day inlets for 2 reagents, 1 inert gas, 1 cleaning sensors pressure, temperature, IR (product analysis) an Invenios company Flow diagram for photo reaction plant reaction loop E1 P1 P3 sensors V3 V4 sensors mixer E2 P2 cooling sensors process control by IR-measurement exposure: XeCl lamp (Heraeus Noblelight) an Invenios company IR- measurement: flow cell transmission measurement flow cell dimensions: length: 8.5 mm depth: 20/30/40 µm Bruker Optics: • FT-IR Spectrometer • 375 cm-1 bis 7500 cm-1 an Invenios company Photo reaction loop E1 V3 E2 P3 - reagents E1 and E2 are mixed - mixture enters photo reaction loop - pump P3 pumpes through loop - IR sensors measures conversion - at maximum conversion valve V4 opens - rinsing of loop with sovent - start again V4 an Invenios company Electronic Control Unit SIMATIC S7 for microreaction systems (in co-operation with SIEMENS) user defined receipt mixing of 2 components automatic modus ....with cooling circuit • recording pressure temperature flow reaction data • controlling pumps valves heater/chiller • runs with operator as well as fully automated (receipt control) • safety features pressure limit leak detection controlled stop function an Invenios company mikroglas Tool Box micromixer microreactors mikroSyn EDU for liquid-liquid reactions sensors interfaces process control mikroSyn II For 2-step-reactions an Invenios company One Platform – Different Applications mikroSyn for gas/liquid reaction with back pressure valve mikroSyn for homogeneous catalysis Different modules can be fixed easily and connected on top of a platform with the "MicroChemTec" standard pitch. mikroSyn for heterogeneous catalysis mikroSyn EDU with data collection an Invenios company New Concept for Multiple Purpose Use mikroSyn (modular) for: - gas/liquid, liquid/liquid reactions - up to 3 reaction steps - up to 5 reactants mikroSyn for gas/liquid reaction with back pressure valve an Invenios company Microreaction System "mikroSyn µflow" - two step reaction - mixing of up to 5 components - syringe pumps for 1µl – 1 ml / min - temperatur control (-20 to 120°C) - Siemens SIMATIC S7 - mikroglas reactor an Invenios company Beispiel einer gelungenen KMUEntwicklung zur "nachhaltigen Chemie" POlyKOndensation im MIkroreaktor Entwicklung und Test einer mikroverfahrenstechnischen Anlage mit Steuerung und On-Line-Analytik zur Durchführung Übergangsmetallkatalysierter C-C-Kupplungen (Suzukikupplung) am Beispiel der Polykondensation zu polymeren, lichtemittierenden Halbleitern in kontinuierlicher Produktion Br Pd (II) Br Pd Pd (II) OH (0) OH B ( O H) 2 B ( O H) 2 OH Pd (II) B ( O H) 3 OH an Invenios company Microreaction plants for different applications ozonation reaction type reactor pumps/tubing detection flow temperature pressure residence time other reduction / hydrogenation polymerization nitration gas/liquid homogeneous liquid/liquid catalytic liquid/liquid/solid two phase liquid/liquid falling film reactor interdigital mixer with long residence time capillary, packed bed reactor, mixing of up to 5 components multiple feed mixer with emulsification piston pumps mass flow controler (gas) rotary pumps teflon tubing gear pumps stainless steel capillaries rotary pumps teflon tubings online MIR sensor online MIR sensor pH sensor viscosity sensor for molecular weight pH sensor NIR sensor temperature sensor liquid: 5 – 10 ml/min gas: 100 ml/min 5 – 20 ml / min 0.1 – 1 ml / min 0.1 – 10 ml / min 0 to -60°C 0 to –15°C 80 – 120°C 10 – 40 °C 1 bar 1 bar 1 – 3 bar 3 – 6 bar 5 – 60 s 1 - 120 min 30 – 120 min 15 – 60 s special safety issues special safety issues an Invenios company Multi-Purpose-Equipment Base Plate Basis Reactants 3 x liquids 1 x gas 1 x solvent Pumps 3 Rotary Pumps 1 syrringe pump 2 gear pumps 1 MFC µ-fluidic Modules Sensors 7 sensor blocks 3 T-sensors 1 IR-sensor Valves 4x 2/2-valves 4x 2/3-valves Reaction Plates Ozonisation Hydrobromation Fluorination Falling film reactor interdigital-mixer residence mod. Superfokus-M. interdigital-mixer residence mod. catapillar-mixer capillary reactor 3 T-sensors 2 T-sensors 2 T-sensors an Invenios company Multi-Purpose-Equipment Baseplate F1, F2, F3: liquid reactants V1 – V4: 3-way valves SB1 – SB3: sensor blocks in reactant stream SBff, SBT: sensor blocks for falling film / temp. IR, T: IR- und temperaturesensors an Invenios company Multi-Purpose-Equipment for Ozonization pump modules massflow controller electronic control module valves sensor blocks reactors exchangable reaction plate an Invenios company Modular Equipment an Invenios company mikroSyn Equipment flexible laboratory equipment for research and development multi-purpose equipment for development and small scale production automated plants for production in chemical facilities an Invenios company