CORNING ADVANCED-FLOW REACTORS for Intensifying Two-Phase Processes

Transcription

1 CORNING ADVANCED-FLOW REACTORS for Intensifying Two-Phase Processes Daniela Lavric Corning Reactor Technologies Corning European Technology Center Avon, France

2 Outline Introduction to Corning Incorporated Corning Advanced-Flow Reactor Technologies Liquid-Liquid Mass Transfer Gas-Liquid Mass Transfer Applications Conclusion Advanced-Flow Reactor Technologies 2013 Corning Incorporated 2

3 Corning Incorporated Founded: 1851 Headquarters: Corning, New York Employees: ~29,000 worldwide Corning is the world leader in specialty glass and ceramics. We succeed through sustained investment in R&D, 160 years of materials science and process engineering knowledge, and a distinctive collaborative culture Sales: $ 8,0 B Fortune 500 Rank (2012): 326 ~ 10 % of annual sales in R&D Headquarters Joint Ventures Manufacturing Sales offices Advanced-Flow Reactor Technologies 2013 Corning Incorporated 3

4 Corning Market Segments and Additional Operations Display Technology Telecom Environmental Technologies Life Sciences Specialty Materials Other Products and Services LCD Glass Substrates Glass Substrates for OLED and high-performance LCD platforms Optical Fiber and Cable Hardware and Equipment Fiber optic connectivity products Emissions Control Products Light-duty gasoline vehicles Light-duty and heavy-duty on-road diesel vehicles Heavy-duty nonroad diesel vehicles Stationary Cell Culture and Bioprocess Assay and High- Throughput Screening Genomics and Proteomics General Laboratory Products Corning Gorilla Glass Display Optics and Components Optical Materials Semiconductor materials Specialty fiber Polarcor Optics Aerospace and Defense Ophthalmic Emerging Display Technology Drug Discovery Technology New Business Development Equity Companies Cormetech, Inc. Dow Corning Corp. Eurokera, S.N.C. Samsung Corning Advanced Glass, LLC (SCG) Samsung Corning Precision Materials Co., LTD (SCP) Advanced-Flow Reactor Technologies 2013 Corning Incorporated 4

5 Corning s Continuous Flow Reactors Build on the Company s 160 Years of Innovation 1879 Glass for Edison s light bulb 1934 Dow Corning silicones 1915 Heat-resistant Pyrex glass 1952 Glass ceramics 1947 TV tube mass production 1970 Low-loss optical fiber 1982 LCD glass 1972 Substrates for catalytic converters 2007 Thin, lightweight, cover glass Ultra bendable fiber Pre Fluidic module AFR* 2010 Thin-film photovoltaic glass * Advanced-Flow Reactors Advanced-Flow Reactor Technologies 2013 Corning Incorporated 5

6 History of Corning Reactor Technologies One decade of expertise Concept development Customers collaborations G1 reactor G2 reactor Bank concept G3 reactor MIT collaboration China applications lab First introduced in 2002 Technology leveraged for larger sizes with advanced materials to increase throughput: Glass Ceramic Worldwide established business operations Collaborations with platforms in Europe European applications lab Low Flow lab system India applications lab G4 Ceramic reactor Advanced-Flow Reactor Technologies 2013 Corning Incorporated 6

7 Corning Advanced-Flow Reactors (AFR) Worldwide presence NA USA SA EUROPE AFRICA ASIA China India S. Korea Advanced-Flow Reactor Technologies 2013 Corning Incorporated 7

8 Corning Advanced-Flow Reactors Offer broad capability from feasibility to production and enable the transition from batch to continuous processes Advanced-Flow Reactor Technologies 2013 Corning Incorporated 8

9 Corning Advanced-Flow Reactors Product Design Engineered fluidic modules: glass or ceramic plates with integrated mass and heat transfer Heat exchange Reactants End Product Reactor design: a modular assembly A+B C C+D E Reactor: A B D quench Corning Advanced-Flow Reactor - Glass Corning Advanced-Flow Reactor - SiC Advanced-Flow Reactor Technologies 2013 Corning Incorporated 9

10 Fluidic Modules (HEART-based) Increase throughput with similar: - Mixing - Residence time distribution - Heat Exchange - Mass transfer in heterogeneous systems ml 250 ml 5-9 ml 0.5 ml ml LF G1 G2 G3 G g/min g/min g/min g/min g/min D. Lavric and P. Woehl, Chemistry Today 27, (2009) Advanced-Flow Reactor Technologies 2013 Corning Incorporated 10

11 Continuous Flow Reactors Production Range Low Flow G1 G2 G3 G ml 8 11 ml ml ml ml T from - 60 to 200 C, P up to 18 bar, metal-free reaction path LF feasibility studies G4 G3 G2 G1 Kg / h Advanced-Flow Reactor Technologies 2013 Corning Incorporated 11

12 Glass & Ceramic Materials Superior corrosion resistance Flow reactor characteristics Transfer Superior mixing & mass-transfer Excellent HE with reaction integration Appropriate residence time Narrow RTD Controls Reduced process fluid hold-up Accurate T,P, & RT control Production Numbering-up to meet capacity Flexible to fit chemistry & market needs Weight loss (mg/cm².year)* H 2 SO 4-96% HNO 3-65% NaOH-10% low T NaOH30% High T HCl-32% 316L SS Glass S-SiC destroyed good good destroyed good good good good good good destroyed good destroyed good good Glass transparency For development in the lab For photochemistry Advanced-Flow Reactor Technologies 2013 Corning Incorporated 12

13 For Production: Scale-up Combined with Internal and External Numbering-up Chemistry Today, 27 (3), (2009) Chemistry Today, 26 (5), 1-4 (2008) Production Pilot scale Lab scale Advanced-Flow Reactor Technologies 2013 Corning Incorporated 13

14 Requirements of Chemical Reactions Reaction needs Contact between the molecules of the reactants Reactor capabilities MIXING / MASS TRANSFER Keep the molecules in contact during a sufficient time to allow the completion of the reaction Enable the same history of the molecules in the reactor Residence Time RTD RT = 5 s Provide isothermal condition HEAT TRANSFER Advanced-Flow Reactor Technologies 2013 Corning Incorporated 14

15 Intense Mass Transfer in Two-Phase Processes in HEART-based Fluidic Modules Periodic merging and break-up of droplets/bubbles leads to a constant renewal of the interface and the active interfacial area is used very efficiently

16 Fluidic Module Performances Hydrodynamics in immiscible fluids: Toluene-Water 20 g/min toluene-20g/min water 40 g/min toluene-40g/min water Advanced-Flow Reactor Technologies 2013 Corning Incorporated 16

17 Fluidic Module Performances Mass transfer in immiscible liquids W/A/T Analysis: GC FID Misek, T., et al., Standard test systems for liquid extraction. EFCE Publication Series 1985, 46 G4 LF G1 G2 G3 1 Saien, J. et al., Chem. Eng. Sci. 2006, 61, (2006) 2 Kashid M. N., et al., 2011, Ind. Eng. Chem. Res., 50, (2011) Advanced-Flow Reactor Technologies 2013 Corning Incorporated 17

18 Fluidic Module Performances Mass transfer in immiscible liquids hexane-water M. Jose Nieves-Remacha, A. A. Kulkarni, and K. F. Jensen, Ind. & Eng. Chem. Res. 51, (2012) Advanced-Flow Reactor Technologies 2013 Corning Incorporated 18

19 Fluidic Module Performances Hydrodynamics in Gas-Liquid: water-n 2 First HEARTs 2 nd row of HEARTs 50 ml/min G 100 NmL/min 100 ml/min G 200 NmL/min Advanced-Flow Reactor Technologies 2013 Corning Incorporated 19

20 Fluidic Module Performances Mass transfer in Gas-Liquid from Low Flow to G4 CO 2 absorption in NaHCO 3 /Na 2 CO 3 buffer solutions Contacting equipment Volumetric mass transfer coefficient, k L a (s -1 ) Plate column Packed column Gas bubble column Stirred bubble absorber Spray column Jet (loop) Multi-stage ELALR Microchannel 2 : V = 25 µl Q G = ml/min Q L = ml/min Corning G1: V = 8 ml Q G = ml/min Q L = ml/min Corning G4 V = 250 ml Q G = ml/min Q L = ml/min K. Mohanty et al., Chemical Engineering Journal 133, (2007). 2 J. Yue et al., Chem. Eng. Sci. 62, (2007). Advanced-Flow Reactor Technologies 2013 Corning Incorporated 20

21 Fluidic Module Performances Gas - Liquid specific surface area and power consumption Air-water Type of micro reactor Specific interfacial area [m 2 /m 3 ] Micropacked bed (1) Microbubble column (1100 µm x 170 µm) Micro bubble column (300 µm x 100 µm) Micro bubble column (50 µm x 50 µm) Falling film microreactor (300 µm x 100 µm) (2) (3) Corning G1 fluidic module air / water (4) CO 2 -NaOH 1.M.W Losey et al., Ind. Eng. Chem. Res. 40, (2001). 2. K.K. Yeong et al., Chem. Eng. Sci. 59, (2004). 3. K. Jähnisch et al., J. Fluorine Chem. 105, (2000). 4. B. Chevalier et al., Chemistry Today 26(2), (2008). 5. M. Jose Nieves-Remacha, A. A. Kulkarni, and K. F. Jensen, Ind. & Eng. Chem. Res. 52, (2013). Advanced-Flow Reactor Technologies 2013 Corning Incorporated 21

22 Fluidic Module Performances Mass transfer in G-L systems 400 µm V = 270 µl 400 µm V = 240 µl CO 2 - NaOH Courtesy of S. Kuhn Kuhn, S., ECCE 8, September 25-29, Berlin, Germany (2011) Advanced-Flow Reactor Technologies 2013 Corning Incorporated 22

23 Fluidic Module Performances Mass transfer in G-L systems 400 µm V = 270 µl V = 8.7 ml Kuhn, S., ECCE 8, September 25-29, Berlin, Germany (2011) Courtesy S. Kuhn Advanced-Flow Reactor Technologies 2013 Corning Incorporated 23

24 Corning Advanced-Flow Reactors Minimize scale-up failures and drastically reduce the time from laboratory to production Advanced-Flow Reactor Technologies 2013 Corning Incorporated 24

25 Applications

26 Nitration Reactions in Corning AFR Reduced solvent usage, higher yield and safer operation Strict control of reaction parameters is crucial for both quality and safety: Temperature Stoechiometry Residence time Shorter Development Cycle Value generated from: reduced solvent usage, higher yield & significant safety improvement HO R OH + HNO 3 HO R Product ONO 2 X O 2 NO R ONO 2 Explosive by-product Substrate Feed preparation Excellent Mixing of immiscible liquids Nitration Quench and neutralization Solvent Flush H 2 O HNO 3 H 2 O NaOH NaOH NaOH Commercial scale demonstration Product Braune, S. et al.,chemistry Today, 26 (5), 1-4, (2008) Advanced-Flow Reactor Technologies 2013 Corning Incorporated 26

27 Scale-up and Numbering-up as well From concept validation in the lab DSM presentation Scale-up conference 2010 to the industrial production. Braune, S. et al., Chemistry Today, 26 (5), 1-4, (2008) R. Guidat, D. Lavric, CHISA 2010, 28 August-1 September, Prague, Czech Republic (2010) Advanced-Flow Reactor Technologies 2013 Corning Incorporated 27

28 TEMPO Reaction: Parametric Study in Low-Flow Improved efficiency of a two-phase L/L reaction by fine-tuning the conditions Initially developed by Anelli et al. (JOC, 1987, 52, 2559) Difficult scale-up due to exothermicity and bleach stability ph and set-up optimization Higher yield achieved at ph = 8 but, the bleach is less stable Solved by optimized set-up with 3 feeds for ph in-line adjustment Advanced-Flow Reactor Technologies 2013 Corning Incorporated 28

29 TEMPO Reaction: Strong Impact of Mixing The unique HEART design allows a permanent and efficient mixing quality Qualitative comparison for the same residence time: T-mixer + tubes (0.32 mm or 0.16 mm internal diameter) slugs at the outlet 1 Low Flow fluidic module + tube 0.16 mm emulsion + slugs 7 Low Flow fluidic modules emulsion Permanent mixing Constant emulsion quality Higher mass transfer Octanol 0.5M in dichloromethane TEMPO 0.05% Temperature: 20ºC (no HE for tubes) Bleach: 1.2 equivalents (9.7%) Buffer: phosphate 1 M (1 eq. / ph=8) Advanced-Flow Reactor Technologies 2013 Corning Incorporated 29

30 Conversion (%) TEMPO Reaction: Scale-up from Low-Flow to G1 Optimized conditions implemented in G1 allow higher productivity 1.2 eq bleach, 0,2%mol TEMPO K 2 HPO 4 CH 2 Cl 2 -H 2 O, ph = 8, 20 C TEMPO in LFR and G1 Low-Flow G1 100,00% 95,00% 90,00% 85,00% G1 LFR Internal volume 5.7 ml 61.7 ml Residence Time 49 s 30 s Flow rate 7 ml/min 120 ml/min 80,00% Residence time (s) Production 0.18 mol/h 3.6 mol/h In-line generation and easy management of unstable reagent Fast (30-60 s) and selective conversion of primary alcohols to corresponding aldehydes Higher volumetric heat and mass transfer coefficients than in batch enable higher productivity Successful scale-up from Low-Flow to G1 with improvement of productivity by a factor 20 Advanced-Flow Reactor Technologies 2013 Corning Incorporated 30

31 Selective Hydrogenation with Slurry Catalyst 98%+ conversion & selectivity (impurity profiles within spec) highly exothermic (>400 kj/mol) 30 µm catalyst in slurry significant catalyst reduction 10h 90s B.Buisson et al., Chemistry Today, 27(6), (2009) Excellent G/L Mixing 35%wt 45%wt 30 C 140 C 0.4% 0.1% Batch Corning AFR Advanced-Flow Reactor Technologies 2013 Corning Incorporated 31

32 Yield Scale-up from lab to pilot Multiphase application: L/L/G Lab G1 80 t/y Production, G t/y G1 G4 Advanced-Flow Reactor Technologies 2013 Corning Incorporated 32

33 How well do we know our product? Long duration lifetime testing Testing on fluidic modules Breakage Design X4RT analysis - fractography Design X4SJHS 1HPA HPA HPA HPA Oblong feature Testing on reactor 1HPA HPA N4 Layer above Sharp angle Example of lifetime model Advanced-Flow Reactor Technologies 2013 Corning Incorporated 33

34 Reliability and auxiliaries characterization Apparatus for gaskets testing Samples of gaskets after testing Control of rupture pressure of piping Impact of vibration on flow meter measurement stability Advanced-Flow Reactor Technologies 2013 Corning Incorporated 34

35 Continuous Flow Reactor Technology is More than Reactor Corning has an unique and global experience in delivering or advising for complete flow reactor systems for specific needs Advanced-Flow Reactor Technologies 2013 Corning Incorporated 35

36 This is one of the reason why more and more customers trust us* Shandong Brother Tech Massachusetts Institute of Technology (MIT) 范上大海学师 * Partial list Advanced-Flow Reactor Technologies 2013 Corning Incorporated 36

37 Instead of Conclusion. To be successful, you have to have your HEART in your business, and your business in your heart Thomas J. Watson, Sr. chairman and CEO of IBM from 1914 to 1956 Advanced-Flow Reactor Technologies 2013 Corning Incorporated 37

38 Acknowledgements A special Thank to the CORNING AFR Team, particularly the Research & Development Group the Reliability and Characterization Group the Global Application Engineer Team the Quality Control Service for making this presentation possible lavricd@corning.com Advanced-Flow Reactor Technologies 2013 Corning Incorporated 38

39 THANK YOU FOR YOUR ATTENTION Advanced-Flow Reactor Technologies 2013 Corning Incorporated 39

40