Process Intensification of the Kolbe-Schmitt- Synthesis by Using Novel Process Windows

Transcription

1 Novel Process Windows in Chemical Engineering - Workshop - December 10, 2009 Osnabrück, Germany Process Intensification of the Kolbe-Schmitt- Synthesis by Using Novel Process Windows Dipl.-Ing. Ulrich Krtschil, Volker Hessel, Patrick Löb, Dorothee Reinhard IMM/ Dept. Mixing and Fine Chemistry Dr. Annegret Stark, Dr. Dana Kralisch, Sabine Hübschmann Friedrich Schiller University of Jena, Technical Chemistry and Environmental Chemistry

2 Outlook 1. History, motivation, project approach and experimentation 2. Aqueous synthesis using oil bath heating 3. Oil bath heated synthesis using reactive ionic liquids 4. Aqueous synthesis using microwave heating 5. Tailor-made microstructured reactors for microwave heating and direct electrical heating 6. Ecological impact 7. Summary and outlook IMM, 2009 IMM Presentation 2

3 History Kolbe-Schmitt reaction Developed by A.W. Hermann Kolbe in 1860 for the synthesis of salicylic acid Improved by Rudolf Schmitt in 1885 First industrial application in 1874 in Dresden/Radebeul start-up company founded by Friedrich von Heyden (assistant of R. Schmitt) Cradle of the modern API manufacturing A.W. Hermann Kolbe (source: Wikipedia) O OH O H Salicylsäurefabrik Dr. F. von Heyden in Radebeul salicylic acid IMM, 2009 IMM Presentation 3

4 Motivation Kolbe-Schmitt reaction: Used as standard method for the fabrication of e.g. - aromatic hydroxy carboxylic acids (e.g. acetylsalicylic acid = Aspirin ) - p-aminosalicylic acid (PAS) - alkyl p-hydroxybenzoate (paraben) Products used as - pharmaceuticals - antimicrobials - fine chemicals Kolbe-Schmitt synthesis is normally carried out batch wise long reaction times Stirred tank (before 1950) Process Intensification of the industrial relevant Kolbe-Schmitt synthesis - continuously processed - use of Novel Process Windows, e.g. high-p,t, increased concentrations IMM, 2009 IMM Presentation 4

5 Project approach Combining flow chemistry with alternative solvents, new reagents and advanced reactor engineering Target reaction Mechanism p=10-40 bar T= o C τ= s Heating method Solvent conventionally Ionic Liquids Near-critical CO 2 Aqueous solution CH-IL-KS CH-A-CO2-KS CH-A-KS microwave M-IL-KS M-A-KS Side and consecutive reactions HCO 3- donating ionic liquids higher temperatures and longer residence times promote side reaction and decomposition IMM, 2009 IMM Presentation 5

6 Experimental set-ups 1/8 inch IMM, 2009 IMM Presentation 6

7 Experimental set-ups 1/16 1/8 inch IMM, 2009 IMM Presentation 7

8 Experimental set-ups 1/16 1/8 inch IMM, 2009 IMM Presentation 8

9 Analytics HPLC (Shimadzu VP series) UV detection at 220 and 260 nm Reported data received when using 220 nm better detection of resorcinol Acidic eluent to avoid deprotonation of the acidic sites Eluent is a mixture of acetonitrile, water and potassium dihydrogen phosphate as buffer IMM, 2009 IMM Presentation 9

10 1. History, motivation, project approach and experimentation 2. Aqueous synthesis using oil bath heating 3. Oil bath heated synthesis using reactive ionic liquids 4. Aqueous synthesis using microwave heating 5. Tailor-made microstructured reactors for microwave heating and direct electrical heating 6. Ecological impact 7. Summary and outlook IMM, 2009 IMM Presentation 10

11 CH-A-KS: Dependency of yield and STY on the capillary dimension Higher Higheryield yieldand STY STY for forthe the1/16 inch inch (O.D.) (O.D.) capillary at at short shortresidence times times Yield 2,4-DHBA [%] C and 35 bar, 1/16 inch 160 C and 35 bar, 1/8 inch STY [kg/(m³ C and 35 bar, 1/16 inch C and 35 bar, 1/8 inch 0 0,000 0,005 0,010 0,015 0,020 0,025 0,030 0,035 0,040 0,045 0,050 0,055 0,060 0,065 0,070 0,075 0,080 0,085 0,090 0,095 0, Residence time [s] (reciprocal) IMM, 2009 IMM Presentation 11

12 CH-A-KS: Selectivity improvements for short residence times Yield 2,4-DHBA and 2,6-DHBA [%] (( at at high high temperaturesand and for for shorter residencetimes: minor minor variationin in yield yield substantial increase in in selectivity 2,4-DHBA, 160 C and 35 bar, 1/8 inch 2,4-DHBA, 180 C and 35 bar, 1/8 inch 2,4-DHBA, 200 C and 35 bar, 1/8 inch 2,6-DHBA, 160 C and 35 bar, 1/8 inch 2,6-DHBA, 180 C and 35 bar, 1/8 inch 5 2,6-DHBA, 200 C and 35 bar, 1/8 inch 1 0 0,0000 0,0100 0,0200 0,0300 0,0400 0,0500 0,0600 0,0700 0,0800 0,0900 0, Residence time [s] (reciprocal) IMM, 2009 IMM Presentation 12

13 Decomposition of the product 2,4-DHBA Conversion (decomposition) of 2,4-DHBA [%] ] C, 1/16 inch 180 C, 1/16 inch 200 C, 1/16 inch 220 C, 1/16 inch 250 C, 1/16 inch 270 C, 1/16 inch T C C Decomposition Decomposition almost almostindependent of of residence residencetime time T < C C Decomposition Decomposition increases increaseswith with residence residencetimes 0 0,0000 0,0100 0,0200 0,0300 0,0400 0,0500 0,0600 0,0700 0,0800 0,0900 0, Residence time (reciprocal) [s] IMM, 2009 IMM Presentation 13

14 Comparison of product formation and decomposition Shorteningof of the the residencetime promotes product formation (results (results for for T T C) C) Yield resorcinol [%] ) C, resorcinol 180 C, resorcinol 200 C, resorcinol 160 C, 2,4-DHBA 180 C, 2,4-DHBA 200 C, 2,4-DHBA Yield 2,4-DHBA [%] /16 inch capillary oil bath heating , , ,0200 0, ,0400 0,0500 0, ,0700 0,0800 0, ,1000 Residence time (reciprocal) [s] IMM, 2009 IMM Presentation 14

15 1. History, motivation, project approach and experimentation 2. Aqueous synthesis using oil bath heating 3. Oil bath heated synthesis using reactive ionic liquids 4. Aqueous synthesis using microwave heating 5. Tailor-made microstructured reactors for microwave heating and direct electrical heating 6. Ecological impact 7. Summary and outlook IMM, 2009 IMM Presentation 15

16 CH-IL-KS: Enhancements in yield and space-time yield % fold increase in STY STY [kg/(m³ h)] % 19 % 19 % Yield 2,4-DHBA [%] IMM, KHCO3, 180 C and 35 bar, 1/16 in. BMIM-HC, 180 C and 35 bar, 1/16 in. 10 KHCO3, 200 C and 35 bar, 1/16 in. BMIM-HC, 200 C and 35 bar, 1/16 in. KHCO3, 250 C and 35 bar, 1/16 in. BMIM-HC, 220 C and 35 bar, 1/16 in. KHCO3, 140 C and 35 bar, 1/8 in ,0000 0,0125 0,0250 0,0375 0,0500 0,0625 0,0750 0,0875 0,1000 0,1125 0,1250 0,1375 0,1500 0,1625 0,1750 0,1875 0,2000 0,2125 0,2250 0,2375 0, s 4 s Residence time [s] (reciprocal) IMM Presentation 16

17 CH-IL-KS: Selectivity improvements compared with KHCO 3 Yield 2,6-DHBA [%] 5,0 4,5 4,0 3,5 3,0 2,5 2,0 1,5 By-product By-productformation formationat at all all temperatures temperaturesand and residence residence times timessignificantly significantlylower lowerfor for ionic ionicliquids EMIM-HC, 220 C KHCO3, 250 C EMIM-HC, 200 C KHCO3, 200 C EMIM-HC, 180 C KHCO3,180 C EMIM-HC, 160 C KHCO3,160 C 1,0 200 o C 0,5 180 o C 0, Resicence time [s] (reciprocal) 0,0000 0,0200 0,0400 0,0600 0,0800 0,1000 0,1200 0,1400 0,1600 IMM, 2009 IMM Presentation 17

18 1. History, motivation, project approach and experimentation 2. Aqueous synthesis using oil bath heating 3. Oil bath heated synthesis using reactive ionic liquids 4. Aqueous synthesis using microwave heating 5. Tailor-made microstructured reactors for microwave heating and direct electrical heating 6. Ecological impact 7. Summary and outlook IMM, 2009 IMM Presentation 18

19 MW-A-KS: Comparison of yield vs. oil bath heating (MW, 1/16") Yield 2,4-DHBA [%] MW 1/4 inch, 130 s MW 1/4 inch, 65 s MW 1/4 inch, 32 s MW 1/4 inch, 16 s MW 1/4 inch, 11 s Oil bath, 1/8 inch, 130 s Oil bath, 1/8 inch, 65 s Oil bath, 1/8 inch, 32 s Oil bath, 1/8 inch, 16 s Oil bath, 1/8 inch, 11 s MW 1/16 inch, 5 s "Oil bath, 1/16 inch, 11 s" 2620 (MW, 1/4") (Oil, 1/16") Trend Trend for for both both heating heating methods methods and and for for short short residence residence times: times: increasing increasing yield yield with with Temp. Temp. for for residence residence times times < < s s s s maximum maximum of of yield yield (<200 (<200 C) C) significantly significantly higher higher STY STY for for the the 1/16 1/16 inch inch capillary capillary Outlet Temperature [ C] IMM, 2009 Microwave: Synthos 3000 (Anton Paar) Capillary: PEEK, 1/4 inch O.D. (1/16 inch) Oil bath: Capillary: CC 405 (Huber) Stainless steel, 1/8 inch O.D. (1/16 inch) IMM Presentation 19

20 MW-A-KS: Comparison of product decomposition vs. oil bath heating 100 Conversion (Decomposition) 2,4-DHBA [%] higher higherdecomposition decompositionrate rate for for microwave microwaveheating heatingat at comparable comparable temperatures temperaturesand and residence residencetimes difference differencebecomes becomesmore moresalient salientfor for lower lowertemperatures Oil bath, 220 C MW 200 W, 131 C C Oil bath, 200 C MW 120 W, 118 C C Oil bath, 180 C MW 100 W, 123 C C Oil bath, 160 C MW 80 W, 64 C C ,0000 0,0100 0,0200 0,0300 0,0400 0,0500 0,0600 0,0700 0,0800 0,0900 0,1000 Residence time (reciprocal) [s] IMM, 2009

21 1. History, motivation, project approach and experimentation 2. Aqueous synthesis using oil bath heating 3. Oil bath heated synthesis using reactive ionic liquids 4. Aqueous synthesis using microwave heating 5. Tailor-made microstructured reactors for microwave heating and direct electrical heating 6. Ecological impact 7. Summary and outlook IMM, 2009 IMM Presentation 21

22 Modular microstructured reactor for microwave heating - Design inlet capillary outlet capillary attenuator microwave cavity threaded ring reactor housing fiberoptically temperature sensor reaction plate gasket cooling plate threaded ring IMM, 2009 IMM Presentation 22

23 Modular microstructured reactor for microwave heating - Concept Developed for continuous operation and adapted to the cavity of the CEM microwave device Discover Designed for pressures up to 40 bar at 150 C Modular construction: different numbers of reaction plates in series or parallel enables simultaneous release of the reaction heat by a microwave transparent cooling fluid (perfluoropolyether) Integrated fibre optical temperature measurement HPLC-connectors IMM, 2009 IMM Presentation 23

24 Electrical heated microstructured reactor for liquids - Design cap outlet casing tube inlet tube with microstructured channels electric heating cartridge exploded view general view part with microstructured channels IMM, 2009 IMM Presentation 24

25 Electrically heated microstructured reactor for liquids - Concept Comparable cross-sectional area with the 1/16 inch capillary use of advantages for small dimensions: higher yields better selectivity 40 fold higher productivity due to (internal) equalling-up Energy savings compared to oil bath heating by reason of thermally controlled power consumption direct electrical heating Promising results of pre-tests with an existing gas heater Scale-up to pilot-scale by external numbering-up using a starlike distributor and collector IMM, 2009 IMM Presentation 25

26 1. History, motivation, project approach and experimentation 2. Aqueous synthesis using oil bath heating 3. Oil bath heated synthesis using reactive ionic liquids 4. Aqueous synthesis using microwave heating 5. Tailor-made microstructured reactors for microwave heating and direct electrical heating 6. Ecological impact 7. Summary and outlook IMM, 2009 IMM Presentation 26

27 Cumulative Energy Demand (CED) Influence of residence time s CED CED reduction reduction by byfactor factor17 17 waste water treatment electrical current Electrical Electricalcurrent current reduction reductionby by factor factor >30 >30 solvent/il potassium hydrogen carbonate resorcinol s L/h 0.03 L/h 0.07 L/h 0.14 L/h 0.2 L/h 0.27 L/h 0.34 L/h 0.55 L/h 17.2 L/h S. Huebschmann, D. Kralisch, V. Hessel, U. Krtschil, V. Kompter, Chem. Eng. Technol. 2009, 32, No. 11, IMM, 2009 IMM Presentation 27

28 1. History, motivation, project approach and experimentation 2. Aqueous synthesis using oil bath heating 3. Oil bath heated synthesis using reactive ionic liquids 4. Aqueous synthesis using microwave heating 5. Tailor-made microstructured reactors for microwave heating and direct electrical heating 6. Ecological impact 7. Summary and outlook IMM, 2009 IMM Presentation 28

29 Progress achieved - Overview % % Yield STY [kg/(m³ h)] 56 % Yield 2,4-DHBA [%] % 10-fold amount of product % KHCO3, 180 C, 35 bar, 1/16 in. BMIM-HC, 200 C, 35 bar, 1/16 in. KHCO3, 140 C, 35 bar, 1/8 in. EMIM-HC, 220 C, 35 bar, 1/16 in. KHCO3, 220 C, 35 bar, microstructured electrical heater 0 0,0000 0,0125 0,0250 0,0375 0,0500 0,0625 0,0750 0,0875 0,1000 0,1125 0,1250 0,1375 0,1500 0,1625 0,1750 0,1875 0,2000 0,2125 0,2250 0,2375 0, ,5 4 Residence time [s] (reciprocal) U. Krtschil, V. Hessel, D. Reinhard, A. Stark, Chem. Eng. Technol. 2009, 32, No. 11, IMM, 2009 IMM Presentation 29

30 Summary Reaction profits from process intensification enabled by Novel Process Windows and micro reaction engineering: Advantages at higher temperatures and the thereby enabled short residence times: massive increase in space-time yields whereas yields are only moderately decreased lowering or almost avoidance of by-product formation predominance of advantages for small dimensions Best yields and space-time yields if reactive ionic liquids are used No increase in yield if additional near-critical CO 2 was applied Improvement for microwave heated capillary reactors compared to oil bath heating with respect to doubling of space-time yield Dedicated microstructured reactor for microwave heating and enabling simultaneous release of the reaction heat by liquid cooling developed and manufactured Electrically heated microstructured reactor for liquids developed, suited for lab and pilot scale by numbering-up IMM, 2009 IMM Presentation 30

31 Outlook Experimental testing of the microstructured reactor in the microwave and comparison to results gained with the capillary reactor Manufacture of the electrically heated microstructured reactor Its application in comparative experiments Erection of a pilot plant and testing of a industrial interesting reaction at industrial site IMM, 2009 IMM Presentation 31

32 Acknowledgement Thank you for your attention! Directorate Micro and Milli Process Engineering IMM, 2009 IMM Presentation 32