Utilizing the STT reactor in Flow Chemistry

Transcription

1 Utilizing the STT reactor in Flow Chemistry Rocky Costello, P.E., R.C. Costello & Assoc., Inc. Dr. Michael A. Gonzalez, US EPA, Chief, Emerging Chemistry and Engineering Branch Dr. David E. Meyer, US EPA, Chemical Engineer Life Cycle Decision Support Branch Phil Lichtenberger, Inventor Annual Congress on Medicinal Chemistry, Pharmacology and Toxicology July 30-31, 2018 Amsterdam, The Netherlands

2 Agenda Accelerated Chemistry with the STT System. 1. Discovery 2. Patented STT Technology 3. Research 4. Application 2

3 Sometimes we stumble onto amazing phenomena by accident. 3

4 Discovery Initial Perplexing Discovery In 1999, using a nanomill to make highly loaded thermoplastics, found chemical reactions occurring in hours that normally take years. 4

5 Discovery In 2000, using a clear glass tube and metal rotor, discovered conditions in a Couette type reactor where Taylor rings were no longer present and chemical reactions were accelerated. Discovery became the basis for the first of many patent applications for the STT System. 5

6 Flow Regimes in Pipes D = Inside Diameter in meters V = Velocity in meters/ sec ϒ = Kinematic Viscosity in meters 2 / sec Re = Reynolds Number - Dimensionless 6

7 Flow Regimes in Rotating Systems Calculation of Reynolds number in rotating systems Re i = the inter cylinder Reynolds Number = Re i = a(b-a) Ω i /v Re o = the outer cylinder Reynolds Number = Re o = b(b-a) Ω o /v a = inter cylinder radius in mm b = outer cylinder radius in mm Ω = Angular velocity in mm/sec V = Kinematic viscosity mm 2 /sec 1. Laminar Flow RE < 1, Transitional Flow 1,000 < Re < 10, Turbulent Flow Re > 10,000 7

8 Flow Regimes 8

9 Taylor Rings 9

10 Youtube demonstration of the STT showing both mixing of different materials and the rapid Clean In Place (CIP) Procedure 10

11 Discovery STT technology creates significant increases in reaction rates where mass transfer is an issue. 11

12 Patented STT Technology Depiction of Spinning Tube in Tube fluid flow. 12

13 Patented STT Technology Product The STT System Spinning Tube in Tube Flow Flowing Film Material B Stator Heat Exchanger Material A Cutaway showing rotor with and without flowing film Annular Zone Between Rotor and Stator 13

14 Patented STT Technology Rapid scale-up. CSTRs do not scale up easily Fluid Gap Width Rotational Velocity Hydraulic Radius Parameters that control chemical processing can be kept constant as the size of the STT reactor is increased from bench top to production scale. Tip speed stays constant and RPM goes down. 14

15 Patented STT Technology Rapid scale-up. Shear Rate = πd 1ω 1 d 1 = πd 2ω 2 d 2 Since d 1 = d 2 D 1 ω 1 = D 2 ω 2 15

16 Patented STT Technology STT technology has broad commercial applications. Chemical Synthesis Polymer Synthesis and Modification (Narrow chain length distribution since hot vessel walls create longer polymers) Solids Synthesis Mixing - Dispersing/Blending/Compounding/ Emulsification/Suspensions Biocatalysts and Bioprocessing Extractions/Separations Nanoparticle synthesis and catalysis 16

17 Nanoparticle Catalysis Organic Chemical Reaction Catalyzed by Magnetite or Magnetite particles with a metal catalyst coating STT 17

18 Patented STT Technology Extensive patent and trademark portfolio. 15 issued US patents and select foreign patents 3 registered trademarks and 2 pending trademarks STT Innovator Magellan Cryon Spinning Tube in Tube 18

19 Patented STT Technology Equipment designs that go from bench-scale. A Magellan bench-top STT system for experimentation and process optimization. 19

20 Patented STT Technology to pilot scale An Innovator pilot scale STT system capable of producing tons of material per year 20

21 Patented STT Technology. to full commercial scale. 50,000,000 LPY of biodiesel per reactor. 21

22 Patented STT Technology Cooperative Research and Development Agreement (CRADA) with US EPA laboratories. Since 2003, research has been conducted on STT technology applications in several chemical manufacturing opportunities including: Esterifications Transesterifications Hydrogenations Oxidations Isomerizations Polymerizations Numerous Pharmaceutical chemistries 22

23 Current Research Cooperative Research and Development Agreement (CRADA) with US EPA laboratories since STT equipment and know-how is provided to the US EPA Labs in Cincinnati, Ohio to demonstrate green chemistry applications EPA provides facilities and personnel EPA researches green chemistry applications, provides independent technology assessment and publication, and provides STT modeling and verification 23

24 Current Research Process Simulation for Sustainability: Process Intensification Using Spinning Tube-in-Tube (STT ) Technology Dr. David E. Meyer and Dr. Michael A. Gonzalez 24

25 REACTOR EQUATIONS Continuous Stirred Tank Reactor Plug Flow Reactor Spinning Tube in a Tube Reactor None 25

26 Current Research A Case Study to Model the STT Why model the STT System? Enhanced experimental design Reduced R&D costs for product development Knowledge to explain STT performance to potential industrial users. Case study: Ritter Reaction R R R OH H2 SO 4 R R R Carbocation intermediate R'CN: R R R N nitrilium ion intermediate R' H +, H 2 O R R R N H O R' alcohol starting material acid starting material Nitrile starting material Temperature = 60 C Rate constant (k) = 3.81e -5 m 3 /mol-min Rate of reaction = k * c_benzonitrile * c_tert-butanol Rotor Speed = 6000 RPM amide product 26

27 Current Research A Case Study to Model the STT Input 1 C i0 T 0, P 0 Input 2 C i0 T 0, P 0 W S (Shaft Work) A + B C L STTR Q (Heat Transfer) Outputs C il T L, P L Parameter Value Units L mm r o 8.29 mm r i 7.65 mm Dr 0.64 mm V 1.3 ml w 6000 rpm t 1.7 min T K Rotor w r i r o Stator Dr = r o r i Channel Gap 27

28 Current Research Estimating k As a first approximation, estimate the reaction rate constant (k) assuming an ideal Plug Flow Reactor. df dτ A k τ V v obs C A C B k obs k int * k MT k MT 1 as J A Assume 2nd Order (-r 1 = kc 1 C 3 ), 1:1 stoichiometry, and k = [(1/(C 3,0 -C 1,0 ))*ln(((c 3,0 -C 1,0 )/X+C 1,0 )/C 3,0 )]/t or F(X,C 1,0,C 3,0 )/t Note: For C 1,0 = C 3,0, k = ((1/X)-1)/C 1,0 /t T t Q TOT F 1,0 F 3,0 C 1,0 C 3,0 F(X,C 1,0,C 3,0 ) k Run Number ( o C) (min) (m3/min) mol 1/min mol 3/min X (mol/m3) (mol/m3) (m3/mol) (m 3.mol -1.min -1 ) Avg E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E-04 28

29 Current Research Deriving the STT Transport Equations The type of flow will determine the simplification of equations. Re z QD νa H CS Laminar Stokes Flow Ta 2 3 Ω rid 2 ν 14,130 Ta Cr * Taylor-Vortex Flow * The STT has laminar flow, which implies no Taylor vortices. 29

30 Current Research Deriving the STT Transport Equations vz = W A Generic Approach Lz Lz α R Ωi Assume concentric cylinders with independent rotation. The cylinders have a finite length of Lz. Stokes flow is valid. Infinitely fast reaction; A + B Products Rin = kr Ωo Rout = R Reference: S. Cerbelli et al. / Chemical Engineering Science 63 (2008)

31 Current Research Deriving the STT Transport Equations Creeping (Stokes) Flow Component Balance for A in Cylindrical Coordinates Reference: S. Cerbelli et al. / Chemical Engineering Science 63 (2008)

32 Current Research Finite Element Method (FEM) A numeric technique for finding approximate solutions to systems of partial differential and integral equations. Good for complex and or changing domains structural integrity, weather prediction Discretization of the continuous domain to finite elements that are meshed to approximate the behavior of the solution within each element. Solution obtained using matrix algebra. 32

33 Current Research Solving the STT Transport Equations through FEM COMSOL Multiphysics Modeling Software (Optional) CAD interface to import equipment drawings. Built-in Mesh Generator Pre-defined physics interfaces Computational Fluid Dynamics (CFD) Chemical Reaction Engineering (Mass Transfer) Heat Transfer Linked simulations using a combination of physics modules. A variety of options for sensitivity analysis and analysis of results (plotting options) The derivation and solution of this model in COMSOL Multiphysics was made possible through collaboration with the US EPA and AltaSim Technologies, a licensed COMSOL consultant firm. 33

34 Current Research The STT in COMSOL Dr = 640 mm The STT Flow Path with Meshing The STTR with Heat Jacket (Blue) 34

35 Current Research The COMSOL Model Laminar Flow with a Moving Wall (Navier-Stokes) Du ρg P μ u ρ Dt 2 ρ = fluid density g = gravity vector P = pressure vector D/Dt = substantial derivative = divergence of a vector with respect to a specified coordinate system (Cartesian, cylindrical, spherical). Moving Wall Boundary Condition u (ri) = uwall = 2πriω 35

36 Current Research Velocity field (m/s) within the STT reactor showing areas of low (blue) and high (maroon) fluid velocity. 36

37 Current Research The COMSOL Model Add Chemical Species Transport with Reaction Transport of Dilute Species Obtained from the CFD module 37

38 Current Research Ritter Reaction Simulation Results Benzonitrile (mol/m3) Tert-butanol (mol/m3) N-tert-butylbenzamide (mol/m3) Species Inlet flow rate (mm 3 /s) Inlet conc. (mol/m 3 ) Outlet conc. (mol/m 3 ) Outlet flow rate (mm 3 /s) Outlet conc-model (mol/m 3 ) Benzonitrile Tert-butanol Sulphuric acid Water N-tert-butylbenzamide

39 Current Research The COMSOL Model Add Heat Transport 39

40 Current Research Simulated STT Heat Profile Temperature distribution in reactor Temperature distribution around inlet ports 40

41 Current Research Next Steps Model Verification Study the reaction of morpholine with acrylonitrile to produce b-cyanoethyl morpholine Use multiple runs with varying conditions to fit model by adjusting k. Compare k STT with k batch and k CSTR 41

42 Application Next generation patented STT technology provides numerous yield enhancements for biodiesel transesterification. Continuous Process One reactor one pass Conversion in less than 1 second Minimal soap formation for methyl and ethyl esters Higher conversion yield Yield 42

43 Comparison of the STT to the Lurgi Process for Methyl Ester production Lurgi Biodiesel technology Two (2) CSTRs in series for a total residence time of 40 minute with glycerin removal after each reactor 43

44 Comparison of the STT to the Lurgi Process for Methyl Ester production STT One (1) reactor total residence time 1 second An increase in reaction of rate 40 x 60/1 or 2,400 times faster 44

45 Comparison of the STT to the Lurgi Process for Methyl Ester production The conversion of soybean oil and methanol to methyl esters has three reactions in the forward direction and three in the backwards direction. Their rate constants are shown below. Noureddini & Zhu k1 =2.07E-03 k3 =1.41E-02 k5 = 6.29E-03 Consider Triglyceride <=====> Diglyceride <=====> Monoglyceride<=====> Glycerin k2 = k4 =5.63E-02 k6 = 2.26E-04 45

46 Unexpected Results 1. Reactions went directly to completion as if the three backwards reactions did not exist. 2. The emulsion of methyl esters and glycerin easily separated into two (2) phases. 46

47 Colin Ramshaw For the first time we are seeing true kinetics versus apparent kinetics Formerly with Imperial Chemical and Considered the father of Process Intensification 47

48 Application Biodiesel plant process skids after placement. Reactor Skids Biodiesel Methanol Stripping Glycerol Methanol Stripping Methanol Cleanup 48

49 Application Up to 3% better yield and lower capital cost. Operating savings Up to 3% better yield and feedstock flexibility Less equipment and real-time control Avoids water recovery costs Capital savings Up to 1/3 less capital for plant processing Shorter time to market with modular construction No water wash avoids disposal requirements More compact and standardized units 49

50 Application New Application Development Lower cost water remediation of: Perchlorate Dioxane MTBE Trihalomethane Chlorinated Solvents (PCE, TCE, etc.) Other Aromatics & Ethers 50

51 For the reaction of acetic acid and ethyl alcohol to produce ethyl acetate and water in ChemCad Induce a sinusoidal change in the acetic acid feed. STT 51

52 Because of the sinusoidal change in the feed rate the output of product out of the reactor is also sinusoidal. The actual volume of the reactor is near zero. Thus there is no reactor volume to dampen the changing feed. 52

53 Future Work 1. Start a simulation with ChemCad 2. Before Reactor dump feed streams and properties into Excel 3. Comsol picks up feed streams and properties from Excel and calculates STT output 4. Comsol dumps output into Excel 5. ChemCad picks up stream data from Excel and moves on to the next unit operation 53

54 Company Tribologiks, LLC Tribologiks is a California LLC founded in November, 2014 Company formed to bring together core critical assets and know-how and decades of proven innovation and commercialization expertise Commercial focus is Intensified Flow Chemistry 54

55 Questions? Separate data sheets are available: - STT Technology Overview - STT Pharma Chemistry Overview - STT Reactor Application Areas - EPA Testing STT, Innovator, Magellan, Cryon and Spinning Tube in Tube are registered trademarks and trademarks of Blue Northern Energy, LLC., all rights reserved. 55

56 Tribologiks Faster, Cleaner and Greener 56

57 References 1. Flow regimes in a circular Couette system with independently rotating cylinders By C. DAVID ANDERECKT, S. S. LIUS AND HARRY L. SWINNEY Department of Physics, The University of Texas, Austin, Texas (Received 20 th December 1984 and in revised form 8 th September 1985) 2. Kinetics of Transesterification of Soybean Oil, H. Noureddini and D. Zhu, Department of Chemical Engineering, University of Nebraska, JAOCS, Vol 74, no. 11 (1997) 3. S. Cerbelli et al. / Chemical Engineering Science 63 (2008)

58 The End Thank You 58