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Utilizing the STT® reactor in
Flow ChemistryRocky 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 EngineerLife Cycle Decision Support Branch
Phil Lichtenberger, Inventor
Annual Congress on Medicinal Chemistry, Pharmacology and Toxicology
July 30-31, 2018 Amsterdam, The Netherlands
Agenda
1. Discovery
Accelerated Chemistry with the STT® System.
4. Application
2. Patented STT® Technology
3. Research
2
Sometimes we
stumble onto
amazing phenomena
by accident.
3
44
Discovery
In 1999, using a nanomill to
make highly loaded
thermoplastics, found
chemical reactions occurring
in hours that normally take
years.
Initial Perplexing 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.
55
Discovery
Discovery became the basis
for the first of many patent
applications for the STT®
System.
Flow Regimes in Pipes
D = Inside Diameter in metersV = Velocity in meters/ secϒ = Kinematic Viscosity in meters2/ secRe = Reynolds Number - Dimensionless
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Flow Regimes in Rotating Systems
Calculation of Reynolds number in rotating systems
Rei = the inter cylinder Reynolds Number = Rei = a(b-a) Ωi/v
Reo = the outer cylinder Reynolds Number = Reo = b(b-a) Ωo/v
a = inter cylinder radius in mmb = outer cylinder radius in mmΩ = Angular velocity in mm/secV = Kinematic viscosity mm2/sec
1. Laminar Flow RE < 1,0002. Transitional Flow 1,000 < Re < 10,0003. Turbulent Flow Re > 10,000
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Flow Regimes
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Taylor Rings
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https://youtu.be/HJubL5D02tQ
Youtube demonstration of the STT® showing both mixing of different materials and the rapid
Clean In Place (CIP) Procedure
Discovery
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STT® technology creates significant increases in
reaction rates where mass transfer is an issue.
Patented STT® Technology
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Depiction of Spinning Tube in Tube™ fluid flow.
Product
Flowing Film
Material “B”
Material “A”
Annular Zone BetweenRotor and Stator
Cutaway showing rotor with and without flowing film
StatorHeat Exchanger
The STT® System
13
Patented STT® Technology
Spinning Tube in Tube™ Flow
Patented STT® Technology
14
Rapid scale-up. CSTRs do not scale up easily
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.
Fluid Gap Width
Hydraulic Radius
Rotational
Velocity
Patented STT® Technology
15
Rapid scale-up.
𝑆ℎ𝑒𝑎𝑟 𝑅𝑎𝑡𝑒 =𝜋𝐷1ω1
𝑑1=𝜋𝐷2ω2
𝑑2
Since d1 = d2
𝐷1ω1 = 𝐷2ω2
Patented STT® Technology
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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
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Nanoparticle Catalysis
STT®
Organic Chemical Reaction Catalyzed by Magnetite or Magnetite particles with a metal catalyst coating
Patented STT® Technology
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Extensive patent and trademark portfolio.
• 3 registered trademarks and
2 pending trademarks
• STT®
• Innovator®
• Magellan®
• Cryon™
• Spinning Tube in Tube™
• 15 issued US patents and select foreign patents
Patented STT® Technology
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Equipment designs that go from bench-scale ….
A Magellan®
bench-top STT®
system for
experimentation
and process
optimization.
Patented STT® Technology
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… to pilot scale ……
An Innovator®
pilot scale STT®
system capable of
producing tons of
material per year
Patented STT® Technology
50,000,000 LPY of biodiesel per reactor.
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…. to full commercial scale.
Patented STT® Technology
22
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
Current Research
23
Cooperative Research and
Development Agreement (CRADA)
with US EPA laboratories since 2003.
• 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
Dr. David E. Meyer and Dr. Michael A. Gonzalez
Process Simulation for Sustainability:
Process Intensification Using Spinning Tube-in-Tube
(STT®) Technology
Current Research
24
REACTOR EQUATIONS
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Continuous Stirred Tank Reactor
Plug Flow Reactor
Spinning Tube in a Tube Reactor None
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
RR
OHH2SO4
R
RR
R'CN:
Carbocation
N
R
R
R'
nitrilium ionintermediate
H+, H2OO
NH
R'R
RR
R
alcohol starting material
intermediate
Nitrile startingmaterial
amide product
acid startingmaterial
Temperature = 60°CRate constant (k) = 3.81e-5 m3/mol-minRate of reaction = k * c_benzonitrile * c_tert-butanolRotor Speed = 6000 RPM
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Current Research
A Case Study to Model the STT®
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Input 1
Ci0
T0, P0
ri row
WS
(Shaft Work)
Outputs
CiL
TL, PL
Q
(Heat Transfer)
Dr = ro – ri
Channel Gap
STTR
Rotor Stator
L
Input 2
Ci0
T0, P0
A + B → C
Parameter Value Units
L 136.5 mm
ro 8.29 mm
ri 7.65 mm
Dr 0.64 mm
V 1.3 mL
w 6000 rpm
t 1.7 min
T 333.15 K
27
Current Research
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Estimating “k”
As a first approximation, estimate the reaction rate constant
(k) assuming an ideal Plug Flow Reactor.
kobs ≈ kint * kMT
kMT → 1 as JA → ∞
BAobsA CCk
dτ
dF
v
Vτ
T t QTOT F1,0 F3,0 C1,0 C3,0 F(X,C1,0,C3,0) k
Run Number (oC) (min) (m3/min) mol 1/min mol 3/min X (mol/m3) (mol/m3) (m3/mol) (m
3.mol
-1.min
-1) Avg.
1 60 2 6.00E-07 2.00E-03 2.00E-03 0.95 3.34E+03 3.34E+03 7.88E-06
2 60 2 6.00E-07 1.60E-03 2.88E-03 0.5 2.66E+03 4.80E+03 1.73E-04 8.63E-05
3 60 2 6.00E-07 1.52E-03 3.04E-03 0.75 2.54E+03 5.07E+03 6.08E-05 3.04E-05
4 60 2 6.00E-07 1.13E-03 3.38E-03 0.89 1.88E+03 5.63E+03 2.11E-05 1.05E-05 3.8E-05
5 60 2 6.00E-07 1.37E-03 2.74E-03 0.86 2.28E+03 4.57E+03 3.43E-05 1.71E-05
6 60 1.5 8.00E-07 1.50E-03 4.51E-03 0.9 1.88E+03 5.63E+03 1.90E-05 1.27E-05
7 60 0.5 2.40E-06 4.51E-03 1.35E-02 0.76 1.88E+03 5.63E+03 5.09E-05 1.02E-04
Assume 2nd Order (-r1 = kC1C3), 1:1 stoichiometry, and k = [(1/(C3,0-C1,0))*ln(((C3,0-C1,0)/X+C1,0)/C3,0)]/t or F(X,C1,0,C3,0)/t
Note: For C1,0 = C3,0, k = ((1/X)-1)/C1,0/t
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Current Research
Deriving the STT® Transport Equations
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The type of flow will determine the simplification of equations.
10.03νA
QDRe
CS
Hz Laminar Stokes Flow
Cr2
3
i
2
Ta14,130ν
drΩTa * Taylor-Vortex Flow
* The STT has laminar flow, which implies no Taylor vortices.
29
Current Research
Deriving the STT® Transport Equations
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A Generic Approach
• Assume concentric cylinders with independent
rotation.
• The cylinders have a finite length of Lz.
• Stokes flow is valid.
• Infinitely fast reaction; A + B → Products
Ωo
Ωi
Lz
Rout = R
Rin = kR
vz = W
R
Lα z
Reference: S. Cerbelli et al. / Chemical Engineering Science 63 (2008) 4396-4411
Current Research
Deriving the STT® Transport Equations
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• Creeping (Stokes) Flow
• Component Balance for A in Cylindrical Coordinates
Reference: S. Cerbelli et al. / Chemical Engineering Science 63 (2008) 4396-4411
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
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)
33
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.
Current Research
The STT® in COMSOLDr = 640 mm
The STT Flow Path with MeshingThe STTR with Heat Jacket (Blue)
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Current Research
The COMSOL Model
• Laminar Flow with a Moving Wall (Navier-Stokes)
• Moving Wall Boundary Condition
u (ri) = uWall = 2πriω
Dt
DuρuμPρg 2
ρ = fluid densityg = gravity vectorP = pressure vectorD/Dt = substantial derivative∇ = divergence of a vector with respect to a specified coordinate system (Cartesian, cylindrical, spherical).
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Current Research
Velocity field (m/s)
within the STT®
reactor showing
areas of low (blue)
and high (maroon)
fluid velocity.
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Current Research
The COMSOL Model
Add Chemical Species Transport with Reaction– Transport of Dilute Species
Obtained from the CFD module
37
Current Research
38
Ritter Reaction Simulation Results
Benzonitrile (mol/m3)
Tert-butanol (mol/m3)
N-tert-butylbenzamide (mol/m3)
Species Inlet flow
rate (mm3/s)
Inlet conc.
(mol/m3)
Outlet conc.
(mol/m3)
Outlet flow
rate (mm3/s)
Outlet conc-model
(mol/m3)
Benzonitrile 3.119 9704.97 167.03
8.433
1716.85
Tert-butanol 2.869 10535.62 167.02 1580.21
Sulphuric acid 2.257 13807.50 4675.98 4559.84
Water 0.809 14667.58 4969.19 4839.80
N-tert-butylbenzamide 0.000 0.00 3173.65 1713.88
38
Current Research
The COMSOL Model
Add Heat Transport
39
Current Research
Simulated STT® Heat Profile
Temperature distribution around inlet ports
Temperature distribution in reactor
40
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 kSTT with kbatch and kCSTR
41
Current Research
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
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
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
Comparison of the STT® to the Lurgi Process for
Methyl Ester production
Noureddini & Zhu
k1 =2.07E-03 k3 =1.41E-02 k5 = 6.29E-03
Consider Triglyceride <=====> Diglyceride <=====> Monoglyceride<=====> Glycerin
k2 =0.003643 k4 =5.63E-02 k6 = 2.26E-04
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.
45
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
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
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Biodiesel plant process skids after placement.
Reactor Skids
Glycerol
Methanol
Stripping
Biodiesel Methanol Stripping
Methanol Cleanup
Application
Operating savings • Up to 3% better yield and feedstock
flexibility
• Less equipment and real-time control
• Avoids water recovery costs
49
Up to 3% better yield and lower capital cost.
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
Application
50
New Application Development
Application
• Perchlorate
• Dioxane
• MTBE
• Trihalomethane
• Chlorinated Solvents (PCE, TCE, etc.)
• Other Aromatics & Ethers
Lower cost water remediation of:
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®
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.
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1. Start a simulation with ChemCad2. Before Reactor dump feed streams and properties into Excel3. Comsol picks up feed streams and properties from Excel and calculates STT output4. Comsol dumps output into Excel5. ChemCad picks up stream data from Excel and moves on to the next unit operation
Future Work
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?
- STT® Technology Overview
- STT® Pharma Chemistry Overview
- STT® Reactor Application Areas
- EPA Testing
Separate data sheets are available:
STT, Innovator, Magellan, Cryon and Spinning Tube in
Tube are registered trademarks and trademarks of
Blue Northern Energy, LLC., all rights reserved.
Faster, Cleaner and Greener
Tribologiks
56
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 78712
(Received 20th December 1984 and in revised form 8th 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) 4396-4411
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The End
Thank You
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