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Process Intensification for Chemical Manufacturing using Continuous Flow Processing
CSIRO MANUFACTURING
Christian Hornung | Senior Research Scientist – Director, Centre for Industrial Flow Chemistry
31 May 2017
RSC Symposium: Continuous Flow Chemistry for Industrial Processes 2017Chemspec Europe - Munich
Vapourtec - Tubular Reactor Systems
Continuous Flow Processing at CSIRO – Lab Discovery
CSIRO. Flow Chemistry Technology
Chip & Tubular Reactor ModulesCapabilities:• Hom. Liquid Phase• Liquid-Liquid• Gas-Liquid• Het. Catalysis• (Slurry Reactions)
Zaiput L-L Separators
Partners / Suppliers:
Uniqsis –
Flow Reactors
Continuous Flow Processing at CSIRO – Scale-up
CRD Shell & Tube Reactors
CSIRO. Flow Chemistry Technology
ChemTrix
Plate type Reactor
CSIRO Tubular Flow Reactor
up to 2 L reactor volume
���� up to >2500 L/day
CSIRO. Flow Chemistry Technology
FloWorks – CSIRO’s Centre for Industrial Flow Chemistry
Project areas:
The Centre for Industrial Flow Chemistry, based in Clayton, is a technology platform providing access to CSIRO’s
flow chemistry technology to chemical manufacturers. � from lab discovery to scale-up and production
Pharmaceuticals
Cosmetics
Polymers
Fine Chemicals Biofuels & Renewables
Construction Materials
Food Additives
Agrochemicals
Nano-materials
Catalysts
Reactor Design
Speciality Chemicals
Health Care & Medical
CHEMICAL
DISCOVERY
REACTION
OPTIMISATION
PROCESS
SCALE-UP
Services:
• process R&D operations for industrial clients
• managing the technology transfer to client site
• in-house training for industrial collaborators
• innovative research on new process technology for
chemical manufacture
launched on 22nd November 2016
CSIRO. Flow Chemistry Technology
FloWorks – New Facility at Clayton, VIC
Partners:
• Academia (Monash, Deakin, …)
• Equipment Manufacturers (Cambridge
Reactor Design, Chemitrix, …)
• Chemical Manufacturers
(Boron Molecular, …)
• VCSCM, Chemistry Australia, …
� operation of laboratory scale and
industrial scale flow chemistry equipment
� accommodating current operations and
development of new flow chemistry solutions
Recent commercial projects include...
• Emulsion polymerisation
slow reaction, low temperature, high viscosity, intensified mixing required
• Synthesis of polymers with very narrow polydispersity
fast reaction, SM difficult to handle, very precise process control needed
• Synthesis of novel monomers
exothermic reaction, moisture sensitive compounds
T. M. Kohl, C. H. Hornung, J. Tsanaktsidis. Molecules 2015, 20, 17860–71.
Space Time Yield [g L-1h-1]Reaction Time
batch batchflow flowProcess Improvements:
• Synthesis of RAFT precursor 8 h 10 min 0.69 768
• Synthesis of dye intermediate n/a 30 min 7.6 235
• Synthesis of API precursor 7 d 10 min 0.44 1336
��� ������
�� · ��
Space Time Yield
M. Brasholz, K. von Kaenel, C. H. Hornung, S. Saubern, J. Tsanaktsidis, Green Chemistry, 2011, 13, 1114-1117.
Carbohydrates as Renewable Feedstock
Bulk Chemicals & BiofuelBiomass
OHO
OHHO
OH
HO
Continuous Flow Dehydration of Sugar
M. Brasholz, K. von Kaenel, C. H. Hornung, S. Saubern, J. Tsanaktsidis, Green Chemistry, 2011, 13, 1114-1117.
CMF
By-Product: HUMIN• aqueous + organic � biphasic flow
• very short residence times: ~1 min
• moderate temperatures: ~100 °C
• inline filtration to remove by-product
• simple and efficient purification byliquid-liquid extraction
Lab-Scale: 10 ml tubular reactor
Vapourtec R2/R4 reactor system
CMF from High Fructose Corn Syrup (HFCS) using Flow
T. Kohl et al. submitted to Reaction Chemistry & Engineering 2017.
CMF as a renewable platform chemical
M. Brasholz, K. von Kaenel, C. H. Hornung, S. Saubern, J. Tsanaktsidis, Green Chemistry, 2011, 13, 1114-1117.
... towards a chemical industry using renewable resources
Bio-refinery Concept for CMF
using lignocellulosic or sugar-based
feedstocks from:
• Agricultural waste
• Food waste
• Refined renewable feed stocks
(sucrose, HFCS)
Scale-up of the RAFT Process
N. Micic, A. Young, J. Rosselgong, C.H. Hornung, Processes, 2014, 2, 58-70.
Synthesis of Block Copolymers in Flow
Reactor system:
Vapourtec - R2/R4
SS - 10 ml coils
Benefits of RAFT polymerisation:
• ‘Tailored’ molecular weight(Mn ~ moles RAFT agent)
• Narrow mol. weight distribution
• Access to complex architectures:blocks, grafts, stars,...
• Conjugation to reactive molecules (drugs, biomolecules, etc.)
Tubular Flow Reactor
with static mixers(reactor volume 108 ml)
RAFT: Reversible Addition-Fragmentation Chain Transfer
Scale-up of the RAFT Process
Problems with
scale-up in batch:
- temperature
gradients
- concentration
gradients
- dead zones
- inefficient mixing
small ‘ideal’
system
Laboratory
large ‘non-ideal’
system
Industry20
30
40
50
60
70
80
90
100
-60 -40 -20 0 20 40 60 80 100
T [
°C]
t [min]
pAAc-2 | 5 ml - MW
pAAc-3 | 20 ml - MW
pAAc-4 | 100 ml - RBF
pAAc-5 | 500 ml - RBF
pAAc-6 | 500 ml - flow
Temperature Profiles:
N. Micic, A. Young, J. Rosselgong, C.H. Hornung, Processes, 2014, 2, 58-70.
Surfactants from Renewable Feedstock
C. H. Hornung, M. Á. Álvarez-Diéguez, T. M. Kohl, J. Tsanaktsidis, Beilstein J Org Chem, 2017, 13, 120–26.
Surfactant for use in household products,
e.g. as stain remover for expensive
garments (wedding dresses and others)
Hydrogenation – Industrial Processes and a New Approach
Heterogeneous catalysis - current state of the art:
slurry – stirred tank fixed or fluidised bed
Our approach:
• continuous flow process
• tubular reactor system with inserts
� favorable flow / processing conditions
• heterogeneous catalyst supported on
tubular inserts using metal deposition methods
• 3D metal printing for manufacture of inserts
• optimize fluid flow and heat and mass
transfer by custom designed static mixer
inserts and evaluate by CFD & EFD
Pd/C
heterogeneous catalyst
CSM – Catalytic Static Mixer
TW8980/AU/PROV 23/12/2015 & TW9197/AU/PROV 03/10/2016 Patents Pending
Impact – Industrial Applications of Hydrogenations
Pharmaceuticals
Fine
Chemicals
R&D
Polymers
Food Processing
Petrochemicals
TW8980/AU/PROV 23/12/2015 & TW9197/AU/PROV 03/10/2016 Patents Pending
Hydrogenation Reactor – Project Plan & Resources
Additive Manufacturing Metal Deposition
Flow ChemistryFluid Dynamics
Organic Chemistry &Reactor Engineering
Electrodeposition & Cold Spraying
3D Metal Printing
CFD &ExperimentalFluid Dynamics
TW8980/AU/PROV 23/12/2015 & TW9197/AU/PROV 03/10/2016 Patents Pending
Catalytic Static Mixers (CSMs)
Different designs:� maximize heat and mass transport for different reaction systems
Catalysts:Ni, Pt, Pd, Cu, Au, Ag, …
Substrate Materials:Ti-alloy, CoCr-alloy, Al-alloy, 316 SS, …
3D Metal Printing
Electroplating Cold Spray
TW8980/AU/PROV 23/12/2015 & TW9197/AU/PROV 03/10/2016 Patents Pending
TW8980/AU/PROV 23/12/2015 & TW9197/AU/PROV 03/10/2016 Patents Pending
Nickel – Cold Spray
Nickel - Electroplating
Platinum – Electroplating
Copper – Electroplating
Palladium - Electroplating
H2 line
liquid
line
liquid pumpheater controller
reactor
Hydrogenation Reactor – Experimental Rig, Part 1
condenser
Prototype Flow Chemistry Reactor:
Mk 1: 4 catalyst zones, each 15 cm
(designed & built by CRD and CSIRO)
TW8980/AU/PROV 23/12/2015 & TW9197/AU/PROV 03/10/2016 Patents PendingA. Avril et al. Reaction Chemistry & Engineering 2017, 2: 180–88. doi:10.1039/C6RE00188B.
A. Avril et al. Reaction Chemistry & Engineering 2017, 2: 180–88. doi:10.1039/C6RE00188B.
Proof of Concept – Hydrogenation using gaseous H2
25.1
1.1
19.7
44.0
55.3
26.8
0
5
10
15
20
25
30
35
40
45
50
55
60
0 1 2 3 4 5 6 7 8 9 10 11
con
ve
rsio
n [
%]
G/L
0 0.8
9.4
16.1
26.120.5
0
8.3
61.2
100
0
10
20
30
40
50
60
70
80
90
100
X-X
-Ti-D
1
Ni-E
P-C
oC
r-D1
Ni-E
P-T
i-D1
Ni-C
S-T
i-D1
Ni-C
S-S
S-D
3
Pt-E
P-T
i-D2
X-X
-Ti-D
1
Ni-E
P-C
oC
r-D1
Ni-C
S-S
S-D
3
Pt-E
P-T
i-D2
con
ve
rsio
n [
%]
oleic acid vinyl acetate
Catalyst Comparison:
78.7
91.6
57.9
66.8
83.2
92.1
24.8
64.2
36.8
58.4
12.5
50.1
73.6
8.311.5
14.8
0
10
20
30
40
50
60
70
80
90
100
9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25
con
ve
rsio
n [
%]
p [bar]
Pt-EP-Ti-D2
Ni-CS-SS-D3
Ni-EP-CoCr-D1
We successfully tested this prototype reactor for the hydrogenation of alkenes, alkynes, carbonyls, nitro-and diazo-compounds, nitriles, imines, and halides, as well as bifunctional molecules such as the following:
• Continuous Flow Processing bridges the gap from laboratory / discovery scale to preparation / production scale, mg to kg, with minimum scale-up efforts.
• Integrated Processing allows for combination of several processing steps to form one continuous production line, e.g. purification, block co-polymers, …
• Efficient Processing is achieved by using micro- and mm scale flow geometries � large surface to volume ratio, enhanced heat and mass transfer, higher STY
Conclusions
CSIRO. Flow Chemistry Technology
Thank youCSIRO Manufacturing – FloWorks Centre for Industrial Flow Chemistry
Christian HornungSenior Research Scientist – Director, FloWorks Centre for Industrial Flow Chemistry
t +61 3 9545 2532e [email protected] www.csiro.au
CSIRO MANUFACTURING
Acknowledgements
John Tsanaktsidis
Thomas Kohl
Ivan Martinez
Boris Bizet
Antoine Avril
Nenad Micic
Alan Young
Charlotte Genet
m Bag 10, Clayton SouthVictoria 3169Australia
Simon Saubern
Oliver Hutt
James Gardiner
Dayalan Gunasegaram
Darren Fraser
Andrew Urban
Mike Horne
Jean-Pierre Veder
Almar Postma
Karin von Känel
Julien Rosselgong
John Chiefari
Kathy Turner
Ezio Rizzardo
San Thang
Graeme Moad
Xuan Nguyen
Stella Kyi
Maria Espiritu
Stuart Littler
Matthew Waterford
Trevor Hadley
Marta Rubio
Michael Batten