process intensification for chemical manufacturing using ... · vapourtec-tubular reactor systems...

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


ChemTrix

Plate type Reactor

CSIRO Tubular Flow Reactor

up to 2 L reactor volume

�� up to >2500 L/day


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


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


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


... 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


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


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



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


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

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