MEMBRANE ENHANCED CHEMICAL AND BIOCHEMICAL PROCESSES€¦ · MEMBRANE ENHANCED CHEMICAL AND...

ROYAL SOCIETY OF CHEMISTRY SYMPOSIUM 2019RE SOURCING OUR RESOURCESREDUCING ENVIRONMENTAL IMPACT

MEMBRANE ENHANCED CHEMICAL AND BIOCHEMICAL PROCESSES

Flemish Institute of Technological Research

The effect of nanomodification of membrane surface on process efficiencies

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Since 2015 : 1284 publications and 1244 patents

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Patents Publications

SUSTAINABLE CHEMISTRY

PROCESS INTENSIFICATION

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Web of science 2019/05/15; Google scholar 2019/05/15Nature 532 (7600), 435-438

Oak Ridge National Laboratory. Materials for Separation Technologies: Energy and Emission Reduction Opportunities (2005).



MEMBRANE TECHNOLOGY

4

Membrane technology is today an additional tool for process chemist, offering alternative and more efficient solutions to existing challenges.

Integrated membrane reactor


CHEMICAL PROCESSES REQUIRING HIGH DILUTION

5

Proof of Concept: Peptide Cyclisation

Benifits

Yield: 71% 95%Conversion: 84% 100%

Product purity

Solvent use: -85%

PMI : 1700 300

Production price




CHEMICAL PROCESSES REQUIRING HIGH DILUTION

reaction/ separation vessel

mixer tank

membrane

V-1

V-2

solution 1

N2

gasP-1

P-2

open chain

peptide (1) in AcOH

reaction reagent in solvent

reaction reagent in solvent

separation vessel

mixer/reaction tank

solution 2

membrane

V-1

V-2

solution 1

N2

gasP-1

P-2

open chain

peptide (1) in AcOH

Head to tail cyclisation

PMI : 45%

Metathesis cyclisation

PMI : 75%



RE USE AND RECYCLE OF VALUABLE HOMOGENEOUS CATALYSTS

COOEtEtOOCCOOEtEtOOC

0.01 mol % catalyst

C13

H20

O4

240.29

C11

H16

O4

212.24

DEDAM

Acetone+

Solvent: DCM, Toluene, Acetone

Cl

ClRu

P

O

C28H45Cl2OPRu

600.6HG-I

Cl

ClRu

P

C19H35Cl2PRu

466.43

Cl

ClRu

NN

O

C31H38Cl2N2ORu

626.63

Cl

ClRu

NN

C22H28Cl2N2Ru

492.45

C54

H69

Cl2N

2PRu

949.09M2

Cl

ClRu

NN

PCy Cy

Cy

Cl

ClRu

NN

C22H28Cl2N2Ru

492.45

Cl

ORu

NN

N

N+

O-

O

C50H47ClN4O3Ru

888.46M41

Cl

ORu

NN

N

N+

O-O

C36H39ClN4O3Ru

712.25

Cl

ClRu

NN

O

O

C32H38Cl2N2O2Ru

654.63

Cl

ClRu

NN

C22H28Cl2N2Ru

492.45

Reaction :

Ru Catalyst : Pre-catalyst :

Peformance on Funmem membrane + benchmark :

Membrane Permeability Catalyst retention Product retention

Funmem®0,9 nm TiO2

Polymeric OSN

6 lm-2h-1bar-1

0.3 lm-2h-1bar-1

0.8 lm-2h-1bar-1

87 %96 %91 %

35 %60 %97 %



RE USE AND RECYCLE OF VALUABLE HOMOGENEOUS CATALYSTS

Off-line processing

V-1

Feed tank (B)

Diafiltration

tank (A)

Membrane unit

N2

gas

P1

P2

V-1

Feed tank (B)

Diafiltration

tank (A)

Membrane unit

N2

gas

P1

P2

V-2

coupling partners & base in solvent

Catalyst in solvent

At-line processing On-line processing

With all processing methods rejection of Pd species > 99 %

Reaction Pd content (ppm) Membrane Pd in product (ppm)

1 nm C8 – TiO2 67

8700 0.9 nm TiO2 7

0.9 nm C8H4F13 – TiO2 6

0.9 nm C8H4F13 – TiO2* 3

*PEPPSI catalyst , other CX-3116/01/2018

©VITO – Not for distribution

INCREASING CATALYST TON

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Catalyst performance in (semi)continuous reaction

Tail in catalyst designed for rejection and impedes cluster formation



INCREASING CATALYST TON

10

Literature example

Yield (%) 93

Substrate –catalyst ratio 50

Pre-catalyst load (ppm) 20000

Catalyst retention (24°C) /

Av. Process permeance (Lm-2h-

1bar-1)/

Isolated product metal

contamination (ppm)/

Mass intensity (reaction) /

Mass intensity (reaction &

product isolation500

solvent 1,4-dioxane

Organometallics Not recovered

Membrane assisted

(commercial catalysts)

Yield (%) 92



Catalyst retention (24°C) 50


1bar-1)6


contamination (ppm)/

Mass intensity (reaction) /



solvent Ethanol

Organometallics(Partially)

recovered

Membrane assisted

(tailed catalysts)

Yield (%) 88



Catalyst retention (24°C) 96


1bar-1)1


contamination (ppm)16

Mass intensity (reaction) 51



solvent Ethanol

Organometallics Recovered




CONTINUOUS FERMENTATION PROCESSES

Challenges in traditional

fermentation

Product toxicity:

▪ Low product concentrations

▪ Low productivity

→ High purification costs

→ High waste water volumes

→ Energy-intensive separation

→ Cost of substrate

Integration with

pervaporation

Integration of

▪ Organophilic pervaporation and

▪ two-stage clostridial fermentation

▪ using a membrane-based in situ product

recovery technique (ISPR)

→ Continuous, selective product withdrawal

from reaction medium

Benefits

2,5 x production increase

by removal of product

inhibition

Fermentor cost ↓

Water footprint -50%

Steam consumption -50%

Applicable to batch &

continuous processes

Production price -10%


http://www.google.be/url?sa=i&rct=j&q=&esrc=s&source=images&cd=&cad=rja&uact=8&ved=0CAcQjRw&url=http://biocrude.org/&ei=ZC0IVancJsfa7Aab84CYAQ&bvm=bv.88198703,d.ZGU&psig=AFQjCNG2K3RzNZ8RFTZQiGWFP8hW4376PQ&ust=1426685650031340

BIOCHEMISTRY

ENZYMATIC SYNTHESIS OF CHIRAL AMINES

Chiral amines in enantiopure forms are important chemical building blocks in pharmaceutical and agrochemical industries

Benzyl acetone isopropyl amine (S-)1-methyl-3-phenylpropylamine Acetone

(BA) (IPA) (S)-MPPA

+ +

Background• Chemical synthesis of chiral amines still remains a challenge because it

requires high chemo-, regio-, diastereo-, and enantio-control• ω-transaminase is a promising catalyst which produces chiral amines

with exquisite enantioselectivity

Limits in aqueous phase: • Low substrate solubility (BA): only 1,48 g/L (or 10 mM)• Severe product inhibition by (S)-MPPA

Targets: • To establish the enzymatic reaction in solvent phase (n-heptane in

preliminary tests) to increase substrate concentration• In-situ product recovery by MPPA extraction into an aqueous phase

by use of a membrane contactor using an aqueous phase as extractant

ResultsHigher substrate conversion

Co-extraction of substrate amine (IPA) solved with NF

Next stepsIncrease the specific productivity

NF optimization

Strategies to retain the donor amine selectively in the

reactor


SUSTAINABLECHEMISTRY

PRODUCT & RAW MATERIALS RECOVERY

▪ Product / raw materials in waste stream

▪ Inhibiting biological waste water plant

▪ End-of-pipe treatment required

▪ In-process membrane technology

product

process water

raw material

process UF RO

Lab test Pilot

batchPilot long

durationPilot

continuous

on-site

Technology

advice

TEA

feasibility

insight

1. 2. 4. 5.3. 6.

Implementation

@ 20.000m³/year

UF RO

▪ CAPEX : 453 kEUR

▪ OPEX: 46 kEUR/year

▪ Return: 437 kEUR/year

Assessment

IMPACT

Recovery/year

▪ 33.3 ton product (3 EUR/kg)

▪ 105 ton raw material

Production process water/year

▪ 14.450 m³ (1.5 EUR/m³)

No waste treatment cost

Pay back time ~1 year


SUSTAINABLECHEMISTRY

PRODUCT & RAW MATERIALS RECOVERY

Challenge

Rinsing water

▪ Contains high concentration of detergent

▪ External treatment → high incineration cost

IMPACT

▪ Reuse detergent stream

▪ Reuse waste water

▪ No waste incineration cost

Testing

Assessment

Industrial

implementation

Screening tubular membranes

UF

NF

PCI pilot

tests

Collaboration

with

▪ Test assistance

▪ Pilot PCI available

RO

SUCCESS

Lab testing

Tim

e-la

pse

2 y

ears



WW TREATMENT

Fouling solution : real foam - produced water (NL)

~700 ppm oil

18h filtration in cross-flow, recovery 50% + use 100ppm de-oiler

Foulants : oil droplets in O/W emulsions

Oil content in the permeateMGR 100 ppm de-oiler 21 ppmMGR no de-oiler 66 ppmNative no de-oiler 250 ppmFlemish Institute of

Technological Research

WE PROVIDE SOLUTIONSWORLDWIDE

227 SCIENTIFIC PUBLICATIONS34 NATIONALITIES

MORE THAN 400 PATENTS

24 NEW PATENTS EVERY YEAR

> €170 MILLIONTURNOVER

784 EMPLOYEES

76 FLEMISH SME’S

91 PHD’S ANDPOSTDOCS

ExpertsProjectsExperts and Projects

SUSTAINABLE ENTREPRENEURIAL INSPIRING CREATIVEFlemish Institute of Technological Research

17/05/2019

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Kreuzlingen, Switzerland

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MEMBRANE ENHANCED CHEMICAL AND BIOCHEMICAL PROCESSES€¦ · MEMBRANE ENHANCED CHEMICAL AND...

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