new directions for the hybsi® membrane concept …...new directions for the hybsi® membrane...

New directions for the HybSi® membrane concept and process

options for the fabrication of acetal

J.F. Vente

Presented at the Workshop Inorganic Membrane Technology - Advanced Production & Design, Montpellier (France), 27-28 March 2012

ECN-L--12-010 April 2012

www.ecn.nl

New directions for the HybSi® membrane concept

and process options for the fabrication of acetal

Jaap Vente et al.

2 13-4-2012 Membrane solutions for energy efficient separations

- Commercially ready and available product

- Process design

- Tailoring properties towards new applications

Take home messages

The agenda

3 13-4-2012

The concept and

preparation

Membrane solutions for energy efficient separations

4 13-4-2012

The HybSi® toolbox

Overview of precursors: Loy: Chem.Rev. 2005, 1431

Tailored network


5 13-4-2012

Preparation of a membrane

Sol – gel technology

Essential issue:

“Particle size” distribution


Sol

Coating

speed

Meniscus

Coating step

Hybrid layer

6 13-4-2012

Towards proving

the technology


7 13-4-2012

Performance in pervaporation

• 150°C

• 3% H2O in BuOH

• Measurement stopped

after 1000 days


8

7

6

5

4

3

2

Wa

ter

flu

x (

kg

/m2h)

10008006004002000

Time on stream (d)

100

98

96

94

92

90

88

Wa

terc

on

ce

ntra

te in

the

pe

rme

ate

(%)

Flux Concentration

Van Veen J. Mem. Sci. 2011, 380, 124-31

8 13-4-2012

Acid stability • 70°C

• 5% H2O in EtOH

• Water content in permeate:

>85%


2.2

2.0

1.8

1.6

1.4

1.2

1.0

Wa

ter

flu

x (

kg

/m2h)

50403020100

Time on stream (d)

0.1 mol% HAc 1 mol% HAc 10 mol% HAc

Kreiter, ChemSusChem, 2009, 2, 158

9 13-4-2012

Gas separation

H2 / N2 selectivity ~20 – 30

Later externally confirmed

Improvements possible adding

metal oxides


2.5

2.0

1.5

1.0

0.5

0.0

10

-7 P

erm

ea

nce

(m

ol/m

2.P

a.s

)

87654321Paverage (bar)

T = 200 °C

H2

N2

CH4

He

CO2

Kreiter, ICIM, Tokyo, 2008 Tsuru, J. Am. Chem. Soc, 2009, 131, 414

Bouwmeester, ChemSusChem, 2010, 3, 1375

10

Scope HybSi® directions

Market opportunities

• Existing & proven concept

- Licenses to manufacturers

- Formation of value chains with end users, OEM, & licensees

- Technology transfer

• Facilitated by application driven research

- System approach

- Process design

- Prediction tools Aspen+

- Creating references

- Industrial tests

- Detailing application window

- Anti-fouling strategies and CIP’s


11 13-4-2012

Process engineering

& design


1,1 diethoxy butane

ethanol

butanal water

+

+

↔ H2O

12 13-4-2012

Acetal production with HybSi® membranes


Bio-additive to diesel completely miscible

low NOx, low particles

Alcohol + aldehyde ↔ acetal + water

Separation issues because of five azeotropes

Agirre

, J C

he

m T

ech

no

l B

iote

ch

no

l, 2

012, 1

0.1

00

2/jctb

.37

04

//upload.wikimedia.org/wikipedia/commons/2/2f/Butanal-skeletal.png

//upload.wikimedia.org/wikipedia/commons/8/82/Ethanol-2D-skeletal.svg

13 13-4-2012

Options


1. Base case

Reactor + Distillation

2. Reactive distillation

+ Distillation

3. Repetitive Reactor

+ Pervap

5. Reactor + Pervap +

recycle

6. Reactor + Pervap +

Distillation + recycle 4. Membrane Reactor Agirre

, J C

he

m T

ech

no

l B

iote

ch

no

l, 2

012, 1

0.1

00

2/jctb

.37

04

14 13-4-2012

Conclusion acetal


Most profitable case:

reactor membrane unit distillation

Avoid azeotropic separation

Small unit sizes, optimization for each step

High conversion: only the reactant are recycled

Low energy consumption

High investment

Costs of reactants is much higher than the production costs (~70€ct/L)

Agirre

, J C

he

m T

ech

no

l B

iote

ch

no

l, 2

012, 1

0.1

00

2/jctb

.37

04

15 13-4-2012

Varying bridging and

terminating groups


Tailored network

16 13-4-2012

The influence of bridging groups

Castricum, Adv. Func Mater, 2011, 21, 2319


M

E

O

P

BP

17 13-4-2012




CO2

Negative Eapp

strong interactions

18 13-4-2012




Octane bridge

High Eapp, high chain mobility

19 13-4-2012

Alkyl terminating groups (I)


Paradis, submitted to Chem. Mater.

Increasing hydrophobic

CH3 C3H7 C6H13 C10H21

3

None

20 13-4-2012

Alkyl terminating groups (II)


Paradis submitted to J. Mem. Sci.

21 13-4-2012

Amino functionalised terminating groups


Paradis, J. Mater. Chem, 2012, 10.139/c2jm15417j

H2 permeability

22 13-4-2012

Amino functionalised terminating groups


Paradis, J. Mater. Chem, 2012, 10.139/c2jm15417j

100% PA


Acknowledgements

• Industrial collaborators

- Pervatech

- CTI

- Sabic IP

- Huntsman

- Air Products

- DSM

- Sulzer Chemtech

- Trion partners

• Financial support

- STW

- AgentschapNL

- DSTI – ISPT

• Knowledge network

• Universities of Twente,

Amsterdam, Bilbao,

Eindhoven

• TNO

Membrane Technology Group

www.ecn.nl/memtech

http://www.ecn.nl/memtech

24

Public available information

Website: www.HybSi.com

Follow us on Twitter: @HybSi_membranes

Sign up: HybSi news letter

Scientific Papers

J. Mater. Chem., 2012, 10.1039/c2jm15417j

J Chem Technol Biotechnol., 2012, 10.1002/jctb.3704

AIChE J. 2012., 10.1002/aic.12692

J. Mem. Sci., 2011, 380, 124-31

Advan. Func. Mater., 2011, 21, 2319

J .Mem. Sci., 2011, 371, 179

J. Sol-Gel Sci Techn., 2011, 57, 245-52

ChemSusChem., 2009, 2, 158-60

J. Mem. Sci., 2008, 319, 126-32

J. Sol-Gel Sci Techn., 2008, 48, 203-11

J. Mater. Chem., 2008, 18, 2150

Chem. Commun., 2008, 1103

For more information

please contact me:

[email protected]

+31 – 224 56 4916


new directions for the hybsi® membrane concept …...new directions for the hybsi® membrane...

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