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
Membrane solutions for energy efficient separations
5 13-4-2012
Preparation of a membrane
Sol – gel technology
Essential issue:
“Particle size” distribution
Membrane solutions for energy efficient separations
Sol
Coating
speed
Meniscus
Coating step
Hybrid layer
6 13-4-2012
Towards proving
the technology
Membrane solutions for energy efficient separations
7 13-4-2012
Performance in pervaporation
• 150°C
• 3% H2O in BuOH
• Measurement stopped
after 1000 days
Membrane solutions for energy efficient separations
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%
Membrane solutions for energy efficient separations
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
Membrane solutions for energy efficient separations
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
Membrane solutions for energy efficient separations
11 13-4-2012
Process engineering
& design
Membrane solutions for energy efficient separations
1,1 diethoxy butane
ethanol
butanal water
+
+
↔ H2O
12 13-4-2012
Acetal production with HybSi® membranes
Membrane solutions for energy efficient separations
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
13 13-4-2012
Options
Membrane solutions for energy efficient separations
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
Membrane solutions for energy efficient separations
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
Membrane solutions for energy efficient separations
Tailored network
16 13-4-2012
The influence of bridging groups
Castricum, Adv. Func Mater, 2011, 21, 2319
Membrane solutions for energy efficient separations
M
E
O
P
BP
17 13-4-2012
The influence of bridging groups
Castricum, Adv. Func Mater, 2011, 21, 2319
Membrane solutions for energy efficient separations
CO2
Negative Eapp
strong interactions
18 13-4-2012
The influence of bridging groups
Castricum, Adv. Func Mater, 2011, 21, 2319
Membrane solutions for energy efficient separations
Octane bridge
High Eapp, high chain mobility
19 13-4-2012
Alkyl terminating groups (I)
Membrane solutions for energy efficient separations
Paradis, submitted to Chem. Mater.
Increasing hydrophobic
CH3 C3H7 C6H13 C10H21
3
None
20 13-4-2012
Alkyl terminating groups (II)
Membrane solutions for energy efficient separations
Paradis submitted to J. Mem. Sci.
21 13-4-2012
Amino functionalised terminating groups
Membrane solutions for energy efficient separations
Paradis, J. Mater. Chem, 2012, 10.139/c2jm15417j
H2 permeability
22 13-4-2012
Amino functionalised terminating groups
Membrane solutions for energy efficient separations
Paradis, J. Mater. Chem, 2012, 10.139/c2jm15417j
100% PA
Membrane solutions for energy efficient separations
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
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:
+31 – 224 56 4916
Membrane solutions for energy efficient separations