Multi-scale Modeling and design of
chemical Reactions and Reactors
http://www.lct.ugent.be
Guy B. Marin
LaboratoryLaboratoryLaboratoryLaboratory forforforfor
Chemical Chemical Chemical Chemical TechnologyTechnologyTechnologyTechnology
Methusalem, Advisory Board Meeting, August 18, 2009
1
AgendaMethusalem, Advisory Board Meeting, August 18, 2009
9h30 – 9h45 Welcome
9h45 – 10h45 Introduction to the Methusalem program and to the funded M2dcR2 (Guy B. Marin)
10h45 – 11h15 Introduction of the advisory board members
11h15 – 12h15 Subprogram 1: SEMK in complex reaction mixtures (Marie-FrançoiseReyniers)
12h15 – 13h15 Lunch
13h15 – 14h15 Subprogram 2 and 3: Catalyst design based on catalyst descriptors & Adsorption by nanoporous materials (Joris Thybaut)
14h15 – 15h15 Subprogram 5 and 6: Reactor design from first principles & From fossil to renewable feedstocks (Chris Stevens and Geraldine Heynderickx)
15h15 – 15h30 Coffee
15h30 – 16h30 Lab tour
16h30 – 17h30 General discussion
17h30 – 17h45 Next meeting: date and format
17h45 Concluding feedback
19h00 Diner2
Introduction
• Methusalem program: general
• Laboratory for Chemical Technology (LCT)
• Methusalem program: M2dcR2
• M2dcR2: advisory board members
Methusalem, Advisory Board Meeting, August 18, 2009
3
Laboratory for Chemical Technology (LCT)
Guy B. MarinGeraldine Heynderickx
Joris ThybaultMarie-Françoise Reyniers
Methusalem, Advisory Board Meeting, August 18, 2009
4
LCT: multi-scale research activities
from atom (nm) to full process (m)
Methusalem, Advisory Board Meeting, August 18, 2009
5
chemistry
transport
LCT research: process design and optimization
process
reactor model
heat and mass transfer
conservationlaws
microkineticmodel
reactionnetwork
elementaryreactions
kinetics and thermo
quantumchemistry
experiment
dimensions
heat duty
temp. field
conc. field
rates
yields
Methusalem, Advisory Board Meeting, August 18, 2009
6
LCT research: application domains
•PVC•ATRP•RAFT•(in-situ)NMP•conjugatedpolymers (PPV’s)
polymerization
Methusalem, Advisory Board Meeting, August 18, 2009
7
chemical processes
radicalar catalytic
•PVC•LDPE•conjugatedpolymers (PPV’s)•ATRP•RAFT•(in-situ)NMP
polymerization•steam cracking•pyrolysis
•bio-oils•alcohols•DMDS•P-amides•P-esters•Si(OEt)4
gas phase•total oxidation•partial oxidation•epoxidation•Fischer-Tropsch•hydroformylation•hydrogenation•hydrotreating
M/Mox/MSulf•hydrocracking•catalytic cracking•MTO•oligomerization•alkane isomerization•CH4 aromatization
acid
LCT: people
•Part-time professors: 2
•Visiting scientists: 1
•Post-docs: 8
•PhD students: 29
•Technical staff: 9
•Administrative staff: 2
Methusalem, Advisory Board Meeting, August 18, 2009
8
LCT: funding
Funding source PhD Postdoc
1 Methusalem (to date) 3 -
2 Teaching assistents 5 -
3 FWO/BOF 8 2
4 GOA/IAP 6 2
5 IWT/SBO/EC 5 3
6 Bilateral agreement companies 2 1
Methusalem, Advisory Board Meeting, August 18, 2009
9
LCT: infrastructure
•Pilot plant set-up: 1
•Lab-scale set-ups: 20
•High-throughput kinetics: 1
•TAP: 1
•Computing resources: 3 64-bit HPCCs (>300 processor cores)
•GC×GC (TOF-MS/FID): 1
Methusalem, Advisory Board Meeting, August 18, 2009
10
•Cold flow set-ups: 2
Introduction
• Methusalem program: general
• Laboratory for Chemical Technology (LCT)
• Methusalem program: M2dcR2
• M2dcR2: advisory board members
Methusalem, Advisory Board Meeting, August 18, 2009
11
Methusalem program: general
•Objectiveto provide stable and substantial funding to the leader of a research group with a proven track record of excellencethat can independently and flexibly be used to acquireand/or strengthen a leading position of the group at aninternational level
•Funding
•Duration: 2008 – ….(evaluation after 7 years)
•Personel: Ph D students, postdocs, technicians
•Equipment
•Operating costs
Methusalem, Advisory Board Meeting, August 18, 2009
12
Methusalem program: evaluation criteria
•Quality of work
•Human resources management
•Research plan for next 7 years
Methusalem, Advisory Board Meeting, August 18, 2009
13
• performed work is outstanding at an international level?
• post-doctoral researchers stimulated to set-up independent research?
• research plan and funding applied for are adequate?
Methusalem program: organizational aspects
•Management committee
•Advisory board (internationally recognised authorities)
•Scientific director: leader of the research group
Methusalem, Advisory Board Meeting, August 18, 2009
14
• responsible for expenditures, research policy and dailymanagement of the research group
• president: leader of the research group
• members: at least faculty of the research group
• manages the research
• defines the research policy
• installs an advisory board
• supports in mapping out long term research policy
• supports in defining research priorities
Introduction
• Methusalem program: general
• Laboratory for Chemical Technology (LCT)
• Methusalem program: M2dcR2
• M2dcR2: advisory board members
Methusalem, Advisory Board Meeting, August 18, 2009
15
Methusalem program: M2dcR2
• Funding: people and equipment
• Aim and strategy
• Organizational aspects
• M2dcR2: multiscale modeling and design
•Scientific director: Guy B. Marin
•Management committee
•Advisory board
Methusalem, Advisory Board Meeting, August 18, 2009
16
M2dcR2: management committee (MC)Three faculties of Ghent University are represented in
management committee
�Engineering: Laboratory for Chemical Technology (LCT)
�Bioscience engineering: Synthesis and Bioresources Chemistry (SynBioC)
�Sciences: Centre for Ordered Materials, Organometalics and Ca talysis (COMOC)
�Prof. P. Van der Voort: catalyst synthesis and design
�Prof. C. Stevens: microreactors and renewable feedstocks
�Prof. G. Heynderickx: reactive fluid dynamics
�Prof. J.Thybaut: catalytic reaction kinetics and reactors
�Prof. M.-F. Reyniers: ab initio radical and catalytic chemistry
Methusalem, Advisory Board Meeting, August 18, 2009
17
M2dcR2: advisory board
• Jaap Schouten (TUEindhoven; NL)
• William H. Green (MIT; USA)
• Rodney Fox (Iowa State; USA)
• Philippe Sautet (ENS-Lyon, F)
• Egbert Lox (Umicore; B)
• Bert Weckhuysen (U Utrecht, NL)
Methusalem, Advisory Board Meeting, August 18, 2009
18
• Christopher Barner-Kowollik (U Karslruhe; G)
Aim M2dcR2: world top centre at UGent
establishment of unique platform for
fully integrated and knowledge based
design of products and processes
Methusalem, Advisory Board Meeting, August 18, 2009
19
M2dcR2: strategy
modeling of complex kinetics
combined with
complex transport phenomena
based on:
• first principles
• experimental validation
�Design of sustainable products and processes guided by:
�Renewable feeds
• transportation fuels and energy carriers
• chemicals
• functional materials (catalysts, nanostructured polymers)
Methusalem, Advisory Board Meeting, August 18, 2009
20
chemistry
transportprocess
product
M2dcR2: reaction and reactor modeling and design
M2dcR2
reactor modeling and
design
mixingdiffusion
momentum transport
structured microreactorsrotary bed
reactionmodeling and
design
reactionnetwork
generationreaction rules
kinetics
catalysisadsorption
catalyst descriptors
controlledpolymerization
Methusalem, Advisory Board Meeting, August 18, 2009
21
M2dcR2: subprograms
subprogram MC member
P1Single event microkinetics (SEMK) in complex reaction mixtures
Joris ThybautMarie-Françoise Reyniers
P2Catalyst design based on catalystdescriptors
Joris ThybautMarie-Françoise ReyniersPascal Van der Voort
P3 Adsorption by nanoporous materialsJoris ThybautMarie-Françoise Reyniers
P4Polymer design accounting for diffusion and mixing
Geraldine HeynderickxMarie-Françoise Reyniers
P5 Reactor design from first principlesGeraldine HeynderickxChris Stevens
P6 From fossil to renewable feedstocksChris StevensJoris ThybautMarie-Françoise Reyniers
Methusalem, Advisory Board Meeting, August 18, 2009
22
M2dcR2: application domains
M2dcR2
biomass to liquids
renewablesto
chemicals
environ-mental
functionalmaterials
catalysts polymers
Methusalem, Advisory Board Meeting, August 18, 2009
23
•Period : 2009 – 2016 …
•People : 9 PhD, 1 postdoc, 1 technician
•Equipment: analysis, kinetics, hydrodynamics
•Funding : k€ 850/year (including M€ 2 investment)
M2dcR2: funding (overview)Methusalem, Advisory Board Meeting, August 18, 2009
24
M2dcR2: funding (equipment)Equipment k€
Analysis 3 dedicated on-line GC’s 157
Gel Permeation Chromatography (GPC) 59
Particle Image Velocimeter (PIV) with a Time Resolution (TR) Laser (20 mJ) and high speed Camera
332
Kinetics High-throughput kinetics set-up 341
Temporal Analysis of Products (TAP) 665
ComputingAnnual investment for High Performance ComputingClusters (HPPC)
254
Total 1808
Equipment not considered in proposal
Pulsed laser polymerization
Pyrolyser for on-line analytical pyrolysis GC×GC
Methusalem, Advisory Board Meeting, August 18, 2009
25
M2dcR2: funded PhD’s
PhD research topic advisors
Steven PylLight olefins from fossil and renewable resources (P1; P6)
GBM; MFR
Pravesh Kumar Single event microkinetics of coking during fluid catalytic cracking (P1, from October 2009 on).
GBM; JT
Karen Leus V containing MOF for selective oxidations (P2) PVDV; (GBM)
Carolina TolozaKinetic modeling of reversible addition fragmen-tation chain transfer (RAFT) polymerization (P4)
GBM; MFR
Anne Cukalovic
Use of structured microreactors for, in decreasing order of priority: coupling of amino acids, addition of cyanide to ketones or aldehydes, amino substituted isosorbide derivatives (ionic liquids), derivatization of hydroxymethylfurfural (P5).
CS; (GBM)
Methusalem, Advisory Board Meeting, August 18, 2009
26
M2dcR2: LCT-PhD’s and postdocs involved
subprogram PhD Postdoc
P1 Single-event microkinetics in complex reaction mixtures 6 4
P2 Catalyst design based on catalyst descriptors9
5
P3 Adsorption by nanoporous materials 3 2
P4 Polymer design accounting for diffusion and mixing 5 -
P5 Reactor design from first principles 4 1
P6 From fossil to renewable feedstocks 3 2
Methusalem, Advisory Board Meeting, August 18, 2009
27
M2dcR2: multi-scale modeling and design
• Catalyst design based on catalyst descriptors (P2)
• SEMK in complex reaction mixtures (P1)
• Adsorption by nanoporous materials (P3)
• Polymer design accounting for mixing and diffusion (P4)
• Reactor design from first principles (P5)
• From fossil to renewable feedstocks (P6)
Methusalem, Advisory Board Meeting, August 18, 2009
28
Complex reaction mixturesGC × GC
Methusalem, Advisory Board Meeting, August 18, 2009
29
Computer generation of reaction networks
Molecules
Elementary Reaction Families
Reaction Rules
– Representation
– Mathematical Operations
– Species Uniqueness
– Thermodynamics
– Termination Criteria
k1 k2
k3
k4
k5 k6k7
k8
k9
k10k11
k12
k13
k14 k15
COMPUTER PROGRAM
– Kinetic Parameters
Methusalem, Advisory Board Meeting, August 18, 2009
30
Reactants and products: matrix representationMethusalem, Advisory Board Meeting, August 18, 2009
e.g. n-C19: 1981 alkanes , 25065 alkenes, 20437 carbenium ions
000000001010
00001000009
00010000008
00101000007
01010000006
00000010015
00000101004
00000010103
10000001012
00000100101
10987654321
000000001010
00001000009
00010000008
00101000007
01010000006
00000010015
00000101004
00000010103
10000001012
00000100101
10987654321
000000001010
00001000009
00010000008
00101000007
01010000016
00000010015
00000101004
00000010103
10000001012
00001100101
10987654321
25065 (de)hydrogenations, 42600 (de)protonations, 12470 alkyl shifts, 15970 PCP branching and 6429 β-scissions
31
2
Reaction networks: C/H/O chemistrycellulose lignin
lignin monomers
Methusalem, Advisory Board Meeting, August 18, 2009
32
terpenes/terpenoids
Reactions: accounting for stereochemistry Methusalem, Advisory Board Meeting, August 18, 2009
33
Reactions: kinetic parametersparameter estimation
quantum chemistry
Methusalem, Advisory Board Meeting, August 18, 2009
34
M2dcR2: multi-scale modeling and design
• Catalyst design based on catalyst descriptors (P2)
• SEMK in complex reaction mixtures (P1)
• Adsorption by nanoporous materials (P3)
• Polymer design accounting for mixing and diffusion (P4)
• Reactor design from first principles (P5)
• From fossil to renewable feedstocks (P6)
Methusalem, Advisory Board Meeting, August 18, 2009
35
Model based catalyst design: a clever way to close the loop
Methusalem, Advisory Board Meeting, August 18, 2009
36
catalyst performance
catalystsynthesis
process application
activity/selectivity library empirically basedfeedback performance
analysis
processoptimization
diffusional phenomena
catalytic chemistry rules
knowledge-based feedback
reaction network
ab initio calculations
catalystdescriptors
kinetics basedcatalyst design
Definition of catalyst functions
fluid phasefluid phasefluid phasefluid phase
physisorption
(de)-hydrogenation
(de)-protonation
alkyl shift
PCP-branching
ß-scission
catalystcatalystcatalystcatalyst
metal sitesmetal sitesmetal sitesmetal sites
acid sitesacid sitesacid sitesacid sites
+
****
****
****
****
****
Methusalem, Advisory Board Meeting, August 18, 2009
37
Definition of space at nano scale0.5 nm
ZSM-22
zeolite Y
MOR
Mordenite
Methusalem, Advisory Board Meeting, August 18, 2009
38
active site
MOR
active site
ZSM-22
Distinguishing different types of active sites
micropores pore mouthsite
Bridgesite: near
Bridgesite: far
pore mouths
ZSM-22 crystallite
Methusalem, Advisory Board Meeting, August 18, 2009
39
Catalyst design: contribution analysis on ZSM-22
monobranched dibranched
tribranchedn-alkanes
crackedproducts
pore mouthbridge sites micropores
23 90
49
7
543
47
2
7
8
1
3280
195
Methusalem, Advisory Board Meeting, August 18, 2009
40
Hayasaka et al, Chemistry- A Eur. J., 13, 10070 (2007)
Catalyst design: nanorod assembled ZSM-22Methusalem, Advisory Board Meeting, August 18, 2009
41
Potential application “nanorod” Pt/H-ZSM-22Methusalem, Advisory Board Meeting, August 18, 2009
42
nC10 hydroconversionP = 4.5 bar, W/F = 2522 kg-smol-1, H2/HC = 375
0
20
40
60
80
100
423 473 523 573
Isom
er Y
ield
/ m
ol%
Temperature / K
improve cold flow properties of jet fuel and diesel
Pt-H/ZSM-22 Si/Al = 30
C-IE /2IE
Tayloring nanoporous materials: ALDMethusalem, Advisory Board Meeting, August 18, 2009
43
•functionalization: select precursors (organometals: Al, Ga, Fe)
•pore dimensions: select precursor size (AlMe3, AlEt3, Al(OEt)3)
Postsynthesis modification of nanoporous materials by ALD
Methusalem, Advisory Board Meeting, August 18, 2009
Defining the kinetic state of the catalyst: TAP Inert zone Catalyst zone
state-defining Pulses
time
Insignificant change
0.0
state-defining Experiment
44
Temporal Analysis of Products
M2dcR2: multi-scale modeling and design
• Catalyst design based on catalyst descriptors (P2)
• SEMK in complex reaction mixtures (P1)
• Adsorption by nanoporous materials (P3)
• Polymer design accounting for mixing and diffusion (P4)
• Reactor design from first principles (P5)
• From fossil to renewable feedstocks (P6)
Methusalem, Advisory Board Meeting, August 18, 2009
45
Catalyst properties: influence on stability/reactivityZSM-22
−22
+13
−3116
−18 −25
95
π,i-but,ai-butoxideπ,i-but,b
tBuC+
ZeOH + i-buteneg
t-butoxide
t-BuC + t-butoxide E act ππππ-i-butene,b ππππ-i-butene,a Eact i-butoxide
FAU +12 – 16 30 – 41 – 32 105 – 27
MOR –10 – 11 28 – 29 – 39 121 – 24
ZSM5 –17 – 22 35 – 33 – 35 – 45
TON –22 +13 16** to t-buC + – 31 – 18 95 – 25
Methusalem, Advisory Board Meeting, August 18, 2009
46
TON
kJ/mol (0K); periodic DFT; PW91, PAW, cut off: 400eV, VASP
∆sphysisortion: n-alkane physisorption in H-MOR
H-MOR (Si/Al = 95)
Methusalem, Advisory Board Meeting, August 18, 2009
47
-180
-160
-140
-120
-100
-80
-60
-40
-20
0
1 2 3 4 5 6 7 8 9 10
∆Sp
hys
iso
rptio
n(J
/mol
K)
carbon numberQM-Pot(MP2//B3LYP) mobile QM-Pot(MP2//B3LYP) immobile
H-MOR (Denayer) H-MOR (Lercher)
M2dcR2: multi-scale modeling and design
• Catalyst design based on catalyst descriptors (P2)
• SEMK in complex reaction mixtures (P1)
• Adsorption by nanoporous materials (P3)
• Polymer design accounting for mixing and diffusion (P4)
• Reactor design from first principles (P5)
• From fossil to renewable feedstocks (P6)
Methusalem, Advisory Board Meeting, August 18, 2009
48
Accounting for diffusional limitationsMethusalem, Advisory Board Meeting, August 18, 2009
49
(A, B = M, Ri, RiX, …)
D: diffusion coefficients
⇒k+diff depends on chain length i
kapp depends onchain length i
kchem: Arrhenius equation kdiff: Smoluchowski equation
)DD(Nk BAAdiff +πσ=+ 4
free volume theory
)i(fVV
expDFH
=
γ−=∗
kchemk+diff
k-diff
CABBA +
−=RT
EexpAk AB,a
ABchem
Controlled radical polymerizationMethusalem, Advisory Board Meeting, August 18, 2009
kttermination
50
homopolymer
block copolymer
graft copolymer
compositionfunctionality topology
end-functional polymers
side-functional polymers
multifunctional polymers
XX
XX
XXX
X
XXX
XXX
YX
X
linearnetwork/
crosslinked
star dendritic/ hyperbranched
ATRP of (meth)acrylates: MMA Methusalem, Advisory Board Meeting, August 18, 2009
BrCu(II)PMDETABr + R°BrCu(I)PMDETA + RBrka kp
kt
P
51
PMDETA
kda
ATRP of MMA: defining requirements for controlMethusalem, Advisory Board Meeting, August 18, 2009
ka,chem[m3 mol-1 s-1]
kda,chem[m3 mol-1 s-1]
106
105
104
103
102
101
107
10-6 10-5 10-4 10-3 10-2 10-1 1
fX < 0.95PDI > 1.3
Controlled ATRP of MMA at T= 363 KfX
PDI
conversion = 90%
52
CH CH2
C
NHR
O
CH CH2
C
NHR
O
CH
C
NHR
O
CH CH2
C
NHR
O
X
CH CH2
C
NHR
O
CH
CH2
CNO
CH C
NHR
O
CH CH2
C
NHR
O
RH
:
+
nn
cyclisation
n
X−
ATRP of acrylamides: including side reactionsMethusalem, Advisory Board Meeting, August 18, 2009
53
full reaction network required
cyclisation of dormant chain
NiPAAm: R = i-Pr
Conjugated polymersMethusalem, Advisory Board Meeting, August 18, 2009
PL base PL -L
P
1,6 elimination
premonomer P P P
monomer (p-quinodimethane derivative)
anionic and/or radical polymerization
thermal
elimination
precursorpolymerPPV
sulfinyl route: L = -Cl; P = -S(O)R
dithiocarbamate route: L = P = -SC(S)NR2
-
-
+ °
°
nn
54
Conjugated polymers: regioregularityMethusalem, Advisory Board Meeting, August 18, 2009
55
R1 R2 R3 R4 LHMDS KOtBu
A Me DMO DMO Me 20 22
B DMO Me DMO Me 17 25
C Me DMO Me DMO 47 27
D DMO Me Me DMO 16 264,05 4,00 3,95 3,90 3,85 3,80 3,75 3,70
a
D
C
BA
(ppm)δ
O
Me O
R3
O
R1
O
R2
ODMO
OR4
MDMO-PPV
Base: LHDMS or KOtBu
LHMDS
n
S
S
Et2N
H3CO
O
S
S
NEt21. Base/THF
2. ∆T
H3CO
O
Accounting for mixing: LDPEMethusalem, Advisory Board Meeting, August 18, 2009
Backmixing: introduction of recycle streams
reactor inlet: initiator decomposition faster than mixing
•from CSTR 3 to CSTR 1
•from CSTR 3 to CSTR 2
1
2
3
56
LDPE: short-chain branchesMethusalem, Advisory Board Meeting, August 18, 2009
CSTR 1 CSTR 2 CSTR 3
Lower rates of backbiting in CSTR 1 & 2 for higher values of R
Higher rate of backbiting in CSTR 3 for higher values of R57
CH2H CH3
n n
°
°
LDPE: long-chain branchesMethusalem, Advisory Board Meeting, August 18, 2009
Higher rates of transfer to polymer in all CSTR’sfor higher values of R
CSTR 1 CSTR 2 CSTR 3
58
+ +i j k i j k
°°
M2dcR2: multi-scale modeling and design
• Catalyst design based on catalyst descriptors (P2)
• SEMK in complex reaction mixtures (P1)
• Adsorption by nanoporous materials (P3)
• Polymer design accounting for mixing and diffusion (P4)
• Reactor design from first principles (P5)
• From fossil to renewable feedstocks (P6)
Methusalem, Advisory Board Meeting, August 18, 2009
59
60
• intrinsic adsorption kinetics
• residence time of gas and particles in reactor: hydrodynamics
CFD: coupling kinetics and hydrodynamicsMethusalem, Advisory Board Meeting, August 18, 2009
Performance determined by:
gas outgas out
solidsrecycle
solidsregeneration
gas in
freshsolids
Riser
Case study: Adsorption of SO2 and NOx (SNAP) Methusalem, Advisory Board Meeting, August 18, 2009
∗→∗+ 22 SOSO
∗→∗+ 22 NONO
( ) ∗+∗→∗∗++ 2222 SO()NO(SOONO
( ) ∗β→∗−β+α+∗ t2222 RSO)1(OSO()NO(
∗β→+∗β s2t ROR
( )∗+→+∗ 3x22 )SO(NOSO3NO
*QO)1(NO2NOR 22t β++α+→+∗β
22 NOO5.0NO →+61
most critical
simultaneous adsorption
complex formation
∗∗→∗+∗ 22 SOSO
slow oxidation
additional adsorption
complex decomposition
primary adsorption
62
2
4
6
8
1 0
1 2
1 4
V6
s o lid . v e lo .5 m /s
o u t2o u t1
2
4
6
8
1 0
1 2
1 4
V6
6 .0 0 E - 0 45 .8 2 E - 0 45 .6 4 E - 0 45 .4 6 E - 0 45 .2 9 E - 0 45 .1 1 E - 0 44 .9 3 E - 0 44 .7 5 E - 0 44 .5 7 E - 0 44 .3 9 E - 0 44 .2 1 E - 0 44 .0 4 E - 0 43 .8 6 E - 0 43 .6 8 E - 0 43 .5 0 E - 0 4
s o lid f r a c( - )
o u t 2o u t1
SNAP: simulation resultsMethusalem, Advisory Board Meeting, August 18, 2009
solid fraction solid velocity
5 ms-1
63
0
2
4
6
8
1 0
1 2
1 4
V6
1 3 0 01 2 0 71 1 1 41 0 2 19 2 98 3 67 4 36 5 05 5 74 6 43 7 12 7 91 8 69 30
S O 2 in g a s, p p m
o u t2o u t1
0
2
4
6
8
1 0
1 2
1 4
V6
5 0 04 6 84 3 64 0 43 7 13 3 93 0 72 7 52 4 32 1 11 7 91 4 61 1 48 25 0
N O in g a s, p p m
o u t2o u t1
0
2
4
6
8
1 0
1 2
1 4
V6
4 03 73 43 12 92 62 32 01 71 41 19630
N O 2 in g a s, p p m
o u t 2o u t 1
SNAP: simulation resultsMethusalem, Advisory Board Meeting, August 18, 2009
SO2 in gas NO2 in gasNO in gas
ppm ppm ppm
64
0102030405060708090
100
2 2.2 2.4 2.6 2.8 3 3.2 3.4 3.6
Inlet SO 2/NO ratio
SO
2 re
mov
al (
mol
%)
20
30
40
50
60
70
80
90
100
NO
re
mov
al (
mol
%)
NO
SO2
simulation
SNAP: simulation resultsMethusalem, Advisory Board Meeting, August 18, 2009
CFD aided design of microstructured reactorsMethusalem, Advisory Board Meeting, August 18, 2009
65
concentration field in microchannel (width 70 µm)
Process intensification: rotary bed reactorMethusalem, Advisory Board Meeting, August 18, 2009
66
• Rotation of powder by tangential feeding of the gas
• Principle: balance between drag and centrifugal force of rotating powder
• Advantage: high heat and mass transfer in particular on powder scale
DR
DE
IO
Rotating solidparticles bed
Rotating solidparticles bed
Tangentialfeed inlets
Rotating solidparticles bed
DR
DE
IO
Rotating solidparticles bed
Rotating solidparticles bed
Tangentialfeed inlets
Rotating solidparticles bed
• Solids particle tracking by means of high-speed camera
• Measurement of solids velocity at several independent variables
• Image capturing at 3000 to 30000 frames per second
• Tracked particles further processed in x-y coordinate domain (only 2D measurements)
Solid particles flow captured by high-speed camera
67
Solid particles velocity measurementMethusalem, Advisory Board Meeting, August 18, 2009
M2dcR2: multi-scale modeling and design
• Catalyst design based on catalyst descriptors (P2)
• SEMK in complex reaction mixtures (P1)
• Adsorption by nanoporous materials (P3)
• Polymer design accounting for mixing and diffusion (P4)
• Reactor design from first principles (P5)
• From fossil to renewable feedstocks (P6)
Methusalem, Advisory Board Meeting, August 18, 2009
68
From biomass to fuels and chemicalsMethusalem, Advisory Board Meeting, August 18, 2009
biomass
transesterification biodiesel
gasification
pyrolysis
synthesis gas
pyrolysisoil
69
From gas to liquidsMethusalem, Advisory Board Meeting, August 18, 2009
70
MeOH oligomerization
oxidativecoupling
aromatization benzene
ethylene
fuel
COH2
MTO
CH4
Introduction
• Methusalem program: general
• Laboratory for Chemical Technology (LCT)
• Methusalem program: M2dcR2
• M2dcR2: advisory board members
Methusalem, Advisory Board Meeting, August 18, 2009
71
Subprogram P1
Marie-Françoise Reyniers
Single-event microkinetics in
complex reaction mixtures (P1)
Methusalem, Advisory Board Meeting, August 18, 2009
72http://www.lct.ugent.be
Laboratory for Laboratory for Laboratory for Laboratory for
Chemical TechnologyChemical TechnologyChemical TechnologyChemical Technology
Subprogram P2 and P3
Catalyst design based on catalyst
descriptors & Adsorption by
nanoporous materials (P2-3)
Joris Thybaut
Methusalem, Advisory Board Meeting, August 18, 2009
73http://www.lct.ugent.be
Laboratory for Laboratory for Laboratory for Laboratory for
Chemical TechnologyChemical TechnologyChemical TechnologyChemical Technology
Subprogram P5 and P6
Reactor design from first principles
& From fossil to renewable
feedstocks (P5-6)
Chris Stevens
Geraldine Heynderickx
Methusalem, Advisory Board Meeting, August 18, 2009
74Research Group SynBioC (www.synbioc.ugent.be)
LaboratoryLaboratoryLaboratoryLaboratory forforforfor
Chemical Chemical Chemical Chemical TechnologyTechnologyTechnologyTechnology
General discussion
•research priorities
•equipment
Methusalem, Advisory Board Meeting, August 18, 2009
75
•strengths?
•weaknesses?
•opportunities?
•threats?
Next advisory board meeting
•date
•reporting/minutes of meeting
•format
Methusalem, Advisory Board Meeting, August 18, 2009
76
Concluding feedback Methusalem, Advisory Board Meeting, August 18, 2009
77
Kinetic state definition of the catalyst : TAP Methusalem, Advisory Board Meeting, August 18, 2009
78
Inlet Outlet Response
Single-pulse=
State-defining
Multi-pulse=
State-altering
Alternatingpulse
0
0.2
0.4
0.6
0.8
1
0 5 10 15
Tijd (s)
0
0.2
0.4
0.6
0.8
1
0 5 10 15
Tijd (s)
0
0.2
0.4
0.6
0.8
1
0 0.5 1 1.5
Tijd (s)
0
0.2
0.4
0.6
0.8
1
0 5 10 15
Tijd (s)
0
0.2
0.4
0.6
0.8
1
0 5 10 15
Tijd (s)
0
0.2
0.4
0.6
0.8
1
0 0.5 1 1.5 2 2.5
Tijd (s)
0
0.2
0.4
0.6
0.8
1
0 5 10 15
Tijd (s)
0
0.2
0.4
0.6
0.8
1
0 5 10 15
Tijd (s)
… …0
0.2
0.4
0.6
0.8
1
0 5 10 15
Tijd (s)
…
30 35 40 45 30 35 40 45 30 35 40 45
79
APD/H: aqueous phase dehydration/hydration
Methusalem, Advisory Board Meeting, August 18, 2009
Conjugated polymers: regioregularityMethusalem, Advisory Board Meeting, August 18, 2009
80
LHMDS � x= 47 KtBuO � x= 27
From biomass to energy and fuelsMethusalem, Advisory Board Meeting, August 18, 2009
81