multi-scale modeling and design of chemical reactions and reactors · 2017-03-12 · 13h15 –...

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

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

Laboratory for Chemical Technology (LCT)

Guy B. MarinGeraldine Heynderickx

Joris ThybaultMarie-Françoise Reyniers

LCT: multi-scale research activities

from atom (nm) to full process (m)

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

yields

LCT research: application domains

•PVC•ATRP•RAFT•(in-situ)NMP•conjugatedpolymers (PPV’s)

polymerization

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

LCT: people

•Part-time professors: 2

•Visiting scientists: 1

•Post-docs: 8

•PhD students: 29

•Technical staff: 9

•Administrative staff: 2

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

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

•Cold flow set-ups: 2

Introduction

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 program: evaluation criteria

•Quality of work

•Human resources management

•Research plan for next 7 years

• 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

• 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: M2dcR2

• Funding: people and equipment

• Aim and strategy

• Organizational aspects

• M2dcR2: multiscale modeling and design

•Scientific director: Guy B. Marin

•Management committee

•Advisory board

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

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)

• 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

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)

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

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

M2dcR2: application domains

M2dcR2

biomass to liquids

renewablesto

chemicals

environ-mental

functionalmaterials

catalysts polymers

•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

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

Kinetics High-throughput kinetics set-up 341

Temporal Analysis of Products (TAP) 665

ComputingAnnual investment for High Performance ComputingClusters (HPPC)

Total 1808

Equipment not considered in proposal

Pulsed laser polymerization

Pyrolyser for on-line analytical pyrolysis GC×GC

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)

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

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

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)

Complex reaction mixturesGC × GC

Computer generation of reaction networks

Molecules

Elementary Reaction Families

Reaction Rules

– Representation

– Mathematical Operations

– Species Uniqueness

– Thermodynamics

– Termination Criteria

k5 k6k7

k10k11

k14 k15

COMPUTER PROGRAM

– Kinetic Parameters

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

Reaction networks: C/H/O chemistrycellulose lignin

lignin monomers

terpenes/terpenoids

Reactions: accounting for stereochemistry Methusalem, Advisory Board Meeting, August 18, 2009

Reactions: kinetic parametersparameter estimation

quantum chemistry

Model based catalyst design: a clever way to close the loop

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

Definition of space at nano scale0.5 nm

ZSM-22

zeolite Y

Mordenite

active site

ZSM-22

Distinguishing different types of active sites

micropores pore mouthsite

Bridgesite: near

Bridgesite: far

pore mouths

ZSM-22 crystallite

Catalyst design: contribution analysis on ZSM-22

monobranched dibranched

tribranchedn-alkanes

crackedproducts

pore mouthbridge sites micropores

Hayasaka et al, Chemistry- A Eur. J., 13, 10070 (2007)

Catalyst design: nanorod assembled ZSM-22Methusalem, Advisory Board Meeting, August 18, 2009

Potential application “nanorod” Pt/H-ZSM-22Methusalem, Advisory Board Meeting, August 18, 2009

nC10 hydroconversionP = 4.5 bar, W/F = 2522 kg-smol-1, H2/HC = 375

423 473 523 573

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

•functionalization: select precursors (organometals: Al, Ga, Fe)

•pore dimensions: select precursor size (AlMe3, AlEt3, Al(OEt)3)

Postsynthesis modification of nanoporous materials by ALD

Defining the kinetic state of the catalyst: TAP Inert zone Catalyst zone

state-defining Pulses

Insignificant change

state-defining Experiment

Temporal Analysis of Products

Catalyst properties: influence on stability/reactivityZSM-22

−3116

−18 −25

π,i-but,ai-butoxideπ,i-but,b

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

kJ/mol (0K); periodic DFT; PW91, PAW, cut off: 400eV, VASP

∆sphysisortion: n-alkane physisorption in H-MOR

H-MOR (Si/Al = 95)

1 2 3 4 5 6 7 8 9 10

carbon numberQM-Pot(MP2//B3LYP) mobile QM-Pot(MP2//B3LYP) immobile

H-MOR (Denayer) H-MOR (Lercher)

Accounting for diffusional limitationsMethusalem, Advisory Board Meeting, August 18, 2009

(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

homopolymer

block copolymer

graft copolymer

compositionfunctionality topology

end-functional polymers

side-functional polymers

multifunctional polymers

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

PMDETA

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]

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

conversion = 90%

CH CH2

cyclisation

ATRP of acrylamides: including side reactionsMethusalem, Advisory Board Meeting, August 18, 2009

full reaction network required

cyclisation of dormant chain

NiPAAm: R = i-Pr

Conjugated polymersMethusalem, Advisory Board Meeting, August 18, 2009

PL base PL -L

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

Conjugated polymers: regioregularityMethusalem, Advisory Board Meeting, August 18, 2009

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

(ppm)δ

MDMO-PPV

Base: LHDMS or KOtBu

NEt21. Base/THF

2. ∆T

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

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

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

+ +i j k i j k

• 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

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

s o lid . v e lo .5 m /s

o u t2o u t1

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

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

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

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

SO2 in gas NO2 in gasNO in gas

ppm ppm ppm

0102030405060708090

2 2.2 2.4 2.6 2.8 3 3.2 3.4 3.6

Inlet SO 2/NO ratio

simulation

CFD aided design of microstructured reactorsMethusalem, Advisory Board Meeting, August 18, 2009

concentration field in microchannel (width 70 µm)

Process intensification: rotary bed reactorMethusalem, Advisory Board Meeting, August 18, 2009

• 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

Rotating solidparticles bed

Tangentialfeed inlets

• 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

Solid particles velocity measurementMethusalem, Advisory Board Meeting, August 18, 2009

From biomass to fuels and chemicalsMethusalem, Advisory Board Meeting, August 18, 2009

biomass

transesterification biodiesel

gasification

pyrolysis

synthesis gas

pyrolysisoil

From gas to liquidsMethusalem, Advisory Board Meeting, August 18, 2009

MeOH oligomerization

oxidativecoupling

aromatization benzene

ethylene

Introduction

Subprogram P1

Marie-Françoise Reyniers

Single-event microkinetics in

complex reaction mixtures (P1)

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

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

74Research Group SynBioC (www.synbioc.ugent.be)

LaboratoryLaboratoryLaboratoryLaboratory forforforfor

Chemical Chemical Chemical Chemical TechnologyTechnologyTechnologyTechnology

General discussion

•research priorities

•equipment

•strengths?

•weaknesses?

•opportunities?

•threats?

Next advisory board meeting

•date

•reporting/minutes of meeting

•format

Concluding feedback Methusalem, Advisory Board Meeting, August 18, 2009

Kinetic state definition of the catalyst : TAP Methusalem, Advisory Board Meeting, August 18, 2009

Inlet Outlet Response

Single-pulse=

State-defining

Multi-pulse=

State-altering

Alternatingpulse

0 5 10 15

Tijd (s)

0 5 10 15

Tijd (s)

0 0.5 1 1.5

Tijd (s)

0 5 10 15

Tijd (s)

0 5 10 15

Tijd (s)

0 0.5 1 1.5 2 2.5

Tijd (s)

0 5 10 15

Tijd (s)

0 5 10 15

Tijd (s)

… …0

0 5 10 15

Tijd (s)

30 35 40 45 30 35 40 45 30 35 40 45

APD/H: aqueous phase dehydration/hydration

Conjugated polymers: regioregularityMethusalem, Advisory Board Meeting, August 18, 2009

LHMDS � x= 47 KtBuO � x= 27

From biomass to energy and fuelsMethusalem, Advisory Board Meeting, August 18, 2009

multi-scale modeling and design of chemical reactions and reactors · 2017-03-12 · 13h15 –...

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