Energy-related research at CVT and methanol-based · PDF fileEnergy-related research at CVT...

KIT – University of the State of Baden-Wuerttemberg and National Research Center of the Helmholtz Association

INSTITUTE OF CHEMICAL PROCESS ENGINEERING CVT (KIT Campus South)

www.kit.edu

Energy-related research at CVT

... and methanol-based technology

B. Kraushaar-Czarnetzki

1st Workshop of the Helmholtz Research SchoolEnergy-Related CatalysisNovember 2010

Institute of Chemical Process Engineering CVT2 Prof. Dr. B. Kraushaar-Czarnetzki

Outline

CVT Profileprocess engineeringcatalysisprocesses under investigationenergy-related projects

Fuels from syngas

Formation of methanol and DME

Olefinsformation from MeOH/DMEconversion to fuels

Formation of gasoline from MeOH/DME

Chemistry of MTG and MTO

Related research at CVT


CVT Profile (I): Process Engineering

Process

microreactors

processsimulation

membrane reactors

experimentalreactor evaluation

design &constructionof research

reactors & units

reactormodelling

process kinetics

processing and novelprocessing concepts


CVT Profile (II): Process Engineering

MPV

VZ

R

NV

TIC

TIC

TIC

TIC

TIC

TIC

TIC

TIC

TIC

TIC

FITI, PI

FITI

FITI, PI

FITI, PI

FITI, PI

FITI, PI

FITI, PI

FITI, PI

FITI

FITI

FITI

FITI

FITI

Edukte

Abgas

Analyse ← left: Taylor-Vortex-Reactor

• reactions in liquids• L/L, L/L/S, L/G, L/S/G• low macroscopic backmixing• intensive micromixing, if desired• several axial feedpoints

right: multisampling reactor →

• single tube in multitub. reactor• adjustable axial T-profile• G/S, for particles & packings• monitoring of axial Ci-profiles


CVT Profile (III): Catalysis

Catalyst

synthesis

formulation& shaping

molecularmodelling

kineticmodelling

basic characterization

functionalcharacterizationmechanisms

spectroscopy& surface science


CVT Profile (IV): Processes

Processes under investigation

• Other ReactionsMTO (methanol to olefins)MTG (methanol to gasoline)syngas to gasolinehydrocacking & hydroisomerisationaromatics hydrogenationmaleate → THF (single stage)acetone → MIBK (single stage) isomerisation (supercritical)

• Selective Oxidationsmethane → formaldehydeo-xylene → phthalic anhydridePROX (CO in H2)propene → acroleinpropane → acrylic acidpropene → propylene oxidebutane → maleic anhydridebutenes → maleic anhydrideraffinate II → maleic anhydride

in blue: finalised, much of experience present


CVT Profile (V): Processes

Energy-related projects

• Other ReactionsMTO (methanol to olefins)MTG (methanol to gasoline)syngas to gasolinehydrocacking & hydroisomerisationaromatics hydrogenationmaleate → THF (single stage)acetone → MIBK (single stage) isomerisation (supercritical)

• Selective Oxidationsmethane → formaldehydeo-xylene → phthalic anhydridePROX (CO in H2)propene → acroleinpropane → acrylic acidpropene → propylene oxidebutane → maleic anhydridebutenes → maleic anhydrideraffinate II → maleic anhydride


Look at posters byAnier and Kyra!

See Steffi's poster!

Partial oxidation of methanein a microreactor

Project leader: Stephanie Renz

Collaboration with IMVT(Dr.-Ing. Peter Pfeifer)

Funded by Start-Up Budget (KIT)and Helmholtz Research School

CVT Profile (VI): Energy-Related Projects

Hydroprocessing of dodecane(model feed) at Fischer-Tropschconditions

Project leader: Anier Freitez

Collaboration with EBI(Prof. Georg Schaub, Kyra Pabst)

Funded by DFG


CVT Profile (VII): Energy-Related Projects

Syngas to gasoline

Project leader: Daniel Haigis

Collaboration with ITC-TAB(Prof. Kolb)

Funded by Start-Up Budget (KIT)

Preferential oxidation of COin H2-rich gases (PROX)

Project leader: Sebastian Lang

Collaboration with ITTK(Prof. Türk)

Funded by DFG Methanol to gasoline

Project leader: Jens Adler

Collaboration with EBI(Prof. Schaub)

Funded by FNR

Methanol to olefins

Project leader: Markus Menges

Funded by FNR and byExxonMobile (4 years


Fuels from Syngas

MOGD(ExxonMobil)

MethanolMethanol DMEDME OlefinsOlefins

Gasoline

Kero & Gasoil

MTO (UOP, Mobil) DTO

MtSynfuels (Lurgi)

DTG

MTG (ExxonMobil)

MTD (Lurgi)

STD (Haldor-Topsoe, Air Products, JFE)

TIGAS (Haldor-Topsoe)

Fischer-Tropsch (Sasol, Shell)ParaffinsParaffins

Fischer-Tropsch (Sasol, BASF)

SyngasSyngas COD (Lurgi)


Fuels from Syngas

MOGD(ExxonMobil)

MethanolMethanol DMEDME

Gasoline

Kero & Gasoil

MTO (UOP) DTO

MtSynfuels (Lurgi)

DTG

MTG (ExxonMobil)

MTD (Lurgi)

STD (Haldor-Topsoe, Air Products, JFE)

TIGAS (Haldor-Topsoe)

Fischer-Tropsch (Sasol, Shell)ParaffinsParaffins

Fischer-Tropsch (Sasol, BASF)

SyngasSyngas OlefinsOlefins


Formation of Methanol and DME (I)


Gasoline

Kero & Gasoil


methanol synthesisCO + 2 H2 ↔ CH3OH∆Hθ = -92 kJ/molcat.: Cu/ZnO-based60-80 bar230-260 °C

DME synthesis2 CH3OH ↔ DME + H2O∆Hθ = -23 kJ/molcat.: γ-Al2O32-30 bar200-250 °C

combination easily possible because:Cu/ZnO also catalyses the shift reaction!CO + H2O → H2 + CO2

catalyst: Cu/ZnO/γ-Al2O3

total: 3 H2 + 3 CO → DME + CO2


Formation of Methanol and DME (II)

advantages of the combination:4 H2 + 2 CO ↔ 2 CH3OH2 CH3OH ↔ DME + H2OCO + H2O ↔ H2 + CO2

total: 3 H2 + 3 CO → DME + CO2

- MeOH equilibrium shifted due to DME formation- DME equilibrium shifted due to WGS reaction⇒ low H2/CO feed ratio possible (1:1)⇒ high conversion at low pressure feasible⇒ low recycle ratio feasible

Equilibrium conversion vs. pressure(240 °C; H2:CO:CO2 = 51:48:1)

N.R. Udengaard (Haldor Topsoe),Houston 2008

STD-processes:- Haldor Topsoe- Air products- JFE


Olefins (I): Formation from MeOH/DME

MTO (methanol to olefins) processes... include a 1st stage for separate DME formation

1st reactor: following reactor(s):2 CH3OH ↔ DME + H2O DME/CH3OH → C2

=, C3=, HCs, H2O

cat.: γ-Al2O3 cat.: ZSM-5 or SAPO342-10 bar 2-10 bar200-250 °C 400-450 °C


Gasoline


fixed bed:- Mobil Oil- Lurgi (MTP = methanol to propylene)

fluidised bed (2nd stage):- Mobil Oil in cooperation with Uhde GmbH and Union

Rheinische Braunkohlen Kraftstoff AG- UOP/Hydro (using SAPO-34 as a Katalysator)

Kero & Gasoil


Olefins (II): Conversion to Fuels


Gasoline

Kero & Gasoil


Principle: acid-catalysed oligomerisation of light olefins Products: methyl-branched iso-olefins till C20,

hydrogenation required for distillates manufacturing

Processes:- to gasoline from C3/C4-olefins: UOP CatCon (UOP Catalytic Condensation)- to gasoline and gasoil from FT-olefins: Lurgi COD (Lurgi Conversion ofOlefins to Distillates)

- to gasoline and middle distillates: MOGD (Mobil Olefin to Gasoline & Distillate)


Olefins (III): Conversion to Fuels

European ethylene and propyleneclosing prices

Product August 3th, 2010 Unit

ethylene 1000 - 1005 $/ton

propylene 925 - 930 €/ton

www.eia.doe.gov

Daily spot prices of regular gasoline

2,2 $/gallon ≈ 660 $/ton gasoline

Gasoline

Kero & Gasoil

OlefinsOlefins ?

www.lookchem.com


Formation of Gasoline from MeOH/DME (I)

Gasoline formation from MeOH/DME

MethanolMethanol DMEDMESyngasSyngas

Gasoline

OlefinsOlefins

...includes olefins as intermediates

2 CH3OH

CH3OCH3

H2O+

HC-pool*

C2H4C3H6

i-C4H8

higher olefinsaromaticsparaffins

coke

*HC-pool theory: Kolboe (1993)

↓↑


Formation of Gasoline from MeOH/DME (II)

Two processes for gasoline (both fixed bed):

MTG (ExxonMobil Research and Engineering/Uhde)

syngas MeOH gasolineMeOH DME

Uhde: gasification & MeOH-synthesis

TIGAS (Haldor Topsoe)

syngas MeOH/DME gasoline


Formation of Gasoline from MeOH/DME (III)

Haldor Topsoe: TIGAS demo plant8 b/d, Houston,TX

ExxonMobil: MTG plantstop: New Plymouth, 1985-1995, 14500 b/dleft: Shanxi (China), since 2009, 2500 b/d


Formation of Gasoline from MeOH/DME (IV)

Similar productqualities have beenreported by HaldorTopsoe for TIGASGasoline


Chemistry of MTG and MTO

2 CH3OH

CH3OCH3

H2O+

HC-pool

C2H4C3H6

i-C4H8

higher olefinsaromaticsparaffins

(coke)

↓↑

MTO processing modeTopt = 450 °Cpopt = 2 barcatalyst = ZSM-5*)

Si/AlZeo = 250*) fixed bed process

MTG processing modeTopt = 350 °Cp > 20 bar (popt = ?)catalyst = ZSM-5Si/AlZeo = 30

C2H4C3H6

T↑ & p↓

cracking!

⇒ in MTO, olefins occur as both: short-life intermediatesand final cracking products


Related Research at CVT

till 2009: MTO only (propene & ethene are more valuable than fuels)development of a coke-resistant catalyst(runtime 3 months at high severity)processing and feedstock studies

since 2009, funded by FNR (collaboration with Prof. Schaub, EBI):studies on the transition MTO/MTGimprovement of the MTG-catalyst stabilitykinetic modellingdevelopment of reactor modelsidentification of factors dominating total yieldsand efficiencies with respect to carbon and energycomparison of MtH-based and FT-based synfuel manufacturing

Energy-related research at CVT and methanol-based · PDF fileEnergy-related research at CVT...

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