VTT TECHNICAL RESEARCH CENTRE OF FINLAND LTD · Christian Frilund 20.10.2015. 10/02/2016 2 Aim of...
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VTT TECHNICAL RESEARCH CENTRE OF FINLAND LTD
CO2 hydrogenation to methanolMaster’s thesis update
Christian Frilund20.10.2015
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Aim of the thesis
Overview of recent state of the art developments in catalytic hydrogenation of CO2 to methanol, focus on copper based catalysts
Special focus on process-intensifying coated catalysts and reactors that can enable small-scale Power-to-Liquid solutions.
Test new formulations of coated catalysts and powder catalysts in a CSTR, obtain basis of design for reactors
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About the project
Started working on this in late May in the Catalysis & Synfuels team VTT
Experimental testing to be completed within 1 month
Supervisor: Francisco Vidal (Paco)In-house catalyst preparation: Mari-Leena Koskinen-Soivi, Matti PutkonenExperimental set-up help: Matti Reinikainen, Mari-Leena Koskinen-Soivi
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Introduction
Paths to reduce CO2 emissions: 1) reduce produced CO2 amounts 2) store CO2 3) use CO2
In a “Methanol Economy” CO2 and renewable H2 would be converted to methanol. Methanol would act as an energy carrier easy, safe to handle
CO2 an attractive C1 building block, with currently limited usage because of its chemical inertness
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Methanol synthesis
Anthropogenic carbon cycle in the ”Methanol Economy” by George A. Olah:
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Conventional Methanol synthesis
Methanol properties: high octane rating, half the energy density of gasoline, suitable for flex fuel vehicles and fuel cells
Produced from syngas, with ideal H2/CO ratio of 2
CO + 2H CH OH H = 90.5
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Methanol synthesis from CO2
CO2 hydrogenation: CO + 3H CH OH + H O H = 49.5
Reverse water-gas-shift (rWGS): CO + H CO + H O H = 41
CO2 hydrogenation has the same reaction network as the syngas route but with different feed compositions.
Cu/ZnO or Pd based catalysts, T = 200 – 300 oC and P = 30 – 100 bar
Methanol yield lower than for syngas produced route
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Methanol synthesis from CO2: Conditions
Low temperature and high pressure preferred.Catalyst activation at over 200 oC!
0
2
4
6
8
10
200 210 220 230 240 250 260
mol
-%
T / Celsius
Equilibrium composition
MeOHCO
02468
10
30 40 50 60 70 80
mol
-%
P / Bar
Equilibrium composition
MeOHCO
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Copper-based catalysts
Cu main active component. Modifiers include Zn, Zr. Typical catalyst being Cu/ZnO/Al2O3
Syngas catalysts deactivate prematurely at high CO2 levels. The water produced in CO2 hydrogenation also deactivates catalysts. Special formulations of catalysts for CO2 hydrogenation needed!
Small-scale decentralized production of methanol requires more robust catalysts
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Cu-based catalysts – Reaction conditions
CO2 conversion increases with increasing temperature, however selectivity to MeOH decreases Maximum MeOHyield typically at 230-250 oC (at 30 – 80 bar)
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Cu-based catalysts
Reaction is catalyst surface sensitive Catalyst preparation methods affect performance significantly
There is important synergy between the copper metal and oxide (ZnO or ZrO2). Reactions occurs at the interfaces.
Thermal sintering at over 300 oC
Reaction mechanism is still debated Better understanding of mechanism is needed to produce more effective catalysts.
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Cu-based catalysts: Kinetics
CO2 hydrogenation: =.
.
..
Reverse water-gas shift: =.
.
Where fi is fugacity for species i.
Fitted against large number of experiments at 207-277 oC and 15 – 50 bar with conventional CuO/ZnO/Al2O3 catalyst
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Coated catalysts
Produced by depositing thin catalyst layer on a monolith or reactor wall more favourable loading of catalyst than conventional packing, interesting for intensified reactorsCoating must be sufficiently thick and homogeneous, mechanically and thermally stableWashcoating most common coating technique Structure submerged in solution
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Coated catalytic reactors
Example: Monolithic reactors:Benefits: high surface areas without high pressure drop, less intraporous mass transfer limitations, easy scale-up
Especially useful for small scale
Issues: ceramic monoliths have bad radial heat transfer, difficult catalyst replacement
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Industrial status of CO2 hydrogenation to methnanol
First CO2-to-methanol plant in Iceland Uses cheap geothermal energy to produce the H2
Bottleneck is the cost of renewable energy for water electrolysis (H2 production)PtL case: Nuclear power off-peak capacity could be used to produce renewable methanolChallenges: Catalyst improvements, reactors for small-scale production of methanol near the renewable energy source needed
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Experimental setup
TIC
HIGH PRESSUREAUTOCLAVE
N2
FC
MIX
FC
BYPASS LINE
OUTLET
VENTDRY GAS
WATER ANDMETHANOL
CONDENSATE
HEATING JACKET
PC
PI
HIGH PRESSURE:
50 bar
VENT
RUPTURE DISK
GC
FI
MIX23.75% CO271.25% H25% N2
INLET
Calib
FC
GC with TCD and FID detectors
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Experimental setup: CSTR
CSTR not typically used for gas-phase reactions Interest in seeing how it works
200 ml autoclave with heating jacket
Isothermal operation
Reacting gases enter autoclave through the hollow stirrer and exit from the top
Catalyst packing or mesh attached to stirrer
TIC
HIGH PRESSUREAUTOCLAVE
OUTLET
HEATING JACKET
RUPTURE DISK
INLET
Catalyst
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Experimental setup: Catalyst types
Two different catalyst types are tested:
1. Catalyst powder in a metallic basket
2. Catalyst coated on a metallic mesh
Gas In
Gas Out
Basket +Catalyst
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Initial experimental results: Catalyst powders
Powder catalyst testing done, coated mesh testing starts this week
Condition testing performed with commercial BASF RP-60 catalyst
Standard screening conditions for in-house catalysts:Temperature: 240 oCPressure: 50 Bar Flow rate: 0.185 l/min or 11.1 l/hCatalyst packing mass: ca. 2 gCatalyst particle size: 200 – 300 µmTime on stream: 3-4 h
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Effect of particle size BASF
Catalyst: BASF RP-60. mcat 2 gT = 240 oC, P = 50 bar, F = 0.185 l/minEquilibrium calculation property method: RKS MHV2
0
5
10
15
20
25
30
200-300 300-1000
CO2
con
vers
ion
(%)
Catalyst particle size / um
CO
MeOH
Conversion
Equilibriumconversion
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Effect of flow rate BASF
Catalyst: BASF RP-60. mcat 2 g, particle size = 200 – 300 µm T = 240 oC, P = 50 bar
0
5
10
15
20
25
30
0.0925 0.185 0.37
CO2
con
vers
ion
(%)
Operating flow rate / l/min
COMeOHConversionEquilibrium conversion
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Effect of pressure BASF
Catalyst: BASF RP-60. mcat 2 g, particle size = 200 – 300 µm T = 240 oC, F = 0.185 l/min
0
5
10
15
20
25
30
30 50
CO2
con
vers
ion
(%)
Operating pressure / Bar
COMeOHConversionEquilibrium conversion
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Effect of temperature BASF
Catalyst: BASF RP-60. mcat 2 g, particle size = 200 – 300 µm P = 50 bar, F = 0.185 l/min
05
10152025303540
200 220 240
CO2
con
vers
ion
(%)
Operating temperature / Celsius
CO
MeOH
Conversion
Equilibriumconversion
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In-house vs. commercial catalyst
NC = Nanocoating, mcat 1.4 - 2 g, particle size = 200 – 300 µm T = 240 oC, P = 50 bar, F = 0.185 l/min
0
5
10
15
20
25
30CO
2 c
onve
rsio
n (%
)
Catalyst
CO
MeOH
Conversion
Equilibriumconversion
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