Carbon Dioxide Hydrogenation...Kashid, Renken, Kiwi-Minsker, Microstructured devices for chemical...

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Transport Processes and Reactions LaboratoryInstitute of Process EngineeringHelena Reymond

Carbon Dioxide HydrogenationSynthetic Perspectives for Chemical Energy Carriers

[email protected]

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Carbon Dioxide

Carbon Capture and Storage

Carbon Dioxide Utilisation

Valuable Chemicals / Fuels

Economic and Environmental IncentivesEmission Mitigation Strategies

0

5

10

15

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25

30

35

1970 1975 1980 1985 1990 1995 2000 2005 2010 2015

Gt

CO

2

World emissions from fuel combustion

32.2 Gt CO2

2013

?

PBL Netherlands Environmental Assessment Agency, trends in global CO2 emissions, 2015 report


Carbon Dioxide

Renewable Energies

Energy Storage

Water splitting

Hydrogen Economy

Electricity and Heat

42%

Transport23%

Industry19%

Others16%

Emissions shares by sector


0

5

10

15

20

25

30

35

1970 1975 1980 1985 1990 1995 2000 2005 2010 2015

Gt

CO

2

World emissions from fuel combustion

32.2 Gt CO2

2013

International Energy Agency (IEA) highlights 2015


Carbon Dioxide





Renewable Energies

Energy Storage

Water splitting

Hydrogen Economy Methanol3 H2 + CO2 CH3OH + H2O

Graves et al., Renewable Sustainable Energy Rev 15 (2011) 1-23


Carbon Dioxide





Renewable Energies

Energy Storage

Water splitting

Hydrogen Economy Methanol

Formic Acid

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60

1 2

H2 H2

CO2

HCOOH

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Thermodynamically hampered Sensitive equilibrium Non-spontaneous

Homogeneous catalysis› Basic media to stabilise HCOOH

Heterogeneous catalysis› Economically advantageous› Unsuccessful: yields methanol

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Formic acid synthesis

H2 + CO2 HCOOH

H2 H2

CO2

HCOOH

Noyori et al., Nature 368 (1994) 231.Noyori et al., Science 269 (1995) 1065.

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Reactants diffusion1. External diffusion 2. Internal diffusion

Reaction3. Adsorption of reactants on the surface4. Catalytic reaction on the surface5. Desorption of the products

Products diffusion6. Internal diffusion of products7. External diffusion of products

Rate determining step? Kinetically controlled Mass transfer limited

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Heterogeneous catalysis

Kashid, Renken, Kiwi-Minsker, Microstructured devices for chemical processing Wiley Verlag, 2015

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Continuous 2-step process

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CO2 + H2

REACTOR 1REACTOR 1

HCOOHCatalyst 1

> 100 bar, 200 – 300°C

MAJOR PROBLEM

Formic acid decomposition back to H2 and CO2

› Conventional heterogeneous catalysts are active in the reverse reaction (metal supported on metal oxides)› Microscopic reversibility suggests some activity in the foward reaction under appropriate conditions

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IDEA

Mitigate the thermodynamic barrier› Shift the reaction equilibrium to the right› Include a reaction consuming FA faster than its decomposition

CO2 + H2

HCOO(H)

???

Stable compound

Catalyst 1

Catalyst 2

REACTOR 1> 100 bar, 200 – 300°C

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IDEA TO MITIGATE THERMODYNAMIC BARRIER

Secondary reaction to transform the FA before decomposition

› Reacting FA with alcohols to yield formate esters

Methyl formate synthesis

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M or MOX

CO2 + H2

CO

O

H

CO

O

H

CO

O

H

Formic acid

CO-H

O

H

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› Reacting FA with alcohols to yield formate esters



M or MOX

CO2 + H2

CO

O

H

CO

O

H

CO

O

H

MeOH

Formic acid

Methyl formate

CO-CH3

O

H

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› Reacting FA with alcohols to yield formate esters› In-situ formed MeOH



M or MOX

CO2 + H2

CO

O

H

CO

O

H

CO

O

H

Methyl formate

Formic acid

MeOH

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METHYL FORMATE› Good chemical properties as fuel› Not economically viable

transient intermediate



CO2 + H2

HCOO(H)

CH3OH

HCOOCH3

Catalyst 1

Catalyst 2

REACTOR 1> 100 bar, 200 – 300°C

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HCOOHCatalyst 3

FORMIC ACID› Industrially produced by hydrolysis of MF (BASF)› MeOH as by-product› Batch or chromatographic reactors

HCOOCH3

CH3OH

REACTOR 210 bar, 40 - 120°C

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FORMIC ACID› Industrially produced by hydrolysis of MF (BASF)› MeOH as by-product› Batch hydrolysis

CO2 + H2

HCOO(H)

CH3OH

HCOOCH3

Catalyst 1

Catalyst 2

REACTOR 1> 100 bar, 200 – 300°C

REACTOR 2

HCOOH

CH3OH

Catalyst 3

10 bar, 40 - 120°C

HCOOCH3

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The overall process requires the rational design of a robust heterogeneous CO2 hydrogenation catalyst selective for formic acid


Catalyst and reactor design

CO2 + H2

HCOO(H)

CH3OH

HCOOCH3

Catalyst 1

Catalyst 2

REACTOR 1> 100 bar, 200 – 300°C

REACTOR 2

HCOOH

CH3OH

Catalyst 3

10 bar, 40 - 120°C

HCOOCH3

Reaction mechanismPhase behaviour


Sinergia collaboration

The overall process requires the rational design of a robust heterogeneous CO2 hydrogenation catalyst selective for formic acid

Reaction mechanismPhase behaviour


Reactor 1: synthesis of methyl formate

CO2 + H2

HCOO(H)

CH3OH

HCOOCH3

Catalyst 1

Catalyst 2

REACTOR 1> 100 bar, 200 – 300°C

REACTOR 2

Catalyst 3HCOOH

CH3OH

10 bar, 40 - 120°C

HCOOCH3


High-pressure hydrogenation setupCatalytic activity measurements and simultaneous in-situ Raman spectroscopy at reaction conditions

3H2 + CO2 CH3OH + H2O

H2 + CO2 CO + H2O

H2 + CO CH3OH


High-pressure hydrogenation setupCatalytic activity measurements and simultaneous in-situ Raman spectroscopy at reaction conditions

Diaphragm compressorpmax = 3000 bar

Pressure transducers

H2 storage in coiled pipe

Hydrogen

Carbon dioxide

Pressure relief valvepmax = 1300 bar

Nickel-clad fused silicaID = 1 µm

Operando Raman microspectrometerλ1 = 355 nmλ2 = 532 nmλ3 = 785 nm

Online gas chromatograph

Pressure regulating valvepmax = 1300 bar

Microreactorwith

view-cell

High-pressure syringe pumppmax = 1300 bar

Stainless steel microreactor ID = 1 mm

Maximum operating conditionsPressure 500 barTemperature 300°C

Flowrate rangeCO2H2 (via ∆p_capillary)

5 – 25000 µL/min40 – 500 µL/minTidona et al., J. Supercrit. Fluids 78 (2013) 70-77

Tidona et al., Chem. Eng. Process.: Process Intensif. 65 (2013) 53-57


High-pressure micro view-cell

Metal sealingsSapphire window

WD = 14 mm

NA = 0.34 40°

FP 1 mm below window

Inner diameter ID = 1 – 1.5 mmLength L = 50 mm


Flow or static conditions


The Raman effect

SPECTROSCOPY = LIGHT – MATTER INTERACTION› Incident electric field› Induced dipole moment› Oscillating molecule

Fingerprint of molecule

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H2 CO2CH4CO

H2OCH3OH

HCOOCH3A

S RI S¦

S

A

A

catalyst packed bed


in situ analysis

SURFACE SPECIES ANALYSIS BY RAMAN SPECTROSCOPY

› Main carbon oxide source ?› Parallel or consecutive RWGS ?› Common or different intermediate species ?

PHASE BEHAVIOUR OF REACTIVE MIXTURES

› Number and nature of phases in reactor ?› Chemical and phase equilibrium ?

3H2 + CO2 CH3OH + H2O

H2 + CO2 CO + H2O

H2 + CO CH3OH


Methanol synthesis: equilibrium conversion

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60

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100

170 190 210 230 250 270 290 310 330

CO

2co

nver

sion

[-]

Temperature [°C]

50 bar V 100 bar V 350 bar V 500 bar V 700 bar V50 bar VL 100 bar VL 350 bar VL 500 bar VL 700 bar VL

PR

ESS

UR

E

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Temperature [°C]

170 180 190 200 210 220 230 240 250 260 270 280 290 300

Sele

ctiv

ity [%

]

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60

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100

350 bar500 bar700 bar

CO

Methanol

Methylformate


Reaction performance GHSV = 22’300 h-1

H2:CO2 = 3:1

Temperature [°C]

170 180 190 200 210 220 230 240 250 260 270 280

CO2 c

onve

rsio

n [%

]

0

10

20

30

40

50

60

70

80

90

100

350 bar500 bar700 bar

Temperature [°C]

170 180 190 200 210 220 230 240 250 260 270 280 290 300

Yiel

d [m

mol

/g h

]

0

10

20

30

40

50

60

70

80

90350 bar500 bar700 bar

CO

Methanol

Methylformate


Raman spectrum of reaction effluent

Raman shift [cm-1]1000 1500 2000 2500 3000 3500 4000

Rel

ativ

e in

ten

sity

[a.u

]

500

350 bar240 °CH2:CO2 = 3:1GHSV = 22’300 h-1

H2 CO2 ProductsProducts Products


Methanol synthesis: in situ condensation

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60

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170 190 210 230 250 270 290 310 330

CO

2co

nver

sion

[-]

Temperature [°C]

50 bar V 100 bar V 350 bar V 500 bar V 700 bar V50 bar VL 100 bar VL 350 bar VL 500 bar VL 700 bar VL

Van Bennekom et al., Ind. Eng. Chem. Res., 51 (2012)

Van Bennekom et al., Chem. Eng. Sci., 87 (2013)


Condensation


Water structural transformations

GAS

LIQUID


Condensation temperature

200 barH2:CO2 = 3:1 condensation


Reactor 2: hydrolysis of methyl formate

CO2 + H2

HCOO(H)

CH3OH

HCOOCH3

Catalyst 1

Catalyst 2

REACTOR 1> 100 bar, 200 – 300°C

REACTOR 2

Catalyst 3HCOOH

CH3OH

10 bar, 40 - 120°C

HCOOCH3


Hydrolysis setup

Stainless steel reactor ID = 2 mm


Flowrates range 0.001 – 100 mL/min

MF Water catalyst packed bed

Methyl formate + Water Formic acid + Methanolcatalyst

MF

MF

MF

MF

MF

WaterFormic acidMethanolMF

MFMF

MFMF

MFP P

P

PPP PP

P

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Ternary Map (Mole Basis)

WATER

MF

MEO

H

0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

0.45

0.5

0.55

0.6

0.65

0.7

0.75

0.8

0.85

0.9

0.95

0.95

0.9

0.85

0.8

0.75

0.7

0.65

0.6

0.55

0.5

0.45

0.4

0.35

0.3

0.25

0.2

0.15

0.1

0.05

Water


Simultaneous phase and chemical equilibria

H2Oaq + MFaq MeOHaq + FAaq

H2Oorg

H2Oaq

MForg

MFaq

MeOHorg

MeOHaq

FAorg

FAaq

H2Oorg + MForg MeOHorg + FAorg

ORG

AN

IC

PHA

SEA

QU

EO

US

PHA

SE

Keq/org(T)

Keq/aq(T)

10 bar, 23°C

Reac

tion

coor

dina

te


Parametric study

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20 30 40 50 60 70 80 90 100 110 120

XM

F[%

]

Temperature [°C]

Water molar excess

14.2

3.6

1.8

0.9

0.000

0.002

0.004

0.006

0.008

0.010

0.012

0.014

0.016

20 30 40 50 60 70 80 90 100 110 120C

once

ntr

atio

n [

mol

/m

L]

Temperature [°C]

Water molar excess

R = 1.8

MF

MeOH

p = 10 barWHSV = 650 h-1


Outlook

CO2 + H2

HCOO(H)

CH3OH

HCOOCH3

Catalyst 1

Catalyst 2

REACTOR 1> 100 bar, 200 – 300°C

CO2

H2HCOOCH3

CH3OH

HCOOH

CH3OH

H2OREACTOR 1 REACTOR 2

CO

REACTOR 2

HCOOH

CH3OH

Catalyst 3

10 bar, 40 - 120°C

HCOOCH3

Thank you for your attention

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