CO2 sorption by hydrotalcite-like compounds in dry and wet conditions

Alessandro Poliandria, Francesca Michelia, Katia Galluccia, Leucio Rossib, Pier Ugo Foscoloa

aDepartment of Industrial Engineering, University of L’Aquila Email: alessandro.poliandri@gmail.com , francesca.micheli@graduate.univaq.it, katia.gallucci@univaq.it, pierugo.foscolo@univaq.it b Department of Physical and Chemical Science, University of L’Aquila Email:leucio.rossi@univaq.it

13TH INTERNATIONAL CONFERENCE MULTIPHASE FLOW IN INDUSTRIAL PLANTS

SESTRI LEVANTE (GENOVA), ITALY - 17-19 SEPTEMBER 2014

mailto:alessandro.poliandri@gmail.commailto:francesca.micheli@graduate.univaq.itmailto:katia.gallucci@univaq.itmailto:pierugo.foscolo@univaq.itmailto:leucio.rossi@univaq.it

Overview

• Aims of the work

• Introduction:

• SEWGS application in gasification and IGCC processes

• Materials: hydrotalcite-like compounds

• Results:

• Kinetic study: TG-DTA signals

• Characterisation before tests: XRD and FT-IR analysis

• Experimental apparatus: PSA plant

• Capture tests: model approach

• Characterisation after tests: XRD and FT-IR analysis

• Conclusions

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Aims of the work

• The objective is to assess the feasibility of the Sorption-Enhanced Water−Gas Shift and Reforming Process (SEWGS and SERP)

▫ for an IGCC (Integrated Gasification Combined Cycle)

▫ and for Coal Gasification processes through a suitable material for CO2 capture,

▫ and in case for H2S capture, at typical WGS (Water Gas Shift) and Tar reforming conditions.

• Synthesized materials are experimentally tested in a Pressure Swing Adsorption (PSA) laboratory scale plant

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• CO from the gasification syngas has to be converted into H2 and CO2 via WGS reaction.

• In SEWGS, the equilibrium of the reaction is shifted to the product side by using a CO2 sorbent.

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IGCC Power production with CO2 capture by SEWGS. Power is generated by gas turbines

(GT) and steam turbines (ST), heat is recovered for steam generation (HRSG).

(from ECN website)

Coal

Air/O2

Steam Syngas

generation SEWGS

Power

generation

GT

HRSG

ST

CO2

Power

Decarbonized

H2 fuel

Introduction

• Global emissions of anthropogenic CO2 and other greenhouse gases (GHG) increase significantly global warming effect.

▫ global CO2 emissions must be reduced of 50-80% within 2050 [IPCC]

• Technologies for carbon-emission-free energy production (CCT) are currently under development, as CO2 capture and storage (CCS).

▫ R&D aim is reducing the fuel costs which are mainly due to

low efficiency of CO2 capture

capital costs of capture process equipments.

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• CO2 capture process can use three different decarbonization techniques:

▫ pre-combustion,

▫ post-combustion,

▫ oxyfuel combustion

• Pre-combustion advantages:

▫ Higher CO2 partial pressure

▫ Lower treated gas volume

▫ Smaller facilities

▫ Integration of pre-combustion CO2 capture within WGS reactor (Sorption Enhanced WGS).

• In case of adsorption of CO2 coupled with WGS, the operating window is 250-400°C.

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Introduction

Project Name Location Feedstock Size MW

Status

Puertollano Spain Coal 14 Operational Sept. 2010

Buggenum Netherlands Coal 20 Operational May 2011

Polk FL, USA Coal 0.3 Mt/yr Operational Apr. 2014

SOTACARBO Carbonia (Italy) Coal-Waste 0.4 Planning

ENEA Rome (Italy) Coal 0.3 Planning

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Project Name Location Feedstock Size MW Status

Schwarze Pumpe

Germany Coal 30 Operational Sept. 2008

Compostilla Spain Coal 30 Operated 2009-2012

Lacq France Oil 35 Operational 2010

Callide-A Oxy Fuel

Australia Coal 30 Operational Dec.2012

http://sequestration.mit.edu/tools/projects/index_pilots.html

Pilot pre-combustion CCS Projects

Pilot oxy-combustion CCS Projects

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http://sequestration.mit.edu/tools/projects/puertollanto.htmlhttp://sequestration.mit.edu/tools/projects/buggenum.htmlhttp://sequestration.mit.edu/tools/projects/polk.htmlhttp://sequestration.mit.edu/tools/projects/polk.htmlhttp://sequestration.mit.edu/tools/projects/polk.htmlhttp://sequestration.mit.edu/tools/projects/polk.htmlhttp://sequestration.mit.edu/tools/projects/polk.htmlhttp://sequestration.mit.edu/tools/projects/vattenfall_oxyfuel.htmlhttp://sequestration.mit.edu/tools/projects/vattenfall_oxyfuel.htmlhttp://sequestration.mit.edu/tools/projects/compostilla.htmlhttp://sequestration.mit.edu/tools/projects/total_lacq.htmlhttp://sequestration.mit.edu/tools/projects/callide_a_oxyfuel.htmlhttp://sequestration.mit.edu/tools/projects/callide_a_oxyfuel.htmlhttp://sequestration.mit.edu/tools/projects/callide_a_oxyfuel.htmlhttp://sequestration.mit.edu/tools/projects/callide_a_oxyfuel.htmlhttp://sequestration.mit.edu/tools/projects/callide_a_oxyfuel.htmlhttp://sequestration.mit.edu/tools/projects/callide_a_oxyfuel.htmlhttp://sequestration.mit.edu/tools/projects/index_pilots.html

Pilot post-combustion CCS Projects

Project Name Location Feedstock Size MW Status

ECO2 Burger OH, USA Coal 1 Operated 2008- 2010

Pleasant Prairie WI, USA Coal 5 Operated 2008-2009

AEP Mountaineer WV, USA Coal 30 Operated 2009-2011

Karlshamn Sweden Oil 5 Operated 2009-2010

Jilin China Nat. Gas 0.2 Mt/yr Operational 2009

Shidongkou China Coal 0.1 Mt/yr Operational 2011

Brindisi Italy Coal 48 Operational Mar. 2011

Ferrybridge UK Coal 5 Operational Nov.2012

Mongstad Norway Gas 0.1 Mt/yr Operational May 2012

Plant Barry AL, USA Coal 25 Operational Aug 2012

Aberthaw Wales, UK Coal 3 Operational Jan. 2013

Boryeong Station South Korea Coal 10 Operational May 2013

Big Bend Station FL, USA Coal 1 Planning

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http://sequestration.mit.edu/tools/projects/berger.htmlhttp://sequestration.mit.edu/tools/projects/pleasant_prairie.htmlhttp://sequestration.mit.edu/tools/projects/pleasant_prairie.htmlhttp://sequestration.mit.edu/tools/projects/pleasant_prairie.htmlhttp://sequestration.mit.edu/tools/projects/aep_alstom_mountaineer.htmlhttp://sequestration.mit.edu/tools/projects/eon_karlshamn.htmlhttp://sequestration.mit.edu/tools/projects/jilin.htmlhttp://sequestration.mit.edu/tools/projects/shidongkou.htmlhttp://sequestration.mit.edu/tools/projects/enel_1.htmlhttp://sequestration.mit.edu/tools/projects/sse_ferrybridge.htmlhttp://sequestration.mit.edu/tools/projects/statoil_mongstad.htmlhttp://sequestration.mit.edu/tools/projects/plant_barry.htmlhttp://sequestration.mit.edu/tools/projects/aberthaw.htmlhttp://sequestration.mit.edu/tools/projects/kepco.htmlhttp://sequestration.mit.edu/tools/projects/kepco.htmlhttp://sequestration.mit.edu/tools/projects/kepco.htmlhttp://sequestration.mit.edu/tools/projects/big_bend.htmlhttp://sequestration.mit.edu/tools/projects/big_bend.htmlhttp://sequestration.mit.edu/tools/projects/big_bend.htmlhttp://sequestration.mit.edu/tools/projects/big_bend.html

Introduction • State-of-the-art of EU programs:

▫ CACHET II (Carbon dioxide capture and hydrogen production with membranes)

▫ CAESAR (CArbon-free Electricity by SEWGS: Advanced materials, Reactor-, and process design) pilot plant installation (35 ton CO2/day) with K-HTC

sorbent, called ALKASORB1. ▫ ASCENT2 (Advanced Solid Cycles with Efficient Novel

Technologies) efficiency of carbon removal of pre-combustion capture

(electricity efficiency up to 52%) cost of CO2 avoided of about 35€/t.

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1Jansen, D., Selow, E.R. van, Cobden, P.D., Manzolini, G., Macchi, E., Gazzani, M., Blom, R., Pakdel Henriksen, P., Beavis, R., Wright, A., ( 2013 ). Energy Procedia, 37, 2265– 2273 2 http://ascentproject.eu/

http://ascentproject.eu/

Introduction

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• A wide range of properties are required for sorbent materials to achieve an industrially feasible process: ▫ high sorbent capacity; ▫ high selectivity; ▫ good mechanical strength; ▫ stable adsorption capacity after cycles; ▫ adequate adsorption/desorption kinetics under

operating conditions; ▫ regenerability of sorbent without extreme temperature

and pressure conditions; ▫ tolerance to the presence of water and impurities (H2S,

NH3, HCl);

Materials: hydrotalcite-like compounds

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• Synthesis method1,2: low supersaturation @ pH= 8÷10

• Thermal treatments: drying at 120°C for 24 h, calcination at 700°C or 450°C for 8 h.

• Incipient wet impregnation with K2CO3 (20%w)

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1Narayanan, S. and Krishna, K., (1998). Applied Catalysis A: General, 174(1-2), 221-229. 2 Gallucci, K., Micheli, F., Parabello, L., Rossi, L. and Foscolo, P.U., (2014). GPE – 4th International Congress on Green Process Engineering, 7-10 April 2014, Sevilla (Spain)

Sample identification Composition Calcination temperature

HT1-700 Mg : Al = 2 : 1

700°C

HT2-700 Ca : Al = 2 : 1

HT3-700 Mg : Ca : Al = 1 : 1 : 1

HT1K-700 HT1 + K2CO3 (20%w)

HT2K-700 HT2 + K2CO3 (20%w)

HT3K-700 HT3 + K2CO3 (20%w)

HT1-450 Mg : Al = 2 : 1

450°C HT3-450 Mg : Ca : Al = 1 : 1 : 1

HT1K-450 HT1 + K2CO3 (20%w)

HT3K-450 HT3 + K2CO3 (20%w)

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Materials: tested sorbents MFIP 2014

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Kinetic study: TG-DTA signals

n = 1.26 · S½

Reaction order

Activation energy

TG-DTA Linseis L81 analyser with L40/2053 gas flow control system

Results

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Decomposed compound

Temperature range (°C)

Reaction order Activation energy (kcal/mol)

HT1 HT2 HT3 HT1 HT2 HT3

Water 70-190 n.a. 1.06 - n.a. 8.36 -

R1 190-280 0.79 0.69 - 19.4 24.6 -

R2 280-405 0.43 - 58.2 -

Carbonates 850-1000 - 1.65 1.51 - 205 216

R1: Dehydroxilation of Al-OH R2: Decomposition of Mg(OH)2 superimposed to CO2 release

XDR characterisation before tests

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XRD patterns of: (a) dry HT1

0 10 20 30 40 50 60 70 80

In

ten

sit

y (

a.u

.)

2θ

(a)

*

**

**

**

*

*

*

*: Hydrotalcite

0 10 20 30 40 50 60 70 80

In

ten

sit

y (

a.u

.)

2θ

(b)

(c)

(d)

Δ

Δ

ΔΔ

Δ

Δ

Δ

Δ

Δ

ΔΔ

Δ: Periclase

x: Aluminum Oxide

■: Dawsonite, potassic

x

x

x

Δ

XRD patterns of: (b) HT1-700, (c) HT1-450, (d) HT1K-450

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PANanalyticalX'Pert PRO XRD diffractometer

16

0 10 20 30 40 50 60 70 80

In

ten

sit

y [

a.u

.]

2θ

(a)

(b)

(c)

: Calcium carbonate

+: Aragonite●: Aluminum Hydroxide

: Lime

#: Calcium Hydroxide

- : Mayenite^: Calcium Aluminum Oxide Hydrate

' : Calcium Oxide

: Potassium Calcium Carbonate

○

○

○○

○

○ ○

○○

○

○○○

○ ○+

++++

++++++

++ +++

○ ○ ○

#

###

##

#

#

#

----

-

-

----

-

--- - --^ ^^^^^^^

^''

'- -

XRD patterns of: (a) dry HT2, (b), HT2-700, (c) HT2K-700

XRD patterns of: (a) dry HT3, (b), HT3-700, (c) HT3-450,

(d) HT3K-700, (e) HT3K-450

0 10 20 30 40 50 60 70 80

In

ten

sit

y (

a.u

.)

2θ

(a)

(b)

(c)

(d)

***

*●*

#'

######

'''

'

ΔΔ

◊ ◊◊◊ ◊ ◊~~

*: Hydrotalcite

: Calcium Carbonate

●: Aluminum Hydroxide

Δ: Periclase

#: Calcium Hydroxide

~: Aluminum Oxide Hydroxide

' : Calcium Oxide

: Potassium Calcium Carbonate

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FT-IR analysis before tests

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IR Vibration [cm-1] samples after drying

1400-1600 Carbonate area

2700-4000 Physically adsorbed water Vibration of OH- groups

HT1 HT2 HT3 “Free anion” 1415: asymmetric stretching 880: out of plane deformation 680: in plane deformation (Busca e Lorenzelli, 1982) 2510: C-O stretching mode of calcite (Andersen and Brecevic, 1991)

1348 2507 2507

867 1014 1380

657 711 1014

871 854

640

IR Vibration [cm-1] samples after calcination

HT1 HT2 HT3 1535-1430: asymmetric stretching of carbonates (Walspurger et al. 2008) OH- stretching of Ca(OH)2 (Fernández-Carrasco L et al. 2012)

1400 1475

1405 1452

1405 1452

3641 3641

ThermoNicolet FT-IR Nexus 870 spectrophotometer

Experimental apparatus: PSA plant

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Flowsheet of the laboratory scale plant: 1: evaporator; 2: microreactor; 3: electric furnace; 4: chiller; 5: analyser.

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Capture tests: operating conditions

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Dry tests Wet tests

Adsorption Regeneration Adsorption Regeneration

Temperature 350°C

Pressure 5 bar

(100% CO2) 1 bar

5 bar (85%v CO2)

1 bar

N2 dilution flowrate 1 Nl/min

CO2 flowrate 50 Nml/min

H2O(l) flowrate - - 6 l/min (15%v as steam)

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Capture tests: Adsorption model

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[CO

2(t

)]/[

CO

2] f

inal

Capture tests: results

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0

0.5

1

1.5

2

2.5

So

rp

tio

n c

ap

ac

ity

[m

mo

lCO

2/g

so

rb

en

t]

Dry conditions

Wet conditions

Characterisation after tests

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0 10 20 30 40 50 60 70 80

Inte

nsi

ty (

a.u

.)

2θ

(a)

(b)

(c)

(d)

Δ

Δ

Δ

Δ

Δ

x

Δ

Δ

Δ

Δ

Δ

x

↓

x

Δ

ΔΔ

Δ Δ

Δ Δ

↓

↓

↓

↓

↓↓

↓

↓

ⱡ

ⱡⱡⱡⱡΔ

Δ

Δ

Δ

ⱡ ↓↓ⱡ

Δ: Periclase

ⱡ: Potassium Carbonate↓: Silicon Oxide

x: Aluminum Oxide

XRD patterns after dry tests of: (a) HT1-700, (b) HT1-450, (c) HT1K-700, (d) HT1K-450

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0 10 20 30 40 50 60 70 80

In

ten

sit

y [

a.u

.]

2θ

(a)

(b)

○

○ ○○○

○

○

○○

◊

○

◊◊◊

○ ○ ○○

#

-

##

#

↓ ↓↓

↓

◊◊

◊

◊

-

-

--

-

-

-

-

-

-

-

---

--

- ----

-

-- ----

: Calcium carbonate

#: Calcium Hydroxide

- : Mayenite : Potassium Calcium Carbonate

↓: Silcon Oxide

XRD patterns of tested samples: (a) HT2-700, (b), HT2K-700

0 10 20 30 40 50 60 70 80

In

ten

sit

y [

a.u

.]

2θ

(a)

(b)

(c)

(d)

: Calcium Carbonate

Δ: Periclase

#: Calcium Hydroxide

~: Aluminum Oxide Hydroxide

: Potassium Calcium Carbonate

: Magnesium Calcite

#

#

#

#

↓ Δ

Δ

# #

#

#

#

◊ ◊#

◊ # # #

◊~

◊◊ ◊

◊ #

~

◊ # ~

XRD patterns of tested samples: (a)HT3-700, (b) HT3-450,

(c) HT3K-700, (d) HT3K-450

FT-IR analysis • Similar results for HT1-450

and HT1-700: Slight increase of the asymmetrical

vibration mode of the carbonate ν3 at 1494 cm-1 and a decrease at 1403 cm-1

• HT1K-450 and HT1K-700 • Increase of ν3 asymmetrical

carbonate peaks • Increase of a peak at 1043 cm-1 • Possible chemical interaction

among potassium, hydrotalcite and CO2

• HT2-700 • Two sharp peaks arise at 1423 and

837 cm-1 derived from the chemisorption of CO2 on CaO (Busca e Lorenzelli, 1982)

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Conclusions

• Sorption capacities increased of 30% at 5bar with respect atmospheric test1

• HT1_700 is the best sorbent in dry conditions (1.6 mmolco2/gsorbent)

• HT1_450 is the best sorbent in wet conditions (1.25 mmolco2/gsorbent)

• Potassium impregnation stabilises trend under cyclic conditions

• Future development: Further studies on potassium impregnation

Long-term cyclic experiments

Higher pressure tests (up to 30 bar, and 400°C) with a new designed reactor.

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1 Gallucci, K., Micheli, F., Parabello, L., Rossi, L. and Foscolo, P.U. GPE – 4th International Congress on Green Process Engineering, 7-10 April 2014, Sevilla (Spain)

ACKNOWLEDGEMENTS

• Authors are grateful to:

▫ Prof. Giuliana Taglieri and MEng Ilaria Aloisi for XRD analysis

▫ Mrs. Fabiola Ferrante for FT-IR and TG-DTA analysis.

▫ ENEA (Italian National Agency for Energy and Environment) for financial support.

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Thank you for your attention!

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