Comparison of commercial and new developed adsorbent … · 2014. 11. 17. · Comparison of commercial and new developed adsorbent materials for pre-combustion CO 2 capture by pressure

Comparison of commercial and new developed adsorbent materials for pre-combustion CO2

capture by pressure swing adsorption

TCCS-6Trondheim, Norway15.06.2011

Johanna Schell, Nathalie Casas, Lisa Joss, Marco Mazzotti - ETH Zurich, Switzerland

Richard Blom, SINTEF Materials and Chemistry, Oslo, Norway

TCCS-6 – Trondheim 15.06.2011 Schell, Casas, Joss, Blom, Mazzotti 2

CO2CO2, H2

CO2 capture in an IGCC power plant

Gasifier Shift CO2 / H2separation

Gas turbine Steam cycleASU

CO2compressionCoal

Air air

CO2

electricity

O2 H2


CO2 to storage:

H2 to gas turbine:

CO2 / H2 separation by PSA promising

Pressure 35 bar

CO2 fraction 40%

H2 fraction 60%

CO2 purity > 95%

Capture > 90%

Pressure 110 bar

H2 purity ≈ 94%

Pressure ≈ 25 bar

CO2 capture in an IGCC power plant

CO2 / H2separation


PSA cycle possibilities

High pressure product

Low pressure product

LPHP HPLPLP HP

Classical Skarstorm cycle used to produce high purity high p product (e.g. H2)

consists of 4 basic steps: Pressurization with Feed Adsorption Countercurrent blowdown Purge with high pressure product

In more advaced cycles more steps are applied, e.g.:

Pressure equalization Purge with other than product Cocurrent blowdown …Steps can be combined in multiple ways

Complex process design


ApproachMaterials

Commercial and new materials


Static experimentsRubothermMSB

ApproachMaterials

Commercial and new materials



Approach

TI

PI

TI

TI

PI

Col

umn

TI

TI

TI

TIC

110 cm

85 cm

60 cm

40 cm

10 cm

TI

Two column PSA setup

Dynamic experiments

MaterialsCommercial and new materials



Approach

TI

PI

TI

TI

PI

Col

umn

TI

TI

TI

TIC

110 cm

85 cm

60 cm

40 cm

10 cm

TI


Dynamic experiments

Process modelingMass, energy and momentum balances, Isotherms & EOS

voidsadsorbent

ε ∗

(1 )ε ∗−icu

inP T

sTwT




Approach

Model-based Process Design TI

PI

TI

TI

PI

Col

umn

TI

TI

TI

TIC

110 cm

85 cm

60 cm

40 cm

10 cm

TI


Dynamic experiments


voidsadsorbent

ε ∗

(1 )ε ∗−icu

inP T

sTwT




Approach


PI

TI

TI

PI

Col

umn

TI

TI

TI

TIC

110 cm

85 cm

60 cm

40 cm

10 cm

TI


Dynamic experiments



voidsadsorbent

ε ∗

(1 )ε ∗−icu

inP T

sTwT


Commercial material Activated carbon AC AP3-60, Chemviron, Germany

New adsorbent material (SINTEF) USO-2-Ni MOF (Ni2(1.4-bdc)2(dabco)∙4DMF∙0.5H2O) Mesoporous silica MCM-41

Adsorbent materials


Commercial material Activated carbon AC AP3-60, Chemviron, Germany

New adsorbent material (SINTEF) USO-2-Ni MOF (Ni2(1.4-bdc)2(dabco)∙4DMF∙0.5H2O) Mesoporous silica MCM-41

Adsorbent materials

New materials synthesized as powder For process application: formulation as pellets crucial No well established method 4 Different formulation methods investigated Particle size: 35 -70 mesh



Approach


PI

TI

TI

PI

Col

umn

TI

TI

TI

TIC

110 cm

85 cm

60 cm

40 cm

10 cm

TI


Dynamic experiments



voidsadsorbent

ε ∗

(1 )ε ∗−icu

inP T

sTwT


Equilibrium measurements

Isotherm measurements using Rubotherm MSB

CO2 H2 N2 Mix

ACT 25-140°C 25-65°C 25-140°C 25°C

p 0.1-210 bar 0.1-140 bar 0.05-200 bar 5-120 bar

MOFT 25-140°C 25-65°C - -

p 0.1-125 bar 1-115 bar - -

MCM-41T 25-140°C In progress - -

p 0.2-154 bar - -

Exp. excess Isotherms


Equilibrium measurements

Isotherm measurements using Rubotherm MSB

CO2 H2 N2 Mix

ACT 25-140°C 25-65°C 25-140°C 25°C

p 0.1-210 bar 0.1-140 bar 0.05-200 bar 5-120 bar

MOFT 25-140°C 25-65°C - -

p 0.1-125 bar 1-115 bar - -

MCM-41T 25-140°C In progress - -

p 0.2-154 bar - -

Exp. excess Isotherms

Excess Absolut

Parameter Fitting

Selection Isotherm eq.

Mathematical description of adsorption equilibrium


AC: pure component isotherms

CO2N2H2

AC AC AC


25°C

45°C

45°C25°C

45°C

25°C

H2

CO2

N2

Isotherm parameters used for: Absolute adsorption Heat of adsorption (Clausius Clapeyron) Prediction of binary adsorption, e.g.:

o Empirical binary isotherm (e.g. Langmuir)o IAST

Cyclic capacity evaluation of suitability

AC: pure component isotherms

CO2N2H2

AC AC AC


Comparison: pure component isotherms

AC

MCM-41MOF

CO2 isotherms at 25°C


Comparison: pure component isotherms

AC

MCM-41MOF

MOF

MCM-41AC

Zeolite [1]

CO2 isotherms at 25°C Cyclic capacitypAds = 1.5 MPa, pDes varying

[1] Xiao et al., Adsorption 14 (2008)



Approach


PI

TI

TI

PI

Col

umn

TI

TI

TI

TIC

110 cm

85 cm

60 cm

40 cm

10 cm

TI


Dynamic experiments



voidsadsorbent

ε ∗

(1 )ε ∗−icu

inP T

sTwT


( ) ( ) ( )ν ενγε ε ε∗ ∗ ∗

=

∂∂∂∂ ∂ ∂ + + − −∆ + − − = ∂ ∂ ∂ ∂ ∂ ∂ ∑s L L

w1g gg

21 0z

nj

jj i

nuTT h KT TH T Tt t C t C z zr C

( ) ενε ε∗ ∗

∂∂ ∂ ∂∂ + + − = ∂ ∂ ∂ ∂ ∂ Li

1 0z

ii i iucc n cDt t z z

1. Mass balances species i

Model equations of an adsorption column

Accumulation Convection Dispersion

2. Energy balances

Heat of adsorption Exchange wallAccumulation Convection

( )∗∂= −

∂ pi

i i in k a n nt

( ) ( )=

∂∂= −∆ + −

∂ ∂∑ s pss

1s s

1 nj

jj

n h aTH T T

t C t C

Dispersion

Exchangegas - solid

Heat of adsorption

3. Constitutive equations

1. Non linear adsorption isotherm:

2. Equation of State: Ideal gas law

3. Pressure: Ergun equation

voidsadsorbent

ε ∗

(1 )ε ∗−icu

inP T

sTwT

Acc

Linear driving force

*i( , , )

iin n p T y∗ =


1. Non linear adsorption isotherm:

2. Equation of State: Ideal gas law

3. Pressure: Ergun equation

1. Mass balances species i

2. Energy balances

Linear driving force

( ) ( ) ( )ν ενγε ε ε∗ ∗ ∗

=

∂∂∂∂ ∂ ∂ + + − −∆ + − − = ∂ ∂ ∂ ∂ ∂ ∂ ∑s L L

w1g gg

21 0z

nj

jj i

nuTT h KT TH T Tt t C t C z zr C

( ) ( )=

∂∂= −∆ + −

∂ ∂∑ s pss

1s s

1 nj

jj

n h aTH T T

t C t C

( )∗∂= −

∂ pi

i i in k a n nt

( ) ενε ε∗ ∗

∂∂ ∂ ∂∂ + + − = ∂ ∂ ∂ ∂ ∂ Li

1 0z

ii i iucc n cDt t z z

Model equations of an adsorption column

voidsadsorbent

ε ∗

(1 )ε ∗−icu

inP T

sTwT

3. Constitutive equations

*i( , , )

iin n p T y∗ =



Approach


PI

TI

TI

PI

Col

umn

TI

TI

TI

TIC

110 cm

85 cm

60 cm

40 cm

10 cm

TI


Dynamic experiments



voidsadsorbent

ε ∗

(1 )ε ∗−icu

inP T

sTwT


Experimental setup: 2-column Lab PSA

Breakthrough experiments

PSA cycles including p equalization

Fully automated

Premixed gases

Column insulation and heating

p and T measurements

Product streams online analyzed by MS


Breakthrough and PSA experiments

Breakthrough experiments Fit the missing

model parameters

H2

CO2

10 cm

40 cm 60 cm 85 cm110 cm

T = 25°Cp = 15 bar


Breakthrough and PSA experiments

Breakthrough experiments Fit the missing

model parameters

PSA experiments Validate the PSA

simulation tool Exp. testing of

full PSA cycles

H2

CO2

10 cm

40 cm 60 cm 85 cm110 cm

H2

CO2

H2

CO2H2 rich product CO2 rich product

T = 25°Cp = 15 bar



Approach


PI

TI

TI

PI

Col

umn

TI

TI

TI

TIC

110 cm

85 cm

60 cm

40 cm

10 cm

TI


Dynamic experiments



voidsadsorbent

ε ∗

(1 )ε ∗−icu

inP T

sTwT


Process Design criteriaCO2 to storage:

H2 to gas turbine

CO2 purity > 95%

Capture > 90%

Pressure 110 bar

CO2 / H2separation

Feed

Specifications & boundary conditions: CO2 purity and capture rate purge with the feed co-current blowdown

Minimize energy penalty (compression costs): no repressurization increase CO2 desorption pressure

Investments cost: max. 3 p-equalization steps


Process Design criteriaCO2 to storage:

H2 to gas turbine

CO2 purity > 95%

Capture > 90%

Pressure 110 bar

CO2 / H2separation

Feed

Specifications & boundary conditions: CO2 purity and capture rate purge with the feed co-current blowdown

Minimize energy penalty (compression costs): no repressurization increase CO2 desorption pressure

Investments cost: max. 3 p-equalization steps

For fixed material, T and pDes: process performance dependent on tads, tblow & tpurge


CO2 purity

CO2 capture rate

Influence of the adsorption step time (AC) Change of time of the adsorption step Time of blowdown and purge step already optimized

T = 308 KpDes = 1 bar


CO2 purity

CO2 capture rate


Change of time of the adsorption step Time of blowdown and purge step already optimized

Trade-off Better shown as pareto front


Influence of the adsorption step time (AC)


AC comparison: process conditions Different desorption pressures T = 308 K

pDes = 2 bar

pDes = 1 bar


AC comparison: process conditions Different desorption pressures T = 308 K

Different process temperatures pDes = 1 bar

pDes = 2 bar

pDes = 1 bar T = 308 K

T = 338 K


Comparison: AC MOF MOF with “real” physical properties

compared to theoretical MOF T = 308 K, pDes = 1 bar

theoretical MOF

“real” MOF


Comparison: AC MOF MOF with “real” physical properties

compared to theoretical MOF T = 308 K, pDes = 1 bar

Theoretical MOF compared to AC T = 308 K, pDes = 1 bar

“real” MOF

theoretical MOF

AC

theoretical MOF


Conclusions

PSA for pre-combustion very promising because of boundary conditions and

process specifications

Model-based process design beneficial due to various process configurations

Model parameters have to be determined in a reliable way

Pareto front to compare different process conditions and materials

MOF shows promising behavior however material formulation very important

for process performance

Documents

Comparison of commercial and new developed adsorbent … · 2014. 11. 17. · Comparison of commercial and new developed adsorbent materials for pre-combustion CO 2 capture by pressure