adsorciÓn de gases aplicadaa procesos deaplicada a...

Universidade

Anos15

Federal do Ceará

ADSORCIÓN DE GASES APLICADA A PROCESOS DEAPLICADA A PROCESOS DE

ALMACENAMIENTO Y SEPARACIÓNSEPARACIÓN

Diana C. S.AzevedoUniversidade Federal do Ceará

Departamento de Engenharia QuímicaGrupo de Pesquisa em Separações por Adsorção

San Luis, 25 de Febrero de 2009

Grupo de Pesquisa em Separações por Adsorção

Universidade

Anos15Brasil – Ceará – Fortaleza UFCFederal do Ceará – UFC

Universidade

Anos15www.deq.ufc.brFederal do Ceará

Universidade

Anos15Nuevas tecnologías para un medio ambiente más limpioFederal do Ceará medio ambiente más limpio

Salvador, Bahia15 a 19 de júnio de 2009Curso de formación complementária de la UNIAwww.unia.es

• El hidrógeno como combustible

TEMAS

galternativo.

• Nanotecnologías y medio ambiente

• Control catalítico de emisiones de NOx

•Nuevos materiales para la obtención de combustibles via Fischer-Tropsch

• Biocombustibles; situación actual y perspectivas

Universidade

Anos15OutlineFederal do Ceará

Adsorption for storage purposes – the case of natural gasp g p p gActivated carbon, the unbeatable sorbent

Measurement of adsorption equilibrium (methods, pros and cons, data)

Charge and discharge cycles (long term performance)

Multicomponent adsorption measurements

Adsorption for separation purposes – the case of CO2 captureSome FAQs about CCS – CO2 capture and storage

Suitable adsorbents and adsorption measurements

Column dynamics and PSA processes

Concluding remarksConcluding remarks

Universidade

Anos15Evolution of publications (W b f S i )Federal do Ceará (Web of Science)

300

Keywords: adsorption and gas and storage

400

Keywords: CO2 and capture Keywords: adsorption and gas and stora

150

200

250

Web

of S

cien

ce)

200

250

300

350

Web

of S

cien

ce)

0

50

100

Publ

icat

ions

(W

0

50

100

150

Publ

icat

ions

(W2000 2002 2004 2006 2008

0

Year

1998 2000 2002 2004 2006 20080

Year

Universidade

Anos15Principles of adsorptionFederal do Ceará

Ex.: H2 and He are practically not

Adsorbedphase

adsorbed.

Bulk fluid phase

Important factors:Volatility (Tc)

P l it (di l / d lPolarity (dipole/quadrupole moment)

Sorbent surface area / pore gases at bi t ditiSorbent surface area / pore

volume / PSD / surface chemistry

ambient conditions

Universidade

Anos15Excess Adsorbed Phase Concentration mFederal do Ceará Concentration, mex

Sorbate gasSorbate gas

AA

nsity

nsity

solidsolid

Compressed gas

Excess adsorbed mass, mex

den

den Compressed gas

in void space

CC

ρρff

ρρ = 0= 0

BB

00 distance from solid surfacedistance from solid surface

ρρ

Universidade

Anos15Absolute Adsorbed Phase Concentration mFederal do Ceará Concentration, mabs

- Dreisbach et al.,

solidsolid Adsorbed layer(s)Adsorbed layer(s) Sorbate gasSorbate gas

Ab l d b d

Dreisbach et al., Adsorption 8, 95, 2002.- Do and Do, Carbon 41, 1777, 2003- Bastos-Neto et al.,

AA

nsity

nsity

Remaining

Absolute adsorbed amount, mabs

Bastos Neto et al., Adsorption 11, 911, 2005

For vapors,

den

den g

compressed gasp ,

ρf << ρads (~ρliq)Hence mex ~ mabs

BB CC

ρρff

ρρ = 0= 0

For gases,ρf is comparable to ρadsH00 LL

Distance from surfaceDistance from surface

ρρHence mex < mabs

Universidade

Anos15Why Store Natural

Gas in Brazil?Federal do Ceará

ENERGY SOURCES (%)2000 2020

Petroleum Derivatives 43 40

Hydro 30 16Hydro 30 16

Ethanol/Bagasse 11 12

Wood 8 6

Coal 5 6

Natural Gas 3 20

Universidade

Anos15Why Store Natural

Gas in Brazil?Federal do Ceará

“Mobile pipelines” alternatives:

Liquified (LNG): 600

Vol Ratio (Gas/Vessel)

Liquified (LNG): 600

Compressed (CNG): 200

Adsorbed (ANG): Today 60-100

DOE Target 150 (180)

Universidade

Anos15What to look for in an adsorbent for gas storage?Federal do Ceará adsorbent for gas storage?

High capacityHigh capacitySelectivity for the target stored moleculemoleculeIrreversibility/regenerabilityLow costLow costChemical inertnessHigh bulk density (if stored volume is High bulk density (if stored volume is an issue)Mechanical resistanceMechanical resistance

Universidade

Anos15Activated carbon: the unbeatable sorbent for NG storageFederal do Ceará sorbent for NG storage

• Hydrophobic character, affinity for organic molecules

• Inexpensive raw material (agroindustrial/lignocellulosic wastes)

• Possibility of tailoring surface area and PSD according to activation proceduresactivation procedures

Universidade

Anos15Coconut shell-based activated carbonsFederal do Ceará

Sample Activation Agent

Pirolysis Conditions

BET area(m2/g)

Micropore Volume (cm3/g)

Stored Methane

(V/V)(cm3/g) (V/V)

Sutcliffe (SRD-21) _ _ 1967 0.945 105

Mead Westvaco - - 1906 0.984 80

CA29W2 (air) H3PO4 450/1/2:00 727 0.384 --CA29W2 (air) H3PO4 450/1/2:00 727 0.384

CA36W2 (air) H3PO4 450/1/2:00 844 0.502 95

CA44W2 (air) H3PO4 450/1/2:00 767 0.440 --

CA51W2 (air) H3PO4 450/1/2:00 779 0.441 59[1][2]

( ) 3 4

CA51W2N H3PO4 450/1/2:00 1441 0.729 82

CAQF-30 ZnCl2 500/4/3:00 2114 1.142 82

CAQ-26 ZnCl2 500/4/3:00 1048 0.705 --

CAQ-29 ZnCl2 500/4/3:00 1266 0.628 --

CAQF-P (0.09) H3PO4 850/10/2:20 -- ~0.600 85

CAQF-Zn (0.25) ZnCl2 850/10/2:20 -- ~ 0.55 86[3]

[1] Azevedo et al. Microporous and Mesoporous Materials 99 (2007) 360. [2] Rios et al. Adsorption (2009) accepted.[3] Prauchner and Rodríguez-Reinoso Microporous and Mesoporous Materials 109 (2008) 581

Universidade

Anos15Which factors determine

adsorption capacity?Federal do Ceará

p p y

Although it is accepted that adsorption capacity is proportional to surface area,

Carbon sample

BET Surface

Area

Average Pore

Width –HK

Total Pore Volume

(cm3.g-1)

Micropore Volume -

DR

Micropore Volume -

MC(m2.g-1) HK

(Å) (cm3.g-1) (cm3.g-1)

C1 1822 15.0 1.114 0.749 0.988

C2 1522 12.5 0.957 0.674 0.850

C3 1261 13.0 0.775 0.550 0.795

C4 1438 12.3 0.924 0.761 0.953

C5 1668 11.1 1.041 0.625 0.901

C6 2021 14.5 1.299 1.123 1.166

C7 1512 12.2 0.873 0.793 0.793

C8 1301 13.8 0.775 0.712 0.461

C9 1052 13.7 0.622 0.576 0.603

C10 2336 13.1 1.431 0.958 1.296

Universidade

Anos15Which factors determine adsorption capacity?Federal do Ceará adsorption capacity?

C10180

C5C1

C10

120140160180

5 ba

r (m

g/g)

C8

C9C7

C3 C2C4

C6

6080

100120

etha

ne @

35

0204060

Ads

orbe

d m

e

0.6 0.8 1.0 1.20A

MC micropore volume (cm3/g)

Bastos Neto et al. Applied Surface Science 253 (2007) 721.

Universidade

Anos15Are all pores of an activated

carbon really slit-like?Federal do Ceará

ySAMPLE 53W2 N

0 5

0,6 Slit pore geometry. Fit Error = 5.09 e-2

SS

1 2 3 4 5

0,1

0,2

0,3

0,4

0,5

P

SD

(cm

3 / g إ

)

3

-2

1 2 3 4 5

3

-2

SLIT

kcal

/ m

ol )

0,3

Light gray: Total PSDD k Slit PSD

Mixed geomatry. Fit Error = 5.44 e-2

)

5 10 15 20 25 30 35 40 450,0

0,1

-4

-3

-4

-3

TRIANGULAR

alue

of U

gs (

k

0,1

0,2Dark gray: Slit PSD

P

SD

(cm

3 / g إ

-6

-5

-6

-5

min

imum

va

5 10 15 20 25 30 35 40 450,0

Pore Size (A)

AZEVEDO et al Journal of Materials1 2 3 4 5

effective size / sigma_gg

AZEVEDO et al. Journal of Materials Chemistry 2009 (in press)

Universidade










Universidade

Anos15Measurement of Adsorption Equilibrium DataFederal do Ceará Equilibrium Data

Pure Gas Isotherm

Gravimetry

Volumetryy

Break through curves

Mixed Gas Isotherm

Volume-Gravimetry

Volumetry with Gas chromatography (GC)

Modified van Ness Method

Sum-Isotherm-Method

Universidade

Anos15GravimetryFederal do Ceará

C lib ti fCAL CAL

electromagnet

Calibration of instrument:sample holder and solid sampleelectromagnet

permanent

solid sample specific volume

Measurement:Tmagnet

position sensor

p, T, mMB

Calculation:

adsorbent ),()(

),(),(TpVV

TpmTpm

fsb

MBex

ρ⋅+

+=

sample

mex is the ACTUALLY and ACCURATELY measured quantity !!!

Universidade

Anos15VolumetryFederal do Ceará

p* pT* Tp pT T

V* V VP

SGS mS

Calibration of instrument: m = m Vads (p T)Calibration of instrument:Volume of vessel ...

Measurement: p, T

mex = mabs - Vads ⋅ ρf(p,T)= V* ⋅ ρf(p*,T*) - (V*+V) ⋅ ρf(p,T)


Universidade

Anos15Breakthrough curvesFederal do Ceará

C t ti 8 Calibration of Concentration

Time

16

7

8

CO

C b o oinstrument:bulk density ...

Measurement:

1234

Temp.Temp.Temp.Temp. °C

°C°C°C

124

5

7 Measurement:concentration c(t),massflow mflowtime t

PressureTemp. °C

bar

12

3

1 Gas supply

He

time t

Calculation:

Vmm ρ=1 Gas supply2 Flowmeter3 Pressure/temp. gauge4 Adsorber

5 Thermocouples6 Capacitor

7 Impedance analyser8 Concentration detector (TCD)

fadsabsex Vmm ρ−=

fcolflow Vtm ρ×−×=•


Universidade

Anos15Measurement of Adsorption Equilibrium Data – pros and consFederal do Ceará

Gravimetry Volumetry Breakthrough curve

Equilibrium Data pros and cons

• Direct measurement of m, p, T

• Mass change during

• Direct measurement of p, T

• “Simple” apparatus

• Direct measurement of c, p, T

• “Simple” apparatus• Mass change during sample preparation

• Uptake curve

• Simple apparatus

• Adsorption isotherm

• Simple apparatus

• Concentration dependency in carrier gas

• Adsorption isotherm, (Kinetics)

• Close to technical separation

G i V l B k h h G i dGravimetry Volumetry Breakthrough Gravimetry dyn.

Δm/m = 0.1 % Δm/m = 0.5 % Δm/m = 0.5 % Δm/m = 0.25 %

R. Staudt, Proceedings of FOA 8, Sedona, USA, 2004

Universidade

Anos15Adsorption isotherms for selected gases at high pressuresFederal do Ceará gases at high pressures

0,6

0,7

0,8 Temperature 298K

CO2 CH4 500

m T = 343 K mc = 641 8 mg/g

0,3

0,4

0,5

,

ex (g

/g)

N2

adso

rbed

[mg/

g]

300

400

mexp, T = 343 KmLF,T , T = 343 Kmexp, T = 328 K mLF,T , T = 328 Kmexp, T = 313 KmLF,T , T = 313 K

mc 641.8 mg/gα = 1.05bC = 1.06 1/MPaE = 13.41 kJ/kmolVpore = 0.56 cm3/g

0,0

0,1

0,2

Me

Exc

ess

amou

nt a

100

200

0 10 20 30 40 50 60-0,1

Pressure ( bar) Pressure [MPa]0 10 20 30 40 50

0

Activated carbon MeadActivated carbon Mead Westvaco WV 1050

CO2 on activated carbon Norit R1 Extra

Universidade

Anos15Adsorption isotherms for natural gas componentsFederal do Ceará gas components

0,12

0,14

carvao: WV1050 - WestvacoMetano

g/g)

0,35

0,40

carvão: WV1050 - WestvacoEtano

g/g)

Amora et al., LAAR 2009 (in press)

0,06

0,08

0,10

0,12

so p

or m

assa

de

carv

ão (

0,15

0,20

0,25

0,30

,

so p

or m

assa

de

carv

ão (g

0 10 20 30 40 50 60 70

0,00

0,02

0,04

mas

sa d

e ex

cess

10 0C 20 0C 30 0C 40 0C 60 0C 80 0C

-0,05

0,00

0,05

0,10

mas

sa d

e ex

cess

10 0C 20 0C 25 0C 30 0C

0 10 20 30 40 50 60 70

pressão (bar)0 5 10 15 20 25 30 35

pressão (bar)

0,4

0,5carvao: WV1050 - WestvacoPropano

de c

arvã

o (g

/g)

0 35

0,40

0,45

0,50

0,55

0 35

0,40

0,45

0,50

0,55

de c

arvã

o (g

/g)

Butano

Propano

0,1

0,2

0,3

a de

exc

esso

por

mas

sa d

20 0C30 0C 0 10

0,15

0,20

0,25

0,30

0,35

0 10

0,15

0,20

0,25

0,30

0,35Etano

ssa

adso

rvid

a po

r mas

sa

Metano

0 1 2 3 4 5 6 7

0,0

mas

sa

pressão (bar)

30 0C

0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,00,00

0,05

0,10

0,00

0,05

0,10

mas

pressão relativa

Universidade

Anos15Determination of isosteric heat of adsorptionFederal do Ceará heat of adsorption

0,10

0,12

vão

(g/g

)

3,23,4

3,63,8

4,0 lnP LnP LnP LnP Linear Fit of Mex1_lnP Linear Fit of Mex2_LnP Linear Fit of Mex3_LnP Linear Fit of Mex4_LnP

0,04

0,06

0,08

sso

por M

assa

de

Carv

1020 2,0

2,2

2,42,6

2,83,0

lnP

0,00

0,02

,

Mas

sa d

e Ex

ces 20

30 40 60 80

0 0028 0 0029 0 0030 0 0031 0 0032 0 0033 0 0034 0 0035 0 0036

1,0

1,21,4

1,61,8

[ ]ln Hp AdsΔ−=⎟

⎞⎜⎛ ∂ [ ]pRH ⎟⎟

⎞⎜⎜⎛ ∂⋅=Δ ln

-10 0 10 20 30 40 50 60 70

Pressão (bar)

0,0028 0,0029 0,0030 0,0031 0,0032 0,0033 0,0034 0,0035 0,0036

1/T

[ ] 2lnRT

pT mex

⎟⎠

⎜⎝ ∂ ( ) [ ]

exmAds p

TRH ⎟⎟

⎠⎜⎜⎝ ∂

=Δ ln1

Universidade

Anos15Adsorption capacity and delivery (methane)Federal do Ceará delivery (methane)

130 130

100

105

110

115

120

125

20°C

Dis

poni

bilid

ade

(V/V

)

90

100

110

120

ou D

ispo

nibi

lidad

e (v

/v)

70

75

80

85

90

95

VARM CAQF30 DARM CAQF30 VARM SRD

me

Arm

azen

ado

ou D

50

60

70

80

sida

de d

e A

rmaz

enam

ento

Densidade de Armazeamento Disponibilidade

30 35 40 45 50 55 6060

65ARM

DARM SRD

Volu

m

Pressão (bar)20 30 40 50 60 70 80

40

50

Den

s

Pressão (bar)

( ) ( )TpVTpmTpm ,),(),( ρ⋅+=

bTpmTRTpV ρ⋅⋅⋅

= ),(),( 0

[ ]TR ⋅

( ) ( )TpVTpmTpm vexarm ,),(),( ρ+

barmarm TpmpM

TpV ρ⋅

),(),(0 [ ]),(),(

0

0 TpmTpmpMTR

D oarmarmbarm −⋅⋅⋅

= ρ

Universidade










Universidade

Anos15Charge and Discharge CyclesFederal do Ceará

Universidade

Anos15Charge and Discharge Cycles (typical

transient behaviour on one cycle)Federal do Ceará

y )

1,2

1,2

1,4

Dados ExperimentaisSimulação

Bastos-Neto et al., Adsorption 11 (2005) 47

0,6

0,8

1,0

ssa

arm

azen

ada

(kg)

0,6

0,8

1,0

,

ssa

arm

azen

ada

(kg)

0 50 100 150 200 250 300

0,0

0,2

0,4

Dados Experimentais Simulação

mas

0 50 100 150 200 250 3000,0

0,2

0,4

mas

0 50 100 150 200 250 300

tempo (min)

0 50 100 150 200 250 300tempo (min)

325

330

dia

(K)

Dados Experimentais Simulação

300

305

310

a (K

)

310

315

320

tem

pera

tura

méd

285

290

295

300te

mpe

ratu

ra m

édia

0 50 100 150 200 250 300

300

305

tempo (min)0 50 100 150 200 250 300

275

280 Dados Experimentais Simulação

tempo (min)

Universidade

Anos15Charge and Discharge Cycles (long-term performance)Federal do Ceará (long term performance)

0.10

0.12

Rios et al., unpublished

0 04

0.06

0.08

rbed

am

ount

(g/g

)

Adsorption of NG

results

Calorific

P i t l Ch E P 44 (2005) 71 0 5 10 15 20 25 30 35 40

0.00

0.02

0.04

adso

r p Adsorption of Methane Adsorption of Pure Methane

T = 25 °Cpower of

delivered gas varies!!!!

Pupier et al., Chem. Eng. Proc. 44 (2005) 71

70

72

74

76

78

80

v/v)

Stored volume (35 bar and 25 OC) Delivered volume (1 bar and 25 OC)

pressure (bar)

60

62

64

66

68

70

stor

ed v

olum

e ( v

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32

56

58

60

cycles

Universidade

Anos15Charge and Discharge Cycles (long-term performance – fast cycles)Federal do Ceará

Qn=η

term performance fast cycles)

1Q=η

Universidade

Anos15Charge and Discharge Cycles (long-term performance) use of guard bedsFederal do Ceará performance) – use of guard beds

Upon charge of storage vessel, heavy alkanes and odorants are t d i th d b dcaptured in the guard bed

Upon discharge of storage vessel heavy alkanes and odorantsUpon discharge of storage vessel, heavy alkanes and odorants are released from the guard bed

Esteves et al., Adsorption 11 (2005) 905

Universidade










Universidade

Anos15Multicomponent adsorption measurements – volumetry w/ GCFederal do Cearámeasurements – volumetry w/ GC

Adsorption

chamberGas chromatograph

nt 1

nt 2 Dosing tank 1

Dosing tank 2

Circulation

Com

pone

n

Com

pone

n

Circulation pump

Concentration of Concentration of Total amount fluid phase adsorbed phase adsorbedΔc/c = 1.0 % Δc/c = 2 - 5 % Δm/m = 1.5 %

Universidade

Anos15Data for Natural Gas components – monocomponent isothermsFederal do Ceará monocomponent isotherms

1112131415 Sample: WV1050

T = 30°C CH4

C2H6

C3H8

COl/g]

6789

1011

Langmuir Toth O'Brien-Myers

CO2

N2

amou

nt [m

mol

123456

adso

rbed

a

0 1 2 3 4 5 6

01

pressure [MPa]

Bazan et al., Adsorption Science and Technology, 2009 (in press)

Universidade

Anos15Data for Natural Gas components –binary mixturesFederal do Ceará binary mixtures

1,00(a)

1,0

CH4 in CH4/CO2 IAST fit Extended Langmuir fit

CH4/N2 CH4/CO2

0,90

0,95

x CH

4

0,7

0,8

0,9

(b)

Sample: WV1050T = 30°C

x CH

4

0,80 0,85 0,90 0,95 1,000,80

0,85


CH4 in CH4/N2 IAST fit Extended Langmuir fit

0,5 0,6 0,7 0,8 0,9 1,00,5

0,6

yCH /C HyCH4

yCH4

0,9

1,0


CH4 in CH4/C2H6 IAST fit Extended Langmuir fit

0,8

0,9

1,0


CH4 in CH4/C3H8 IAST fit Extended Langmuir fit

CH4/C2H6 CH4/C3H8

0 6

0,7

0,8

(c)x CH 4

0,5

0,6

0,7

(d)

x CH

4

0,5 0,6 0,7 0,8 0,9 1,00,5

0,6

yCH4

0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,00,3

0,4

yCH4

Bazan et al., Adsorption Science and Technology, 2009 (in press)

Universidade

Anos15CO2/N2 in AC Norit R1Federal do Ceará

12

14

mm

ol/g

] pure CO2

6

8

10

nt a

dsor

bed

[m

2

4

6

xces

s am

oun

Pure N2

0

0 1 2 3 4 5 6 7

0.00.2

0.40.6

0.8

Ex

Pressure [MPa]

Conc. yCO2

Bazan and Staudt (unpublished results)

Universidade

Anos15CH4/CO2/N2 in AC Norit R1, T = 298 KFederal do Ceará

12

[mm

ol/g

]

10

12yCH4 = 0,72 / yCO2 = 0,12 / yN2 = 0,16

nTOTAL

n CO

2, n

tot

6

8 nCH4+ nCO2

nTOTAL

nC

H4

+ n

2

4nCH4

0 1 2 3 4 5 6 7

n CH

4,

0

2

Pressure [MPa]

Bazan and Staudt (unpublished results)

Universidade









C l di kConcluding remarks

Universidade

Anos15http://www.ipcc.chFederal do Ceará

Universidade

Anos15Some FAQs about CCSFederal do Ceará

What is CO2 capture and storage ?

Carbon dioxide (CO2) capture and storage (CCS) is a processconsisting of the separation of CO2 from industrial and energy-related sources transport to a storage location and long termrelated sources, transport to a storage location and long-termisolation from the atmosphere.

What are the characteristics of CCS?What are the characteristics of CCS?

Capture of CO2 can be applied to large point sources. The CO2would then be compressed and transported for storage inp p ggeological formations, in the ocean, in mineral carbonates, or foruse in industrial processes.

In most CCS systems, the cost of capture (includingcompression) is the largest cost component.

Universidade

Anos15Possible CCS scenariosFederal do Ceará IPCC Special Report on CCS, Cambridge Univ. Press, 2005

MAIN EMISSIONSPower gener.

Cement productionpOil refineriesCO2

Universidade

Anos15CO2 capture systemsFederal do Ceará

Figueroa et al., Int. J. of Greenhouse Gas Contr. 2 (2008) 9

The concentration of CO2 in the gasof CO2 in the gas

stream, the pressure of the gas stream and g

the fuel type(solid or gas) are important factors

in selecting thecapture system.

Universidade

Anos15Cost reduction benefitsVs. Time to commercialization

Federal do Cearás e to co e c a at o

Figueroa et al., Int. J. of Greenhouse Gas Contr. 2 (2008) 9

Universidade

Anos15Capture ToolboxFederal do Ceará

Sepa ration

Process Streams Post-combustion Capture

Oxy-fuel Combustion

Pre-combustion Capture

IPCC Special Report on CCS, Cambridge Univ. Press, 2005

ration task CO2/CH4 CO2/N2 O2/N2 CO2/H2

Capture technol.

Current Emerging Current Emerging Current Emerging Current Emerging

Absor tion

Physical Solvs. Chemical Solvs.

Improved solvs. And proc designContact

Chemical Solvents

Improved solvs. And proc designContact

n.a. Biomimetic solvents i.e.Hemo globyn

Improved solvs. And proc designContact equipm

equipm equipmg yderivatives

q p

Mem branes

Polymeric CeramicEnhanced transportCarbon

Polymeric CeramicEnhanced transportCarbon

Polymeric Ion-transport membranes

Polymeric Ceramic Palladium Reactors ContactorsCarbon Carbon s Contactors

Adsorp tion

Zeolites Activ. Carbon


CarbonateCarbon-based sorbents


Adsorbents for O2/N2 separation perovskite

Zeolites Activ. Carbon Alumina

Carbonates Hydrotalcites Silicates MOFs

perovskite

Cryogenic

Ryan-Holmes Process

Liquefaction

Hybrid processes

Distillation Improved destillation

Liquefaction

Hybrid processes

Universidade










Universidade

Anos15Classical sorbents for CO adsorptionFederal do Ceará CO2 adsorption

0,30 0 25

0,30Zeolite 13 X

(Bezerra et al., 2009, unpublished results)

0,15

0,20

0,25

,

exc (g

|g)

CH4

CO2

T=25 oC

AC Norit CN2 0,10

0,15

0,20

0,25

q exc

(g/g

)

CO2

CH4

T = 25oC

0 2 4 6 8 10

0,00

0,05

0,10q e

0 10 20 30 40 50 60

0,00

0,05

P (bar)Dantas et al., Sep. Sci. Technol., 2009 (submitted)

P (bar)

0,6

0,7

0,8

AC 0.6

0.8

1.0

301 K323 K373 K

423 KMain disadvantage: capacity loss

t hi h t t

0 1

0,2

0,3

0,4

0,5

q exc

(g/g

)

CO2

CH4

N2

T = 25؛ oC

AC Westvaco 1050 0.2

0.4

0.6

Run 1 Run 2 Run 3Run 4

C/C

o at high temperatures

0 10 20 30 40 50 60-0,1

0,0

0,1

P (bar)

0 100 200 300 400 500 6000.0

Run 4 LDF model

time, min.

Universidade

Anos15Emerging sorbentsFederal do Ceará

Amines incorporated on inorganic Amines incorporated on inorganic supports (silicas, zeolites)

Knowles et al Fuel ProcKnowles et al., Fuel Proc. Technol. 86 (2005) 1435 Knowles et al., Ind. Eng. Chem. Res. 45 (2006)

2626

Universidade


But,

AP – aminopropylsilylED th l di i [ l( il l)]ED - ethylenediamine[propyl(silyl)]-DT - diethylenetriamine[propyl(silyl)]-

Knowles et al., Ind. Eng. Chem. Res. 45 (2006) 2626

Universidade


Chatti et al., Microp and Mesop Materials, 2009 (in press)

Table 6: Equilibrium adsorption capacities of zeolite 13X and MEA modified zeolite 13X (50 w%) at 75ºC and 1 bar gauge pressure.( ) g g p

Equilibrium qadsorption

capacity(mg/g)(mg/g)

13X matrix 37.3313X/MEA 48.64/

Universidade


“Molecular basket”

Song, Catalysis Today 115 (2006) 2

adsorbentsFill pores of mesoporous matrices with PEI, which would capture CO2in terminal amino- groups

75oC

Universidade


Xu et al. Microp Mesop Mat 62 (2003) 29

Universidade










Universidade

Anos15Steps of a one-column PSA cycleFederal do Ceará cycle

gas

CO2 CO2 Dil t CO2

Pressurização Adsorção Dessorção PurgaP

CO2 + gas

CO2 Dilute CO2

T

Universidade

Anos15A two-column PSA for air separationFederal do Ceará separation

Universidade

Anos15Basic Principles of a PSA process – column dynamicsFederal do Ceará

Fixed bed – unit cell of P S i Ad ti (PSA)

process column dynamics

Adsorption front progression along the bed

Breakthrough curveConcentration history in

Pressure Swing Adsorption (PSA) processes

0,45C

along the bed Concentration history in column outlet

MTZ

0,20

0,25

0,30

0,35

0,40 C0

(mM

ol/L

)

CbC = 0 C = 0 C0 0 20 40 60 80 100 1200,00

0,05

0,10

0,15

0,20

CbC

b 0 0 20 40 60 80 100 120

Tempo (min)

Universidade

Anos15CO2( ) / N2( ) breakthrough curvesFederal do Ceará curves

1.2

1.4

1.2

1.4

Dantas et al., Sep. Sci. Technol., 2009 (submitted)

0.6

0.8

1.0

C/C

o

0.6

0.8

1.0

C/C

o301 K

373 K

0 50 100 150 200 250 3000.0

0.2

0.4

(a)

1 4 0 20 40 60 80 1000.0

0.2

0.4

(c)

1 4

373 K

time, min.

0.8

1.0

1.2

1.4

o

0 20 40 60 80 100time, min.

1.0

1.2

1.4

323 K

0.2

0.4

0.6

0.8

C/C

0.4

0.6

0.8C

/Co323 K

423 K

0 50 100 150 200 250 3000.0 (b)

time, min.0 20 40 60 80 100

0.0

0.2

(d)

time, min.

Universidade

Anos15Adding amines to activated carbonsFederal do Ceará carbons

4

5

Norit R20300 .8

1 .0

Dantas et al., Sep. Sci. Technol., 2009 (submitted)

2

3

4

q, m

ol/k

g

0 .4

0 .6

0 .8

(b )

R u n 5 R u n 6 R u n 7R u n 8

C/C

o

0 1 2 3 4 50

1

q

0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 00 .0

0 .2

R u n 8 L D F M o d e l

1 0P,bar

3

4

5

3-chloropropylamine doped carbon

tim e , m in

0.6

0.8

1.0

(b)

Run 5

1

2

3

q, m

ol/K

g

0.2

0.4

Run 5 Run 6 Run 7 Run 8 LDF Model

C/C

o yF = 0.20

0.0 0.2 0.4 0.6 0.8 1.00

P, bar

0 40 80 120 160 2000.0

time, min

Universidade

Anos15Improvements in process designFederal do Ceará design

Layered bedsS. Cavenati et al., Chem. Eng. Sci. 61 (2006) 3893

Layered bedsNatural gas purification

301KCH4/N2 separation

323K

CO2 adsorption

Universidade

Anos15Improvements in process design El t i S i Ad tiFederal do Ceará design – Electric Swing Adsorption

CO2 concentration (4X achieved)2 ( )Activated carbon honey comb

Grande and Rodrigues, Int. J. of Greenhouse Gas Cont. 2 (2008) 194

Universidade

Anos15Concluding remarksFederal do Ceará

Design, optimization and control of Design, optimization and control of storage and capture adsorption-based systems relies on:

Materials development (field for activated carbon and eventually mesoporous matrices)matrices)Accurate adsorption measurements (single and multicomponent)Innovative process schemesModeling (simplicity X accuracy) tools, from micro and macro (process) from micro and macro (process) perspectives

Universidade

Anos15Acknowledging partners...Federal do Ceará

INC – Uni LeipzigUFSC and Univ of Porto

Univ of Alicante

UFC team

INFAP - UNSL

Universidade

Anos15¡¡¡ Gracias !!!Federal do Ceará

2008 Campina Grande

Paraíba Brasil

¿ Comentários ?¿ Preguntas ?

25 a 27 de junio 7º EBA - Encuentro Brasileño de Adsorción

1er SISA - Simposio Sudamericano sobre Ciencia y Tecnología de la Adsorción ¿ Preguntas ?

di @ f b

23 a 24 de junio

ra [email protected]

1ra ESADEscuela Sudamericana de Adsorción

1ra Circular

adsorciÓn de gases aplicadaa procesos deaplicada a...

Documents