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  • University of SiegenInstitute of Fluid- & Thermodynamics

    Prof. Dr. sc. techn. Jrgen U. KELLER

    Measurement Methods for Single- and

    Multi-Component Gas Adsorption Equilibria

    JUERGEN U. KELLER, FRIEDER DREISBACH1), NADIA IOSSIFOVA, MARC SEELBACH,

    WOLFGANG ZIMMERMANN AND REINER STAUDT2)

    Inst. Fluid- and Thermodynamics, University of Siegen, D-57068 Siegen, Germany1)Rubotherm GmbH, Bochum, Germany

    2)Inst. Non-Classical Chemistry, University of Leipzig, Leipzig, Germany

    keller@ift.maschinenbau.uni-siegen.de, 1)dreisbach@rubotherm.de, 2)staudt@inc.uni-leipzig.de

    1. Volumetry / Manometry and Densimetry

    2. Gravimetry and Densimetry

    3. Oscillometry

    4. Impedance Spectroscopy

    5. Calorimetry and Volumetry

    6. Calorimetry and Spectroscopy

    Acknowledgements

  • University of SiegenInstitute of Fluid- & Thermodynamics

    Prof. Dr. sc. techn. Jrgen U. KELLER

    Volumetry/Manometry and Densimetry

    94,22547 g

    Gas SupplySystem

    Microbalance

    Thermostat

    T

    MagneticSuspension

    Thermometer

    PermanentMagnet Manometer

    SorbentSinker

    AdsorptionChamber

    VAC

    VacuumPump

    Gas CirculationPump

    T p

    StorageVessel 1

    StorageVessel 2 T

    Instrument for volumetric-densimetric measurements of binary

    coadsorption equilibria of gas mixtures on porous solids without

    using a gas chromatograph. The sorptive gas prepared in the

    system is assumed to be a binary mixture with known initial molar

    concentrations (y*1, y*2). IFT University of Siegen, 2002.

  • University of SiegenInstitute of Fluid- & Thermodynamics

    Prof. Dr. sc. techn. Jrgen U. KELLER

    DVMs / Theory

    Mass balances a * fi i im m m

    EOS

    i 1, 2 (1)

    (2)

    (3)

    (4)

    (5)

    (6)

    * ** i SVi i*

    y p Vm M

    R T Z

    * *iZ Z p ,T, y

    Sorptive gas massesf f1 2(m ,m )

    f f f * as1 2m m V V

    * asf f1 2

    1 2 i

    p V Vm m

    M M R T Z p,T, w

    fi

    i f f1 2

    mw

    m mi 1, 2

    as sHeV V

    a * f * si i 1iGE i He

    i i 1 i

    M p Mm m V V

    M M R T Z p,T, w

    (1 4)

  • University of SiegenInstitute of Fluid- & Thermodynamics

    Prof. Dr. sc. techn. Jrgen U. KELLER

    Installation for DGMs

    of Binary Coadsorption

    Equilibria of Premixed

    Gases (y1, y2)* *

    Schematic Diagram DGMs

  • University of SiegenInstitute of Fluid- & Thermodynamics

    Prof. Dr. sc. techn. Jrgen U. KELLER

    First performance of DGMs using a MSB (3)

    on 1998-02-11 in Lab PB-A0126 of IFT/USI

    First Instrument MSB (3)

  • University of SiegenInstitute of Fluid- & Thermodynamics

    Prof. Dr. sc. techn. Jrgen U. KELLER

    Mass balances

    Total gas mass supplied

    Sorptive gas masses

    a * fi i im m m i 1,2 (1)

    (2)

    (2A)

    (3)

    (4)

    (5)

    (6)

    * * * a a f f1 2 1 2 1 2m m m m m m m

    * f *m V

    * * *i im w m

    * asf f1 2

    1 2 i

    p V Vm m

    M M R T Z p,T, w

    f f f * as1 2m m V V

    a * f * si i 1iGE i He

    i i 1 i

    M p Mm m V V

    M M R T Z p,T, w

    as sHeV V(1, 2A, 3, 4)

    DGMs / Theory

  • University of SiegenInstitute of Fluid- & Thermodynamics

    Prof. Dr. sc. techn. Jrgen U. KELLER

    2 4

    i i

    2 4 CO CH

    i i 2 4

    Coadsorption equilibria of CO / CH at T 293K, y 20.4%mol, y 79.6%mol

    on AC D47 /3. Correlation by GAI : n n (bp) 1 (bp) , i CO , CH

    Diagram CO2/CH4

    0.0

    0.5

    1.0

    1.5

    2.0

    2.5

    3.0

    3.5

    4.0

    4.5

    5.0

    0.0 0.3 0.6 0.9 1.2 1.5

    Pressure p [MPa]

    nC

    O2, n

    tot =

    nC

    O2 +

    nC

    H4 [

    mm

    ol/g

    ]

    ntot = nCO2 + nCH4 nCO2

    yfCO2 : y

    fCH4 = 0.204 : 0.796

    T = 293 K

    AC D 47/3

  • University of SiegenInstitute of Fluid- & Thermodynamics

    Prof. Dr. sc. techn. Jrgen U. KELLER

    Vacuum Pump

    T

    Gas supply

    Microbalance

    Sorption Chamber

    T

    ppRotationalPendulum

    Sorption

    Chamber

    Gas Circulation Pump

    m

    Polymer

    Sorbent

    Experimental setup for oscillometric-gravimetric measurements

    Schematic Diagram OVMs

  • University of SiegenInstitute of Fluid- & Thermodynamics

    Prof. Dr. sc. techn. Jrgen U. KELLER

    220 0

    s 2EE

    1m1

    m 1

    220 02

    EEs

    0 0* *

    11

    1m

    m 1

    sIdeal Pendulum m ,m * sPhysical Pendulum m ,m ,m

    * * *, ... empty pendulum m , vacuum

    * s0 0, ... pendulum and adsorbent m ,m , vacuum

    * sE E, ... pendulum, adsorbent, adsorbate m ,m ,m , gas

    Oscillometric measurements of gas adsorption equilibria. Theory

    Theory OscillometricMs

  • University of SiegenInstitute of Fluid- & Thermodynamics

    Prof. Dr. sc. techn. Jrgen U. KELLER

    Ring slit of rotational pendulum filled with polycarbonate pellets

    Photo ring slit of rot. pendulum

  • University of SiegenInstitute of Fluid- & Thermodynamics

    Prof. Dr. sc. techn. Jrgen U. KELLER

    Swelling and sorption isotherm of polycarbonate / CO2 at 293 K

    Swelling and sorption isotherms of PC/CO2

    p [MPa]

    0 1 2 3 4 5 6 7

    Vas /

    (m

    a+

    ms)

    [cm

    3/g

    ]

    0.80

    0.85

    0.90

    0.95

    1.00

    1.05

    mg/g

    ]

    ma [

    mg/g

    ]

    -50

    0

    50

    100

    150

    200

    250 Vas

    / (ma+m

    s)

    grav

    osc

    ma

  • University of SiegenInstitute of Fluid- & Thermodynamics

    Prof. Dr. sc. techn. Jrgen U. KELLER

    Vacuum Pump

    Gas Supply

    p*

    T

    p

    Adsorption

    Chamber

    Gas Circulation Pump

    T*

    Storage Vessel

    V*

    Capacitor

    Gas Chromatograph

    mS

    Impedance

    Analyzer

    IA

    Sorbent

    Heasfas**

    MG VV,)T,p(VVmmM,V

    MGDE m)T,p(DE

    Experimental setup for volumetric-dielectric measurements

    Schematic Diagram Vol-Diel-Ms

  • University of SiegenInstitute of Fluid- & Thermodynamics

    Prof. Dr. sc. techn. Jrgen U. KELLER

    Impedance spectra of CO2 on zeolite (DAY), T=298K

    Impedanc Spectra (DAY/CO2)

    f/ kHz

    2000 4000 6000 8000 10000 12000 14000

    C/

    F

    5.1e-12

    5.2e-12

    5.3e-12

    5.4e-12

    5.5e-12

    5.6e-12Vakuum

    0.01 MPa

    0.1961 MPa

    0.9916 MPa

    1.5001 MPa

    1.9924 MPa

  • University of SiegenInstitute of Fluid- & Thermodynamics

    Prof. Dr. sc. techn. Jrgen U. KELLER

    Uptake curves of H2S on MS 13X, T=298K

    Uptake Curves MS13X/H2S

    Time [h]

    0.0 0.2 0.4 0.6 0.8 1.0

    Rela

    tive u

    pta

    ke

    0

    1

    2

    3

    4

    5

    6

    Impedance spectroscopy

    Gravimetry

  • University of SiegenInstitute of Fluid- & Thermodynamics

    Prof. Dr. sc. techn. Jrgen U. KELLER

    Schematic diagram of a

    Sensor Gas Calorimeter (SGC)

    Schematic Diagram SGC

  • University of SiegenInstitute of Fluid- & Thermodynamics

    Prof. Dr. sc. techn. Jrgen U. KELLER

    Calibration experiments in the SGC 0.5J to 5J

    Sensor gas N2 (1.6bar), T=298K, =10s

    Ohms heat release (red lines) Pressure signal (blue lines)

    0

    20

    40

    60

    80

    100

    120

    0 100 200 300 400 500 600 700 800

    Time [s]

    Dif

    fere

    nce

    P

    ress

    ure

    [P

    a]

    0

    50

    100

    150

    200

    250

    300

    350

    400

    450

    500

    Ele

    ctri

    cal P

    ow

    er

    [m

    W]

    Calibration SGC

  • University of SiegenInstitute of Fluid- & Thermodynamics

    Prof. Dr. sc. techn. Jrgen U. KELLER

    Heat of adsorption for CO2 / Na13X, T=298K

    0 1 2 3 4 5

    10

    20

    30

    40

    50

    60

    70

    Heat of Condensation for CO2 (5,25 kJ/mol)

    Differental heat of adsorption

    Derivative of polynomial interpolation

    of the integral heat of adsorption

    Dif

    fere

    nti

    al

    hea

    t o

    f a

    dso

    rpti

    on

    [k

    J/m

    ol]

    CO2 ads. [mmol/g]

    0

    20

    40

    60

    80

    100

    120

    140

    160

    180

    200 Integral heat of adsorption

    Polynomal Interpolation

    In

    tegra

    l h

    eat

    of

    ad

    sorp

    tion

    [J

    /g]

    Heat of adsorption Na13X/CO2

  • University of SiegenInstitute of Fluid- & Thermodynamics

    Prof. Dr. sc. techn. Jrgen U. KELLER

    Schematics of combined

    calorimetric-dieletric-volumetric

    gas adsorption measurements

    Schematic Diagram GSC with Capacitor

    12.33 1000.0 6.14

    Impedance Analyzer

    Capacitor

  • University of SiegenInstitute of Fluid- & Thermodynamics

    Prof. Dr. sc. techn. Jrgen U. KELLER

    Calculation of absolute adsorbed masses from DE-C-measurements

    0H

    hm

    b a0( m)B

    A

    m

    b a0

    0

    ( m)h B

    AH *)

    2

    i i

    h b,B m a,b,A,B, ,H H

    2

    k k

    a,A m a,b,A,B, ,H Min

    a, A, b, B (*) m

    (CI) hbp

    0h Be

    (DI) ap

    0 Ae

    0h h

    b a0B

    A

    h m

    H

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