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University of SiegenInstitute of Fluid- & Thermodynamics
Prof. Dr. sc. techn. Jürgen 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
[email protected], 1)[email protected], 2)[email protected]
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. Jürgen 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. Jürgen 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. Jürgen 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. Jürgen 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. Jürgen 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. Jürgen 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. Jürgen U. KELLER
Vacuum Pump
T
Gas supply
Microbalance
Sorption Chamber
T
ppRotational
Pendulum
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. Jürgen 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. Jürgen 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. Jürgen 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. Jürgen 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. Jürgen 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. Jürgen 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. Jürgen U. KELLER
Schematic diagram of a
Sensor Gas Calorimeter (SGC)
Schematic Diagram SGC
University of SiegenInstitute of Fluid- & Thermodynamics
Prof. Dr. sc. techn. Jürgen U. KELLER
Calibration experiments in the SGC 0.5J to 5J
Sensor gas N2 (1.6bar), T=298K, =10s
Ohm’s 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. Jürgen 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. Jürgen 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. Jürgen U. KELLER
Calculation of absolute adsorbed masses from DE-C-measurements
0
Hh
m
b a0( m)
BA
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
m
University of SiegenInstitute of Fluid- & Thermodynamics
Prof. Dr. sc. techn. Jürgen U. KELLER
Absolute masses (ma) and Gibbs excess masses (mGEV, mGEG)
of CO2 adsorbed on wessalite (DAY-zeolite) at T=298K
Absolute and Gibbs excess masses DAY/CO2
14.12
20.87
45.54
29.74
1.410 6.60
86.45
14.66
34.83
1.445.76
89.67
1.444
5.77
0
10
20
30
40
50
60
70
80
90
100
0 1000 2000 3000 4000 5000
mg/g
p [hPa]
100 499 1009 1961 4003
a
GEV
GEG
m ... Dielectric Caloric Meas.(RS, ESch, JUK)
m ... Volumetry, He Vol. (ESch)
m ... Gravimetry, He Vol. (RS)
University of SiegenInstitute of Fluid- & Thermodynamics
Prof. Dr. sc. techn. Jürgen U. KELLER
Measurement Methods
Gas Mixture Sorption
University of SiegenInstitute of Fluid- & Thermodynamics
Prof. Dr. sc. techn. Jürgen U. KELLER
GVC-GET Thermodynamic-Conference Würzburg, 2001
Thermodynamic-conference Würzburg