Measurement Methods for Single- and Multi-Component Gas Adsorption Equilibria

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University of Siegen Institute of Fluid- & ThermodynamicsProf. 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, Germany

1)_{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

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Volumetry/Manometry and Densimetry

94,22547 g Gas Supply System Microbalance Thermostat T Magnetic Suspension Thermometer Permanent Magnet Manometer Sorbent Sinker Adsorption Chamber V_AC Vacuum Pump Gas Circulation Pump T p Storage Vessel 1 Storage Vessel 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

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University of Siegen Institute of Fluid- & ThermodynamicsProf. Dr. sc. techn. Jürgen U. KELLER DVMs / Theory Mass balances ma_i m*_i mf_i EOS i 1, 2 (1) (2) (3) (4) (5) (6) * * * _i _SV i _* i y p V m M R T Z * * i Z Z p , T, y

Sorptive gas masses

f f 1 2 (m , m ) f f f * as 1 2 m m V V * as f f 1 2 1 2 i p V V m m M M R T Z p, T, w f i i _f _f 1 2 m w m m i 1, 2 as s He V V a * i f i 1 * s iGE i He i i 1 i M p M m m V V M M R T Z p, T, w (1 – 4)

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University of Siegen Institute of Fluid- & ThermodynamicsProf. Dr. sc. techn. Jürgen U. KELLER Installation for DGMs of Binary Coadsorption Equilibria of Premixed Gases (y*₁, y₂*) Schematic Diagram DGMs

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First performance of DGMs using a MSB (3) on 1998-02-11 in Lab PB-A0126 of IFT/USI

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Mass balances Total gas mass supplied

Sorptive gas masses

a * f i i i m m m i 1, 2 (1) (2) (2A) (3) (4) (5) (6) * * * a a f f 1 2 1 2 1 2 m m m m m m m * f * m V * * * i i m w m * as f f 1 2 1 2 i p V V m m M M R T Z p, T, w f f f * as 1 2 m m V V a * i f i 1 * s iGE i He i i 1 i M p M m m V V M M R T Z p, T, w as s He V V (1, 2A, 3, 4) DGMs / Theory

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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] nCO 2 , n to t = n CO 2 + n CH4 [ m m o l/ g ] n_tot = n_CO2 + n_CH4 nCO2 y f CO2 : y f CH4 = 0.204 : 0.796 T = 293 K AC D 47/3

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University of Siegen Institute of Fluid- & ThermodynamicsProf. Dr. sc. techn. Jürgen U. KELLER Vacuum Pump T Gas supply Microbalance Sorption Chamber T p p Rotational Pendulum Sorption Chamber

Gas Circulation Pump m

Polymer Sorbent

Experimental setup for oscillometric-gravimetric measurements

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University of Siegen Institute of Fluid- & ThermodynamicsProf. Dr. sc. techn. Jürgen U. KELLER 2 2 0 0 s 2 E E 1 m 1 m 1 2 2 0 0 2 E E s 0 0 * * 1 1 1 m m ₁ s

Ideal Pendulum m , m Physical Pendulum m , m , m* s

* * *

, ... empty pendulum m , vacuum

* s

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

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

Oscillometric measurements of gas adsorption equilibria. Theory

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Ring slit of rotational pendulum filled with polycarbonate pellets

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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 V as / (m a +m s ) [ c m 3 /g] 0.80 0.85 0.90 0.95 1.00 1.05 m g/ g] m a [ m g/ g] -50 0 50 100 150 200 250 Vas / (ma+ms) grav osc ma

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University of Siegen Institute of Fluid- & ThermodynamicsProf. 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 He as f as * * MG m V V (p,T), V V m M , V MG DE (p,T)m DE

Experimental setup for volumetric-dielectric measurements

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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-12 Vakuum _{0.01 MPa}

0.1961 MPa 0.9916 MPa 1.5001 MPa 1.9924 MPa

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University of Siegen Institute of Fluid- & ThermodynamicsProf. 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 R e la ti v e u p ta k e 0 1 2 3 4 5 6 Impedance spectroscopy Gravimetry

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Schematic diagram of a

Sensor Gas Calorimeter (SGC)

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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] D if fe re n ce P re ss u re [P a] 0 50 100 150 200 250 300 350 400 450 500 E le ct ri ca l P ow e r [ m W ] Calibration SGC

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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

D if fe re nt ia l he a t o f a dso rpt io n [ k J /m o l] CO₂ ads. [mmol/g] 0 20 40 60 80 100 120 140 160 180 200

Integral heat of adsorption Polynomal Interpolation Int eg ra l he a t o f a dso rpt io n [ J /g ]

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Schematics of combined

calorimetric-dieletric-volumetric gas adsorption measurements

Schematic Diagram GSC with Capacitor

12.33 _6.141000.0

Impedance Analyzer Capacitor

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Calculation of absolute adsorbed masses from DE-C-measurements

H h₀ m b a 0 ( m) B A m b a 0 0 ( m) h B A H _*) 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) h h₀ Be bp (DI) ₀ Ae ap h h0 b a 0 B A h m H m

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Absolute masses (ma) and Gibbs excess masses (m_GEV, m_GEG) 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 1.44 5.76 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)

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Measurement Methods

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GVC-GET Thermodynamic-Conference Würzburg, 2001