Measureent Methods for Single- and Multi-Coponent Gas Adsorption Equilibria JUERGEN U. KELLER, FRIEDER DREISBACH 1), NADIA IOSSIFOVA, MARC SEELBACH, WOLFGANG ZIMMERMANN AND REINER STAUDT 2) Inst. Fluid- and Therodynaics, University of Siegen, D-57068 Siegen, Gerany 1) Rubother GbH, Bochu, Gerany 2) Inst. Non-Classical Cheistry, University of Leipzig, Leipzig, Gerany keller@ift.aschinenbau.uni-siegen.de, 1) dreisbach@rubother.de, 2) staudt@inc.uni-leipzig.de 1. Voluetry / Manoetry and Densietry 2. Gravietry and Densietry 3. Oscilloetry 4. Ipedance Spectroscopy 5. Calorietry and Voluetry 6. Calorietry and Spectroscopy Acknowledgeents
Voluetry/Manoetry and Densietry 94,22547 g Microbalance Magnetic Suspension Adsorption Chaber Peranent Magnet T Manoeter p Therostat Storage Vessel 1 Gas Supply Syste V AC Sinker T Theroeter Sorbent Storage Vessel 2 T Vacuu Pup Gas Circulation Pup Instruent for voluetric-densietric easureents of binary coadsorption equilibria of gas ixtures on porous solids without using a gas chroatograph. The sorptive gas prepared in the syste is assued to be a binary ixture with known initial olar concentrations (y* 1, y* 2 ). IFT University of Siegen, 2002.
Mass balances EOS Sorptive gas asses f f (, ) 1 2 (1 4) a * f i i i * * * yi p VSV i * R T Z M f f f * as 1 2 V V f f 1 2 p V i * as 1 2 i i f i f f 1 2 as s i 1, 2 (1) * * Z Z p,t, y i V M M R T Z p,t, w w V V He i 1, 2 (2) (3) (4) (5) DVMs / Theory M p M V V a * i f i 1 * s ige i He Mi Mi 1 R T Z p,t, wi (6)
Scheatic Diagra DGMs Installation for DGMs of Binary Coadsorption Equilibria of Preixed * * Gases (y 1, y 2 )
First Instruent MSB (3) First perforance of DGMs using a MSB (3) on 1998-02-11 in Lab PB-A0126 of IFT/USI
Mass balances Total gas ass supplied a * f i i i i 1, 2 (1) * * * a a f f 1 2 1 2 1 2 * f * V * * * i wi (2) (2A) Sorptive gas asses (1, 2A, 3, 4) f f f * as 1 2 V V f f 1 2 p V * as V M M R T Z p,t, w 1 2 i as s V V He (3) (4) (5) DGMs / Theory M p M V V a * i f i 1 * s ige i He Mi Mi 1 R T Z p,t, wi (6)
n CO2, n tot = n CO2 + n CH4 [ol/g] University of Siegen Diagra CO2/CH4 5.0 4.5 4.0 3.5 n tot = n CO2 + n CH4 n CO2 y f CO2 : y f CH4 = 0.204 : 0.796 T = 293 K AC D 47/3 3.0 2.5 2.0 1.5 1.0 0.5 0.0 0.0 0.3 0.6 0.9 1.2 1.5 Pressure p [MPa] Coadsorption equilibria of CO / CH at T 293K, y 20.4%ol, y 79.6%ol 2 4 CO CH 2 4 on AC D47 /3. Correlation by GAI : n n (bp) i 1 (bp) i, i CO, CH i i 2 4
Scheatic Diagra OVMs Gas supply Rotational Pendulu p p Microbalance T Polyer Sorbent T Sorption Chaber Sorption Chaber Vacuu Pup Gas Circulation Pup Experiental setup for oscilloetric-gravietric easureents
Theory OscilloetricMs Ideal Pendulu 2 1 0 0 s 2 E E 1 2 s, 1 s 1 1 1 2 0 0 2 E E 0 0 * * 2 1 * s Physical Pendulu,, * * *,... epty pendulu, vacuu 0 0 E * s,... pendulu and adsorbent,, vacuu E * s,... pendulu, adsorbent, adsorbate,,, gas Oscilloetric easureents of gas adsorption equilibria. Theory
Photo ring slit of rot. pendulu Ring slit of rotational pendulu filled with polycarbonate pellets
Swelling and sorption isothers of PC/CO2 g/g] a [g/g] 250 V as / ( a + s ) 200 150 100 50 0 grav osc a 1.05 1.00 0.95 0.90 0.85 V as / ( a + s ) [c 3 /g] -50 0.80 0 1 2 3 4 5 6 7 p [MPa] Swelling and sorption isother of polycarbonate / CO 2 at 293 K
Gas Supply Gas Circulation Pup Capacitor Scheatic Diagra Vol-Diel-Ms p p * T * Storage Vessel V * T Adsorption Chaber Sorbent S Ipedance Analyzer IA Gas Chroatograph Vacuu Pup V, M DE MG * V (p,t) * V DE MG as f (p,t), Experiental setup for voluetric-dielectric easureents V as V He
Ipedanc Spectra (DAY/CO2) 5.6e-12 5.5e-12 Vakuu 0.01 MPa 0.1961 MPa 0.9916 MPa 1.5001 MPa 1.9924 MPa C/ F 5.4e-12 5.3e-12 5.2e-12 5.1e-12 2000 4000 6000 8000 10000 12000 14000 f/ khz Ipedance spectra of CO 2 on zeolite (DAY), T=298K
Uptake Curves MS13X/H2S 6 5 Ipedance spectroscopy Gravietry Relative uptake 4 3 2 1 0 0.0 0.2 0.4 0.6 0.8 1.0 Tie [h] Uptake curves of H 2 S on MS 13X, T=298K
Scheatic Diagra SGC Scheatic diagra of a Sensor Gas Calorieter (SGC)
Difference Pressure [Pa] Electrical Power [W] University of Siegen Calibration SGC 120 100 80 60 40 20 0 0 100 200 300 400 500 600 700 800 Tie [s] 500 450 400 350 300 250 200 150 100 50 0 Calibration experients in the SGC 0.5J to 5J Sensor gas N 2 (1.6bar), T=298K, =10s Oh s heat release (red lines) Pressure signal (blue lines)
Differential heat of adsorption [kj/ol] Integral heat of adsorption [J/g] University of Siegen Heat of adsorption Na13X/CO2 70 60 50 Integral heat of adsorption Polynoal Interpolation Differental heat of adsorption Derivative of polynoial interpolation of the integral heat of adsorption 200 180 160 140 120 40 30 100 80 60 20 10 40 20 Heat of Condensation for CO 2 (5,25 kj/ol) 0 0 1 2 3 4 5 CO 2 ads. [ol/g] Heat of adsorption for CO 2 / Na13X, T=298K
Scheatic Diagra GSC with Capacitor Scheatics of cobined calorietric-dieletric-voluetric gas adsorption easureents Capacitor 1000.0 12.33 6.14 Ipedance Analyzer
(CI) h h0 Be bp H h0 B ( ) A 0 ba (DI) h h 0 h B H 0 Ae A ap 0 ba i k ba ( ) H h 0 0 B * A ) H h b,b a,b,a,b, H, a,a a,b,a,b, H, Min 2 i 2 k a, A, b, B (* ) Calculation of absolute adsorbed asses fro DE-C-easureents
Absolute and Gibbs excess asses DAY/CO2 g/g 100 90 80 70 60 100 499 1009 1961 4003 89.67 86.45 50 40 30 20 10 0 1.444 1.410 6.60 1.44 5.77 5.76 20.87 14.12 14.66 45.54 34.83 29.74 0 1000 2000 3000 4000 5000 p [hpa] Absolute asses ( a ) and Gibbs excess asses ( GEV, GEG ) of CO 2 adsorbed on wessalite (DAY-zeolite) at T=298K a... Dielectric Caloric Meas. (RS, ESch, JUK)... Voluetry, He Vol. (ESch) GEV... Gravietry, He Vol. (RS) GEG
Gas Mixture Sorption Measureent Methods
Therodynaic-conference Würzburg GVC-GET Therodynaic-Conference Würzburg, 2001