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Department Chemie Lehrstuhl für Technische Chemie II Prof. Johannes A. Lercher

Diffusion and Separation Characteristics of Binary Hydrocarbon-Mixtures in MFI

Diffusions- und Trenneigenschaften von Kohlenwasserstoffmischungen in MFI

Master Thesis ----------------------------------------------------------------Vorgelegt von Bsc. (TUM) Robin Kolvenbach

Betreuer: Prof. Dr. J. A. Lercher

Garching, April 2010

„Wer die erhabene Weisheit der Mathematik tadelt, nährt sich von Verwirrung“ Leonardo da Vinci

Acknowledgement

A

Acknowledgement There are a lot of people without whom this thesis had not been written and whom I owe my deepest gratitude. First of all Prof. Lercher for giving me the opportunity to work in his group and trusting me with the most challenging issue for my work. Then I would like to thank PD Dr. Jentys for guiding me through this thesis and also over the last years during my study at Technische Universität München. I would like to address my deepest gratitude to Oliver Gobin who is an archetype for every scientist. I owe my gratitude to him for his guidance and excellent advice throughout this thesis. The intense discussions we had showed me how to perform scientific work in a proper way. I would like to thank the whole group for their support during this thesis. I have to address my special thanks to Xaver Hecht and the whole technical team without whom this thesis would have been impossible. Of course I would like to thank my wonderful parents and my family, brothers and my sister for supporting me my whole live.

Therefore several parameters were varied: different measurement and activation temperatures as well as compacting pressures were examined. These were mainly an equilibrium separation factor of 1 and the form of the transmission curves which were both independent on the change of experimental conditions. The time until stationary conditions were reached as well as the transmission time were clearly influenced by the capacity of the adsorber. As a consequence the transport mechanism in the Wicke Kallenbach wafer can be assumed to be Knudsen diffusion through the mesopores. 100 and 150 mg. Therefore. The steady state diffusion coefficients were 10-6 m2/g obtained by the Wicke Kallenbach measurements. This report analyzes the transport mechanism and tries to falsify two models. Considering the transport mechanism the diffusion through the mesopores was found to be the rate determining step once the system was under stationary conditions. The pore size of the mesopores was confirmed either by calculations from the Wicke Kallenbach experiments applying the theory of Knudsen diffusion or nitrogen physisorption isotherms using DFT analysis.Abstract B Abstract The diffusion and separation characteristic of binary hydrocarbon mixtures through zeolitic wafers were studied with a Wicke Kallenbach cell. It was found that the model of the classical bed adsorber suits the experimental results. The capacity was determined by the temperature during the experiment and activation as well as the weight of the wafer. . A pore size of 6 to 15 nm was found in which the transport through the 6 nm pores seem to be the determining step of the rate of diffusion. the transport of a benzene/p-xylene mixture and a p-xylene/m-xylene mixture was examined in ZSM5 powder pressed to wafers of 50. which are much faster than the diffusion coefficients of 10-15 m2/g of the parent MFI as measured by pressure modulation frequency response experiments and uptake rate measurements. the statistically dense membrane and the classical bed adsorber.

Der Transport durch den Wafer unter stationären Bedingungen wurde durch die Diffusion in den Mesoporen determiniert. zum einen die Idee einer statistisch dichten Membran und den klassischen Bettadsorber. . 100. dass das Modell des Bettadsorbers in der Lage ist. Die Porengröße wurde daraufhin durch zwei Methoden bestimmt.und Aktivierungstemperatur als auch den Pressdruck während der Herstellung des Pellets. Dieser Bericht analysiert die Transportmechanismen innerhalb des Wafers und falsifiziert zwei Modelle. die experimentellen Ergebnisse hinreichend gut zu beschreiben. dass die Diffusion in den Poren einer Knudsen Diffusion in den Mesoporen entspricht. Es wurde eine Porengröße von 6 bis 15 nm gefunden wobei der Transport in den 6 nm Poren den gesamten Diffusionstransport determiniert. Zum einen durch eine DFT Analyse einer Stickstoffphysisorptionsisotherme und zum anderen durch Berechnung aus den experimentellen Wicke Kallenbach Daten unter Benutzung der Theorie der Knudsen Diffusion. Die Diffusionskoeffizienten des Pulvers wurden mittels pressure modulation Frequenz Antwort Methode und Uptake Rate Messungen bestimmt. unter anderem die Experiment. 150 mg durch Pressen des Pulvers hergestellt. Hierbei wurden verschiedene Parameter variiert. Es wurde festgestellt. welche charakteristisch für Adsorber ist. Es wurden Diffusionskoeffizienten von 10-6 m2/g in den Wicke Kallenbach Messungen gefunden welche im Vergleich zu 10-15 m2/g für das korrespondierende Pulver deutlich größer waren. Hierbei wurden Gemische aus Benzol/p-Xylol und m-Xylon/p-Xylol an einem Wafer aus ZSM5 untersucht. Diese waren vornehmlich ein Trennfaktor von 1 und die Form der Durchbruchskurve. Hierbei hängt die Zeit bis zum Erreichen des Gleichgewichts genauso wie die Durchbruchzeit von der Kapazität des Adsorbers ab. Diese wiederum wurde beeinflusst von der Experiment.Zusammenfassung C Zusammenfassung Die Diffusion und die Trennung einer Mischung bestehend aus zwei Kohlenwasserstoffen wurde in einer Wicke Kallenbach Zelle untersucht.und Aktivierungstemperatur als auch von der Dicke des Wafers. Anhand der gemessenen Diffusionskoeffizienten kann angenommen werden. Es wurden Pellets zu 50.

feed normalized gas phase concentration time dependent concentration [mol/l] concentration at infinite time [mol/l] concentration of diffusing component [mol/m3] initial adsorbed phase concentration [mol/m3] equilibrium adsorbed phase concentration [mol/m3] steady state adsorbed phase concentration [mol/m3] concentration in the adsorbed phase [mol/m3] equilibrium concentration inside the particle [mol/m3] adsorbate concentration in the feed [mol/m3] .Abbreviations D Abbreviations A Aper poke Aper successful poke amplitude of FR experiment surface area needed statiscally for one poke [m2] surface area needed statiscally for a poke leading to sorption of the adsorbent into the pore system [m2] AS Aw a surface species Cross section of the wafer [m2] parameter corresponding to the amount of adsorbate in the pores cB and on the surface cA B BP b amount of gas present in the sheet adsorbate inside the channel system parameter corresponding to the amount of adsorbate in the pores cB and on the surface cA C Ct C∞ c c0 co c∞ cA ce c(1.2).

eff DLS dp EA.D F FHe Fmolecules effective heat capacity of the adsorbent sample [J/kgK] surface concentration [mol/m2] concentration dependent diffusion coefficient pre exponential factor of the Arrhenius ansatz diffusion coefficient in the pore system [m2/s] effective Knudsen diffusion coefficient [m2/s] dynamic light scattering pore diameter [m] activation energy of diffusion [kJ/mol] volumetric flow rate [m3/s] volumetric flow rate of the sweep gas [m3/s] Number of molecules transmitting through wafer per second [molecules/s] ∆H h J K heat of adsorption [J] external heat transfer coefficient [W/m2K] diffusive molar flow rate [mol/m2s] parameter proportional the slope of the adsorption isotherm KH k ka L Henry constant Boltzmann constant [J/mol] rate constant of Adsorption [1/s] characteristic length of diffusion [m] . measurement adsorbate concentration in the permeate during the measurement [mol/m3] cp cs D(c) D0 Deff DK.2).Abbreviations E c(1.

Abbreviations F mean value of characteristic length of diffusion [m] M MFC m(t) m0 m∞ N molar weight [kg/mol] mass flow controller mass dependent on the time starting mass end mass statiscal number of successful pokes during the transmission of the adsorbate through the wafer NA n P P0 Pe Avogadro constant [1/mol] number of parallel transport processes partial pressure [Pa] standard pressure (1 bar) partial pressure of the diffusion component in the gas phase at equilibrium condition [Pa] p pB Q Q0 pressure amplitude of FR experiment pressure amplitude of blak of FR experiment dimensionless concentration in the adsorbed phase equilibrium value of the average dimensionless adsorbed phase concentration R r ra S SAd gas constant [J/molK] radius of the Wicke Kallenbach pellet [m] rate of adsorption [mol/s] separation factor adsorption cross section [m2/mol] .

Abbreviations G Sw SBET Sext SEM T T0 TI TEM t tHasley cross section of the adsorbent bed BET surface area [m2/g] external surface area [m2/g] Scanning electron microscopy temperature [K] experimental temperature (FR) [K] initial and final steady state temperature [K] transmission electron microscopy time [s] thickness of a monolayer of physisorbed nitrogen according to the theory of Halsey [nm] UHV VFR Ve.max Vmol Wsat X XRD x ultra high vacuum volume of the FR system [m3] equilibrium volume (FR) [m3] macropore volume [cm3/g] mesopore volume [cm3/g] micropore volume [cm3/g] maximum micropore volume [cm3/g] molar volume [m3/mol] maximum amount of adsorbed gas = W0 [mol/m2] adsorbate in the gas phase X-Ray diffraction space coordinate .FR Vma Vme Vmi vmicro.

Abbreviations H xAdsorbate molar ratio of the adsorbate either in the feed or the permeate y Zw length coordinate [m] Number of hits of a molecule with the wall [1/m2s] .

Abbreviations I Greek Symbols α β δ the dimensionless parameter describing the heat transport the dimensionless parameter describing the heat transport characteristic function of FR experiment mean value of the characteristic function of FR experiments εp χ γ κ η φ φB ρ ρB θ τ τF υ ω porosity factor phase lag of the concentration inside the sheet relative amplitude rate constant of the surface barrier dimensionless radial coordinate phase of the FR experiment phase of the blank FR experiment effective density of the adsorbent sample [kg/m3] density of adsorbent bed surface coverage dimensionless time tortuosity factor amplitude of the perturbation frequency of perturbation [1/s] .

.......... 4 2......2 Wicke Kallenbach Experiments .................................................................................................................................................................I 1.. 21 3.................................... Uptake rate measurements ............ 19 3...................................................1..........................2.................4.... 14 3............................1 Wicke-Kallenbach experiments ......................4...... Frequency Response experiments .................................................. Sample preparation ...................................................................1 Sample preparation ......................... 10 2....................Table of Contents J Table of Contents Acknowledgement ............ 27 4............................................. 21 3. C Abbreviations ........................................... 29 ........ Experimental Setup.. 27 3....................................... Experimental ........... Experimental Setup..........................4..........................................3.............................. 19 3........................................1........... 2.................. Material .........................................................................................1 Sample preparation ...............2...................................................................................................................... Wicke Kallenbach experiments ........................................4.................. D Greek Symbols...................... Uptake rate measurements ............................................1 Zeolites .........................................3........................................2....... Introduction... A Abstract ............................... 29 4....................... 25 3......................................................................... 27 3............................. Results ............................................................... 8 2................. 22 3.......2.................. B Zusammenfassung....................................................................................................................................................................... 25 3.......................3............................... 4 2....3.. 26 3........................3... Frequency response experiments .......................................................................... 1 Theoretical Section ........................................................2 Experimental setup ...........................

.......... 69 Literature ........... Nitrogen physisorption isotherms.........3..... 41 4..................................Table of Contents K 4. 43 4... 6.... Uptake Rate measurements ............................................................................................................. 71 Appendix ..............................................................................4................. Frequency Response experiments .. Discussion ............2........................... 49 Conclusion ............................................................................................................................................................... 47 5......

Furthermore microscopic IR techniques offer the possibility to monitor the diffusion process in a sample [20.8.2]. . To be able to determine the intracrystalline diffusivity many different methods were developed in the last decades among these uptake rate measurements [6.9] as for instance zero length column [10.11]. Since then the method was used for several different types of experiments either in the classical form or modified to fit the requirements. The difference in the diffusivity of two components due to the pore diameter of a porous substrate can also be used for separation by size exclusion.19] and rapid scan IR- spectroscopy[4. The enhanced separation is caused by a surface modification with a silica layer of 3 nm thickness [4. Moreover it is possible to increase the selectivity of a process by shape selective catalysts [1.Introduction 1 1.17. This over-layer leads to a variation of the sticking probability on the modified surface which speeds up selectively the sorption rate in the porous over-layer and has in combination with the intrinsic size exclusion of the MFI micropores the consequence of an enhancement of the sorption rate. meso. Introduction The understanding of diffusion processes in porous media is crucial for the development of new and more effective catalysts and molecular sieves.5.15].14.18. Originally Wicke and Kallenbach invented the method for monitoring the diffusivity of CO2 in active coal [22].5].7. frequency response experiments [16. Another widely used method is the measurement in a Wicke Kallenbach cell. This experiment offers the possibility to determine the diffusive flow through a micro-. Sakai et al. different NMR techniques for example the widely applied pulsed field gradient method [12. Another approach to enhance the separation of hydrocarbons by zeolites was recently published by our group. Especially the diffusion in micropores became a very important field as this is often the rate controlling step in a complex reaction network. showed the separation of p-xylene from a ternary mixture of the xylene isomers with the help of a MFI-type zeolite membrane [3].or macroporous wafer. Most of the time these are zeolites or related materials because the pore structure can be tuned to favor the desired product.13.21].19].

helium.5 nm by applying a modified Wicke-Kallenbach cell [25]. applied the method to measure intracrystalline diffusivity of fast transport processes such as methane in Silicalite 1 [23]: they mounted large silicalite crystals (100x100x300 μm) at the center of an aluminum disk where both sides of the crystals were exposed by using an epoxy resin. The experiments should also give more insight in the separation behavior of hydrocarbons of such wafers. Separation factors larger than 600 were obtained in a temperature range between 298 and 473 K. They examined the transport of ternary mixtures made of hydrogen. propane and butane. Many other authors used zeolite membranes grown on a support. They also tried to model the transport processe with the DGM and in addition with the mean pore transport mode model. [26]. demonstrated for example the possibility to separate mixtures of molecules with small and large kinetic diameters [24]. which were in agreement with previously reported intracrystalline diffusivities determined by frequency response techniques. nitrogen or argon in mesoporous alumina wafers. The aim of this report is the examination and understanding of transport phenomena of binary mixtures consisting of strong adsorbing substances during the transmission through a pressed wafer of ZSM5 in a Wicke Kallenbach cell. They should answer the question if these wafers act like a membrane or analogue to a bed adsorber.2-dimethylbutane as large molecule. Keizer et al. The experimental part consists of Wicke Kallenbach experiments applying pressed wafers of ZSM5 . quantified the amount of surface diffusion of non adsorbing gases in porous glass with a pore radius of 3. Tuchlenski et al. They obtained excellent results in describing the diffusion of a non-adsorbing gas through the membrane by applying the dusty gas model (DGM). most of the time alumina to investigate intrapore transport processes. They preformed the measurement with methane. ethane. Similar experiments were carried out by Arnóst et al. Unfortunately they found out that it is impossible to model this process as the molecules influence each other in the gas during the transmission through the wafer. N-hexane was chosen as small and 2.Introduction 2 Sun et al. The experiments showed excellent results.

Introduction 3 and binary mixtures of benzene and p-xylene as well as p-xylene and m-xylene as adsorbates to see whether it is possible to separate these compounds. To investigate the differences between the powder and the pressed wafer. These techniques allow the determination of the time constant of the diffusion and the examination of the transport mechanism by fitting the experimental data to theoretical models. . The combination of all these different techniques should answer the question which diffusion mechanism occurs in a pressed Wicke Kallenbach wafer and shows if it is possible to separate hydrocarbons with a pressed zeolitic wafer. pressure modulation frequency response and uptake rate measurements were performed.

isomerization [32. Because every zeolite is a potential catalyst. Nowadays over 180 different zeolite structures are known among them 40 natural and 140 synthetic topologies. Zeolites consist of SiO44. in particular fluid catalytic cracking [31]. They are identified by a three letter code defined by the IUPAC (International Union of Pure and Applied Chemistry) [37] and the IZA (International Zeolite Association) [38] e.35].33] and alkylation [34. methanol to gasoline [29] or selective catalytic reduction of nitric oxide by ammonia [30].and AlO45. The name Zeolite was used for the first time in 1756 by the mineralogist A. Theoretical Section 2. Figure 1:Primary and secondary building units (PBU. These secondary building units (SBU) can be separated in 20 .Theoretical Section 4 2. One of the most important operation areas is the petrochemical industry.g. adsorber or cation exchanger they are applied in several processes [28] e.tetrahedrons as primary constitution which built up a three dimensional secondary structure by linking through the oxygen atoms (Figure 1). Cronsted who observed bubbles while heating the mineral Stilbite.1 Zeolites Zeolites are microporous tecto-silicates which are nowadays widely used in industrial processes [27]. SBU) of zeolitic frameworks. The origin of the name zeolite are the two greek words “zeon”(to boil) and “lithos”(stone) [36].F.g. FAU = Faujasite.

The pores have a diameter below 1. This property gives the opportunity to perform size exclusive as well as shape selective reactions. Figure 2: Pore size distribution of zeolites in comparism to the standard adsorbents silica gel and active cole [39]. quaternary ammonium ion or proton [40] (Figure 3). .and pore .Theoretical Section 5 different unique polyhedrons. Additionally selective adsorption of a molecule from a reaction mixture becomes possible because molecules larger than the pore openings cannot enter in contrast to smaller ones. Due to the regular structure of the material the pore size distribution is very sharp.systems. Figure 2 shows the pore size distribution of several different adsorbents in comparism. The general elemental formal for zeolites is Mx/m[(AlO2)x(SiO2)y]•wH2O where m is the charge of the cation and w the number of water atoms is the cage.3 nm which means they are in the range of kinetic diameters of molecules. The combination of the primary and secondary units leads to huge and complex structural diversity with three dimensional channel. The isomorphous exchange of Si4+ by Al3+ opens out into a negative charge which has to be compensated either by an inorganic or organic cation consequently an alkali. cages and super – cages [38]. earth alkali cation.

Although the microporousity is one of the main advantages of zeolites it is a disadvantage at the same time. The reason for this is the slow diffusion in the micropores which leads to limitations of the rate of chemical reactions. a molecular dimension of the pores. high thermal and hydrothermal stability. The aluminum content is one of the characteristics determining the reactivity of a zeolite by the density of negative charge in the framework. Si/Al ratios from 1 to infinity which describes pure silica zeolites are common. the thermal stability and hydrophilic properties [43].Theoretical Section 6 Thereby the Si/Al ratio is defined by the ratio of y/x and has to be greater than 1 due to the Löwenstein rule [41]. the ion exchange capability. This has enormous consequence for the density and strength of the Brønstedt acid sites. Figure 3: Structural formulas showing the effect of isomorphic exchange of silicon by aluminum and the compensation by either an inorganic or organic cation M+ (a) or proton (b) [42]. . high ion-exchange capability. To solve this problem intense activities are ongoing over the last years. This dependence provides the opportunity to tune the reaction properties of a zeolite by altering the degree of aluminum in the framework. Summarizing the physical and chemical properties [44] of zeolites it may be adhered that they have a high surface area. a high adsorption capacity. This rule indicates that Al-O-Al linkages are forbidden in zeolite frameworks. the possibility of modulation the electric properties of the active sites and the possibility for pre-activating the molecules in the pores by strong electric fields and molecular confinement.

g. These reactive gels are produced from hydrated aluminum and silicon species e. A structure directing agent (SDA) is added to the reaction mixture to control zeolite growth in means of pore size and network dimensions. Metalpowder or salts dissolved in sodium hydroxide solution usually serve as aluminum source. Figure 4: Two different method of ZSM5 synthesis [ 48]. These two different methods are described in Figure 4. .g. The synthesis of zeolites is usually performed under hydrothermal conditions using reactive gels in alkaline media at 80 – 200 °C. Inside this gel zeolitic nuclei occurs which then starts the crystal growing. One is to make nano sized particles [45] and the other one is to synthesize mesoporous materials like MCM-41 [46]. The pH of the reaction mixture is adjusted between 9 and 13. hydroxides. In this high temperature and pressure conditions a reactive gel is formed. Usually tertiary amines serve as SDA e. a tertiary-propyl-ammonium salts in the case of ZSM5. Depending on the synthesis method zeolite crystals or polycrystalline zeolite material is formed. The silicon source which is normally the colloidal dioxide is combined with the aluminum containing solutions under hydrothermal conditions [47].Theoretical Section 7 There are mainly two ways to overcome this problem.

If the experiment is performed with two or more substances it is possible to determine the ability of the sample to separate the adsorbates by comparing the feed concentration to the concentration in the permeate.51. One of the flows is loaded with probe substances and the other one contains of pure sweep gas (Figure 5).1) If a separation is observed during the experiment the separation factor has to differ from 1. 2. Furthermore it is possible to calculate the diffusion coefficient of . They were extensively reviewed before [49.50. Therefore.2 Wicke Kallenbach Experiments This method for investigating the diffusivity in porous media was developed by Wicke and Kallenbach in 1941 [22]. The diffusion through the wafer is driven by the concentration difference between both flows.2. the volumetric flow rate of the loaded and the unloaded stream has to be the same.52] and will not be discussed here. Hence it is possible to calculate a separation factor by: (2. Figure 5: Flow scheme of the Wicke Kallenbach cell showing the fluxes going in and out of the cell and indication where the diffusive transport takes place.Theoretical Section 8 During the last 50 years many other preparation methods were developed. In principle two countercurrent gas flows graze the sample wafer in a 90° angle. The pressure on both sides of the cell has to be the same to avoid pressure driven transport through the sample. The sample is placed into the cell as a wafer which is either produced by compacting of powder or as a grown membrane.

The conditions for this kind of diffusion are summarized in the following table [53]: Table 1: Depence of the occurring of Knudsen diffusion on the partial pressure of the adsorbate and the pore size dp [nm] p [105 Pa] <1000 0. (2. In principle three different kinds of diffusion have to be considered in porous media. As a result the diffusion process can be described analogue to the free vacuity by the first fickian law by substituting the diffusion coefficient by an effective diffusion coefficient (Deff). r is the radius of the pellet.2.4) .2.4) [53].2. In the case of molecular diffusion the mean free path of a molecule is shorter than the pore diameter. respectively.2.Theoretical Section 9 the adsorbates inside the pellet from the steady state molar ratios of these experiments by (2.3) If the pore size is small or the gas pressure is low the mean free path is longer than the pore diameter.2) In this equation L is the characteristic length of diffusion. FHe is the volumetric flow rate of the sweep gas and x Adsorbate is the molar ratio in the feed and in the permeate at steady state conditions.2) (2. The latter consists of an additional porosity factor (εp) which describes the ratio of pore openings compared to the total surface area as well as a tortuosity-factor (τF) specifying the differences of the pore geometry from the ideally assumed cylinder [53]. Consequently the molecules hit the pore walls much more often than other molecules.1 <100 1 <1 10 <2 50 The diffusive flow in the Knudsen theory can mathematically be expressed by equation (2. (2. In this case the so called Knudsen diffusion is observed.2.

The dependence of the effective diffusion coefficient on the pore diameter is shown in Figure 6.2. In this method the volume of the reaction vessel is altered periodically by ±1 % while tracking the pressure simultaneously.Theoretical Section 10 In here dp is the pore diameter.5) The third kind diffusive transport is the diffusion in pores with a diameter below 1 nm ocurring in zeolites. [54].2.5) [53]. Therefore the diffusion coefficients found in zeolites are much lower than the molecular or Knudsen coefficients.3. In this case the pore radius is in the range of the minimum kinetic diameter of the diffusing molecule. The solutions for all of these constraints can be found in Crank et al. R is the gas constant. The mathematical description is the first fickian law for a system in a steady state as shown in (2. By changing the volume the adsorption/desorption . Analogue to the fickian law the effective diffusion coefficient can be described by equation (2. M is the molar mass and c the concentration of the diffusing component. Figure 6: Dependence of the effective diffusion coefficient on the pore size of porous adsorbents. T is the temperature. (2. Frequency Response experiments The frequency response method offers the opportunity to determine transport pathways and their kinetics in a batch adsorber [60]. For non steady state situations the second fickian law is used and calculated separately for each specific case.2.3). 2.

Theoretical Section 11 equilibrium is disturbed and tries to equilibrate again. In this work two different transport mechanisms are examined: the diffusion in an . φB is the phase of the blank measurement and δ is the characteristic function.3. The model equations used for the curve fitting can be found by solving the mass balance in a closed volume as described previously by Yasuda et al. the volume of the system (VFR) and the gas constant (R). [16]. the temperature (T).2) (2. pB is the corresponding pressure amplitude in a blank experiment. φ is the phase of the experiment.3) Where p is the pressure amplitude of the experiment. This equilibration can be followed by tracking the pressure (Figure 7).1) (2. They obtained two characteristic functions characterizing the system: (2. Figure 7: Simulated data of a frequency response experiment with a square wave volume perturbation showing the signal of the magnet which describes the volume (blue) and the corresponding pressure trend (red) against the time. Furthermore K is a parameter proportional the slope of the adsorption isotherm.3.3. The experimental data is then compared to the solution of theoretical models in order to find the best match. Herein n is the number of parallel transport processes. Blank experiments are needed to exclude the non-idealities of the apparatus itself from the outcome of the experiment [60]. The characteristic functions (δ) are solutions of the second fickian law using the right boundary conditions. By matching the experimental data to the models the mechanism of the transport process and its kinetic parameters can be obtained.

φ and χ are the phase lags both depending on the frequency ω. R is the gas constant.3. ω is the frequency of perturbation and t is the time.3.10) (2.5) herein Ve. υ is the amplitude of the perturbation.3.4) where P is the pressure in the system. The vapor pressure of the diffusing substance and the concentration in the pores can generally be described by: (2. [56]: (2.3. ce is the equilibrium concentration inside the particle.3.12) . T 0 is the experimental temperature and B is the amount of gas present in the sheet. D(c) is the concentration dependent diffusion coefficient and x is the space coordinate.3. The mass balance of an infinite sheet without surface barrier is defined as [17]: (2. The diffusion inside the pores is described by the second fickian law: (2.3.FR is the equilibrium volume.3. p (∆p/2) and γ are the relative amplitudes. B.9) In this work we consider the case of one dimensional diffusion in sheet with plane boundaries at x=0 and x=L. Since the perturbations are defined to be small fick´s law eases to: (2. The boundary conditions define the concentration at the boundaries to be proportional to the sinusoidal changing vapor pressure in the gas phase [55].Theoretical Section 12 infinite sheet and an infinite sheet with surface resistance.11) As a consequence the integral of the amount of gas present inside the sheet. Assuming the volume is changed sinusoidal we can formulate the volume as: (2.3. V is volume.8) Herein c is the concentration in the pores.6) (2.7) where Pe is the partial pressure of the diffusion component in the gas phase at equilibrium condition. is given by: (2.

3.3. Therefore we have to add another equilibrium upstream to the one we considered before describing the surface adsorption.3.3.20) where κ is the rate constant of the surface barrier and a and b are parameters corresponding to the amount of adsorbate in the pores cB and on the surface cA [60]: .1) and (2.3. V and B result in these in.3. L is the length of the sheet and D is the diffusion coefficient. p is the relative amplitude of the pressure.3. Furthermore the coefficient ψ in equation (2. The amplitude A is expressed by [56]: (2.12) is defined by: (2.Theoretical Section 13 Where Be is the equilibrium amount if gas present inside the sheet. ω is the frequency.14) where KH is Henry´s law constant.3. The corresponding material balance is defined by: (2. A S is the surface species and BP is the adsorbate inside the channel system.3.3.and out of phase functions [16]: (2.2) where the in and out-of-phase functions are given by: (2.4) leads to the two equations (2.17) The other mechanism we want consider is surface controlled diffusion.16) (2.13) (2.18) The solution using the previously described terms for P.15) Substituting (2.3.19) (2.3. This leads to the following reaction network [57]: X ↔ AS ↔ B P where X is the adsorbate in the gas phase.3.12) into the material balance (2.

2. It has the following assumptions: 1) 2) The sample consists of a ensemble of spherical particles Intracrystalline diffusion is the only significant resistance to mass transfer. The time constant and thereby the diffusivity can be obtained by matching the experimental data to an appropriate model describing the diffusion process. The experiment is performed under isothermal conditions. respectively.Theoretical Section 14 (2.or microporous diffusion. meso.24) Herein and describing the mean values of the characteristic function and the thickness of the sheet.21) (2.3. [58] for systems controlled by intracrystalline diffusion.2) changed. In the case of a surface barrier it is defined by [57]: (2.3. 3) 4) The diffusivity is constant and the equilibrium relationships are linear. The altering of the pressure surroundings causes a shift in the surface concentration of the adsorbate species which can be described by the diffusional time constant (D/r2) [7].4.3.3. Therefore the sorbate concentration at the surface of the particles is always in equilibrium with the adsorbate in the surrounding fluid phase. A general mathematical model is applied developed by Ruthven et al.3.1) and (2. . The method can be used for either macro-.23) Because most of the zeolites do not have a uniform particle size a normal distribution is introduced which modifies the characteristic functions [60]: (2. Uptake rate measurements To determine the kinetics of adsorption processes in porous materials a step change of the adsorbate pressure is performed and the change in mass of the sample is tracked.22) Additionally the definition of the parameter K of the characteristic functions (2.3.

2) (2.4.7) where cs is the surface concentration and co the equilibrium adsorbed phase concentration. TI is the initial and final steady state temperature. Based on the first fickian law the first one defines the behavior of the dimensionless adsorbed phase concentration (Q) dependent on the dimensionless time (τ): (2.5) and its time dependence (2.4.6) where Q is the dimensionless concentration in the adsorbed phase.8) and (2. c0 is the initial adsorbed phase concentration and c ∞ is the steady state adsorbed phase concentration. T is the temperature. cp is the effective heat capacity of the adsorbent sample. The second and third equation describe the average of the adsorbed phase concentration over the particle (2. η is the dimensionless radial coordinate. As a result the concentration of the adsorbed phase at the particle surface can be defined by (2.9): .3).4. This set of equations is solved with the initial boundary conditions (2. τ is the dimensionless time as defined in (2. c0 is the initial adsorbed phase concentration.4.4. h is the external heat transfer coefficient. c∞ is the final steady state adsorbed phase concentration. cA is the concentration in the adsorbed phase. D is the Diffusion coefficient and L is the radius of the particles (= characteristic length of diffusion).4.1) (2. ρ is the effective density of the adsorbent sample. Obviously the heat transfer has to be taken into account even if it is disregarded later due to the isothermal conditions.3) in here η is the dimensionless radial coordinate.4.4.5) (2.7): (2.6): (2.4.Theoretical Section 15 According to these approximations the system can be described by the following differential equations. ∆H is the heat of adsorption.4.4.4.

4.11) where qn is given by the roots of: (2. By knowing the length of diffusion the diffusion coefficient can be obtained.4. which is only valid for monolayer adsorption. 2.4. to multilayer adsorption.4.4. .5.4.4. α and β are the dimensionless parameters describing the heat transport and are formulated by (2.10) (2.4.8) (2.4.14) (2. Analysis of physisorption isotherms The mostly applied method to analyze nitrogen physisorption isotherms was developed by Brunauer.15) This equation is then used to perform curve fitting with the fit parameter τ.4.14) Considering the assumption of isothermic conditions (α ∞ and β 0) the solution for the average dimensionless adsorbate concentration reduces to (2.9) in here the first initial boundary condition indicates that the starting adsorbate of the experiment is zero.13) and (2. It offers the possibility to determine the surface area of a solid sample. Emmett and Teller in 1938 [59].4.10) and (2.Theoretical Section 16 (2.15): (2.11): (2.12) thereby Q0 is defines the equilibrium value of the average dimensionless adsorbed phase concentration.4. The second one defines that the concentration of the adsorbed phase does not change in the center of the particles.13) (2. In principle it is an extension of the classical Langmuir isotherm. The solution taking the boundary conditions into account can be obtained by Laplace transformation and is shown in (2.4.

In this thesis the method of Halsey [70] is used to produce the standard isotherm.3) In here Vm is the volume of a monolayer.1 is the linearized form of this equation.2) Furthermore it is possible to determine the surface area (2.5. Additionally it is possible to analyze the isotherm concerning the micro.5. 2. (2.1) with VAd equals the total amount of adsorbate adsorbed on the sample.5. The corresponding equation is: (2.3) if the adsorption cross section of the adsorbing molecule is known. A the possible way is the t-plot method: the experimentally obtained isotherm is compared to a standard isotherm by plotting them against each other at the same P/P0 points.4) .5. Vmol is the molar volume of the adsorbing gas.and mesopore volume.5. NA is the Avogadro constant. The standard isotherm is thereby represented by the thickness of adsorbed layers.Theoretical Section 17 The following assumption corresponds to this theory: 1) gas molecules adsorb in an infinite number of layers 2) each layer is treated independently which means that it has no interaction with other layers 3) each layer can be treated with the theory of Langmuir adsorption This leads to the BET equation: (2. Based on this the monolayer coverage can be obtained from the slope and the intercept of the resulting graph shown in 2.5.5. P is the partial pressure of the adsorbate. P0 is the standard pressure and Vm is the volume of a monolayer.2: (2. SAd is the adsorption cross section of the adsorbing molecule and M is the molecular weight of the adsorbing molecule.

It can be described by: (2. According to equation 2.and the mesopores. The last step is to determine the mesopore volume.and mesopore volume.5) In here vmicro. For standard units k is defined by 1/(4.max defines the volume of the micropores.5.354 nm. The second linear region with a positive slope describes the region shortly after the mesopore condensation. Linear regions of the resulting plot correspond to regions where the standard and the experimental isotherm have the same physical properties.Theoretical Section 18 The obtained values are then plotted against the experimentally observed data. the units of vads and Sext.5.3532xtHasley) with tHasley representing the thickness of a monolayer in the case of nitrogen 0.and mesopore volume is subtracted by the previously obtained micropore volume. To do so the value of the combination micro. Consequently the intercept of the second linear region identifies the addition of the micro. kt is a coefficient depending on the layer thickness.5 the intercept of the first linear region defines the micropore volume whereas the external surface area can be obtained from the slope of the graph. These regions can be described mathematically to determine the micro. . The first linear region with a positive slope is defined as the point closely after the micropores are completely filled and before the mesopore condensation begins.

22 Sext [m2/g] 65 Vtot [cm3/g] 0.04 Vma [cm3/g] 0. Figure 9: αs plot of the parent (a) material.38 Table 2: [60. The macro-.0 0.5 1. SBET [m2/g] Parent 423 Vmi [cm3/g] 0.5 2.Experimental 19 3. S ext is the external surface area and Vmi.1 1 0. the macro-.1 and 0.5]: Results of the nitrogen physisorption experiment for the parent ZSM5 sample.01 0.10.5 corresponding to the micropore volume and at αs= 1.and micropore volume as well as the total pore volume (Table 2) were determined by nitrogen physisorption (Figure 8) and applying the Brunauer-Emmett-Teller (BET) theory in the range from 0. meso and micropore volume obtained by using the αs comparative plot Additionally the Langmuir surface area was determined by performing a Langmuir plot in the relative pressure range up to 0.and mesopore volume [4].1.03 to 0. The specific and the external surface area.0 Relative Pressure (-) s Figure 8: Nitrogen physisorption isotherms of the parent H-ZSM5 material (a) [5]. meso. Vme. Experimental 3. 200 180 160 150 (a) Amount Adsorbed (cm STP g ) Amount Adsorbed (cm STP g ) 125 Vmi + Vme (b) -1 140 120 100 80 60 40 20 0 1E-5 (a) 3 (b) 3 -1 100 75 Vmi 50 1E-4 1E-3 0. SBET is the total surface area determined by applying the BET theory. Vma and Vtot are the micro-. Between 0. The nitrogen physisorption isotherms were obtained using a PMI automated sorptometer at liquid nitrogen temperature (77 K) after outgassing under vacuum for at least 6 hours.10 mbar.3 mbar the plot was not linear with a negative intercept (BET C constant). .0 1.2 belonging to the sum of micro.12 Vme [cm3/g] 0. Material Polycrystalline H-ZSM5 samples with a particle size < 100 nm and a Si/Al ration of 45 [60] were provided by Südchemie AG. Two linear regions can be found at αs=0.

Step size was 0.Experimental meso. The powdered samples were suspended in an ethanol solution and dried on a copper-carbon grid prior to the measurement. 20 Figure 10: Scanning electron microscopy of the H-ZSM5 parent material [60]. As shown in Figure 10 the particles contain of larger agglomerates of smaller particles with a diameter of 0.and micropore volumes were obtained by using a αs comparative plot (Figure 9) [61] with nonporous hydroxylated silica [62] as reference adsorbent. Figure 12). SEM images were produced on a REM JEOL5900 LV microscope operating at 25 kV with a resolution of 5 nm and a nominal magnification of 3.17 µm. Both methods show that the primary particle size is below 100 nm (Figure 11. The powder diffraction patterns were measured on a Phillips X`pert Pro XRD instrument operating at the Cu-Kα radiation at 40 kV with a Nickel filter to remove the Cu-Kβ.017° with a scan time of 115s per step.36 ± 0. Prior to the measurement the sample was dispersed in water with help of an ultrasonic bath where it was kept for several hours. The particle size distribution was determined by dynamic light scattering (DLS) and scanning electron microscopy (SEM). The size of the primary particles was obtained by transmission electron microscopy (TEM) and X – Ray diffraction (XRD) methods. DLS measurements were performed on a Malvern Zetasizer Nano ZS. The samples were used without pretreatment. The samples were used without further purification. The TEM images were recorded on a JEOL-2011. The measurements were repeated at different concentrations several times.0 x 106. Powder patterns were produced using a spinner system with a ¼ inch divergence slit between two angles of 5 an 70°. .

The sample was then subsequently built into the Wicke Kallenbach cell and was flushed with helium for 30 minutes. 3.3. The XRD of the parent material shows sharp reflexes at the characteristic positions of ZSM5 (Figure 12).5 % GC standard) were supplied by Sigma Aldrich and were used without further purification.2. Figure 12: XRD of the parent H-ZSM5 material showing the characteristic reflexes of ZSM5 [60]. Wicke Kallenbach experiments 3. Thereby the loading with benzene was . Benzene and p-xylene (> 99. Afterwards the sample was activated at 723 K for 1 hour in a helium flow of 50 ml/min for each of the two flows and an incremental heating rate of 10 K/min.Experimental 21 Figure 11: TEM images of the parent H-ZSM5 sample[4]. The experiments were performed at a constant gas flow of 50 ml/min for each of the two countercurrent flows.1 Sample preparation All powdered samples were compacted into a stainless steel (b) ring at 20 kN for 2 minutes using the pressing instruments shown in Figure 13.

33/1 bezene/p-xylene in the feed. Also the influence of the compacting pressure and the activation temperature was tested. Figure 15 shows a CAD Model of the saturators . measurements at 130°C (403.2.2 Experimental setup The cell shown in Figure 14 is made of 6 pieces. In addition the sensitivity of the wafer thickness was examined in testing wafers of 150. To determine the temperature dependence of the separation. Assuming 100% saturation of the streams this leads to a ratio of 1. These MFCs are computer controlled by Flow DDE V4. The loading of the gas stream with benzene and p . 3.Experimental 22 performed with a volumetric flow rate of 2 ml/min and p-xylene was saturated with 18 ml/min.f) and two rings. two endplates (a. the ring inserted in the cell (b) and the stamp pad (c). Figure 13: CAD model of the pressing instruments used to produce wafers for the Wicke Kallenbach cell containing of a plunger (a).09 (Bronkhorst).15 K).41 and Flow View V1. 100°C (373.e). The whole instrument consists of stainless steel. 100 and 50 mg. The flow rate is controlled by 4 mass flow controllers (MFC) Bronkhorst EL-flow select.xylene is performed via two saturators. two of them with a range of 200 ml/min used for the sweep gas and the other two with a range of 20 ml/min leading to the saturators. cooled down to 15°C in a thermostat (Huber K12-cc-NR) with a 1:1 glycol/water mixture as cooling agent to avoid condensation of the adsorbate inside the system.15 K) and 70°C (343. one holding the sample wafer (d) and the other holding the screws (c) and two 2 mm thick graphite sealings (b. The temperature of the cell is regulated via an Eurotherm 2404 PID controller.15 K) were executed.

Figure 15: CAD Model of the saturator used to load the gas stream with adsorbates benzene and p – Xylene. an aluminum ring holding the screws (c) and the inner stainless steel ring clamping the sample (d). two sealings made out of graphite (b. Figure 14: CAD Model of the Wicke Kallenbach cell containing two end plates (a. .Experimental 23 used. These saturators consist of two nearly identical parts which are connected.e).f).

After passing this station the stream gets back into the system through another 2 way valve (d) which connects the bypass (b) and the saturator.b) and serves as a flask for the adsorbate. the mass flow controllers (MFC) the saturators and the electronic for controlling the temperature and the flows.piece and tube which is welded up (a. The gas flow enters the saturator at point (c).Experimental 24 The base body comprises a half inch t . An image of the total setup is shown in Figure 16. Figure 16: Setup for the Wicke Kallenbach experiments containing the Wicke Kallenbach cell. The permeate stream is connected to a vacuum system via a heated capillary and differential pumped inlet system. To save the system from floating with adsorbate in the case of low-pressure inside the system an empty second tube (b) is connected to the first flask. It can either enter the tube filled with adsorbate (a) or go through the bypass (e) back into the system. The following 2 way valve controls the direction of the flow. The bypass is needed to clean the system before and after the measurement. The UHV is produced by a turbo- .

by a nonlinear parameter fitting using a CMA evolutional strategy in matlab [63].3. The objective minimized to find the best consistency was the root mean square error normalized to the variance of the data.3.3. During the measurements the vacuum is 10-5 mbar. Sample preparation Two different kinds of samples. During the experiment the volume of the setup was changed periodically in a frequency range of 5 to 10-3 Hz and a square waved volume perturbation ±1% in amplitude. The resulting characteristic functions were fitted with the model equations described in 2.Experimental 25 molecular pump TMH 071-003 (Pfeiffer Vacuum). To be sure that the best parameters were found which is equal to the . Furthermore two types of pressed wafers were studied: Wicke Kallenbachwafers of 100 mg and IR wafers 6 mg weight. In the case of the powdered samples 35 mg were carefully dispersed on glass-wool at the bottom of a quartz tube to have isolated particles and thereby avoid bed effects. The adsorbate was added with a partial pressure of 0. 3. Hiden Analytical) in the MID mode controlled by MASSoft Professional (Hiden Analytical) computer software.1.31 mbar at a temperature of 373 K until the adsorption equilibrium was fully established. The permeate is analyzed by a mass-spectrometer (WR 13302. were used in this experiment. specifically powdered and pressed samples. The pressure response was fourier transformed by obtaining the amplitude and the phase lag. This allows pressures down to 10-9 mbar. Frequency response experiments 3. placed into an oven and pumped to 10-7 mbar. The samples were activated at 723K for 1 hour with a temperature ramp of 10 K/min at ultra high vacuum conditions to remove the adsorbed water. Glass-wool was placed at the bottom of the sample holder to have the same conditions as in the experiments with powdered samples. In both cases the glass-tube was connected to a UHV setup. Both were carefully broken into smaller pieces to fit in the quartz tube sample holder.

3. The pressure is recorded online via a Baratron pressure transducer (MKS 16A11TCC). The system is controlled via HP VEE based software. Experimental Setup An overview of the setup for the frequency response experiments is given in Figure 17. The UHV is produced by a turbo-molecular pump TMH 071-003 (Pfeiffer Vacuum). To enable the turbo pump to start a zeolite trap is build into the system to produce vacuum of about 10-2 mbar. the sample cell and the dosing system.Experimental 26 global minimum the calculation was performed three times with different starting parameters. The setup is basically a UHV unit equipped with volume perturbation part which consists of two magnetically driven plates sealed with UHV bellows.2. the vacuum chamber. Figure 17: Image of the frequency response setup showing the modulation unit. This allows pressures down to 10-8 mbar. The . 3.

4.1 Sample preparation A Wicke Kallenbach wafer of 100 mg was pressed as described in 2. 3. Uptake rate measurements 3. 3.4. Additionally an oil pump is connected to the system to produce on the one hand the fore-vacuum of 10-3 mbar crucial for a turbo-pump system and on the other hand pumping the inlet system for the adsorbates. by nonlinear parameter fitting using a CMA evolutional strategy in matlab [63]. The procedure was identical to the one described in section 3.1. This normalized data was then fitted with theoretical models described in 2. The adsorbate was added in a pressure jump with partial pressures of 0.1) where m0 is the mass at the beginning of the experiment and m∞ is the mass at the end.3. and broken afterwards into small pieces of 6 to 10 mg.2.Experimental 27 adsorbing substrate is added by a separately pumped dosing system with an all metal regulating valve UDV 040 (Pfeiffer Vacuum) to put the gas phase corresponding to the liquid adsorbate into the system.4. Experimental Setup The main item of the setup is a Seteram TG-DSC 111 microbalance (Figure 18) equipped with quartz insertions and crucibles being heat insensitive. The balance was connected to an UHV system and pumped 10-7 mbar.4. The mass of the sample was normalized afterwards by: (3. One of these pieces was subsequently filled into the quartz crucible which was then placed into the balance. .1. The balance is connected to a UHV unit with a turbo-pump TMH 071-003 (Pfeiffer Vacuum) which is able to produce a vacuum of 10-8 mbar. The sample was activated at 723 K in UHV conditions to remove the adsorbed water and cooled down to the experiment temperature of 373 K.4. 1. 2 and 10 mbar and was kept constant during the whole experiment while the sample mass was monitored by a Seteram TG-DSC 111.

. the pressure and the heat signal. A HP VEE based software is used to control the system and to track all relevant data which is the mass.Experimental 28 The inlet system contains of a ¼ inch connection to fit the round bottomed flask filled with adsorbate to the system. The whole system is operated by a Seteram controller which is connected to a computer. This fitting is linked to an all metal regulating valve UDV 040 (Pfeiffer Vacuum) connecting the inlet part to the vacuum system. vacuum system with a mass spectrometer. Figure 18: System used for uptake rate measurements consisting of a microbalance. a dosing system and a controller.

100°C.Results 29 4. In here the p-xylene concentration was multiplied by the ratio of benzene and p-xylene (1. time diagram of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 and a mixture of benzene (black) and p-xylene (red). In general the shape of the benzene concentration curve was exponential with a clear overshooting. An example of the concentration graph is shown in Figure 19 for 100 °C. The uptake time of benzene and p-xylene differed by more than an hour. the thickness of the wafer and the compacting pressure. . The concentration gradient of p-xylene showed also an exponential form but without the over-swinging behavior. The ratio between the equilibrium concentration of benzene and p-xylene had a constant value around 1. a wafer of 100 mg and 50 ml/min volume flow. 100mg wafer weight and 50 ml/min volume flow.43). 10 -4 10 -5 10 c [mol/l] -6 Benzene p-Xylene 10 -7 10 -8 10 -9 10 -10 0 10 20 30 40 time [min] 50 60 70 80 90 100 Figure 19: Concentration vs.43 for every performed experiment and hence similar to the feed. This equals a separation factor of 1 valid for each experiment. This behavior was independent on the temperature during experiment and activation. Thereby the maximum of the overswinging of the benzene curve occured at the time the p-xylene uptake started.1 Wicke-Kallenbach experiments The diffusion and separation of benzene and p-xylene in H-ZSM5 have been studied using the Wicke-Kallenbach method. Results 4.

The breakthrough time of p-xylene was also temperature dependent changing from 15 minutes for 130°C to 37 minutes in the case of 70°C as shown in Figure 22. To study whether the uptake and thus the separation factor was influenced by the temperature. . It points out that the separation factor was 1 in the beginning. a mixture of benzene/p-xylene and 50 ml/min volume flow. Figure 20 shows this time dependence. Figure 21 displays the trend of the concentration of benzene at these three temperatures. It shows as well that the benzene uptake curve kept its exponential form thus the over swinging got stronger with increasing temperature.Results 30 Because the uptake time for benzene and p-xylene differed as shown in Figure 19 the separation factor was clearly depending on the time. started increasing very fast after 5 minutes and reached a sharp maximum of 104 after 20 minutes corresponding to the maximum of the benzene breakthrough curve. 100mg wafer weight. 10 6 10 Seperation Factor [-] 4 10 2 10 0 10 -2 0 50 100 150 time [min] 200 250 300 350 Figure 20: Time dependence of the separation factor of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 at 100°C. 100 and 70°C were carried out. experiments at 130. It points out that the time to the breakthrough of benzene varied between 7 minutes for 130 °C and 18 minutes for 70 °C. After 100 minutes the graph had a constant value of 1 due to the equilibrium concentration of benzene and p-xylene.

As in the case of benzene the overall form of the uptake curve stayed exponential but the graph got steeper the higher the temperature was. time diagram of benzene breakthrough curves at 130°C (black). 10 -4 10 -5 10 c [mol/l] -6 130 °C 100 °C 70 °C 10 -7 10 -8 10 -9 0 50 time [min] 100 150 Figure 22: Concentration vs. 100°C (red) and 70°C (blue) in a Wicke Kallenbach experiment with a pressed H-ZSM5-wafer of 100mg. 100°C (red) and 70°C (blue) in a Wicke Kallenbach experiment with a pressed H-ZSM5-wafer of 100mg. a mixture of benzene/p-xylene and a volume flow of 50ml/min. Figure 23 shows that the maximum shifted from 15 minutes towards 37 minutes with decreasing .Results 31 10 -5 c [mol/l] 130 °C 100 °C 70 °C 10 -6 10 -7 0 10 20 30 40 time [min] 50 60 70 80 90 Figure 21:Concnetration vs. a mixture of benzene/p-xylene and a volume flow of 50ml/min. Similar time dependence was found in the separation factors. time diagram of p-xylene breakthrough curves at 130°C (black). The breakthrough time as well as the time to the equilibrium concentration decreased with increasing temperature.

. 100 and 150 mg were used at constant temperature of 100°C keeping the other experimental conditions untouched. The obtained graph for benzene is shown in Figure 24. a weight of 100 mg and a volume flow of 50ml/min. But independent of the temperature the constant value 1 was reached. Consequently the chart got less steep in exponential region and had a longer over-swinging period the higher the weight of the wafer was. time diagram at different temperatures of 130 (blue). 10 4 130°C 100°C 70°C Seperation Factor [-] 10 2 10 0 10 -2 20 40 time [min] 60 80 100 120 Figure 23: Seperation factor vs. a mixture of benzene/p-xylene. To examine whether the amount of adsorbent or the thickness of the wafer had an influence on the uptake or the separation factor pellets with weights of 50. It can be seen that the transmission time got longer the more material was used for the wafer and hence with increasing thickness of the wafer. Considering the form of the graphs it can be seen that curves were stretched increasing the thickness of the wafer keeping the overall exponential form with an over-swinging before reaching the equilibrium concentration.Results 32 temperature. 100 (red) and 70°C (black) in a Wicke Kallenbach experiment with a pressed H-ZSM5-wafer. Furthermore the equilibrium concentration got smaller with increasing thickness of the wafer.

Looking at the form of the breakthrough curves it is . a mixture of benzene/p-xylene. a temperature of 100°C and a volume flow of 50ml/min 10 -5 50 mg 100 mg 150 mg c [mol/l] 10 -6 10 -7 10 -8 0 50 100 150 time [min] 200 250 300 350 Figure 25: Concentration vs. As in all other measurements before an over-swinging is not observed. time diagram of p-xylene breakthrough curves with a wafer weight of 50mg (black). As in the case of benzene the uptake time got longer with more material used for making the wafer. a temperature of 100°C and a volume flow of 50ml/min Similar to the benzene curves the graph of p-xylene (Figure 25) got less steep with increasing weight of the wafer. time diagram of benzene breakthrough curves with a wafer weight of 50mg (black). a mixture of benzene/p-xylene. 100mg (red) and 150mg (blue) in a Wicke Kallenbach experiment with a pressed H-ZSM5-wafer. 100mg (red) and 150mg (blue) in a Wicke Kallenbach experiment with a pressed H-ZSM5-wafer.Results 33 10 -5 50mg 100mg 150 mg c [mol/l] 10 -6 10 -7 10 -8 0 50 100 150 time [min] 200 250 300 350 Figure 24: Concentration vs.

As a result the separation factor stayed 1 independent on the thickness of the wafer. Differences could be observed in the breakthrough time and the total uptake time. The breakthrough time was shortened by 6 minutes from 12 to 6 minutes for benzene and by 9 minutes from 26 to 17 minutes in the case of p-xylene. Remarkable is the time dependence of the separation factors: similar to the uptake curves of benzene and p-xylene the maximum separation factor shifted to longer time periods with increasing thickness of the wafer (Figure 26). a mixture of benzene/p-xylene. As shown in Figure 27 and Figure 28 the overall form of the transmission curves was independent on activation temperature. a temperature of 100°C and a volume flow of 50ml/min In another experiment the influence of the activation temperature on the separation was examined. In order to do so the activation was performed at 150 °C instead of 450 °C as in the previous experiments. 100 (red) and 50 mg (black) in a Wicke Kallenbach experiment with a pressed H-ZSM5-wafer.Results 34 obviously exponential for all of the three weights but was also stretched for thicker wafers. time diagram of wafers with weights of 150 (blue). . 10 4 150mg 100mg 50mg 10 Seperation Factor [-] 2 10 0 10 -2 0 50 time [min] 100 150 Figure 26: Seperation factor vs. The breakthrough curves got more flat in both cases which results in a less overshooting in the case of benzene and longer uptake times in both cases. The equilibrium concentration was smaller by the same percentage than in the case of benzene.

450°C (red) in a Wicke Kallenbach experiment with a pressed HZSM5-wafer of 100 mg. But even if the uptake time got longer a constant separation factor is reached earlier specifically after 80 instead of 120 minutes (Figure 29). a mixture of benzene/p-xylene. 450°C (red) in a Wicke Kallenbach experiment with a pressed HZSM5-wafer of 100 mg. time diagram of benzene breakthrough curves with a activation temperature of 150 (black). 10 -4 10 -5 150°C 450°C c [mol/l] 10 -6 10 -7 10 -8 0 50 100 150 time [min] 200 250 300 350 400 Figure 28: Concentration vs. a mixture of benzene/p-xylene. a temperature of 100°C and a volume flow of 50ml/min.Results 35 10 -4 10 -5 150°C 450°C c [mol/l] 10 -6 10 -7 10 -8 0 50 100 150 time [min] 200 250 300 350 400 Figure 27: Concentration vs. a temperature of 100°C and a volume flow of 50ml/min. The constant separation factor equals the previous experimental results with a value of 1. . time diagram of p-xylene breakthrough curves with a activation temperature of 150 (black).

450°C (red) in a Wicke Kallenbach experiment with a pressed H-ZSM5-wafer of 100 mg. whether the pressure of the compacting had an influence on the result of the experiment a wafer of 100 mg were pressed with minimum force of 10 kN.swinging in the benzene transmission curve but in a less extend as previously observed and the pure exponential curve of the p-xylene graph.Results 36 10 4 150°C 450°C 10 Seperation Factor [-] 2 10 0 10 -2 10 -4 0 20 40 60 80 time [min] 100 120 140 160 180 200 Figure 29: Seperation factor vs. The curves shown in Figure 30 and Figure 31 revealed the same behavior as the previously described with the over. time diagram with a activation temperature of 150 (black). a mixture of benzene/p-xylene. time diagram of benzene breakthrough curves with a compacting pressure of 10kN (black). a temperature of 100°C and a volume flow of 50ml/min. 20kN (red) in a Wicke Kallenbach experiment with a pressed HZSM5-wafer of 100 mg. To check. . a temperature of 100°C and a volume flow of 50ml/min. a mixture of benzene/p-xylene. 10 -5 10 kN 20 kN c [mol/l] 10 -6 10 -7 10 -8 0 50 100 time [min] 150 200 Figure 30: Concentration vs.

The separation factor was identical to the former experiments 1. respectively. time diagrams with a compacting pressure of 10kN (black). Differences were seen in the breakthrough times. 20kN (red) in a Wicke Kallenbach experiment with a pressed H-ZSM5-wafer of 100 mg. 20kN (red) in a Wicke Kallenbach experiment with a pressed HZSM5-wafer of 100 mg. a mixture of benzene/p-xylene. a mixture of benzene/p-xylene. a temperature of 100°C and a volume flow of 50ml/min. Even if the breakthrough time differed the overall uptake times stayed the same which were 200 for benzene and 240 minutes in the case of p-xylene. time diagram of p-xylene breakthrough curves with a compacting pressure of 10kN (black). The time dependence of the separation factor is shown in Figure 32. They were 7 instead of 12 and 19 instead of 26 minutes for benzene and p-xylene. 10 3 10kN 20kN 10 Seperation Factor [-] 2 10 1 10 0 10 -1 0 20 40 60 80 time [min] 100 120 140 160 180 200 Figure 32: Seperation vs. a temperature of 100°C and a volume flow of 50ml/min.Results 37 10 kN 20 kN 10 -5 c [mol/l] 10 -6 10 -7 10 -8 0 50 100 time [min] 150 200 250 300 Figure 31: Concentration vs. .

The point of the maximum is shifted from 20 to 15 minutes for 10 kN corresponding to the faster uptake for the less compacted sample. . Therefore.5 3 2. This temperature was then hold for 1 hour and subsequently cooled down stepwise to 100°C.5 c [mol/l] -5 Benzene p-Xylene 2 1.5 1 0. 4 x 10 3.5 0 0 200 400 600 800 1000 1200 1400 1600 1800 2000 time [minutes] Figure 33: Desorption-curve of benzene (blue) and p-xylene (red) at 100°C until 3090 min then the desorption was performed with a heating of 1°C per minute until 450°C and afterwards cooled down stepwise to 100 °C again. After the concentrations of the adsorbates reached a constant level the adsorbed species were desorbed with unloaded sweep gas streams of 50 ml/min each until both concentrations equaled zero. a normal uptake procedure was performed as described before. In here the desorption-curve of benzene was much steeper than the one of pxylene. In addition the desorption (Figure 33) of benzene and p-xylene from the WickeKallenbach-wafer of 100 mg was evaluated at 100°C.Results 38 The form stayed untouched of the compacting even the height of the maximum is precisely the same with values around 700. At that point an activation program with a heating rate of 1°C per minute was started with a final temperature of 450°C. In contrast to that the p-xylene desorption curve equals zero after 177 minutes and showed a clear maximum in desorption after the temperature was increased corresponding to a temperature of 176°C. It reached zero after 37 minutes and showed no more desorption even if the temperature was raised.

Thereby m-xylene showed a breakthrough time of 10 minutes whereas p-xylene needed 40 minutes to transmit. 100°C. . Differences could be found in transmission and the uptake times. In contrast the uptake time was much longer for m-xylene than for p-xylene specifically 350 and 100 minutes for mxylene and p-xylene . time diagram of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 and consecutively p-xylene (black) and m-xylene (red). 100mg wafer weight and 50 ml/min volume flow.Results 39 An identical Wicke Kallenbach experiment using a standard 100 mg wafer as described previously was also performed with m-xylene and p-xylene as single components due to experimental constraints. respectively. The form of both curves was identically exponential with a large slope in the starting region. As m. The result is shown in Figure 34.and p-xylene have the same mass distribution in a mass spectrometer it was not possible to determine the separation in one experiment. 10 -5 p-Xylene m-Xylene c [mol/l] 10 -6 10 -7 0 50 100 150 time [min] 200 250 300 350 Figure 34: Concentration vs. Hence the transmission of the single components was examined.

96 2.03 1.73 1.22 2.66 Experiment Uptake Number Time Benzene.14 1.Results 40 Table 3: Experimental results of the Wicke-Kallenbach experiments Sample Experiment Number Wafer Weight [mg] 100 100 100 150 50 100 100 100 Compacting pressure [kN] 20 20 20 20 20 20 10 20 Uptake Time p-Xylene [min] 185 210 250 240 450 300 370 100 Experimental Activation Temperature Temperature [K] [K] 373 353 403 373 373 373 373 373 723 723 723 723 723 423 723 723 Breakthrough Time Benzene [min] 12 19 7 23 3 7 7 Breakthrough Time m-xylene [min] Breakthrough Time pXylene [min] 27 41 17 47 9 16 17 40 Separation factor H-ZSM5 H-ZSM5 H-ZSM5 H-ZSM5 H-ZSM5 H-ZSM5 H-ZSM5 H-ZSM5 1 2 3 4 5 6 7 8 10 Equilibrium Concentration m-Benzene [mmol/l]x102 Equilibrium Concentration p-xylene [mmol/l]x102 2.81 1.94 1.4 3.7 3.91 1.6 3.23 .76 2.51 5.01 0.6 2. [min] 1 2 3 4 5 6 7 8 270 290 270 295 250 350 400 Uptake Time m-Xylene [min] Equilibrium Concentration Benzene [mmol/l]x102 3.53 3.49 2.55 2.11 0.28 1.4 1.75 350 0.

Results 41 The most important factor. the next with very thin wafers which were of a weight between 6 and 10 mg and lastly with a wafer of the same type as used in the Wicke Kallenbach cell with a weight of 100 mg. The characteristic functionns obtained from the measurements of the powder and the thin wafer are compared in Figure 35 and Figure 36. [60] which defines the reciprocal value of the maximum of the out-of-phase function to be the time constant. All experiments are summarized in Table 3. 4.3.52 p-xylene/mxylene. This maximum corresponds to a time constant of 50. the separation factor. using on the one hand a simple pore diffusion model in an infinite plane sheet and on the other a more sophisticated model assuming a surface resistance control.02 Hz. The first measurement was performed with a powdered sample. respectively.25s using the method described by Gobin et al. The fits for the surface resistance model are also shown in Figure 35 and Figure 36.2.15x10-15 and 2. The functions of the Wicke Kallenbach wafer are not shown here because the time constant (L2/D) was too large and therefore no suitable data was obtained. The obtained transport parameters for all theoretical models and both samples are summarized in Table 4 and Table 5.36x10-15 m2/s for the thin wafer and the powdered sample. Frequency Response experiments To understand which transport mechanism is rate determining in the Wicke Kallenbach experiment three different frequency response experiments were carried out. Assuming a particle size of 0. was 1. The out of phase function (Figure 35) was nearly identical for both samples showing a maximum at 0. In addition the diffusion coefficients were calculated by simply dividing L2 by the time constant.23 in this experiment taking the ratio of feed concentration into account which was 2. The wafers were broken into smaller pieces before starting the measurement to fit into the quartz sample holder. .4μm obtained by SEM the diffusion coefficients were 2. Curve fitting was applied employing the model equations described in 2. Both models were used with and without a particle size distribution to see the impact of a non-uniform size distribution.

05 0 -3 10 10 -2 frequency [Hz] 10 -1 10 0 10 1 Figure 36: In of phase function of the ZSM5 sample in powdered state (black) and pressed to a thin wafer (red) including the fit (lines) with a surface resistance model in a non-uniform sheet.04 -0.35 0.06 -0.1 0.08 -3 10 10 -2 frequency [Hz] 10 -1 10 0 10 1 Figure 35: Out of phase function of the ZSM5 sample in powdered state (black) and pressed to a thin wafer (red) including the fit (lines) with a surface resistance model in a non-uniform sheet.1 0.02 -0.24 and 0.02 0 -0. K showed values between 0. All of the models had a apparently good fitting probability confirmed by the normalized root mean square errors which were in an acceptable range of 0.40 to 0.2 0.15 0.27. The time constant was in the range of 67 to 75 seconds.3 in-of-phase characteristic function [-] powder fit powder thin wafer fit thin wafer 0.08 0.59 x 10 -15 m2/s. 0.52.16 and 2. the corresponding diffusion coefficient was between 2.04 0.25 0. Thereby the model with .Results K = 0.06 out-of-phase characteristic function [-] powder fit powder fit thin Wafer thin Wafer 0.25392 42 0. Both samples showed nearly the same parameters independent on the assumed model.

40 Non-uniform infinite sheet with 74. 2 and 10 mbar and 373 K.20 2.27 0. a uniform infinite sheet with surface resistance control a non-uniform infinite sheet and a non-uniform infinite sheet with surface resistance control Model L2/D [s] D x 1015 K NRMS-error [m2/s] Uniform infinite sheet 68.58x102 and 5.19 2. a uniform infinite sheet with surface resistance control a non-uniform infinite sheet and a non-uniform infinite sheet with surface resistance control Model L2/D [s] D x 1015 K NRMS-error [m2/s] Uniform infinite sheet 70. All of the curves showed an exponential uptake with a large time constant (L2/D) between 3.25 0.27 0.40 0. Table 4: Transport parameters for a powdered sample of ZSM5 obtained by curve fitting assuming theoretical models describing a uniform infinite sheet.24 0.26 0.27 0.25 0.34 0.74 2. .52 Uniform infinite sheet with surface 70.26 0.18 surface resistance 4.40 2.1.34 2.32 resistance Non-uniform infinite sheet 73.24 0.3. 1.24 surface resistance Table 5: Transport parameters for a thin wafer of ZSM5 obtained by curve fitting assuming theoretical models describing a uniform infinite sheet.44 Non-uniform infinite sheet with 67.59 2.77x103 seconds obtained by curve fitting with the theoretical model described in 2. Uptake Rate measurements The gravimetric uptake curves of an 8 mg piece of a 100 mg Wicke Kallenbach wafer having a thickness of 1 mm were obtained at adsorbate partial pressures of 0.45 0.4.52 0.Results 43 non-uniform particle sizes and a surface resistance had the best correlation with the experimental data.48 2.16 0.36 resistance Non-uniform infinite sheet 61.38 0.27 2.44 Uniform infinite sheet with surface 68.43 0.

This indicates a clear dependence of the diffusion coefficient on the concentration which can be calculated by .4 0.1mbar (black). 1 0. It also shows the good quality of the fit and therefore of the applied model.2 0 0 500 time [s] 1000 1500 Figure 37: Uptake curve of benzene in an H-ZSM5 Wicke Kallenbach wafer of 100 mg at a partial pressure of 1 mbar and 373K.4 0. 2mbar (blue) and 10 mbar (green). The figure shows the experimental data (black) and the result of the curve fitting (red) applying an infinite plane sheet model of 1mm thickness.Results 44 1.6 0.6 0.8 0. Figure 37 shows an example of such an uptake curve for the case of 1 mbar having a clear exponential behavior. 1mbar (red).8 normalized mass [-] 0.4 1.2 0 0 0. Thereby the graphs got steeper with increasing partial pressure of the adsorbate which is equal to a decreasing time constant with the loading.2 1 normalized concentration [-] 0.1 mbar 1 mbar 2 mbar 10 mbar 200 400 600 time [s] 800 1000 1200 1400 1600 Figure 38: Fitted uptake curves of benzene in an H-ZSM5 Wicke Kallenbach wafer of 100 mg at 373K at partial pressures of 0. Figure 38 summarizes the uptake measurements by showing the results of the curve fitting.

00E+01 4. 1.00E+01 2.Results 45 dividing L2 by the time constant. The obtained parameters are summarized in Table 6.00E+01 7.64 To see how the diffusion coefficients of benzene in a ZSM5 Wicke Kallenbach wafer depend on the partial pressure they were plotted with the partial pressure on the x-axes and the diffusion coefficient on the y-axes.00E+00 0 2 4 6 partial pressure [mbar] 8 10 12 Figure 39: Dependence of the diffusion coefficient on the partial pressure of Benzene in a Wicke Kallenbach wafer of 100mg.00E+01 0.00E+01 3.73 0.00E+01 5.1 1 2 10 L2/D x 102 [s] 57. The adsorbate benzene was dosed into the system in steps of 0. A linear dependence is obtained. In order to do so 4.75 3.3 mg of the powder was dispersed on glass wool analogue to the pressure frequency response experiments to avoid bed effects.37 3.98 NRMS-error 0.23 6.30 0.7 18.3 7. The outcome is shown in Figure 39. Table 6: Summary of the parameters obtained curve fitting of the experimental data of a HZSM5 Wicke – Kallenbach wafer of 100mg applying a theoretical model describing an isothermal infinite plane sheet of the thickness 1mm Partial pressure [mbar] 0.5 mm equals L. Diffusion coefficient x 1011[m2/s] . To determine differences between the Wicke Kallenbach wafer and the powdered sample the uptake rate of a powdered sample was also measured. 8.1.00E+01 6.00E+01 1. 2 and 10 mbar by simultaneously tracking the mass.26 0.43 1.58 D x 1010 [m2/s] 0. Thereby half of wafer thickness which is 0.

28 The characteristic length of diffusion is defined here as the particle size of 0.21 5.22 2.36 0. In contrast to the wafer the diffusion coefficient decreased with increasing partial pressure which can also be seen in Figure 41.93 4.4 6.1mbar (black). This is most likely due to non idealities of the experiment.2 0 0 0.25 0.1 mbar 1 mbar 2 mbar 10 mbar 50 time [s] 100 150 200 Figure 40:: Fitted uptake curves of benzene in H-ZSM5 powder at 373K at partial pressures of 0.61 NRMS-error 0.4 μm.6 0.4 0. 1mbar (red). Consequently the bigger the change of partial pressure is the longer the uptake takes which means that it is further away from the ideal step function.7 3. This means that the adsorption .Results 46 1 0.29 0. A linear decrease of the diffusion coefficient with the pressure was obtained.4 μm Partial pressure [mbar] 0. Table 7: Summary of the parameters obtained curve fitting of the experimental data of a powdered H-ZSM5 applying a theoretical model describing isothermal infinite plane sheet of the thickness 0.14 D x 1016 [m2/s] 7. Especially it is impossible to perform the uptake of partial in a step function. Data processing was performed identical to the other experiment by non-linear parameter fitting using a CMA evolutional strategy in matlab which resulted the fitting shown Figure 40 and Table 7. 2mbar (blue) and 10 mbar (green).8 normalized mass [-] 0.1 1 2 10 L2/D x 102 [s] 2.71 2.

00E+00 0.00E+00 7. .00E+00 6.00E+00 4.20E+00 P/P0 [-] Figure 42:Nitrogen physisorption isotherms of H-ZSM5 parent powder material (black) and the same material pressed to a wafer of 100 mg (red).00E+00 5.1).00E-01 4.00E+00 0 2 4 6 partial pressure [mbar] 8 10 12 4.4. Vads[cm3/g] 250 200 150 100 50 0 0.Results 47 process of benzene in this MFI powder sample is too fast to get a reliable result from the gravimetric uptake.00E-01 1.00E+00 2.00E+00 3. 350 300 Diffusion coefficient x 1016[m2/s] Figure 41: Trend of the diffusion coefficient of H-ZSM5 powder obtained by uptake rate measurements.00E+00 1.00E+00 1. 8.00E+00 2.00E-01 8.00E-01 6. Nitrogen physisorption isotherms The procedure of the nitrogen physisorption measurement of the Wicke Kallenbach wafer was identical to the one described in the experimental section (3. The outcome compared to the isotherm of the parent material is shown in Figure 42 and Figure 43.

The data was then analyzed applying the BET formula resulting in a BET surface area of 4 46 m2/g. Both curves are typical type 4 isotherms.2 to 0. The pressure region from the starting point until 0.00E-01 P/P0 [-] Figure 43: Nitrogen physisorption isotherms of H-ZSM5 parent powder material (black) and the same material pressed to a wafer of 100 mg (red) in the range of 0.00E-01 7.2 the hysteresis starts to open in the case of the wafer which occurred at 0. At 0.2 was nearly identical for either the powder or the wafer.00E-01 9. A remarkable change was observed after pressing the powder to a wafer.8 in the case of the powder.00E-01 3.Results 48 350 300 Vads[cm3/g] 250 200 150 100 50 0 2.00E-01 4. Moreover the total size of the loop obtained was much bigger in the case of wafer than for the powder.00E-01 5.00E-01 6. .9 p/p0.00E-01 8.

Consequently it has an adsorption region (Figure 45) . This model assumes a steady state during the diffusion. Figure 45: Principle of a classical bed adsorber [72]. hence the system is not in equilibrium at any time. On the one hand a statistically dense membrane and on the other hand the classical bed adsorber. Discussion In order to understand how the ZSM5 wafer behaves during a Wicke Kallenbach experiment two theories were postulated describing the wafer. Statistically dense membrane represents in this context a mesoporous layered wafer in which the diffusing molecule has to pass at least one particle during the diffusion process (Figure 44). Figure 44: Principle of a statistically dense membrane. In contrast to the dense membrane this model is based on the assumption of thermodynamic control.Discussion 49 5. This model assumes an adsorption front going through the particle bed until the adsorbent is saturated. The other possible model is a flow adsorber showing transmissions curves as described extensively before [53]. This means the whole transport mechanism is controlled by the diffusion through the particle which defines the kinetic of the pore diffusion as rate determining.

Discussion 50 where the system is not in equilibrium but the overall rate is controlled by the strength of adsorption. The explanation for the adsorber model is the decreasing capacity with the increasing temperature as indicated by the isotherms. This can be explained for the membrane with an increase of the diffusion coefficient with increasing temperature as described in the literature [60]. They show a decrease of loading at increasing temperature. The explanation for the model of a statistically dense membrane is simple. The next interesting result was the temperature dependence. A clear decrease of the transmission time with increasing temperature was found which would also be typical for both models. In the case of the dense membrane the faster diffusing component would penetrate faster. This is in agreement with both models. An increase of the breakthrough time with increasing thickness was observed. Based on the theory the weaker adsorbing substance penetrates first. But on the other hand this breakthrough time distribution is also typical for flow adsorbers. . As a result less substance can be adsorbed at the adsorbent which have to lead also to a decreased transmission time. the thicker the wafer is the more particles have to be passed statistically. It assumes an established adsorption/desorption equilibrium in the wafer after the breakthrough of the adsorbates is finished.28x10 -13 and 2. The first remarkable aspects in the obtained data were the breakthrough times. respectively. who determined adsorption enthalpies of benzene and pxylene of -51 kJ/mol and 94 kJ/mol. This assumption would be in good accordance with Gobin et al. The higher diffusion coefficient leads to a faster transport through the pore system resulting in a decreased breakthrough time at higher temperatures. Furthermore an influence on the wafer thickness was found. The overall trend was that the breakthrough of benzene was faster than the one of p-xylene. This matches the found breakthrough times which are in good agreement with Mukti et al. This behavior can be explained with both models. [60] who found intra crystalline diffusion coefficients of 5. respectively [64].46x10-13 m2/s for benzene and p-xylene.

In this case benzene adsorbs faster than p-xylene but the adsorption is weaker. Increasing the wafer thickness has the same effect as decreasing the temperature: it results in a higher adsorption capacity. in this case p-xylene [64]. As a consequence shorter transmission times are expected. Considering the adsorber model a higher water loading lowers the capacity because less adsorption places are reachable for the diffusing substance. Thus. In contrast to this the adsorbate with the higher adsorption enthalpy. the form of the transmission curve can be explained by the model of a classical adsorber. Therefore. In the experiments an overshooting in the benzene graph and a pure exponential uptake of p-xylene was observed in every experiment with H-ZSM5 as adsorbent independent on the temperature. Consequently benzene is displaced by p-xylene which then occupies the adsorption centers and by this leads to an accumulation of benzene in the non-equilibrium zone.Discussion 51 On the other hand this observation agrees with the adsorber model. As discussed before the weaker adsorbing substance broke through first and showed an overshooting. This type of breakthrough curves is typical for bed adsorbers [53]. . the experimental data also agreed with the postulate of a bed adsorber analogue. The transmission times clearly decreased when the activation temperature was decreased to 423K because the water was not removed completely from the zeolite. Once the equilibrium in the adsorber is established the concentrations of benzene and p-xylene are constant. It follows that the concentration of benzene shortly after the breakthrough is higher than the steady state concentration which can be seen as an overshooting of the graph. As a result the breakthrough time should had been increased or at least stayed constant and not decreased as it is shown in Figure 27 and Figure 28. activation temperature or compacting pressure. had a longer breakthrough time and showed no overshooting at all. Based on this theory a higher capacity leads to a longer breakthrough time [65]. After discussing the breakthrough times the form of the transmission curve has to be considered. This is inconsistent with the membrane model because a higher loading makes it harder to diffuse through a particle. The overshooting arises due to the competitive adsorption of benzene and pxylene. wafer thickness.

KH is the Henry constant and L is the thickness of the wafer.Discussion 52 To allow the comparison of the experimental data with the postulate of the dense membrane the experimental data was tried to fit numerically. This means that it is not possible to describe the experimentally obtained data with the model of a membrane. [23] it is possible to calculate the concentration in the permeate at steady state conditions by: (5. [54] for the diffusion through a membrane was used: (5. The most important parameter for this process is the separation factor because the aim of these wafers was the separation of benzene and p-xylene.2) where AW is the cross section of the wafer. D is the intracrystalline diffusion coefficient.3) . The concentration of p-xylene in steady can be calculated from the ratio of the pxylene/benzene concentration. This result can`t be explained with the dense membrane model. A solution of the second fickian law derived by Crank et al. D is the diffusion coefficient which was previously determined by Gobin et al. [60] and L is the characteristic length of diffusion Unfortunately it was impossible to fit the experimental data with a sufficient goodness of fit. [60] the diffusion of benzene is by an order of 2 faster than the diffusion of p-xylene inside the ZSM5 pore system.1) where Cω is the concentration at infinite time. As the model assumes a kinetic control the permeation flows of benzene and p-xylene must had been different from each other which would had led to a separation. This strongly suggests that the model of a statistically dense membrane is not describing this particular Wicke Kallenbach experiments in a proper way. This equals taking V>> AxDxK/L into account: (5. According to Sun et al. If the transport process would had been controlled by pore diffusion a separation factor higher than 1 had to be found because according to Gobin et al. Unfortunately the separation factor in the experiments equaled independent on any changes 1.

The time until the maximum was reached increased with increasing capacity produced by a lower temperature during experiment and activation and a higher thickness of the wafer. The amount of adsorbed species was then determined by integration with respect . The maximum of the separation factor occurred at the same time as the maximum of the over swinging of the benzene concentration curve.97 2. Assuming this model it is possible to calculate the theoretically expected separation factors according to the previously reported diffusion coefficients [60].67] is expected as the diffusion coefficient varies with the temperature which would had influenced separation factor as well. [60] T [°C] Diffusion coefficient Diffusion coefficient Benzene x 10-15 p-xylene x 10-15 [m2/s] [m2/s] 3. It was identical with the breakthrough time of p-xylene.02 Seperation factor [-] 4.Discussion 53 According to 5. As expected the position of the maximum corresponded to the capacity of the adsorber. The observed behavior fits perfectly the model of an adsorber. The results are shown in Table 8. the compacting pressure and the activation temperature.08 2.96 7. afterwards the adsorbate stream was stopped and the adsorbate was desorbed with the help of sweep gas (50 ml/min).9 0. In order to do so adsorption until equilibrium conditions was achieved. To determine the amount of adsorbed species on the pellet a desorption experiment was carried out.66. But the results show that neither the expected temperature dependence nor a separation factor at all was observed in the experiments. Table 8: Theoretically expected separation factors of the Wicke Kallenbach experiment assuming a statiscally dense membrane applying the diffusion coefficients reported by Gobin et al.48 6.96 2.3 the separation factor can be mathematically described by Dp-xylene/Dbenzene for the model of a membrane.14 70 100 130 Also a temperature dependence on the permeation flux [3.34 12. the wafer thickness. Furthermore the separation factor showed a clear dependence on the time which means that it reached a maximum after 10 to 50 minutes depending on the temperature.

By this means the concentration ratio inside the sheet must be equal to the ratio calculated from the isotherms which depend on the adsorption enthalpies.86 x 10-4 and 1. m is the mass of one molecule. This led to a ratio of benzene/p-xylene of 0. the concentration of adsorbed species inside the wafer equals the integration with respect to t of the tracked concentration signal multiplied by 2.Discussion 54 to t of the resulted data.4) where P is the partial pressure of the adsorbate in the feed. The starting point of the calculation is the overall number of wall collisions depending on the partial pressure of adsorbate and the temperature derived from the kinetical gas theory [68]: (5. This is important because it has to be shown that it is possible to establish an adsorption/desorption equilibrium during the transmission time. To be able to calculate how many hits a molecule has with the walls of the mesopores during the transmission through the wafer. This result is in good accordance with the adsorption enthalpies measured by Mukti et al. Hence. The integration resulted in a concentration of 5. This parameter describes the probability that a poke between the adsorbate and the outer surface of a porous material leads to a pore entering. k is the Boltzmann constant and T is the temperature [K]. [64]. the flow of molecules per second entering the sample has to be calculated: .33 x 10-3 mol/l for benzene and p-xylene. [4] having values of 2.44 which means that the concentration of p-xylene was more than two times higher than the concentration of benzene. To confirm the theory of the adsorber the number of hits was calculated which the molecules have with the pore wall during one transmission through the wafer. The obtained values were then multiplied by 2 because the desorption occurred in both directions of the cell but the amount was only tracked at one of the streams.10x10-7 and 2.18x10-7 for benzene and pxylene. The base of the calculation were the sticking probabilities obtained by Reitmeier et al. It is another hint for the adsorber theory because this model predicts that the process is thermodynamically controlled. If it is impossible to build up an equilibrated state the whole adsorber theory is no longer supportable.

54 3.57 3.24 1.49 The number of successful pokes is in the range of 350 per molecule during the transmission through the wafer.75 3.86 Nx102 [-] Benzene Benzene Benzene p-Xylene p-Xylene p-Xylene 343 313.10 4.82 4.6) In the next step the surface area needed for poke leading to the sorption of the adsorbate is identified by taking the sticking coefficient into account: (5. T is the temperature.83 1. Consequently the theory of an adsorption zone is also valid.82 1.75 1. F(He) is the flow of the sweep gas and NA is the Avogadro constant. With this data it is possible to determine the surface area of the adsorbent needed for one poke of the adsorbate: (5.32 1.2 4. Table 9: Results of the calculation considering the number of pokes leading to a pore entering during the transmission of benzene and p-xylene through the Wicke Kallenbach wafer Adsorbate T [K] PFeed [Pa] Zw x 10-24 [1/(m2s)] Fmolec.23 3.2 5.Discussion 55 (5. R in the gas constant.46 3.98 1.10 2.84 403 313.x10-16 [Molec.8) The results for temperatures of 343.71 3. This means that the establishing of an adsorption/desorption equilibrium as postulated in the adsorber theory is in good accordance with the previous determined sticking coefficients.2 4.5) In here p defines the partial pressure of the adsorbate in the feed.21 3.64 3.81 1. poke x102 [m2] 1.78 1.78 1.06 3.04 373 313.65 343 234 373 234 403 234 3./s] Aper poke x109 [m2] Aper suc. 373 and 403 K and the adsorbates benzene and p-xylene are summarized in Table 9.88 1.7) As the external surface area of the wafer is known the successful hits during the transmission of the adsorbate through the wafer could be obtained by: (5. Furthermore it is possible to estimate the length of the zone which is not in equilibrium known as adsorption zone because it equals the length between .00 4.68 3.86 1.

This is significantly different to our experiment. M-xylene can only reach the outer surface having a BET surface area of 65 m2/g. Sakai et al. This is a totally different behavior compared to the previously reported separation of p-xylene from a mixture of o-. The final evidence for the assumed bed adsorber analogue gave the comparison of the uptake curves of m-xylene and p-xylene which had to be measured in two consecutive experiments due to experimental constraints.9x10-3 mm. Obviously m-xylene transmitted after 10 minutes where as breakthrough of p-xylene took 40 minutes.2. The result is shown in Figure 34. m.and p-xylene with the help of an MFI membrane [3]. This is due to the consecutive measurement: the overshooting as previously seen in benzene is only observed if two adsorbates are present and the adsorption enthalpies differ clearly [53]. In contrast to the theory a bed adsorber describes the experimental data very good. Comparing this to the observed BET total surface area of 446 m2/g of the wafer it can be concluded . The other adsorbate p-xylene was able to access the pore system to adsorb there which led to a transmission time of 40 minutes. This experiment shows that the pressed Wicke Kallenbach wafer did not act similar to a membrane and by this means the theory of a statically dense membrane is not valid for this system. The form did not change compared to the experiments of benzene and p–xylene and showed both the same exponential form as p–xylene in the previous measurements. The transmission times can be understood by the accessible adsorption centers. The sorption into the pores of the zeolite to adsorb at the adsorption places inside the pore system is very slow due to the minimum kinetic diameter. This value can simply be evaluated by taking the reciprocal value of N and multiplying it with the total length of diffusion. The separation factor calculated as described in 2. This process could be seen in the slow uptake in the late time region of the uptake curve. demonstrated that the differences in permeability due to the larger minimum kinetic diameters of m-xylene in comparism to p-xylene lead to a separation factor of 10 p-xylene/m-xylene at 373 K.Discussion 56 two successful pokes.23 which equals 1 taking the error of the experiment into account. This leads to a length of the adsorption zone of 2.1 had a value of 1.

2. This is in good agreement with the postulated bed adsorber. All these facts summarized in Table 10 show that the model of an adsorber describes the wafer of the Wicke Kallenbach experiment bes Table 10: Summary of the experimental facts and check of consistency to the adsorber and the statistically dense membrane model Experimental Fact/Model breakthrough time temperature dependence on breakthrough time Adsorber Membrane consistent consistent of consistent consistent benzene/p-xylene influence of wafer thickness on breakthrough time of consistent inconsistent benzene/p-xylene dependence of the activation temperature on the consistent inconsistent breakthrough time of benzene/p-xylene form of the uptake curves consistent - equilibrium/ steady state separation factor = 1 benzene/p.5) as the speed of this transport type is independent on the kinetic diameter.consistent inconsistent xylene equilibrium/ steady state separation factor = 1 p-xylene/m.consistent inconsistent xylene missing temperature dependence on the separation factor consistent inconsistent of benzene/p-xylene time dependence of the separation factor of benzene/p.consistent xylene sticking probalities no activation energy of the diffusion consistent consistent consistent inconsistent . As m-xylene and p-xylene have the same mass the Knudsen diffusion coefficients have to be identical (2.Discussion 57 that the uptake time has a clear dependence on the accessible adsorbtion centers. The fact that no separation occurred was due to the rate determining step which was the Knudsen diffusion through the mesopores after the adsorption/desorption equilibrium is established.

32 6.88 6.02 8.14 6.61 5.54 6.39 7. Furthermore the pore diameters calculated from these diffusion coefficients assuming Knudsen diffusion are reviewed Sample Wafer Weight [mg] 100 100 100 150 50 100 100 Compacting Experimental Activation pressure Temperature Temperature [kN] [K] [K] 20 20 20 20 20 20 10 373 343 403 373 373 373 373 723 723 723 723 723 423 723 Diffusion coefficient Benzene x 10-7 [m2/s] 6.39 6.96 6.20 6.62 7.16 pore diameter calculated from DBenzene x 10-9 [m] 6.74 6.Discussion 58 Table 11: Summary of the results of the calculatng the diffusion coefficients of benzene and p-xylene in a Wicke Kallenbach wafer consisting of HZSM5.96 6.60 5.77 3.14 6.56 4.35 3.11 6.88 H-ZSM5 H-ZSM5 H-ZSM5 H-ZSM5 H-ZSM5 H-ZSM5 H-ZSM5 .18 5.61 Diffusion coefficient p-xylene x 10-7 [m2/s] 6.18 7.51 6.24 pore diameter calculated from Dp-xylene x 10-9 [m] 7.53 6.18 4.

5). The results of the calculation are shown in Table 11.2. Figure 46: SEM image of the surface of a Wicke Kallenbach wafer. The transposed equation is expressed by: (5. . M is the molar mass.11) where R is the gas constant. This means that the diffusion in pressed wafers was limited by the transport in mesopores of 6 to 8 nm size. FHe is the flow rate of the sweep gas helium and xAdsorbate is the molar ratio of the adsorbate in the feed and the permeate at equilibrium conditions. Pores of this size were defined as mesopores [69] by the IUPAC (International Union of Pure and Applied Chemistry). respectively.2) from the equilibrium molar ratios: (5. From the observed diffusion coefficients which were in the range of 10 -6 m2/s we could assume Knudsen diffusion. Consequently it was the possible to calculate the diffusion coefficients by equation (2. The assumed Knudsen diffusion is confirmed by the calculated pore diameters which are in the range of 6 to 8 nm. in contrast to the radius of on particle as in the case of the statistically dense membrane model.10) where L is characteristic length. T is the temperature. As a consequence it was possible to calculate the radius of the pores by transposing (2.Discussion 59 This fact leads to a characteristic length of diffusion equally to the thickness of the wafer. r is the radius of the wafer.2.

2 P/P0 which corresponds to mesopores formed during the pressing procedure.232 cm3/g. As previously described the isotherm had a much larger loop even at low pressures of 0.147 cm3/g and 0.35 0.048x + 0.3789 vads [cm3/g STP] 0.1 0. 0.25 0.132 cm3/g micro– and mesopore volume. we can assume that the calculated pore diameters are the smallest which occurred in the Wicke Kallenbach pellets as they determined the transport rate. The . The total volume of the micro. A clear enhancement of the mesopore volume was obtained compared to the pore volume of the parent material [5] which was 0. The assumption of Knudsen diffusion determining the transport through the wafer is also in good agreement with the physisorption isotherm of nitrogen.2 0. The BET surface area did not change from the powder to the pressed disk and stayed at 420 to 450 m2/g.Discussion 60 This result fits to the impression of the SEM image which shows separated particles (Figure 46) It indicates as well that the wafer had pores of larger diameters than the calculated ones of 6 to 8 nm but these pores were obviously not rate determining.45 0.05 0 0 1 2 3 4 5 6 7 8 9 y = 0. It resulted in a total micropore volume of 0.0095x + 0.147 cm3/g and a mesopore volume of 0.5 0. The results are summarized in Table 12.15 0.147 tHasley [nm] Figure 47: t-plot produced with the method of Hasley for the H-ZSM5 Wicke Kallenbach wafer. Thus.4 y = 0.and mesopores was determined using a t-plot (Figure 47) produced with the method of Halsey [70].3 0.

232 The DFT analysis (Figure 48) showed an increase of mesopores with a maximum of the distribution at a pore diameter of 17 nm. This is in good agreement with the pore diameters calculated from the diffusion measurements which were 6 to 8 nm. The huge pores indicated by the SEM image are not found in the physisorption isotherm as they are larger than 65 nm.00E-04 0.147 0.50E-03 1.147 VMeso [cm3/g] 0.00E-03 5.132 0.00E-03 dV [cm3/Å/g] 1.50E-03 2. This is not influenced by the pressing of the powder and consequently the micropore volume had to stay the same.00E+00 50 150 250 350 450 550 650 pore size [Å] Figure 48: pore size distribution of the parent H-ZSM5 material (black) and the Wicke Kallenbach wafer (red) obtained by DFT calculation. 2. To have a closer look on the mesopores a DFT analysis of the physisorption isotherm was performed to obtain the pore diameter of mesopores shown in Figure 48. . Table 12: Results of the analysis if physisorption isotherms of H-ZSM5 in the powdered and the pressed form applying the BET equation [59] and the t-plot method [70] Material powder 100 mg Wafer SBET [m2/g] 420 446 VMicro [cm3/g] 0.Discussion 61 micropore volume stayed untouched which is the expected characteristic as the micropores built up by the zeolite framework.

96 kJ/mol for benzene and p-xylene. EA. The results are shown in Table 13.13 it was possible to obtain the activation energy of the diffusion of benzene and p-xylene for the rate determining step inside the sheet by plotting 1/T against ln (D) (Figure 49).13) In here D is the diffusion coefficient.1 0. .14) The mean value of the obtained pore diameters from Table 11 was used for the calculation. The calculation resulted in activation energies of -1.D is the activation energy of diffusion.03 and -2. Table 14 and Figure 50.0029 ln(D) [-] -14. Taking the error of the system including the inlet system and the mass spectrometer into account the activation energy of diffusion was in the range of zero. According to 5.0024 benzene p-xylene -14.12) (5. respectively. -14.3 -14.2 0.4 1/T [1/K] Figure 49: Determination of the activation energy of benzene (black) and p-xylene (red) by an Arrhenius ansatz. Afterwards the ideal activation energy of the Knudsen diffusion in the examined system was determined by calculation the diffusion coefficients with: (5. R is the gas constant and T is the temperature.Discussion 62 The assumption of Knudsen diffusion could also be confirmed by looking at the activation energy which was determined by an Arrhenius ansatz describing the diffusion coefficient by [66]: (5.

54 kJ/mol for both substances which shows that the Knudsen diffusion has nearly no activation energy in this system. This fact is also inconsistent with the previously described theory of a dense membrane because the apparent diffusion of benzene and p-xylene in the used ZSM5 sample has activation energies according to Gobin et al.Discussion 63 Table 13: Calculated ideal Knudsen diffusion coefficients of benzene T [K] 343 373 403 D x 10-7 [m2/s] 6.70 5.4 -14.93 0.65 6.1 0. [60] of 23 and 35 kJ/mol. The aim of this method is to fit kinetic . respectively.0028 benzene p-xylene ln(D) [-] -14.0023 -14. Additionally curve fitting was preformed with the transmission curves of the Wicke Kallenbach experiment.5 1/T [1/K] Figure 50: Theoretical evaluation of the activation energy of benzene (black) and p-xylene (red) from the calculated Knudsen diffusion coefficients by a Arrhenius ansatz. the obtained activation energies of the measurements are in good agreement with the theory and are consequently another hint for the existence of Knudsen diffusion.91 Table 14: Calculated ideal Knudsen diffusion coefficients of p-xylene T [K] 343 373 403 -14. The results imply activation energies of 1. Thus.47 5.2 D x 10-7 [m2/s] 5.3 -14.38 6.

The fitting parameters were F and ka.16) These set of differential equations can be solved analytically according to Bohart et. t is the reaction time. One example of the obtained fits is shown in Figure 51. ka is the reaction rate coefficient and c is the concentration of the adsorbate in the gas phase. al [73]. c0 is the concentration in the feed.17): (5. ρB is the density of the bed. S is the section of the adsorbent bed and F is the gas flow rate. In order to do so a kinetic model was assumed and tried to fit the experimental data. Nonlinear parameter fitting was performed using a genetic algorithm implemented in matlab. The breakthrough curve was in this case specified by two differential equations.17) where C is the normalized concentration in the gas phase calculated by c/c0. These formulas define the concentration dependent on time of the adsorbate where the solid phase concentration is replaced by the surface coverage (Θ). The mass balance of the fluid phase describes the concentration of the adsorbate dependent on the time [72] (5. WSat is maximum amount of adsorbed gas. one for the gaseous and one for the solid phase. (5.15) In here Θ is the normalized surface coverage [71]. The solution is shown in (5. Hence. . The data was fitted with a set of differential equations describing an adsorber with an irreversible Langmuir adsorption. the rate of adsorption can be formulated by (6) [53].Discussion 64 parameters from the transmission curves of the Wicke Kallenbach experiments. ka denotes the reaction rate coefficient. The objective minimized was the normalized root mean square error divided by t 3 to get a better fit in initial region of the curves.

01 0 60 70 80 90 100 T [°C] Figure 52: Trend of the parameter k with the temperature.07 0.6 1.6 0.Discussion 65 1.4 0. time diagram of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 and a mixture of benzene (black) and p-xylene (red).2 1.2 1 0.8 t [s] 1 1.02 0.6 0. Nevertheless it was possible to find trends for the strength of adsorption and the diffusion coefficient. 110 120 130 140 Due to the very primitive model and the in comparison to that very complex adsorption behavior of the system the fits were poor.06 ka [1/s] 0.05 0. [60] the pore entering step and F is proportional to the diffusion coefficient as the transport through the pellet is a fully diffusive. 100°C. 100mg wafer weight and 50 ml/min volume flow and the corresponding fit for benzene (black) and p-xylene (blue).2 0 fit Benzene measurement Benzene fit p-Xylene measurement p-xylene 0.03 0.08 0.8 normalized concentration [-] 0.2 0 -0. … 0.8 x 10 2 4 Figure 51: Concentration vs.4 1.09 0.04 0. Hereby ka served as the parameter describing the limiting factor of the adsorption on particle level which is according to Gobin et al. .2 0.4 0.

It proves that the . It was found that the diffusion coefficient of the powdered sample was about 2. These trends are shown in Figure 52 and Figure 53.50E-11 2. But even if these parameters show a trend in the temperature it is very difficult to interpret the outcome with respect to the experiment.00E-11 5.Discussion 66 The only trend observed was the dependence on the temperature.00E+00 60 70 80 90 100 T [°C] Figure 53: Trend of the parameter k with the temperature. Interestingly the time constant did not change after pressing the particles to thin wafers of 6 to 10 mg and diameters of 20 mm. As intensely discussed by Gobin et al. Nevertheless it was shown that the fitting gave the same information as the experiment itself. In conclusion the curve fitting shows that the used model is much too trivial to be able to describe the complex behavior of the Wicke Kallenbach system we looked at. This can be seen in the benzene fits.50E-11 4.00E-11 2. k and F increased with increasing temperature which was the expected behavior as activated transport process getting faster with increasing temperature. [60] the rate determining step is in the case of such small particles no longer the intracrystalline diffusion but the surface adsorption and the pore entering step.50E-11 1.00E-12 0.00E-11 4.00E-11 1. This can be a good starting point for applying a more sophisticated model and try to understand the mechanism inside the pellet by mathematical modeling.5x10-15 m2/s for benzene in H-ZSM5 which is much slower than the measured diffusion coefficients in particles with a larger diameter. 110 120 130 140 Looking at the frequency response experiments is as well interesting.00E-11 3. In here both parameters. 5.50E-11 F [m3/s] 3.

This led to diffusion coefficients of 10-10 m2/s.5 mm). the uptake rate measurements were performed because this method is able to determine large time constants.08 0.4 μm).04 -3 10 -2 -1 0 1 10 Frequency [Hz] 10 10 10 Figure 54: In of phase (blue) and out of phase (red) functions obtained by a pressure frequency response experiment with a Wicke Kallenbach wafer of 100mg and benzene as adsorbate. This denotes that the diffusion in a thin wafer can be described in the same way as for a powdered sample. With this method time constants of 350 to 5700 s were found which are impossible to obtain with the frequency response method. 0.12 0. The characteristic functions for this experiment were not interpretable due to a very large time constants as can be seen in Figure 54.02 -0.02 0 -0.1 characteristic functions [-] fit-v1 in fit-v1 out 0.04 0.14 0.Discussion 67 characteristic length of diffusion equals the one for a powder and a thin wafer which means that the rate controlling transport step is in both cases the same. The maximum of the out-of-phase function was below 10-3 Hz which means that they are not in the range of the frequency response experiment. The behavior changed dramatically if the powder was pressed to Wicke Kallenbach pellets of 1 mm thickness. Taking into account the values obtained by the Wicke Kallenbach experiments (10-6 m2/s ) valid for the mesopores and the diffusivities for the powdered sample (10-15 m2/s) it can be assume that the adsorption in a Wicke Kallenbach wafer is controlled by a mixture of both processes. in contrast to the particles (0. The characteristic length of diffusion differed for the Wicke Kallenbach wafer as discussed before which was half of the wafer thickness (0.06 0. But it can be seen from the . Therefore.

Surprisingly the time constant increased with increasing benzene partial pressure which means that the diffusion became slower with increasing vapor pressure. This behavior showed clearly the non idealities of the system. Therefore. This is in good agreement with the pressure modulation experiments and thereby with the previously reported diffusivities [60]. Applying the powder to the uptake rate measurement of benzene time constants of 220 to 614 s were found. It can be concluded that the dosing of adsorbate into the system had the biggest influence on the result. This means that it is impossible to perform a step change of the adsorbate concentration with the used setup. .Discussion 68 Wicke Kallenbach experiment that the flow through the wafer once the adsorption desorption equilibrium is reached is only controlled by the transport through the mesopores. the diffusion of benzene in H-ZSM5 powder is too rapid for uptake rate measurements.

activation temperature. Experimental results confirmed that the wafer could be described as a bed adsorber analogue. At equilibrium conditions. which means after saturation of the wafer the transport process was limited to the rate of diffusion through the mesopores. The diffusion coefficient previously reported by Gobin et al. The change in rate determining transport steps from the powder to the wafer was also approved by the combination of pressure modulation frequency response and uptake rate measurements. This could be seen in the experiments applying either p-xylene benzene mixtures or a blend of p-xylene and m-xylene. [60] for the . Conclusion The transport processes of strong adsorbing substances on pressed wafers in a Wicke Kallenbach cell were investigated. They show an increase of time constants of two orders of magnitude by compacting the powder to a wafer which is due to a increase of the charactistic length of diffusion from 0.Conclusion 69 6. During the pressing procedure mesopores of 6 to 15 nm diameter were formed which was confirmed by DFT calculations of the nitrogen physisorption isotherm and calculations from the Wicke Kallenbach experiment. In order to do so the system HZSM5 with adsorbates benzene and p-xylene was examined. wafer thickness and compacting pressure for molecules having a similar molar mass. the activation temperature and the compacting pressure. So unfortunately it is impossible to separate hydrocarbons with a pressed membrane of MFI particles. the uptake time and the form of the breakthrough curve on the temperature.4 μm to 1 mm. the wafer thickness. proved to be wrong. Thus the separation factor is 1 independent of external parameters like temperature. The previously reported assumption. The wafer was a mesoporous accumulation of ZSM5 powder with the same BET surface area as the non-compacted sample of 430 m2/g. that the pressed wafer acts like a grown membrane and could separate pxylene from a mixture of xylenes as described in the literature applying a MFI membrane [3]. The results leading to this conclusion were in particular the clear dependences of the transmission time. Especially the measurement with m-xylene and p-xylene varified that the wafer acted like a bed adsorber.

Conclusion 70 parent wafer was confirmed whereas the uptake rate measurements showed an increase in the diffusion coefficient by 5 orders of magnitude approving that the uptake in the wafer is determined by a combination of Knudsen diffusion and the pore entrance step. Nevertheless the Wicke Kallenbach experiments showed that once the adsorption desorption equilibrium is established the Knudsen diffusion controls the transmission rate. .

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100mg wafer weight and 50 ml/min volume flow.1Variation of the temperature -4 10 10 -5 10 c [mol/l] -6 Benzene p-Xylene 10 -7 10 -8 10 -9 10 -10 0 50 100 150 time [min] 200 250 300 350 Figure I: Concentration vs.1 Wicke Kallenbach experiments A. . 10 -4 10 -5 10 c [mol/l] -6 Benzene p-Xylene 10 -7 10 -8 10 -9 10 -10 0 50 100 150 time [min] 200 250 300 350 Figure II: Concentration vs. Results A. 70°C. time diagram of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 and a mixture of benzene (black) and p-xylene (red). 100°C.1. 100mg wafer weight and 50 ml/min volume flow. time diagram of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 and a mixture of benzene (black) and p-xylene (red).Appendix A: Results I A.

Appendix A: Results

II

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Benzene p-Xylene

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10

-7

10

-8

10

-9

0

50

100

time [min]

150

200

250

300

Figure III: Concentration vs. time diagram of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 and a mixture of benzene (black) and p-xylene (red), 130°C, 100mg wafer weight and 50 ml/min volume flow.

10

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Seperation Factor [-]

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1

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Figure IV: Time dependence of the separation factor of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 at 70°C, 100mg wafer weight, a mixture of benzene/p-xylene and 50 ml/min volume flow.

Appendix A: Results

III

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Figure V: Time dependence of the separation factor of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 at 100°C, 100mg wafer weight, a mixture of benzene/p-xylene and 50 ml/min volume flow.

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Figure VI: Time dependence of the separation factor of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 at 130°C, 100mg wafer weight, a mixture of benzene/p-xylene and 50 ml/min volume flow.

Appendix A: Results

IV

A.1.2 Variation of the wafer thickness

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Figure VII: Concentration vs. time diagram of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 and a mixture of benzene (black) and p-xylene (red), 100°C, 50mg wafer weight and 50 ml/min volume flow.

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Figure VIII: Concentration vs. time diagram of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 and a mixture of benzene (black) and p-xylene (red), 100°C, 150mg wafer weight and 50 ml/min volume flow.

a mixture of benzene/p-xylene and 50 ml/min volume flow. 10 4 10 3 10 Seperation Factor [-] 2 10 1 10 0 10 -1 10 -2 0 100 200 time [min] 300 400 500 600 Figure X: Time dependence of the separation factor of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 at 100°C.Appendix A: Results V 10 4 10 3 10 Seperation Factor [-] 2 10 1 10 0 10 -1 10 -2 0 100 200 300 time [min] 400 500 600 700 800 Figure IX: Time dependence of the separation factor of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 at 100°C. 150mg wafer weight. . a mixture of benzene/p-xylene and 50 ml/min volume flow. 50mg wafer weight.

time diagram of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 and a mixture of benzene (black) and p-xylene (red).Appendix A: Results VI A. a mixture of benzene/p-xylene and 50 ml/min volume flow. activated at 423 K. 100mg wafer weight. 100mg wafer weight and 50 ml/min volume flow.1. . 10 4 150°C 450°C 10 Seperation Factor [-] 2 10 0 10 -2 10 -4 0 20 40 60 80 time [min] 100 120 140 160 180 200 Figure XII: Time dependence of the separation factor of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 at 100°C.3 Variation of the activation temperature -4 10 10 -5 Benzene p-Xylene c [mol/l] 10 -6 10 -7 10 -8 0 50 100 150 time [min] 200 250 300 350 400 Figure XI: Concentration vs. 100°C. activated at 423 K (black) and 723 K (red).

compacted with pressure of 10 kN (black) and 20 kN (red) . 100mg wafer weight and 50 ml/min volume flow. a mixture of benzene/p-xylene and 50 ml/min volume flow. compacted with a pressure of 10 kN. 100°C.Appendix A: Results VII A.4 Influence of the compacting pressure 10 -5 Benzene p-Xylene c [mol/l] 10 -6 10 -7 10 -8 0 50 100 time [min] 150 200 250 300 Figure XIII: Concentration vs. 10 3 10kN 20kN 10 Seperation Factor [-] 2 10 1 10 0 10 -1 0 20 40 60 80 time [min] 100 120 140 160 180 200 Figure XIV: Time dependence of the separation factor of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 at 100°C. time diagram of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 and a mixture of benzene (black) and p-xylene (red).1. 100mg wafer weight.

05 0 -0.1 0.1 H-ZSM5 powder 0.05 0 -0.2 Frequency Response experiments A.05 -0.(black) and out-of-phase (red) functions of the batch FR experiment of H-ZSM5 powder.2 characteristic functions [-] in-of-phase out-of-phase fit in-of-phase fit out-of-phase 0. .(black) and out-of-phase (red) functions of the batch FR experiment of H-ZSM5 powder. 0.2. The fit was produced by applying a non-uniform infinite sheet model with surface resistance.Appendix A: Results VIII A.15 0.05 -0.25 0.15 0.1 0. The fit was produced by applying a non-uniform infinite sheet model.1 -3 10 -2 -1 0 1 10 Frequency [Hz] 10 10 10 Figure XVI: In.25 0.3 0.3 0.2 characteristic functions [-] in-of-phase out-of-phase fit in-of-phase fit out-of-phase 0.1 -3 10 -2 -1 0 1 10 Frequency [Hz] 10 10 10 Figure XV: In.

.05 -0.3 0.05 -0.3 0.1 -3 10 -2 -1 0 1 10 Frequency [Hz] 10 10 10 Figure XVII: In. The fit was produced by applying a non-uniform infinite sheet model. 0.1 -3 10 -2 -1 0 1 10 Frequency [Hz] 10 10 10 Figure XVIII: In.(black) and out-of-phase (red) functions of the batch FR experiment of an HZSM5 Wicke Kallenbach wafer.15 0.2 characteristic functions [-] in-of-phase out-of-phase fit in-of-phase fit out-of-phase 0.2.(black) and out-of-phase (red) functions of the batch FR experiment of an HZSM5 Wicke Kallenbach wafer.25 0.1 0.2 characteristic functions [-] in-of-phase out-of-phase fit in-of-phase fit out-of-phase 0.2 H-ZSM5 thin wafer 0.1 0.05 0 -0. The fit was produced by applying a non-uniform infinite sheet model with surface resistance.05 0 -0.15 0.25 0.Appendix A: Results IX A.

4 0. The figure shows the experimental data (black) and the result of the curve fitting (red) applying an infinite plane sheet model of 1mm thickness.2 0 0 20 40 60 80 time [s] 100 120 140 160 180 200 Figure XX: Uptake curve of benzene in H-ZSM5 powder at a partial pressure of 1 mbar and 373K. The figure shows the experimental data (black) and the result of the curve fitting (red) applying an infinite plane sheet model of 1mm thickness.1 H-ZSM5 powder 1.2 1 normalized mass [-] experiment fit 0.6 0.3 Uptake Rate measurements A.3.4 0.2 1 experiment fit normalized mass [-] 0.2 0 0 50 100 time [s] 150 200 250 Figure XIX: Uptake curve of benzene in H-ZSM5 powder at a partial pressure of 0.8 0.4 1.Appendix A: Results X A. .6 0.4 1.8 0. 1.1 mbar and 373K.

The figure shows the experimental data (black) and the result of the curve fitting (red) applying an infinite plane sheet model of 1mm thickness.2 1 normalized mass [-] experiment fit 0.Appendix A: Results XI 1.6 0.8 0.2 1 normalized mass [-] experiment fit 0. The figure shows the experimental data (black) and the result of the curve fitting (red) applying an infinite plane sheet model of 1mm thickness. .6 0.4 1.8 0. 1.4 0.4 0.2 0 0 50 100 time [s] 150 200 250 Figure XXI: Uptake curve of benzene in H-ZSM5 powder at a partial pressure of 2 mbar and 373K.4 1.2 0 0 100 200 300 400 time [s] 500 600 700 800 900 Figure XXII: Uptake curve of benzene in H-ZSM5 powder at a partial pressure of 10 mbar and 373K.

8 0.4 1.6 0.4 0. The figure shows the experimental data (black) and the result of the curve fitting (red) applying an infinite plane sheet model of 1mm thickness.8 0.Appendix A: Results XII A.4 0.3.6 0.2 0 0 experiment fit 200 400 600 800 time [s] 1000 1200 1400 1600 1800 Figure XXIII: Uptake curve of benzene in an H-ZSM5 Wicke Kallenbach wafer of 100 mg at a partial pressure of 0.2 1 normalized mass [-] experiment fit 0.4 1. . The figure shows the experimental data (black) and the result of the curve fitting (red) applying an infinite plane sheet model of 1mm thickness. 1.2 H-ZSM5 Wicke Kallenbach wafer 1.2 1 normalized mass [-] 0.1 mbar and 373K.2 0 0 200 400 600 time [s] 800 1000 1200 Figure XXIV: Uptake curve of benzene in an H-ZSM5 Wicke Kallenbach wafer of 100 mg at a partial pressure of 1 mbar and 373K.

4 0. .2 0 0 experiment fit 200 400 600 800 1000 time [s] 1200 1400 1600 1800 2000 Figure XXVI: Uptake curve of benzene in an H-ZSM5 Wicke Kallenbach wafer of 100 mg at a partial pressure of 10 mbar and 373K.8 0.4 0.Appendix A: Results XIII 1.6 0.8 0. 1.4 1.2 1 normalized mass [-] 0. The figure shows the experimental data (black) and the result of the curve fitting (red) applying an infinite plane sheet model of 1mm thickness.4 1.2 0 0 experiment fit 200 400 600 time [s] 800 1000 1200 1400 Figure XXV: Uptake curve of benzene in an H-ZSM5 Wicke Kallenbach wafer of 100 mg at a partial pressure of 2 mbar and 373K.6 0.2 1 normalized mass [-] 0. The figure shows the experimental data (black) and the result of the curve fitting (red) applying an infinite plane sheet model of 1mm thickness.

.00E+00 2.Appendix A: Results XIV A.25 0.3 0.1 H-ZSM5 powder 300 250 200 150 100 50 0 0.4.0304x + 0.00E-01 4.15 0.9908 vads [cm3/g STP] 0.9979 tHasley [nm] Figure XXVIII: t-plot produced with the method of Hasley for H-ZSM5 powder.00E-01 1.1 0.05 0 0 1 2 3 4 5 y = 0.45 0.35 y = 0.00E-01 8.4 Nitrogen physisorption isotherms A. 0.00E+00 1.2 0.1471 R² = 0.20E+00 Vads[cm3/g] p/p0 Figure XXVII: Nitrogen physisorption isotherm of ZSM-5 parent powder material.4 0.00E-01 6.2787 R² = 0.0542x + 0.

00E-028.20E+00 p/p0 [-] Figure XXX: Nitrogen physisorption isotherm of a H-ZSM5 Wicke Kallenbach wafer.00E+00 y = 0.00E-025. .4.00E-027.00E-04 3.00E-024.2 H-ZSM5 Wicke Kallenbach wafer 350 300 250 Vads[cm3/g] 200 150 100 50 0 0.00E-026.00E-04 6.00E-04 4.00E+001.00E-04 0. A.00E-04 2.00E-04 5.00E-04 1.00E+00 1.00E-01 1.00E-04 (p/p0)/Vads*(1-p/p0) [g/cm3] 7.00E-01 6.00E-02 p/p0 [-] Figure XXIX: Linearization of the nitrogen physisorption isotherm in the low pressure range according to the BET theory of an H-ZSM5 powder sample.Appendix A: Results XV 9.00E-01 4.9999 0.00E-01 8.00E-029.0104x + 3E-06 R² = 0.00E-022.00E-04 8.00E-023.00E+00 2.

00E+001.05 0 0 1 2 3 4 5 6 7 8 9 y = 0.00E-024.3 0.00E-027.147 R² = 0.0098x + 5E-08 R² = 1 0.00E-029. 0.35 0.1 0.00E-028.0007 0.5 0.00E-02 p/p0 [-] Figure XXXII: Linearization of the nitrogen physisorption isotherm in the low pressure range according to the BET theory of an H-ZSM5 Wicke Kallenbach wafer.15 0. .0004 0.0095x + 0.0006 0.048x + 0.Appendix A: Results XVI 0.3789 R² = 0.00E-022.0001 0 0.5502 vads [cm3/g STP] 0.0008 (p/p0)/Vads*(1-p/p0) [g/cm3] y = 0.00E-025.2 0.00E-023.0002 0.4 y = 0.45 0.0003 0.9966 tHasley [nm] Figure XXXI: t-plot produced with the method of Hasley for a H-ZSM5 Wicke Kallenbach wafer.0005 0.0009 0.00E-026.25 0.

I_MZX3 = MZ3 ( m3 : end.* I_MZB2. m2 = find ( t_MZ2 == Start2 ). t_MZ2 = t_MZ2 . 'Zeolite H- °C HZSM-5' ). c_MZX1 = c_MZX1 . t_MZ1 = MZ1 ( :. 'r+' ) xlabel ( 'time [min]' ).* I_MZB1. I_MZB1 = MZ1 ( m1 : end. S2. m1 = find ( t_MZ1 == Start1 ).* I_MZX1. [ MZ2 ] = textread ([ dirpath filename ]). c_MZB1. c_MZB1 = 6936.44. Start2 = 2. 4 ). 'p-Xylene' ) [ filename dirpath ] = uigetfile ( '100'). 3 ). S1 = c_MZB1 . c_MZX1 = 10173 .* I_MZX3. ylabel ( 'c [mol/l]' ). c_MZX2. t_MZ1. c_MZB3 = 6936. 'ks'. ylabel ( 'Seperation Factor 130 title ( 'Trend of Seperation Factor' ) figure( 2 ) semilogy ( t_MZ1. ylabel ( 'Seperation Factor 100 title ( 'Trend of Seperation Factor' ) figure( 4 ) semilogy ( t_MZ2. ylabel ( 'c [mol/l]' ).5.* 1.* ( 10 ^ 6 ). [ MZ3 ] = textread ([ dirpath filename ]). t_MZ2 = MZ2 ( m2 : end. S2 = c_MZB2 . [ MZ1 ] = textread ([ dirpath filename ]).93 .* ( 10 ^ 6 ).17 . t_MZ3 = MZ3 ( m3 : end. 'r+') xlabel ( 'time [min]' ). I_MZB2 = MZ2 ( m2 : end. I_MZB3 = MZ3 ( m3 : end.44.legend ( 'Benzene'. c_MZX3 = 10173 . c_MZX2 = c_MZX2 . t_MZ2 = MZ2 ( :./ ( c_MZX1 ).1 . t_MZ2.* I_MZX2.44. 1 ). 'p-Xylene' ) [ filename dirpath ] = uigetfile ( '70'). c_MZB2. t_MZ1 = t_MZ1 . c_MZX2 = 10173 .* 1. t_MZ1 = MZ1 ( m1 : end.* ( 10 ^ 6 ). c_MZX1. 'ks'.1 . 1 ). 4 ).t_MZ2 ( 1 ).Appendix A: Results XVII A. 1 )./ 60000. 1 ). title ( ZSM5 130 °C' ).legend ( 'Benzene'. figure( 1 ) plot ( t_MZ1. 1 ). 1 ). I_MZX1 = MZ1 ( m1 : end. 3 ). c_MZB2 = 6936.1 . Start1 = 2. t_MZ2 = t_MZ2 . 'r+') xlabel ( 'time [min]' )./ ( c_MZX3 ). m3 = find ( t_MZ3 == Start3 ). title ( ZSM5 100 °C' ). S1./ 60000.26 . 'Zeolite H- .1 Processing of Wicke Kallenbach experimental data function f_Trennfaktor_gegen_Zeit_und_TAbhaengigkeit [ filename dirpath ] = uigetfile ( '130'). S3 = c_MZB3 . 3 ). c_MZX3 = c_MZX3 .t_MZ1 ( 1 ). t_MZ1 = t_MZ1 . figure( 3 ) plot ( t_MZ2. 4 ).* I_MZB3.* 1. Start3 = 2. t_MZ3 = MZ3 ( :./ ( c_MZX2 ). °C H-ZSM5' ). I_MZX2 = MZ2 ( m2 : end.5 Matlab source code A. 'r+' ) xlabel ( 'time [min]' ).

title ( 'Zeolite HZSM5 70 °C' ). c_MZB3. 'ro'.t_MZ3. '100 °C'.legend ( 'Benzene'. t_MZ2. title ( 'Trend of Seperation Factor' ) figure( 6 ) semilogy ( t_MZ3. c_MZB2. 'r+' ) xlabel ( 'time [min]' ). 'rs' ) xlabel ( 'time [min]' ). c_MZX1. c_MZB1. ylabel ( 'c [mol/l]' ). t_MZ2.Appendix A: Results t_MZ3 = t_MZ3 . 'kx'. c_MZX2. ylabel ( 'c [mol/l]' ). 'rx'. S3. c_MZB3.Äbhängigkeit p-Xylol' ). legend ( '130 °C'. c_MZX3. 'r+') figure( 7 ) xlabel ( 'time [min]' ). t_MZ3 = t_MZ3 . '70 °C' ) figure( 8 ) semilogy ( t_MZ1. legend ( '130 °C'. 'ks'. 'ks' ) xlabel ( 'time [min]' ). ylabel ( 'c [mol/l]' ). ylabel ( 'Seperation Factor 70 °C HZSM-5' ). t_MZ3.Äbhängigkeit Benzol' ). '70 °C' ) XVIII . 'ko'.t_MZ3 ( 1 ). figure( 5 ) plot ( t_MZ3.t_MZ3. c_MZX3. '100 °C'./ 60000. title ( 'Zeolite HZSM5 T . 'p-Xylene' ) semilogy ( t_MZ1. title ( 'Zeolite HZSM5 T .

100°C.2 0 -0. .2 0.6 0.5 2 2. time diagram of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 and a mixture of benzene (black) and p-xylene (red).4 1. 1.2 1 0.8 x 10 2 4 Figure XXXIV: Concentration vs.5 4 x 10 Figure XXXIII: Concentration vs.2 0 fit Benzene measurement Benzene fit p-Xylene measurement p-xylene 0. 100mg wafer weight and 50 ml/min volume flow and the corresponding fit for benzene (black) and pxylene (blue).8 normalized concentration [-] 0.5 1 time [s] 1.2 0 -0.2 1 0.4 0. time diagram of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 and a mixture of benzene (black) and p-xylene (red).6 0.2 1. 70°C.4 0.6 1.4 0.8 normalized concentration [-] 0.Appendix B: Simulation XIX B.1 Simulation Curve fitting of Wicke Kallenbach experiments 1. 100mg wafer weight and 50 ml/min volume flow and the corresponding fit for benzene (black) and pxylene (blue). B.2 0 fit Benzene measurement Benzene fit p-Xylene measurement Benzene 0.8 t [s] 1 1.6 0.

2 0 fit Benzene measurement Benzene fit p-Xylene measurement p-xylene 0. .2 0 -0.6 0. time diagram of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 and a mixture of benzene (black) and p-xylene (red). 130°C.2 0 fit Benzene measurement Benzene fit p-Xylene measurement Benzene 0.4 0.2 1 0. 1.6 1.5 time [s] 2 2. 100mg wafer weight and 50 ml/min volume flow and the corresponding fit for benzene (black) and pxylene (blue).5 x 10 4 4 Figure XXXVI: Concentration vs.5 1 1.4 1. time diagram of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 and a mixture of benzene (black) and p-xylene (red).8 normalized concentration [-] 0.4 0.6 0.2 0. 50mg wafer weight and 50 ml/min volume flow and the corresponding fit for benzene (black) and pxylene (blue).Appendix B: Simulation XX 1.6 0.8 x 10 2 4 Figure XXXV: Concentration vs.8 normalized concentration [-] 0.2 1 0.5 3 3.2 1.8 time [s] 1 1.4 0. 100°C.2 0 -0.

Appendix B: Simulation XXI 1. 100°C.8 normalized concentration[-] 0.300 F [m3/s] 2.54x10-12 .45x10-11 7.5 4 4.14x10-11 3.2 0 fit Benzene measurement Benzene fit p-Xylene measurement p-xylene 0. 150mg wafer weight and 50 ml/min volume flow and the corresponding fit for benzene (black) and pxylene (blue).047 0.5 2 time[min] 2.053 0.50x10-11 3.013 0. Table I: Parameters obtained by non-linear curve fitting of the transmission curves of the Wicke Kallenbach experiments Benzene T [K] 343 373 403 373 373 Weight [g] 100 100 100 50 150 k [1/s] 0.2 1 0.5 1 1.4 0.010 F [m3/s] 1. time diagram of the Wicke Kallenbach experiment using a pressed wafer of ZSM5 and a mixture of benzene (black) and p-xylene (red).08x10-11 4.012 0.00x10-11 1.71x10-11 p-Xylene k [1/s] 0.082 0.00x10-11 2.5 3 3.2 0 -0.1x10-11 9.94x10-12 2.6 0.014 0.5 4 x 10 Figure XXXVII: Concentration vs.029 0.014 0.

^ -8 ).* Wsat .18 * ( 10 . S = 4.* c0X . I_Xylol = Xylol ( n : end.9999 .9999 .2 Matlab source code of Wicke Kallenbach curve fitting B.9999 .9999 .0. rhoB = 1. Xylol ] = textread ([ dirpath filename ]). C_Xylol ) %In the last step the solutions are plotted together with the experimental %data Wsat = 0. . c0X = 9./ max ( I_Benzol ).* c0B ./ ( FX ( m ))) . end for m = 1 : 1 : length ( kX ) XX = (kX ( m ) TX = kX ( m ) . t = t .* S ./ 1000.* Wsat . % Then the normalized concentration vs. C_Benzol ) [ kX FX ] = f_Wicke_Kallenbach_ga_fit_breakthrough_curve_xylene( t. c0B = 0.* rhoB . % Afterwards the curve fitting is performed applying a genetic algorithm [ kB FB ] = f_Wicke_Kallenbach_ga_fit_breakthrough_curve_Benzene( t.(0.2.13.* TB )) + exp ( XB ./ max ( I_Xylol ). n = find ( t == Start1 ). CB ( :. t = t ./ ( FB ( n ))) . C_Xylol = I_Xylol .* t./ ( exp ( TB . 4 ). 3 ).* t. I_Benzol = Xylol ( n : end.* rhoB . t = Xylol ( n : end.0744.^ 3. 1 ).Appendix B: Simulation XXII B.* TB )) .1 Main program function [] = f_Wicke_Kallenbach_curve_fitting ( start ) % [ [ t In the first part the data is read and converted filename dirpath ] = uigetfile ( 'Xylol' ).exp ( .* x.(0. C_Benzol = I_Benzol .44 * 10 . 1 ).t ( 1 ). . .* x. n ) = exp ( TB .* TB )) .* ( 10 . time diagram is calculated from the % experimental data Start1 = start.* S . = Xylol ( : . x = 10 ^ -3.77 . for n = 1 : 1 : length ( kB ) XB = (kB ( n ) TB = kB ( n ) .* TB )).^ -2 ).(0.

rep([10^-5.1 ) . 1. 'HorizontalAlignment'..(0. end for n = 1 : 1 : length ( kB ) for m = 1 : 1 : length ( kX ) x = kB ( n ).(0. 'r-'. NVAR1]). .9999 .[1..exp ( .. MAXGEN = 3000..5...2 Genetic algorithm % This script implements the Simple Genetic Algorithm described % in the examples section of the GA Toolbox manual.1]. created NVAR1 = 1. 1./ ( exp ( TX . NVAR2 = 1.num2str(y)]... how many new individuals are % Number of variables % Number of individuals % Number of generations % Precision of binary representation % Build field descriptor FieldD1 = [rep([PRECI]. 1 .0. ['FB = '..9999 .1].2.* TX )) .. 'HorizontalAlignment'. NVAR1]). 'HorizontalAlignment'. [1. z = kX ( m ). 'measurement Benzene'....num2str(u)]. i = 3 + ( n .[1.9999 .(0. 'k+'... NIND = 40. 0. PRECI = 20. CB ( :.. t. 'measurement p-xylene' ) text( 20000.num2str(x)]. 'HorizontalAlignment'.* TX )) + exp ( XX . 'fit p-Xylene'.* TX )) . t.'center') text( 20000. 0. GGAP = .. y = FB ( n ). C_Benzol. ['kB = '.'center') text( 20000.* length ( kX ) + m. C_Xylol. n ). 0.9.. % Generation gap.'center') text( 20000..num2str(z)].. u = FX ( m ).9999 . 'b*'.. m ).'center') end end XXIII B. rep([1. ['FX = '.* TX )).75. t. 'go' ) legend ( 'fit Benzene'.Appendix B: Simulation CX ( :... figure ( i ) plot ( t... ['kX = '. NVAR1])]. CX ( :. m ) = exp ( TX ... CB_fit ) %imax = 3. % % Author: Andrew Chipperfield % History: 23-Mar-94 file created % % tested under MATLAB v6 by Alex Shenfield (22-Jan-03) function [ kB FB ] = f_Wicke_Kallenbach_ga_fit_breakthrough_curve_Benzene( t.

NVAR2*PRECI). CB_fit ).Appendix B: Simulation FieldD2 = [rep([PRECI].. % Select individuals for breeding SelCh1 = select('sus'. Chrom1. t. SelCh2 = mut(SelCh2). call objective function x = [bs2rv(SelCh1.FieldD1) bs2rv(SelCh2. [ObjV] = f_Wicke_Kallenbach_simulate_breakthrough_curve_Benzene_fit ( x. % Evaluate offspring.ObjV.0. ylabel('log10(f(x))').1.'Units'.. drawnow. [1.1.SelCh2.7). % Assign fitness-value to entire population FitnV = ranking(ObjV). NVAR1*PRECI). [Chrom2 ObjV]=reins(Chrom2.SelCh1. SelCh2 = select('sus'. text(0. % generational counter % Evaluate initial population x = [bs2rv(Chrom1. NVAR2]). % Reinsert offspring into current population [Chrom1 ObjV]=reins(Chrom1. % Reset counters Best = NaN*ones(MAXGEN. % Recombine selected individuals (crossover) SelCh1 = recombin('xovsp'. 10^-5]..'normalized'). NVAR2]).SelCh2. CB_fit ).1].95. rep([1. Chrom2.SelCh1.ObjVSel).7). GGAP).1 * 10^-10. % Update display and record current best individual Best(gen+1) = min(ObjV). FitnV. t. % Generational loop while gen < MAXGEN.'ro').0.[1. figure(2) plot(log10(Best). Chrom2 = crtbp(NIND.xlabel('generation').ObjVSel).5. num2str(Best(gen+1))].FieldD2)]. % best in current population gen = 0. % Increment generational counter gen = gen+1. FitnV.FieldD2)]. 1 .['Best = '.1.1.ObjV. ObjVSel = ObjVSel'.FieldD1) bs2rv(Chrom2.1). NVAR2])]. % Initialise population Chrom1 = crtbp(NIND.0. 0. % Perform mutation on offspring SelCh1 = mut(SelCh1). ObjV = ObjV'. GGAP). % Track best individual and display convergence Best(gen+1) = min(ObjV). SelCh2 = recombin('xovsp'. [ObjVSel] = f_Wicke_Kallenbach_simulate_breakthrough_curve_Benzene_fit ( x.[1. rep([0. figure(2) XXIV .

y = ( x ( 2 : end ) .TB .9999 )) .Appendix B: Simulation plot(log10(Best).3 Fitness function function [ObjV] = f_Wicke_Kallenbach_simulate_breakthrough_curve_Benzene_fit ( x. 2 ).5.2.* x. Wsat = 0.^ 3 ) . P2 = bs2rv(Chrom2. xlabel('generation').9999 )) .9999 )).* 0.* S . P1 = bs2rv(Chrom1.0./ ( exp ( TB . rhoB = 1. ylabel('log10(f(x))').* t ( 2 : end ) .FieldD2).* c0B .FieldD1). % End of GA XXV B./ ( FB ( n ))) . ( 2 ).0744.( TB .^ -8 ). FB = x ( : .^ 3. CB_fit ) ka = x ( : .13.'Units'. 1 ). x = (( CB . text(0.* 0.* t.* 0. c0B = 0.['Best = '.9999 )) + exp ( XB ./ FitnV ( n ) = sum( y ). FB = P2 ( I ).CB_fit ) . end I = find(ObjV == (min(ObjV))).( TB .* Wsat .^ 2 ).exp( .* 0.* rhoB . drawnow. end ObjV = FitnV. .( TB . TB = ka ( n ) . S = 4.18 * ( 10 . kB = P1 ( I ).'ro').44 * 10 .'normalized').95. CB = exp ( TB . x = 10 ^ -3. for n = 1 : 1 : length (ka) XB = (ka ( n ) . num2str(Best(gen+1))]. t.

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