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JOSE MUGGE, HANS BOSCH AND TOM REITH Faculty of Chemical Technology, University ofTwente, P.O. Box 217, 7500 AE Enschede, The Netherlands, (e-mail: j.m.mugge@ct.utwente.nl)

Gas adsorption kinetics in porous activated carbon is modeled using a nonisothermal, nonisobaric Maxwell-Stefan model. Mass transfer is described by three mechanisms: pore diffusion (molecular and Knudsen diffusion), viscous flow and surface diffusion. To distinguish between the different types of transport in the porous particles two types of kinetic uptake measurements were performed; responses to carbon dioxide pressure steps and responses to concentration steps of carbon dioxide at constant feed pressure. The unknown transport parameter, the surface diffusion coefficient, was determined by fitting the model to both types of experiments.

Introduction

In previous work [1,2] a new experimental method to determine gas adsorption isotherms from Temperature Programmed Physisorption (TPP) was described. Since TPP requires operation sufficiently close to local equilibrium the experimental conditions must be chosen such that mass and heat transfer limitations are negligible. To investigate this a mathematical model would be very helpful to determine the relative contributions of various mechansims of mass transport in a single adsorbent particle. Numerous kinetic models have been published [3,4,5], examples of earlier approaches are the LDF model with a single effective diffusion coefficient [6] and models with the resistance to mass transport in the macropores and/or micropores [7,8]. In this work we follow the approach of Taqvi and LeVan [9], Serbezov and Sotirchos [10] and Do and Do [11] who based their kinetic models on Maxwell-Stefan types of mass transport equations for pore diffusion, viscous flow and surface diffusion. Experimental methods like the zero length collumn (ZLC) and the differential adsorbent bed (DAB) are designed such that heat effects are minimized. However these methods are restricted by the experimenal conditions: small amount of adsorbent, low concentrations, high flow rates. While gravimetric uptake rates are not isothermal, kinetic data can still be obtained in a broad range of experimental conditions. In this work we measured gravimetrically uptake rates of C0 2 on activated carbon as a response to both concentration and pressure steps and determined the unknow mass transfer parameter with a nonisothermal model that takes into account the mechanisms of mass transport mentioned above. 2 Nonisothermal, nonisobaric model for adsorption in a single porous particle

2.1 Mass Balance The mass balance for a single particle is given in Equation 1. The Maxwell-Stefan approach is used to describe the total molar flux in the pores due to the various transport mechanisms: pore diffusion, viscous flow and surface diffusion (Equations 2 .. 5).

fllotol _ ^diffusion

^viscous

rfurfact

^ \

452

NM. =

^viscous =

_[ B ]-iV.-EHI B __Ea. v . pM RT f

for

N,^ = _|- D -p v p

A

^.y(-y)=~ + 2 -jjr

(5)

i,j(i*j) = -~jjr

(6a)

(6b)

VY_n,75

The surface flux (Equation 5) contains the only unknown parameter in this model, Dsj, which has an Arrhenius type of temperature dependence. The activation energy and the pre-exponential constant were determined by simultaneously fitting of the model to all experimental results. Physical properties and transport parameters are calculated as a function of temperature. The diffusivities are adjusted to the structure of the porous medium (pore size and tortuosity) with the relations given in Equation 6b. The binary diffusivities at reference conditions, Dn are calculated from the Chapman-Enskog equation [12]. The mean mesopores were assumed to be the transport pores for viscous flow (Equation 4). 2.2 Heat balance As a result of adsorption, heat is released within the particle. For a proper description of the adsorption kinetics both mass and energy balance must be solved simultaneously. Temperature gradients inside the particle should be taken into account, however, under all experimental conditions in this work the internal temperature gradients are smaller than the external gradients (BiH<0.01); heat effects are therefore calculated for uniform particle temperatures. The heat balance is given in Equation 7; the heat transfer coeficient, h, is determined experimentally. ( 1 " sp )PsCp, , - j + pAHt & = 2A 3 Experimental 3.1 Apparatus and materials The gravimetrical adsorption measurements were performed in a fully automated Intelligent Gravimetric Analyser (IGA) of Hyden Analytical (UK). The system was operated from vacuum (10"4 mbar) to atmospheric pressure in no flow mode during the pressure step experiments. During the concentration step experiments the system was operated in flowing mode with a total molar flow rate of 0.4 mmol s ' (linear velocity 1.5 cm s "'). Temperature was 304 K in all experiments. Norit RB4 activated carbon extrudates (solid density 2.3 kg m"3, particle porosity 0.25, mean meso pore radius 200 run), with a length of 11 mm and a diameter of 4 mm were used as adsorbents. The cylindrical surface of the particles was sealed with epoxy resin, leaving only the top and bottom or only the top free for diffusion; thus, responses of particles with a diffusion lenght of 5.5 mm and 11 mm could be compared. During the adsorption experiments three identical particles were used to ensure sufficient weight change. The particles were suspended by a wire in the gravimetrical analyser in such a

(Tb

_n

(7)

453

manner that the gas could flow around the particles. Prior to the adsorption experiments the samples were degassed at 10"4 mbar for 4 hours at 393 K. 3.2 Heat transfer coefficient Heat transfer coefficients were determined from the particle response to a temperature change of 40 K. The heat transfer coefficient was measured in helium at zero flow and at the same flow rate that was used in the gravimetrical analyser. 3.3 Responses to pressure and concentration changes Pressure step experiments were performed from 0 to 100 mbar, 100 to 500 mbar and 500 to 1000 mbar. Concentration step experiments were performed from 0 to 10 %, 0 to 50 % and 0 to 100 % C0 2 . AH experiments were carried out using particles with a diffusion length of 5.5 mm and 11 mm respectively. Gas mixing effects in the analyser were taken into account by using the measured pressure or concentration ramp as a time dependent boundary condition. 4 Results 4.1 Heat transfer coefficient The resulting values of the heat transfer coefficient of the sealed particles in helium were 13 Wm"2K"' at zero flow (pressure step) and 18 Wm'2K"' at flowing conditions (concentration step). These values were adjusted to the change in gas composition applying the usual Nusselt relation for single particles [12]. 4.2 Responses to pressure and concentration steps The results of the pure component pressure step experiments and the concentration step experiments are shown in Figure I and 2. The surface diffusion coefficient, determined by fitting, is given by a pre-exponential constant of 1.4-10" m s"1 and an activation energy of 16.5 kJ mol"1. The activation energy is about 0.7 times the heat of adsorption, which is in the range (0.3-1) that was found in literature on surface diffusion [13]. The contribution of the various mass transport processes, calculated at the maximum flux in a slab of 5.5 mm, are summarized in Table 1 for the responses to pure component pressure step

_. 2

_k-4

+*"

1.5

"

-a-n-uyjj-L

r *?*

0

l j y i yi u -

800 lime(s)

-!

400

1200

Figure 1. Experimental (open symbols: diffusion lenght 5.5mm, closed symbols: diffusion length 11mm) and calculated (solid lines) responses to pressure steps of 10 to 100 mbar ( * ) , 100 to 500 mbar <P*) and for 500 to 1000 mbar ().

Figure 2. Experimental (open symbols: diffusion lenght 5.5mm, closed symbols: diffusion length 11mm) and calculated (solid lines) responses to concentration steps of 0 to 10% C0 2 (P*), 0 to 50% CO, (Q*) and 0 to 100% C0 2 (<>).

454

changes as well as the responses to concentration step changes at constant feed pressure. Similar results are found for a slab of 11 mm.

Table 1. Relative contributions of pore diffusion, viscous flow and surface diffusion in a slab.

N diBu.i.

(0/o)

Nv"cou' (%)

NT/o)

5

0-10%

0-50%

0-100%

-0.033 76 9 15

-0.17 55 38 7

-0.37 59 38 3

Discussion Good agreement was found between most experimental and modeled uptake curves as a response to changes in both pressure and concentration. The transport processes molecular and Knudsen diffusion, viscous flow and surface diffusion all contribute significantly to the adsorption process in the broad experimental range. The influence of the micropore structure on the uptake kinetics is lumped in the value of the surface diffusion coeffcient, therefor this model is applicable to various porous materials. Our future plans include experiments to demonstrate this.

0.3-

0.2-

-A

ra ? 0.1m

1000 Ume(s) 1500 2000

Figure 3a. Calculated uptake after a concentration step of 0 to 10% C0 2 () and the equilibrium amount adsorbed (- -) at sample temperature (...).

Figure 3b. Calculated uptake after a concentration step of 0 to 100% C02 () and the equilibrium amount adsorbed (- -) at sample temperature (...).

The Figures 3a and 3b show the uptake curve, the sample temperature and the equilibrium amount adsorbed at this temperature. The temperature rise due to the heat of adsorption varies from less then 2 C for a concentration step of 10% to 26 C for a concentration step of 100%. These figures cleary demonstrate that in all cases mass transfer parameters can be determined as long the uptake curve differs sufficiently from the equilibrium amount adsorbed. The sample temperature was calculated by considering just the cylindrical part of the extrudates. For almost all uptake curves given in Figures 1 and 2 this is sufficient, model curves agree with the experimental results. Only for the experiment with the highest adsorption rates (short diffusion length, 100% concentration change) the influence of the ends is no longer negligible. However this has no effect on the resulting surface diffusion coefficient since this parameter was determined from the initial part of the uptake curve, where mass transfer dominates.

455

Conclusion

A nonisothermal, nonisobaric Maxwell-Stefan model for gas asdorpion kinetics in single porous particles has been used to describe responses to pressure and concentrations steps. This model is valid in a broad range of operating conditions due to the contribu tion of three different mass transport processes leading to pressure and concentration equalisation: bulk and Knudsen diffusion, viscous flow and surface diffusion. In future this model will be used to describe multicomponent gas adsorption, such as determination of the criteria for mass and heat transfer limitations in TPP systems. List of Symbols aH particle shape factor (-) B matrix containing effective binary and Knudsen diffusivities (s m'2) B n viscous flow parameter (m2) Bi Biot number for heat transfer (-) d particle diameter (m) surface diffusion coefficients (m2 s'1) Knudsen diffusion coefficient (m2 s"1) D,; binary diffusion coefficient (m s ) IJ h ' heat transfer coefficient (W m" 2 ^ 1 ) AHj adsorption enthaply (J mol 'K'1) N flux (mol m V ) p partial pressures of the gases (N m"2) Pm q r R t T Tb Vj total pressure (N m'2) vector containing isotherms (mol kg"1) pore radius (m) gasconstant (J mol'K" 1 ) time (s) sample temperature (K) bulk temperature (K) mole fraction (-)

Greek symbols Ep particle porosity (-) u viscosity ( k g m's"1) ps solid density (kg m"3) TXTK) (Knudsen) tortuosity(-)

Acknowledgement: We wish to thank Cormac Murphy for his experimental work. References 1. Foeth, F., J.M.Mugge, H. Bosch and T. Reith, Adsorption 2 (1996) pp. 279-286. 2. Mugge, J.M., H. Bosch, and T. Reith, Gas Adsorption Isotherms from Temperature Programmed Physisorption, Proceedings of the Sixth International Conference of Fundamentals of Adsorption, PresquHe de Giens (Elsevier, France, 1998). 3. Yang, R., Gas separation by adsorption processes (Butterworths Series in Chemical Engineering, Boston, 1987). 4. Ruthven, D.M., Principles of adsorption and adsorption processes (John Wiley & Sons, New York, 1984). 5. Do, D.D., Adsorption Analysis: Equilibria and Kinetics (Imp. College Press 1998). 6. Haul, R., and H. Stemming, Nonisothermal Sorption Kinetics in Porous Adsorbents, Journal of Colloid and Interface Science 97(2) (1983) pp. 348. 7. Ruthven, D.M., Z. Xu, S. Farooq, Sorption kinetics in PSA systems. Gas Separation and Purification 7(2) (1993) pp. 75. 8. Haq, N. and D.M. Ruthven, Chromatographic study of sorption and diffusion in 4A zeolite, Journal of Colloid and Interface Science 112 (1986) pp. 154. 9. Taqvi, S.M., M.D. LeVan, Role of convection and diffusion in a single pore with adsorptive walls, Adsorption 2 (1996) pp. 229-309. 10. Serbezov, A.S., S.V.Sotirchos, Math Modeling of Multicomponent Nonisothermal Adsorption in Sorbent Particles Under PSA Conditions Adsorption 4 (1998) pp. 93. 11. Do,H.D.,D.D. Do, Chemical Engineering Science 53(6) (\998) pp. 1239-1252. 12. Bird, R.B., W.E. Stewart, and E.N. Lightfoot, Transport Phenomena. (John Wiley & Sons, New York, 1960). 13. Kapoor, A., R.T. Yang, and C. Wong, Surface diffusion, Catalysis Reviews - Science and Engineering 31 (1989) pp. 129-214.

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