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www.elsevier.com/locate/ces

n-butane adsorption from diluted streams

Gregorio Marbán ∗ , Teresa Valdés-Solís, Antonio B. Fuertes

Instituto Nacional del Carbón, CSIC, Francisco Pintado Fe, 26, 33011 Oviedo, Spain

Received 8 August 2005; received in revised form 31 January 2006; accepted 6 March 2006

Available online 13 March 2006

Abstract

A complete breakthrough model is proposed and solved in this work to describe the removal of volatile organic compounds from a diluted

single-component gas stream passing through a microporous activated carbon ﬁber monolith (ACFM) under isothermal conditions. All signiﬁcant

parameters are considered in the model, including type of adsorption isotherm, resistance to external gas diffusion, non-instantaneous adsorption

kinetics at the external surface and type of gas diffusion within the pore system. n-Butane was employed as the test compound for obtaining

the experimental breakthrough curves. The model including non-instantaneous adsorption at the external surface and surface pore diffusion

describes properly the experimental adsorption results.

䉷 2006 Elsevier Ltd. All rights reserved.

Keywords: Activated carbon; Carbon ﬁbers; Volatile organic compounds; Adsorption; Mass transfer; Diffusion; Simulation; Modeling

1. Introduction VOCs (Centeno et al., 2003; Fuertes et al., 2003). However, the

use of granular packed beds has serious drawbacks, such as the

Low-density activated carbon ﬁber monoliths (ACFMs) have high pressure drop associated with the ﬂow of gas through the

been developed recently (Burchell et al., 2000; Burchell and packed media, attrition of the granular material, channeling, gas

Judkins, 1997; Lee et al., 1997; Marbán et al., 2000; Vila- bypassing, etc. These disadvantages can be avoided with the

plana-Ortego et al., 2002) for several gas–solid applications utilization of ACFM that, in addition, exhibits a narrow poros-

due to their properties such as light-weight, high mechanical ity in the micropore range (< 2 nm). Micropores are primarily

strength and fast adsorption kinetics. The monolithic structure responsible for adsorption at low VOCs concentrations in am-

makes them easier to handle than packed beds and produces a bient air environments due to the overlapping of the attractive

low resistance to bulk gas ﬂow. Thus, among the possible appli- forces of opposite pore walls (Derbyshire et al., 2001; Foster

cations, ACFMs are of interest for the adsorption and recovery et al., 1992). In many cases n-butane has been employed as

of organic vapors (Fuertes et al., 2003; Marbán and Fuertes, a reference molecule to compare the VOC adsorption capac-

2004), CO2 adsorption (Burchell et al., 1997; Burchell and Jud- ity of various materials (DeLiso et al., 1997; Gadkaree, 2001;

kins, 1997), as catalysts or catalyst support for the removal of Valdés-Solís et al., 2004).

SOx and NOx from ﬂue gas (Marbán et al., 2003), water treat- The adsorption of VOCs in carbonaceous materials has

ment (Suzuki, 1991) and for CH4 storage (Muto et al., 2005). received increasing attention in recent years, and several at-

The removal of volatile organic compounds (VOCs), com- tempts to model the process have been published for granular

monly performed by adsorption, is of great interest for the air active carbon (Linders et al., 2001, 2003), ACF (Cheng et al.,

quality control. At a low-concentration level, adsorption on ac- 2004; Das et al., 2004) and carbon-coated ceramic monoliths

tive carbon is the most employed method for the removal of (Valdés-Solís et al., 2004). In general, the models found in liter-

ature include several simpliﬁcations; such as considering only

∗ Corresponding author. Tel.: +34 985 11 90 90; fax:+34 985 29 76 62. gas diffusion in the pores or assuming instantaneous adsorption

E-mail address: greca@incar.csic.es (G. Marbán). kinetics (Cheng et al., 2004; Linders et al., 2001, Valdés-Solís

0009-2509/$ - see front matter 䉷 2006 Elsevier Ltd. All rights reserved.

doi:10.1016/j.ces.2006.03.008

G. Marbán et al. / Chemical Engineering Science 61 (2006) 4762 – 4772 4763

time. Then, every approximate solution has its own restricted Textural properties of the adsorbent material (ACFM) and bulk parameters

used during the dynamic adsorption experiments

scope of validity which should be accurately deﬁned.

The objective of this work is to propose and solve a math- Textural properties

ematical breakthrough model for low-concentration gas ad- SBET (m2 /g)a 1306

N2

sorption in ACF monoliths which takes into consideration all Vpore (cm3 /g)b 0.46(5)

CO2

signiﬁcant parameters (non-linear adsorption equilibrium, Vpore (cm3 /g)c 0.44

axial dispersion, ﬁnite mass transfer resistance, type of pore L0 (nm)d 0.93

Adsorbed n-butane (mmol/g) at C0 = 106 ppm(30 ◦ C) 4.55

diffusion, etc). Thus, a systematic approach is performed,

Adsorbed n-butane (mmol/g) at C0 = 1500 ppm(30 ◦ C) 2.02

starting from a simpliﬁed and unrealistic model (gas phase Adsorbent characteristic energy; E0 (kJ/mol) 20.3

diffusion in the micropores with instantaneous adsorption), (Dubinin–Radushkevich)

going through a more complex and realistic model that permits

Fiber dimensions

to analyze the effect of the equilibrium adsorption isotherm

(Dubinin–Radushkevich, Freundlich, Toth, etc) on the surface Diameter DF (m) 11.6

diffusion-controlled process, to ﬁnally include the possibility Bulk parameters

of non-instantaneous adsorption kinetics at the external surface Wcarbon (mg) 48

of the ﬁbers, thanks to which the simulation results permit to Diameter D (mm) 5.5

Height H (mm) 10.6

eventually match the experimental breakthrough curves.

Aspect ratio (H/D) 1.9

Bulk carbon density b (g/cm3 ) 0.19

2. Experimental Bulk porosity (b ) 0.8

a BET speciﬁc surface area obtained by N adsorption at −196 ◦ C

2

b Pore volume obtained by N adsorption at −196 ◦ C (percentage of meso-

2.1. Adsorbent material 2

pore volume in brackets).

c Micropore volume obtained by CO adsorption at 20 ◦ C

2

The preparation of activated monolith (ACFM) is reported d Mean micropore width obtained from n-butane adsorption experiments as

elsewhere (Marbán et al., 2000). Brieﬂy, rejects of Nomex姠 reported in (Centeno et al., 2003).

ﬁbers (DuPont) were carbonized in N2 at 850 ◦ C (heating rate:

5 ◦ C min−1 ; soaking time: 1 h). Afterwards, they were milled cess of the gas through the carbonaceous samples. With these

by conventional blade-mills and the fraction of size 0.1–0.4 mm conditions, and considering a fast (adsorbent fully loaded in

was dry-mixed with powdered phenolic resin (Novolak) in a 10 s) and linear adsorption rate, and negligible gas bypassing,

mass ratio of 3/1. The mixture was moulded, cured (in air at the value of the adsorption rate was estimated be below 1.2%

180 ◦ C) and carbonized (in N2 at 700 ◦ C). The carbonized com- the value of the n-butane molar ﬂow rate, which clearly estab-

posite with a bulk density of around 0.25 g cm−3 was activated lished differential regime. However, it was determined that a

at 700 ◦ C with a stream of water (∼ 25 vol% in N2 ) until acti- high degree of gas bypassing through the annulus between the

vation degree (burnoff) of 42 wt% was reached. crucible and the TGA chamber impeded to attain strict differ-

ential conditions, and therefore the TGA results are discussed

2.2. Adsorbent characterization in the corresponding section from a qualitative perspective.

The textural properties (speciﬁc surface area and pore vol- 2.4. Dynamic adsorption experiments

ume) of the adsorbent material were evaluated by means of N2

adsorption isotherms (−196 ◦ C) obtained with a Micromerit- The adsorption chamber used for obtaining the breakthrough

ics ASAP 2010 analyzer, and by CO2 adsorption at 20 ◦ C with curves was a cylindrical pipe (7 mm i.d.) made of quartz. The

a thermogravimetric analyzer (TG CI Electronics). The results cylindrical ACFM was tightly ﬁtted to the internal wall of the

obtained are presented in Table 1. Data on n-butane adsorption chamber by means of Teﬂon strips and vacuum grease (ther-

experiments performed with the TG system, including parame- mally stable up to 210 ◦ C). In this way gas bypassing was com-

ters for the Dubinin–Radushkevich isotherm (i.e., E0 ) are also pletely avoided. The bulk parameters of the ACFM used are

indicated in Table 1. shown in Table 1.

For the analysis of dynamic n-butane adsorption, the gas

2.3. TGA experiments mixture (500–2000 ppm in He; ﬂow rate = 150 mL/ min) was

led into the adsorption chamber by means of a set of mass ﬂow

A differential adsorption experiment was attempted in the controllers. The composition of the gases exiting the adsorp-

thermogravimetric analyzer at 30 ◦ C. In order to approach dif- tion chamber was analyzed continuously by a mass spectrom-

ferential conditions a very low sample weight (1.475 mg) and a eter (Baltzers, Omnistar model 300O) using mass fragments

high value of n-butane gas concentration (100 vol%) were used 18 for water and 58 for n-butane. The adsorbent temperature

at the maximum ﬂow rate allowed by the experimental setup was measured by a thermocouple inserted into the adsorption

(82 mL/min, 1 atm). The crucible used for these experiments chamber. Prior to the adsorption experiments the adsorbent was

was specially fabricated with a wired mesh to assure fast ac- heated in He at 160 ◦ C for 30 min.

4764 G. Marbán et al. / Chemical Engineering Science 61 (2006) 4762 – 4772

librium at Cp , and is given by the adsorption isotherm at Cp .

For modeling the dynamic behavior of ACF monoliths under Rearranging:

isothermal conditions, axially dispersed plug ﬂow is assumed

(DF /D 1), while mass transfer to the external surface is 4t0 Deff

implemented by a Sherwood relationship coupled with a non- 2 2

jy Deqv j y 2 jy

instantaneous rate of adsorption. The gas phase mass balance of = + . (6)

j qe (C0 ) je j2 j

the single-adsorptive (n-butane) in the monolithic column can p +

be calculated, in dimensionless form as (see notation below): C0 jy

je /jy can be calculated as the slope of the adsorption

jx 1 j2 x 1 jx 1 − b qe (C0 ) j

= − − , (1) isotherm. For a D–R (Dubinin–Radushkevich) isotherm a cor-

j P ep j2 j b C0 j

rection must be made at the range of the small reduced pressures

where below the inﬂection point of the curve (y/ys < 1.4 × 10−16 ),

1 in which the Henry regime must be considered to ensure ther-

=3 2 d. (2) modynamic correctness. Thus, two equations can be derived

0 considering the two zones as included below:

y 1 y 1

Henry regime: < exp − 2 D.R regime: exp − 2

ys 2 ys 2

2

ys

1 y e = s exp − ln , (8)

e = s exp , (7) y

42 ys

2

je 2 y ys

je s 1 = 2

s

ln

s

exp − ln . (10)

= exp , (9) jy y y y

jy ys 42

The effective diffusivity in the pore system can be calcu-

Re ∼ 0.02) can be estimated as (Linders, 1999; Ruthven, 1984):

lated by means of the Wakao and Smith equation, in which the

a tortuosity factor was approximated to 1/p (Wakao and Smith,

Pep = , a = 0.3.0.4. (3)

ReSc 1962):

Depending on the regime and type of adsorbent, the value

2p

of (j/j) will be calculated by different expressions. Two Deff = , (11)

−1 −1

different regimes, described below, are considered: DM + DK

R1. Gas phase diffusion inside the micropores with instan-

taneous equilibrium adsorption: It is generally accepted that where the Knudsen diffusivity (DK ) is a function of the average

surface diffusion plays an important role when dealing with pore size (Doraiswamy and Sharma, 1984):

adsorption on narrow micropores (Ruthven, 1984), being how- 0.5

−8 Tads

ever less important for meso/macroporous systems (i.e., active DK = 4.85 × 10 × L(nm) × . (12)

carbon), for which gas phase diffusion inside the pore system is MW

thought to be the dominating diffusion process. Nevertheless, For the continuity between the axial concentration proﬁle

gas phase diffusion will be considered here as a possible option (Eq. (1)) and the intraparticle concentration proﬁle (Eq. (6)) the

for checking and comparative purposes. The appropriate form following equations are considered:

of the Fickian diffusion equation for a gas diffusion-controlled

system may be obtained from a differential mass balance on a

j 6b Sh C0

spherical shell element: = (x − y=1 ), (13)

j Bo2 qe (C0 )

qe (C0 ) j jy 4t0 Deff j2 y 2 jy

+ p = + . (4) jy DM Sh

C0 j j 2

Deqv j2 j = (x − y=1 ). (14)

j =1 Deff 2

Assuming equilibrium adsorption within the micropores:

Thus, Eq. (14) is the border equation for solving (6) and getting

j de jy the value of y=1 . With this value, the axial concentration proﬁle

= , (5)

j dy j can be evaluated by Eqs. (13) and (1).

G. Marbán et al. / Chemical Engineering Science 61 (2006) 4762 – 4772 4765

The Sherwood number (Sh) is estimated here by the stan- In a similar way, the Darken equation can be applied to any

dard Ranz and Marshall correlation (Bird et al., 2002; Ruthven, kind of isotherm (e.g. Langmuir, Toth, etc.). Since adsorption

1984): is instantaneous:

Sh = 2 + 0.6Re1/2 Sc1/3 . (15) j 6b Sh C0

= (x − y=1 )

j Bo2 qe (C0 )

Although this correlation is valid for Re > 2, we have decided

= kext (x − y=1 ). (21)

to employ it because, according to Ruthven (Ruthven, 1984),

most correlations for Re < 2 usually underestimate the Sher- Combining (1) and (21):

wood number, and therefore it seems advisable to use a correla-

tion that yields the value of Sh=2 for the limiting case of Re=0 jx 1 j2 x 1 jx 1 − b

= − −

(inﬁnite stagnant ﬂuid around an isolated spherical particle). j P ep j2 j b

R2. Adsorption on highly dispersed microporous particles qe (C0 )

(i.e., ﬁbrous monoliths): In this kind of systems it is assumed × kext (x − y=1 ). (22)

C0

that diffusion inside the ﬁbers occurs via surface migration

along their small micropores. Different situations can be found: Coupling (17) and (21) we can obtain the border equation

that expresses the continuity between the axial and the radial

• R2.1: External mass transfer towards the external surface of proﬁle:

the ﬁbers, with instantaneous adsorption at the surface;

j kext

• R2.2: Resistance to adsorption at the external surface of the = (x − y=1 )

j =1 3

ﬁbers (non-instantaneous adsorption).

DM Sh C0

= (x − y=1 ). (23)

It is desirable to use an expression for j/j that consider Dso 2 qe (C0 )

all the above resistances, following a similar formalism to that R2.2. Non-instantaneous surface adsorption: In this case the

used when modeling chemical processes. axial proﬁle is expressed as in the former case by Eq. (22),

R2.1. Instantaneous surface adsorption: In this case, only the radial proﬁle is calculated by the mass balance of Eq. (16)

external mass transfer and intraparticle diffusion control the and the external mass transfer resistance is given by Eq. (21),

process. The intraparticle diffusion resistance can be expressed whereas the resistance to external surface adsorption can be

by the following mass balance: accounted by the following equation, which assumes Lang-

j j j muir kinetics and resembles that used in the old Thomas model

= 2 2 (Thomas, 1944, 1948):

j j j

2

j 2 1 j j j j =1

= + + . (16) = ka t0 C0 y=1 (s − =1 ) − . (24)

j2 j j j j Ka

Similar to Eq. (2) we can integrate (16) to obtain By considering the equilibrium isotherm, constant Ka can

be removed from Eq. (24), which turns into

j j

= 3 . (17)

j j =1 j =1

= ka t0 C0 s y=1 1 − , (25)

j e,=1

The dimensionless surface diffusivity now depends on the

instantaneous adsorption and can be evaluated by the thermo- where e,=1 is the dimensionless adsorbed amount in equi-

dynamic relation expressed by the Darken equation: librium with y=1 . By equaling (21) and (25) and removing

d Ln(x) y=1

= . (18)

d Ln() j kext ka t0 C0 s (1 − =1 /e,=1 )x

= . (26)

Thus, application of the Darken equation to the D–R isotherm j kext + ka t0 C0 s (1 − =1 /e,=1 )

gives

1 1

Henry regime: < exp − 2 D.R regime: exp − 2

s 4 s 4

1

= 1, = ,

2[Ln(s /)]1/2

j j 1

= 0, (19) = [Ln(s /)]−3/2 . (20)

j j 4

4766 G. Marbán et al. / Chemical Engineering Science 61 (2006) 4762 – 4772

for the D–R isotherm as follows:

y=1 1 y=1 1

Henry regime: < exp − 2 D.R regime: exp − 2

ys 2 ys 2

2

e,=1 ys

e,=1 y=1 1 = exp − ln . (28)

= exp , (27) s y=1

s ys 42

=0 for = 0. (39)

y=1 j

e,=1 = . (29)

when

= 1, this equation takes into consideration the low was performed by means of an ad hoc-designed Visual Basic

adsorptive concentration (dilute gas stream) and thus assumes macro included in an Excel datasheet. For discretizing the ra-

a Henry regime at the external surface, qe = KC, in which the dial proﬁle a three-point-based generalized three-level scheme

Henry constant is was used, whereas the program allowed the procedure for dis-

cretizing the axial proﬁle to be selected among several implicit

qe (Cs ) schemes (backwards difference, Crank Nicholson, three level

K= exp{−[ ln(Cs /C0 )]2 }. (30)

C0 schemes) by using either three-point or ﬁve-point derivatives.

In this way, the D–R isotherm is considered also at the exter- For solving the set of non-linear coupled equations the Thomas

nal surface when the breakthrough proﬁle is fully developed. algorithm was used together with a Newton–Raphson iterative

The D–R isotherm can also be considered for any value of y=1 procedure.

by calculating the appropriate value of

in any iteration step.

Coupling (17) and (26) the border equation that expresses 4. Results and discussion

the continuity between the axial and the radial proﬁle can be

obtained as: 4.1. Differential adsorption

j kext ka t0 C0 s (1 − =1 /e,=1 )x Fig. 1 shows the experimental variation with time of the rel-

= . (31)

j =1 3[kext + ka t0 C0 s (1 − =1 /e,=1 )] ative mass increase () for ACFM obtained in the TGA at near

differential conditions (see experimental section). As compari-

This general expression can be simpliﬁed by using Eq. (29). son, the results obtained by other authors (Linders et al., 2001)

In this way, Eqs. (21), (25) and (29) permit to obtain the fol- with a commercial active carbon are also included (Kureha ac-

lowing expression for calculating y=1 : tive carbon (10.8 mg), 3.7 vol% n-butane/He, F =200 mL/ min,

kext x + ka t0 C0 s (

=1 ) 1 atm, 30 ◦ C, experiment performed in a TEOM).

y=1 = , (32) According to the results displayed in the ﬁgure, both the ac-

kext + ka t0 C0 s tive carbon pellets and the ACFM seem to attain equilibrium at

with this, Eq. (31) becomes a similar rate. However, as commented before, in the case of

the ACFM, the data were obtained with a TGA that had speciﬁc

j kext ka t0 C0 s (x −

=1 ) structural features that made it impossible the establishment of

= . (33)

j =1 3[kext + ka t0 C0 s ] strict differential conditions. Therefore, under strict differential

conditions it should be expected that the ACFM adsorbent pre-

It can be noticed that this equation becomes Eq. (23) when sented a faster rate of n-butane adsorption than that shown in

ka = ∞. The rest of border equations are the following: Fig. 1 (experimental results) and consequently also faster than

x=0 for < 0 and for all , (34) that reported for Kureha AC. As will be seen now, the results

of the model conﬁrm this expectation.

x = x0 for 0 and = 0[or x = x0 × (t/ti ) for t < ti By applying the model at differential conditions with the ki-

for linear increase of feed concentration], (35) netic parameters that better ﬁt the dynamic breakthrough pro-

ﬁles for the ACFM (see Section 4.2 Breakthrough proﬁles)

=0 for < 0 and for all , (36) curves A (obtained with values of gas ﬂow and concentration as

jx those used for differential experiment with ACFM) and B (ob-

=0 for = 0, (37) tained with values of gas ﬂow and concentration as those used

j

for differential experiment with Kureha active carbon (Linders

jx et al., 2001)) in Fig. 1 were obtained (surface diffusion, Darken

=0 for = 1, (38)

j equation applied to D–R isotherm, Dso = 1.5 × 10−12 m2 s−1 ,

G. Marbán et al. / Chemical Engineering Science 61 (2006) 4762 – 4772 4767

C Table 3

1.0 Expressions of evaluated by the Darken equation for different isotherms

A,D

Isotherms (Ds /Dso )

0.8 B

θ [x for curve A]

0.6

1

Dubinin–Radushkevich (20)

0.4 2[Ln((s /)]1/2

(D–R) isotherm (Eq. (9))

ACFM

0.2

Kureha active carbon (Linders et al., 2001)

1

Langmuir isotherm (40)

(1 − /s )

0.0

0 5 10 15 20

time (s) 1

Chen and Yang for diffusion (41)

(1 − (1 − )/s )

Fig. 1. Differential adsorption experiments performed with the ACFM in

100 vol% n-butane ﬂow. Data for Kureha active carbon were taken from (Chen and Yang, 1992)

(Linders et al., 2001). Also included the results of the model applied to

ACFM at differential conditions (curves A to D). ( = 0.5 for calculations)

1

Freundlich isotherm (42)

Table 2 n(1 − /s )

Parameter values of simulation curves plotted in Fig. 1 (square n-butane (n = 0.6 for calculations)

concentration steps)

(ppm) (mL/min) type (m2 s−1 ) Toth isotherm (43)

1 − (/s )t

A 106 82 Surface (D–R) 1.5 × 10−12 20

(t = 2 for calculations)

B 37000 200 Surface (D–R) 1.5 × 10−12 20

C 106 82 Gas 3.0 × 10−8 ∞

D 106 82 Surface (D–R) 1.5 × 10−12 ∞

ka = 20 m3 mol−1 s−1 ). This procedure is contrary to that gen- differential conditions (C0 = 106 ppm).

erally followed, which consists of ﬁrstly evaluating the intra- Application of the model at differential conditions can of-

particle diffusion parameters via ﬁtting the experimental curves fer us two practical conclusions for the modeling of the break-

obtained at differential conditions and then predicting the dy- through proﬁles. First of all, the surface diffusion-controlled

namic proﬁles with the so-obtained parameters. However, it is regime can be analyzed by considering different adsorption

followed in this work because of the impossibility to use dif- isotherms which will relate in different ways the surface dif-

ferential conditions with the available TGA (Table 2). fusivity with the amount of n-butane adsorbed at any moment

Curves A and B clearly show that ACFM adsorbent be- inside the pore system. This relationship is performed through

comes fully loaded at differential conditions in less than 3 s, the Darken equation (18). In this work, six expressions of

which is an indication of the high adsorption rate attained corresponding to different situations and isotherms listed in

with this microporous material. Only when considering in the Table 3 have been analyzed.

model gas phase diffusion inside the pores a faster adsorp- In principle, all these expressions of should yield different

tion rate is obtained (curve C). Obviously the latter is not trends in the resulting plot of versus time for a given initial

an operative regime in the microporous adsorbent, as will be value of surface diffusivity (Dso ). This is clearly observed in

demonstrated with the simulated breakthrough proﬁles obtained Fig. 2a. Except for the case of constant diffusivity, all expres-

under gas phase diffusion conditions (Section 4.2 Breakthrough sions of predict an increasing value of Dso with the local

proﬁles). amount of n-butane adsorbed (). This is correspondingly re-

It is also interesting to note that at differential conditions ﬂected in the trends observed in Fig. 2a, for which the slow-

there seems to be no inﬂuence of the external adsorption re- est rate to attain equilibrium belongs precisely to the case of

sistance (ka ) on the results, as deduced from the overlapping constant diffusivity. The fastest rate is obtained when the D–R

of curves A (ka = 20 m3 mol−1 s−1 ) and D (ka = ∞; Fig. 1), isotherm applies, as is the case for highly microporous adsor-

although a clear inﬂuence was observed under dynamic con- bents such as ACF monoliths. On the other hand, from a practi-

ditions on the breakthrough proﬁles (see Section 4.2 Break- cal point of view it is not clear whether the differences observed

through proﬁles). As will be proved at the end of this section, in Fig. 2a are an important modeling issue or not, since all

this is just a consequence of the high value of n-butane con- isotherms seem to produce converging results for speciﬁc values

4768 G. Marbán et al. / Chemical Engineering Science 61 (2006) 4762 – 4772

6 -12

Co= 1x10 Co= 1x106 Dso= 1.50x10 ka = 0.1

1.0 1.0 Dso= 1.50x10-12

ka ≥ 10

0.8 0.8

0.6 0.6

D.R.

θ

Co= 1x106 Co= 1x106

θ

-13

0.4

Freundlich ka ≥ 10 ka = 0.1

Square step Co= 500 Co= 500

Toth 0.2 Dso= 1.50x10-12 Dso= 1.50x10

-12

0.2 Dso=1.5×10-12 ka = 20

Yang ka = ∞ Square step

(ka=∞) D-R

Constant 0.0

0.0 0 1 2 3 4 5

0 1 2 3 4 5 time (s)

(a) time (s)

Fig. 3. Application of the model at differential conditions for different values

of C0 , Dso and ka .

1.0

Square step

0.8 ka . As observed, at high values of gas concentration (106 ppm),

(ka=∞)

the resistance to external surface adsorption exerts no effect

on the model results for values of ka over 10 m3 mol−1 s−1 ,

0.6

Dso=1.50×10-12 whereas for low values of gas concentration (500 ppm) clear

D.R.

differences are observed between the curves corresponding to

θ

Dso=2.00×10-12

0.4 Langmuir

-12 ka = 20 m3 mol−1 s−1 and ka = ∞ (dashed curves in Fig. 3).

Freundlich Dso=2.75×10

Dso=3.50×10-12

This fact has a clear mathematic explanation since parameter

Toth

0.2 Co=1×106 ppm C0 is multiplying ka in the equation that expresses the adsorp-

Yang Dso=9.50×10-12

Co=500 ppm

tion resistance (Eq. (33)). Due to the microporous character of

Constant Dso=1.60×10-12

0.0

ACFM adsorbents, they are thought to have excellent perfor-

0.0 0.5 1.0 1.5 2.0 2.5 3.0 mance in the removal of contaminants at low concentration.

(b) time (s) Therefore, according to the results shown in Fig. 3, any possible

external adsorption resistance will be detrimental at these spe-

Fig. 2. Application of the model at differential conditions for: (a) different ciﬁc conditions, whereas it can be unnoticed in environments

adsorption isotherms at a given value of Dso (C0 = 106 ppm); (b) different with a high concentration of the adsorptive.

adsorption isotherms at different values of Dso and C0 .

Since adsorption at the external surface and surface diffusion

inside the pores of the ﬁbers are serial processes, the external

of Dso . This is appreciated in Fig. 2b, in which values of Dso adsorption resistance has a less marked effect on the model

were found in such a way that all expressions of yielded an results for lower values of surface diffusivity, as can be clearly

almost identical curve (solid lines for C0 = 106 ppm). However, observed in Fig. 3. Finally, from the modeling point of view,

when using a much lower gas concentration (C0 =500 ppm), the it is not possible to ﬁnd a combination of [Dso , ka ] values that

same values of Dso produced very different curves, as indicated produces the same curve as that obtained under instantaneous

by dashed lines in Fig. 2b. Under dynamic conditions, before adsorption and, therefore, the existence of non-instantaneous

the breakthrough is attained, the gas phase inside the monolith adsorption is a clear modeling issue that can eventually be used

may present values from C = 0 to C0 . Therefore, it is obvious to improve the curve ﬁtting of the breakthrough proﬁle.

that the breakthrough proﬁles will be affected by the associated

differences in adsorption at varying values of gas concentration 4.2. Breakthrough proﬁles

(Fig. 2b) which permits to conclude that selection of the cor-

rect expression for the isotherm to be employed in the model is Fig. 4 shows the results of applying the model to ACFM

a key modeling issue. In this work the D–R isotherm was used (C0 = 500 ppm) under two different gas diffusion models. As

for ﬁtting the experimental breakthrough proﬁles. The values of expected (see previous section), the curve corresponding to

the parameters of the D–R equation (Table 1) were determined gas phase diffusion inside the micropore system (regimen R1)

gravimetrically in speciﬁc experiments of n-butane adsorption. cannot reproduce the experimental results. Changing the effec-

A second observation, already pointed when commenting tive diffusivity to lower values, apart from lacking of physical

curves A and D of Fig. 1, refers to the effect of external adsorp- signiﬁcance since Eq. (11) is not accomplished any more, nei-

tion resistance in the shape of the plot of versus time. Fig. 3 ther permitted to simulate the actual shape of the experimental

shows the simulated curves obtained by applying the model un- breakthrough proﬁle. The other simulated curve displayed

der differential conditions for different values of C0 , Dso and in Fig. 4 was obtained by considering surface diffusion

G. Marbán et al. / Chemical Engineering Science 61 (2006) 4762 – 4772 4769

1.0 Dso=1.5x10-12m2s-1 ka

1.0 ka= 20 m3mol-1s-1

ka=∞

3

ka= 20 m mol s -1 -1

0.8

0.8 ka= ∞

0.6

xξ=1

xξ=1

0.6 Co= 500 ppm

0.4 Deff=1.38x10-8m2s-1

ka=∞ Dso=1.5×10-12m2s-1

0.4

0.2 s

Co=500 ppm Experimental

0.0 0.2 Experimental

700 900 1100 1300 1500 Model

0.0

time (s)

700 900 1100 1300 1500

Fig. 4. Experimental and simulated breakthrough proﬁles obtained for different (a) time (s)

diffusion models (gas phase diffusion and surface diffusion).

1.2

1.0

Dso=7.0×10-13m2s-1 ka= ∞

1.0

Dso =1.0×10-12m2s-1 0.8

0.8 Dso=1.5×10-12m2s-1

xξ=1

0.6

xξ=1

Dso=1.5×10-12m2s-1

Co=500 ppm 0.4

0.4

s ka=∞

0.2 ka Experimental

0.2 Experimental

Model

Model

0.0

0.0

250 300 350 400 450 500

700 900 1100 1300 1500

(b) time (s)

(a) time (s)

Fig. 6. Experimental and simulated breakthrough proﬁles obtained at different

values of ka : (a) for C0 = 500 ppm; and (b) for C0 = 2000 ppm.

Dso=7.0×10-13m2s-1 Dso

1.0

Dso =1.0×10-12m2s-1

deal with the high-concentration gradient produced at the ex-

0.8 Dso=1.5×10-12m2s-1

ternal surface in such a way that the whole breakthrough curve

could be resolved in a reasonable time. Added to this, D–R

0.6

xξ=1

Co=2000 ppm of the particles and not at their external surface.

0.4

ka=∞ A value of initial surface diffusivity of 1.5 × 10−12 m2 /s

produced a simulated breakthrough proﬁle that matched the

0.2 Experimental

Dso ﬁrst zone of the experimental curve (up to x=1 ∼ 0.5) with

Model a signiﬁcant degree of agreement (Fig. 4). This value of sur-

0.0

250 300 350 400 450 500

face diffusivity is higher than those reported for n-butane

time (s)

adsorption in molecular sieves (zeolites and molecular sieve

(b)

carbons) which are around 1 × 10−14 m2 /s (Ruthven, 1984).

Fig. 5. Experimental and simulated breakthrough proﬁles obtained at different Nevertheless, the average pore size of the ACFM is also

values of Dso : (a) for C0 = 500 ppm; and (b) for C0 = 2000 ppm. somewhat higher (∼ 1 nm) than that existing in typical molec-

ular sieves (∼ 0.5 nm) so that a higher surface diffusion rate is

expected for the former.

(D–R)-controlled regime, with Henry regime at the external However, there is a patent discrepancy between the simulated

surface (Eq. (29)), and instantaneous adsorption at the exter- breakthrough proﬁle and the experimental curve for values of

nal surface (ka = ∞, regime R2.1). When instantaneous D–R x=1 over ∼ 0.5 (Fig. 4). Apart from Dso and ka , the rest of the

adsorption was considered at the external surface (Eq. (9)) the model parameters are determined by the adsorption conditions,

constant step resolution used in the VB program avoided to the adsorbent characteristics and few standard correlations

4770 G. Marbán et al. / Chemical Engineering Science 61 (2006) 4762 – 4772

Experimental 5. Conclusions

Model

1.0

In this work a model to predict the breakthrough proﬁle

0.8 of the adsorption n-butane by microporous ﬁbrous adsorbents

Co = 2000 ppm

Co = 1500 ppm

Co = 1000 ppm

(ACFM) is proposed. The model includes non-instantaneous

Co = 500 ppm

0.6

xξ=1

0.4 the pores of the ﬁbers. It has been proved that the external

surface resistance to adsorption for the lower concentrations

0.2

cannot be neglected. The selection of the appropriate expres-

(a) 0.0 sion for the isotherm to be employed in the model is a key

Dso =1.5×10-12m2s-1

issue to obtain a suitable ﬁt between the experimental data and

ka= 20 m3mol-1s-1 the model, especially for the low-concentration experiments.

1.2E-02

The model solved for non-instantaneous surface adsorption and

dXξ=1/dt(s-1)

Model

8.0E-03 simulates the breakthrough proﬁles for adsorption of n-butane

in diluted streams, since a good agreement between the experi-

mental and the simulated data is obtained for the whole proﬁles

4.0E-03

at different values of n-butane concentration in the inlet gases.

0.0E+00

0 500 1000 1500 Notation

(b) time (s)

D v

Fig. 7. Experimental and best ﬁtting simulated breakthrough proﬁles obtained

B0 Re Sc = DeqvM s , Bodenstein number according to

at different values of C0 : (a) Breakthrough proﬁles; and (b) breakthrough Levenspiel (Levenspiel, 1996)

rates. C adsorptive concentration in the gaseous bulk at

an axial position z in the monolith (0 < z < H ),

(i.e., Sherwood and Peclet numbers). Therefore, it was decided mol mgas−3

to make a survey on Dso and ka in an attempt to produce a C0 adsorptive concentration in the gaseous bulk at

better ﬁtting of the upper zone of the breakthrough proﬁle with −3

z < 0, mol mgas

the following conditions: (1) not to provoke a worsening of the Cp adsorptive concentration in the intraparti-

ﬁtting in the lower zone of the breakthrough proﬁle and (2) to cle gaseous phase at an absolute position

permit simultaneously a reasonable ﬁtting of the breakthrough −3

(r, z)(0 < r < Deqv /2; 0 < z < H ), mol mgas

proﬁles obtained at higher n-butane concentrations in the inlet Cs saturation adsorptive concentration at

gas (1000, 1500 and 2000 ppm). −3

Tads , mol mgas

Fig. 5a shows that a decrease in the value of initial surface D monolith diameter, m

diffusivity allows the curve ﬁtting to be improved in the upper Dax axial diffusivity, m2 s−1

zone of the breakthrough proﬁle corresponding to the experi- Deff effective diffusivity in the pore system, m2 s−1

ment performed at C0 = 500 ppm, without provoking a signiﬁ- Deqv equivalent diameter of the ﬁbers = 1.5 × DF , m

cant worsening of the ﬁtting for x=1 < 0.5. However, the same DF ﬁber diameter, m

procedure applied to the proﬁle obtained at C0 = 2000 ppm DK Knudsen diffusivity, m2 s−1

produced a signiﬁcant deterioration of the curve ﬁtting in both DM molecular diffusivity, m2 s−1

zones of the proﬁle (x=1 < 0.5 and x=1 > 0.5), as clearly ob- Dso surface diffusivity in the pore system at = 0,

served in Fig. 5b. m2 s−1

Introducing in the model some resistance to n-butane adsorp- E0 characteristic energy of the adsorbent, J mol−1

tion on the external surface of the ﬁbers, or, in other words, H monolith height, m

decreasing the value of ka coefﬁcient, also permitted to im- 3 m −3

K Henry constant, mgas part

prove the curve ﬁtting in the upper zone of the breakthrough

ka external surface adsorption coefﬁcient,

proﬁle obtained at C0 = 500 ppm (Fig. 6a), but in this case the 3 mol−1 s−1

mgas

proﬁles obtained at higher values of C0 were also reasonably 3 m −2 s−1

well simulated (Fig. 6b). It was found in this way that values kext external mass transfer coefﬁcient, mgas part

for Dso and ka of 1.5 × 10−12 m2 s−1 and 20 m3 mol−1 s−1 , MW adsorptive molecular weight, g mol−1

Deqv vs

respectively, produced a satisfactory ﬁtting of the proﬁles ob- Pep Dax b , Bodenstein or particle Peclet number

tained at the different values of n-butane gas concentration, as according to CRC Handbook (CRC, 1984). Axial

shown in Fig. 7. It is worth noting that the time derivative of dispersion number according to Levenspiel

x=1 is also well reproduced by the model for the different val- (Levenspiel, 1996)

ues of C0 (Fig. 7b), which expresses the authentic goodness of q instantaneous amount of adsorbate, per adsorbent

−3

the curve ﬁtting. volume, at an absolute position (r, z), mol mpart

G. Marbán et al. / Chemical Engineering Science 61 (2006) 4762 – 4772 4771

(Deqv /2 ),dimensionless radial position in the ﬁbers

−3

sorbent volume, mol mpart (0 < < 1)

g gas phase density, g mgas −3

qe (C0 ) amount of adsorbate in equilibrium at C0 , per ad-

−3 4t0 Dso

sorbent volume, mol mgas D2

, surface diffusion group

eqv

qe (Cs ) amount of adsorbate in equilibrium at Cs , per ad- t

−3

sorbent volume, mol mpart t0 , dimensionless time

r radial position in the particle, m

R universal gas constant, 8.31441 J K −1 mol−1 Acknowledgments

g vs Deqv

Re , Reynolds number

TVS acknowledges the CSIC-ESF for the award of an I3P

Sc g DM , Schmidt number postdoc contract.

Deqv kext

Sh DM , Sherwood number

H 2 b

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