Carbon 41 (2003) 87–96

Adsorption of volatile organic compounds by means of

activated carbon fibre-based monoliths
A.B. Fuertes a , *, G. Marban
´ a , D.M. Nevskaia b
a
´ ( CSIC), Apartado 73, 33080 Oviedo, Spain
Instituto Nacional del Carbon
b
´
Departamento de Quımica ´
Inorganica ´
y Tecnica , Facultad de Ciencias ( UNED) c / Senda del Rey, 9, 28040 Madrid, Spain
Received 8 May 2002; accepted 18 July 2002

Abstract

Activated carbon fibre monoliths (ACFMs) were prepared from the rejects of polymeric fibres (Nomex姠). These were
carbonised, agglomerated with a phenolic resin and steam activated at burnoff degrees between 0 and 40%. Adsorption
experiments with n-butane at 30 8C show that, at high adsorbate concentrations, the amount adsorbed is a function of pore
volume, but at low concentrations this mainly depends on pore size distribution. The porosity of Nomex-based ACFMs is
formed by narrow micropores, which permit higher amounts of vapour to be adsorbed in low concentrations compared to
monoliths prepared from different commercial activated fibres and a commercial granular activated carbon, which exhibits
wider pores. The agglomeration of Nomex-fibres to form ACFMs does not cause any loss in adsorption properties with
respect to non-agglomerated activated fibres. From the adsorption experiments of different vapours on a Nomex-based
ACFM (40% burnoff) it was found that at high concentrations ( p /po 51) the adsorbed volume was independent of the nature
of the adsorbate and depended only on pore volume. However, at low vapor concentrations ( p /po 50.004), the amount
adsorbed depended on the adsorbate being well correlated to the molecular parachor and the polarizability of the adsorbates
 2003 Elsevier Science Ltd. All rights reserved.

Keywords: A. Activated carbon; Carbon fibers; B. Activation; C. Adsorption; D. Microporosity

1. Introduction Recommended strategies for reducing organic vapours

Volatile organic compounds (VOCs) are highly evapora-
tive chemicals (low-boiling liquids) that off-gas into the
atmosphere from many different sources and contribute
negatively to human health. They are often found in low
concentrations at the gas exit in working environments
where paints, varnishes, chemical cleaners, solvents, etc.,
are handled. VOCs consist of aromatic compounds such as
toluene or benzene as well as many aliphatic compounds
such as n-hexane or 2-methylbutane. Organic compounds
with functional groups, such as acetone, ethanol or pro-
pylene glycol methyl ether, and chlorinated hydrocarbons,
such as trichloroethylene or methylchloroform are also
listed as VOCs [1]. As an example of their importance, the
production levels of chlorinated compounds amount to
80 000–100 000 tons a year in Japan alone [2].
*Corresponding author. Tel.: 134-985-28-0800; fax: 134-
985-29-7662.
E-mail address: abefu@incar.csic.es (A.B. Fuertes).
include product substitution or reformulation, thermal or
catalytic incineration and activated carbon adsorption
(followed by regeneration of the adsorbent and VOC
recovery or catalytic incineration of the highly concen-
trated stream). Adsorption units based on activated carbon
can reduce up to 99% of VOC present in gas streams at
concentrations below 5000 ppm [3]. Typically activated
carbons are obtained in a finely powdered form, and are
granulated later to make them suitable for handling in
special devices. However, in spite of the widespread
utilisation of granular packed beds, there are some draw-
backs: the high-pressure drop associated with the flow
through the packed media, attrition of the granular material
and particle entrainment, channelling, gas bypassing, etc.
There is an additional drawback in the case of the
utilisation of active carbon granules for the adsorption of
VOCs in diluted streams. This is the relatively wide pore
distribution achieved during the activation stage, which
ranges from micro- (,2 nm) to mesopore (2–50 nm) size.
During the adsorption of low concentrations of VOCs,

0008-6223 / 03 / $ – see front matter  2003 Elsevier Science Ltd. All rights reserved.
PII: S0008-6223( 02 )00274-9
88 A.B. Fuertes et al. / Carbon 41 (2003) 87–96
micropores, rather than larger macro- and mesopores, are
preferentially filled at low relative pressures due to the
overlapping of the attractive forces of opposite pore walls.
In a similar manner, micropores are primarily responsible
for adsorption at low VOC concentrations in ambient air
environments. This is fully described in the literature [4,5].
An alternate adsorbent material that overcomes the above-
mentioned drawbacks is based on activated carbon fibres
(ACFs). These are obtained from the carbonisation and
activation of polymeric fibres with diameters in the range
of 10–20 mm. This small diameter allows a homogeneous
activation of the fibres, thus yielding a material with a
narrow pore size distribution in the micropore range. For
instance, Jaroniec et al. [6] analysed in detail the nitrogen
adsorption isotherms of cellulose-based and PAN-based
ACFs and found that both materials have 85 vol% micro-
pores of uniform size and only 15 vol% of fine mesopores.
In addition, thin fibres with diameters below 20 mm clearly
ensure fast intraparticle adsorption kinetics compared to
pelletised or granular activated carbon. This results in
higher effective amounts of adsorption, which decreases
the size of the adsorption units considerably. The fibrous
form is also favoured because it is easy to handle when it
is used in felt or fabric forms [7]. In this way, particle
entrainment is avoided and a low-pressure drop through
the adsorption unit is assured. Rigid monoliths formed by
activated carbon fibres are now in the stage of develop-
ment. Thus, Wilson et al. [8] and Marban ´ et al. [9] have
developed methods for manufacturing an activated carbon
fibre monolith (ACFM), which can be easily fitted to any
adsorption device. Another advantage of the use of
ACFMs, is the possibility of in situ electrical regeneration.
This possibility permits the design of more simple devices
to be placed in the polluted environment. An example of
this has been provided by Dalla Betta et al. [10]. In their
device, two adsorbent bodies are used in a cyclical way.
When one of the bodies is adsorbing VOCs from the
polluted air stream, the other one is being regenerated and
the desorbed VOC is being swept by a regeneration gas.
The use of rigid monoliths formed by activated carbon
fibres has mainly been investigated in relation with gas
separation [11,12], methane storage [13] and as catalyst
supports [14,15]. Recently, Burchell et al. [16,17] dis-
closed a preparation method of activated carbon fiber
composites for gas separation (PSA), purification and
catalytic processing. Only a few works can be found in the
literature in relation with the use of ACFMs in VOC
removal. In one of these, Andrews et al. [18] prepared
carbon fibre composites prepared from petroleum pitch-
based fibres and analysed the adsorption of butane on
carbon fibre composite beds.
One of the main drawbacks of the utilisation of activated
carbon fibres for adsorption purposes is its high price
compared to that of activated carbon. However, their use
as precursors of coal pitch-based fibres or inexpensive
rejects of commercial polymeric fibres for the production
of activated carbon fibres would decrease their price
considerably.
In this paper the adsorption of VOCs on ACFMs
prepared from inexpensive rejects of commercial poly-
meric fibres (Nomex) is analyzed. The effect of the
activation degree on the adsorption characteristics of
ACFMs is evaluated. In addition, a comparison between
Nomex-based ACFMs and those prepared from different
commercial activated carbon fibres is made.
2. Experimental
2.1. Preparation of activated carbon based-based
monoliths
The preparation of activated monoliths has been re-
ported elsewhere [9]. Briefly, rejects of Nomex姠 fibres
(DuPont) were carbonised in N 2 at 850 8C (heating rate,
5 8C min 21 ; soaking time, 1 h). Afterwards, they were
milled by conventional blade-mills and the fraction of size
0.1–0.4 mm was dry-mixed with powdered phenolic resin
(Novolak) in a mass ratio of 3 / 1. The mixture was
moulded, cured (in air at 180 8C) and carbonised (in N 2 at
700 8C). The carbonised composites with a bulk density of
around 0.25 g cm 23 were activated at 700 8C with a stream
of water (steam, |25 vol.%) in N 2 . The activation rate
expressed as the weight loss fraction per time unit was on
average 0.02 h 21 . The bulk density of the activated
composites was in the 0.25–0.16 g cm 23 range, depending
on burnoff. ACFMs with activation degrees between 0 and
40% were prepared.
The ACFMs from commercial activated carbon fibres
were prepared as indicated above, except that in this case
an activation stage was not necessary.
2.2. Characteristics of the materials
The textural characteristics of the fibres and monoliths
were obtained by physical adsorption of N 2 (2196 8C) and
CO 2 (20 8C). Nitrogen adsorption was carried out in a
volumetric system (ASAP 2010). The samples were de-
gasified under vacuum (,10 26 atm) at 200 8C for 12 h.
The specific surface area was calculated by applying the
BET method in the 0.1–0.3 relative pressure range and the
pore volume was estimated at a relative pressure of 0.95.
The CO 2 isotherm was obtained in a gravimetric system
(CI Electronics) and analysed by the Dubinin–Radusck-
evitch (DR) method to obtain the micropore volume. Table
1 shows the main textural characteristics (BET surface
area, n-butane uptakes and pore volumes obtained from
adsorption with nitrogen, CO 2 and n-butane) of the
selected materials: activated Nomex-based carbon fibres
(N-40, activated up to 40%), commercial activated carbon
fibres (from coal pitch, PAN and phenolic resin) and a
pelletised activated carbon used as reference (Norit, RB3).
 A.B. Fuertes et al. / Carbon 41 (2003) 87–96 89

Table 1
Adsorption characteristics of non-agglomerated samples
Sample N 2 (2196 8C) CO 2 (20 8C) n-Butane (30 8C)e
2 3 Wo (cm 3 / g)
Precursor ACF SBET (m / g) Vp (cm / g) Vp (cm 3 / g) n-Butane uptake
in g / 100 g
Nomex N-40 1100 0.36 (0)d 0.44 0.44 25.3
Coal Pitch A-10 a 1130 0.40 (4)d 0.43 0.49 28.6
A-15 a 1520 0.58 (17)d 0.36 0.67 38.5
A-20 a 2570 1.11 (41)d 0.39 0.92 53.1
Phenolic Resin PRb 1920 0.69 (6)d 0.58 0.81 46.8
PAN PN c 1088 0.44 (20)d 0.32 0.49 28.5
Pelletised active carbon, Norit
(RB3) 1220 0.50 (18)d 0.38 0.47 26.8
a
ACF supplied by Osaka Gas.
b
ACF supplied by Kuraray Chemical (FT-300).
c
ACF supplied by Toho Rayon (FE-400).
d
In brackets the percent of pore volume, which corresponds to mesopores (2–50 nm) is given.
e
At p /po 50.35.

From the results shown in Table 1 it can be observed that
there are samples that are essentially microporous (i.e.,
N-40, A-10 and PR), whereas other samples contain an
appreciable fraction of mesoporosity (i.e., A-15, A-20,
PAN, RB3).
2.3. Adsorption measurements
the degree of dilution and the temperature of the bath, the
VOC concentration in the system was fixed at the selected
value. By using this method it was possible to measure the
adsorption of VOCs in a relative pressure range of 10 24 –
1. The saturation pressure of each temperature for the
different VOCs was estimated from the Antoine equation
[19].

The VOC adsorption experiments were carried out in a

gravimetric system (CI Electronics). The adsorption tem-
perature was fixed at 30 8C and was controlled by means of
a thermostatic water bath (Haake P5). Before each experi-
ment, the sample was degasified at 450 8C (2 h) by purging
with helium. Except for n-butane, to achieve the desired
VOC concentration in the adsorption system, helium was
fluxed through a flask containing the pure liquid adsorbate.
The flask was immersed in a thermostatic bath (Haake
K15), which allowed the temperature to be controlled to a
high degree of accuracy in a temperature range between
230 8C and 150 8C. By controlling the helium flow rate,
3. Results and discussion
3.1. Dependence of adsorption on the activation degree
of ACFMs
Table 2 contains the textural characteristics of ACFMs
prepared at different activation degrees together with those
of pellets of a commercial activated carbon (Norit RB3),
which is especially appropriate for the removal of small
concentrations of contaminants from gas streams [20].
Because of this feature, Norit RB3 was selected as a

Table 2
Adsorption characteristics of Nomex-based ACFM with different activation degrees
Activation degree N 2 (2196 8C) CO 2 (20 8C) n-Hexane (30 8C)b n-Butane (30 8C)b
(%) / Code Wo (cm 3 / g) Vp (cm 3 / g)
SBET (m 2 / g) Vp a (cm 3 / g) Vp (cm 3 / g) n-Butane uptake in
g / 100 g and (g / 100 cc)
0 / N-0 148 0.05 (0) 0.28 – 0.04 2.45 (0.6)
6 / N-6 – – 0.37 – 0.21 12.1 (2.9)
12 / N-12 810 0.27 (0) 0.39 0.26 0.27 15.3 (3.4)
21 / N-21 973 0.31 (0) 0.40 0.32 0.32 18.6 (3.9)
30 / N-30 1222 0.41 (1) 0.45 0.39 0.38 22.1 (4.2)
40 / N-40 1306 0.47 (5) 0.46 0.45 0.46 26.4 (4.8)
RB-3 1220 0.50 (18) 0.38 0.49 0.47 26.8 (12.6)
(Pelletised AC)
a
In brackets the percent of pore volume, which corresponds to mesopores (2–50 nm) is given.
b
At p /po 50.35.
90 A.B. Fuertes et al. / Carbon 41 (2003) 87–96
reference for comparing the results obtained with ACFMs.
The nitrogen adsorption isotherms of ACFMs activated at
different burnoffs are type I, which is typical of micropor-
ous materials. The specific surface area measured by N 2
adsorption shows a large increase with activation, from
148 m 2 g 21 for the non-activated sample to 1306 m 2 g 21
for the material activated at a burnoff of 40 wt%. By
comparing pore volumes estimated with different adsor-
bents, it was observed for activation degrees lower than
30% that the micropore volumes (Wo ) calculated from the
CO 2 isotherm (D–R method) are significantly higher than
those estimated from nitrogen or n-butane. This means that
for low burnoff degrees a fraction of the microporosity is
formed by very narrow pores (ultramicropores), which are
not accessible to nitrogen and n-butane. For high burnoffs
(i.e., 40%) the values of pore volumes estimated from
CO 2 , N 2 , n-hexane and n-butane are similar. This is an
indication of uniform microporosity development during
activation, without the formation of either ultramicropores,
in which case Vp (CO 2 ).[Vp (N 2 ) or Vp (nC4)] or super-
micropores, in which Vp (CO 2 ),[Vp (N 2 ) or Vp (nC4)] [21].
These results suggest that the gasification of ACFMs
occurs uniformly throughout the samples.
The n-butane uptakes measured at 30 8C ( p /po 50.35)
are indicated in Table 2 on a mass and volumetric basis.
As expected, the n-butane uptake shows a large increase
with the activation degree. The values of pore volumes
estimated from nitrogen, n-hexane and n-butane are very
close, which proves that the pore network is accessible to
all these adsorbates to the same extent (Gurvich rule).
From these considerations, it can be concluded that the
amount adsorbed at high adsorbate concentrations depends
on the pore volume of the sample.
From a comparison of the adsorption characteristics of
pelletised AC Norit RB3 (shown in Table 2) with the
ACFMs, it can be seen that the RB3 sample is very similar
to ACFM activated at 40% in terms of BET surface area,
pore volume and n-butane uptake (mass basis). Further-
more, the n-butane uptakes of N-40 and RB3 are very
similar on a mass basis, but on a volumetric basis RB3
exhibits an uptake which is more than 2.5 times higher
than N-40. This is clearly a limitation of the ACFM with
respect to the granular bed formed by AC particles. This is
a consequence of the differences in bulk densities between
the two materials (N-40, 0.21 g cm 23 ; RB3, 0.47 g cm 23 ).
Although ACFMs with bulk densities greater than 0.21 g
cm 23 can be easily fabricated, this would result in a loss of
permeability and possibly an unacceptable high pressure
drop through the monolith. This matter will be discussed
more deeply in Section 3.5.
Fig. 1 displays the n-butane adsorption isotherms mea-
sured at 30 8C for the monoliths activated at different
burnoffs, from 0 to 40%. It can be observed that for
n-butane concentrations higher than 2000 ppm the ad-
sorbed amount is a function of the activation degree.
However, at low concentrations (,2000 ppm) the amount
Fig. 1. Adsorption isotherms of n-butane at 30 8C on ACFM
activated at different degrees (h, 0%; 앳, 6%; n, 12%; 3, 21%;
1, 30%; s, 40%) and on a pelletised activated carbon used as
reference (d, RB3).
of n-butane adsorbed does not follow the order of activa-
tion degree, as the isotherms show crossover points. Thus,
for this concentration range (,2000 ppm), ACFMs acti-
vated at low burnoffs (i.e., 10–20%) exhibit higher
adsorption capacities than those prepared at high burnoff
(i.e., 40%). This is better illustrated in Fig. 1 (inset) where
it can be seen that for C5500 ppm the sample activated at
20% exhibits the highest n-butane adsorption capacity. A
similar behaviour has been previously reported by other
authors [4,22] from the analysis of commercial phenolic
resin-based activated carbon fibres with different surface
areas, between 900 and 2000 m 2 g 21 . To understand this
behaviour the relationship between the micropore size and
the amount adsorbed at low concentrations must be taken
into account. Thus, as hypothesised by Magnun et al. [22],
for narrow micropores the overlapping of adsorption
potentials between pore walls results in a greater potential
for adsorption than that corresponding to wider micro-
pores. Taking into account the relationship between the
potential of adsorption and the amount adsorbed at a low
relative pressure, materials containing narrower micropores
will adsorb more than other materials with wider micro-
pores, independently of the value of the total micropore
volume. A more detailed analysis of the dependence of the
amount adsorbed at low concentration on micropore size
distribution is given elsewhere (Centeno TA, Marban ´ G,
Fuertes AB. Unpublished work, 2002).
The adsorption potential depends not only on the
characteristics of the adsorbent but also on those of the
adsorbate. In this case, the crossover regime changes with
the type of adsorbate. Thus, Magnun et al. [22] observed
that the crossover regime shifted to lower concentrations as
the boiling point of the adsorbate increased. Fig. 2 shows
 A.B. Fuertes et al. / Carbon 41 (2003) 87–96 91

the porosity in ACFMs is more uniform and corresponds

mainly to narrow micropores.
These results show that ACFMs are highly appropriate
for adsorbing contaminants at very low concentrations. In
addition, in order to optimise the adsorption process, the
adsorption capacity of ACFMs in different polluted en-
vironments can be tailored by varying their burnoff degree,
since it has been proved that burnoff for maximum
adsorption is a function of both the type of contaminant
and its concentration in the gas stream.

3.2. Comparison of ACFMs prepared from different

activated carbon fibres

Table 3 contains the textural characteristics of ACFMs

Fig. 2. Adsorption isotherms of n-hexane at 30 8C on ACFM
activated at different degrees (n, 12%; 3, 21%; 1, 30%; s,
40%) and on a pelletised activated carbon used as reference (d,
RB3).
the adsorption isotherms of n-hexane for ACFMs activated
at different burnoff degrees. In this case the crossover is
not observed for the ACFMs, even in concentrations as
low as 100 ppm. It can be hypothesised therefore that
crossover points must exit at lower concentrations.
A comparison of ACFMs with the RB3 sample (Figs. 1
and 2) shows that, whereas at high concentrations, RB3
exhibits comparable (Fig. 1) or even higher (Fig. 2)
adsorption uptakes than N-40, at low concentrations, the
amount adsorbed by RB3 is lower in the case of n-butane
and n-hexane than that adsorbed by ACFMs activated at
burnoffs .10%. This behaviour is a consequence of the
nature of the porosity of RB3, which is formed by wide
micropores and mesopores (around 18% of its pore volume
is in the mesopore range as indicated in Table 2), whereas
prepared with activated commercial carbon fibres derived
from different precursors. The A-10 and PR monoliths are
essentially microporous (only around 5% of their pore
volumes correspond to mesopores) and in this respect they
are very similar to N-40, which is also microporous with
around 5% of its pore volume falling within the mesopore
range (see Table 3). By contrast, the A-15, A-20 and PN
monoliths, and RB3 contain a high fraction of mesoporosi-
ty, as shown in Table 3.
As with the Nomex-based ACFMs (Section 3.1, Table
2), the results shown in Table 3 for ACFMs prepared from
different precursors reflect good agreement between the
pore volumes obtained from N 2 , n-hexane and n-butane.
This confirms the view that at high adsorbate concen-
trations, the amounts adsorbed depend on pore volume.
Unlike the N-40 sample, the ACFMs from commercial
ACFs show values of Wo micropore volume determined by
CO 2 that are smaller than the pore volumes (Vp ) estimated
from N 2 , n-hexane and n-butane. This implies that these
monoliths contain a considerable fraction of supermicro-
pores and mesopores that have not been detected by the
CO 2 molecule. Moreover, at low adsorbate concentrations,
the adsorbed amount is a function of pore size, as

Table 3
Adsorption characteristics of ACFM from different precursors
Sample N 2 (2196 8C) CO 2 (20 8C) n-Hexane (30 8C)e n-Butane (30 8C)e
2 d 3 Wo (cm 3 / g) Vp (cm 3 / g)
Precursor ACF SBET (m / g) Vp (cm / g) V ep (cm 3 / g) n-Butane uptake
in g / 100 g
Nomex N-40 1306 0.47 (5) 0.46 0.45 0.44 25.3
Coal pitch A-10 a 1028 0.36 (5) 0.24 0.39 0.40 23.1
A-15 a 1341 0.52 (17) 0.32 0.53 0.54 31.2
A-20 a 1703 0.75 (40) 0.34 0.78 0.77 44.3
Phenolic resin PRb 1511 0.54 (4) 0.45 – 0.61 35.2
PAN PN c 900 0.36 (19) 0.26 – 0.37 21.5
a
ACF supplied by Osaka Gas.
b
ACF supplied by Kuraray Chemical (FT-300).
c
ACF supplied by Toho Rayon (FE-400).
d
In brackets the percent of pore volume, which corresponds to mesopores (2–50 nm) is given.
e
At p /po 50.35.
92 A.B. Fuertes et al. / Carbon 41 (2003) 87–96
Fig. 3. Adsorption isotherms of n-butane at 30 8C on ACFM
prepared from various precursors. Nomex-based ACFM (40%
burn off) (d), PAN-based ACFM (PN) (3), phenolic resin-based
ACFM (PR) (1) and pitch-based ACFM (s, A-10; h, A-15; n,
A-20).
discussed in Section 3.1. This is illustrated in Figs. 3 and 4
by the isotherms of n-butane (Fig. 3) and n-hexane (Fig.
4) measured at 30 8C. Thus, at low adsorbate concen-
trations (500 ppm for n-butane and 100 ppm for n-hexane),
the highly microporous ACFMs (N-40, PR and A-10)
show higher uptakes than the monoliths with a high
fraction of mesoporosity (A-15, A-20 and PN). This is
illustrated by the insets in Figs. 3 and 4. As an example,
Fig. 4. Adsorption isotherms of n-hexane at 30 8C on ACFM
prepared from various precursors. Nomex-based ACFM (40%
burn off) (d), pitch-based ACFM (s, A-10; h, A-15; n, A-20)
and on a pelletised activated carbon used as reference (앳, RB3).
sample A-20 with a high pore volume (0.75 cm 3 g 21 ) and
a high fraction of mesoporosity (40% of total pore
volume), exhibits the highest adsorbate uptakes at a
concentration of 10 6 ppm and the lowest at 500 ppm.
Furthermore, the higher n-butane capacity measured at 500
ppm for N-40 (Vp 50.47 cm 3 g 21 , 5% mesoporosity)
compared to PR (Vp 50.54 cm 3 g 21 , 4% mesoporosity),
which appears to have similar characteristics, suggests that
the micropores of N-40 are narrower than those of PR. In
fact, Wo ¯Vp for the N-40 sample, whereas in the case of
PR, Wo ,Vp , which suggests that the PR sample contains a
high fraction of supermicropores.
3.3. Effect of the agglomeration of carbon fibres on
adsorption properties
By comparing the textural characteristics indicated in
Table 3 for ACFMs derived from commercial ACFs with
those indicated in Table 1 for non-agglomerated ACFs, it
can be concluded that monolith formation causes a signifi-
cant loss in BET surface area and pore volumes (measured
by N 2 , CO 2 and n-butane). This may be a consequence of
the plugging of a fraction of the ACF porosity by the
carbonised binder. As a result, the n-butane uptake of
ACFMs obtained by the agglomeration of ACFs falls by
around 20% with respect to non-agglomerated ACFs
(Table 1). By contrast, the textural characteristics of
ACFMs prepared from carbonised Nomex fibres are
similar to those of the non-agglomerated activated fibres
and there is no loss of surface area or pore volume due to
monolith formation. In this case, the monolith was formed
by mixing the binder with carbonised fibres, instead of
activated carbon fibres, as occurred with the commercial
samples. After the subsequent carbonisation stage, the
binder (phenolic resin) is transformed into carbon, which is
activated at the same time as the carbonised fibres. The
pore volume and surface area developed in the carbonised
binder during the activation stage seems to compensate for
the losses that occurred due to plugging in the carbon
fibres. This behaviour is illustrated in Fig. 5 with the
n-butane isotherms measured at 30 8C for non-agglomer-
ated ACFs (N-40 and A-20) and the corresponding
ACFMs. Whereas for the N-40 sample the adsorption
isotherms for non-agglomerated fibres and ACFM are
superimposed, the isotherm of the non-agglomerated A-20
is higher than that of the derived ACFM, the divergence
widening as the concentration increases.
3.4. Effect of the nature of the adsorbate on adsorption
The adsorption process is influenced by the characteris-
tics of both the adsorbent and the adsorbate. In relation
with this, an important question to be answered is why the
adsorbed volumes at low concentration are adsorbate-
dependent. In order to assess the effect of the nature of the
adsorbate on the adsorption process, the adsorption of
 A.B. Fuertes et al. / Carbon 41 (2003) 87–96 93

amount adsorbed (in cm 3 g 21 ) at high vapor concen-

trations is independent of the nature of the adsorbate and is
only a function of the pore volume of the adsorbent.
In contrast with previously reported results, at low
relative pressures the adsorbed volume shows a strong
dependence on the nature of the adsorbate. This is clear
from Table 4 where the adsorbed volumes at a relative
pressure of 4310 23 (V ) are shown. It can be seen that
non-polar adsorbents (i.e., n-butane, n-hexane) or vapors
with low dipole moments (i.e., toluene, trichloroethylene)
exhibit very similar specific sorption volumes, in the range
0.29–0.32 cm 3 / g. For these substances, the micropore
filling ratio (V /Vs ) is in the range 0.6–0.8. By contrast,
polar adsorbents (i.e., ethanol, MEK) show low (V /Vs )
ratios, in the 0.2–0.4 range.
At low relative pressures the D–R equation describes
the adsorption process well. This can be written as

FS DG
Fig. 5. Comparative results of n-butane adsorption (30 8C) on
agglomerated and non-agglomerated ACFs derived from Nomex
(40% burn off) (d, non-agglomerated; s, agglomerated) and V 5 Wo exp
RT ln ]
2 ]]]
po
pS D 2

(1)
A-20 (pitch-based ACF) (m, non-agglomerated; n, agglomer-
b Eo
ated).
where V is the volume of adsorbed per weight unit of
sample at a relative pressure p /po and Wo is the micropore
volume, which for a microporous material such as N-40 is
different vapours with varying physicochemical properties nearly Vs . The parameters b and Eo are specific to the
was performed on ACFM N-40 at 30 8C. The sorption system ( b is a characteristic of the adsorbate and Eo is
uptakes at p /po 51, expressed as specific sorption volumes related to the adsorbent).
(volume adsorbed at p /po 51, Vs ), are very similar for all According to Eq. (1), the only variable that is adsorbate-
the adsorbates (Table 4), and are also close to the pore dependent is the affinity coefficient ( b ). From Eq. (1), for
volumes measured for N 2 and n-butane, in accordance a given adsorbent and at a given relative pressure, b is
with the Gurtvich rule. This suggests similar accessibility related to the (V /Wo ) ratio as b ~2[ln(V /Wo )] 20.5 . Thus b
for all tested adsorbates to the micropore network of the can be obtained experimentally by referring to the standard
adsorbent. The general conclusion may be drawn that the value of benzene ( b 51) [23]. Moreover, b has a physical
meaning and can also be estimated theoretically from the
Table 4 adsorbate properties that have an influence on the ad-
Adsorption volumes measured at relative pressures p /po 51 (Vs ) sorption process. These are molar polarizability, molar
and p /po 54310 23 (V ). (Sample: N-40, Temperature: 30 8C) volume and Sudgen’s parachors [24]. The molecular
parachor (V ) can be calculated from the molar volume
Adsorbate Vs V V /Vs
(cm 3 / g) (cm 3 / g)
(Vm ) and the surface tension (g ) of the liquid as V 5Vm
g 1 / 4 . Fig. 6 offers a comparison between the affinity
n-Butane 0.46 0.31 0.68 coefficients determined experimentally from the V /Vs val-
n-Hexane 0.44 0.30 0.68 ues (Table 4) and those obtained from the adsorbate
Benzene 0.43 0.29 0.68
properties (polarizability, molar volume and molecular
Toluene 0.42 0.33 0.78
Cyclohexane 0.40 0.29 0.73 parachor). The adsorbate properties were taken from Wood
Water 0.38 ,0.01 ,0.03 [24]. The best correlation is obtained with the affinity
Methanol 0.41 0.03 0.07 coefficients estimated from the (adsorbate / benzene) ratio
Ethanol 0.42 0.11 0.26 of molecular parachors and molar polarizabilities. This
2-Propanol 0.42 0.20 0.48 shows that these properties can be used to predict ad-
1-Propanol 0.42 0.25 0.60 sorption at low concentrations.
2-Butanol 0.42 0.27 0.64
Methyl-ethyl-ketone 0.41 0.17 0.42
Acetone 0.41 0.21 0.51 3.5. Permeability and electrical conductivity of ACFM
Chloroform 0.42 0.25 0.595
Trichloroethylene 0.43 0.29 0.67 The pressure drop through the ACFMs is a key concern
112-Trichloroethane 0.42 0.28 0.67
in relation with their use in practical conditions. This can
94 A.B. Fuertes et al. / Carbon 41 (2003) 87–96

permeability values given in Table 5 for different ACFMs

Fig. 6. Correlation between the affinity coefficients deduced from
(V /Vs ) values and the D–R equation, and those estimated from: (a)
ratio of molar polarizabilities substance / benzene (s); (b) ratio of
molar volumes substance / benzene (d); and (c) Ratio of parachors
substance / benzene (3).
show that the intraparticle voids increase with the bulk
porosity of ACFM. This evidences that the permeability of
the monoliths can be controlled by changing their bulk
density (compression ratio). Additionally, the pressure drop
through the ACFMs can also be controlled by modifying
the monolith’s dimensions (A, H ) in accordance with Eq.
(2). In order to optimise the design of ACFMs, a com-
promise between bulk density and permeability must be
reached, since both parameters determine the volumetric
sorption uptake (bulk density) and pressure drop in the
monolith (permeability).
The electrical conductivity of these materials is of
interest in relation with the regeneration of the saturated
adsorbent. Thus, the passing of a small current through the
monolith allows a rapid increase in its temperature, thereby
causing the desorption of the adsorbed species. The
electrical conductivity of the monoliths was measured by a
two-point method. The values obtained for Nomex-based
ACFMs with different activation degrees are indicated in
Table 5. The conductivities decrease with increasing
activation degree, from 1.1 (V?cm)21 (0% burn off) to
0.08 (V?cm)21 (40% burn off). This change reflects a loss
of interconnectivity between the carbon units that make up
the monoliths as a consequence of carbon gasification.

be characterised by measuring gas permeability through

the monolith (K), which is defined as: 4. Conclusions

K 5 (F /A) /(DP/H ) f 5 g m 3 (STP) ? m ? m 22 ? s 21 ? Pa 21 Nomex-based activated carbon fibre monoliths (ACFMs)

(2)
where F is the flow rate, H and A the length and
transversal area of the monolith, and DP the pressure drop
induced in the monolith. Once the permeability parameter
is known, the pressure drop originated by the gas passing
through the monolith, can be estimated easily from Eq. (2),
by taking into account the dimensions of the monolith and
the gas flow rate. In this work, the permeability was
determined at ambient temperature by measuring the
pressure drop at different air flow rates. This parameter is
an intrinsic property of the monolith and is a function of its
bulk porosity and the size of the intraparticle voids. The
are prepared by the agglomeration of carbonised rejects of
polymeric fibres (Nomex姠) and further activation with
steam. The porosity of these ACFMs is formed by narrow
micropores (,1 nm).
For high VOC concentrations, the amount adsorbed
increases with the activation degree. However, at low VOC
concentrations, samples activated at high burnoffs show
lower adsorbed amounts than samples activated at lower
activation degrees. This is a consequence of the influence
that micropore size has on adsorption. Thus, narrower
micropores associated with samples activated at low
burnoffs and therefore with high adsorption potentials,
exhibit high adsorption capacities at low concentrations.

Table 5
Permeability and electrical conductivity of ACFM
Sample Bulk Bulk Permeability Electrical
density porosity (m 3 ?m?m 22 ?s 21 ?Pa 21 ) conductivity
(g / cm 3 ) (V?cm)21
A-20 0.23 0.63 4.7310 27 –
N-0 0.21 0.81 9.5310 27 1.1
N-20 0.20 0.84 19.4310 27 0.13
N-40 0.21 0.77 7.8310 27 0.08
 A.B. Fuertes et al. / Carbon 41 (2003) 87–96
As an example, the amount of n-butane adsorbed at a
concentration of 500 ppm exhibits a maximum at an
activation degree of |20%.
The porosity of monoliths prepared from commercial
activated carbon fibres is formed by wider pores than those
of Nomex-based ACFM. In consequence, the Nomex-
based samples exhibit higher adsorption capacities at low
VOC concentrations. This evidences the importance of a
uniform development of narrow microporosity in order to
optimise VOC adsorption at low concentrations.
The agglomeration of commercial activated carbon
fibres causes a loss in surface area, porosity and VOC
adsorption uptake with respect to the same parameters for
non-agglomerated fibres. This could be because the po-
rosity is partially plugged by the binder. However, when
the fibres were activated after agglomeration (as was the
case of Nomex-based ACFM), no loss in adsorption
properties was detected. This proves that it is better to use
carbonised fibres rather than activated ones in the fabrica-
tion of ACFMs to optimise their adsorption properties.
The amount of VOC adsorbed at high concentrations
( p /po |1) is independent of the nature of the adsorbate and
only depends on the pore volume of the sample. On the
other hand, at low VOC concentrations, the amount
adsorbed depends on the characteristics of the adsorbate. In
this respect it was observed that the amount adsorbed at
low concentrations could be predicted with reasonable
accuracy from the value of the molecular parachor of the
adsorbate.
The gas permeability of ACFM is a key concern in
relation with its use for VOC adsorption. This property can
be controlled by modifying the bulk density (compression
ratio) of the monolith. However, in practice, a compromise
between bulk density and permeability must be reached,
since both parameters determine the volumetric sorption
uptake (bulk density) and pressure drop in the monolith
(permeability).
Acknowledgements
The financial support of the ECSC Programme (Contract
7220-PR113), Accion´ Especial (PPQ2000-3112-CE) and
Dupont Iberica is acknowledged.
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