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Profissional Documentos
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1988
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mGreatBritain.
REVIEW
ARTICLE
of Materials
BRIAN MCENANEY
Science, University of Bath,
(Received
IN
19 Oclober 1987)
Abstract-The
microporous
structure of carbons consists of a tangled network of defective carbon layer
planes in which micropores
are the spaces between the layer planes. Adsorption
of gases in micropores
is characterized
by (1) strong adsorption
at low pressure due to overlap of force fields from opposite
pore walls, (2) activated diffusion effects caused by constrictions
in the microporous
network.
and (3)
molecular
size and shape selectivity
(molecular
sieving). The surface fractal dimension
of activated
carbons decreases
from three to two with increasing
activation,
indicating that activation
smoothens
pore surfaces. Calculated adsorption potentials for slit-shaped model micropores show that adsorption
potentials
are enhanced
by a factor of up to 2 and enable critical dimensions
for diffusion of gases
through micropores
to be estimated. The Brunauer-Emmett-Teller
equation is unsuitable for analyzing
adsorption
with a significant microporous
contribution
but may be used to estimate the nonmicroporous
surface area, provided that the microporous
contribution
can be removed. The Dubinin-Radushkevich
and Dubinin-Astakhov
equations
have been more successful when applied to microporous
carbon5
because they reflect the influence of adsorbent
heterogeneity.
as they result from an approximation
to
the generalized
adsorption
isotherm (GAI). More exact solutions of the GA1 enable adsorption
energy
distribution
functions to be obtained.
The possibility of extracting
micropore
size distributions
from
adsorption
measurements
is briefly considered.
Key Words-Adsorption,
microporous
carbons,
activated
microstructure
micropores.
Definitions
of pore sizes follow recommendations
of the International
Union of Pure
& Applied Chemistry (IUPAC): micropores-width
less than 2 nm; mesopores-width
2 to 50 nm:
macropores-width
greater than 50 nm[3].
The major sources of industrial, microporous
active carbons are coals (lignites, bituminous
coals,
and anthracites),
peat, wood, and a wide range of
organic by-products
of industry
and agriculture.
About 90% of active carbons are produced in granular or powder form, with most of the remainder in
pelleted form[4]. In addition to these conventional
sources. an increasingly
wide range of specialized
industrial
microporous
adsorbents
has been produced (e.g., active carbon textiles[5,6],
and molecular sieve carbons[7,8]).
During carbonization
the
organic precursor
is thermally
degraded
to form
products that undergo either condensation
or volatilization reactions,
the competition
between these
processes determining
the carbon yield. The carbon
residue is formed by condensation
of polynuclear
aromatic compounds
and expulsion
of side chain
groups. However, industrial carbons retain a :,ignificant concentration
of heteroelements.
especially 0
and H, and many contain mineral matter. The adsorptive capacity of the carbonized materials is usually too low for practical applications,
so porosity in
the carbon is developed
by activation (i.e., by reaction of the carbon with oxidizing gases (e.g., Hz0
or COz) or by incorporation
of inorganic additives
(e.g., ZnCL) prior to carbonization.
For coal-based
1. INTRODUCTION
The literature
on adsorption
in porous carbons
ranges widely from theoretical
studies of adsorption
from the vapor and liquid phases to technical studies
of the many applications
of carbon adsorbents.
This
article is not a comprehensive
review of the subject,
nor is it a complete
survey of the many isotherm
equations
that have been proposed
to analyze adsorption in microporous
carbons. Instead, it is confined to consideration
of the effects of the microporous structure of carbons on adsorption
of gases.
Although
most nongraphitizing
(hard)
carbons
contain numerous
micropores,
not all are practical
adsorbents,
since the micropores
in them may not
be accessible to gases to a useful degree. However.
much valuable structural
information,
relevant to
microporous
carbon adsorbents,
has been obtained
from the study of materials
such as poly(acrylonitrile)-based
(PAN-based)
carbon
fibers[l]
and glasslike (vitreous)
carbons[2].
Many industrial porous carbons
(e.g., coal-based
active carbons) in addition to micropores
contain macropores
and mesopores
that may be important
in adsorption. However,
the role of these larger pores is not
considered
in this article, since the effectiveness
of
most active carbons used for gas adsorption depends
primarily on the nature and extent of the accessible
carbons,
at Carbon
267
268
B. MCENANEY
active carbons, Table 1 illustrates how the proportion of the different pore types varies with the nature
of the precursor[4]. By judicious choice of the precursors and careful control of carbonization and activation, it is possible to tailor active carbons to suit
particular applications.
2.
THE STRUCTURE
OF MICROPOROUS
CARBONS
Microporous
carbons have a very disordered
structure as revealed by high resolution electron microscopy and various model structures have been
proposed based on studies of polymer carbons[2,9],
carbon fibers[l],
carbonized
coals and kerogens[lO,ll], and active carbons[l2,13]. Although the
models differ in detail, the essential feature of all of
them is a twisted network of defective carbon layer
planes, cross-linked by aliphatic bridging groups.
The width of layer planes varies, but typically is
about 5 nm[12]. Simple functional groups (e.g.,
C-OH,
C===O)and heteroelements
are incorporated into the network and are bound to the periphery of the carbon layer planes. Functional groups
can have an important influence on adsorption[l4],
but detailed consideration of their effects is outside
the scope of this review. In microporous carbons the
layer planes occur singly or in small stacks of two,
three, or four with variable interlayer spacings in the
range 0.34 to 0.8 nm[ll]; Fryer[l2] found an average
layer plane separation of 0.7 nm for a steam-activated anthracite carbon, and separations in the range
0.6 to 0.8 nm for Carbosieve. There is considerable
microporosity in the form of an interconnected network of slit-shaped pores formed by the spaces between the carbon layer planes and the gaps between
the stacks. Thus the widths of pores formed by interlayer spacings (typically from about 0.34-0.8 nm)
are significantly less than 2 nm, the arbitrarily defined[3] upper limit for micropore widths. Constrictions in the microporous network are particular
features of the structure that control access to much
of the pore space. Constrictions may also occur due
to the presence of functional groups attached to the
edges of layer planes[l5,16] and by carbon deposits
formed by thermal cracking of volatiles.
3. ADSORPTION
IN MICROPOROUS
CARBONS
The complex and disorganized structure of microporous carbons, in which the dimensions of the pore
space are commensurate with the dimensions of adsorbate molecules, makes interpretation of adsorpTable 1. Pore volumes (ml/g) for coal-based active carbons[4]
Coal Precursor
Anthracite
Bituminous
Lignite
Blended
Micropores
Mesopores
Macropores
0.51
0.43
0.22
0.42
0.07
0.17
0.58
0.11
0.11
0.26
0.32
0.33
ANALYSIS OF MICROPOROUS
CARBONS
CALCULATIONS
OF ADSORPTION
POTENTIALS
There have been several theoretical studies of adsorption potentials in model micropores[25-271. Adsorption potentials were calculated by Everett and
269
co
0.541
co2
0.542
2.0
1.a
02
0.544
022
THE BRUNAUER-EMMETT-TELLER
(BET) EQUATION
Fig. 1. Adsorption potentials Q * in model slit-shaped micropores, relative to the adsorption potential Q on a free
surface, as a function of pore half-width, d, relative to the
collision radius of the adsorptive, r,; calculated using 10:4
potential functionsf271.
The equation
most widely used to analyse adsorption isotherms to obtain surface areas, the BET
equation[e.g.,
321, is subject to severe limitations
when applied to microporous carbons. Values of surface areas, up to about 4000 m2/g for some highly
activated carbons[33] are unrealistically high, since
B. MCENANEY
270
800
800
8
9
480
-8 -
200
I0
0.5
I.0
I.5
alpha
layer
plane,
40
60
80
InaPolP
Table 3. Parameters obtained from u-plots (Fig. 2) for adsorption of Ar at 77 K on coal-based activated
carbons[40]
Carbon
ABl
AB2
AB3
AB4
Fig. 3. Adsorption of CO, at 195 K on an activated cellulose triacetate carbon heat-treated to 1600C plotted in
DR coordinates to illustrate the principle of isotherm subtraction[Q].
the calculated
20
S(m2/g)
S(m*/g)
V&nl/g)
SIS
595
773
877
1006
47
80
61
74
0.24
0.31
0.37
0.41
0.08
0.10
0.07
0.07
7. THE
DUBININ-RADUSHKEVICH
(DR)
EQUATION
Because adsorption in microporous carbons occurs by primary or micropore filling, Dubinin and
his group originally modeled microporous adsorption using the Polanyi potential theory. Dubinin
found empirically that the characteristic curves for
adsorption on many microporous carbons could be
linearized using the DR equation[46]:
271
8. THE
GENERALIZED
ISOTHERM
(1)
20
40
60
80
ln2P,/
ADSORPTION
(GAI)
-1.4
-_I
IO
In2 P,I P
15
Fig. 5. Adsorption
of Ar at 77 K on activated
carbons
from: Saran, n ; almond shells, 0; olive stones, A. The
downward
deflections
at low Pi PO(high In* PO/P) are due
. ..^_. P.,. .^7
to activated dittuslon(4U,4X].
B. MCENANEY
272
= lu@YP, q)f(q)
&,
P E 4
(2)
where f is the site energy distribution function defined on a domain fl and 4 is the domain of P; this
integral equation is the GAI. Solving the GA1 for
f, given 0 and G, is ill-posed, that is, small perturbations in 8 (e.g., experimental errors) can result
in widely different solutions for f. The general approach to solving the GA1 is to restrict the class of
possible solutions by imposing constraints on f that
correspond to assumptions about or prior knowledge
of the system. The solution is then considered to be
the f in this restricted class that gives the best fit to
the experimentally determined total isotherm (e.g.,
by least squares). One approach is to constrain f to
be a smooth, analytic function which, with a suitable
equation for G, allows the GA1 to be integrated to
give an analytic function for 8. A recent example
of this approach was presented by Sircar[SO], who
chose the Langmuir equation for the local isotherm
and a gamma-type function for f. A solution to the
GA1 can also be obtained by a numerical method
called regularization[5 1,521. A third method used to
solve the GA1 is the condensation approximation
(CA)[53] in which the local isotherm is approximated by a step function. Applying the CA to the
Langmuir local isotherm results in the relationship
A = q - go, where go is a constant, minimum ad-
sorption energy.
distribution
f(4) =
If
f is assumed to be a Weibull
n(q - So)-
E
exp -
[VI,
(3)
OF MICROPORE
SIZES
0.6
f(q)
0.4
O-5
l-0
(q- q&E
Fig. 6. The influence of the DA parameter n on the shape
of the Weibull distribution function f(q) of eqn (3).
(4)
(5)
(6)
SUMMARY
213
walls, (2) activated diffusion effects caused by constrictions in the microporous network, and (3) molecular size and shape selectivity, with preferential
adsorption of flat molecules. These properties have
enabled molecular sieve carbons to be developed for
the separation of gases. Fractal analysis of adsorption in microporous carbons suggests that the surface
fractal dimension D, decreases from about 3 to about
2 with increasing activation, indicating that activation smoothens pore surfaces.
Adsorption potentials may be calculated for slitshaped model micropores formed between singlelayer planes. These calculations show that adsorption potentials in micropores are enhanced by a
factor of up to 2 compared to the free surface and
lead to critical dimensions for diffusion of gases
through micropores. The nature of the adsorption
process in micropores renders the Brunauer-Emmett-Teller (BET) equation unsuitable for analyzing adsorption isotherms with a significant microporous contribution.
The BET equation can be
used to estimate the nonmicroporous surface area,
provided that the microporous contribution to adsorption can be removed. Various techniques have
been developed to do this such as t plots, LYplots,
n-nonane preadsorption, and isotherm subtraction.
The Dubinin-Radushkevich
(DR) and DubininAstakhov (DA) equations have been more successful when applied to adsorption on microporous carbons, because they reflect the influence of adsorbent
heterogeneity on the adsorption process. The DR
and DA equations result from an approximation to
the generalized adsorption isotherm (GAI); more
exact solutions of the GA1 enable site-energy distribution functions for microporous carbons to be
obtained. Micropore size distributions for molecular
sieve carbons can be obtained from measurements
of adsorption of molecules of different size. Single
parameter estimates of pore sizes can be obtained
from the DR constant E,,. In principle, micropore
size distribution functions can also be obtained from
the energy distribution function f of the GAI.
Acknowledgments-Thanks
go to T. J. Mays for valuable
discussions, to S. Ah for the use of unpublished data. and
to J. Wang for help in the production of the figures.
REFERENCES
274
B. MCENANEY
40. S. A.-R. M. Ali, A study of microporous and nonmicroporous adsorption in activated carbons, MSc.,
Thesis, University of Bath, UK (1984).
41. S. J. Gregg and J. F. Langford, Trans. Faraday Sot.
65, 1394 (1969).
(1984).
F. Rodriguez-Reinoso,
M.
45. J. M. Martin-Martinez,
Molina-Sabio, and B. McEnaney, Carbon 24, 255
(1986).
49. M. Jaroniec,
A. Patrykiejew
and M. Borowko, In
Vol. 14
(Edited by D. A. Cadenhead and J. F. Danielli), Academic Press, New York, pp. l-68 (1981).
50. S. Sircar, J. Colloid Znterfnce Sci. 101, 452 (1984);
idem.. J. Chem. Sot.. Faradav Trans. I. 80. 1101
(1984).
51. J. A. Britten, B. J. Travis, and L. F. Brown, A.1.Ch.E.
Progress in Membrane