Carbon, Vol. 33, No. 5, pp.

561-567, 1995
Copyright 0 1995 Elsevier Science Ltd
Pergamon Printed in Great Britain. All rights reserved
ooO8-6223/95 $9.50 + .OO

0008-6223(94)00141-3

CARBON MOLECULAR SIEVES PRODUCED

FROM WALNUT SHELL

ZHONGHUA Hu and E. F. VANSANT

Laboratory of Inorganic Chemistry, Department of Chemistry, University of Antwerp (UIA),
Universiteitsplein 1, 2610 Wilrijk, Belgium

(Received I September 1994; accepted in revised form 22 November 1994)

Abstract-Recently, the development of carbon molecular sieves (CMS) for the separation of various gases,
particularly air into oxygen and nitrogen, has gained widespread attention. In this paper, a simple method
was presented for preparing carbon molecular sieves. Carbonized walnut shells were impregnated with a
small amount of potassium hydroxide (KOH) and pyrolysed. In this way, the pore size can be easily con-
trolled in the range around 0.5 nm. The produced samples were further modified by a carbon deposition
to form the final CMS. 3-methylpentane (3-MP) was used as a carbon source for the deposition. The CMS
samples were characterized by the adsorption of nitrogen, oxygen, and a series of molecular probes to es-
timate the surface area, pore volume, and the pore size distributions. Due to the small pore entrances, only
a very small nitrogen adsorption was found on the CMS at 77 K. Therefore, the oxygen adsorption iso-
therms at 77 K were used to calculate the surface area and pore volume. We are able to prepare CMS with
a narrow pore size distribution in the range 0.33-0.43 nm and with an oxygen-to-nitrogen separation se-
lectivity, D,,/D,,, as high as 9.2.
Key Words-Carbon molecular sieves, adsorption, walnut shell, molecular probe, air separation, carbon
deposition.

1. INTRODUCTION CMS having a desired pore structure. Coal and coco-

nut shells have been used as starting materials. But,
Carbon molecular sieves have effective micropore
no studies have been reported on CMS produced from
diameters ranging from 0.4 to 0.9 nm, which is
about
walnut shells.
comparable with the molecular diameter of the adsor-
This work presents a new and simple method to
bates to be separated[ 11. The micropore size distribu-
produce CMS having the desired pore size to separate
tion of such sieves is much narrower than in a typical
air components, using walnut shells as a starting ma-
activated carbon; therefore, CMS adsorbents are widely
terial. The intention is to control the micropore size
used in gas separation processes. The most important
in the chars by adding small quantities of KOH to the
large-scale application is for air separation[2-41. These
walnut shells, so that highly microporous substrates
adsorbents separate oxygen from air on a kinetic basis,
adsorbing the smaller oxygen (kinetic diameter 0.346 with pore widths of <0.5 nm can be obtained. Then,
the carbon deposition technique was used to decrease
nm) molecules more rapidly than the larger nitrogen
(0.364 nm) molecules. In addition to their application the pore entrances by pyrolysing 3-MP on the micro-
pore mouths. The produced CMS samples were char-
to gas separation, CMS materials are receiving in-
acterized by molecular probe adsorption to estimate
creased attention as catalysts[5-91.
the pore size distribution, and by nitrogen or oxygen
The ability to control the size of the pore openings
adsorption isotherms at 77 K to calculate the surface
in a CMS, to tune the specifications to tenths of an
area and pore volume. The separation efficiency was
angstrom in the case of air separation, is a major chal-
tested by an analysis of the single gases, oxygen and
lenge in preparing CMS adsorbents. Since adsorption
nitrogen, with respect to their adsorption rates at room
is a key part in the entire separation process, improved
temperature.
CMS adsorbents are needed to reduce the cost of
pressure-swing adsorption (PSA) systems. The CMS
used for air separation are unusual microporous car-
2. EXPERIMENTAL
bons, produced with a precise control of their pore size
distribution in the range of 0.3-0.4 nm. It is remark-
able to note that these materials are made in tonnage 2.1 Materials
quantities throughout the world with good quality. In Walnut shells were used as a starting material. Po-
the literature, several methods have been proposed for tassium hydroxide with a 97% purity was obtained from
producing CMS materials[lO-201. Most of these meth- JANSSEN-CHIMICA. The probe molecules were ox-
ods intend to modify slightly the pores created during ygen, nitrogen, carbon dioxide, ethane, butane, iso-
the carbonization of carbonaceous materials. Because pentane, 3-methylpentane, and carbon tetrachloride.
the pore structure of carbonized materials is highly de- All adsorbates with a minimum purity of 99% were
pendent on the starting materials, selection of a proper supplied by L’AIR LIQUIDE, JANSSEN-CHIMICA,
starting material is a key factor in the production of and MERCK.

561
562 Z. Hu and E. F. VANSANT

2.2 Preparation of CA4S a,,~, the limiting micropore volume, a0 the limiting
The char, obtained by a thermal treatment of wal- amount adsorbed in micropores, v the molar volume
nut shells at 250°C for 3 hours, was crushed and sieved of the absorbate, 0 the similarity coefficient of the
to a particle size of l-2 mm, then mixed with a solu- characteristic curves, and W the adsorbed volume.
tion of KOH. The mixture was dehydrated at 300°C W, can be determined from the intercept of the In W
for 3 hours and finally activated at elevated tempera- vs ln*(Pe/P) plot. Assuming that the diameters of
ture in the absence of air. The formed products were the micropores are larger than that of the adsorbed
extensively washed with deionized water and dried at molecule, the micropore volume distribution of each
room temperature. Carbon deposition on the chars sample was estimated.
was used for reducing the pore entrances by pyrolys-
ing 3-methylpentane. The following samples were pre- 2.4 CO,, N,, and O2 adsorptions
pared under different conditions: Nz and O2 adsorption isotherms for the CMS at
77 K were recorded by an Autosorb-1-MP (QUANTA-
CMS-A: Only char without KOH, activation at CHROME), in order to determine the surface areas
800°C for 1 hour and pore volumes. The samples were outgassed at
CMS-B: KOH/char ratio 1: 20, activation tempera- 200°C for 3 hours. The surface areas were calculated
ture 8OO”C, time 1 hour using the BET equation, and the pore volumes were
CMS-C: KOH/char ratio 1: 20, temperature 8OO”C, estimated from the liquid volume of the adsorbate
time 1 hour; washing and drying. Carbon (0, or N,) at a relative pressure of 0.90. The surface
deposition: introducing a pure 3-methyl- areas were also calculated from the Langmuir equa-
pentane vapor at a pressure of 100 mmHg tion, if the adsorption data correlated better with this
over night and carbonized at 800°C for 1 hour equation than with the BET equation.
CMS-D: KOH/char ratio 1: 20, activation tempera- Measurements of nitrogen and oxygen adsorption
ture 8OO”C, time 1 hour; washing and dry- rates on the carbon samples were performed with both
ing. Then carbon deposition: introducing a a constant volumetric and a gravimetric adsorption ap-
pure 3-methylpentane vapor at saturation paratus. About 0.5 g and 0.12 g of sample were used
pressure overnight, carbonized at 700°C for in the volumetric and gravimetric adsorption appara-
1 hour. tus, respectively. Adsorption rates were determined at
77 K and 295 K with pressures of < 1 atm. The rate of
2.3 Determination of the pore carbon dioxide adsorption was measured only at room
size distribution temperature.
Pore size distributions were measured using a mo- If uptake of the sorbate by the adsorbent is small
lecular probe method. Adsorptions at room temper- relative to the total quantity of sorbate introduced into
ature of various gases having different molecular size the system, the ambient sorbate concentration will re-
by the samples, over a 24-hour period, were measured main essentially constant following the initial step
by a gravimetric system using a quartz spring balance. change. The adsorption rate curve can be given by the
About 0.12 g of the sample was introduced in the expression[27]:
quartz spring balance. As a pretreatment step, the
samples were degassed at 200°C for 3 hours until a ml ( -n27r2Dt)
__l-AC+exp (3)
pressure below lop3 mbar was achieved. The follow- mcX a2 n=l n r2
ing molecular probes of different kinetic diameter:
carbon dioxide (CO*, 0.33 nm), ethane (C2H6, 0.4 where m,/rn, is the fraction approaching equilib-
nm), butane (n-C4Hn,, 0.43 nm), isopentane (i-C5HL2 rium, D the diffusivity, r radial coordinate for micro-
0.5 nm) and carbon tetrachloride (CC14, 0.6 nm), particle or crystal, t the adsorption time. Expression
were chosen for adsorption at room temperature to eqn (3) converges rapidly in the long time region since
evaluate the porosity of the sorbents. The physical the higher terms of the summation become very small.
properties of the probe molecules are presented in For fractional uptakes greater than 70%, the expres-
literature[21-231. sion can be written by the first term:
Adsorption data were used to characterize the CMS
by the Dubinin-Radushkevich (DR) equation[24-261. 1-3
(4)
mcc
W = Woexp[-(A/&Eo)2] (1)
At 70% uptake, this expression deviates by less than
where A is the Polanyi’s adsorption potential, calcu- 2% from the complete eqn (3).
lated from the saturated vapor pressure, PO, and the In the long time region, a plot of ln(1 - m,/m,)
adsorption pressure P by versus t should be linear, with a slope of -a2D/r2
and with an intercept of ln(6/a2). Such a plot pro-
A = RTln(P,/P) (2) vides, in principle, a simple method to both checking
the conformity of an experimental uptake curve with
E, is the characteristic energy, which is a function of the diffusion eqn and determining the diffusional time
the microporous structure of a given adsorbent, W, = constant, D/r*.
 Carbon molecular sieves produced from walnut shell 563

3. RESULTS AND DISCUSSION adsorb oxygen at 77 K, suggesting that there are no

pores or pores too small to accept oxygen.
3.1 Surface area and pore volume The surface area and pore volume calculated from
of the CMS the O2 and Nz adsorption isotherms are shown in
It is customary to use N2 adsorption isotherms at Table 1 (assuming that the surface area of a molecule
77 K to characterize micropore adsorbents. Hence, all and the liquid density are 14.3 A2 and 1.20 g/cm3 for
the CMS samples were subjected to a Nz adsorption 02, 16.2 A and 0.81 g/cm3 for N2, respectively[30,31]).
at 77 K. However, except for CMS-A, no significant The pore volumes were estimated to be the liquid vol-
adsorption could be observed. Since adsorption is nor- ume of oxygen or nitrogen at a relative pressure of
mally favored at low temperatures, the lack of N, ad- 0.90. These pore volumes must be regarded as micro-
sorption is attributed to pores of the sample being pore volumes, because CMS-B, -C and -D adsorb little
smaller than the kinetic diameter of N2 (0.364 nm) or nitrogen at 77 K. The pore volumes, as well as the sur-
to the accessibility of Nz into the pores being hin- face areas accessible to 02, decrease in the order
dered because of activated diffusion effects[28,29]. CMS-A > CMS-B > CMS-C > CMS-D. Since the sam-
O2 adsorption at 77 K was also measured for all ples CMS-B and CMS-C excluded almost all the ni-
the samples. In contrast with N, adsorption, 0, ad- trogen molecules, indicating that the micropores are
sorption was appreciable, except for the sample CMS- <O.S nm[32], the calculated surface areas are micro-
D. Adsorption isotherms for nitrogen and oxygen on porous surface areas.
the CMS samples are shown in Fig. 1. It is clear that These results indicate that the carbonization mech-
the adsorption isotherms are of type I, indicating anism and porosity of carbonaceous adsorbents are
highly microporous materials. The results of the ni- highly dependent upon the addition of KOH during
trogen and oxygen adsorptions suggest that the CMS the pyrolysis period. Sample CMS-B, treated with a
samples CMS-B and CMS-C exhibit an important mo- small quantity of KOH (about 5% by weight), has
lecular sieving effect at 77 K. CMS-A adsorbed a com- a smaller micropore volume and surface area than
parable amount of nitrogen and oxygen, indicating CMS-A. During pyrolysis, the impregnated KOH de-
that there is a considerable amount of pores larger hydrates the walnut shells, resulting in charring and
than the nitrogen molecule. However, CMS-D did not carbonizing the carbon skeleton with creation of a po-
rous structure. The activating agent, KOH, influences
the pyrolytic decomposition and inhibits the forma-
tion of tar, resulting in a decrease in the formation of
‘--I I
compounds like acetic acid and ethanol and, thus, en-
hancing the carbon yield[33].
To decrease the pore size to the desired range, a
carbon deposition was carried out on the substrate
CMS-B by pyrolysing 3-methylpentane. Changes in
the surface area and pore volume are significant, par-
ticularly for the sample CMS-D. Details of the varia-
tion in pore size will be discussed in the following
section.

3.2 Pore size distribution

Relative pressure.
The pore size distributions of the CMS samples
P/P0 were estimated by the molecular probe technique. Due
to the small pore entrances of the carbons, the probe
molecules, C2H6, n-C4Hlo, i-CSH,2, and CC14, dif-
fuse very slowly into the adsorbents. Therefore, the
adsorption isotherms were measured over 24 hours.

Table 1. Surface areas and pore volumes calculated from the

N, and 0, adsorption isotherms

Surface area
b (m’/g)
Pore volume
o- .*-‘:“-‘-;LIIIIe Sample ID Adsorbate BET Langmuir (cm3/g)
0 0.2 0.4 0.6 0.8 1
Relative pressure, P/P0 CMS-A 333.1 416.9 0.170
NZ
CMS-A 02 459.4 614.8 0.197
Fig. 1. (a) Adsorption isotherms at 77 K on CMS-A;
W =
CMS-B 02 366.9 533.5 0.171
N,; A = 0,. (b) Adsorption isotherms for 0, at 77 K on
CMS-C 02 343.1 468.8 0.151
CMS adsorbents W = CMS-A; + = CMS-B; 0 = CMS-C;
CMS-D 0, 0.2 0.4 o.ooo4
A = CMS-D.
564 Z. Hu and E. F. VANSANT

0.16

I
m 0.12

E
2 0.08
9
z
0
a 0.04

-3.5\
0 5 10 15 20 25 30 35 40 45 5’0
0.00
0.33-0.4 0.4-0.43 0.43-0.5 0.5-0.6 z-0.6
In qPo/P) Pore size, nm

m CMS-A 0 CMS-6 m CMS-C a CMS-D

Fig. 2. Typical DR plot of CMS-A; probe molecules: n =
CO,; + = C,H,; * = C,H,,; 0 = isopentane.
Fig. 4. Pore size distribution of CMS adsorbents.

The typical DR equation plots are shown in Fig. 2.

Volumes of the probes takeup were calculated using nm and certainly smaller than 0.43 nm[34]. Compared
to the observed pore size distributions of CMS-SA,
the DR equation, assuming that the density of the ad-
sorbed phase is the same as the density of the bulk CMS4A, and a commercial CMS3A used for air sep-
liquid. These volumes are shown in Fig. 3. Volumes aration[35], it is evident that the pores of our CMS
takeup decrease in the order CMS-A > CMS-B > samples are smaller than those of CMS-4A or CMS-SA,
but slightly larger than that of CMS-3A.
CMS-C > CMS-D. It should be noted that pore vol-
umes estimated from 0, adsorption are in reasonable The reduction in pore diameter can be accom-
agreement with those obtained from CO2 adsorption, plished by carbon deposition. There are three possi-
bilities for carbon deposition, as shown in Fig. 5. The
except for CMS-D, where the pore volume calculated
from the CO2 isotherm is much larger. This indicates
that CMS-D has a considerable amount of pores
which are too small for O2 molecules at 77 K, whereas
these pores are accessible for COZ molecules at room
temperature.
To have a better idea of the pore structures, the
WC~He was subtracted from WcoZ, Wn_C4Hlo from
WCZHg, and so on. In this way, the pore size distribu-
tions between 0.33 to 0.6 nm were obtained, as shown
Fig. 4. It was found that the average pore size decreases
in the same order as the variation in pore volume. The
main pore volume is situated between 0.43-0.5 nm
for CMS-A, 0.4-0.5 nm for CMS-B, 0.33-0.5 nm for
CMS-C and 0.33-0.43 nm for CMS-D. To separate
Carbon deposition
oxygen from nitrogen, the pore should be about 0.38

Probe size. nm
T
onto/into
deposition
B
Fig. 5. Schematic representation of the carbon deposition
a pore. A = uncoated micropore <0.5 nm; B =
of carbon via pyrolysis of 3-MP resulting in a
blockage of the pore; C = deposition of carbon via pyroly-
Fig. 3. Microporosity of CMS adsorbents: n = CMS-A; sis of 3-MP on the pore walls; D = deposition of carbon via
+ = CMS-B; m = CMS-C; q = CMS-D. pyrolysis of 3-MP on the pore openings.
 Carbon molecular sieves produced from walnut shell

deposition of carbon in the interior has to be carefully

controlled so that the gas diffusion is not limited and
the adsorption capacity does not decrease significantly.
Because 3-methylpentane has a limited adsorption in
CMS-B, an optimal carbon deposition can occur. This
observation can be related to the adsorption of 3-MP
at the pore mouths, so that with pyrolysis of 3-MP the
pores are reduced mainly in the pore entrances for
CMS-B.
Since the variation in the pore volume was small, it
can be concluded that the carbon deposition occurred
mainly on the pore mouths. Therefore, the carbon de-
position by pyrolysing 3-MP has improved effectively
the microporosity (i.e., the pore size was reduced,
whereas the capacity reduction was very limited).

3.3 Adsorption kinetics of CO,, O,, and N2

The micropore diffusivities of carbon dioxide, ox-
ygen, and nitrogen in the CMS samples were evaluated
by analyzing the adsorption rate curves. Carbon di-
oxide adsorption rates were recorded on the gravimet-
ric adsorption apparatus at room temperature at an
equilibrium pressure of 60 mmHg. The usefulness of
the CO2 adsorption rate is to evaluate the effect of
the pore size as demonstrated in Fig. 6. The CO2 ad-
sorption is fast on the un-deposited samples CMS-A
and CMS-B, indicating that these samples show no sig-
nificant diffusion effects for COZ. The deposited
samples CMS-C and CMS-D, however, show a signif-
icant continued adsorption during 36 minutes, indicat-
ing a significant diffusion effect resulting from a slow
COz uptake. According to eqn (4) plot of ln(1 -
m,/m,) versus t were linear, yielding the diffusional
constants D/r2 for CMS-A, -B, -C, and -D of
0.00589, 0.00508, 0.00168, and 0.00121 s-‘, respec-
tively. The order is in good agreement with the pore
size distributions in the samples.
Figure 7 shows the oxygen and nitrogen adsorption
kinetics, measured on a constant volume adsorption
apparatus at 77 K and 295 K. It should be noted that,
in these measurements, the initial pressures are iden-
tical (about 360 mmHg). However, the equilibrium
pressures were not the same due to the different ad-
” ity is low. Oxygen diffuses faster and was adsorbed
I more than nitrogen into CMS-D.
Fig. 6. CO, adsorption rates at room temperature and an
equilibrium pressure about 60 mmHg on CMS adsorbents:
n = CMS-A; + = CMS-B; * = CMS-C; 0 = CMS-D.
Fig. 7. Adsorption kinetics for nitrogen and oxygen by the
volumetric adsorption method on CMS adsorbents: a =
CMS-A; b = CMS-B; c = CMS-C; d = CMS-D. W = 0, at
77 K; + = N, at 77 K; * = 0, at 295 K; 0 = N, at 295 K.
Initial pressures = 360 mmHg.
sorption capacities of the carbon samples. At 77 K, a
clear difference in the adsorption rate and adsorption
amount for the two gases can be observed. The oxy-
gen adsorption rate and adsorbed amount decrease in
the order CMS-A > CMS-B > CMS-C > CMS-D. The
diffusion effect for oxygen increases from CMS-A to
CMS-D, reflecting the decrease in pore size of the
adsorbent.
As previously observed, except for the CMS-A, the
CMS-B and CMS-C adsorb only a small amount of
nitrogen, whereas in the sample CMS-D a complete
exclusion of nitrogen is observed. Therefore, it can be
concluded that the four CMS samples reveal a signif-
icant molecular sieving behavior between oxygen and
nitrogen at 77 K. At 295 K, both gases are adsorbed
rapidly on CMS-A, -B, and -C, but adsorption capac-
To obtain further information, nitrogen and oxy-
gen adsorptions were carried out at an equilibrium
pressure of 600 mmHg using a gravimetric adsorption
technique. Figure 8 shows the oxygen and nitrogen ad-
sorption rate at 295 K. The results are similar to those
observed by the volumetric method. Oxygen adsorp-
tion is faster than nitrogen by the CMS samples.The
diffusion constants and selectivity for oxygen are sum-
marized in Table 2. Clearly, adsorption rates from ni-
trogen and oxygen both decrease with decreasing pore
sizes in the sorbent. However, the effect of the pore
size on the adsorption rate is more significant for ni-
trogen than for oxygen. Therefore, the selectivity or-
566 2. Hu and E. F. VANSANT

Table 2. Diffusion constants, selectivities, and adsorption capacities

Diffusivity Ads. capacity

(lo-4ss’) (mg/g)*
Micropore Selectivity
Sample ID (nm) Do,/? D&r2 DoJD,, 0, N2

CMS-A 0.43-0.5 15.2 8.97 1.7 8.86 7.21

CMS-B 0.4-0.5 13.2 5.23 2.5 7.81 7.41
CMS-C 0.33-0.5 10.2 2.63 3.9 8.65 7.83
CMS-D 0.33-0.43 8.85 0.958 9.2 9.56 8.65

*Adsorption capacities were estimated at an equilibrium pressure of 600 mmHg.

der is: CMS-A < CMS-B < CMS-C < CMS-D. The 4. CONCLUSION
results indicate that carbon deposition improves the
Results demonstrate that carbon molecular sieves
oxygen selectivity significantly. Sample CMS-D shows
with uniform pores smaller than 0.5 nm can be pre-
a large difference between oxygen and nitrogen in the
pared by pyrolysing a walnut shell-KOH mixture. The
initial adsorption rate, particularly within 1 minute,
concept behind this method is to modify the carbon-
so that this material is suitable for the separation of
ization behavior of walnut shells. In order to further
the air components in a pressure-swing adsorption
reduce the pore size, a carbon deposition technique was
system.
used by pyrolysing hydrocarbons, such as 3-methyl-
The results indicate that the carbon deposition has
pentane. The hydrocarbons were cracked and depos-
increased the 0, selectivity significantly. Higher selec-
ited in the entrances of the micropores. Therefore, the
tivity values could be obtained by cracking hydrocar-
micropores are effectively narrowed to the point that
bons in the pore openings of the CMS substrates.
they discriminate O2 and N2 by size. Due to the low
Since the CMS-D reveals a large difference in the ini-
cost and simple procedure, this method should be con-
tial adsorption rate between nitrogen and oxygen, it
sidered for producing CMS with a desired uniform
can be concluded that the pore diameter was success-
microporosity. We are able to prepare CMS with an
fully adjusted to around 0.3-0.4 nm, which is the crit-
effective size in the range of 0.33-0.43 nm. One of
ical pore size for a kinetic separation of oxygen from
the produced CMS was judged to be efficient for sep-
nitrogen.
aration of oxygen from nitrogen, based on kinetic
adsorption.

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