Escolar Documentos
Profissional Documentos
Cultura Documentos
ofPentchev,
University ChemicalB.Technology
Weinberger,and
F. Darkrim Lamari
Metallurgy, 42, 1, 2007, 77-84
1
University of Chemical Technology and Metallurgy Received 27 February 2007
8 Kl. Ohridski, 1756 Sofia, Bulgaria Accepted 10 March 2007
E-mail: chocho_72@abv.bg
2
Laboratoire d’ Ingénierie des Matériaux
et des Hautes Pressions, CNRS UPR1311,
99 Av. J.B.Clément, 93430 Velletaneuse, France
ABSTRACT
The topic of this work is to compare several experimental methods such as volumetric and volumetric-gravimetric
methods for measuring the equilibrium states of pure gases being adsorbed on the surface of solid materials. The investi-
gation of different type methods and their advantages end disadvantages are discussed. The installations used for measur-
ing the adsorption equilibrium by these methods are discussed in details. The installation for measuring the helium density
of materials, i.e. volumetric density of solid adsorbents is also presented.
Keywords: measurement of excess adsorption, porous adsorbent, pure gases, high pressure.
77
Journal of the University of Chemical Technology and Metallurgy, 42, 1, 2007
where V ( y ) is the volume filled by the set (y) of all This surface mass excess represents the differ-
molecules of the adsorbate, i.e. all molecules of the sorp- ence between the absolute amount adsorbed in a vol-
tive fluid influenced by or exerted to the surface forces ume V and the amount of volume that could be occu-
of the sorbent material. This is an energetic criterion pied by molecules with the same density as that of the
determining whether a molecule from the fluid is bulk. Thus the surface mass excess is positive if the ad-
adsorbed on the surface of the solid material or not. If sorption density in the volume V is greater than the
the energy of the molecules (E) is: bulk density (see Fig. 1).
It is negative when the adsorption density is less
E = E kin + E Pf + E ps (2) than the bulk density everywhere throughout the vol-
ume V. According to [14] for the absolute amount
where Ekin is the kinetic energy of the translation, adsorbed:
f
E is the potential energy of interaction of the mol-
p
ma = mGE + ρ bulk V ADS (6)
ecules with other molecules from the fluid phase (f),
s
end E p is the potential energy of interaction of the were V ADS is the volume of the adsorbed phase.
molecules with the molecules of the solid.
78
Ch. Chilev, I. Pentchev, B. Weinberger, F. Darkrim Lamari
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Journal of the University of Chemical Technology and Metallurgy, 42, 1, 2007
2. The adsorbent is regenerated at high tempera- equilibrium. The volumetric gas adsorption experiments
ture; consist in: a given amount of sorptive gas is expanded
3. The system of heating of the adsorption cell is into a vessel which includes a sorbent sample and which
switched on and the process of heating is regulated at initially has been evacuated. Upon expansion the sorp-
rate of increasing 20C/min up to 1000C; tive gas is partly adsorbed on the (external and internal)
4. During the secondary degasification the tem- surface of the sorbent material, partly remaining as gas
perature increases to 4000C; phase around the sorbent. By a mass balance, the amount
5. The adsorption cell is cooling at ambient tem- of gas being adsorbed can be calculated if the void vol-
perature; ume of the sorbent, i. e. the volume which can not be
6. The valve is closed and the pump is stopped; penetrated by the sorptive gas molecules is known at
7. The mass of the activated material is deter- least approximately. On Fig. 4 the installation for mea-
mined; surement of adsorption equilibrium by volumetric
8. The system is connected to the reservoir; method is represented.
9. Points 3-4 are repeated; An instrument for volumetric measurements of
10. Helium is injected to the reservoir; pure gas adsorption basically consists of a gas storage
80
Ch. Chilev, I. Pentchev, B. Weinberger, F. Darkrim Lamari
mGE =VSV [ρ0 ( p0 ,T0 ) − ρBulk( p1,T1 )] − (VAC −VAds)ρBulk( p1,T1 ) (8)
VOLUMETRIC - GRAVIMETRIC MEASUREMENT 200 GPa) with a length of 1520 mm, where a load of 0.1
OF PURE GASADSORPTION EQUILIBRIUM mg at the free end induces a deviation of the capillary
tube equal to 0.02 mm. If the length of the tube is 1, the
Volumetric/manometric measurements and gravi- axial deviation is given by:
metric measurements can be performed simultaneously
on the same gas adsorption system in a single instru-
FG I 3
y=
ment. The experimental measurements are based on the
3E
(
π De4 − d i4 ) (10)
gravimetric-volumetric method [3,10-12]. In Fig.5 the 64
schematic setup used is shown.
The mass of the gas present in the system is dy-
namically measured. Moreover, after each state of equi-
librium, the gas is re-injected to the system. As illus-
trated in Fig. 5, the system is weighed directly and the
gas is injected by a capillary tube. To avoid the system-
atic errors due to the gas mass, the pressure vessel must
be symmetrical and the axis should remain vertical. The
vertical alignment of the system is obtained with a coun-
terweight. This one compensates both due to the weight
of the capillary tube. A precision adjustment is possible
starting from the micrometric table (Fig. 6). At the left
end of the capillary, the balance is connected and on the
right-the micrometric table. The axial deviation (y) of
the balance is slightly influenced by elasticity (E) of the
capillary tube. We used a capillary tube (stainless 316L, Fig. 6. B, Balance; MT, micrometric table; X, length of capillary;
CW, counterweight; CT, capillary tube; R, Reactor; V- Valve.
81
Journal of the University of Chemical Technology and Metallurgy, 42, 1, 2007
mGas − ρ Gas (TInt , P )[Vc (TInt ) − V Ads (TInt )] − ρ Gas (TInt , P )VCap (TExt )0.5
ma =
mAds M Gas
(11)
Fig. 7. Comparison of hydrogen measurements obtained by
where mGas is the total mass of gas, ρ Gas - bulk the gravimetric-volumetric device (LIMHP) and volumetric device
(AL) on the zeolite 13X.
density of the gas, TInt - the temperature inside the cli-
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Ch. Chilev, I. Pentchev, B. Weinberger, F. Darkrim Lamari
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Journal of the University of Chemical Technology and Metallurgy, 42, 1, 2007
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