Note: Descriptions are shown in the official language in which they were submitted.
CA 01174221 1994-03-22
This invention relates to a multilayer glass structure, and
more specifically, to a multilayer glass structure which is so
constructed as to prevent effectively not only the condensation of
a water vapor and a vapor of an organic solvent in spaces within
the glass structure but also the occurrence of dust from an
adsorbent included in the glass structure.
A multilayer glass structure constructed by joining the
edge portions of a plurality of glass sheets by a sealant through
spacers having a dessicant included therein has been used hereto-
fore in various buildings as a windowpane having excellent thermal
and acoustic insulating effects.
One problem with this multilayer glass structure is that
when the temperature of air in the spaces between the glass sheets
decreases to below the dew point, vapors in these spaces are
condensed to reduce the visual field of the windowpane. It is
known that such vapors include not only a water vapor in the air
originally existing in the spaces between the glass sheets and a
water vapor contained in the air leaking through the spaces
between the glass sheets and the spacers, but also a vapor of an
organic solvent which is contained in the sealant and evaporates
off with the lapse of time.
It is known to use synthetic zeolites, active alumina,
silica gel, etc. as dessicants or adsorbents for the adsorption
of these vapors. These adsorbents, however, have not proved to
be entirely satisfactory for the
_ 2 - ~'_ _
CA 01174221 1994-03-22
purpose of adsorbing and removing a mixture of a water
vapor and an organic solvent vapor in such a way as to
prevent "fogging" despite a wide range of temperature
variations. For example, it is said that among the
above-mentioned adsorbents, silica gel is most suitable
for the adsorption of an organic solvent vapor. But in a
system including both water and an organic solvent,
silica gel tends to adsorb water selectively and pre-
ferentially, and therefore, its effect is questionable in
the ad sorpt ion of both.
From this viewpoint, the use of a combination of
adsorbents for a multilayer glass structure has already
been proposed. For example, Japanese Laid-Open Patent
Publication No. 71650/1980 discloses the use of a combi-
nation of 3A-type molecular sieve zeolite with hydrocarbon-
adsorptive silica gel, active alumina or activated carbon
or a mixture of such hydrocarbon-adsorptive adsorbents,
and suggests that activated carbon should be used carefully
so as not to permit it to come out of the spacers because
its color is unusual.
In addition to the aforesaid adsorbing property in
a system containing both a water vapor and an organic
solvent vapor, adsorbents for multilayer glass structures
present a problem of ~;iving off dust. Zeolite, activated
carbon, etc. are liab-le to yield dust, although to varying
degrees, when subjected to vibration, etc. imparted during
the transportation and setting of multilayer glass structures
or during their use as windowpanes. Disadvantageously,
the dust comes into the spaces between the glass sheets
throu;;h adsorbing openings provided in the spacers, a.nd
- 3 -
CA 01174221 1994-03-22
adheres to the glass surfaces to reduce vision or form a nucleus that acceler-
ates fogging.
Certainly, some proposals have previously been made as to adsorbents
for multilayer glass structures, but to the best of the knowledges of the
present inventors, almost nothing has been proposed about the prevention of
such dust occurrence.
According to this invention, there is provided a multilayer glass
structure consisting of a plurality of glass sheets joined at their edge
portions through spacers and sealed by a sealant between their edge portions
and the outer surfaces of the spacers, that spacer which is located in at
least
one side of the glass sheets having an adsorbent filled therein; characterized
in that said adsorbent comprises a combination of a granular zeolite composed
of a core of a synthetic zeolite/clay binder mixture containing the synthetic
zeolite in an amount larger than its average content in the granular zeolite
and a shell of a synthetic zeolite / clay binder mixture containing the clay
binder in an amount larger than its average in the granular zeolite content,
with granular activated carbon having on its surface 1 to 20% by weight, based
on the activated carbon, of a coating of a synthetic resin latex.
According to this invention, there is also provided an adsorbent for
multilayer glass structures, said adsorbent comprising a combination of (a) a
granular zeolite composed of a core of a synthetic zeolite/clay binder mixture
containing the synthetic zeolite in aii amount larger than its average content
in the granular zeolite and a shell of a synthetic zeolite/clay binder mixture
containing the clay binder in an amount larger than its average content in the
- 4 -
CA 01174221 1994-03-22
granular zeolite and (b) granular acti.vated carbon having at its surface 1 to
20% by weight, based on the activated carbon, of a coating of a synthetic
resin
latex, the weight ratio of (a) to (b) being from 80:20 to 50:50.
The invention is described in more detail, by way of example, in
connection with the attached drawings, in which:
Figures 1 and 2 are a three-dimensional view and a sectional view,
respectively, of the multilayer glass structure used in Example 1 of this
application, in which the numerical figures between arrows show sizes in mm;
- 4a -
CA 01174221 1994-03-22
Figure 3 is a view showing the sectional structure of
the granular zeolite used in this invention;
Figure 4 is the sectional view of the granular activated
carbon used in this invention;
Figure 5 is an adsorption isotherm of water in
Referential Example 6;
Figure 6 is an adsorption isotherm of methyl ethyl ketone
(MEK) in Referential Example 6;
Figure 7 is an adsorption isotherm of m-xylene in
Referential Example 6; and
Figure 8 shows the gas-circulating adsorption tester
described in Referential Example 6.
With reference to Figures 1 and 2 showing the structure of
the multilayer glass structure of this invention, a pair or glass
sheets la and lb are laid together through a spacer member 2 dis-
posed at four sides of the glass sheets, A both-surface adhesive
tape 3 is disposed
- 5 -
CA 01174221 1994-03-22
between the side surface of the spacer member 2 and the
inside surface of t~_e glass sheet to bond the spacer 2
to the inside surface of the glass sheet. Thus, a space
4 of a certain width determined by the spacer 2 is formed
between the two glass sheets la and lb.
A sealing agent or sealant 5 is applied to the edge
portion of the glass-spacer assembly, i.e. to the outer
surface of the spacer 2, thereby sealing the space 4
between the glass sheets la and lb by the sealant 5.
The spacers 4 are hollow in structure, and an adsorbent
6 is f'illed in the inside hollow portion of at least one
of the four spacers 2 located at the four side edge por-
tions o-f the glass sheets la and lb. The spacer 2 contain-
ing the adsorbent 6 has a small opening 7 for vapor ad-
sorption which comm~.Lnicates with the space 4.
According to this invention, a water vapor and an
organic solvent vaoor evaporated from the sealant 5,
which are present in the space 4 of the multilayel- glass
structure, can be completely adsorbed by the adsorbent 6
which consists of a combination of coated granular zeolite
and coated granular activated carbon to be described in
detail hereinbelow. As a result, fogging to be caused by
the condensation ofC such vapors at low temperatures and
consequent dew deposition can be prevented, and moreover,
even when the multilayer glass structure is handled under
severe conditions, the occurrence of dust and various
troubles attributed to it can be effectively eliminated.
The coated granular zeolite and the coated granula.r
activated carbon can be caused to be present in ar.v desired
ratio in the multila-y er glass structure. Good results
- 6 -
CA 01174221 1994-03-22
can be obtained in regard to the prevention of dew forma-
tion when they are present in a weight ratio of from
95:5 to 30:70, especially from 90:10 to 40:00.
Granular zeolite
witr_ reference ;.o Figure 3 showing the sectional
structure o=' the gran=_,lar zeolite used in this invention,
the granular zeolite shown at 11 has a sectional structure
composed of a core 12 and a shell 13. The marked charac-
teristic of the granular zeolite is that the core 12
contains a synthetic zeolite in a proportion larger than
its average content in the entire granular zeolite and the
shell. 13 contains a clay binder in a proportion larger
than its average content in the entire granular zeolite.
Specifically, the granular zeolite used in this invention
is characteristic over a conventional granular zeolite
comprising a synthetic zeolite and a clay binder present
at the same ratio throughout its entire section in that
it exhibits markedly improved powderization resistance
(abrasior: resistance) and compression strength as a result
of adjusting the proportion of the clay binder in the shell
to a value larger than its average content in the granular
zeolite, and shows better zeolitic properties such as a
combination. of high absorption rate and absorptive
capacity as a result of adjusting the proportion of the
synthetic zeolite in the core to a value larger than its
average corltent in the granular zeolite. Such improve-
ments in a combinatior- of the mechaniaal properties and
zeolitic properties ca~: also be achieved when the shell
has a very small thic~~ess.
It is also important from the standpoint of the speed
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CA 01174221 1994-03-22
of adsorption that the shell of this granular zeolite is
formed of a mixture of the clay binder ar d the synthetic
zeolite. In fact, it is observed that the granular zeo_ite
used in this invention has a considera~ly higher speed
of adsorption than a granular zeolite whose shell is
composed solely of t:.e clay binder. T:; s is presumably
because the s5mthetic zeolite present -in the shell serves
as a passage for a substance to be adsorbed. The con-
stitution of the core by a mixture of the synthetic zeolite
and the clay binder is also important in order to increase
the strength of the entire granular zeolite. It should be
understood that the granular zeolite used in this invention
permits a marked decrease in the total content of the clay
binder and shows a marked improvement in adsorption
speed and adsorptive capacity in comparison with a conven-
tional. granular zeolite hav i_ng the same level of powderi-
zation resistance (abrasion resistance) and compression
strength, and that it has markedly improved powderization
resistance (abrasion resistance) and compression resistar-ce
in comparision with a conventional granular zeolite having
the same level of adsorptive capacity.
n-nhe ratio of the core to the shell in the granular
zeolite used in this invention differs slightly depending
upon the particle diameter of the granular zeolite.
Generally, the suitable weight ratio of the core to the
shell is within the range of from 99:1 to 80:20, especially
within the range of from 98:2 to 85:15. When the propor-
tion of the shell is small, the mechanical properties,
such as ]owderization resistance, of the granular zeolite
ten d to be deteriorated, and when it is larger, its zeo-
litic properties suc:_- as adsorptive power tend to be
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CA 01174221 1994-03-22
deteriorated. The proportion of the shell can be adjusted
to relatively small values when the particle diameter
of the granular zeolite as a whole is large, and can 'be
adjusted to relatively large values when its particle
diameter is small.
The mixt,.:_re constituting the core 12 of the
granular zeolite used in this invention contai_ns the
synthetic zeolite and the clay binder in a weight ratio
of from 90:10 to 60:40, especi ally from 88:12 to 70:30.
The mixture constituting the shell 13, on the other hand,
contains the clay binder and the synthetic zeolite in a
weight ratio of from 95:5 to 30:70, especially from 70:30
to 50:50. Desirably, in order to provide a balanced
combination of mechanical strength and zeolitic properties,
the shell s'nould contain the clay binder in an amount at
least l0;0", ~specially at least 150%, by weight larger than
the clay binder content of the core.
The synthetic zeolite used in this invention may,
for example, be one or more of zeolite A, zeoli te X,
zeolite Y, and synthetic mordenite. Cations of these
zeolites can exist in any desired form such as a sodiuy:,
potassiuM or calcium form. The synthetic zeolite used in
this invention has a particle size of ger_.erally 0.01 to
100 microns, especially 0.1 to 50 microns.
Examples of the clay binder used in this invention
incliide kaolinite-group clay minerals such as kaolin, -
-s.. ..
paly,;orskite-group clay minerals such as attapuljite,
smec,~ite-type clay minerals such as acid clay, -ontr:orii-
lonite and bentonite, and allophane. They can be used
singly or in a combination of two or more. m,~e clav
binder used has a particle d:ia:neter of 0.1 to 1~, micrors,
- 9 -
CA 01174221 1994-03-22
especially 0.5 to 5 microns.
In the production of the granular zeolite used in
this invention, a synthetic zeolite/clay binder mixture
having the aforesaid composition for core formation is
granulated into core particles using an aqueous solution
of a water-soluble polymeric binder as a granulating
medium. Mixing of the synthetic zeolite with the clay
binder can be effected by a dry-blending method using a
known mixer such as a ribbon blender, a conical blender
or a Henschel mixer. The mixture can be granulated in
the aforesaid aqueous solution of polymeric binder as a
granulating medium by granulating means known per se, such
as tumbling granulation, extrusion granulation, spray
granulation, tableting granulation, fluidization granula-
tion, etc. In view of the mechanical strength of the gra-
nular zeolite, the tumbling granulating method is espe-
cially preferred. Granulation is performed by first
preparing seed particles of the aforesaid synthetic
zeolite/clay binder mixer, and adhering a powder of the
above mixture to the seed particles wetted with the
granulating medium, thereby to grow the particles.
The water-soluble polymeric binder can be used in an
amount of 0.01 to 5% by weight, especially 0.05 to 2g3' by
weight, as solids, based on the total weight of the
synthetic zeolite and the clay binder. The amount of the
aqueous solution used as the granulating medium differs
..,., .
depending upon the granulating means, but is preferably
20 to 7C~; by weight, especially 30 to 60% by weight, based
on the total weight of the synthetic zeolite and the
clay binder.
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CA 01174221 1994-03-22
Examples of useful water-soluble polymeric binders
are starch, cyanoethylated starch, carboxymet:~ylated
starch, carboxymethyl cellulose, methyl cellulose,
hydroxyethyl cellulose, polyvinyl alcohol, a vinyl ether/
,. ..s._
maleic acid copolymer, sodium alginate, sodium lignosul-
fonate, aum arabic and tragacanth gum.
The core particles obtained by the above method are
dry-blended with a powder mixture of the synthetic zeolite
and the clay binder having the aforesaid composition for
shell formation to form a coating of the powdery mixture
on the surface of the core particles. The amount of the
powdery mixture to be 'Lnlended with the core particles i s
within the range already specified hereinabove. The core
particles prepared by the above procedure still contains
the solution used as the granulating medium, and by this
solution, the powder of the shell-forming mixture adheres
fi:rmly to the surface of the core particles to form a
coating. Preferably, the dry-blending of the core parti-
cles with the powdery mixture can be easily performed by
charging the powdery mixture, at a time or in a rr.ultipli-
city of portions, into a tumbling granulator including
the as-formed core particles, and operating the granulator.
In preparing the coated branular zeolite, the synthe-
tic zeolite and the clay bir_der forming the shell may be
the sa.~ie as, or different from, the synthetic zeolite
and the clay binder forming the core.
The resulting granular product of the core-shell
structure is dried in the air, and then calcined at a
temperature of 300 to 6500C for 10 to 300 minutes to obtain
a final granular zeolite product.
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CA 01174221 1994-03-22
Desirably, the granular zeolite has a particle size
of gerierally 5 to 32 mesh on a Tyler's standard s ieve .
Granular activated carbon
With reference to Figure 4 showing the sectional
structure of the granular activated carbon used in the
preserlt invention, the granular activated carbon shown at
14 is composed of granular active carbon 15 and a synthe-
tic resin latex coating 16 formed on its surface. The
markeci characteristic of this coating 16 is that because
it is formed of a synthetic resin latex, it can greatly
inhibit the occurrence of dust without substantially
reducing the adsorptive power of activated carbon for an
organic solvent. This advantage will become immediately
clear from the results of working examples to be given
hereinbelow.
It has not been fully clear why the granular activated
carbor. used in this invention has improved powderization
resistance without a marked reduction in its adsorptive
power for an organic solvent. It is presumed however
that since the coating 16 is denived from a synthetic
resin latex, it is in the form of a film having a number
of pores or a netting, it is permeable to a vapor of an
organic solvent but acts as a coating sufficient to prevent
wear of activated carbon, and moreover this coating acts
as a a:r~:ioning material for absorbing shock, etc.
The granular activated carbon itself used in this
invention may be obtained from"coal, petroleum residues,
charcoal, fruit shells, etc. by an activating method using
any of a gas such as steam or carbon dioxide gas and a
chemical such as zinc chloride and phosphoric acid. It
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CA 01174221 1994-03-22
may have aBFT specific surface area of 500 to 2,000
m2/g and a particle size of 4 to 30 mesh and be in a
spheri_cal, cylindrical or irregular form. From the
viewpoint of powderization resistance, spherical particles
of activated carbon are especiall_y preferred.
The synthetic resin latex coating agent is an aqueous
emulsion of a synthetic resin, and one, or a combination
of twc> or more, of the following synthetic resins can, for
example, be used as the synthetic resin.
1) A butadiene polymer, or a copolymer of butadiene
with styrene, a styrene derivative, acrylonitrile, methac-
ryloni.tril, isoprene, isobutylene, etc.
2) A copolymer of isoprene with styrene or a styrene
derivative.
3) A chloroprene poly?~er, or a-copolymer of chloro-
prene with styrene, a styrene derivative, acrylonitrile or
isoprene.
L) A copolymer of an acrylate ester with styrene, a
styrer.Le derivative, vinyl chloride, vinyl acetate, acrylo-
nitrile, or a methacrylate ester.
5) A methacrylonitrile polymer and a copolymer of
methacrylonitrile with styrene, etc.
6) A vinyl acetate polymer, and a vinyl chloride
polymer.
These synthetic resins may be carboxy-modified or
modified by other suitable treatments.
-,.. .
The amount of the latex used is 1 to 20% by weight,
preferablv 2 to 50/6 bv weight, as solids based on the
weight of the activated carbon itself. If the amount of
the latex is less than 10/0' bv weight, the effect of improving
- 13 -
CA 01174221 1994-03-22
powderization resi stance is small. When it is more tra~bv wei,;'r:t , the er
fect of improving po~~:derization
resistance is ;;reat, but the gas adsorbing abilit,~- of
the oroduct is reduced.
The suitable solias concentration of t:e late,. use;
is 10 to 5Cx; ',-;y weight, a.nd the amount of t:e latex usee
is preferably 0.2 to 1.0 times the weight o_ the activated
carbon.
CoatinS of the surface of the activated carbo n ma,:
be performed by spra,ring the latex onto the surface of t he
activated carbon by a suitable method, or imnregnating the
activated carbon in the latex. The coated product is then
dried at 100 to 150 C to give coated granular activated
carbon havinp improved powder.ization resistance.
CoLbirlation adsorbent
The granular zeolite used in this invention has the
property of adsorbing a very large F-mount of water ever
whe n the hum:iuity is extremely low, and also of a adsor'c-
ir_F: a f ixed amour_t of water almost irrespec t_ 1e of the
relative humidity of r20 (i .e ., the partial pressure of
0
water vapor -:er saturated water vapor pressu_e at 20 C).
On the other hand, the granular activated carbon has t he
proo ert y of adsorbing a much larger amount o f an organi c
so:~vent such as xylene and methyl ethyl ketone than otrer
adsorbents, and o-I adsorbing a fixed amount of the or~a.:.ic
solvent almosr i rresnective of the specific pressure of
.... .
the organic solvent vanor. In addition, the 'õanu?ar
activated car'_~o:7 has the property of selectively adsor;.i ng
organic solvents even in tre presence of a water vanor.
;0 Thus, b:,=_,sing the granular zeolite anc t?:e -ranular
- 14 -
CA 01174221 1994-03-22
activated carbon in combination in accordance with this
invention, vaporous components within a multilayer glass
structure are most effectively adsorbed, and dew deposi-
tion on the glass or fogging can be prevented stably
over a long period of time even when the temperature
varies considerably.
~urthermore, the granular zeolite and granular
activated carbon used in this invention have excellent
powderization resistance against handling under severe
condi'tions. In addition, even a mixture of these materials
having different properties shows outstandingly good
powderization resistance, and the occurrence of dust is
scarcely observed even during handling under severe
condi-tions .
In the present invention, the= granular zeolite and
the granular activated carbon can be caused to be present
in an,desired state in the multilayer glass structure so
long as they exist together in the glass structure.
Specifically, they can be present separately in different
spaces within the spacer of the glass structure, or they
may be present as a mixture in the same space in the
spacer. For example, in the former case, the granular
activated carbon may be filled in a spacer portion
located at the lower side of the glass structure, and the
granular zeolite, in a spacer portion located at the
upper or lateral side of the glass structure. According
.s.. .
to this embodiment, segregation between the granular zeo-
lite and the granular activated carbon and the consequent
nonuniformity in composition can be prevented, and
abrasion or pot:derization which may be caused by the mixing
- 15 -
CA 01174221 1994-03-22
of the dissimilar materials can be completely prevented.
In the latter case, the operation of producing the
multilayer glass structure becomes easy if the granular
activated carbon and the granular zeolite are mixed in
advance at a predetermined ratio.
The adsorbent used in the multilayer glass structure
of this invention may, as desired, contain another adsor-
bent in addition to the aforesaid essential components.
In one embodiment of this invention, not more than
70% by weight, especially 10 to 600/6 by weight, based on
the total weight of the granular zeolite and the granular
activated carbon, of granular alumina-silica gel is
additionally used. This results in a further improvement
in water adsorbing ability under high humidity conditions,
and a, multilayer glass structure having better adsorbing
properties can be obtained. Such a granular alumina-
silica gel is known per se, and those described in the
specifications of Japanese Patent Publications Nos.
17002/1963, 16347/1965 and 8446/1972 can be suitably
used.
The suitable amount of the combination adsorbent
described hereinabove is generally 20 to 300 g, especially
40 to 200 g, per unit area (m2) of the multilayer glass
although it may vary depending upon the distance between
ad6acent glass sheets.
All sealants heretofore used in this type of multilayer
-f.-b
glass structures can erused as the sealant in accordance
with this invention. r~,xa.mples include two-component type
sealants based on polysulfide-type rubbers, one-component
type elastic sealants based on butyl rubber, and one-component
- 16 -
CA 01174221 1994-03-22
type elastic sealants based on urethane rubber.
According to this invention, excellent ability to
prevent dew formation can be obtained even when such
sealants are of the organic solvent type.
The following examples illustrate the present inven-
tion in greater detail.
Referential Example 1
'I'wenty parts by weight of a dry powder of kaolin
dried at 150 C was mixed with 80 parts by weight of a
dry powder of 4A-type synthetic zeolite dried at 1500 C,
and they were fully mixed by a V-shaped mixer to form a
powdery mixture of synthetic zeolite and kaolin. A por~
tion (about 25 ko) of the resulting powdery mixture was
put in a tu.mbling granulator, and molded while spraying
water by means of a spray nozzle. The product ivas sieved
to remove fine particles and obtain spherical granules
having a size of 0.25 to 0.5 mm.
The resulting spherical granules were used as a
nucleus and tumbled by a tumbling granulator, and the
powdery mixture prepared above and a 0.5% aqueous solu-
tion of sodium lignosulfonate were gradually added to
the granules. In this way, a zeolite layer was grown on
the surface of the nucleus over the course of 2 hours to
produce a wet spherical zeolite core.
- 17 -
CA 01174221 1994-03-22
Table 1
Powdery mi;-.ture as a shell comnonent
Invention
S-1 95 parts by weight of kaolin and 5 parts
by weight of zeolite
S-2 50 parts by weight of kaolin and 50 parts
by weight of zeolite
Comparison
S-3 Kaolin alone
S-4 Dried and-calcined without coating
Sixty kilograms of the core produced as above was
put in a tumbling granulator, and while it was being tumbled,
3 kg of the powder S-1 shown in Table 1 was added to coat
the surface of the core to give a spherical zeolite having
a narticle diameter of 0.3 to 3.0 mm. By a similar
method, products coated with the powders S-2 and S-3
respectively were obtained. Also, a spherical zeolite
having a particle diameter of 0.5 to 3.0 mm was produced
without performing the aforesaid coating (the product is
designated as S-4).
The resulting wet spherical zeolite was dried in the
air (spontaneously dried), dried in an atmosphere kept at
100 to 150 C for 3 hours, a.nd then calcined at 550 + 300 C
for 3 hours. The resulting abrasion-resistant zeolites
7.:ere examined for co,:,pression strength, percent ahrasioji,
pac'king density, equilibrium amount of water adsorption,
water adsorption speed, and percent powderization bv the
~o1lowin;; methods, and the results are shown in Table 2.
I. Co -mpression streno th
The comtiression brea'cino strengths of 20 samples were
measured by a hardness meter (maxi:-n_:~: measured
- 18 -
CA 01174221 1994-03-22
value 10 kg; supplied by Kiya Seisakusho, Japan). The
maximum and minimu7, measured values were excluded, and
an averaoe of the remaining 18 measured values was cal-
culated and expressed as the compression strength.
2. Percent: abrasion
A 130 rie glass vessel was charged with 40 g of the
sample, to which -water was adsorbed to saturation and
which was then dried at 15 0 C for 3 hours, and 100 m4 of
wat er . Tr.en, the glass vessel was attached to a pai nt
conditioner (supplied by Red Devil Inc.) and shaken for
30 minutes. After the powder adhering to the sample was
removed, the sample was dried at 150 C and its weight
was measured. The percent abrasion (%) was calculated from
the folloi=iing equation.
Weight of the
sample after
Percen -, abrasion the wear test x 100
Weight of the
sample before
the test
3. Packing density
A 500 m..e graduated cylinder was charged with 200 g
of the sample. The cylinder was placed on a rubber plate,
and lightly tapped. The volume V (liter) of the sample
was read when it no longer showed a change. The packing
density of the sample was calculated from the follo,aing
ea_uatior_.
200
Packin~ density (g/liter) _
V
4. Equilibrium amount of water adsorption
T~_e sar-ple (0.15 g) was placed in a quartz micro-
balar.~.ce water adsorption tester, and deaeration was
carried out at 200 , lor 2 hours. Then, the equilioriu n
- 19 -
CA 01174221 1994-03-22
amount of water adsorption at a temperature of 20 C and
a relative humidity of 755' was calculated from the
following equation.
Amount (g) of
E~'quilibrium amou:-_t (~) = adsorbed water x 100
of water adsorption
Amount (g) of
the sample
5. :,,later adsorption speed
The sample (0.15 g) having a particle size of 1.5 to
1.6 mm was placed ir_ a quartz microbalance water adsorntion
tester, and deaeration was carried out at 2000 C for 2
hours. The amount (mg) of water adsorbed was measured
at a temperature of 20 C and a relative humidity of 20;.3'
every 1 minut:e. The t_me (in minutes) and the amount (in
milligrams) of adsorbed water were plotted on the abscissa
and o:rdir_ate, respectively, to obtain a water adsorption
curve. The gradier.t of a straight line formed by connec-
ting the amount of adsorbed water corresponding to an
adsorption time of 110, minutes to the origin was deter-
mined, and defined as the water adsorption speed. The
water adsorption speed was expressed in g/100 g of sarspie/
min.
6. Percent powderization
F'iftv grams oT the sample which was caused to absorb
moisture fully by being left to stand at room temperature
for 48 hours was put in a standard sieve (JIS Z-8801).
The sieve was mounted on a shaking machine, and subjected
-, . . ,.
for 30 minutes to the rotating movement of the shaking
machine and the impact force of the ha.-=er. The weight
loss of the sample was measured, and the percer_t powderi-
zation was calculate-' rrom the following equation.
~ ~..
CA 01174221 1994-03-22
Amount of the
(Amount of 1- r sample after
Percent pow- _- 1 the samplel 'the test
derization (g~) x 100
Amount of the sample
More specific -iesting conditions were as follows:
Standard sieve (JIS Z-8801): consisting of a 28-.;~esh
sieve, a 60-mesh sieve and a 4-mesh sieve each
havinj a diameter 15 cro stacked in this order.
The sample was put in the 28-mesh sieve.
Amount of the sample: 50 g of the moisture-zbsorbed
sample.
Shaking machine: the machine described in JIS R-6002
(1978); rotating speed 290.cycles/min.; the
number of impacts 156/min.
- 21 -
Table 2
Compression Percent Packing Equilibrium amount Water adsorp- Percent
stren~th abrasion ( o) density of water adsorption tion speed powderiz
(k~~ (;J J2) (9a) (gll00 g of tion (; )
sample/min.)
Invention
S-1 5.1 1.7 880 18.20 0.90 0.3
~-2 4.3 4.0 870 21.90 1.30 0.2
Comparison
6.3 1.2 885 15.56 0.50 0.2
;;-4 2.0 12.8 840 22.E30 1..IEg 2.8
CA 01174221 1994-03-22
It is seen from Table 2 that the 4A -type spherica=
zeolite S-3 produced in the comparative run i s inferior
in the equilibrium a-"-nount of water adsorption and the
water adsorption speeu and the zeolite S-4 in the compara-
tive run has a hign aercent powderization, and therefore,
both of these zeolites are unsuitable as the adsorbent
used for the objects of the present invention.
Referential Example 2
Sixty parts by ;aeight of a dry powder of 4A-type
synthetic zeolite was mixed fully with 40 parts by weig~_t
of a dry powder of kaolin in a V-shaped mixer to produce
a powdery mixture of synthetic zeolite and kaolin. The
resulting powdery mixture was molded by a tumbling
granulator through the formation of a nucleus in the sa-e
way as in Referential Example 1 to produce a wet granul-,::-
zeolite core. Sixty kilograms of the wet granular zeolite
core was put in a tumbling granulator, and with tumblinz-,
6 kg of a powdery mixture of .50 parts by weight of kaol_~
and 50 parts by weiF~nt of synthetic zeolite for shell
formation, prepared bv thorough mixing, was added and
coated on the surface of the wet granular zeolite core
the same way as in Referential Example 1 to form a spher_cal
granulated product having a particle diameter of 1.5 to
3.0 mm. The product is designated as S-5.
For comparison, 50 parts by weight of a dry powder or
4a-type synthetic zeolite was fully mixed with 50 parts
'weight of a dry pol;rder of kaolin by a V-shaped mixer to
prepare a powdery mixture of synthetic zeolite and kaol_~.
The powdery mixture was molded by a tumbling granulator
throuoh the for:nation of a nucleus in the same wav as i-
-23-
CA 01174221 1994-03-22
Referential Example 1 to produce a wet sDherical zeolite
core. Sixty kilograms of the wet granular zeolite was
put in a tumbling granulator, and with tu-mbling, 6 kg of
a mixture of 60 parts bv weight of kaolin and 40 parts
by weight of synthetic zeolite, prepared by thorough
mixing, was was added and coated on the surface of the
granular zeolite core in the same way as in Referential
Example 1 to give a spherical granulated product having
a particle diameter of 1.5 to 3.0 mm. This product is
designated as S-6.
Each of S-5 and S-6 was dried and calcined in the
same way as in Referential Example 1. The compression
st rength, percent abrasion, packing density, equilibrium
amount of water adsorption, water adsorption speed and
percent powderization of the products were measured as
in,Referential Example 1, and the results are shown in
Table 3.
Table 3
Compression Percent Packing Equilibrium amount Water a asorp= l-)ercent
stren th abrasion (%) density of water adsorption tion speed powderiza-
(k~~ W-0 (/) (p/100 g of tion (;)
sample/min.)
S-5 9.5 0.7 890 17.5 0.85 0.1
(invention)
S-6
(compari- 12.6 0.5 900 14.5 0.40 0.1
son)
CA 01174221 1994-03-22
It is s"n from Table 3 that since the 4n-t,*pe
spherical zeolite S-6 produced in the compar2.tive ran
has a lovr percent powderization but is inferior i n the
equilibrium amount of water adsorption and the water
adso-ffstion speed, it. is unsuitable as the adsorbent used
for the objects of this inver_t:on.
Referential Example 3
Plinety parts by weight of a dried powder of 4A-type
synthetic zeolite was mixed fully with 10 parts by weight
of a dr1y, powder of attap'ulgite by a
V-s'iaped mixer to prepare a powdery mixture of synthetic
zeolJ.te a*_'1ct attapulgite.. The powdery mixture was molded in a
tumblin- granulator through th e formation of a nucleus in
the same way as in Referential F,xample 1 to produce a wet
spherical zeolite core.
Sixty kilograms of the wet granular zeolite core was
put in a tumbling granulator, ar_d with tumbling, 6 kg of
a powder S-7 shoi,rn in Table 4 as a shell-forming component
was adde:. and coated on the surface of the core i n the
same wa%: as in Referential Example 1 to give a spherical
zeolite having a particle diameter of 1.5 to 3.0 mm.
For comparison, a spherical zeolite was obtained bv
a similar raethod to the above using the powder S-c shown
in Table 4 .
-2 6-
CA 01174221 1994-03-22
Table 4
Designation Powdery mixture as a shell-forming
comuonent
S-7 (invention) 70 parts by weight of zeolite and 30
parts by weig?it of attapulgite
S-8 (co~:nari- 80 parts by weight of zeolite and 20
son) parts by weight of attapulgite
S-9 (comnari- 30 parts by wei ght of zeolite and 70
son) parts by weight of attapulgite
For comparison, 95 parts by weight of a dry powder of
4A-type synthetic zeolite and 5 parts by weight of
attapulgite were fully mixed by a V-shaped
mixer to prepare a powdery mixture of synthetic zeolite
and attapulgite. The powdery mixture was molded in a tumbling
granulating machine through the formation of a nucleus
in the same way as in Referential Example 1 to prodizce a
wet spherical zeolite core. Sixty kilograms of the wet
granular zeolite was put in a tumbling granulator, and
with tumbling, 6 kg of the powder S-9 shown in Table 4
for shell formation was added and coated on the surface -
of the core in the sa-me way as in Referential Exarmle 1
to give a spherical zeolite having a particle diameter
of 1.5 to 3.0 mm.
The compression strength, percent abrasion, packing
densitv, equilibrium amount of water adsorption, water
adsorption speed and percent bowderization of the resulting
products S-7, S-8 and S-9 were measured in the same way
as in Referential Example 1, and the results are shown
in Table 5.
Table 5
Compression Percent Packing Equilibrium amount Water adsorp- Percent
strength abrasion ( o] density of watcr adsorption tion speed powderiza-
(kg) (/) (g/100 g of tion (io)
sample/min.)
( i nvc r;t ion) 3.2 5.0 820 22 .50 1.30 0.3 ~;-F3
(comparison) 2.8 7.0 800 22.70 1.32 2.5
N o
~ r
~
1.0 13.5 780 23.00 1.40 4.5 "
(comparison)
0
W
N
CA 01174221 1994-03-22
It is seen from Table 5 that the 4A-type spherical
zeolites S-8 and S-9 produced in the comparative runs
are unsuitable as the adsorbent used for the objects of
this invention because they show a high percent powderi-
zation.
Referential Example 4
A synthetic rubber latex (a carboxyl-modified styrene-
butadiene copolymer latex; solids concentration 47 16 by
weight) was diluted with water to form a diluted emulsion
having a solids concentration of 10g,0' by weight. Then,
10 m.e, 25 mX or 50 m.Q of the diluted emulsion was sprayed
by a hand sprayer onto 100 g of spherical coal-base acti-
vated'carbon having a BET specific surface area of 1,080
m2/g and a particle diameter of 1.68 to 0.5 mm and obtained
by a steam activating method, while the activated carbon
was agitatec.. The activated carbon was then dried by an
air bath dryer at 100 C. Thus, activated carbons S-10,
S-11 and S-12 treated to reduce powderization a.nd having
different amounts of the latex used were obtained.
For comparison, 5 m-0 of the diluted synthetic rubber
latex was sprayed onto 100 g of the same activated
carbon as above by operating in the same way as above to
give ari activated carbon S-13 treated to reduce powderi-
zation and containing a different amount of the latex.
The followin-g properties of the treated activated
carbons were measured by the methods described. The results
are sho)rm in Table 6.
1. Abrasion resistant strength
The abrasion resistance of the sample was measured by
a micro-strength method, and the percent powderization of
- 29 -
CA 01174221 1994-03-22
the activated carbon particles was calculated and compared
with that of a non-treated product (control).
Conditions for the measurement oi' micro-strength
Sample receptacle: A 150 m.9 stainless steel cylinder
having a diameter of 25 mm and a height of 305 mm
rmount of the sample filled: 50 mX
F.otating speed: 20 rpm
Rotating time: 30 minutes
Total numbe.r of rotations: 600
Method of measuring the percent powderization
Amount of \ Amount of the
Percent ~the sample ) - ~ sample after ~
powderi- = weighed / the measurement x 100
zation (/) Amount of the sample weighed
The samples both before and after the measurement
were those left on a 32-mesh sieve after sievino on it
for 5 minutes using a Ro-Tap Sieve Shaker.
2. Equilibrium amount of acetone adsorbed
ir accordance with the method of JIS K-1474, the
eauilibrium amount of acetone gas (37.5 g/m3) adsorbed
was i~easured at 25 C C.
-30-
CA 01174221 1994-03-22
1.7able 6
Sample _ryo. :-mount o= the Percent Equilibrium
latex used powderi- amount of acetone
(solids, 4rt~-S) zation(;'~) adsorbed (~~)
S-i0 1.0 0.65 28.5
S-11 2.5 0.12 28.3 S-12 S.C. 0.10 27.9
S-13 0 .; 2.4 28.5
( c ompari sor )
Untreated
activated 0 2.6 ,28 .5
carbon
I The treated activated carbon produced in the com-
parative ru:.n had the excellent ability to adsorb an
organic gas as sho',m by its equilibrium amount of
acetone adsorbed, but had low abrasion-resistant
strenoth represented by its percent powderization. Hence,
it is u_nsuitable as the adsorbent used for the ob,4ects
of this invent ion .
Referenti al Example 5
A s%mthetic rubber latex (a carboxyl-modified
butadier_e-ac-rvlonitrile copolymer latex; solids concen-
tra-tion 45;)' by weight) was diluted with water to prepare
a dilutea', e-nulsion havino a solids concentration of 2a,
by weight. Then, 75 m.0 or 100 m.0 of the diluted emulsion
was sprayed by a hand sprayer on 100 g of coconut-oase
cylindrical activate:: carbon having a BET specific
surface . area of 1,150 m2/g and a particle diameter of
2.38 to 1.41 and o'etained by a steam activatin,,,,
method ,w:<<le the activated carbon was agitated . T~ e
activated carbon was then dried in an air bath dryer at
100 C. Tiius, activated carbons S-14 and S-15 treate::
- 31 -
CA 01174221 1994-03-22
to reduce nowderizat_on and having different amounts of
the latex used were o~tained.
For comparison, 83 m.9 of a diluted emulsion havir.7
a solids concentration of 30 ,o by weight obtained by
diluting the aforesa=d synthetic rubber latex with wateT
was sprayed onto 1GC, ? of the same activated carbon as
above to give an act_vated carbon S-16 treated to reduce
powderization and ha-/ing a different amount of the latex
used.
In the same way as in Referential Example 4, the
Properties of the treated activated carbons were mea-
sured, and the results are shown in Table 7.
Table 7
Sample Tv'o. Amount o_ Percent Equilibrium amount of
the latex powderi- acetone adsorbed (c.6)
used (scl- zation
ids , w1~:') (;o
S-14 15.0 0 24.0
3-15 20.0 0 15.0
s-16 24.9 0 4.5
( comparison )
The treated activated carbon produced in the compa-
rative run had excellent abrasion-resistant strength
shov.m by its percent powderization, but had the low
ability to adsorb an organic gas shown by its equil.i-
,rium amount of acetone adsorbed. Hence, it is unsui-
table as the adsorbent used for the obJects of this
invenfiion.
Ref erent i al Example -5
The water adsor-t_on isotherms of the 4A-type
spherical zeolite S--,-' nroduced in aeferential ;xanDle 1
a..nd the treated sp::e:rical activated carbon 3-12 are shou-_
CA 01174221 1994-03-22
in Figure 5. Furthermore, Figures 6 and 7 show the
methyl ethyl ketone (I~K) and m-xylene (solvents for
sealing agents for a multilayer glass structure) adsorp-
tion isotherms of the aUove zeolite S-2 and activated
carbon S-12 at a relative humidity of 43% and 20",
res?oectivel,,r. For comnarison, the results obtained with
commercially available 4A-type zeolite an:: silica gel
are also shown in Figures 5, 6 and 7. In these Figures,
the refer.ence numeral 21 refers to the curve of the zeo-
lite S-2; 22, the curve of the activated carbon S-12;
23, the curve of the commerci.ally available silica gel;
and 21_4, the curve of the commercially available 4A-type
zeolite.
The above properties were measured by the following
testi.ng, methods.
(1) ',later adsorption isotherms
By using the quartz microbalance-type water absorp -
tion tester used i_n Referential EVample 1, the eauilib-ated
anourit of water adsorbed at each relative hLenidity was
measured.
(2) TfiEK or m-xylene adsorption isotherms
B?T using the gas circulating-type adsorption testing
device shown in Figure 8, these isotherms were determined
under the following condit ions .
Measuring operation;-
(1) By operatino a gas flow passage switching cock G,
..,.. .,
tne gas circulating passage in Figure 8 was changed to
a by-path fio:=: passage F. About 2 grams of the sample
was prec is el1. weighed and filled i n a sample colu_TMn L
3C made of glass a.na having a diameter of 37.5 mm. The
_ ~~ _
CA 01174221 1994-03-22
columr -rras then set in the device.
(2) A diaphragm pump B was operated, and while circu-
lat ing air having a fixed humidit-%T in a gas holder A,
a predetermined amount of TTEK or m-xylene was injected
from a gas in;;ecting port E. :nile continuing the cir-
culation of the gas, the gas was sampled froin the gas
sampling port E and its concentration was analyzed by
gas chro:natography.
(3) ;;hen the concentration of the gas became steady,
the cock G was operated to switch the gas flow passage
over to the side of the sample column D. The gas was
sampled every predetermined time to measure periodic
variations in the concentration of the gas.
(4) ',dhen the concentration of the gas in the gas holder
A became steady and reached an equilibrium, the cock G
was operated to switch the gas flow passage over to the
by-path F. The operation s(2) and (3) were then repeated,
and the equilibrium point of the concentration o'L the ~as
.
was measured s iTM~ilarly.
2C (5) An equilibrium absorption curve could be obtained
by the following procedure from the results o.i the above
measurei-ient.
In Figri.zre 8, ti,.e reference letter C represents a
flow ineter, and the reference letter H, a saturat-ed
potassium acetate solution (,~~ 20;0) or a saturated
potassium carbonate solution (RH 43 /).
=:s. Y
With regard to the results of the measurement of t:;e
periodic variations of the co ncentration of the gas, t_ e
concent_ation of the gas at the time when it became
;0 steady ti%,as taken as the equilibrium concentration. Fro---34-
CA 01174221 1994-03-22
the amourt of MEK or m-xylene injected until the equil?-
briu.m corcentration was reached, the amount of T1EK or
m xylene remainino in the system after the measurement,
and also from the amount of the sample used in the
measure-~e~it, the equilibrium amount of adsorption was
calculated in accordance with the following equation, and
plotted a;ainst t~e corresponding equilibrium concen-
tration. Thus, an equilibrium adsorption curve was
obtained.
VCo(1 - Cs/Co)
G =
w
wherei.n
C: the equilibrium amount of adsorption (mg/g-
a.dsorbent )
tr: the total volume of the gas (liter)
Co: the initial concentration of the gas (mg/liter)
Cs: the equilibrium concentration of the gas
(mg/liter)
;r: the amount of the sample (g)
Example 1
In a room kept at a temperature of 250 C and a rela-
tive humidity of 5 a"), 15 g of a mixed adsorbent composed
of 951"6 b~,r weight of the 4A-type spherical zeolite 5-2
having a particle diameter of 1.68 to 0.84 mra produced
in Referential Example 1 and 5% bv wei g_ht of the treated
spherica activated carbon S-12 having a particle diameter
..f=, r
of 1.68 to 0.50 mr-i produced iri Referential Example 4
was filled in alu~i um spacers for a r:~;ltilayer glass
structure of the t-pe shoz,m in Figures 1 and 2. B-y
connectirn~ trie cor:1e_ portions of the spacers by neans
CA 01174221 1994-03-22
of correr ::el-s, amultilaver glass windov, frame was
constructed. Then, those parts of the spacers to which
glass s_:eei:s were to be bonded were fully cleane-d by a
cloth i=regnated with toluene, and dried. Then, a
both slarface-adhesive tape was applied to the c2eaned
portions, and glass sheets having a thickuness of 3 mm
were bon::ed to the tane. A sealant obtained by fully
kneading a polysulfide type (Thiokol) liquid polymer and
a vulcanizer in a ratio of 100:10 was filled in the
spaces between the spacers and the glass sheets bv
using a sealing gu-n, and then allowed to stand indoors
for 24 hours to cure the sealant. Thus, a oultilayer
glass structure, 30 cm in length, 30 cm in width and 12
mm iri t1_ickness, was constructed. The dew point of the
multilayer glass structure was measured under the follow-
ing conditions in accordance.with JIS R-3209 (1979) 8.4,
and the res-..ilt s are shown in Table 8.
De-v: po.int rleasuri ng conditions : -
(1) In:itial dew point: After maintaining the sample
at 20 C for 12 hours, the deti;, point was
measured.
(2) riic;h temperature hioh humidity resistant test:
The dew point was measured after the sample
was e:tiposed for 14 days under the conditions
8 =5 =2 of JIS R-3209.
E.xa.. ~ l e 2
A - _Itii~.yer glass structure, 30 cm ir. ler>~th, 30
cm in :=:~::t:=, and 12 in thickness, was constructed in
the sar..~_ as in E.t:am, le 1 except th at 7;; of a
c''..v.c..or,--e._., cC'i"~DoseQ C'i_ 71~;.') :elbT .t o1 tl1e
- ~ .~
CA 01174221 1994-03-22
sp:-.erical zeolite S-5 havin27 a part_cle diameter of 1.63
to 0.84 mm ;,-_rod-aced in PLeferential _x-ample 2 and 30c;
b~r weizht oi' the treated spherical activated carbon havin,'-
a particle diameter of 1.65 to 0.50 TT: produced in ?eferen-
tial Example 4 ti=,,as filled in the spacers. The
deN~
poin-t oi thegiass structure was measured ir_~ ti:e sa!7:e
we.t>r as in ~;_.a-nle 1. The results are sho:=m in ~able S.
D;amnle 3
A Mul -.; layer ~;lass structure, :;0 cm in len~th, 30
cm, in widtil and 12 mm in thickness, was constructed in
the same way as i n Example 1 excep t that 10.0 ~ oi a
mixed adsor-Cent composed of 30, by i.reio'ht of the 4?-tvpe
sn::ericc,l zeolite S-2 having a particle diameter of 1.68
to 0.84 mm *orociuced in Referential Exa::ple 1 and 70;;
bv veight o= the treated sn_:erical activated car or
S-12 havir..'; a particle dia.meter of 1.b8 to 0.5:,mm produccd
in Referential '-7xa~le 4 was filleu in the snacers. "he
dew point of the glass structure was measured in the same
wa:r as in :~',;a..:_ple 1. ~he results are shot=rn in ~a--le 8.
D;a_mple 4
A multilaver c-lass structure, 30 cm in ler.'th, 30
cir in .Vidth and 12 mm in thickness, was constr,.:cted in
the sar:e -aa~- as in Example 1 exce~t that 12.0 ~ of a
mixed adsor: ent co::,, osed o~ 7 Cx b1- .;,eignt of tne 4~,-t,rpe
sp1-ierical zeolite S-2 havinE a nart_cle diameter of 2.38
to 1.41 mm produced in -jefrrer_tial ;xample 1 an;_ 3G;
by weight of the treated s-:,herical activa.ted car': or. s,-14
I7 '~,. . L mm a 1?a.i 1Cle d~I',!"_?C-er of 2. i~ ~O 1 1 : :='Dd' ced
eiel"e' ~~ .._ Exui::ale as .~_1in t:@ SDacers ~'11e
.
C' e.v Dol.nt of the ~lass structure ~.s*as measured =.. the
CA 01174221 1994-03-22
same way as in Example 1. ~~e results are sho-::-:-_ in
TaUle 8.
Comparative Example 1
.A mult-ilayer Llass str_ctare, 30 cm in le_:-tn,
30 cm i n and 12 mm in tr i ckness, was' co-_structed
in the sa_e v.,ay as in Exarp =e 1 except t:~at 15 of t:_e
4A-t;rpe snherical zeolite 2-2 having a partic-e diameter
of 1.68 to 0.84 rnm produced in Referential Exa---~ile 1
alone was filled as an adsorbent in the spacers. The
de~,~ point of' the glass struct~.zre was meastared iNthe same
way as in Ex:ample 1. The res=slts are shov.rr: in ~ahle E.
Compa.rative ;xample 2
? multilayer ~lass structure, 30 cm in leõ'th, 30
cm _r width and 12 r:m in th.:c:=:ness, v,,as const_ ucted in
the same vray as in Example 1 except that 10.0 1- of the
treated spherical activated carbon S-12 havinc-; a parti cle
diaTMeter of 1.68 to 0.50 mm, nroduced in Referential
Example 4 alone was filled _r the spacers. T:,~.e devj
point of the glass structure -.~as measured in tne_ same
~ ,,iay as in Example l. The re-s-_ilts are sho::=n -able S.
Com-oarative Example 3
A multilaver L,-,lass structure, 30 cm in ler :-th, 30
c,~n i- ~,ridt'n, and 12 mm in t:_c~ess, was constr.:cted in
the same way as ir_ Example i except that 15 E of a
mixed adsorbent com~osed of 5Cc; by weight of L'-type
spherical zeolite having a p,aNticle di s_meter of 1.68 to
C.84 m~~: and 5:r6 by wei -ht of sjheri cal sil i ca _ e- havir~;
a p rt_cle v_ameter oi' 1.6S to 0.84 both _
-1 ~
com:7,erciallv availa'cle as acsor'tent for mult;, -er
~~~ ',lass str.zctures, :ras fille~ _n the spacers. ~: e de.,
CA 01174221 1994-03-22
point of t':-Ie glass structure was measar ea in the same
way as in ~xample 1. ~ne -results are snovrn in Table E.
-39-
Table 8
i;xample "aixin,~; ratio of the Amount of the new point ( C)
aC) sor be n t:, (wt." i '~ " ":~Vl" ..4J""'Cil'" i~'~_ ~
~ ~ ~b~.ll. ~)
Initial After the high tem-
Zeolite Activated perature high humidi,
carbon resistant
te~t
1 95 ~ 15 -60.0 -66.5
2 70 30 7 -47. 0 -1~~3 . 0
70 1C>
4 70 30 12 -52.0 -59 . 0
( i N
Comp. px. 1 100 0 15 -32 . 0 -21 .O
. ,,
Comp. Tx . 2 0 100 10 -23 . 0 -10 , 0
Comp. Ex. 3 zeolite ~ilica gel 15 -Q.0 -33 .0
50 50
'~~r=p"I e 5 CA 01174221 1994-03-22
A ru lt:.1_ 'er c-;1ass s t1_ _,ct-:::re, 30 cri
c~'. in width and 12 ~n t--ic!.'_"iess, was conS trucZe~.i 1n
.he same wav as in E-c-r--le 1 excent that 15 _n total
o the 4-t ~e sr_heri ce.i zeolite S-2 havinS :-~e.rt;_cle
4iameter o= 1.68 to 0.S U~oduced in refere:-itial
7xamn-le 1 and the treated s-oh'rical 2.ctivatec carcon S-12
havin;; a particle diaTeter o_ 1.68 to 0.50 mw produced
' n Referential Erample L t:Tere separately filled in a
ratio of 80:20 in the soac ers . The dew point of the
-lass structure <<,as *;ee.sured in the same way as in
~a:nple 1. The resuI.ts are s:o,,tirn ir. Table 9.
x ar~le o.
A multi:Lay er glass struc ture, 30 cm in length, 30
c:~. in widt:, and 12 nL_. irthickness, iias constructed in
the same t.,a_: as in -7_-a---=e 1 except that 10 g in total
o, the 4A-t ype spherical zeolite S-2 havinv a particle
.:iameter of 1..68 to C.2L :~_:~ produced in Referential
:_:,x; mple 1ar.d the treated sJhe.rical e,ctivated car,--a:-l
3-12 havir;r- a particle d_a_-eter of 1.68 to 0.J
r oauced ir. Referentiai D:a-7ple 4 were filled separatel y
a rati-o of 40:60 in t-.e sDacers . The .::~eiv Doint of
tne },lass structure %-ras -:eas,_,red i n the same wG,; as
ir ~xamnl e 1. The re s~it s are shown in Table 9.
Li
CA 01174221 1994-03-22 O \
a-~~le :=_atio of t:~e motal DeT.! Noi:~t ( C1
adsoN'wents ( ay.:ount
b-,~ z::eio~ t_n e T_nitial ;f1er t1-) e
adsor- nic,n ter=jere.-
Zeoli te ~-ct-vated bents ture hi~~n
t
c'.~..õ - on (~) h',.ii~ i d l 1 ~yr
i.
resistant test
80 2~ 15 -60.0 -,8.0
6 40 -48.0 -52.5
a~nle 7
multila;rer ~lass structure, 30 cm in len;tn,
30 cr~ in w; dtn and 12 mm in tnickness, was constructed
5 in the sarrie way as i n D~amnle 1 except that 15 E of a
mixed adsorbent coTMposed of 50~1' by wei;ht of the 4?-type
spheri cal zeolite S-7 havin' a narticle diameter of 1.60
to 0.84 :mm produce:~ yn Referentie,l Example 3, 30~; by
vlei;~1t of silica-al,.~:ina ~el :iaving a particle dia.rleter
of 1.68 to 0.84 r= ~õoduced 'c,r the method di sclosed in
Japanese Patent Fu'2Iications '.;os . 17002/1963 and 1634','/
1965, and 2CY,'o bi,~ ti.rei:_-ht of t:-e treated snherical activa-
ted carbon S-12 nav4-2- a part; cle diameter of 1.68 to
0.84 mm prowuced in :eferential Example 4 was filled in
the s-oacers. The a'ev.r point of the glass structure was
measu.red in the sar-e way as in Example 1. The results
are sl.o,,,m ir.. ~able -~ .
- 42 -
CA 01174221 1994-03-22
i'C~U1C 1V
Exam=- Ratio of the adsor- Total point ( C)
nle bents (wt alaount
of the ?r__'_al After the
Zeo- Si lica- Activa- adsor- high ten-~)era-
lite alumina ted bents ture ni~-,h
Eel carbon f:Med huTMidity
(~) resistant
test
7 2 -52.C)
4 J -
