CA1174221A - Multilayer glass structure - Google Patents
Multilayer glass structureInfo
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- CA1174221A CA1174221A CA000405711A CA405711A CA1174221A CA 1174221 A CA1174221 A CA 1174221A CA 000405711 A CA000405711 A CA 000405711A CA 405711 A CA405711 A CA 405711A CA 1174221 A CA1174221 A CA 1174221A
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- zeolite
- granular
- activated carbon
- synthetic
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Abstract
Abstract of the Disclosure A multilayer glass structure constructed by joining the edge portions of a plurality of glass sheets by a sealant through spacers having an adsorbent filled therein. According to this invention, the adsorbent comprises a combination of a granular zeolite composed of a core of a synthetic zeolite/clay binder mix-ture 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 in an amount larger than its average content in the granular zeolite, 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. The adsorbent can effectively adsorb a water vapor and a vapor of an organic solvent evaporated from the sealant, and prevent dew deposition on the glass surface. Moreover, it does not yield dust even when the glass structure is handled under sever conditions.
Description
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 - ~'_ _ 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 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 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 -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 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 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 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 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, 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.
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.
- li -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 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.
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 - ~'_ _ 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 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 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 -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 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 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 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 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, 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.
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.
- li -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 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 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 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 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 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 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.
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 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_.
Packin~ density (g/liter) _ V
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 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 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 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 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 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.
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 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_.
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 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
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.
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.
~ ~..
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.
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 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-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) (compari- 12.6 0.5 900 14.5 0.40 0.1 son) 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 .
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) W
N
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 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.
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::
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-_ 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 _ ~~ _ 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-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 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 - ~ .~
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 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., point of t':-Ie glass structure was measar ea in the same way as in ~xample 1. ~ne -results are snovrn in Table E.
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 '~~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 -~ .
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
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.
~ ~..
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.
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 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-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) (compari- 12.6 0.5 900 14.5 0.40 0.1 son) 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 .
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) W
N
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 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.
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::
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-_ 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 _ ~~ _ 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-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 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 - ~ .~
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 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., point of t':-Ie glass structure was measar ea in the same way as in ~xample 1. ~ne -results are snovrn in Table E.
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 '~~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 -~ .
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)
Claims (11)
1. 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 binde-in an amount larger than its average content in the granular zeolite, 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.
2. The structure of claim 1 wherein said granular synthetic zeolite and said granular activated carbon are present in a weight ratio of from 95:5 to 30:70.
3. The structure of claim 1 or 2 wherein said adsorbent further comprises not more than 70% by weight, based o-the total weight of said granular zeolite and granular activated carbon, of granular alumina-silica gel.
4. The structure of claim 1 wherein the amount of said adsorbent is 20 to 300 g per square meter of the area of the multilayer glass structure.
5. The structure of claim 1 wherein in said granular zeolite, the core and the shell exist in a weight ratio of from 99:1 to 80:20.
6. The structure of claim 1 wherein the core of said granular zeolite contains said synthetic zeolite and said clay binder in 2 weight ratio of from 90:10 to 60:40, the shell of said granular zeolite contains said clay binder and said synthetic zeolite in a weight ratio of from 95:5 to 30:70, and said shell contains the clay binder in an amount at least 10% larger than the amount of the clay binder in said core,
7. The structure of claim 1 wherein the synthetic zeolite in said granular zeolite is A-type zeolite, X-type zeolite, Y-type zeolite or synthetic mordenite.
8. The structure of claim 1 wherein the clay binder in said granular zeolite is a kaolinite-group clay mineral, a palygorskite-group clay mineral, a smectite-group clay mineral, or allophane.
9. The structure of claim 1 wherein the activated carbon itself in the granular activated carbon has a BET specific surface area of 500 to 2,000 m2/g.
10. The structure of claim 1 wherein the coating of the granular activated carbon is applied in the form of an aqueous emulsion.
11. 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 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 content in the granular zeolite and (b) granular activated 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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9603181A JPS58243A (en) | 1981-06-23 | 1981-06-23 | Adsorbent for plural-layered glass |
| JP96031/81 | 1981-06-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1174221A true CA1174221A (en) | 1984-09-11 |
Family
ID=14154043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000405711A Expired CA1174221A (en) | 1981-06-23 | 1982-06-22 | Multilayer glass structure |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS58243A (en) |
| CA (1) | CA1174221A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11028637B2 (en) | 2017-06-30 | 2021-06-08 | Panasonic Intellectual Property Management Co., Ltd. | Glass panel unit, building component, and method for activating gas adsorbent |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4822492A (en) * | 1984-09-28 | 1989-04-18 | Uop | Latex polymer bonded crystalline molecular sieves |
| ES2746198T3 (en) * | 2008-12-22 | 2020-03-05 | Glatt Systemtechnik Gmbh | Adsorbent granule of composite material, process for its production and gas separation process |
| KR101780185B1 (en) * | 2010-12-10 | 2017-09-21 | 삼성전자주식회사 | Absorbent shell and manufacturing method thereof |
| JP5757179B2 (en) * | 2011-07-01 | 2015-07-29 | 住友電気工業株式会社 | Gas sorption recovery apparatus and gas sorption recovery method |
| CN111231043A (en) * | 2020-01-17 | 2020-06-05 | 广东玛格家居有限公司 | Processing technology of solid wood door frame |
| KR20230101813A (en) * | 2020-11-02 | 2023-07-06 | 미쯔비시 케미컬 주식회사 | Zeolite, method for producing zeolite, composition, liquid composition, liquid encapsulant, resin composite, encapsulant, method for producing encapsulant, and device |
-
1981
- 1981-06-23 JP JP9603181A patent/JPS58243A/en active Granted
-
1982
- 1982-06-22 CA CA000405711A patent/CA1174221A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11028637B2 (en) | 2017-06-30 | 2021-06-08 | Panasonic Intellectual Property Management Co., Ltd. | Glass panel unit, building component, and method for activating gas adsorbent |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58243A (en) | 1983-01-05 |
| JPS6319212B2 (en) | 1988-04-21 |
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