JP2680823B2 - White spherical adsorbent and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a white spherical adsorbent and a method for producing the same, and more particularly to a white spherical adsorbent having a wide adsorption spectrum and being white and free from dust scattering. And its manufacturing method. (Prior art and its problems) Conventionally, granular activated carbon has been widely used as an adsorbent for various gases, volatile substances, liquids, etc., but this granular activated carbon is high for hydrophobic organic gas and organic compounds. Although it exhibits adsorption performance, it is inferior in adsorption performance to highly polar low molecular weight gases such as hydrogen sulfide and ammonia.
In order to improve this, acid-impregnated activated carbon or alkali-impregnated activated carbon has been used, but its adsorption performance is still unsatisfactory. Further, since the color of activated carbon is not normal, there is a problem of dust generation during transportation or use, and the advent of a white adsorbent having excellent stain resistance is desired. Therefore, an object of the present invention is to provide a spherical adsorbent having a wide adsorption spectrum and being white and free from dust scattering, and a method capable of producing the same. (Means for Solving the Problems) According to the present invention, a core made of a granulated material of granular activated carbon or a powdered adsorbent containing powdered activated carbon and an inorganic or organic binder, and a dense core around the core Strongly adhered, hunter whiteness of 70% or more, hiding power (JIS K 5101) of 250
cm ² / g or less, ammonia adsorption capacity is 0.1 mmol / g or more and hydrogen sulfide adsorption capacity is 0.05 mmol / g or more having a particle structure consisting of a shell of an inorganic white fine powder, and the inorganic white fine powder is zinc There is provided a white spherical adsorbent containing a phyllosilicate or a phylloaluminosilicate containing a component and / or a magnesium component. According to the present invention, a core composed of a granulated product of a granular adsorbent containing powdered activated carbon or powdered activated carbon and an inorganic or organic binder, has a Hunter whiteness of 70% or more, and a hiding power (JIS K 5101). Of 250 cm ² / g or less, ammonia adsorption capacity of 0.1 mmol / g or more and hydrogen sulfide adsorption capacity of 0.05 mmol / g or more, and containing a phyllosilicate or a phylloaluminosilicate containing a zinc component and / or a magnesium component. Provided is a method for producing a white spherical adsorbent, which comprises densely adhering an inorganic white fine powder as a shell around the core. The fine powder is preferably adhered as a shell by rolling granulation. The weight ratio of the activated carbon core to the fine powder shell is 2:98 to 80:20, especially 5: 9.
It should be in the range of 5 to 50:50. (Operation) In FIG. 1 showing the cross-sectional structure of the spherical adsorbent according to the present invention, the spherical adsorbent comprises a core 1 made of granular activated carbon or powdered activated carbon granules, and a Hunter whiteness densely adhered around the core. 70% or more, especially 85% or more, hiding power (JI
SK 5101) is 250 cm ² / g or less, especially 230 cm ² / g or less, ammonia adsorption capacity is 0.1 mmol / g or more, especially 0.5 mmol / g
The above, and the shell 2 of inorganic fine white powder having a hydrogen sulfide adsorption capacity of 0.05 mmol / g or more, particularly 0.1 mmol / g or more. Specific examples of the inorganic white fine powder having this property include a fluorosilicate or zinc fluoroaluminosilicate containing a zinc component and / or a magnesium component. A fluorosilicate or fluoroaluminosilicate containing a zinc component and / or a magnesium component is SiO ₄ or Si.
It has a basic structure in which a tetrahedral layer of Al ₄ O ₄ of O ₄ and an octahedral layer of MO ₆ (M represents Zn and / or Mg) are combined in two or three layers. It is characterized by having strong adsorptivity to both basic substances and acidic substances. Phyllo (alumino) silicate has excellent adsorption performance for various substances by physical adsorption based on the layers of the multilayer structure and chemical adsorption based on each layer, but basic substances and acidic substances Although the chemical adsorption of (3) is less likely to be affected by moisture, the physical adsorption of a neutral organic substance tends to be more susceptible to moisture. This problem is due to the fact that the method of adsorbing water tends to occur preferentially between the layers of the fluoro (alumino) silicate as compared with the adsorption of neutral organic substances. On the other hand, the adsorption of activated carbon is due to physical adsorption by fine voids in the porous carbon, which has an advantage that the adsorption of neutral organic matter is relatively easy even in the presence of water. Thus, according to the present invention, the use of an adsorbent comprising a core of activated carbon and the shell of the above inorganic fine powder, the shell has a high adsorption to not only hydrogen sulfide and ammonia but also amines, organic acids and phenols. In addition to exhibiting properties, the activated carbon exhibits high adsorbability for mercaptans, sulfides, aromatic hydrocarbons, aldehydes, alcohols, alkaloids, etc., and an adsorbent having an extremely broad adsorption spectrum is obtained. Moreover, there is an advantage that this adsorption performance does not deteriorate so much even in the presence of water. The adsorbent of the present invention can be advantageously used not only for adsorption treatment of various gases and volatile components, but also for adsorption treatment of specific components contained in water or various liquids, such as coloring components and odorous components. become. Further, according to the present invention, since a highly white fluorosilicate or a fluoroaluminosilicate is densely adhered around the activated carbon core having an undesired color tone by means such as rolling granulation, the whiteness is extremely high. In addition to being excellent, the particle structure is strong, and since it is spherical, generation of dust is prevented even under wear conditions. (Preferred embodiment of the invention) The granular activated carbon body used in the present invention is coal, petroleum residue,
Charcoal, fruit shells and the like may be obtained by any of a gas activation method such as steam and carbon dioxide or a chemical activation method such as zinc chloride and phosphoric acid, and a BET specific surface area of 500 to 2000.
m ² / g, spherical, cylindrical with a particle size of 4-30 mesh,
Or irregular shaped activated carbon can be used,
Spherical ones are particularly preferably used from the viewpoint of powder resistance. In addition, powdered activated carbon is used by granulating synthetic resin latex various clay minerals, kaolin, halloysite, bentonite, acid clay, synthetic clay, etc. as binders so as to have the above viscosity and BET specific surface area. As the inorganic fine powder containing a fluorosilicate or a fluoroaluminosilicate, ZnO and / or MgO is contained at 5 to 70% by weight, particularly 20 to 50% by weight, and 0.1 to 100 μm,
Especially median diameter of 1 to 10 μm, 30 to 900 m ² / g, especially 2
Those having a BET specific surface area of 00 to 700 m ² / g and an oil absorption of 40 to 300 ml / 100 g, in particular 70 to 200 ml / 100 g, are preferably used. Suitable examples of phyllosilicates or fluoroaluminosilicates are: Flypontite-type zinc aluminosilicate described in JP-A-61-10021, 61-275127 and 61-275128. Laminated irregular type layered magnesium fluorosilicate described in JP-A-61-10020. Sauconite type zinc fluorosilicate described in JP-A-61-10019. Fluoro (alumino) magnesium silicate having a flypontite type crystal structure described in JP-A-61-116579. Consists of a composite of amorphous and porous silica or silica-alumina and an aluminum-containing fluorosilicate layer, with a three-component composition ratio of SiO ₂ 5 to 60 mol%, MO (where M is zinc and magnesium) Showing an atom selected from the group) 5 to
It has a chemical composition of 65 mol% and Al ₂ O ₃ 1 to 60 mol%, has substantially no peak in the interplanar spacing dx8.40 to 6.40Å in X-ray diffraction, and has the interplanar spacing dx2.71 to 2.56. Å and surface spacing dx1.56 ~
A composite having a peak at 1.52 Å, a specific surface area of 200 m ² / g or more, and a pore volume of 0.25 cc / g or more at a pore diameter of 10 to 300 Å. The spherical adsorbent is conveniently produced by supplying the core and the wet inorganic fine powder into a rotating dish, a rotating cylinder, or a rotating truncated cone, and growing agglomerated granules. It is not limited to this. The fine inorganic powder can be used alone for shell formation, or can be used for shell formation in combination with various inorganic binders or organic binders. In this case, as the inorganic binder, water glass, natural or synthetic smectite type clay mineral, silica sol, alumina sol, silica-alumina sol, titanate sol and the like can be used. Further, as the organic binder, starch, cyanated starch, ethyl cellulose, hydroxyethyl cellulose,
Carboxymethyl cellulose, polyvinyl alcohol,
Examples thereof include water-soluble polymers such as maleic anhydride-vinyl ether copolymer, gum arabic, tragacanth and alginate, and various synthetic resins and aqueous latex of synthetic rubber. For the purpose of preventing the shell from collapsing in the liquid, it is preferable to use a latex of synthetic resin or synthetic rubber. For example, the following are used alone or in combination of two or more kinds. 1) butadiene polymer or butadiene and styrene,
Copolymers with styrene derivatives, acrylonitrile, methacrylonitrile, isoprene, isobutylene, etc. 2) A copolymer of isoprene, styrene and a styrene derivative. 3) A chloroprene polymer or a copolymer of chloroprene and styrene, a styrene derivative, acrylonitrile, or isoprene. 4) Copolymers of acrylic acid esters with styrene, styrene derivatives, vinyl chloride, vinyl acetate, acrylonitrile, and methacrylic acid esters. 5) Methacrylonitrile polymers and copolymers of methacrylnitrile and styrene. 6) Vinyl acetate polymers and vinyl chloride polymers. Those obtained by subjecting these to an appropriate modification treatment such as carboxy modification may be used. The binder such as resin latex is preferably used in a solid content of 0.5 to 20% by weight, particularly 1 to 10% by weight, based on the inorganic fine powder. The diameter of the spherical adsorbent is preferably in the range of 0.5 to 10 mm, particularly 1 to 5 mm. (Effect of the invention) According to the present invention, the activated carbon is a core and a fine powder of a specific phyllokenate or a fluoroaluminosilicate is a spherical adsorbent in the form of shell, so that it is composed of a single particle, An adsorbent having a wide adsorption spectrum could be provided. This adsorbent is white, has a strong particle structure, and is excellent in abrasion resistance and dust scattering resistance. The present invention will be described with the following examples. Test method The test method of each characteristic in the present example is as follows. 1. Hiding power measurement method According to the method specified in JIS K 5101 Pigment Test Method. 2. BET specific surface area Automatic BET (specific surface area) measuring device (Sorp manufactured by CARLO-ERBA)
tomatic Series 1800). For details of the BET method, refer to the following documents. S.Brunauer, PHEmmett, E.Teller, J.Am.Ohem.Soc, Vol.6
0, 309 (1938) It should be noted that the measurement of the specific surface area in this specification is performed in advance.
What was dried to 150 ° C. was placed in a weighing bottle of 0.5 to 1.6 g, dried in a thermostatic oven at 150 ° C. for 1 hour, and immediately weighed precisely. This sample is put into an adsorption sample tube and heated to 150 ° C, degassed until the degree of vacuum in the adsorption sample tube reaches 10 ^-4 mmHg, and after allowing to cool, put the adsorption sample tube into liquid nitrogen at about -196 ° C. , PN ₂ / P ₀ = 0.05 to 0.35 (PN ₂ : nitrogen gas pressure, P ₀ = atmospheric pressure at the time of measurement), measure the adsorption amount of N ₂ gas at 4 to 5 points. Then, the adsorption amount of N ₂ gas from which the dead volume is subtracted is converted into the adsorption amount at 0 ° C. and 1 atm and substituted into the BET formula to obtain Vm [ml / g] (necessary to form a monolayer on the sample surface. It shows the amount of nitrogen gas adsorbed). The specific surface area is calculated by the following equation. SA = 4.35 x Vm [m ² / g] 3. Decolorizing power of methylene blue Measured according to JIS K-1470 Activated carbon test method. 4. Hunter whiteness Hunter whiteness was measured using an automatic reflectometer TR-600 type manufactured by Tokyo Denshoku Co., Ltd. 5. Oil absorption (ml / 100g) Measured according to JIS K 5101 pigment test method. Sample is 0.5g
And 6. Method for measuring ammonia and hydrogen sulfide adsorption capacity The apparatus shown in Fig. 2 was used. The gas reservoir 3 is filled with complete air containing the following predetermined concentrations of ammonia and hydrogen sulfide, respectively, and is passed through the column 4 filled with the adsorbent sample at a flow rate of 200 ml / min by the tube type liquid feed metering pump 6. The deodorizing capacity (mmol / g) was determined by measuring the amount of gas until each gas came out in the passing gas through the detector tube 5. Hydrogen sulphide: 10,000ppm, Ammonia: 5000ppm 7. Dust scattering resistance 100g sample is placed in a 300ml beaker and placed on a magnetic stirrer, glass length 40mm, diameter 7mm
Stir the sample in the beaker at 60 rpm for 1 minute using the rod-shaped rotator, and set the Gakken dust measuring device at a height of 15 mm on the beaker and suck at 5 / minute for 5 minutes. As a result, the dust generated by stirring the sample is sucked into the measuring device, the dust is attached to the paper surface mounted inside the measuring device, and the value (%) obtained by dividing the amount of the attached dust by the sample weight is scattered. And then the whiteness of the dust-attached paper (%) (Hunter whiteness of the unused paper
The relative value of 100%) was measured and the dust scattering resistance was evaluated according to the following criteria. Reference Example 1 (Production of inorganic fine powder containing fluoroaluminosilicate) 330 g of sodium silicate No. 3 (SiO ₂ : 22.0%, Na ₂ O: 7.0%)
Silica sol prepared by neutralizing reaction under acidic conditions of pH 2 to 4 with about 80 g of 35% hydrochloric acid was gelated by heating and washed with water to obtain silica hydrogel. The obtained hydrogel was crushed with a household mixer together with water to obtain an amorphous silica slurry liquid (SiO ₂ content: 4.8%) (first step). 205 g of sodium silicate No. 3 and 221 g of sodium hydroxide (NaOH content: 5.5 mol) were dissolved in water to make the total amount 1, and this was liquid A (SiO ₂
Min: 0.75 mol). On the other hand, zinc chloride (anhydrous salt) 180g
And 241g of aluminum chloride (hexahydrate) are dissolved in water to make the total amount 1, and this is liquid B (ZnO content: 1.2 moles, Al ₂ O ₃ content: 0.6).
Mol). 1.5K silica slurry obtained in the first step
g (SiO ₂ min: 1.2 mol) is placed in a 5 beaker and stirred,
Solution A and solution B were simultaneously added at a rate of 25 cc / min while maintaining the solution temperature at 40 ° C. After the addition was completed, the pH of this reaction solution was about 7.2. Stirring was further continued and aged for 1 hour.
The reaction solution was washed with suction and water and dried at 110 ° C. The cake obtained was crushed using a small impact crusher (sample mill) to obtain a white fine powder (second step). The BET specific surface area of the obtained white fine powder is 290 m ² / g, whiteness is 95%, oil absorption is 150 ml / 100 g, hiding power is 11 cm ² / g, methylene blue decolorization power is 160 ml / g, ammonia adsorption amount is 1.9. The adsorption capacity for hydrogen sulfide was 3.5 mmol / g. Reference Example 2 (Manufacture of phyllosilicate) 250 g of a clay (acid: 3 mm) from Nakajo Town, Niigata Prefecture, which has been roughly crushed and then linearly molded (diameter: 3 mm), contains aluminum, magnesium, and calcium contained in the clay. , Sulfuric acid corresponding to 3.5 times the gram equivalent of all gram equivalents of basic metal components such as iron, sodium, potassium and titanium (1.14 gram equivalent / 100g dry matter), that is, 700 ml of 34% sulfuric acid is added, Acid treatment was carried out by heating in a water bath for 15 hours.
It was washed with water to obtain a cake. 110 a small amount of the cake
After drying at ℃, crushing and quantitative analysis, SiO ₂ content is 92.7%
(110 ° C. dry matter standard). The obtained cake was put in a pot mill, water was added, and wet pulverization was performed together with Korean balls to obtain a slurry containing 15% of SiO ₂ content. Next, 200 g (SiO ₂ min: 30 g) of the obtained slurry and 22 g of magnesium hydroxide (first-grade reagent) were placed in an autoclave container of 1, and 370 g of water was further added, and the mixture was stirred at 500 ° C./min at 160 ° C. for 5 times. The hydrothermal synthesis reaction was carried out for an hour. After cooling, the reaction product was taken out and water was separated by filtration.
Dried at 0 ° C. The dried product was crushed with a small bench sample mill to obtain a white fine powder. The white fine powder obtained has a BET specific surface area of 530 m ² / g and whiteness
The oil absorption was 93%, the oil absorption was 170 ml / 100 g, the hiding power was 6 cm ² / g, the methylene blue decolorization power was 210 ml / g, the ammonia adsorption capacity was 2.1 mmol / g, and the hydrogen sulfide adsorption capacity was 0.15 mmol / g. Example 1 Water was added to 100 g of commercially available spherical activated carbon (16 to 32 mesh),
A sufficiently moistened product was put into a tumbling granulator, and 100 g of the white composite zinc fluorosilicate fine powder obtained in Reference Example 1 was gradually added while water was sprayed with a spray nozzle, and tumbling molding was performed. The obtained molded product was obtained and used as the core. This core was put into a tumbling granulator again, and while spraying water with a spray nozzle, 100 g of the white composite zinc fluorosilicate fine powder obtained in Reference Example 1 was gradually added and tumbling molded.
It was dried at 0 ° C for 12 hours to obtain a white spherical granule. Example 2 100 g of water was added to 70 g of commercially available powdered activated carbon (ingredient A) and 30 g of the white magnesium fluorosilicate fine powder (ingredient B) obtained in Reference Example 2 and thoroughly kneaded to form a granulation plate having a diameter of 1 mm. It was molded by an extrusion molding machine having the above to obtain a columnar granulated product, which was used as a core. This core was put into a tumbling granulator, and 100 g of the white magnesium fluorosilicate fine powder (component C) obtained in Reference Example 2 was gradually added while water was sprayed with a spray nozzle to tumbl granulate. The mixture was dried at 0 ° C. for 12 hours to obtain a slightly gray white spherical granule (Example 2-1). In the same manner, add 30 g and 1 g of component A, component B and component C
White spherical granules (Example 2-2) were obtained as 5 g and 150 g. Example 3 To 70 g of commercially available powdered activated carbon and 30 g of the white magnesium fluorosilicate fine powder obtained in Reference Example 2, 100 g of 20 g of commercially available vinyl acetate emulsion (concentration about 35%) diluted with 80 g of water was added and kneaded sufficiently. The product was molded by an extrusion molding machine having a granulation plate with a diameter of 1 mm to obtain a columnar granulated product, which was used as a core. This core was put in a tumbling granulator, and 100 g of the white magnesium fluorosilicate fine powder obtained in Reference Example 2 was gradually added while spraying a vinyl acetate emulsion diluted with water to a concentration of 5% with a spray nozzle. Rolled granulation and drying at 130 ° C. for 12 hours gave white spherical granules. Example 4 80 g of water was added to 100 g of commercially available spherical activated carbon (16 to 32 mesh) and sufficiently moistened to form a core. This core was put in a tumbling granulator, and 100 g of the white magnesium fluorosilicate fine powder obtained in Reference Example 2 was gradually added while spraying a vinyl acetate emulsion diluted with water to a concentration of 5% with a spray nozzle. Rolling-molded and dried at 130 ° C for 12 hours to obtain white spherical granules. Example 5 To 60 g of commercially available powdered activated carbon and 40 g of the white composite zinc fluorosilicate fine powder obtained in Reference Example 1, 10 g of kaolin powder having an average particle size of 2 μm and 100 g of water were added and sufficiently kneaded to give a diameter of 1 mm.
It was molded by an extrusion molding machine having a granulation plate of No. 1 to obtain a columnar granulated product, which was used as a core. This core was put into a tumbling granulator, and while spraying water with a spray nozzle, 10 g of the same kaolin powder was gradually added to 100 g of the white composite zinc fluorosilicate fine powder obtained in Reference Example 1 for rolling treatment. Then, add 20 parts of titanium dioxide powder to this granule.
g was gradually added, tumbled and granulated, and dried at 130 ° C for 12 hours,
A white spherical granule was obtained. Example 6 Commercially available granular coconut husk activated carbon (16-33 mesh) 100 g was added with water and sufficiently moistened was placed in a tumbling granulator, which was obtained in Reference Example 1 while spraying water with a spray nozzle. 100 g of white composite zinc fluorosilicate fine powder was gradually added and rolling granulated to obtain a spherical granulated product, which was used as a core. This core was put into the tumbling granulator again, and while spraying water with a spray nozzle, 70 g of the white composite zinc fluorosilicate fine powder obtained in Reference Example 1 was gradually added to tumbl granulate.
It was dried at ℃ for 12 hours to obtain white spherical granules. Powder of spherical adsorbents obtained in Examples 1, 2, 3, 4, 5 and 6, Comparative Example 1 (commercially available activated carbon for food addition) and Comparative Example 2 (commercially available powder activated carbon 70 g and powder according to Reference Example 2 200 g) The results of measuring ammonia, hydrogen sulfide adsorption capacity, and methylene blue decolorizing power of the mixture) are shown in Table 1. Application Example Using the adsorbents obtained in Examples 1, 2, 3 and 4,
Adsorption treatment was carried out for seafood extracts such as oysters, mussels and skipjacks and soy sauce under the conditions shown in Table 2 using the apparatus shown in FIG. Then, sensory evaluation by a paired comparison method was performed on the taste and odor of the purified liquids obtained by separating the adsorbents, using a panel of 5 persons. Each of the collected purified solutions with a BX concentration of 20 to 40 ° was diluted to a BX concentration of 5 ° and heated to 50 to 60 ° C to obtain a test solution. For comparison, prepare untreated concentrates with BX concentration of 20-40 °, dilute to BX concentration of 5 ° and heat to 50-60 ° C respectively. F2, G2,
H2, I2, J2, K2, L2 and M2. As a result, the taste is shown in Table 3 and the aroma is shown in Table 4. The numbers in Tables 3 and 4 indicate the number of panelists who answered that the recovered and purified test liquid had a better taste or aroma than the untreated comparative test liquid.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a sectional view of a spherical adsorbent obtained in Example 1 of the present invention. FIG. 2 is an explanatory view of an apparatus used for measuring the adsorption capacity of ammonia and hydrogen sulfide in the example of the present invention. FIG. 3 is an explanatory diagram of an apparatus used for purification processing of various extracts in the application example of the present invention. 1 ... Core, 2 ... Shell, 3 ... Gas reservoir, 4 ... Column, 5 ... Detector tube, 6 ... Tube type liquid feed metering pump, 7 ... Unprocessed extract reservoir, 8 ... Tube type liquid feed metering pump, 9 …… Column 10 …… Reserved refined extract.

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Akira Ueno               15 Owada Nitta, Yachiyo City, Chiba Prefecture                (56) References JP-A-58-27639 (JP, A)                 JP-A-61-10020 (JP, A)                 JP 63-175637 (JP, A)                 JP 63-185811 (JP, A)

Claims (1)

(57) [Claims] A core composed of a granulated material of a powdered adsorbent containing granular activated carbon or powdered activated carbon and an inorganic or organic binder, and a whiteness of Hunter of 70 adhered densely and firmly around the core.
%, The hiding power (JIS K 5101) is 250 cm ² / g or less, the ammonia adsorption capacity is 0.1 mmol / g or more, and the hydrogen sulfide adsorption capacity is 0.05 mmol / g or more. A white spherical adsorbent having the inorganic white fine powder, which contains a phyllosilicate or a phyloaluminosilicate containing a zinc component and / or a magnesium component. 2. Granules of granular activated carbon or a powder adsorbent containing powdered activated carbon and an inorganic or organic binder are used as cores, with a Hunter whiteness of 70% or more and a hiding power (JIS K 5101) of 250 cm ² / g.
Hereinafter, an inorganic white fine powder containing a phyllosilicate or a phylloaluminosilicate that has an ammonia adsorption capacity of 0.1 mmol / g or more and a hydrogen sulfide adsorption capacity of 0.05 mmol / g or more and contains a zinc component and / or a magnesium component. A method for producing a white spherical adsorbent characterized in that it is densely adhered to the periphery of the core as a shell. 3. The method according to claim 2, wherein the inorganic white fine powder is attached by tumbling granulation. 4. 2:98 to 80: 2 with a core containing activated carbon and a fine powder shell
The method according to claim 2, which is used in a weight ratio of 0. 5. The method for producing a white spherical adsorbent according to claim 2, characterized in that a shell component, which is preliminarily mixed with an inorganic or organic binder, is densely adhered to the periphery of the core. 6. The method according to claim 5, wherein the core and the shell component are attached by tumbling granulation. 7. The binder is 0.5 to 2 per solid component of the solid content.
The manufacturing method according to claim 5, which is used at 0% by weight.