WO2010041441A1 - 有害物質吸着成形体 - Google Patents
有害物質吸着成形体 Download PDFInfo
- Publication number
- WO2010041441A1 WO2010041441A1 PCT/JP2009/005213 JP2009005213W WO2010041441A1 WO 2010041441 A1 WO2010041441 A1 WO 2010041441A1 JP 2009005213 W JP2009005213 W JP 2009005213W WO 2010041441 A1 WO2010041441 A1 WO 2010041441A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- adsorbent
- harmful substance
- tablet
- powder
- Prior art date
Links
Images
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01C—PLANTING; SOWING; FERTILISING
- A01C21/00—Methods of fertilising, sowing or planting
- A01C21/002—Apparatus for sowing fertiliser; Fertiliser drill
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/14—Diatomaceous earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28042—Shaped bodies; Monolithic structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3014—Kneading
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/22—Agents rendering paper porous, absorbent or bulky
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/62—In a cartridge
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
- D21H21/52—Additives of definite length or shape
Definitions
- the present invention relates to a harmful substance adsorption molded body that can be released from the fear of soil contamination in fields, paddy fields, rivers, ground water, lakes and the like. More specifically, the present invention presupposes a harmful substance adsorption molded body formed by a binder using a powder adsorbent that adsorbs a harmful substance from soil or water contaminated environment as a raw material.
- One of the materials used in manufacturing includes harmful substance-adsorbing powder, and the harmful substance-adsorbing powder is embodied from the viewpoint of its particle form, and the particle size has a particle diameter that passes 200 mesh.
- the present invention relates to a harmful substance-adsorbed molded body prepared by blending additives for providing the above-mentioned materials and using these blended materials as raw materials.
- the present invention provides a harmful substance adsorbent that becomes a porous fine powder having the predetermined particle form from the viewpoint that the harmful substance adsorption molded article can be provided in different forms.
- the present invention relates to a harmful-substance-adsorbed molded article that includes an additive having other functions and can be provided as a water-soluble sheet or tablet.
- the present invention from the viewpoint of application effects of the harmful substance adsorption molded body, in its use in a polluted environment, it can be applied by dispersing the powder without scattering and without exerting labor, In the applied polluted environment, the harmful substance adsorption molded body can be effectively disintegrated and dispersed, and the harmful substance in the polluted environment is adsorbed and fixed to the harmful substance adsorbent contained in the adsorbed molded body and adsorbed and captured.
- the present invention relates to a harmful substance-adsorbed molded body that can prevent harmful substances from flowing out from an adsorbent and thereby protect against the expansion of pollution in the application environment.
- the porous fine powder adsorbent added to the harmful substance adsorption molded body includes the binder, Additives to give other functional materials that may be added according to the treatment, the kneaded material is treated so as to adhere to or be applied to the sheet material, and then the kneaded material is prepared from a water-soluble sheet material prepared in advance. By attaching or coating on the surface, it is produced as a multifunctional water-soluble sheet having a harmful substance adsorption function.
- the paste component is first added to the porous fine powder adsorbent, and other functional materials that may be added as necessary. Additives to give odors, and additionally blend fine powders with a specific gravity of 1 or more to make a blend of mixed powders. It is also produced as a multifunctional tablet.
- Powder spraying work such as agricultural chemical spraying and modifier spraying by agricultural workers has been a physical burden on the elderly. Moreover, in the spraying operation, uniform spraying on the soil has been difficult due to the scattering property of the spray agent.
- dioxins banned agricultural chemicals, volatile organic substances, heavy metals, and other harmful substances penetrate into the soil, and these harmful substances are diffused by moisture such as rainwater and groundwater. It is known to go.
- the method (h) is a method in which the soil is washed with water, and harmful substances are adsorbed on activated carbon and recovered. Since a large amount of chemicals is used to regenerate the activated carbon, the environmental load is high, and the period and cost are also high. This method has a problem that it may remove even components in the soil necessary for agricultural crops and organisms, and is not suitable as a soil regeneration material.
- paddy fields and other special places where there is a lot of water include water-soluble single-packed medicines and (J) effervescent medicine tablets.
- a fertilizer component is contained in or applied to a water-soluble sheet to constitute a sheet fertilizer, and an appropriate amount of ingredients necessary for plants can be given simply and accurately, and a sheet fertilizer with improved handling properties 2003-104788)
- a pesticide formulation for throwing paddy fields Patent No. 2815535
- an active ingredient in which a water-floating pesticide solid agent containing a diffusing agent is packaged in an expandable water-soluble paper is dispersed or dissolved in water.
- the conventional sheet-shaped adsorption molded body described above has a part that cannot be treated with the sheet-shaped adsorption molded body when it is applied to a high-concentration contaminated part containing a large amount of adsorbent.
- a method of attaching a finely pulverized product to a sheet that collapses or decomposes it has not been possible to form a sheet so that the finely pulverized product can be uniformly attached without degrading the performance of the finely pulverized product. . From the above, there has been a demand for a simple method that can prevent recontamination without installing a large-scale facility and can fix harmful substances.
- water-soluble sheets have been applied to water-polluted environments such as rivers, lakes, and groundwater as an application in the water environment. Unlike the case where the water-soluble sheet is dissolved, there is still a problem in making the distribution of the harmful substance adsorbent uniform. Moreover, it was difficult in flowing rivers and lakes. In addition, there has been an urgent need for methods for adsorbing pollutants that have flowed into groundwater and rivers and preventing diffusion of pollutants that have accumulated in the bottom of rivers and lakes. Alternatively, for application to river and lake sediments, it was not sufficient to deposit the sheet adsorbent on the bottom.
- a tablet manufacturing technique by tableting As a tablet manufacturing technique by tableting, a tablet with a small tablet weight deviation and maintaining a tablet disintegrating property while having a practical tablet hardness, a dry-type tablet manufactured by a manufacturing method using the dry direct-striking method.
- a quick-disintegrating tablet Japanese Patent Laid-Open No. 2007-197357.
- the disintegration rate according to the Japanese Pharmacopoeia that is, the time is usually set to disintegrate under human body temperature, and it is assumed that the disintegration will occur with low-temperature water when applied to an external polluted environment.
- the present inventors assumed a lake and put each tablet sample prepared by tableting into a beaker filled with water for testing.
- a powder with a specific gravity of 1 or more was added to the solution for floating the harmful substance adsorbent powder, and the tablet was applied as a tablet in a water-contaminated environment filled with a contaminated sample. I found it to sink. However, even if it sinks, it cannot fulfill its intended function of adsorbing harmful substances if it does not dissolve at the sinking position. Therefore, a verification experiment on the dissolution state of the tablet of the present invention was further attempted.
- the powder included in the tablet as an adsorbed molded body has a particle size of a particle diameter passing through 200 mesh, a particle density of an average particle size of 100 ⁇ m or less, and a proportion of the particle weight.
- a porous fine powder exceeding 80% was used as a harmful substance adsorbent, it was confirmed that if this harmful substance adsorbent was made into a tablet that was tableted, it would sink to the bottom of the beaker and dissolve. .
- the form of the powder used in the preparation of this adsorbent is the porous fine particle included in the hazardous substance adsorption multifunctional water-soluble sheet for the attribute specified value regarding the particle size of the porous fine powder included in the harmful substance adsorbent.
- the attribute specified value regarding the particle size of the porous fine powder included in the harmful substance adsorbent is passed through 200 mesh. If the particle density is a porous fine powder having an average particle size of 100 ⁇ m or less and a ratio exceeding 80% of the particle size weight, this is applied to a sheet or tablet.
- the present invention is a harmful substance adsorption molding processed to prevent the adsorbed powder from scattering and floating.
- the harmful substance adsorbent of the harmful substance adsorption molded body captures and adsorbs the harmful substance accumulated in the environment, and stops in that environment. And it is to prevent penetration and diffusion to other places.
- the harmful substance-adsorbed molded article can have only a harmful substance-adsorbing performance by appropriately adding an additive having other functions to the harmful substance-adsorbing agent of the formulation for producing the molded article as necessary.
- the present invention reduces the burden on the body of the harmful substance adsorbent molded body, even for elderly employees in the work of preventing the fine powder of adsorbent from being scattered and preventing the outflow. It is to provide a multifunctional water-soluble sheet that adsorbs harmful substances in the form. In this case, even if the soil environment to which the harmful substance adsorption molded body is applied is sloping ground, the harmful substance adsorption molded body can be crushed, etc.
- this invention is providing the said harmful substance adsorption molded object as a tablet which adsorb
- a tablet that adsorbs this harmful substance it is provided as a tablet that adsorbs a harmful substance that can have dissolution controllability while using a compound common to the case of a water-soluble sheet.
- the tablet does not settle and remains floating, or does not disintegrate even if it settles. To disintegrate and disperse.
- the present invention provides a harmful substance-adsorbed molded article formed by a binder using a powder adsorbent that adsorbs a harmful substance from soil or water contaminated environment as a raw material, and an additive for imparting other functions to the raw material.
- a material for adhering a blend containing the adsorbent and additive to a flexible water-soluble sheet or a material for molding as it is the material can be made flexible.
- the present invention also embodies the harmful substance-adsorbing porous fine powder, and the adsorbed powder is a mineral such as calcite, zeolite, activated clay, diatomite, ilmenite, or the like, or a fast-acting adsorption performance of heavy metals or It contains at least one substance of polyamino acid, polysaccharide, polyacrylic acid, inorganic salt, chelating agent or activated carbon of 800 m2 / g or more having a water retention function, or embodies the additive to decompose harmful substances
- a harmful substance-adsorbed molded article containing at least one of an oxidant, a reducing agent, a decomposing bacterium, an oxygen sustained-release agent, and a fungal active nutrient component.
- the present invention presupposes a harmful substance adsorption molded body according to claim 1, the adsorbent powder, an additive having other functions, and a composition containing a water-soluble binder as an adhesion material,
- a flexible water-soluble sheet made of any one or a combination of a film, water-soluble paper, water-degrading paper, or unsuccessful cloth as a main raw material having a high degradability such as polysaccharides, cellulose, polyvinyl alcohol, carbomethyl cellulose, and starch.
- a harmful substance-adsorbing molded body using the harmful substance-adsorbing molded body as a sheet is provided.
- the present invention also provides a water-soluble sheet-type harmful substance-adsorbing molded article including at least one of a fertilizer, an agrochemical, a pH adjuster, and an antibacterial disinfectant as a specific example of the additive. Furthermore, the present invention presupposes the harmful substance-adsorbed molded article according to claim 1, and adsorbent powder, an additive having other functions, an excipient serving as a binder, and a fine powder having a specific gravity of 1 or more.
- the harmful substance-adsorbed molded body in which these blends are directly used as a tablet material and pressure-integrated to form a tablet capable of controlling buoyancy is provided.
- the present invention embodies the excipient as crystalline cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, starch, lactose, silicon dioxide, polysaccharides, mannitol, anhydrous calcium hydrogen phosphate, at least one of them.
- harmful substance-adsorbing tablets including one.
- the harmful substance adsorption molded body as a general invention according to claims 1 to 3 enables uniform adsorbent distribution to a polluted environment,
- the harmful substances accumulated in the environment contaminated by the fine powder harmful substance adsorbent included in this environment are uniformly adsorbed and captured and fixed within the applicable environment, preventing penetration and diffusion to other areas, environmental pollution Can solve the problem.
- an additive having other functions as required it is possible not only to adsorb and fix harmful substances in the application environment, but also to provide other functions such as fertilization at the same time to be multifunctional. Furthermore, it is possible to reduce the labor burden of the adsorbent powder spraying work for elderly employees.
- the harmful substance-adsorbing molded body in the form of the flexible water-soluble sheet according to claims 4 and 5 is provided with a multifunctional water-soluble sheet in addition to the effect of the invention according to claim 1.
- a small amount of moisture such as rainwater, including fine powder adsorbents and additives with other functions, it can be efficiently dispersed in the soil without using surfactants that may contaminate groundwater,
- the absorbent can be properly adhered to the soil, and furthermore, the re-scattering of the absorbent is prevented, the absorption into the plant is prevented and the contamination of the groundwater is prevented. Can do.
- the water-soluble adsorption sheet does not inhibit the adsorption efficiency because it is water-soluble.
- the harmful substance-adsorbed molded article controlled to precipitate disintegration in the form of the tablet described in claims 6 and 7 is added to the tablet in addition to the effect of the invention described in claim 1.
- the tablet is allowed to settle, and the disintegration time can be controlled in the course of the tablet sinking.
- the installation treatment work can be made very simple by throwing and spraying, etc.
- Adsorbent buoyancy can be controlled. And it can improve a worker's and the safety measures of neighborhood while aiming at prevention of scattering of fine powder and dust explosion.
- Tablet materials are composed of cellulosic materials with low environmental impact, highly stable minerals, carbon, etc., and product design with sufficient consideration for safety is possible.
- fine powdered adsorbents can be efficiently dispersed in soil with a small amount of moisture such as rainwater, such as soil in dry zones.
- the harmful substances can be fixed to the adsorbent to prevent absorption by plants and contamination to groundwater.
- the tableting method by direct compression, the hardness of the porous outer surface of the porous fine powder increases during the tableting process, and the air present in the porous voids is compressed and confined.
- the tablet When the tablet is exposed to an environment with a high amount of moisture during use, it collapses at once by absorbing a large amount of moisture in the porous voids and expelling the trapped air simultaneously by capillary action (Fig. 10). From such a phenomenon, it is presumed that the air expelled from the porous voids plays the role of a foaming agent, and from this knowledge, the present invention is formed by direct compression including porous fine powder. Tablets are believed to absorb moisture and promote disintegration.
- the tablet of the present invention can be disintegrated without including a disintegrant, but it can also be accelerated to include a disintegrant. Thereby, it is possible to disintegrate more rapidly, and it is possible to arbitrarily select whether or not to include a disintegrant.
- the present invention includes a harmful substance adsorbent in one of a plurality of materials included in manufacturing a predetermined harmful substance adsorption molded body, and the harmful substance adsorbent has a particle shape attribute.
- the adsorbent blend the harmful substance adsorbent and binder, and other additives with other functions as needed in addition to this harmful substance adsorption, and process these ingredients in the raw materials.
- it can be prepared as a water-soluble sheet that can be easily dissolved or as a tablet that can be easily disintegrated and diffused.
- (A) is a schematic perspective view of a modified example in which the adsorbent is entirely bonded to one sheet, and (b) shows some cross-sectional examples along the line XX.
- (b) is a cross section for the entire surface of one side of the sheet, (b2) is a cross section for the entire surface of the sheet, and (b3) is a sheet.
- a cross section in which the adsorbent is kneaded is shown as a whole.
- the harmful substance adsorbing molded body is a water-soluble sheet, in which the adsorbent is divided and dispersed on one side of the sheet
- the water-soluble sheet of Example When applying the water-soluble sheet of Example to potted soil, it is a graph of experimental data showing a comparison of the concentration of dieldrin in the cucumber stalks and leaves as a change depending on the presence or absence of the activated carbon sheet and the amount of activated carbon, by a bar graph. . It is a photograph which shows the construction state at the time of distributing and constructing the water-soluble sheet
- the water-soluble sheet of Example 1 As an example of the water-soluble sheet of Example 1, when a multifunctional water-soluble sheet containing potassium hydrogen carbonate and citric acid was used for the water-soluble sheet coated with activated carbon, moisture was given to the sheet distributed to the soil. It is the photograph which compares and shows the state by stirring immediately after that, and after 10 minutes, and shows the wet state immediately after giving water
- the dispersion time standard / diffusive activated carbon tablet produced at the blending ratio shown in Example 1 of the present invention in Table 1 is a photograph of the dispersion state before and after water dropping. It is a later photo.
- Example 2 in the photograph of the dispersion state before and after water dropping of the dispersion time delayed / precipitated activated carbon tablet produced in Table 1 with the blending ratio of the product example 3 of the present invention, It is a photograph. It is the photograph 60 seconds after putting a tablet in water.
- Example 2 As a tablet example of Example 2, it is the photograph of the dispersion
- FIG. (A) is a photograph of the activated carbon tablet before water dripping. It is the photograph of the dispersion
- the tablet As an example of the tablet of Example 2, the tablet is dispersed while generating bubbles in the adsorption performance test of the chemical substance released from the collected river bottom to water.
- the state of the conventional fine powder activated carbon of the conventional product which is the comparative example 2 described in Table 1 shows a state immediately after the water temperature of 15 ° C. is added.
- the present invention relates to a tablet made of only crystalline cellulose, which is a conventional excipient, which is Comparative Example 3 described in Table 1, and shows the state 600 seconds after being put into water having a water temperature of 15 ° C. It relates to a tablet of fine powder activated carbon hardened with polyvinyl alcohol which is a water-soluble resin, which is Comparative Example 4 shown in Table 1, and shows a state after 600 seconds of water injection at 15 ° C. in water.
- the present invention provides a harmful substance-adsorbed molded article formed by a binder using a powder adsorbent that adsorbs a harmful substance from soil or water contaminated environment as a raw material, and an additive for imparting other functions to the raw material.
- a material for adhering a blend containing the adsorbent and additive to a flexible water-soluble sheet or a material for molding as it is the material can be made flexible.
- the present invention is a multifunctional water-soluble sheet obtained by adhering or kneading fine powder kneaded with a water-soluble binder to a water-soluble sheet, and adsorbing fine powder whose powder composition adsorbs harmful components Using powder consisting of any one or combination of additives and other additives that may be added if necessary, the particle size of the fine powder adsorbent passes 200 mesh
- a multi-functional product having a particle diameter of 20 ⁇ g / m 2 or more and a fine particle powder having an average particle size of 100 ⁇ m or less and a proportion exceeding 80% of the particle weight.
- a water-soluble sheet is provided. In this case, a multifunctional water-soluble sheet in which the fine powder is adhered between two or more water-soluble sheets can also be provided.
- This invention provides the multifunctional water-soluble sheet
- all or a part of the adsorbent contains porous or adsorbent calcite, zeolite, activated clay, diatomaceous earth and other naturally derived minerals, Hydroxides, carbonates, bicarbonates, phosphates that are activated carbons that have an adsorption performance of a specific surface area of 800 m ⁇ 2> / g or more in whole or in part, or that make insoluble salts of heavy metals in the whole or part of the adsorbent.
- This invention can provide the multifunctional water-soluble sheet
- seat for agriculture containing plant essential amino acids, nitrogen content, phosphorus content, and potassium content as said additive, Addition of carbonate or hydrogen carbonate such as potassium carbonate contained in fertilizer as said additive It is possible to provide a multifunctional water-soluble sheet containing a foaming dispersant obtained by mixing an agent and a solid acid such as citric acid or ascorbic acid.
- a water-soluble multifunctional sheet containing soil sterilization, disinfection, pest control agent as the additive, a multifunctional water-soluble sheet containing an alcohol content of alcohol concentration of 10 to 80%, as the additive,
- a multifunctional water-soluble sheet contained in the agrochemicals or chemicals described in the positive list as the additive a water-soluble adhesive that does not impair the basic performance of the fine powder, and uses an adhesive composed of a mixture of alcohols and polysaccharides
- the multifunctional water-soluble sheet can be provided, and the multifunctional water-soluble sheet using the adhesive, wherein the water-soluble adhesive is a mixture of alcohol, polyvinyl alcohol, and polysaccharide thickener.
- the water-soluble sheet is any one of a film, water-soluble paper, hydrolyzed paper, and unemployed cloth, which is a main raw material having a high degradability such as polysaccharides, cellulose, polyvinyl alcohol, carbomethyl cellulose, and starch.
- a multifunctional water-soluble sheet consisting of one or a combination can be provided.
- the present invention can provide a multifunctional water-soluble sheet whose constituent material is any one or a combination of ingredients derived from food additives. From the above, the present invention is also applicable to dry area soil and agriculture that can adsorb harmful components in soil when it is laid on the soil surface or in the soil and dissolved by watering, rainfall, snowfall or moisture in the soil.
- a multifunctional water-soluble sheet with high safety that can be used can be provided.
- the present invention can also be provided as a harmful substance-adsorbing tablet.
- it is possible to freely design the conditions such as size adsorbent blending ratio, tablet disintegration speed, etc. depending on the shape and use situation, and it is possible to perform tableting molding by reducing the molding pressure, so a special machine is required.
- it can be manufactured with a rotary tableting machine used for foods and pharmaceuticals. Regardless of whether it is in water or soil, tablets formed with a fine powder adsorbent can be installed easily by throwing and spraying.
- a fine powder porous adsorbent and a specific gravity of 1 or more It is an adsorbent mixed and kneaded with powder, and the particle size of the fine powder adsorbent has a particle size that passes 200 mesh, the particle density is an average particle size of 100 ⁇ m or less, and the proportion is 80% of the particle size weight Is a powder of an adsorbent obtained by pressure bonding or kneading a powder having a specific gravity of 1 or more.
- the adsorbent performance can be freely designed depending on the contamination state that the adsorbent is composed of one or a combination of an organic component adsorbent and an inorganic component adsorbent.
- the blended powder contains a substance composed of a combination of one or more of excipients and lubricants in addition to the porous material, and a mixture that can be directly compressed as a single layer or multilayer tablet.
- the adsorbent includes a porous adsorbent capable of mixing substances adsorbed for each type, such as harmful organic compounds and harmful inorganic compounds.
- Adsorbents that can be adsorbed and immobilized in accordance with the contaminants can be selected, and the adsorption performance for harmful components can be designed freely according to the high concentration of contamination.
- a powder having a specific gravity of 1 or more any one of naturally occurring minerals such as porous inorganic minerals, calcite, zeolite, activated clay, diatomaceous earth, granite pegmatite, ilmenite and the like to control buoyancy or
- a substance composed of a plurality of combinations may be included, or a substance composed of any one or a combination of artificial zeolites with controlled pore sizes may be included.
- activated carbon having a specific surface area of 800 m @ 2 / g or more is included in the whole or a part of the adsorbent, and further, the immediate adsorption performance or water retention function of heavy metal is provided in the whole or a part of the adsorbent.
- the excipient is any one of crystalline cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, starch, lactose, silicon dioxide, polysaccharides, mannitol, anhydrous calcium hydrogen phosphate.
- a substance composed of one or a plurality of combinations can be included, but a combination of crystalline cellulose, silicon dioxide, and polysaccharides composed of a food additive-derived ingredient or a pharmaceutical that is harmless to humans and has a low environmental impact is particularly desirable.
- a substance composed of a combination of an oxidizing agent or a reducing agent may be used for the whole or a part of the adsorbent, or an organic substance-degrading bacterium may be used without killing the bacterium by being capable of low-pressure tableting. In this way, it is possible to promote the decomposition of harmful substances capable of bioremediation.
- the present invention is installed on the soil surface or in the soil and, when dissolved by watering, rainfall, snowfall or moisture in the soil, can adsorb harmful components in the soil and can be used in dry soil and agriculture.
- a highly safe harmful substance-adsorbing tablet can be produced.
- a harmful substance-adsorbing tablet of the best form in which the adsorption performance and disintegration / dispersion performance can be freely designed it is in the form of a tablet having a simple structure, and the adsorbent has a specific surface area of 800 m 2 / g or more and A combination of crystalline cellulose and silicon dioxide is most desirable as a powder mixture having fine powder activated carbon having an average particle size of 100 ⁇ m or less and 50% or less of the tablet weight and having a specific gravity of 1 or more.
- FIG. 1 shows an embodiment of a harmful substance-adsorbing water-soluble sheet adhered to a surface of a flexible water-soluble sheet containing at least a powder adsorbent that adsorbs harmful substances.
- A is a schematic perspective view of one harmful substance-adsorbing water-soluble sheet, and (b) is a sectional view taken along line XX. In production, it contains at least a powder adsorbent that adsorbs harmful substances, kneaded a formulation containing a binder to make a kneaded product, this kneaded product adheres to the surface of the water-soluble sheet 1, A harmful substance-adsorbing water-soluble sheet 1 is used.
- the powder adsorbent that adsorbs harmful substances is a fine powder in order to mix well with the soil, and the following fine powder specification is desirable, that is, the particle size is a particle size that passes 200 mesh. And a fine particle powder having an average particle size of 100 ⁇ m or less and a ratio exceeding 80% of the particle size weight, and containing 20 g / m 2 or more.
- the powder adsorbent that adsorbs harmful substances is a porous fine powder capable of mixing substances adsorbed for each type, such as harmful organic compounds and harmful inorganic compounds.
- the whole or a part of the adsorbent is porous or adsorbent, and any one or a combination of natural minerals such as calcite, zeolite, activated clay, diatomaceous earth, etc. Or an activated carbon having an adsorption performance of a specific surface area of 800 m ⁇ 2> / g or more, or a hydroxide that produces a sparingly soluble salt of heavy metal in the whole or part of the adsorbent.
- a substance comprising any one or a combination of salts, carbonates, hydrogen carbonates, phosphates, sulfides, sulfates, ilmenites and chelating agents and a pH adjuster, or the adsorbent It contains polyglutamic acid, which has a function of quickly acting as a fertilizer after decomposition in the soil, with a heavy metal immediate effect adsorption performance, water retention function, All or part of the serial adsorbent, microorganisms degrading bacteria, oxygen release preparations may also contain porous adsorbent containing a substance consisting of a combination of fungal active nutrients.
- the harmful substance adsorbent that is in a fine powder and porous form adheres to the surface of the water-soluble sheet 1 by adhering the kneaded material blended with the various materials described above and kneaded together with the binder. It is possible to provide a multifunctional function in the production of an adhesive sheet, and it can be said that a harmful substance-adsorbing multifunctional water-soluble sheet is provided here.
- design change with a high freedom degree of adsorption agent is attained with respect to the soil component to process.
- the present invention includes, as an additive, all or part of the additive, plant essential amino acids as a fertilizer, nitrogen content, phosphorus content, potassium content.
- plant essential amino acids as a fertilizer, nitrogen content, phosphorus content, potassium content.
- a carbonate or bicarbonate additive such as potassium carbonate contained in fertilizers for the purpose of mixing the soil and promoting the collapse of the sheet and mixing the fine powder contained in the soil with the soil
- it can be produced as an agricultural multifunctional water-soluble sheet containing the obtained foaming dispersant.
- soil sterilization, disinfection, pest control agent may be included as the additive, in particular, an ethyl alcohol component having an alcohol concentration of 10 to 80% may be included as a disinfectant, and a pesticide ingredient or drug described in the positive list may be included.
- a water-soluble adhesive additive that does not interfere with the basic performance of the fine powder, and uses an adhesive made of a mixture of alcohols and polysaccharides, or the water-soluble adhesive additive
- the water-soluble sheet is composed of any one or a combination of a film, water-soluble paper, hydrolyzed paper, non-woven fabric, which is a main raw material having a high degradability such as polysaccharides, cellulose, polyvinyl alcohol, carbomethyl cellulose, and starch.
- a flexible water-soluble sheet can be used.
- this invention can take the form which divided
- the multifunctional water-soluble sheet with the adsorbent applied in a dispersed manner shown in FIG. 2 may be double-sided instead of one side or kneaded into the water-soluble sheet. You can also.
- the degree of dispersion can be easily made by changing the degree of dispersion of the adsorbent to be applied according to the level of the required function depending on the environment in which it is laid.
- the present invention shall be prepared as a multifunctional water-soluble sheet that is sandwiched between two water-soluble sheets by covering and sandwiching a water-soluble sheet that is divided into one surface and adsorbed adsorbent in a dispersed manner. can do.
- it can be devised not to contact highly reactive drugs such as microbial-degrading bacteria, oxygen sustained-release agents, substances consisting of combinations of fungal active nutrients, substances consisting of combinations of oxidizing agents or reducing agents.
- a multi-layered or partially coated type of adsorbents and additives can be produced.
- the multifunctional water-soluble sheet of this specification is collapsed when it comes into contact with moisture, and the reaction can be controlled for the first time.
- it can also be produced as a multifunctional water-soluble sheet held by two or more multilayer water-soluble sheets.
- FIG. 3 is a graph showing experimental data obtained in this small-scale test (pot test) in a bar graph comparing the concentration of dieldrin in the cucumber stalks and leaves with and without the activated carbon sheet and with the content of the activated carbon sheet. It is.
- the test method is as follows. The following sheets were prepared in the soil to which the fertilizer was added, and cucumber growing experiments were conducted on the condition that the activated carbon sheets prepared were added and not added, or the amount of activated carbon sheets added was doubled.
- the working conditions for the analysis of plant bodies in this small-scale test are as follows. Extraction: 100 ml of acetone was added to 10 g of the sample and pulverized and extracted, followed by filtration with 0.3 ⁇ m glass filter paper. The extract can be concentrated to 3 mL to produce a multifunctional water-soluble sheet supported by two or more multilayer water-soluble sheets. And purified by high resolution GC / MS.
- the instrumental analysis measurement conditions are as follows.
- the adsorbent-added water-soluble sheet is the same as the adsorbent-added water-soluble sheet after watering. In the dissolved state, it was shown that the single-sided partial coat sticking has higher sheet disintegration and better water solubility than double-sided front face adhesive.
- FIG. 4 is a photograph showing a construction state when the multifunctional water-soluble sheet of the present invention is distributed and constructed on outdoor soil.
- FIG. 4a shows the state of sprinkling assuming raining outdoors
- FIG. 4b is the state of stirring in the soil with a cultivator after sprinkling.
- a water-soluble paper 30CD-2 slowly disintegrating carboxymethylcellulose sheet
- mishima Paper Co., Ltd. currently Nippon Paper Papillia Co., Ltd.
- the activated carbon sheet A is prepared so as to be 100 g / m 2, and is in a state of being stirred in the soil with a cultivator after 10 minutes of watering with the amount of water spraying assuming rainfall outdoors. There was no fear that the sheet would disperse in the soil without being wound around the cultivator and re-scatter after the soil had dried.
- the processing liquid was sprayed uniformly on the surface of the water-soluble paper and then dried to obtain an experimental sample.
- Processed and unprocessed products with and without spraying of processing fluid were obtained, and water was poured on these experimental samples to compare the collapse rates of the processed and unprocessed sheets.
- the processed product sheet showed a disintegration rate of 3 times, and deformed into a shape that did not retain the original shape while foaming.
- FIG. 5 shows a multifunctional water-soluble sheet according to the present invention, wherein a water-soluble sheet coated with activated carbon is a multifunctional water-soluble sheet containing potassium bicarbonate and citric acid, and moisture is applied to the sheet distributed to the soil. It is a photograph which shows the state immediately after giving, and the state by stirring ten minutes after that.
- FIG. 5a shows a state of sheet collapse in a wet state immediately after moisture is given
- FIG. 5b shows a state in which the soil has been soaked ten minutes after moisture is given, and also by stirring. Each of the stirring states is well mixed with the soil.
- aqueous solution 30CD-2 was mixed with 85 parts of activated carbon, 5 parts of polyvinyl alcohol, 5 parts of potassium hydrogen carbonate and 5 parts of citric acid in a 90% aqueous ethyl alcohol solution, and the working solution was prepared by stirring. After spraying the processing liquid uniformly on the surface of the water-soluble paper, it was dried immediately to obtain a multifunctional water-soluble sheet (hereinafter, a sheet to which a foaming additive was added is referred to as “water-soluble sheet c”).
- water-soluble paper 30CD was used, and 95 parts of activated carbon and 5 parts of polyvinyl alcohol were placed in a 90% ethyl alcohol aqueous solution and stirred to prepare a processing solution.
- the processing liquid was sprayed so as to be uniform on the surface of the water-soluble paper and dried to obtain a multifunctional water-soluble sheet (hereinafter, a sheet to which no foaming additive was added was referred to as “water-soluble sheet d”).
- water-soluble sheet d a sheet to which no foaming additive was added.
- the present invention provides an adsorbent with a specific surface area of 800 m 2 / g or more as an example of a disintegration-controllable multifunctional adsorbent tablet for obtaining a harmful substance adsorbent tablet in the best form that can freely design adsorption performance and disintegration dispersion performance.
- a combination of crystalline cellulose and silicon dioxide is most desirable as a powder mixture having a fine powder activated carbon having an average particle size of 100 ⁇ m or less and 50% or less of the tablet weight and having a specific gravity of 1 or more.
- Table 1 is used as an example. Explained.
- Table 1 above shows whether or not the tableting formability when changing the blending ratio of the adsorbent and each powder added in combination, the disintegration time in the soil, the disintegration dispersion state in water, and the buoyancy status of the tablets.
- the comparison results are shown in Examples 1 to 6 of the present invention.
- Comparative Examples 1 to 4 are also shown. Comparative Examples 1 to 4 are powders of only activated carbon as an adsorbent or a combination of activated carbon and powder molded with polyvinyl alcohol, or a powder of only crystalline cellulose and silicon dioxide (no activated carbon as an adsorbent) in the present invention example. This is an example of a sample.
- Table 1 summarizes the soil and underwater disintegration time / dispersion situation according to individual shapes and blending ratios in Example 2 in the product examples 1 to 6 of the present invention, and the tablets of Comparative Examples 1 to 4 and the like. is there.
- the tableting results of the product examples 1 to 6 and comparative examples 1 to 4 of the present invention are disintegratable, “soil spraying”, “soil disintegration time”, “water spraying”, “water disintegration time” listed in the vertical items of Table 1
- the tableting conditions are as described in “Hardness” and “Tablet pressure” listed in the column item.
- Example 1 of the present invention porous inorganic fine powder is used as the adsorbent
- Example 2 of the present invention finely powdered activated carbon having a specific surface area of 1000 m @ 2 / g and an average particle size of 30 .mu.m is used. Used a similar specification.
- the content of each adsorbent was 20%, and the rest was tableted with a mixture of crystalline cellulose and silicon dioxide as excipients to obtain tablets.
- the present invention product example 1 and the present invention product example 2 have a good disintegration property against the soil by adding water, and as shown in FIG. It was possible to produce amphibious tablets.
- Examples 1 and 2 since tablets were produced without using a foaming agent, long-term stability was exhibited during storage.
- the ratio of the adsorbent is reduced to 1/2 (10%) of the previous example, and in the product example 4 of the present invention, the ratio of the other powder is not changed in the excipient.
- the example of the increased tablet is shown.
- Invention product example 5 shows an example of a tablet in which the ratio of the adsorbent is increased to 50% and at the same time the silicon dioxide powder is increased to 50%. In this example, it was dispersed and precipitated immediately after being added to water. When the amount of the adsorbent was increased by increasing the amount of silicon dioxide powder, it was possible to produce tablets with high disintegration and dispersibility without using a foaming agent, that is, without a foaming agent.
- This invention product example 6 is an example in which 10% of a foaming agent is additionally added.
- 10% of the foaming agent was additionally added, it was dispersed and precipitated immediately after being added to water as in Example 5 of the present invention.
- this tablet when it was not stored for a long time within 6 months, it floated for a long time and then dispersed and settled, and it was able to float in water for a long time approximately in proportion to the storage period.
- Production of fast-disintegrating and dispersible harmful substance-adsorbing tablets that can be floated in water for a long time if the tablet is mixed with a foaming agent as in Example 6 of the present invention and not stored for 6 months or longer in the tablet state. Is also possible.
- Comparative Example 1 was a commercially available finely powdered activated carbon, which was tableted using only finely powdered activated carbon, but could not be molded even with the maximum pressure of the tableting machine. Thereby, it turned out that tablet formation is impossible only with fine powder activated carbon for tablet manufacture.
- Comparative Example 2 was a commercially available finely powdered activated carbon, and dust floated on the soil and floated on the water surface as shown in FIG. 11 because the specific gravity was small in water. Thus, it has been found that when the activated carbon fine powder is provided in this form, it is inappropriate for any application to soil or water in a contaminated environment.
- Comparative Example 3 is a tablet obtained by tableting crystalline cellulose containing 2%, which is a commercially available excipient for direct compression. According to the results of the tablets, the moldability is good, but in the soil, even if water is sprayed on the tablets, it is difficult to disintegrate and sinks in water as shown in FIG. 12, but the dispersive dispersion state in water is a water temperature of 15 ° C. Was 600 seconds or more and was difficult to disintegrate and disperse. As a result, it was found that, in application to an environmentally polluted part, the disintegration value is extremely low in an environment that receives low-temperature moisture, so that there is a problem in application.
- Comparative Example 4 is obtained by mixing, molding, drying and solidifying 5 parts of the fine powdered activated carbon using 1 part of water-soluble polyvinyl alcohol.
- water-soluble polyvinyl alcohol improves the tableting moldability of the fine activated carbon by this addition, it floats on the water and, like Comparative Example 3, collapses even under the formation of the water environment of the contaminated part. As a result, it was found that this additive is not suitable.
- FIG. 9 is an experiment showing disintegration assuming a case in which tablets with a diameter of 20 mm, which are tableted at the blending ratio shown in Example 1 of the present invention in Table 1, are used in soil.
- FIG. 9 (a) shows a state where the tablet of Product Example 1 of the present invention is placed on the soil
- FIG. 9 (b) shows that 25 ml of water is dropped on the tablet three times at 10 second intervals with a pipette. It is a photograph 60 seconds after the start of dropping.
- FIG.9 (b) it turned out that it collapse
- a highly safe harmful substance-adsorbing tablet that can be used in dry soil and agriculture can be provided with a small amount of water.
- Test 2 (Chemical substance adsorption test in the applied water environment of Examples 1 to 6 of the present invention)
- the tablets used in this adsorption performance test were prepared as three types of tablets with reference to the product examples of the present invention shown in Table 1, and “Tablet A type”, “Tablet B type” and “Tablet C type” having different adsorbent addition amounts. 0.4 g of each tablet was used. A large amount of silicon dioxide powder is contained, and each tablet using adsorbents with different mixing ratios is used for the purpose of adsorbing harmful chemical substances in order to quickly disperse and disperse in water without using a foaming agent. That is, the adsorption performance test of chemical substances released from sludge into water was performed under the following conditions.
- the activated carbon which is the fine powder adsorbent of each tablet was commonly used with a specific surface area of 1000 m 2 / g and an average particle size of 30 ⁇ m.
- “Tablet A type” was prepared by mixing 0.18 g of silicon dioxide with 0.02 g of the activated carbon, and the remaining weight was tableted using crystalline cellulose as an excipient, and used as input sample tablet A.
- “Tablet B type” 0.10 g of silicon dioxide was kneaded with 0.10 g of the activated carbon, and the remaining weight was tableted using crystalline cellulose as an excipient, and used as input sample tablet B.
- Tablet C type was prepared by mixing 0.02 g of silicon dioxide with 0.18 g of the activated carbon and compressing the remaining weight using crystalline cellulose as an excipient to make input sample tablet C.
- the working conditions for the sample experiment in this small-scale experiment are as follows.
- sample collection method Take 20g of air-dried soil of the collected river sediment (sludge), put the weighed soil in a container, add 600mL of pure water, seal the container, and then rotate the shaker 100 times assuming the flow of river water
- the sample was shaken at room temperature for 1 week under the conditions of 1 min / min, and 200 mL of supernatant water collected from each sample every week was used as each sample. Then, 200 mL of supernatant water is collected. Thereafter, 0.4 g tablets of “Tablet A type”, “Tablet B type” and “Tablet C type” are put into this supernatant water for 7 tablets each. Water was collected under the above conditions every week for 3 weeks and analyzed. In order to maintain the elution equilibrium of the chemical substances in each sample, 200 mL of pure water was added, shaken again under the above conditions, and the same operation was repeated for 3 weeks.
- Example extraction Each week, 200 mL of supernatant water in each sample was filtered with glass filter paper, added to a separatory funnel containing 100 mL of hexane, shaken for 30 minutes, and subjected to liquid / liquid extraction three times. The hexane layer was then concentrated and purified using 100 mL of 25% dichloromethane / 75% hexane on a Florisil column and 10 mL of hexane on Enbicarb SPE. High resolution GC / MS was used for the measurement.
- GC oven temperature is 120 ° C (0.5 min) -10 ° C / min-180 ° C (0 min) -4 ° C / min-210 ° C (0 min) -10 ° C / min-300 ° C (10 min)
- GC column ENV-8MS (0.25mm inner diameter x 30m)
- injection method is splitless
- injection volume is 1 ⁇ L
- ionization method is EI +
- resolution is more than 10000 (10% trough)
- analysis method is SIM method and accurate mass (m / z) is divided into a low mass side and a high mass side so that multi-component simultaneous measurement can be performed.
- the internal standard method using 13C of each compound was performed.
- Table 2 shows the results of the adsorption performance test results of chemical substances released from the collected river bottom into water using the tablets with different adsorption performance shown in Table 1 as examples of the present invention. It is the graph represented as a change of the POPs reduction effect for every progress.
- Table 3 is a graph of reduced data excerpts related to the HCB and HCH systems from Table 2.
- Table 4 is a graph of reduced data excerpts from Table 2 regarding the remainder excluding the HCB and HCH systems.
- Table 5 above is a graph of reduced data related to the HCB system from Table 2, and is a graph showing a tendency of reducing harmful chemical substances eluted from the sediment into water.
- the tablet surface of the present invention was observed with a scanning electron microscope.
- the tablet for observation includes calcite, zeolite, activated clay, diatomaceous earth, granite pegmatite having porous, adsorption performance or powder having a specific gravity of 1 or more in whole or part of the adsorbent or fine powder.
- activated carbon black part
- powder white part having a specific gravity of 1 or more
- the activated carbon is pressed onto the powder surface.
- the remainder is mixed by mixing with activated carbon and silicon dioxide and mixed, and then compressed by tableting to give tablet hardness.
- tablet is poured into water, it is considered that when the water permeates into the gaps in the adsorbent or the porous portion of the powder, the excipient easily swells and the powder and the adsorbent are easily dispersed.
- the surface of the tablet-molded product is a scanning electron microscope. From the tablet surface photograph (35 times), it was observed that powders of various shapes were dispersed.
- This technology which can produce tablets that can be disintegrated by using porous powders and fine powder adsorbents, can be applied to the pharmaceutical field, and instead of adsorbents, sustained-release drugs If a porous fine powder impregnated with is used, it can be used for a rapidly disintegrating tablet having strong hardness that can simplify the production process.
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Soil Sciences (AREA)
- Environmental Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Processing Of Solid Wastes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
Description
一方、土壌汚染の問題として、土壌中にダイオキシン類、使用禁止となった農薬、揮発性有機物質、重金属、その他の有害物質が浸透し、これらの有害物質が雨水や地下水などの水分によって拡散されていくことが知られている。この土壌汚染問題を解決するため、上記した有害物質の吸着を目的とする吸着処理方法として、(a)土壌を入れ替える客土法、(b)土壌を洗浄し活性炭等の吸着剤に処理した水を付着させ回収する方法、(c)有害物質を分解する微生物を土壌と撹拌する方法、(d)酸化還元剤の地盤注入で分解する方法、(e)土壌の焼却方法などがあった。しかし、上記(a)の場合、隔壁や水処理施設を設けない限り、汚染未処理部分からまた水により移動し、再汚染が起こり、また上記(b)の場合、シルト分が除去されるので、反って地盤を不安定化させ、また植物に必要な栄養分を除去してしまう為、農業用の土壌には不向きな方法であるばかりでなく、さらに前記(a)(b)(c)の各方法は土壌の入れ替え、洗浄、分解無毒化等にそれぞれ、多額の費用を要すると共に相当の整備期間(数ヶ月から年相当)を必要とするものであった。
そこで、さらに、本発明錠剤について溶解状態の検証実験を試みた。この試験では、吸着成形体としての錠剤に包含される粉体について、その粒度が、200メッシュを通過する粒子径を有し、且つその粒子密度が平均粒度100μm以下で、その割合が粒度重量の80%を超える多孔質微細粉体を有害物質吸着剤とした場合には、この有害物質吸着剤を打錠加工した錠剤とした場合であれば、ビーカー底面に沈下し溶解することが確かめられた。この吸着剤の作製において採用する粉体の形態は、有害物質吸着剤に包含される多孔質微細粉体の粒度に関する属性規定値については、有害物質吸着多機能水溶性シートに包含する多孔質微細粉体のそれと同一のものでもよいことが確認された。
以上から、この有害物質吸着成形体の作製において採用する吸着剤の粉体について、有害物質吸着剤に包含される多孔質微細粉体の粒度に関する属性規定値を、その粒度が、200メッシュを通過する粒子径を有し、且つその粒子密度が平均粒度100μm以下で、その割合が粒度重量の80%を超える多孔質微細粉体であるとした場合には、これをシート又は錠剤への応用の加工処理を施した上で、少なくとも有害物質吸着水溶性シート又は沈殿可溶性有害物質吸着錠剤なる具体的な形で、低温水下でも効果的な崩壊制御を可能とする有害物質吸着成形体を提供できることを見出した。
本発明は、土壌又は水の汚染環境から有害物質を吸着する粉体の吸着剤を原料としバインダーにより成形される有害物質吸着成形体において、前記原料に他の機能を与えるための添加剤によってもバインダー機能をもたせることができ、且つ前記吸着剤と添加剤を含んだ配合物を可撓性の水溶性シートに付着するための素材又はそのまま成形するための素材として、当該素材を可撓性の水溶性シートと一体化し又はそのまま一体化した有害物質吸着成形体となし、ここで前記吸着剤の粉体は、その粒度が、200メッシュを通過する粒子径を有し、且つその粒子密度が平均粒度100μm以下で、その割合が粒度重量の80%を超える多孔質の微細粉体であり、一体化した成形体が水分による崩壊分散制御性を有するものであることを特徴とする有害物質吸着成形体を提供するものである。本発明はまた、前記有害物質吸着性の多孔質微細粉体を具体化して、前記吸着する粉体が、カルサイト、ゼオライト、活性白土、珪藻土、イルメナイトなどの鉱物、重金属の即効性吸着性能または保水機能をもつポリアミノ酸、多糖類、ポリアクリル酸、無機塩、キレート剤、若しくは800m2/g以上の活性炭の少なくとも1つ物質を含むものとしたり、また前記添加剤を具体化して、有害物質を分解促進する酸化剤、還元剤、分解菌、酸素徐放剤、菌活性栄養成分の少なくとも1つを含むものとした有害物質吸着成形体をも提供する。
また本発明は、請求項1記載の有害物質吸着成形体を前提とし、前記吸着体の粉体と、他の機能をもつ添加剤と、水溶性バインダーを含んだ配合物を付着素材となし、多糖類、セルロース、ポリビニルアルコール、カルボメチルセルロース、でんぷん等の分解性が早い主原料とするフィルム又は水溶紙又は水解紙又は、不職布のいずれか一つまたは組み合わせからなる可撓性の水溶性シートに付着し一体化し、前記有害物質吸着成形体をシートとした有害物質吸着成形体を提供する。ここで、本発明はその前記添加剤を具体化したものとして、肥料、農薬、PH調整剤、抗菌消毒剤の少なくとも一つを包含する水溶性シート型の有害物質吸着成形体をも提供する。
さらに本発明は、請求項1記載の有害物質吸着成形体を前提とし、吸着剤の粉体と、他の機能をもつ添加剤と、バインダーとなる賦形剤と、比重1以上の微粉体とを含み、これらの配合物をそのまま錠剤素材となして加圧一体化し、前記有害物質吸着成形体を浮力制御可能な錠剤とした有害物質吸着成形体を提供する。ここで、本発明は前記賦形剤を具体化するものとして、結晶性セルロース、カルボキシメチルセルロース、ヒドロキシプロピルセルロース、澱粉、乳糖、二酸化ケイ素、多糖類、マンニトール、無水リン酸水素カルシウム、少なくともいずれか1つを包含する有害物質吸着錠剤をも提供する。
本発明は、請求項4、5に記載した可撓性水溶性シートの形態とした有害物質吸着成形体によれば、請求項1記載の発明による効果に加えて、多機能付き水溶性シートを、微粉末の吸着剤および他の機能を持つ添加剤を含めて雨水などの少量の水分による場合でも、地下水汚染の恐れのある界面活性剤を用いることなく効率よく土壌に分散させることができ、また、土壌撹拌後または層状に埋設後、吸収剤を土壌に適度に密着させることができ、さらに、吸収剤の再飛散を防止し、植物への吸収を阻止し地下水への汚染を防止することができる。水溶性吸着シートは、水溶性であることから吸着効率を阻害しない。
本発明は、請求項6、7に記載した錠剤の形態とした、沈殿崩壊制御される有害物質吸着成形体によれば、請求項1記載の発明による効果に加えて、錠剤に追加配合された比重1以上の無機質微粉体によって、水中に放置されたとき、錠剤を沈降させると共に、錠剤が沈下する過程で崩壊時間の制御することができる。
要すれば、本発明は、所定の有害物質吸着成形体を製造する上で包含される複数の素材の一つに有害物質吸着剤を包含し、当該有害物質吸着剤について、その粒子形態属性の観点から具体化し、その粒度が、200メッシュを通過する粒子径を有し、且つその粒子密度が平均粒度100μm以下で、その割合が粒度重量の80%を超える多孔質微細粉体である有害物質吸着剤とし、当該有害物質吸着剤とバインダーと、さらに、この有害物質吸着以外に必要に応じて他の機能を具えた添加物を配合し、これらの配合材を原料に含んで加工処理することにおいて、容易に溶解可能な水溶性シート或いは容易に崩壊拡散可能な錠剤として作製することができ、この場合いずれも成形体をなす固体物として作製されているので、汚染環境への散布適用において、従来の微粉体の吸着剤の場合に必然的に発生していた飛散粉体による環境汚染の問題を解消すると共に、適用された土壌等環境への馴染みを良好にし、所期の有害物質吸着機能を効果的に遂行することができる。
以下、本発明の具体的な実施形態について述べる。
本発明は、水溶性シートに、水溶性のバインダーの練り込まれた微細粉体を付着または混練した多機能水溶性シートであって、粉体の組成が有害成分を吸着する微細粉体の吸着剤と必要に応じて添加することのある他の機能を付与するための添加剤のいずれか一つまたは組み合わせからなる粉体を使用し、微細粉体の吸着剤の粒度が、200メッシュを通過する粒子径を有すると共に、その粒子密度が、平均粒度100μm以下で、その割合が粒度重量の80%を超える微細粉体を20g/m2以上含む微細粉体物であることを特徴とする多機能水溶性シートを提供する。
この場合、前記微細粉体を、2枚以上の水溶性シートの間に付着させたものとする多機能水溶性シートを提供することもできる。
また、前記添加剤として、土壌殺菌、消毒、害虫駆除剤を含ませたり、特に殺菌剤としてアルコール濃度10~80%のエチルアルコール分を含ませたり,ポジティブリスト記載の農薬成分または薬剤を含ませたり,微細粉体の基本性能を阻害しない水溶性付着型の添加剤であって、アルコール類と多糖類の混合物からなる付着剤を使用したものであったり,前記水溶性付着型の添加剤が特にエチルアルコール、ポリビニルアルコール、多糖類増粘剤の混合物からなる付着剤を使用することが望ましい。上記において、シート全面に有害物質吸着剤を貼加するに際して、図1(b)の断面例に示すように、(b1)の片面全体に代えて、(b2)に示す両面全体にしたり、(b3)に示すように、水溶性シートに全体に混練したものとしたりすることもできる。
水溶性シートの吸着性能を確認するため、小規模試験(ポットテスト)として、きゅうり茎葉部におけるディルドリンの濃度を活性炭有無等により比較する実験をした。図3は、この小規模試験(ポットテスト)において得られた実験データを、キュウリ茎葉部におけるディルドリンの濃度比較を、活性炭シートの有無により、また活性炭シートの含有量により対比して棒グラフにより示す図である。
試験方法は次のとおりである。肥料を添加した土壌に次のシートを作成し、それぞれに作成した活性炭シートを添加した場合と添加しない場合、活性炭シートの添加量を倍増した場合などを条件として、きゅうり育成実験を行った。
三島製紙(株)「現日本製紙パピリア(株)」の水溶紙30MDP(速崩壊性カルボキシメチルセルロース類シート)を使用し、比表面積が1000m2/gであり、200メッシュを通過する粒子径を有すると共に、その粒子密度が、平均粒度100μm以下で、その割合が粒度重量の80%を超える仕様である異なるメーカーの市販活性炭A、市販活性炭Bを用い、90%エチルアルコール水溶液の中にそれぞれ活性炭95部、ポリビニルアルコール5部を入れ攪拌し各加工液を調整した。加工液を水溶紙の表面に均一になる様散布後乾燥し、それぞれ活性炭含有量100g/m2になる様に活性炭シートA、活性炭シートB作成し、活性炭シートなし場合との比較を比較する。
図3によれば、活性炭シートなし(活性炭無添加)のとき、100%で濃度変化はなかった。一方、活性炭添加の場合(活性炭シートA又は活性炭シートB)は、濃度比較値30~40%となり、大幅に低減することが判明した。さらに、活性炭の量について、100g/m2、200g/m2とで対比試験では、100g/m2の場合の濃度比較値は30~40%であったのに対し、200g/m2の場合の濃度比較値は略18%となり、活性炭単体で用いるのと同等な性能を示し、シート化による影響もなく、活性炭目付けを増量すると、ディルドリンの量を減量することが判った。 また、上記きゅうり育成実験では、活性炭添加に場合でも、きゅうりの成長阻害もなく、シートの無添加と比べても成長速度の差異は認められなかった。
抽出:試料10gに対してアセトン100mLを加えて粉砕抽出した後、0.3μmガラスろ過紙でろ過した。その抽出液を3mLまで濃縮してフロリジ二枚以上の多層水溶性シートで担持した多機能水溶性シートとして作製することもできる。
ルカラムおよびENVI-Carbカラムで精製して高分解能GC/MSで定量した。機器分析測定条件は以下である。
GCオーブンの温度120℃(0.5min)-10℃/min-180℃(0min)-4℃/min-210℃(0min)-10℃/min-300℃(10min)、GCカラムENV-8MS(0.25mm内径×30m)、注入法はスプリットレス、注入量は1μL、イオン化法はEI+、分解能は10000以上(10%谷)、分析方法はSIM法で精密質量 (m/z)269.8804, 71.8775を測定した。各化合物の13Cを用いた内部標準法で行った。
本発明の多機能水溶性シートを土壌に配布して施工する場合の一連の施行順序は、先ずビニールハウス内土壌表面に、所定幅の吸着性添加水溶性シートを展延敷設し、次いで散水後吸着性添加水溶性シートを溶解させ、耕耘機を走行して土壌を攪拌する。この土壌撹拌方法を採用するものとし、吸着剤添加面、片面と両面の場合の水溶性シートの崩壊性を検証したところ、吸着性添加水溶性シートは、散水後の吸着性添加水溶性シートの溶解状態において、片面部分コート貼着の方が両面前面粘着に比べ、シートの崩壊性が高く、水溶性に優れるものであることを示すものであった。
図4は、本発明の多機能水溶性シートを、屋外の土壌に配布して施工した場合の、施工状態を示す写真である。(図4a)は屋外で降雨を想定した散水中の状態を示し、(図4b)は散水後、耕耘機で土中攪拌している状態である。実験には、三島製紙(株)「現日本製紙パピリア(株)」の水溶紙30MDPより崩壊性の遅い安価な水溶紙30CD-2(遅崩壊性カルボキシメチルセルロース類シート)を使用し、比表面積が1000m2/gであり、200メッシュを通過する粒子径を有すると共に、その粒子密度が、平均粒度100μm以下で、その割合が粒度重量の80%を超える仕様である市販活性炭Aを用い、活性炭含有量100g/m2になる様に活性炭シートAを作成し、屋外で降雨を想定した散水量で、散水10分後、耕耘機で土中攪拌している状態である。耕耘機にシートが巻き付くことなく土壌に分散し、土壌が乾燥した後に再飛散する恐れもなかった。
本発明の多機能水溶性シートとしての、炭酸水素カリウム、クエン酸を含む多機能水溶性シート1cに水分を与えた場合のシートの状態変化について検証した。この検証試験によれば、当該シートは、水分を与えた直後ではシートの形を示す状態であったが、水分を与えたのち、すぐに発泡し、崩壊した状態となるものであった。実験には、三島製紙(株)「現日本製紙パピリア(株)」の水溶紙30CD-2を使用し、90%エチルアルコール水溶液の中に炭酸水素カリウム5部、クエン酸5部を入れ攪拌し加工液を調整した。加工液を水溶紙の表面に均一になる様散布後乾燥し実験サンプルを得た。加工液散布の有無による加工品と未加工品を得て、これらの実験サンプルに水を掛け、加工品と未加工品のシートの崩壊速度を比較した。その結果、未加工品の水溶紙に比べ、加工品シートは崩壊速度が3倍を示し、発泡しながら原形を留めない形に変形した。
図5は、本発明の多機能水溶性シートとして、活性炭コートした水溶性シートに、炭酸水素カリウム、クエン酸を含ませた多機能水溶性シートを使用し、土壌に配布した当該シートに水分を与えた直後の状態と、その十数分後の撹拌による状態を示す写真である。(図5a)は水分を与えた直後のウェット状態で、シート崩壊している状態を示し、(図5b)は水分を与えた十数分後の土壌に染込んだ状態を示し、撹拌によっても、土とよく混合されている撹拌状態をそれぞれ示す。比較のため活性炭コートした多機能水溶性シートの場合、これに水分を与えた直後のウェット状態では、原型をとどめる状態であった。この実験では、三島製紙(株)「現日本製紙パピリア(株)」の水溶紙30MDPより崩壊性の遅い安価な水溶紙30CD-2(遅崩壊性カルボキシメチルセルロース類シート)を使用した場合は、微細粉体付着加工に伴い未加工シート単体よりも崩壊性が遅くなる。
発泡性の添加剤を、吸着剤の微細粉体に混入するか又はシートとして加工し、得られたシートにより崩壊性を早めることができるかどうかその検証を行った。
ここでは構成が簡単な吸着剤として活性炭を入れた系での実験を示す。
水溶紙30CD-2に、90%エチルアルコール水溶液の中に活性炭85部、ポリビニルアルコール5部、炭酸水素カリウム5部、クエン酸5部を入れ攪拌し加工液を調整した。加工液を水溶紙の表面に均一になる様散布後直ちに乾燥し多機能水溶性シート(以下発泡性の添加剤を添加したシートを「水溶性シートc」と称する)を得た。また、同様に水溶紙30CDを使用し、90%エチルアルコール水溶液の中に活性炭95部、ポリビニルアルコール5部を入れ攪拌し加工液を調整した。加工液を水溶紙の表面に均一になる様散布後乾燥し多機能水溶性シート(以下発泡性の添加剤を添加しなかったシートを「水溶性シートd」と称する)を得た。水分を添加した場合、一方の水溶性シートdは水分添加後原型をとどめていたが、他方の多機能水溶性シートcは水を接触した直後に発泡しシート崩壊を始め、十数分後にはほぼ土壌に染込んだ状態が得られ、棒で攪拌後にはほとんど土壌と区別つかない状態となった。前記同様の実験で、吸着剤の種類を変更した場合や添加剤の種類を変えて場合においても検証したが吸着剤の吸収性能低下、シート崩壊性の遅延、添加剤の機能低下は見られなかった。
表1は、実施例2における個別の形状、配合割合に伴う、土壌、水中崩壊時間・分散状況比較を本発明品例1~6にまとめ、比較例1~4の錠剤等と共にまとめたものである。
本発明品例1~6及び比較例1~4に係る打錠結果の崩壊性可否については、表1の縦項目に挙げた「土壌散布」「土壌崩壊時間」「水中散布」「水中崩壊時間」に係る各横欄において記載したとおりであり、また、打錠条件については、縦欄項目に挙げた「硬度」「打錠圧」に記載したとおりである。
本発明品例1においては、吸着剤に多孔質の無機系微粉末を用い、本発明品例2においては吸着剤に比表面積1000m2/g、平均粒度30μmの微粉末活性炭を用い、微粉末活性炭はこれと同様な仕様のものを使った。本発明品例1、2において、前記各吸着剤の配合を20%とし、残りを賦形剤である結晶性セルロースと二酸化ケイ素の混合物で打錠し、錠剤を得た。
前記本発明品例1と本発明品例2は、水を加えることによって土壌に対する崩壊性がよく、図6で示すように水中にそれぞれ投入すると一度沈んで発泡しながら浮かび上がり、分散するという特徴を示し、水陸両用の錠剤の製造が可能となるものであった。またこの品例1,2においては、発泡剤を用いないで錠剤を制作しているので保存に長期安定性を示した。
本発明品例5は吸着剤の割合を50%に増やし、同時に二酸化ケイ素の粉体を50%に増やした錠剤の例を示す。この例では、水に投入直後に分散沈殿した。二酸化ケイ素の粉体が増えることにより、吸着剤の量を増加したときには、発泡剤を用いることなく、即ち発泡剤なしで、崩壊分散性の早い錠剤を作ることが出来た。
比較例1は市販の微粉末活性炭であり、微粉末活性炭のみ使用して打錠したが、打錠機械の最大圧力でも成型できなかった。これにより、錠剤作製上、微粉末活性炭のみでは打錠成形が不可であることが判った。
比較例2は市販の微粉末活性炭であり、土壌では粉塵が舞い、水中では比重が小さいために図11で示すように水面に浮いてしまった。これにより、活性炭微粉末がこの形態のままで提供される場合には、汚染環境の土壌又は水面へのいずれの適用においても不適切であることが判った。
同様に比較例4は水溶性のポリビニルアルコール1部を用いて前記微粉末活性炭5部を混合し成型、乾燥し固めたものである。これを土壌に使用した場合では、水を散水しても崩壊分散せず、水中使用の場合には、図13に示すように水に浮き、1日以上たっても溶けなかった。
これにより、水溶性のポリビニルアルコールでは、この添加により微細活性炭の打錠成形性が改善されるとしても、水に浮き、また比較例3と同様、汚染箇所の水環境の形成下でも崩壊することがないことから、この添加剤は適切なものではないことが判った。
図9は、上述した表1の本発明品例1で示した配合割合で打錠した直径20mmの錠剤を土壌で使用する場合を想定した崩壊性を示す実験である。 図9(a)は本発明品例1の錠剤を土壌の上に置いた状態を示し、図9(b)は前記錠剤に水25mlを10秒間隔で、3回ピペットで滴下し、水の滴下開始60秒後の写真である。図9(b)では、土壌に対し少量の水で30秒以内に崩壊し、土壌の隙間に微粉末吸着剤が流れ込む様子がわかった。そして土壌と吸着剤がよく密着していた。
本発明品例1によれば、少量の水分で、乾燥地域土壌や農業にも使用可能な安全性の高い有害物質吸着錠剤を提供することができた。
この吸着性能試験で使用の錠剤は、表1の本発明品例を参考に3種類の錠剤を作製し、吸着剤添加量の異なる「錠剤Aタイプ」、「錠剤Bタイプ」及び「錠剤Cタイプ」の各錠剤0.4gを使用した。二酸化ケイ素の粉体が多く含まれ、発泡剤を利用しないで水中に速崩壊分散し、有害化学物質を吸着する目的で、配合率の異なる吸着剤を用いた前記各錠剤を、河川の底質つまりヘドロから水へ放出する化学物質の吸着性能試験を下記の条件で行った。
「錠剤Aタイプ」は、前記活性炭0.02gに二酸化ケイ素0.18g混練し、残りの重量は賦形剤に結晶性セルロースを用いて打錠したものを投入試料錠剤Aとした。同様に「錠剤Bタイプ」は、前記活性炭0.10gに二酸化ケイ素0.10g混練し、残りの重量は賦形剤に結晶性セルロースを用いて打錠したものを投入試料錠剤Bとした。また、「錠剤Cタイプ」は、前記活性炭0.18gに二酸化ケイ素0.02g混練し、残りの重量は賦形剤に結晶性セルロースを用いて打錠したものを投入試料錠剤Cとした。
なお、この小規模実験における試料の実験に際しての作業条件は次の通りである。
採取した河川底質(ヘドロ)の風乾した土壌を20gとり、秤量した土壌を容器に入れ、次に純水600mL加え、容器密閉後、川の水の流れを想定して横振とう機100回転/分の条件下におけて1週間室温で振とうを行い、毎週各試料における上澄み水200mL採取したものをそれぞれの試料とした。そして上澄み水200mL採取する。その後、この上澄み水に「錠剤Aタイプ」、「錠剤Bタイプ」及び「錠剤Cタイプ」の0.4gの錠剤を各7錠あて投入する。3週間に亙り、1週ごとに水を前記条件で採取し、分析した。各試料における化学物質の溶出平衡を保つため、200mLの純水を添加し、再び前記条件で振とうを行い、3週間同様の作業を繰り返した。
(試料の抽出):毎週各試料における上澄み水200mLをガラスろ紙でろ過し、ヘキサンが100mL入った分液ロートに加えて、30分間振り、3回液・液抽出を行った。その後、ヘキサン層を濃縮してフロリジルカラムにおいて25%ジクロロメタン/75% ヘキサンを100mL、そしてエンビカルブSPEにおいてヘキサン10mLを用いて精製した。
測定は高分解能GC/MSを用いた。
GCオーブンの温度は120℃(0.5分)-10℃/分-180℃(0分)-4℃/分-210℃(0分)-10℃/分-300℃(10分)、GCカラムENV-8MS(0.25mm内径×30m)、注入法はスプリットレス、注入量は1μL、イオン化法はEI+、分解能は10000以上(10%谷)、分析方法はSIM法で以下のよう精密質量(m/z)の低質量側と高質量側に分け、多成分一斉測定ができるようにした。各化合物の13Cを用いた内部標準法で行った。
(高質量側(m/z)):トランス,シス-ヘプタクロルエポキサイド 352.8442, 354.8413,
13C トランス,シス-ヘプタクロルエポキサイド 362.8778, 364.8748, トランス,シス-クロルデン 372.826, 374.823, 13C トランス,シス-クロルデン382.8595, 384.8566, オキシクロルデン386.8052, 388.8023, 13C
オキシクロルデン396.8388, 398.8358, トランス,シス-ノナクロル406.787, 408.784, 13C トランス,シス-ノナクロル 416.8205, 418.8176,
(低質量側(m/z)):ヘキサクロロシクロヘキサン(HCH) 216.9145, 218.9116, 13C ヘキサクロロシクロヘキサン222.9347, 224.9317, ジクロロジフェニルトリクロロエタン(DDT), ジクロロジフェニルジクロロエタン(DDD)235.0081, 237.0052, 13C DDT, DDD 247.0484, 249.0454, ジクロロジフェニルジクロロエチレン(DDE) 246.0003, 247.9974, 13C DDE 258.0406, 260.0473, アルドリン、ディルドリン、エンドリン 262.857, 264.854, 13C アルドリン、ディルドリン、エンドリン269.8804, 271.8775, マイレックス、ヘプタクロル271.8102, 273.8072, 13C マイレックス、ヘプタクロル276.8269, 278.824, ヘキサクロロベンゼン(HCB)283.8102, 285.8072, 13C ヘキサクロロベンゼン289.8303, 291.8273に2回に分けて測定を行った。
実験の結果を表2~5によって示す。
結果は各錠剤A、錠剤B、錠剤Cともに水への速い崩壊性を示し、泡を出しながら崩壊する様子の例を図10に示す。上記した表2から表5に示す通り、「錠剤無添加」で示す錠剤未投入部分では、水への有害化学物質の溶出が確認され、錠剤無添加の場合は溶出された有害化学物質がほぼ一定であるのに対し、各錠剤A、錠剤B、錠剤Cを投入した後には、各有害化学物質の吸着速度には物質により時間差はあるが、ほとんどの検出された各有害化学物質の水への溶出量が大幅に少なくなっていることが確認できた。表5は、表2より抜粋した水への底質からの溶出した有害化学物質「α-HCH 」の挙動の一例である。
本発明の錠剤表面を走査型電子顕微鏡で観察した。
ここで観察用の錠剤には、吸着剤または微細粉体の全体または一部に、多孔質、吸着性能または比重1以上の粉体をもつ、カルサイト、ゼオライト、活性白土、珪藻土、花崗岩ペグマタイト、イルメナイトなどの天然由来鉱物や、多孔質または吸着性能をもつ、空孔の大きさが制御された人工ゼオライトのいずれか1つまたは複数の組み合わせからなる物質を含むもののうち、微粉末吸着剤に比表面積1000m2/g、平均粒度30μmの活性炭を用い、粉体に多孔質の二酸化ケイ素、賦形剤に結晶性セルロースを用いた。
残りは活性炭と二酸化ケイ素と混ぜ、混練することにより入り込み、打錠することにより圧着し、錠剤硬度が出る。錠剤は水中への投擲の際、水分が吸着剤または粉体の多孔質部分にある隙間に浸透することにより、賦形剤が膨潤しやすく、粉体と吸着剤が分散しやすくなると考えられる。
走査型電子顕微鏡(600倍)によれば、活性炭、多孔質の粉体、賦形剤の混合物における錠剤成型品の表面に、微粉末の活性炭(黒色部分)、粉体(白色部分)、錠剤表面上の亀裂をそれぞれ観察することができた。
錠剤硬度が変わらず、多孔質の二酸化ケイ素の含有率が高いほど崩壊性が早く、賦形剤である量も減る傾向にあった。
表面には、多孔質の二酸化ケイ素の含有率が高いほど錠剤表面にひび割れが多く存在したが、硬度に影響はなかった。このことから、表面のひび割れにより、内部に水が浸透しやすくなっていると考えられる。
2 吸着剤
3 添加剤
Claims (7)
- 土壌又は水の汚染環境から有害物質を吸着する粉体の吸着剤を原料としバインダーにより成形される有害物質吸着成形体において、前記原料に他の機能を与えるための添加剤によってもバインダー機能をもたせることができ、且つ前記吸着剤と添加剤を含んだ配合物を可撓性の水溶性シートに付着するための素材又はそのまま成形するための素材として、当該素材を可撓性の水溶性シートと一体化し又はそのまま一体化した有害物質吸着成形体となし、ここで前記吸着剤の粉体は、その粒度が、200メッシュを通過する粒子径を有し、且つその粒子密度が平均粒度100μm以下で、その割合が粒度重量の80%を超える多孔質の微細粉体であり、一体化した成形体が水分による崩壊分散制御性を有するものであることを特徴とする有害物質吸着成形体。
- 請求項1において、前記吸着剤の粉体が、カルサイト、ゼオライト、活性白土、珪藻土、イルメナイトなどの鉱物、重金属の即効性吸着性能または保水機能をもつポリアミノ酸、多糖類、ポリアクリル酸、無機塩、キレート剤、若しくは800m2/g以上の活性炭の少なくとも1つ物質を含むものであることを特徴とする有害物質吸着成形体。
- 請求項1又は2において、前記添加剤として、有害物質を分解促進する酸化剤、還元剤、分解菌、酸素徐放剤、菌活性栄養成分の少なくとも1つを含むことを特徴とする有害物質吸着成形体。
- 請求項1から3のいずれかにおいて、前記吸着剤の粉体と、他の機能をもつ添加剤と、水溶性バインダーを含んだ配合物を付着素材となし、多糖類、セルロース、ポリビニルアルコール、カルボメチルセルロース、でんぷん等の分解性が早い主原料とするフィルム又は水溶紙又は水解紙又は、不職布のいずれか一つまたは組み合わせからなる可撓性の水溶性シートに付着し一体化し、前記有害物質吸着成形体をシートとしたことを特徴とする有害物質吸着成形体。
- 請求項4において、前記添加剤に、肥料、農薬、PH調整剤、抗菌消毒剤の少なくとも一つを包含することを特徴とする有害物質吸着成形体。
- 請求項1から3のいずれかにおいて、前記吸着剤の粉体と、他の機能をもつ添加剤と、バインダーとなる賦形剤と、比重1以上の微粉体とを含み、これらの配合物をそのまま錠剤素材となして加圧一体化し、前記有害物質吸着成形体を浮力制御可能な錠剤としたことを特徴とする有害物質吸着成形体。
- 請求項6において、前記賦形剤が結晶性セルロース、カルボキシメチルセルロース、ヒドロキシプロピルセルロース、澱粉、乳糖、二酸化ケイ素、多糖類、マンニトール、無水リン酸水素カルシウム、少なくともいずれか1つを包含することを特徴とする有害物質吸着成形体。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09818981A EP2366451A1 (en) | 2008-10-08 | 2009-10-07 | Hazardous substance adsorbing formed body |
CN2009801400367A CN102176965B (zh) | 2008-10-08 | 2009-10-07 | 有害物质吸附成形体 |
US13/079,466 US20110269217A1 (en) | 2008-10-08 | 2011-04-04 | Hazardous substance adsorbing tablet |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008-261258 | 2008-10-08 | ||
JP2008261258A JP2010089005A (ja) | 2008-10-08 | 2008-10-08 | 多機能水溶性シート |
JP2009-107293 | 2009-04-27 | ||
JP2009107293A JP5596936B2 (ja) | 2009-04-27 | 2009-04-27 | 有害物質吸着錠剤 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/079,466 Continuation-In-Part US20110269217A1 (en) | 2008-10-08 | 2011-04-04 | Hazardous substance adsorbing tablet |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010041441A1 true WO2010041441A1 (ja) | 2010-04-15 |
Family
ID=42100402
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2009/005213 WO2010041441A1 (ja) | 2008-10-08 | 2009-10-07 | 有害物質吸着成形体 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20110269217A1 (ja) |
EP (1) | EP2366451A1 (ja) |
KR (1) | KR101592620B1 (ja) |
CN (1) | CN102176965B (ja) |
WO (1) | WO2010041441A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103608104A (zh) * | 2011-02-03 | 2014-02-26 | 萨里大学 | 含多孔碳基材的复合吸附材料 |
KR101516095B1 (ko) | 2010-08-24 | 2015-05-04 | 저장 지안종 뱀부 인더스트리 씨오., 엘티디. | 다공질 탄소립 공기정화제 및 그 생산방법 |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3000496B1 (fr) * | 2012-12-28 | 2015-12-04 | Pintat Benoit Marcel | Composition pour surface exterieure |
GB201317035D0 (en) * | 2013-09-26 | 2013-11-06 | Bcuk Aquatics Ltd | Water treatment |
CN104449751B (zh) * | 2014-10-23 | 2017-07-28 | 江苏盖亚环境工程有限公司 | 一种降低高浓度钴、铅污染的土壤修复剂及其应用 |
CN108079970A (zh) * | 2017-11-28 | 2018-05-29 | 农业部环境保护科研监测所 | 有机物吸附凝胶材料、凝胶吸附体及其制备方法和应用 |
WO2019171472A1 (ja) * | 2018-03-06 | 2019-09-12 | 進一郎 糸井 | 農業用マット |
CN108637008B (zh) * | 2018-06-22 | 2020-09-08 | 煜环环境科技有限公司 | 一种阶梯释放型重金属污染土壤固化稳定化修复方法 |
CN109233375B (zh) * | 2018-08-30 | 2019-11-26 | 武汉理工大学 | 一种高吸附性、高粘结强度焙烧硅藻泥及其制备方法 |
CN109174961B (zh) * | 2018-08-31 | 2020-04-10 | 成都理工大学 | 一种土壤修复用微生物缓释球 |
KR102183844B1 (ko) * | 2018-12-06 | 2020-11-27 | 한국기초과학지원연구원 | 방사성 세슘 제염제 및 이를 이용한 수심-맞춤형 방사성 세슘 제염방법 |
CN110404508A (zh) * | 2019-08-06 | 2019-11-05 | 中南大学 | 一种用于吸附并降解大气颗粒污染物的土壤及其制备方法 |
KR102142494B1 (ko) * | 2020-03-31 | 2020-08-07 | 강연균 | 누출 화학물질 제독용 중화흡수제 및 그 제조방법과 이를 충진한 중화기 |
CN111575016B (zh) * | 2020-06-18 | 2021-08-24 | 四川时代绿洲环境修复股份有限公司 | 一种重金属污染土壤修复材料及其制备方法和使用方法 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05212373A (ja) * | 1992-02-04 | 1993-08-24 | Soko Seiren Kk | 農薬等の除去シート |
JP3008806U (ja) * | 1994-05-06 | 1995-03-20 | アサヒカーボン株式会社 | 臭い消し |
JPH09202706A (ja) * | 1996-01-25 | 1997-08-05 | Hinata:Kk | 排水用殺菌洗浄剤 |
JP2815535B2 (ja) | 1992-12-04 | 1998-10-27 | 三共株式会社 | 拡展性水溶紙分包農薬固形剤 |
JP2003104788A (ja) | 2001-09-27 | 2003-04-09 | Kobayashi Hardware Kk | シート状肥料及びその製造方法・使用方法 |
JP2004358027A (ja) * | 2003-06-06 | 2004-12-24 | Lintec Corp | 消臭剤組成物および水解性消臭体 |
JP2005314149A (ja) * | 2004-04-28 | 2005-11-10 | Kuraray Chem Corp | 活性炭成型体の製造方法 |
JP2006116382A (ja) * | 2004-10-19 | 2006-05-11 | Taimei Chemicals Co Ltd | 易水中崩壊性珪藻土成形物及びその製造方法 |
JP2007197357A (ja) | 2006-01-26 | 2007-08-09 | Toa Yakuhin Kk | 乾式直打速崩壊性錠剤 |
JP2008261258A (ja) | 2007-04-11 | 2008-10-30 | Toyota Motor Corp | 内燃機関のegrシステム |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3596334B2 (ja) | 1999-02-26 | 2004-12-02 | マツダ株式会社 | 吸着処理剤の製造方法 |
JP2002253649A (ja) | 2001-03-02 | 2002-09-10 | Union Pack Kk | 錠剤の製造方法 |
-
2009
- 2009-10-07 KR KR1020117008189A patent/KR101592620B1/ko active IP Right Grant
- 2009-10-07 WO PCT/JP2009/005213 patent/WO2010041441A1/ja active Application Filing
- 2009-10-07 EP EP09818981A patent/EP2366451A1/en not_active Withdrawn
- 2009-10-07 CN CN2009801400367A patent/CN102176965B/zh active Active
-
2011
- 2011-04-04 US US13/079,466 patent/US20110269217A1/en not_active Abandoned
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05212373A (ja) * | 1992-02-04 | 1993-08-24 | Soko Seiren Kk | 農薬等の除去シート |
JP2815535B2 (ja) | 1992-12-04 | 1998-10-27 | 三共株式会社 | 拡展性水溶紙分包農薬固形剤 |
JP3008806U (ja) * | 1994-05-06 | 1995-03-20 | アサヒカーボン株式会社 | 臭い消し |
JPH09202706A (ja) * | 1996-01-25 | 1997-08-05 | Hinata:Kk | 排水用殺菌洗浄剤 |
JP2003104788A (ja) | 2001-09-27 | 2003-04-09 | Kobayashi Hardware Kk | シート状肥料及びその製造方法・使用方法 |
JP2004358027A (ja) * | 2003-06-06 | 2004-12-24 | Lintec Corp | 消臭剤組成物および水解性消臭体 |
JP2005314149A (ja) * | 2004-04-28 | 2005-11-10 | Kuraray Chem Corp | 活性炭成型体の製造方法 |
JP2006116382A (ja) * | 2004-10-19 | 2006-05-11 | Taimei Chemicals Co Ltd | 易水中崩壊性珪藻土成形物及びその製造方法 |
JP2007197357A (ja) | 2006-01-26 | 2007-08-09 | Toa Yakuhin Kk | 乾式直打速崩壊性錠剤 |
JP2008261258A (ja) | 2007-04-11 | 2008-10-30 | Toyota Motor Corp | 内燃機関のegrシステム |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101516095B1 (ko) | 2010-08-24 | 2015-05-04 | 저장 지안종 뱀부 인더스트리 씨오., 엘티디. | 다공질 탄소립 공기정화제 및 그 생산방법 |
CN103608104A (zh) * | 2011-02-03 | 2014-02-26 | 萨里大学 | 含多孔碳基材的复合吸附材料 |
Also Published As
Publication number | Publication date |
---|---|
CN102176965B (zh) | 2013-11-20 |
US20110269217A1 (en) | 2011-11-03 |
KR101592620B1 (ko) | 2016-02-05 |
KR20110066174A (ko) | 2011-06-16 |
EP2366451A1 (en) | 2011-09-21 |
CN102176965A (zh) | 2011-09-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2010041441A1 (ja) | 有害物質吸着成形体 | |
Ekebafe et al. | Polymer applications in agriculture | |
Fernández-Pérez et al. | Alginate and lignin-based formulations to control pesticides leaching in a calcareous soil | |
EP2307333B1 (de) | Materialverbund aus polymermaterialien und einer porösen, mineralischen matrix sowie deren herstellung und anwendung | |
Céspedes et al. | Modifying sorbents in controlled release formulations to prevent herbicides pollution | |
Fernández-Pérez et al. | Prevention of chloridazon and metribuzin pollution using lignin-based formulations | |
EP2282628B1 (de) | Bodenhilfsstoff | |
Jain et al. | Effect of a synthetic polymer on adsorption and leaching of herbicides in soil | |
DE102009034137A1 (de) | Flüssigkeiten speicherndes und expandierbares Kompositmaterial sowie dessen Herstellung und Anwendung | |
CN105754605A (zh) | 一种土壤多种重金属污染物的处理修复颗粒和处理修复方法 | |
Onyido et al. | Environmentally friendly formulations of trifluralin based on alginate modified starch | |
JP2010089005A (ja) | 多機能水溶性シート | |
US7824129B2 (en) | Low-impact delivery system for in situ treatment of contaminated sediment | |
KR100955703B1 (ko) | 아스파르틱산-알킬아스파르틱산 공중합체를 함유하는 염류장해 경감과 식물 활착이 개선된 친환경 토양개량제 조성물 및 이의 용도 | |
JP5596936B2 (ja) | 有害物質吸着錠剤 | |
JPH0460561B2 (ja) | ||
US10798885B2 (en) | Granular compositions and methods for drought mitigation | |
CN105733591A (zh) | 一种土壤有机物污染的处理修复颗粒和处理修复方法 | |
CN109504391B (zh) | 一种铜污染土壤原位长效修复材料 | |
Kumawat et al. | Adsorption studies of methyl parathion on papaya seed activated carbon: an ecofriendly approach | |
KR102015327B1 (ko) | 바이오차를 이용한 토양에 잔류하는 유기염소계 살충제의 식물 내 흡수를 억제하는 방법 | |
CN105733590A (zh) | 一种土壤无机物污染的处理修复颗粒和处理修复方法 | |
Okeola et al. | Remediation of aqueous solution of cypermethrin and chlorpyriphos using derived adsorbent from Jatropha curcas | |
JP2007211223A (ja) | 分解性を特長とする融雪材および/または土壌改良材。 | |
Aloo | Pollution of Ground and Surface Waters with Agrochemicals |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200980140036.7 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09818981 Country of ref document: EP Kind code of ref document: A1 |
|
DPE1 | Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101) | ||
ENP | Entry into the national phase |
Ref document number: 20117008189 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009818981 Country of ref document: EP |