WO2014027613A1 - 硫酸還元菌の選択的制菌方法、前記方法により硫酸還元菌の増殖を抑制する石膏組成物、石膏系固化材及び石膏系建材 - Google Patents
硫酸還元菌の選択的制菌方法、前記方法により硫酸還元菌の増殖を抑制する石膏組成物、石膏系固化材及び石膏系建材 Download PDFInfo
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- WO2014027613A1 WO2014027613A1 PCT/JP2013/071612 JP2013071612W WO2014027613A1 WO 2014027613 A1 WO2014027613 A1 WO 2014027613A1 JP 2013071612 W JP2013071612 W JP 2013071612W WO 2014027613 A1 WO2014027613 A1 WO 2014027613A1
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- WIPO (PCT)
- Prior art keywords
- gypsum
- sulfate
- bacteria
- chelated
- reducing bacteria
- Prior art date
Links
- 239000010440 gypsum Substances 0.000 title claims abstract description 184
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 184
- 241000894006 Bacteria Species 0.000 title claims abstract description 114
- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 49
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 title claims description 44
- 239000004566 building material Substances 0.000 title claims description 18
- 230000035755 proliferation Effects 0.000 title abstract description 3
- 230000012010 growth Effects 0.000 claims description 36
- 239000002738 chelating agent Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 13
- 239000003446 ligand Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 9
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- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 9
- 230000009422 growth inhibiting effect Effects 0.000 description 8
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- 238000011156 evaluation Methods 0.000 description 7
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
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- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 230000001028 anti-proliverative effect Effects 0.000 description 2
- AFYNADDZULBEJA-UHFFFAOYSA-N bicinchoninic acid Chemical compound C1=CC=CC2=NC(C=3C=C(C4=CC=CC=C4N=3)C(=O)O)=CC(C(O)=O)=C21 AFYNADDZULBEJA-UHFFFAOYSA-N 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 241001509319 Desulfitobacterium Species 0.000 description 1
- 241000186539 Desulfotomaculum ruminis Species 0.000 description 1
- 241000605747 Desulfovibrio africanus Species 0.000 description 1
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
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- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
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- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
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- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
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Images
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/06—Aluminium; Calcium; Magnesium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/02—Biological treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
- C04B28/142—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements
- C04B28/144—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being a flue gas desulfurization product
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/2092—Resistance against biological degradation
Definitions
- the present invention relates to a selective sterilization method for sulfate-reducing bacteria that suppresses only the growth of sulfate-reducing bacteria without inhibiting the growth of other bacteria. Moreover, this invention relates to the gypsum composition which can suppress generation
- a sulfate-reducing bacterium is a bacterium that acquires energy by oxidizing organic substances using sulfate ions as electron acceptors.
- the growth temperature range of the sulfate-reducing bacteria varies depending on the type, and there are thermophilic bacteria, mesophilic bacteria, psychrophilic bacteria and psychrophilic bacteria.
- thermophilic bacteria mesophilic bacteria
- psychrophilic bacteria psychrophilic bacteria
- psychrophilic bacteria psychrophilic bacteria.
- bacteria that grow well near neutrality and bacteria that grow well under acidic or alkaline conditions there are bacteria that grow well under acidic or alkaline conditions.
- the survival area covers a wide area such as marine mud, general soil, hydrothermal eruption area, and pipeline.
- hydrogen sulfide which is a reduced form of sulfate ions
- this hydrogen sulfide is highly toxic and corrosive and emits a bad odor, it causes a problem if it is produced in a large amount.
- hydrogen sulfide is generated when sulfate-reducing bacteria acquire energy using sulfate ions contained in natural water, fertilizers (ammonium sulfate, etc.) as an electron acceptor, which inhibits the growth of crops in farmland, or iron materials (embedded) There are known problems such as corrosion of pipes).
- Waste gypsum board contains paste and paper (nutrients) in addition to calcium sulfate (sulfate ion), which is the main component. Therefore, sulfate-reducing bacteria in the soil may assimilate waste gypsum board and generate hydrogen sulfide.
- the present applicant has disclosed a method of suppressing the growth of sulfate-reducing bacteria and suppressing the generation of hydrogen sulfide by adding an anthraquinone compound to a soil treatment material mainly composed of gypsum (patent) Reference 1).
- Patent Document 1 has a problem in terms of manufacturing cost because an extremely expensive anthraquinone compound is used.
- applications that are used in large quantities, such as soil treatment materials there has been a situation where the cost is an obstacle and the use is not expanded.
- a method of suppressing the growth of sulfate-reducing bacteria and suppressing the generation of hydrogen sulfide is also disclosed (see Patent Document 2).
- Patent Document 2 Since the method described in Patent Document 2 uses an aluminum compound that is cheaper and easier to obtain than an anthraquinone compound, the method described in Patent Document 1 can solve the problem of manufacturing cost. However, there is still room for improvement in the following points.
- the present invention has been made to solve the above-described problems of the prior art. That is, the present invention provides a method for selectively sterilizing sulfate-reducing bacteria, a gypsum composition, and a gypsum-based solidifying material that can selectively inhibit the growth of sulfate-reducing bacteria without inhibiting the growth of other bacteria. And a gypsum-based building material.
- Method for selective sterilization of sulfate-reducing bacteria That is, according to the present invention, the selective control of sulfate-reducing bacteria is characterized by selectively inhibiting the growth of the sulfate-reducing bacteria by coexisting chelated Al in the environment where the sulfate-reducing bacteria are present.
- a fungal method is provided.
- the Al 3+ source is at least one Al compound selected from the group consisting of Al 2 O 3 , AlCl 3 , Al (OH) 3 and Al 2 (SO 4 ) 3.
- the sulfate-reducing bacteria are preferably bacteria that inhabit in a medium temperature range (20 to 45 ° C.) and a neutral range (pH 5 to 9).
- Gypsum composition Further, according to the present invention, gypsum (A) and chelated Al (B) are contained, and the chelated Al (B) is 0.01 to 20 masses per 100 mass parts of the gypsum (A). A gypsum composition characterized by containing in a range of parts is provided.
- the composition of the present invention preferably contains an Al 3+ source (b-1) and a chelating agent (b-2) instead of the chelated Al (B).
- the Al 3+ source (b-1) is selected from the group consisting of Al 2 O 3 , AlCl 3 , Al (OH) 3 and Al 2 (SO 4 ) 3. It is preferably at least one kind of Al compound.
- part or all of the gypsum is preferably waste gypsum, and part or all of the gypsum is preferably calcined gypsum.
- Gypsum-based solidifying material, gypsum-based building material Furthermore, according to the present invention, there is provided a gypsum-based solidifying material characterized in that a part or all of the gypsum is calcined gypsum among the gypsum composition. Further, according to the present invention, there is provided a gypsum-based building material obtained by adding water to a part or all of the gypsum composition, which is calcined gypsum, molding and solidifying the gypsum composition. Is done.
- the selective sterilization method and gypsum composition of the present invention can selectively inhibit the growth of sulfate-reducing bacteria. Therefore, the growth of sulfate-reducing bacteria can be suppressed and the production of hydrogen sulfide can be suppressed.
- the selective sterilization method and gypsum composition of the present invention do not inhibit the growth of other bacteria, the microflora such as soil is not destroyed, the generation of malodors, plant growth disorders, etc. There is no risk of problems.
- the present invention relates to a selective sterilization method that selectively suppresses the growth of sulfate-reducing bacteria.
- sulfate-reducing bacteria are bacteria that acquire energy by oxidizing organic substances using sulfate ions as electron acceptors. This bacterium is widely distributed in anaerobic environments such as general soil and sewage sludge.
- the kind of sulfate-reducing bacteria to which the present invention is applied is not particularly limited. For example, gram-negative bacteria, gram-positive bacteria, or archaea may be used.
- Desulfovibrio (Desulfovibrio; Gram-negative anaerobic gonococcus, Helicobacteria), Desulfuromonas (Desulfuromonas; Gram-negative anaerobic gonococcus, Helicobacteria), Desulfitobacterium (Gram-negative)
- Desulfate-reducing bacteria such as obligately anaerobic bacteria and Desulfotomaculum (Gram-positive endospore-forming rods).
- bacteria belonging to the genus Desulfobibrio include Desulfovibrio vulgaris, Desulfovibrio africanus, Desulfovibrio desulfuricans, Desulfovibrio desulfuricans, Desulfobibrio gigas ( Desulfovibrio gigas) and the like.
- bacteria belonging to the genus Desulfotomaculum can include Desulfotomaculum ruminis.
- the method of the present invention exerts an inhibitory effect on the sulfate-reducing bacteria in general, that is, on gram-negative bacteria, gram-positive bacteria, and archaea.
- it can be suitably used for sulfate-reducing bacteria that live in a medium temperature range (20 to 45 ° C.) and a neutral range (pH 5 to 9).
- the above-mentioned desulfobibrio bulgaris, desulfobibrio africanus, desulfobibrio desulfuricans, desulfobibrio gigas, desulfotomacurum luminis are "medium temperature range (20-45 °C) and neutral range "Sulphate-reducing bacteria that inhabit (pH 5-9)".
- the chelated Al acts on the sulfate reduction mechanism of the sulfate-reducing bacteria, thereby stopping the sulfate-reducing mechanism of the sulfate-reducing bacteria and, as a result, selectively suppressing the growth of the sulfate-reducing bacteria.
- Selective means that the growth inhibitory effect is specific to sulfate-reducing bacteria. That is, it means that the growth inhibitory effect on sulfate-reducing bacteria is recognized, but the growth inhibitory effect on bacteria other than sulfate-reducing bacteria (other bacteria) is hardly recognized.
- Other fungi include Escherichia coli (Escherichia coli; facultative anaerobic gram-negative bacillus, Japanese name: E. coli), Clostridium butyricum; Gram-positive endospore-forming bacillus, Japanese name: Butyric acid bacteria).
- the “antibacterial” referred to in the present invention means to suppress the growth of bacteria. That is, it is not necessary to reduce the number of bacteria directly like sterilization or sterilization.
- Chelated Al The method of the present invention is characterized in that chelated Al coexists in an environment where sulfate-reducing bacteria are present.
- the “environment where sulfate-reducing bacteria are present” is not particularly limited as long as the presence of sulfate-reducing bacteria can be confirmed. Examples thereof include anaerobic environments such as general soil and sewage sludge in which sulfate-reducing bacteria are widely distributed.
- “Chelating Al” refers to a complex formed of Al 3+ and a chelating agent, and more specifically, a complex in which a chelating agent is coordinated to Al 3+ serving as a central ion. Chelated Al is rapidly formed by mixing an Al 3+ source and a chelating agent described later.
- a “chelating agent” is a multidentate ligand that coordinates to Al 3+ to form chelated Al.
- the type of chelating agent is not particularly limited. For example, it may be a chain ligand or a cyclic ligand.
- chain ligands include polyvalent carboxylic acids such as oxalic acid, malonic acid, tartaric acid, glutaric acid, malic acid, citric acid, and maleic acid (both are bidentate ligands); ethylenediamine (EDA, bidentate) Ligands) and other polyamines; ethylenediaminetetraacetic acid (EDTA, hexadentate ligand) and other aminopolycarboxylic acids; 2,2′-bipyridine, 1,10-phenanthroline (both bidentate ligands) ) And the like; and the like.
- polyvalent carboxylic acids such as oxalic acid, malonic acid, tartaric acid, glutaric acid, malic acid, citric acid, and maleic acid (both are bidentate ligands); ethylenediamine (EDA, bidentate) Ligands) and other polyamines; ethylenediaminetetraacetic acid (EDTA, hexadentate ligand
- cyclic ligand examples include porphyrins (tetradentate ligand); crown ethers (the number of conformations varies depending on the compound. For example, 18-crown-6 is a hexadentate ligand); .
- chelating agents a chelating agent that coordinates with Al 3+ and easily forms chelated Al is preferable. Further, since the present invention is often carried out in a natural environment, a chelating agent that does not adversely affect the environment is more preferable. Specific examples include citric acid, malonic acid, tartaric acid, glutaric acid, malic acid, maleic acid and the like.
- the amount ratio of Al 3+ to the chelating agent is not particularly limited.
- the molar ratio for forming a stable complex with Al 3+ varies depending on the type of chelating agent. However, it is desirable to adjust the addition amount (molar ratio) of the chelating agent so that the total amount of the added Al 3+ source is chelated and Al 3+ is dissolved.
- the molar ratio in which an Al 3+ source and oxalic acid form a stable complex is 1: 3
- the molar ratio in which an Al 3+ source and citric acid form a stable complex is 1: 2
- the Al 3+ source and EDTA The molar ratio for forming a stable complex is 1: 1.
- chelated Al can be formed from an inexpensive and readily available aluminum compound, and the production cost can be reduced as compared with the case of using an anthraquinone compound.
- the chelating agent when a divalent to tetravalent organic acid that is inexpensive and easily available is used as the chelating agent, the effect of reducing the production cost is great.
- Al 3+ source The chelated Al may add itself (that is, Al 3+ already chelated) to an environment where sulfate reducing bacteria are present, or an Al 3+ source and a chelating agent may be added to the environment.
- the chelated Al may be generated in the environment. Even when the Al 3+ source and the chelating agent are added separately, chelated Al is rapidly formed in the environment.
- Al 3+ source is a substance capable of generating Al 3+ which becomes a chelate central ion in the presence of water.
- Specific types of substances are not particularly limited. However, it is preferably at least one Al compound selected from the group consisting of Al 2 O 3 , AlCl 3 , Al (OH) 3 and Al 2 (SO 4 ) 3 .
- one of the above compounds may be used alone, or two or more of the above compounds may be used in combination.
- Al 2 O 3 , AlCl 3 , Al (OH) 3 and Al 2 (SO 4 ) 3 includes these anhydrides as well as hydrates. These compounds may be in the form of crystals or amorphous (for example, amorphous alumina). Furthermore, it is not necessary to use pure substances as these compounds, and mixtures may be used. For example, minerals containing these compounds can also be used as the Al 3+ source.
- Gypsum composition is a gypsum composition containing gypsum (A) as a main component, and contains chelated Al (B) in addition to the gypsum (A), and 100 parts by mass of gypsum (A).
- chelating Al (B) is contained in the range of 0.01 to 20 parts by mass.
- Gypsum The “gypsum” referred to in the present invention is a mineral mainly composed of calcium sulfate, and examples thereof include calcium sulfate hemihydrate, dihydrate, and anhydrous. Accordingly, in the present invention, one of the gypsum can be used alone, or two or more can be mixed and used. Calcium sulfate hemihydrate (CaSO 4 .1 / 2H 2 O) is also called hemihydrate gypsum or calcined gypsum. For example, ⁇ type hemihydrate gypsum, ⁇ type hemihydrate gypsum and the like can be mentioned.
- a part or all of the said gypsum is calcined gypsum.
- the “calcined gypsum” referred to in the present invention includes, in addition to the above-mentioned hemihydrate gypsum, anhydrous calcium sulfate (CaSO 4 , soluble anhydrous gypsum, or type III anhydrous gypsum) that easily changes to hemihydrate gypsum by absorbing moisture in the air. Is also included).
- ⁇ -type hemihydrate gypsum ⁇ -type hemihydrate gypsum
- One type of type III anhydrous gypsum can be used alone, or two or more types can be mixed and used.
- any of natural products (basisingte etc.), by-product gypsum, and waste gypsum can be used.
- chelated Al In the gypsum composition of the present invention, chelated Al similar to the sterilization method of the present invention already described can be used.
- the form of the chelating agent is not particularly limited. However, it is preferable to use a powdered chelating agent. Usually, powdery gypsum is used as the main material of the gypsum composition of the present invention. Therefore, like the gypsum, the handling becomes easier when a powdery chelating agent is used.
- the gypsum composition of the present invention contains 0.01 to 20 parts by mass of the chelated Al (B) with respect to 100 parts by mass of the gypsum (A).
- B chelated Al
- A gypsum
- chelated Al (B) in the range of 0.1 to 10 parts by mass, and in the range of 0.2 to 2 parts by mass with respect to 100 parts by mass of gypsum (A). More preferably.
- production of hydrogen sulfide can be suppressed more reliably by content of chelating Al (B) being 0.1 mass part or more.
- the suppression effect does not increase according to the amount. Therefore, by making the content of chelated Al (B) 10 parts by mass or less, it is possible to prevent the production cost from increasing more than necessary.
- Al 3+ source The gypsum composition of the present invention includes those containing an Al 3+ source (b-1) and a chelating agent (b-2) in place of the chelated Al (B). Even if the Al 3+ source and the chelating agent are separately added, chelated Al is rapidly formed in the gypsum composition by water added during the production process or use of the gypsum composition. As the Al 3+ source and the chelating agent, the same antibacterial method of the present invention as described above can be used.
- the gypsum composition of the present invention contains gypsum and chelated Al in a predetermined ratio. Accordingly, the present invention includes all gypsum compositions that satisfy the above composition. That is, the use is not limited.
- a gypsum composition used in an application not using a chemical reaction (hydration reaction) of gypsum is also included in the scope of the present invention.
- Examples of the gypsum composition used in applications that do not utilize a hydration reaction include white wire line materials, fertilizers, rubble treating agents, and the like used in sports fields.
- the gypsum composition of the present invention can be suitably used as an application utilizing the hydration reaction of gypsum, specifically as a gypsum-based solidifying material or a gypsum-based building material.
- the gypsum-based solidifying material of the present invention is characterized in that the gypsum composition of the present invention contains a part or all of gypsum that is calcined gypsum.
- the gypsum-based building material of the present invention is characterized in that, in the gypsum composition of the present invention, a part or all of the gypsum is calcined gypsum, and water is added to form and solidify. is there.
- Calcined gypsum (semihydrate gypsum, including type III anhydrous gypsum) is easily converted to dihydrate gypsum (CaSO 4 .2H 2 O) by a hydration reaction, and has the property of forming a solidified product with high strength. Therefore, among the gypsum compositions of the present invention, those in which part or all of the gypsum is calcined gypsum can be suitably used as a gypsum-based solidifying material and a gypsum-based building material.
- the gypsum-based solidifying material and gypsum-based building material of the present invention can selectively suppress the growth of sulfate-reducing bacteria and suppress the generation of hydrogen sulfide without suppressing the growth of other bacteria. Moreover, it has performance (strength, fire resistance, sound insulation, earthquake resistance, etc.) comparable to conventional gypsum-based solidifying materials and gypsum-based building materials and construction workability.
- the gypsum-based solidifying material may solidify itself, or may be mixed with other materials to solidify the entire mixture.
- wet materials gypsum type wet coating material
- gypsum plaster coating wall material
- the joint processing material putty
- the solidification material for soil processing etc. gypsum system soil improvement material
- solidifying construction residual soil sludge, mud, etc.
- Examples of the gypsum-based building materials include gypsum plates or gypsum blocks used for ceiling materials, wall materials, floor materials, and the like.
- Examples of the gypsum plate include a gypsum board in which the surface of the gypsum plate is coated with a base paper for board; a glass mat gypsum board in which the surface of the gypsum plate is coated with a glass fiber mat (sheet); It includes a plaster board in which a glass fiber mat (sheet) is embedded within 1 to 2 mm. Further, the use of the plaster board is not limited to the structure.
- the present invention can also be applied to functional gypsum boards having functionalities such as cosmetics, sound absorption, and moisture absorption.
- “deionized water / Al aqueous solution” means deionized water in a system in which the prepared Al aqueous solution has a concentration of 0 mM, and an Al solution described later in a system in which the prepared Al aqueous solution has a concentration of 2 mM and 20 mM. Indicates that it was used.
- AlCl 3 aqueous solution Preparation of Al solution (AlCl 3 aqueous solution)
- AlCl 3 aqueous solution A predetermined amount of AlCl 3 .6H 2 O was added to distilled water, heated and dissolved in an autoclave, and then an appropriate amount of KOH aqueous solution was added to adjust the pH to around 7.0.
- the concentration of the AlCl 3 was prepared 2 mM, the AlCl 3 solution for 20mM media added.
- This AlCl 3 aqueous solution was subjected to the method of Comparative Example 1.
- Example 2 In the same manner as in Example 1, except that oxalic acid and water in an equimolar amount with AlCl 3 in the aqueous solution were added to the AlCl 3 ⁇ 6H 2 O aqueous solution dissolved by heating, the oxalic acid ⁇ Al chelate A concentration of 2 mM and 20 mM of chelating Al aqueous solution for medium addition was prepared. This chelated Al aqueous solution was subjected to the method of Example 2.
- the concentration of EDTA ⁇ Al chelate was the same as in Example 1 except that EDTA in an equimolar amount with AlCl 3 in the aqueous solution and water were added to the AlCl 3 ⁇ 6H 2 O aqueous solution dissolved by heating. Prepared 2 mM and 20 mM chelating Al aqueous solutions for medium addition. This chelated Al aqueous solution was subjected to the method of Example 3.
- the Al-added medium (100 ml) was poured into a sterilized 100 ml (nominal) vial, and degassed nitrogen gas was blown into the medium for a certain period of time to make the inside of the vial anaerobic.
- the subcultured cells (sulfuric acid-reducing bacteria, Escherichia coli, butyric acid bacteria) were inoculated into this medium so that the cell concentration was 10 6 cells.
- the vial was sealed with a butyl rubber stopper and an aluminum seal, and shaking culture was performed in a 37 ° C. incubator.
- the shaking culture was performed at the number of shakings (110 times / min) that does not precipitate the hydroxide.
- a sample was extracted from the culture and used for evaluation.
- Example 1 With respect to the method of Example 1 (addition of citric acid / Al chelate), a graph showing the bactericidal effect against sulfate-reducing bacteria is shown in FIG. 1, a graph showing the bactericidal effect against E. coli is shown in FIG. A graph showing the fungal effect is shown in FIG.
- a graph showing the bactericidal effect on sulfate-reducing bacteria is shown in FIG. 4
- a graph showing the bactericidal effect on E. coli is shown in FIG.
- the graph showing the effect is shown in FIG. In these graphs, the horizontal axis indicates the elapsed time (unit: time), and the vertical axis indicates the logarithmic value of the protein amount (unit: mg / L).
- Example 1 addition of citric acid / Al chelate, as shown in FIG. 1, an increase in the amount of protein was suppressed in the culture solution of sulfate-reducing bacteria. That is, the growth of sulfate-reducing bacteria was suppressed.
- Examples 4 to 8 and Comparative Examples 2 and 3 (gypsum composition): [Preparation of gypsum composition] Gypsum compositions having the compositions described in Table 4 were prepared (Examples 4 to 8, Comparative Examples 2 and 3). As the gypsum, calcined gypsum obtained by pulverizing and firing waste gypsum was used. AlCl 3 was used as the Al 3+ source. Citric acid was used as a chelating agent.
- the inside of the vial was made anaerobic by blowing deoxygenated nitrogen gas into the vial for a certain period of time. Furthermore, the subcultured sulfate-reducing bacteria were inoculated into the medium so that the cell concentration was 10 6 . Thereafter, the vial was sealed with a butyl rubber stopper and an aluminum seal, and shaking culture was performed in a 37 ° C. incubator for 100 hours. The shaking culture was performed at the number of shakings (110 times / min) that does not precipitate the hydroxide. The culture conditions were such that hydrogen sulfide was easily generated in order to generate hydrogen sulfide. That is, the culture condition is not a reproduction of a soil improvement site or an illegal dumping site.
- the amount of hydrogen sulfide generated and the amount of protein were significantly reduced in the gypsum compositions of Examples 4 to 8, and sulfate-reducing bacteria Growth was suppressed.
- the reason why the amount of hydrogen sulfide generated did not become zero is considered to be that hydrogen sulfide slightly dissolved in the culture broth was detected.
- the gypsum compositions of Examples 5 to 8 Al chelate 0.2 to 20 parts by mass
- the gypsum compositions of Examples 6 to 8 (2 to 20 parts by mass of Al chelate) were able to almost completely suppress the generation of hydrogen sulfide.
- the gypsum composition of Example 8 it is considered that the generation of hydrogen sulfide can be sufficiently suppressed when 10 parts by mass of Al chelate is added. Therefore, considering the production cost, it can be said that the gypsum compositions of Examples 4 to 7 (Al chelate 0.02 to 10 parts by mass) are preferable. Further, the gypsum composition of Example 5 or 6 (Al chelate 0.2 to 2 parts by mass) is more preferable in that the generation of hydrogen sulfide can be almost completely suppressed and can be produced at low cost. It can be said.
- the gypsum compositions of Examples 4 to 8 are gypsum plaster (described in JIS A6904), gypsum board joint treatment material (described in JIS A6914), or gypsum board product (described in JIS A6901). ) And the like were not caused on the production line.
- the gypsum plaster and the joint material for gypsum board are a powdery gypsum composition and a gypsum-based solidifying material that is cured by reacting with water.
- the gypsum board product is a gypsum-based building material obtained by adding water to a gypsum composition, forming it into a plate shape, and solidifying it.
- the gypsum compositions of Examples 4 to 8 had no adverse effects on the performance and construction workability of the gypsum plaster, the joint treatment material for gypsum board, the gypsum board product and the like. Furthermore, when a similar test was conducted using a gypsum board or gypsum plaster produced using the gypsum composition of Examples 4 to 8 as a sample, the generation of hydrogen sulfide was clearly suppressed as compared with the conventional one. It was.
- the antibacterial method of the present invention can be used to suppress the growth of sulfate-reducing bacteria, and thus suppress the production of hydrogen sulfide.
- the gypsum composition of the present invention can be suitably used as a gypsum composition capable of suppressing the generation of hydrogen sulfide, a gypsum-based solidifying material, and a gypsum-based building material. More specifically, as gypsum-based solidification materials such as plaster plaster (painted wall material), joint treatment material for gypsum board (putty), solidification material for soil treatment (solidification material that solidifies construction soil, sludge, mud, etc.) Can be used.
- plaster plaster painted wall material
- solidification material for soil treatment solidification material that solidifies construction soil, sludge, mud, etc.
- gypsum boards (including gypsum boards) for ceiling materials, wall materials, flooring materials, gypsum blocks, structural gypsum boards, functional gypsum boards (functional gypsum for cosmetics, sound absorption, moisture absorption, etc.) It can be used as a gypsum building material. Furthermore, it can be used as other gypsum compositions such as white wire line material, fertilizer, and debris remover.
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Abstract
Description
即ち、本発明によれば、硫酸還元菌の存在する環境に、キレート化Alを併存させることにより、前記硫酸還元菌の増殖を選択的に抑制することを特徴とする硫酸還元菌の選択的制菌方法が提供される。
また、本発明によれば、石膏(A)と、キレート化Al(B)とを含有し、前記石膏(A)100質量部に対し、前記キレート化Al(B)を0.01~20質量部の範囲で含有していることを特徴とする石膏組成物が提供される。
更に、本発明によれば、前記石膏組成物のうち、前記石膏の一部又は全部が焼石膏であるものを含有することを特徴とする石膏系固化材が提供される。また、本発明によれば、前記石膏組成物のうち、前記石膏の一部又は全部が焼石膏であるものに水を加え、成形し、固化させてなることを特徴とする石膏系建材が提供される。
本発明は、硫酸還元菌の増殖を選択的に抑制する選択的制菌方法に関するものである。
本発明の方法は、硫酸還元菌の存在する環境に、キレート化Alを併存させる点に特徴がある。「硫酸還元菌の存在する環境」は、硫酸還元菌の存在が確認可能な限り、特に制限はない。例えば硫酸還元菌が広く分布する一般土壌や下水汚泥等の嫌気環境を挙げることができる。「キレート化Al」とは、Al3+と、キレート剤とから形成されており、より具体的には、中心イオンとなるAl3+にキレート剤が配位した錯体を指す。キレート化Alは、後述するAl3+源とキレート剤を混合することで速やかに形成される。
キレート化Alは、それ自体(即ち、既にキレート化されているAl3+)を硫酸還元菌の存在する環境に添加してもよいし、前記環境に、Al3+源及びキレート剤を添加して、前記環境中で前記キレート化Alを生成させてもよい。Al3+源とキレート剤を個別に添加した場合でも前記環境中で速やかにキレート化Alが形成される。
本発明の石膏組成物は、石膏(A)を主たる成分とする石膏組成物であり、前記石膏(A)に加えて、キレート化Al(B)を含有し、石膏(A)100質量部に対し、キレート化Al(B)を0.01~20質量部の範囲で含有していることを特徴とするものである。
本発明にいう「石膏」とは、硫酸カルシウムを主成分とする鉱物であり、硫酸カルシウムの1/2水和物、二水和物、無水和物等を挙げることができる。従って、本発明においては、前記石膏のうちの1種を単独で、或いは2種以上を混合して用いることができる。硫酸カルシウムの1/2水和物(CaSO4・1/2H2O)は、半水石膏や焼石膏とも称される。例えばβ型半水石膏、α型半水石膏等を挙げることができる。
III型無水石膏のうちの1種を単独で、或いは2種以上を混合して用いることができる。
本発明の石膏組成物においては、既に説明した本発明の制菌方法と同様のキレート化Alを用いることができる。キレート剤の形態は特に限定されない。但し、粉末状のキレート剤を用いることが好ましい。通常、本発明の石膏組成物の主材となる石膏としては粉末状のものが用いられる。従って、前記石膏と同様に、粉末状のキレート剤を用いた方が取り扱いが容易となる。
本発明の石膏組成物には、キレート化Al(B)の代わりに、Al3+源(b-1)及びキレート剤(b-2)を含有するものも含まれる。Al3+源とキレート剤が個別に添加されていても、石膏組成物の製造過程又は使用時に添加される水によって、石膏組成物中に速やかにキレート化Alが形成される。Al3+源、キレート剤については、既に説明した本発明の制菌方法と同様のものを用いることができる。
既述のように、本発明の石膏組成物は、石膏及びキレート化Alを所定比率で含有するものである。従って、本発明には前記組成を満たす全ての石膏組成物が含まれる。即ち、その用途は限定されない。例えば、石膏の化学的反応(水和反応)を利用しない用途で用いられる石膏組成物も本発明の範囲に含まれる。水和反応を利用しない用途で用いられる石膏組成物としては、運動場等で使用する白線用ライン材、肥料、瓦礫処理剤等を挙げることができる。
本発明の石膏組成物、石膏系固化材及び石膏系建材は、これらが硫酸還元菌の存在する環境下に置かれた場合に、他の菌の増殖を抑制することなく、硫酸還元菌の増殖を選択的に抑制して、硫化水素の発生を抑制するという効果を奏する。
[前培養]
実施例及び比較例においては、代表的な基準株である以下の菌株を用いた。Desulfovibrio vulgariss DSM 644Tについては、ドイツ国の標準菌株保存機関であるDSMZ(Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH)から入手した。その他の菌については製品評価技術基盤機構バイオテクノロジーセンターから入手した。これらの菌株については分譲機関指定の培地を用いて前培養を行った。前培養期間は約1週間とした。
(1)硫酸還元菌:Desulfovibrio vulgariss DSM 644T
(2)大腸菌:Escherichia coli NBRC 102203T
(3)酪酸菌:Clostridium butyricum NBRC 13949T
前培養を行った後、菌体のみを回収し、各菌について表1~表3に示す組成の培地にて継代培養を行った。前記継代培養後、集菌・洗浄した菌体を、実施例及び比較例にて使用した。なお、表中の「脱イオン水/Al水溶液」は、調製したAl水溶液の濃度が0mMの系では脱イオン水を用い、調製したAl水溶液の濃度が2mM、20mMの系では後述するAl溶液を用いたことを示す。
所定量のAlCl3・6H2Oを蒸留水に添加し、オートクレーブにて加熱溶解した後、KOH水溶液を適量添加して、pHを7.0付近に調整した。これにより、AlCl3の濃度が2mM、20mMの培地添加用AlCl3水溶液を調製した。このAlCl3水溶液を比較例1の方法に供した。
所定量のAlCl3・6H2Oを蒸留水に添加し、オートクレーブにて加熱溶解した後、加熱溶解したAlCl3・6H2O水溶液に、前記水溶液中のAlCl3と等モル量のクエン酸、及び水を添加し、1時間撹拌した。その後、KOH水溶液を適量添加して、pHを7.0付近に調整した。これにより、クエン酸・Alキレートの濃度が2mM、20mMの培地添加用キレート化Al水溶液を調製した。このキレート化Al水溶液を実施例1の方法に供した。
前記のように調製したAlCl3水溶液またはキレート化Al水溶液に、予めオートクレーブにて滅菌処理した表1~表3に記載の培地の成分を、表1~表3に記載の組成比となるように添加し、Al添加培地を調製した。このAl添加培地を水酸化カリウムと塩酸を適量添加して、表1~表3に記載のpHに調整して用いた。
滅菌済み100ml(公称)バイアル瓶に、前記Al添加培地100mlを注入し、前記培地に脱酸素した窒素ガスを一定時間吹き込むことによって、前記バイアル瓶内を嫌気状態とした。この培地に、菌体濃度が106個となるように、継代培養した各菌体(硫酸還元菌、大腸菌、酪酸菌)を植菌した。その後、ブチルゴム栓およびアルミシールによりバイアル瓶を密封し、37℃のインキュベータ内で振盪培養を行った。振盪培養は、水酸化物が沈殿しない程度の振盪回数(110回/分)で行った。培養液からサンプルを抜き取り、評価に使用した。
バイアル瓶から培地1mlを採取し、培地成分を取り除き、滅菌蒸留水1mlに懸濁させた。その懸濁液から超音波破砕機によってタンパクを抽出し、BCA法(ビシンコニン酸法)によりタンパク量を測定した。このタンパク量により各菌体に対する増殖抑制効果(制菌効果)を評価した。
実施例1の方法(クエン酸・Alキレートの添加)について、硫酸還元菌に対する制菌効果を表したグラフを図1に、大腸菌に対する制菌効果を表したグラフを図2に、酪酸菌に対する制菌効果を表したグラフを図3に示す。また、比較例1の方法(AlCl3の添加)について、硫酸還元菌に対する制菌効果を表したグラフを図4に、大腸菌に対する制菌効果を表したグラフを図5に、酪酸菌に対する制菌効果を表したグラフを図6に示す。これらのグラフにおいて、横軸は経過時間(単位:時間)を示し、縦軸はタンパク量(単位:mg/L)の対数値を示す。
[石膏組成物の調製]
表4に記載の組成を有する石膏組成物を調製した(実施例4~8、比較例2及び3)。石膏としては、廃石膏を粉砕し焼成して得られた焼石膏を用いた。Al3+源としては、AlCl3を用いた。キレート剤としては、クエン酸を用いた。
バイアル瓶から培地1mlを採取し、培地成分を取り除き、滅菌蒸留水1mlに懸濁させた。その懸濁液から超音波破砕機によってタンパクを抽出し、BCA法(ビシンコニン酸法)によりタンパク量を測定した。このタンパク量により各菌体に対する増殖抑制効果(制菌効果)を評価した。その結果を表5に示す。
バイアル瓶から採取した培養液を孔径0.22μmのメンブレンフィルターで濾過し、蒸留水によって適宜希釈してHPLC(高速液体クロマトグラフィー)により硫化水素発生量を測定した。HPLCとしては、ポンプ、カラムオーブン、陰イオン分析カラム、UV検出器からなる東ソー社製のHPLCシステムを使用した。その結果を表5に示す。
Claims (15)
- 硫酸還元菌の存在する環境に、キレート化Alを併存させることにより、前記硫酸還元菌の増殖を選択的に抑制することを特徴とする硫酸還元菌の選択的制菌方法。
- 前記硫酸還元菌の存在する環境に、Al3+源及びキレート剤を添加して、前記環境中で前記キレート化Alを生成させる請求項1に記載の選択的制菌方法。
- 前記Al3+源が、Al2O3、AlCl3、Al(OH)3及びAl2(SO4)3からなる群より選択される少なくとも一種のAl化合物である請求項2に記載の選択的制菌方法。
- 前記硫酸還元菌が、中温域(20~45℃)かつ中性域(pH5~9)で生息する菌である請求項1~3のいずれか一項に記載の選択的制菌方法。
- 石膏(A)と、キレート化Al(B)とを含有し、
前記石膏(A)100質量部に対し、前記キレート化Al(B)を0.01~20質量部の範囲で含有していることを特徴とする石膏組成物。 - 前記キレート化Al(B)の代わりに、Al3+源(b-1)及びキレート剤(b-2)を含有している請求項5に記載の石膏組成物。
- 前記Al3+源(b-1)が、Al2O3、AlCl3、Al(OH)3及びAl2(SO4)3からなる群より選択される少なくとも一種のAl化合物である請求項6に記載の石膏組成物。
- 前記石膏の一部又は全部が、廃石膏である請求項5に記載の石膏組成物。
- 前記石膏の一部又は全部が、廃石膏である請求項6又は7に記載の石膏組成物。
- 前記石膏の一部又は全部が、焼石膏である請求項5又は8に記載の石膏組成物。
- 前記石膏の一部又は全部が、焼石膏である請求項6、7又は9に記載の石膏組成物。
- 請求項10に記載の石膏組成物を含有することを特徴とする石膏系固化材。
- 請求項11に記載の石膏組成物を含有することを特徴とする石膏系固化材。
- 請求項10に記載の石膏組成物に水を加え、成形し、固化させてなることを特徴とする石膏系建材。
- 請求項11に記載の石膏組成物に水を加え、成形し、固化させてなることを特徴とする石膏系建材。
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