WO2010110477A1 - Asbestos-dissolving agent and wet treatment method for asbestos detoxification - Google Patents
Asbestos-dissolving agent and wet treatment method for asbestos detoxification Download PDFInfo
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- WO2010110477A1 WO2010110477A1 PCT/JP2010/055615 JP2010055615W WO2010110477A1 WO 2010110477 A1 WO2010110477 A1 WO 2010110477A1 JP 2010055615 W JP2010055615 W JP 2010055615W WO 2010110477 A1 WO2010110477 A1 WO 2010110477A1
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- WIPO (PCT)
- Prior art keywords
- asbestos
- acid
- juice
- plant
- dissolving agent
- Prior art date
Links
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- 229910052895 riebeckite Inorganic materials 0.000 title claims abstract description 83
- 239000003795 chemical substances by application Substances 0.000 title claims description 11
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- 238000001784 detoxification Methods 0.000 title claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 44
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- 150000002500 ions Chemical class 0.000 claims abstract description 24
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- 239000000463 material Substances 0.000 claims description 11
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- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
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- 239000000292 calcium oxide Substances 0.000 claims description 5
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- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 5
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 5
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 235000011148 calcium chloride Nutrition 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 229940093915 gynecological organic acid Drugs 0.000 claims description 4
- 235000005985 organic acids Nutrition 0.000 claims description 4
- 238000003672 processing method Methods 0.000 claims description 4
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 3
- GHOKWGTUZJEAQD-UHFFFAOYSA-N Chick antidermatitis factor Natural products OCC(C)(C)C(O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-UHFFFAOYSA-N 0.000 claims description 3
- 241000207199 Citrus Species 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
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- 229940087305 limonene Drugs 0.000 claims description 3
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims 1
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- 239000011810 insulating material Substances 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000005720 sucrose Substances 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 15
- 239000007800 oxidant agent Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 4
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- 230000006378 damage Effects 0.000 abstract 2
- 239000011777 magnesium Substances 0.000 description 33
- 229910052749 magnesium Inorganic materials 0.000 description 14
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- 238000006243 chemical reaction Methods 0.000 description 10
- CWBIFDGMOSWLRQ-UHFFFAOYSA-N trimagnesium;hydroxy(trioxido)silane;hydrate Chemical compound O.[Mg+2].[Mg+2].[Mg+2].O[Si]([O-])([O-])[O-].O[Si]([O-])([O-])[O-] CWBIFDGMOSWLRQ-UHFFFAOYSA-N 0.000 description 10
- 229910052612 amphibole Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
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- 241000234671 Ananas Species 0.000 description 6
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
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- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 5
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Images
Classifications
-
- 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
- B09B3/0066—Disposal of asbestos
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/36—Detoxification by using acid or alkaline reagents
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D3/00—Calcareous fertilisers
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/41—Inorganic fibres, e.g. asbestos
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
- A62D2203/04—Combined processes involving two or more non-distinct steps covered by groups A62D3/10 - A62D3/40
Definitions
- the present invention relates to an asbestos-detoxifying wet processing method for dissolving asbestos-containing waste materials using a mixed acid based on a plant skin juice composition containing plant organic acids, orthophosphoric acid and natural mineral ions as an asbestos solubilizer.
- Asbestos is a fibrous needle-like crystal that has excellent heat and fire resistance, chemical resistance, wear resistance, earthquake resistance, etc. without deterioration in strength for a long period of time. It has been used in various fields such as wall materials, slate materials and electrical products, automobile brake pads, heat-resistant gaskets, household products, etc., but in recent years, asbestos fibrous acicular crystals have scattered in the atmosphere and lungs. It has been found to cause health problems such as cancer and malignant mesothelioma, and its use is prohibited. At present, asbestos waste is handled as general waste, but asbestos fibrous acicular crystals are scattered into the atmosphere, and asbestos fibrous acicular crystals are used for health and safety measures. There is an urgent need for detoxification treatment measures that make it non-fibrous.
- Patent Document 1 As an asbestos detoxification treatment method in which asbestos waste is dissolved with an inorganic acid and then sulfuric acid is added thereto to form gypsum.
- Patent Document 2 discloses a simple asbestos analysis method in which a material containing a fibrous substance is dissolved with a hydrochloric acid solution or an acetic acid solution, carbon dioxide in the sample is removed, and then thermogravimetric analysis is performed. JP 2008-246445 A JP 2008-39660 A
- serpentinite and olivine amphibolite Asbestos is known as serpentinite and olivine amphibolite, serpentinite white asbestos chrysotile [Mg 6 Si 4 O 10 (OH) 8 ], amphibolite tea asbestos amosite [(Fe, Mg) 7 Si 8 O 22 (OH) 2 ], amphiboleous blue asbestos crocidolite [Na (Fe 2+ , Mg) 3 Fe 3+ 2 Si 8 O 22 (OH, F) 2 ] It is known to be used as an asbestos building material.
- amphibole-based anthophyllite [Mg 7 Si 8 O 22 (OH) 2 ] tremolite [Ca 2 Mg 5 Si 8 O 22 (OH) 2 ], actinolite [Ca 2 (Mg, Fe) 5 Si 8 O 22 (OH) 2 ] is known, but it is widely used for friction-resistant materials, heat-resistant materials, and the like, and is known to be extremely rarely used for building materials.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2008-246445 discloses that a waste material containing asbestos is dissolved as an inorganic acid using one or more of hydrochloric acid, hydrofluoric acid, phosphoric acid, nitric acid, fluoride acid, and the like. It is described that insoluble calcium sulfate is precipitated by adding sulfuric acid to a solution containing calcium or magnesium.
- the composition of the three types of chrysotile, amosite, and crocidolite that are industrially used for asbestos building materials as described above contains Mg, Fe, Na, and Si, but does not contain Ca. Japanese Patent Application No.
- 2008-246445 is a solution in which calcium, which is a component of cement and slaked lime in asbestos waste, is dissolved with an inorganic acid, and calcium is dissolved not from calcium dissolved in asbestos but from acicular crystals of asbestos. As such, there is no chemical basis for adding sulfuric acid to produce calcium sulfate, and there is a problem.
- Patent Document 2 Japanese Patent Application No. 2008-39660 discloses that when qualitative analysis of a fibrous material in asbestos, hydrochloric acid or acetic acid is used as an acid to remove carbonates such as cement adhering to asbestos. This is a simple analysis method for asbestos that removes the interference peaks. Japanese Patent Application Laid-Open No. 2008-39660 describes that a lime carbonate component of a cement component adhering to asbestos is preferentially dissolved with an acid.
- the asbestos-containing waste material contains a large amount of calcium carbonate, which is a cement component used in the adhesive, and there are many difficulties and problems in the sole dissolution treatment with an acid.
- the present invention as an asbestos solubilizer, dissolved asbestos-containing waste material using a mixed acid composed of plant organic acid, orthophosphoric acid and natural mineral ion-containing plant skin juice liquid composition, then converted to an insoluble salt and solidified
- the present invention provides an asbestos solubilizer and an asbestos-detoxifying wet processing method for the purpose of treating and producing an agricultural fertilizer.
- the inventors treated isovaleric acid [(CH 3 ) 2 CHCH 2 COOH] and orthophosphoric acid (H 3 PO 4 ), which are the main components of a pineapple peel juice of a vegetable organic acid, in treating waste materials containing asbestos. It was found that magnesium (Mg) and iron (Fe), which are main components of asbestos, are dissolved as ions in the immersion liquid when the fibrous needle-like crystal of asbestos is immersed using a mixed acid.
- Mg magnesium
- Fe iron
- Asbestos-containing waste material fibrous acicular crystals used in the present invention are serpentinite chrysotile [Mg 6 Si 4 O 10 (OH) 8 ] and amphibole amosite [(Fe, Mg) 7 Si 8 O 22 (OH) 2 ] and the like were confirmed by differential thermal balance analysis and X-ray diffraction.
- the serpentinite chrysotile [Mg 6 Si 4 O 10 (OH) 8 ] is composed of 4Mg (OH) 2 , 2MgO, and 4SiO 2 oxides or hydroxides to form fibrous acicular crystals.
- Chemical reaction formulas are shown in chemical formulas (1) and (2).
- Formulas (3) and (4) show reaction formulas in which the serpentine eutectic Mg (OH) 2 , MgO, and isovaleric acid [(CH 3 ) 2 CHCH 2 COOH] react and dissolve to form magnesium ions.
- the vegetable organic acid of the present invention includes isovaleric acid [(CH 3 ) 2 CHCH 2 COOH] and butyric acid [CH 3 CH 2 CH 2 COOH], which are the main components of pineapple peel juice, and caproic acid [coconut juice] CH 3 (CH 2 ) 4 COOH] and caprylic acid [CH 3 (CH 2 ) 6 COOH], citrus peel juice limonene (C 10 H 16 ), ascorbic acid (C 6 H 8 O 6 ), pantothenic acid It is a complex plant organic acid such as (C 9 H 17 NO 6 ).
- the natural mineral ion-containing plant skin juice composition will be described.
- the natural mineral ion-containing plant skin juice composition is composed of barley stone, Io stone, leech stone, etc., using plant organic acids mainly composed of pineapple skin juice, and the mineral components Al, Ca, K, Mn , Fe, Ti, Si, P, and the like, and DMPO (5-Dimethyl, phylloline1-oxide) measured by ESR (Electron Spin, Resonance) to contain a large amount of OH radical (.OH) which is a kind of active oxygen. ) Confirmed by spin trapping method using scavenger.
- the present invention has been proposed in Japanese Patent Application No. 2008-293888 as a natural mineral ion-containing plant skin juice composition.
- the OH radical which is a kind of active oxygen in the natural mineral ion-containing plant skin juice liquid composition of the present invention will be described in detail.
- the present inventors have confirmed many phenomena in which the oxidizing power of dissolved oxygen (DO) from the atmosphere is remarkably increased only by adding a very small amount of a natural mineral ion-containing plant skin juice liquid composition.
- the present inventors have found that this phenomenon is due to the oxidizing power caused by the inclusion of OH radicals, which are a kind of active oxygen produced when metal oxides such as barley stone, meiolite, and leechite are mineralized. I thought.
- ESR Electro spin resonance
- OH radical which is a kind of active oxygen
- Natural ionic ion-containing plant skin juice composition which is a kind of active oxygen, is a highly reactive oxidant, along with hydrogen peroxide and ultrafine titanium dioxide, asbestos amphibole It has a role of promoting the oxidation of divalent iron contained in amosite [(FeMg) 7 Si 8 O 22 (OH) 2 ], etc., and the divalent iron of amosite is oxidized to become trivalent iron. Reactions with organic acids such as isovaleric acid and orthophosphoric acid are easy, and elution with a single acid is difficult to leach and dissolve by the combined use of an oxidizing agent such as a plant skin juice composition containing natural mineral ions. I found out that
- amphibole-based amosite [(Fe, Mg) 7 Si 8 O 22 (OH) 2 ] and orthophosphoric acid containing an oxidizing agent will be described.
- Amphibole-based amosite [(Fe, Mg) 7 Si 8 O 22 (OH) 2 ] is [6 (Fe, Mg) O] [(Fe, Mg) (OH) 2 8SiO 2 ], that is, 6FeO. Fe (OH) 2 and 8SiO 2 , and 6MgO, Mg (OH) 2 and 8SiO 2 .
- the oxidation reaction formulas of the divalent iron oxide and the iron hydroxide with the oxidizing agent are shown in chemical formulas (5) and (6).
- the reaction formula of trivalent iron oxide and orthophosphoric acid is shown in chemical formula (7).
- the reaction of MgO, Mg (OH) 2 with orthophosphoric acid and isovaleric acid is shown in chemical formulas (1), (2), chemical formulas (3), and (4).
- One reason that the dissolution and leaching of amphibole-based asbestos has not been easy so far is that the crystalline body contains divalent iron in the form of fibrous needle-like crystals. It is a completely new idea in the invention.
- the natural mineral ion-containing plant skin juice composition of the present invention has an effect as an oxidizing agent.
- the combined use of hydrogen peroxide and ultrafine titanium dioxide added at the same time further increases the synergistic effect of each and promotes the oxidation reaction. , Asbestos-containing waste materials can be easily dissolved.
- the present invention is a first step of dissolving asbestos-containing waste material with the asbestos-dissolving agent of the present invention, and the magnesium-containing solution in the first step contains asbestos using quick lime and slaked lime containing soluble calcium carbonate and calcium chloride. It consists of a second step in which the components are insoluble salts and a third step in which the converted solidified product obtained in the second step is an agricultural fertilizer.
- the asbestos-containing waste material of the conventional method is dissolved in an acid and then reused, so that the asbestos composition is converted at room temperature without being subjected to a high temperature treatment of 800 to 1000 ° C. or more after solidification.
- a high temperature treatment of 800 to 1000 ° C. or more after solidification 800 to 1000 ° C. or more after solidification.
- the asbestos-containing waste material is an asbestos-dissolving agent comprising plant organic acid and orthophosphoric acid, a plant skin juice composition containing natural mineral ions, hydrogen peroxide, ultrafine titanium dioxide, and potassium alum.
- the solubilized calcium carbonate and calcium chloride are dissolved in the solution after the soaking process.
- the converted solidified agricultural fertilizer raw material is converted into an insoluble salt using quicklime containing lime and slaked lime, and in the third step, this can be dried and pulverized to produce an agricultural fertilizer.
- the preferred spraying amount of the asbestos-dissolving agent with respect to the refractory material of the wall material, the spraying asbestos material and the like is 15 to 40 g per 1 m 2 when the thickness is 5 cm, and the most preferable amount is 30 g. If the amount is less than this, the penetration of the asbestos dissolving agent into the asbestos wall material is low, and the peeling work environment is lowered.
- the amount of asbestos-containing waste material immersed in the asbestos dissolving agent of the present invention is 30 to 70%, preferably 40 to 50%.
- the concentration of orthophosphoric acid (H 3 PO 4 , 98%) in the asbestos solubilizer of the present invention is 5 to 15%, preferably 8 to 10%. Even if the concentration is lower or higher than this, dissolution is not easy.
- the preferred concentration of the vegetable organic acid of the present invention is 5 to 25% isovaleric acid [(CH 3 ) 2 CHCH 2 COOH] or butyric acid [CH 3 (CH 2 ) 2 COOH], and the most preferred concentration is 15%.
- coconut juice is caproic acid [CH 3 (CH 2 ) 4 COOH], caprylic acid [CH 3 (CH 2 ) 6 COOH], capric acid [CH 3 (CH 2 ) 8 COOH] lauric acid [CH 3 ( CH 2 ) 10 COOH] mytilinic acid [CH 3 (CH 2 ) 12 COOH] etc. 3-20%, most preferred concentration is 10%
- citrus peel juice is limonene (C 10 H 16 ) ascorbic acid (C 6 H 8 O 6 ), pantothenic acid (C 9 H 17 NO 5 ) 3-15%, most preferred concentration is 10%.
- the mineral ion concentration and free isovaleric acid concentration of the natural mineral ion-containing plant skin juice composition of the present invention are K: 5 to 15 g / l, Ca: 0.5 to 1.5 g / l, Mn: 0.1 0.5 g / l, Fe: 5-20 g / l, Al: 3-15 g / l, Ti: 0.5-1.5 g / l, free isovaleric acid [(CH 3 ) 2 CHCH 2 COOH]: When the concentration is within a range of 10 to 30 g / l, the oxidant has a high accelerating effect when dissolved.
- the preferred concentration range is specifically exemplified in the examples.
- the preferred concentration of hydrogen peroxide as the oxidizing agent is H 2 O 2 : 10 to 30 g / l, and that of ultrafine titanium dioxide is 0.1 to 3 g / l. At concentrations lower than this, dissolution of asbestos (divalent iron-containing amphibolite) becomes difficult.
- the preferred concentration of potash alum [KAl (SO 4 ) ⁇ 12H 2 O] is 5 to 20 g / l, the most preferred concentration is 10 g / l, and a bad odor generated during spraying on asbestos spray wall material. It is effective to remove. At lower concentrations than this, the effect is low, and at high concentrations, the effect is equivalent.
- Example 1 The examples further illustrate the present invention.
- a present Example is only one Embodiment of this invention, is not limitedly interpreted at all, and a design change is possible within the scope of the present invention.
- Example 1
- Asbestos amphibole-based tea asbestos amosite [(Fe, Mg) 7 Si 8 O 22 (OH) 2 ] rough stone 50 g (particle size 3 mm ⁇ or less 80%) and orthophosphoric acid (H 3 PO 4 , 98%) 20 g and plant Organic acid pineapple peel juice (isovaleric acid 15%, butyric acid 10%) mixed acid 200ml, hydrogen peroxide (35%) 5g, ultrafine titanium dioxide 5g, potassium alum 3g, plant skin containing natural mineral ions It was immersed in an asbestos solution added with 20 ml of a fruit juice composition and stirred at room temperature for 30 minutes. This was subjected to solid-liquid separation to obtain a solution after dissolution treatment and a dissolution residue.
- Example 2 90 g of asbestos-containing waste material (particle size of 5 mm ⁇ or less 80%) is immersed in 10 g of orthophosphoric acid (H 3 PO 4 , 98%) and 200 ml of asbestos solution used in ⁇ Example 2 >> and stirred at room temperature for 30 minutes And dissolved. This was solid-liquid separated to obtain a solution and a residue after dissolution treatment. As a result of qualitative analysis of the solution after dissolution treatment, magnesium (Mg) and trivalent iron (Fe 3+ ) were confirmed. As a result of X-ray diffraction, SiO 2 was confirmed from the residue, but chrysotile, amosite and the like of the asbestos composition were not confirmed.
- Mg magnesium
- Fe 3+ trivalent iron
- Example 3 In 100 ml of the solution after dissolution treatment obtained in ⁇ Example 3 >>, 30 g of soluble calcium carbonate, 10 g of calcium chloride, and 10 g of quick lime (shell calcined CaO) were added to obtain 80 g of a solidified product having a water content of 40%. As a result of X-ray diffraction after drying this solidified product, MgCO 3 , Mg (OH) 2 and MgCl 2 were confirmed.
- Example 5 Example 5
- the present invention provides an asbestos solution comprising a plant skin juice composition containing natural mineral ions, hydrogen peroxide, ultrafine titanium dioxide, and potassium alum, in addition to the main components of a vegetable organic acid and orthophosphoric acid (H 3 PO 4 ). It was possible to cut and detoxify the fibrous needle-shaped crystals at room temperature safely and at low cost by immersing or spraying asbestos-containing waste materials. It is expected to make a significant contribution to the promotion of asbestos treatment measures.
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Abstract
Asbestos-containing destruction rubbish is immersed in a solution of a mixed acid comprising a plant-derived organic acid and orthophosphoric acid to dissolve the asbestos in order to convert the fibrous acicular crystals of the asbestos into a noncrystalline non-asbestos substance. Hydrogen peroxide, a plant-derived peel/fruit juice composition containing natural mineral ions, ultrafine titanium dioxide particles, and potassium alum are added as oxidizing agents to a mixed acid comprising a plant-derived organic acid and orthophosphoric acid in order to dissolve the asbestos of asbestos-containing destruction rubbish. It has thereby become possible to cleave and dissolve the fibrous acicular crystals of asbestos.
Description
本発明は、アスベスト溶解剤として、植物性有機酸とオルトリン酸および天然ミネラルイオン含有植物皮果汁液組成物による混合酸を用いてアスベスト含有廃材を溶解するアスベスト無害化湿式処理方法に関する。
The present invention relates to an asbestos-detoxifying wet processing method for dissolving asbestos-containing waste materials using a mixed acid based on a plant skin juice composition containing plant organic acids, orthophosphoric acid and natural mineral ions as an asbestos solubilizer.
アスベストは、繊維状の針状結晶物で、長期間強度劣化することなく、耐熱耐火性、耐薬品性、耐摩耗性、耐震性等に優れ、安価であることから、建設資材の耐火吹付け、壁材、スレート材や電気製品、自動車のブレーキパッド、耐熱ガスケット、家庭用品等様々な分野で使用されてきたが、近年、アスベストの繊維状の針状結晶物が大気中に飛散して肺ガンや悪性中皮腫等の健康障害を引き起こす要因となることが分かり、その使用は禁止されている。
現在、アスベストの廃材は一般廃棄物として取扱われているが、アスベストの繊維状針状結晶物の大気中への飛散が問題となり、健康、安全対策のため、アスベストの繊維状針状結晶物を非繊維化する無害化処理対策が急務となっている。 Asbestos is a fibrous needle-like crystal that has excellent heat and fire resistance, chemical resistance, wear resistance, earthquake resistance, etc. without deterioration in strength for a long period of time. It has been used in various fields such as wall materials, slate materials and electrical products, automobile brake pads, heat-resistant gaskets, household products, etc., but in recent years, asbestos fibrous acicular crystals have scattered in the atmosphere and lungs. It has been found to cause health problems such as cancer and malignant mesothelioma, and its use is prohibited.
At present, asbestos waste is handled as general waste, but asbestos fibrous acicular crystals are scattered into the atmosphere, and asbestos fibrous acicular crystals are used for health and safety measures. There is an urgent need for detoxification treatment measures that make it non-fibrous.
現在、アスベストの廃材は一般廃棄物として取扱われているが、アスベストの繊維状針状結晶物の大気中への飛散が問題となり、健康、安全対策のため、アスベストの繊維状針状結晶物を非繊維化する無害化処理対策が急務となっている。 Asbestos is a fibrous needle-like crystal that has excellent heat and fire resistance, chemical resistance, wear resistance, earthquake resistance, etc. without deterioration in strength for a long period of time. It has been used in various fields such as wall materials, slate materials and electrical products, automobile brake pads, heat-resistant gaskets, household products, etc., but in recent years, asbestos fibrous acicular crystals have scattered in the atmosphere and lungs. It has been found to cause health problems such as cancer and malignant mesothelioma, and its use is prohibited.
At present, asbestos waste is handled as general waste, but asbestos fibrous acicular crystals are scattered into the atmosphere, and asbestos fibrous acicular crystals are used for health and safety measures. There is an urgent need for detoxification treatment measures that make it non-fibrous.
これまで、アスベストの無害化対策として、アスベスト廃材を無機酸により溶解した後、これに硫酸を加えて石膏化するアスベスト無害化処理方法が特許文献１に開示されている。また、繊維状物質を含む材料を、塩酸溶液や酢酸溶液により溶解し、試料中の炭酸ガスを除去した後、熱重量分析するアスベスト簡易分析法が特許文献２に開示されている。
特開２００８－２４６４４５号公報
特開２００８－３９６６０号公報
So far, asbestos detoxification measures have been disclosed in Patent Document 1 as an asbestos detoxification treatment method in which asbestos waste is dissolved with an inorganic acid and then sulfuric acid is added thereto to form gypsum. Further, Patent Document 2 discloses a simple asbestos analysis method in which a material containing a fibrous substance is dissolved with a hydrochloric acid solution or an acetic acid solution, carbon dioxide in the sample is removed, and then thermogravimetric analysis is performed.
JP 2008-246445 A JP 2008-39660 A
アスベストは、蛇紋岩系とカンラン岩質角閃石とが知られ、蛇紋岩質白石綿クリソタイル〔Ｍｇ６Ｓｉ４Ｏ１０（ＯＨ）８〕、角閃石質茶石綿アモサイト〔（Ｆｅ，Ｍｇ）７Ｓｉ８Ｏ２２（ＯＨ）２〕、角閃石質青石綿クロシドライト〔Ｎａ（Ｆｅ２+，Ｍｇ）３Ｆｅ３+
２Ｓｉ８Ｏ２２（ＯＨ，Ｆ）２〕のクリソタイル、アモサイト、クロシドライトの三種が工業的にアスベスト建材として使用されていることが知られている。
この他、角閃石系のアンソフィライト〔Ｍｇ７Ｓｉ８Ｏ２２（ＯＨ）２〕トレモライト〔Ｃａ２Ｍｇ５Ｓｉ８Ｏ２２（ＯＨ）２〕、アクチノライト〔Ｃａ２（Ｍｇ，Ｆｅ）５Ｓｉ８Ｏ２２（ＯＨ）２〕が知られているが、耐摩擦材、耐熱材等に多く用いられ、建材用の利用は極めて少ないことが知られている。 Asbestos is known as serpentinite and olivine amphibolite, serpentinite white asbestos chrysotile [Mg 6 Si 4 O 10 (OH) 8 ], amphibolite tea asbestos amosite [(Fe, Mg) 7 Si 8 O 22 (OH) 2 ], amphiboleous blue asbestos crocidolite [Na (Fe 2+ , Mg) 3 Fe 3+ 2 Si 8 O 22 (OH, F) 2 ] It is known to be used as an asbestos building material.
In addition, amphibole-based anthophyllite [Mg 7 Si 8 O 22 (OH) 2 ] tremolite [Ca 2 Mg 5 Si 8 O 22 (OH) 2 ], actinolite [Ca 2 (Mg, Fe) 5 Si 8 O 22 (OH) 2 ] is known, but it is widely used for friction-resistant materials, heat-resistant materials, and the like, and is known to be extremely rarely used for building materials.
この他、角閃石系のアンソフィライト〔Ｍｇ７Ｓｉ８Ｏ２２（ＯＨ）２〕トレモライト〔Ｃａ２Ｍｇ５Ｓｉ８Ｏ２２（ＯＨ）２〕、アクチノライト〔Ｃａ２（Ｍｇ，Ｆｅ）５Ｓｉ８Ｏ２２（ＯＨ）２〕が知られているが、耐摩擦材、耐熱材等に多く用いられ、建材用の利用は極めて少ないことが知られている。 Asbestos is known as serpentinite and olivine amphibolite, serpentinite white asbestos chrysotile [Mg 6 Si 4 O 10 (OH) 8 ], amphibolite tea asbestos amosite [(Fe, Mg) 7 Si 8 O 22 (OH) 2 ], amphiboleous blue asbestos crocidolite [Na (Fe 2+ , Mg) 3 Fe 3+ 2 Si 8 O 22 (OH, F) 2 ] It is known to be used as an asbestos building material.
In addition, amphibole-based anthophyllite [Mg 7 Si 8 O 22 (OH) 2 ] tremolite [Ca 2 Mg 5 Si 8 O 22 (OH) 2 ], actinolite [Ca 2 (Mg, Fe) 5 Si 8 O 22 (OH) 2 ] is known, but it is widely used for friction-resistant materials, heat-resistant materials, and the like, and is known to be extremely rarely used for building materials.
特許文献１（特開２００８－２４６４４５号公報）は、アスベストを含有する廃材を無機酸として塩酸、フッ酸、リン酸、硝酸の他フッ化物酸等、１種ないしそれ以上を用いて溶解処理するもので、カルシウムまたはマグネシウムが含まれる溶解処理液中に硫酸を添加して不溶性の硫酸カルシウムを析出されることが記述されている。
しかし、前述した工業的にアスベスト建材に用いられている三種のクリソタイル、アモサイト、クロシドライトの組成分中には、Ｍｇ、Ｆｅ、Ｎａ、Ｓｉが含有されているもののＣａは含有されていない。特願２００８－２４６４４５号公報は、アスベスト廃材中のセメントや消石灰の成分であるカルシウムを無機酸で溶解したものであって、アスベストから溶解したカルシウムではなく、アスベストの針状結晶からカルシウムが溶解するとして、これに硫酸を添加して硫酸カルシウムを生成させたとする化学的根拠は全くなく、課題がある。 Patent Document 1 (Japanese Patent Application Laid-Open No. 2008-246445) discloses that a waste material containing asbestos is dissolved as an inorganic acid using one or more of hydrochloric acid, hydrofluoric acid, phosphoric acid, nitric acid, fluoride acid, and the like. It is described that insoluble calcium sulfate is precipitated by adding sulfuric acid to a solution containing calcium or magnesium.
However, the composition of the three types of chrysotile, amosite, and crocidolite that are industrially used for asbestos building materials as described above contains Mg, Fe, Na, and Si, but does not contain Ca. Japanese Patent Application No. 2008-246445 is a solution in which calcium, which is a component of cement and slaked lime in asbestos waste, is dissolved with an inorganic acid, and calcium is dissolved not from calcium dissolved in asbestos but from acicular crystals of asbestos. As such, there is no chemical basis for adding sulfuric acid to produce calcium sulfate, and there is a problem.
しかし、前述した工業的にアスベスト建材に用いられている三種のクリソタイル、アモサイト、クロシドライトの組成分中には、Ｍｇ、Ｆｅ、Ｎａ、Ｓｉが含有されているもののＣａは含有されていない。特願２００８－２４６４４５号公報は、アスベスト廃材中のセメントや消石灰の成分であるカルシウムを無機酸で溶解したものであって、アスベストから溶解したカルシウムではなく、アスベストの針状結晶からカルシウムが溶解するとして、これに硫酸を添加して硫酸カルシウムを生成させたとする化学的根拠は全くなく、課題がある。 Patent Document 1 (Japanese Patent Application Laid-Open No. 2008-246445) discloses that a waste material containing asbestos is dissolved as an inorganic acid using one or more of hydrochloric acid, hydrofluoric acid, phosphoric acid, nitric acid, fluoride acid, and the like. It is described that insoluble calcium sulfate is precipitated by adding sulfuric acid to a solution containing calcium or magnesium.
However, the composition of the three types of chrysotile, amosite, and crocidolite that are industrially used for asbestos building materials as described above contains Mg, Fe, Na, and Si, but does not contain Ca. Japanese Patent Application No. 2008-246445 is a solution in which calcium, which is a component of cement and slaked lime in asbestos waste, is dissolved with an inorganic acid, and calcium is dissolved not from calcium dissolved in asbestos but from acicular crystals of asbestos. As such, there is no chemical basis for adding sulfuric acid to produce calcium sulfate, and there is a problem.
次に、特許文献２（特願２００８－３９６６０号公報）は、アスベスト中の繊維状物質を定性分析する際、アスベストに付着するセメント等の炭酸化物を除去するのに、酸として塩酸や酢酸を用いた、分析妨害ピークを除去するアスベストの簡易分析法である。
特開２００８－３９６６０号公報には、アスベストに付着したセメント成分の炭酸石灰分を酸で優先溶解することが記述されている。 Next, Patent Document 2 (Japanese Patent Application No. 2008-39660) discloses that when qualitative analysis of a fibrous material in asbestos, hydrochloric acid or acetic acid is used as an acid to remove carbonates such as cement adhering to asbestos. This is a simple analysis method for asbestos that removes the interference peaks.
Japanese Patent Application Laid-Open No. 2008-39660 describes that a lime carbonate component of a cement component adhering to asbestos is preferentially dissolved with an acid.
特開２００８－３９６６０号公報には、アスベストに付着したセメント成分の炭酸石灰分を酸で優先溶解することが記述されている。 Next, Patent Document 2 (Japanese Patent Application No. 2008-39660) discloses that when qualitative analysis of a fibrous material in asbestos, hydrochloric acid or acetic acid is used as an acid to remove carbonates such as cement adhering to asbestos. This is a simple analysis method for asbestos that removes the interference peaks.
Japanese Patent Application Laid-Open No. 2008-39660 describes that a lime carbonate component of a cement component adhering to asbestos is preferentially dissolved with an acid.
かくの如く、アスベスト含有廃材は、接着剤に用いたセメント成分の炭酸カルシウムを多く含有し、酸による単独での溶解処理には多くの困難と課題がある。
As described above, the asbestos-containing waste material contains a large amount of calcium carbonate, which is a cement component used in the adhesive, and there are many difficulties and problems in the sole dissolution treatment with an acid.
本発明は、アスベスト溶解剤として、植物性有機酸とオルトリン酸および天然ミネラルイオン含有植物皮果汁液組成物による混合酸を用いてアスベスト含有廃材を溶解処理した後、これを不溶性塩に変換固形化処理し、農業用肥料とすることを目的とするアスベスト溶解剤およびアスベスト無害化湿式処理方法を提供するものである。
The present invention, as an asbestos solubilizer, dissolved asbestos-containing waste material using a mixed acid composed of plant organic acid, orthophosphoric acid and natural mineral ion-containing plant skin juice liquid composition, then converted to an insoluble salt and solidified The present invention provides an asbestos solubilizer and an asbestos-detoxifying wet processing method for the purpose of treating and producing an agricultural fertilizer.
発明者らは、アスベストを含有する廃材を処理するに当たり、植物性有機酸のパイナップル皮果汁液の主成分であるイソ吉草酸〔（ＣＨ３）２ＣＨＣＨ２ＣＯＯＨ〕とオルトリン酸（Ｈ３ＰＯ４）との混酸を用いてアスベストの繊維状針状結晶物を浸漬すると、浸漬液中にアスベストの主成分であるマグネシウム（Ｍｇ）や鉄（Ｆｅ）がイオンとして溶解されることを見出した。
The inventors treated isovaleric acid [(CH 3 ) 2 CHCH 2 COOH] and orthophosphoric acid (H 3 PO 4 ), which are the main components of a pineapple peel juice of a vegetable organic acid, in treating waste materials containing asbestos. It was found that magnesium (Mg) and iron (Fe), which are main components of asbestos, are dissolved as ions in the immersion liquid when the fibrous needle-like crystal of asbestos is immersed using a mixed acid.
さらに、発明者らは、鋭意研究を重ね、植物性有機酸のパイナップル皮果汁液の主成分であるイソ吉草酸とオルトリン酸との混酸の中に、酸化剤である過酸化水素と、超微粒子二酸化チタンと、カリミョウバンおよび天然ミネラルイオン含有植物皮果汁液組成物を添加することにより、アスベストの繊維状針状結晶物の溶解処理が容易となることが分かり本発明を完成するにいたった。
Furthermore, the inventors have conducted extensive research, and in the mixed acid of isovaleric acid and orthophosphoric acid, which are the main components of pineapple skin juice of vegetable organic acid, hydrogen peroxide as an oxidizing agent and ultrafine particles It has been found that the addition of titanium dioxide and a composition of plant skin juice containing potassium alum and natural mineral ions facilitates the dissolution treatment of fibrous needle-like crystals of asbestos, thereby completing the present invention.
本発明に用いたアスベスト含有廃材の繊維状針状結晶物は、蛇紋岩系のクリソタイル〔Ｍｇ６Ｓｉ４Ｏ１０（ＯＨ）８〕と角閃石系のアモサイト〔（Ｆｅ，Ｍｇ）７Ｓｉ８Ｏ２２（ＯＨ）２〕などが含有されることを示差熱天秤分析とＸ線回折により確認した。
Asbestos-containing waste material fibrous acicular crystals used in the present invention are serpentinite chrysotile [Mg 6 Si 4 O 10 (OH) 8 ] and amphibole amosite [(Fe, Mg) 7 Si 8 O 22 (OH) 2 ] and the like were confirmed by differential thermal balance analysis and X-ray diffraction.
本発明のアスベストの蛇紋岩とオルトリン酸による溶解反応について説明する。
蛇紋岩のクリソタイル〔Ｍｇ６Ｓｉ４Ｏ１０（ＯＨ）８〕は、４Ｍｇ（ＯＨ）２と２ＭｇＯと４ＳｉＯ２それぞれの酸化物または水酸化物との共晶により繊維状針状結晶物を成していることが分かる。
次に、クリソタイル〔Ｍｇ６Ｓｉ４Ｏ１０（ＯＨ）８〕のＭｇ（ＯＨ）２とＭｇＯとがオルトリン酸と反応し溶解してマグネシウムイオンとなることを溶解液中のＭｇ２+を蛍光X線定性分析により確認した。化学反応式を化（１）、（２）に示す。
The dissolution reaction of asbestos serpentine and orthophosphoric acid according to the present invention will be described.
The serpentinite chrysotile [Mg 6 Si 4 O 10 (OH) 8 ] is composed of 4Mg (OH) 2 , 2MgO, and 4SiO 2 oxides or hydroxides to form fibrous acicular crystals. I understand that
Next, chrysotile [Mg 6 Si 4 O 10 (OH ) 8 ] of Mg (OH) 2 and MgO and is fluorescence Mg 2+ in the lysate to be a magnesium ions dissolved reacted with orthophosphoric acid X Confirmed by linear qualitative analysis. Chemical reaction formulas are shown in chemical formulas (1) and (2).
蛇紋岩のクリソタイル〔Ｍｇ６Ｓｉ４Ｏ１０（ＯＨ）８〕は、４Ｍｇ（ＯＨ）２と２ＭｇＯと４ＳｉＯ２それぞれの酸化物または水酸化物との共晶により繊維状針状結晶物を成していることが分かる。
次に、クリソタイル〔Ｍｇ６Ｓｉ４Ｏ１０（ＯＨ）８〕のＭｇ（ＯＨ）２とＭｇＯとがオルトリン酸と反応し溶解してマグネシウムイオンとなることを溶解液中のＭｇ２+を蛍光X線定性分析により確認した。化学反応式を化（１）、（２）に示す。
The serpentinite chrysotile [Mg 6 Si 4 O 10 (OH) 8 ] is composed of 4Mg (OH) 2 , 2MgO, and 4SiO 2 oxides or hydroxides to form fibrous acicular crystals. I understand that
Next, chrysotile [Mg 6 Si 4 O 10 (OH ) 8 ] of Mg (OH) 2 and MgO and is fluorescence Mg 2+ in the lysate to be a magnesium ions dissolved reacted with orthophosphoric acid X Confirmed by linear qualitative analysis. Chemical reaction formulas are shown in chemical formulas (1) and (2).
蛇紋岩の共晶体のＭｇ（ＯＨ）２とＭｇＯとイソ吉草酸〔（ＣＨ３）２ＣＨＣＨ２ＣＯＯＨ〕とが反応し溶解してマグネシウムイオン化する反応式を化（３）（４）に示す。
Formulas (3) and (4) show reaction formulas in which the serpentine eutectic Mg (OH) 2 , MgO, and isovaleric acid [(CH 3 ) 2 CHCH 2 COOH] react and dissolve to form magnesium ions.
本発明の植物性有機酸について説明する。本発明の植物性有機酸はパイナップル皮果汁液の主成分であるイソ吉草酸〔（ＣＨ３）２ＣＨＣＨ２ＣＯＯＨ〕や酪酸〔ＣＨ３ＣＨ２ＣＨ２ＣＯＯＨ〕と、ココナツ果汁液のカプロン酸〔ＣＨ３（ＣＨ２）４ＣＯＯＨ〕およびカプリル酸〔ＣＨ３（ＣＨ２）６ＣＯＯＨ〕と、柑橘皮果汁液のリモネン（Ｃ１０Ｈ１６）、アスコルビン酸（Ｃ６Ｈ８Ｏ６）、パントテン酸（Ｃ９Ｈ１７ＮＯ６）等複合植物性有機酸である。
The vegetable organic acid of the present invention will be described. The vegetable organic acid of the present invention includes isovaleric acid [(CH 3 ) 2 CHCH 2 COOH] and butyric acid [CH 3 CH 2 CH 2 COOH], which are the main components of pineapple peel juice, and caproic acid [coconut juice] CH 3 (CH 2 ) 4 COOH] and caprylic acid [CH 3 (CH 2 ) 6 COOH], citrus peel juice limonene (C 10 H 16 ), ascorbic acid (C 6 H 8 O 6 ), pantothenic acid It is a complex plant organic acid such as (C 9 H 17 NO 6 ).
蛇紋岩のクリソタイル〔Ｍｇ６Ｓｉ４Ｏ１０（ＯＨ）５〕とイソ吉草酸との溶解反応式を化（３）、（４）に一例として記述したが、イソ吉草酸のみでなく、その他の上記した有機酸成分の化学反応の相乗効果により溶解が推移すると考えている。
The dissolution reaction formula of serpentinite chrysotile [Mg 6 Si 4 O 10 (OH) 5 ] and isovaleric acid was described as an example in (3) and (4), but not only isovaleric acid but other It is believed that dissolution will shift due to the synergistic effect of the chemical reaction of the organic acid component described above.
天然ミネラルイオン含有植物皮果汁液組成物について説明する。
天然ミネラルイオン含有植物皮果汁液組成物は、麦飯石、医王石、ヒル石等を、パイナップル皮果汁液を主成分とする植物性有機酸を用いて、ミネラル成分のＡｌ、Ｃａ、Ｋ、Ｍｎ、Ｆｅ、Ｔｉ、Ｓｉ、Ｐ等を含有すると共に、活性酸素の一種であるＯＨラジカル（・ＯＨ）を多量に含むことをＥＳＲ（Ｅｌｅｃｔｏｒｏｎ Ｓｐｉｎ， Ｒｅｓｏｎａｎｃｅ）測定のＤＭＰＯ（５－Ｄｉｍｅｔｙｌ， ｐｈｙｒｒｏｌｉｎｅ１－ｏｘｉｄｅ）捕捉剤を用いるスピントラッピング法により確認している。
本発明は、特願２００８－２９３８８８に天然ミネラルイオン含有植物皮果汁液組成物として提案を行ってきている。
本発明の天然ミネラルイオン含有植物皮果汁液組成物中の活性酸素の一種であるＯＨラジカルについて詳しく説明する。
本発明者らは、天然ミネラルイオン含有植物皮果汁液組成物を極く少量添加するだけで大気中からの溶存酸素（ＤＯ）の酸化力が著しく増大する現象を数多く確認して来ている。本発明者らは、この現象は、麦飯石、医王石、ヒル石等の金属酸化物がミネラルイオン化する際に生成する活性酸素の一種であるＯＨラジカルが含有することによって起こる酸化力によるものではないかと考えた。
本発明は、この考えを科学的に実証するため、本発明の天然ミネラルイオン含有植物皮果汁液組成物のＥＳＲ（Ｅｌｅｃｔｏｒｏｎ ｓｐｉｎ ｒｅｓｏｎａｎｃｅ＝電子スピン共鳴）測定のスピントラッピング法により、ＤＭＰＯ－ＯＨ捕捉を確認し、天然ミネラルイオン含有植物皮果汁液組成物を少量添加することにより、活性酸素の一種であるＯＨラジカルが含有することを確認し、本発明の極めて重要なアスベスト溶解剤の成分組成要素となることが分かった。 The natural mineral ion-containing plant skin juice composition will be described.
The natural mineral ion-containing plant skin juice composition is composed of barley stone, Io stone, leech stone, etc., using plant organic acids mainly composed of pineapple skin juice, and the mineral components Al, Ca, K, Mn , Fe, Ti, Si, P, and the like, and DMPO (5-Dimethyl, phylloline1-oxide) measured by ESR (Electron Spin, Resonance) to contain a large amount of OH radical (.OH) which is a kind of active oxygen. ) Confirmed by spin trapping method using scavenger.
The present invention has been proposed in Japanese Patent Application No. 2008-293888 as a natural mineral ion-containing plant skin juice composition.
The OH radical which is a kind of active oxygen in the natural mineral ion-containing plant skin juice liquid composition of the present invention will be described in detail.
The present inventors have confirmed many phenomena in which the oxidizing power of dissolved oxygen (DO) from the atmosphere is remarkably increased only by adding a very small amount of a natural mineral ion-containing plant skin juice liquid composition. The present inventors have found that this phenomenon is due to the oxidizing power caused by the inclusion of OH radicals, which are a kind of active oxygen produced when metal oxides such as barley stone, meiolite, and leechite are mineralized. I thought.
In order to scientifically demonstrate this idea, the present invention captures DMPO-OH by a spin trapping method of ESR (Electron spin resonance = electron spin resonance) measurement of the natural mineral ion-containing plant skin juice composition of the present invention. By confirming and adding a small amount of a natural mineral ion-containing plant skin juice composition, it is confirmed that OH radical, which is a kind of active oxygen, is contained, and the component composition element of the extremely important asbestos solubilizer of the present invention I found out that
天然ミネラルイオン含有植物皮果汁液組成物は、麦飯石、医王石、ヒル石等を、パイナップル皮果汁液を主成分とする植物性有機酸を用いて、ミネラル成分のＡｌ、Ｃａ、Ｋ、Ｍｎ、Ｆｅ、Ｔｉ、Ｓｉ、Ｐ等を含有すると共に、活性酸素の一種であるＯＨラジカル（・ＯＨ）を多量に含むことをＥＳＲ（Ｅｌｅｃｔｏｒｏｎ Ｓｐｉｎ， Ｒｅｓｏｎａｎｃｅ）測定のＤＭＰＯ（５－Ｄｉｍｅｔｙｌ， ｐｈｙｒｒｏｌｉｎｅ１－ｏｘｉｄｅ）捕捉剤を用いるスピントラッピング法により確認している。
本発明は、特願２００８－２９３８８８に天然ミネラルイオン含有植物皮果汁液組成物として提案を行ってきている。
本発明の天然ミネラルイオン含有植物皮果汁液組成物中の活性酸素の一種であるＯＨラジカルについて詳しく説明する。
本発明者らは、天然ミネラルイオン含有植物皮果汁液組成物を極く少量添加するだけで大気中からの溶存酸素（ＤＯ）の酸化力が著しく増大する現象を数多く確認して来ている。本発明者らは、この現象は、麦飯石、医王石、ヒル石等の金属酸化物がミネラルイオン化する際に生成する活性酸素の一種であるＯＨラジカルが含有することによって起こる酸化力によるものではないかと考えた。
本発明は、この考えを科学的に実証するため、本発明の天然ミネラルイオン含有植物皮果汁液組成物のＥＳＲ（Ｅｌｅｃｔｏｒｏｎ ｓｐｉｎ ｒｅｓｏｎａｎｃｅ＝電子スピン共鳴）測定のスピントラッピング法により、ＤＭＰＯ－ＯＨ捕捉を確認し、天然ミネラルイオン含有植物皮果汁液組成物を少量添加することにより、活性酸素の一種であるＯＨラジカルが含有することを確認し、本発明の極めて重要なアスベスト溶解剤の成分組成要素となることが分かった。 The natural mineral ion-containing plant skin juice composition will be described.
The natural mineral ion-containing plant skin juice composition is composed of barley stone, Io stone, leech stone, etc., using plant organic acids mainly composed of pineapple skin juice, and the mineral components Al, Ca, K, Mn , Fe, Ti, Si, P, and the like, and DMPO (5-Dimethyl, phylloline1-oxide) measured by ESR (Electron Spin, Resonance) to contain a large amount of OH radical (.OH) which is a kind of active oxygen. ) Confirmed by spin trapping method using scavenger.
The present invention has been proposed in Japanese Patent Application No. 2008-293888 as a natural mineral ion-containing plant skin juice composition.
The OH radical which is a kind of active oxygen in the natural mineral ion-containing plant skin juice liquid composition of the present invention will be described in detail.
The present inventors have confirmed many phenomena in which the oxidizing power of dissolved oxygen (DO) from the atmosphere is remarkably increased only by adding a very small amount of a natural mineral ion-containing plant skin juice liquid composition. The present inventors have found that this phenomenon is due to the oxidizing power caused by the inclusion of OH radicals, which are a kind of active oxygen produced when metal oxides such as barley stone, meiolite, and leechite are mineralized. I thought.
In order to scientifically demonstrate this idea, the present invention captures DMPO-OH by a spin trapping method of ESR (Electron spin resonance = electron spin resonance) measurement of the natural mineral ion-containing plant skin juice composition of the present invention. By confirming and adding a small amount of a natural mineral ion-containing plant skin juice composition, it is confirmed that OH radical, which is a kind of active oxygen, is contained, and the component composition element of the extremely important asbestos solubilizer of the present invention I found out that
天然ミネラルイオン含有植物皮果汁液組成物の、一種の活性酸素であるラシカルＯＨ（・ＯＨ）は、反応性に富む酸化剤であり、過酸化水素や超微粒子二酸化チタンと共に、アスベストの角閃石系アモサイト〔（ＦｅＭｇ）７Ｓｉ８Ｏ２２（ＯＨ）２〕等に含まれるニ価鉄の酸化を促進する役割があり、アモサイトの二価鉄が酸化されて三価鉄になることにより、植物性有機酸のイソ吉草酸やオルトリン酸との反応が容易となり、単独酸では溶出が困難であったものが、天然ミネラルイオン含有植物皮果汁液組成物等の酸化剤の併用により浸出溶解が可能となることを見出した。
Natural ionic ion-containing plant skin juice composition, radical OH (· OH), which is a kind of active oxygen, is a highly reactive oxidant, along with hydrogen peroxide and ultrafine titanium dioxide, asbestos amphibole It has a role of promoting the oxidation of divalent iron contained in amosite [(FeMg) 7 Si 8 O 22 (OH) 2 ], etc., and the divalent iron of amosite is oxidized to become trivalent iron. Reactions with organic acids such as isovaleric acid and orthophosphoric acid are easy, and elution with a single acid is difficult to leach and dissolve by the combined use of an oxidizing agent such as a plant skin juice composition containing natural mineral ions. I found out that
角閃石系アモサイト〔（Ｆｅ，Ｍｇ）７Ｓｉ８Ｏ２２（ＯＨ）２〕と酸化剤入りオルトリン酸による溶解反応について説明する。
角閃石系のアモサイト〔（Ｆｅ，Ｍｇ）７Ｓｉ８Ｏ２２（ＯＨ）２〕は、 〔６（Ｆｅ，Ｍｇ）Ｏ〕［（Ｆｅ，Ｍｇ）（ＯＨ）２８ＳｉＯ２］であり、つまり６ＦｅＯ、Ｆｅ（ＯＨ）２、８ＳｉＯ２であり、６ＭｇＯ、Ｍｇ（ＯＨ）２、８ＳｉＯ２である。
二価鉄酸化物および水酸化鉄の酸化剤による酸化反応式を化（５）（６）に示す。
The dissolution reaction of amphibole-based amosite [(Fe, Mg) 7 Si 8 O 22 (OH) 2 ] and orthophosphoric acid containing an oxidizing agent will be described.
Amphibole-based amosite [(Fe, Mg) 7 Si 8 O 22 (OH) 2 ] is [6 (Fe, Mg) O] [(Fe, Mg) (OH) 2 8SiO 2 ], that is, 6FeO. Fe (OH) 2 and 8SiO 2 , and 6MgO, Mg (OH) 2 and 8SiO 2 .
The oxidation reaction formulas of the divalent iron oxide and the iron hydroxide with the oxidizing agent are shown in chemical formulas (5) and (6).
角閃石系のアモサイト〔（Ｆｅ，Ｍｇ）７Ｓｉ８Ｏ２２（ＯＨ）２〕は、 〔６（Ｆｅ，Ｍｇ）Ｏ〕［（Ｆｅ，Ｍｇ）（ＯＨ）２８ＳｉＯ２］であり、つまり６ＦｅＯ、Ｆｅ（ＯＨ）２、８ＳｉＯ２であり、６ＭｇＯ、Ｍｇ（ＯＨ）２、８ＳｉＯ２である。
二価鉄酸化物および水酸化鉄の酸化剤による酸化反応式を化（５）（６）に示す。
Amphibole-based amosite [(Fe, Mg) 7 Si 8 O 22 (OH) 2 ] is [6 (Fe, Mg) O] [(Fe, Mg) (OH) 2 8SiO 2 ], that is, 6FeO. Fe (OH) 2 and 8SiO 2 , and 6MgO, Mg (OH) 2 and 8SiO 2 .
The oxidation reaction formulas of the divalent iron oxide and the iron hydroxide with the oxidizing agent are shown in chemical formulas (5) and (6).
三価鉄酸化物とオルトリン酸との反応式を化（７）に示す。
なお、ＭｇＯ、Ｍｇ（ＯＨ）２とオルトリン酸およびイソ吉草酸との反応については化（１）、（２）および化（３）、（４）に示した。
これまで角閃石系のアスベストの溶解浸出が容易でなかったことの一つの原因は、繊維状針状結晶物の二価鉄が結晶体に含有されているためであることに着目したのは本発明で全く新規な着想である。 The reaction formula of trivalent iron oxide and orthophosphoric acid is shown in chemical formula (7).
The reaction of MgO, Mg (OH) 2 with orthophosphoric acid and isovaleric acid is shown in chemical formulas (1), (2), chemical formulas (3), and (4).
One reason that the dissolution and leaching of amphibole-based asbestos has not been easy so far is that the crystalline body contains divalent iron in the form of fibrous needle-like crystals. It is a completely new idea in the invention.
これまで角閃石系のアスベストの溶解浸出が容易でなかったことの一つの原因は、繊維状針状結晶物の二価鉄が結晶体に含有されているためであることに着目したのは本発明で全く新規な着想である。 The reaction formula of trivalent iron oxide and orthophosphoric acid is shown in chemical formula (7).
One reason that the dissolution and leaching of amphibole-based asbestos has not been easy so far is that the crystalline body contains divalent iron in the form of fibrous needle-like crystals. It is a completely new idea in the invention.
本発明の天然ミネラルイオン含有植物皮果汁液組成物の酸化剤としての効果は、同時に添加する過酸化水素、超微粒子二酸化チタンを併用することにより、それぞれの相乗効果が一層高まり酸化反応が促進され、アスベスト含有廃材の溶解が容易となる。
The natural mineral ion-containing plant skin juice composition of the present invention has an effect as an oxidizing agent. The combined use of hydrogen peroxide and ultrafine titanium dioxide added at the same time further increases the synergistic effect of each and promotes the oxidation reaction. , Asbestos-containing waste materials can be easily dissolved.
本発明のアスベスト溶解剤を壁材やスレート材等への噴霧吹付けや溶解作業を行う際、アスベスト廃材中に吸着された悪臭源が酸との反応により激しく発生し、作業環境が著しく悪化するため、本発明の天然ミネラルイオン含有植物皮果汁液組成物や過酸化水素、超微粒子二酸化チタンの酸化作用により消臭され、作業環境が改善される。またカリミョウバンは悪臭の低減改善剤としての働きを強化する作用がある。
When spraying or dissolving the asbestos-dissolving agent of the present invention on wall materials or slate materials, a bad odor source adsorbed in the asbestos waste material is vigorously generated by reaction with acid, and the working environment is significantly deteriorated. Therefore, it is deodorized by the oxidizing action of the natural mineral ion-containing plant skin fruit juice composition of the present invention, hydrogen peroxide, and ultrafine titanium dioxide, and the working environment is improved. Potash alum has the effect of strengthening its function as a odor reduction and improvement agent.
本発明は、アスベスト含有廃材を、本発明のアスベスト溶解剤で溶解処理する第一工程と、第一工程でのマグネシウム含有溶解液を可溶性炭酸カルシウムおよび塩化カルシウムを含む生石灰と消石灰を用いてアスベスト含有成分を不溶性塩とする第二工程と、第二工程で得られる変換固形化物を農業用肥料とする第三工程と、からなる。
The present invention is a first step of dissolving asbestos-containing waste material with the asbestos-dissolving agent of the present invention, and the magnesium-containing solution in the first step contains asbestos using quick lime and slaked lime containing soluble calcium carbonate and calcium chloride. It consists of a second step in which the components are insoluble salts and a third step in which the converted solidified product obtained in the second step is an agricultural fertilizer.
本発明によれば、従来法のアスベスト含有廃材を酸溶解した後、再利用するため、固化物とした後８００～１０００℃以上の高温処理したりすることがなく、常温でアスベスト組成分を変換固形化し農業用肥料とすることを可能にしたことは、アスベスト処理対策としての効果は多大である。
According to the present invention, the asbestos-containing waste material of the conventional method is dissolved in an acid and then reused, so that the asbestos composition is converted at room temperature without being subjected to a high temperature treatment of 800 to 1000 ° C. or more after solidification. The fact that it became solid and made into agricultural fertilizer has a great effect as an asbestos treatment measure.
本発明の実施の形態について以下に説明する。
本発明の第一工程においては、アスベスト含有廃材を植物性有機酸とオルトリン酸、天然ミネラルイオン含有植物皮果汁液組成物、過酸化水素、超微粒子二酸化チタン、カリミョウバンからなるアスベスト溶解剤の中に浸漬または、壁材の耐火材、吹付けアスベスト材等への噴霧吹付け処理して、アスベスト組成分を溶解処理した後、第二工程においては、溶解処理後液に可溶性炭酸カルシウムおよび塩化カルシウムを含む生石灰、消石灰を用いて不溶性塩として変換固形化物農業用肥料原料とし、第三工程では、これを乾燥、粉砕し、農業用肥料とすることが可能となる。 Embodiments of the present invention will be described below.
In the first step of the present invention, the asbestos-containing waste material is an asbestos-dissolving agent comprising plant organic acid and orthophosphoric acid, a plant skin juice composition containing natural mineral ions, hydrogen peroxide, ultrafine titanium dioxide, and potassium alum. In the second step, the solubilized calcium carbonate and calcium chloride are dissolved in the solution after the soaking process. The converted solidified agricultural fertilizer raw material is converted into an insoluble salt using quicklime containing lime and slaked lime, and in the third step, this can be dried and pulverized to produce an agricultural fertilizer.
本発明の第一工程においては、アスベスト含有廃材を植物性有機酸とオルトリン酸、天然ミネラルイオン含有植物皮果汁液組成物、過酸化水素、超微粒子二酸化チタン、カリミョウバンからなるアスベスト溶解剤の中に浸漬または、壁材の耐火材、吹付けアスベスト材等への噴霧吹付け処理して、アスベスト組成分を溶解処理した後、第二工程においては、溶解処理後液に可溶性炭酸カルシウムおよび塩化カルシウムを含む生石灰、消石灰を用いて不溶性塩として変換固形化物農業用肥料原料とし、第三工程では、これを乾燥、粉砕し、農業用肥料とすることが可能となる。 Embodiments of the present invention will be described below.
In the first step of the present invention, the asbestos-containing waste material is an asbestos-dissolving agent comprising plant organic acid and orthophosphoric acid, a plant skin juice composition containing natural mineral ions, hydrogen peroxide, ultrafine titanium dioxide, and potassium alum. In the second step, the solubilized calcium carbonate and calcium chloride are dissolved in the solution after the soaking process. The converted solidified agricultural fertilizer raw material is converted into an insoluble salt using quicklime containing lime and slaked lime, and in the third step, this can be dried and pulverized to produce an agricultural fertilizer.
本発明における壁材の耐火材、吹付けアスベスト材等に対するアスベスト溶解剤の噴霧吹付け量の好適量は、厚み５ｃｍの場合、１ｍ２当たり１５～４０ｇ、最も好適量は３０ｇである。これ以下の量ではアスベスト溶解剤のアスベスト壁材への浸透が低く、剥離作業環境が低下する。
In the present invention, the preferred spraying amount of the asbestos-dissolving agent with respect to the refractory material of the wall material, the spraying asbestos material and the like is 15 to 40 g per 1 m 2 when the thickness is 5 cm, and the most preferable amount is 30 g. If the amount is less than this, the penetration of the asbestos dissolving agent into the asbestos wall material is low, and the peeling work environment is lowered.
本発明のアスベスト溶解剤に対するアスベスト含有廃材の浸漬量は、３０～７０％であり、好適には４０～５０％である。
The amount of asbestos-containing waste material immersed in the asbestos dissolving agent of the present invention is 30 to 70%, preferably 40 to 50%.
本発明の実施の最良の形態について、アスベスト溶解剤のアスベスト含有廃材溶解の好適条件について説明する。
本発明のアスベスト溶解剤中のオルトリン酸（Ｈ３ＰＯ４、９８％）の濃度は５～１５％で、好適には８～１０％である。これより低濃度であっても高濃度であっても溶解が容易でなくなる。 As for the best mode for carrying out the present invention, the preferred conditions for dissolving the asbestos-containing waste material of the asbestos solubilizer will be described.
The concentration of orthophosphoric acid (H 3 PO 4 , 98%) in the asbestos solubilizer of the present invention is 5 to 15%, preferably 8 to 10%. Even if the concentration is lower or higher than this, dissolution is not easy.
本発明のアスベスト溶解剤中のオルトリン酸（Ｈ３ＰＯ４、９８％）の濃度は５～１５％で、好適には８～１０％である。これより低濃度であっても高濃度であっても溶解が容易でなくなる。 As for the best mode for carrying out the present invention, the preferred conditions for dissolving the asbestos-containing waste material of the asbestos solubilizer will be described.
The concentration of orthophosphoric acid (H 3 PO 4 , 98%) in the asbestos solubilizer of the present invention is 5 to 15%, preferably 8 to 10%. Even if the concentration is lower or higher than this, dissolution is not easy.
本発明の植物性有機酸の好適含有濃度は、イソ吉草酸〔（ＣＨ３）２ＣＨＣＨ２ＣＯＯＨ〕や酪酸〔ＣＨ３（ＣＨ２）２ＣＯＯＨ〕５～２５％、最も好適濃度は１５％であり、ココナツ果汁液はカプロン酸〔ＣＨ３（ＣＨ２）４ＣＯＯＨ〕、カプリル酸〔ＣＨ３（ＣＨ２）６ＣＯＯＨ〕、カプリン酸〔ＣＨ３（ＣＨ２）８ＣＯＯＨ〕ラウリル酸〔ＣＨ３（ＣＨ２）１０ＣＯＯＨ〕ミスチリン酸〔ＣＨ３（ＣＨ２）１２ＣＯＯＨ〕等３～２０％、最も好適濃度は１０％、柑橘皮果汁液は、リモネン（Ｃ１０Ｈ１６）アスコルビン酸（Ｃ６Ｈ８Ｏ６）、パントテン酸（Ｃ９Ｈ１７ＮＯ５）３～１５％、最も好適濃度は１０％である。
The preferred concentration of the vegetable organic acid of the present invention is 5 to 25% isovaleric acid [(CH 3 ) 2 CHCH 2 COOH] or butyric acid [CH 3 (CH 2 ) 2 COOH], and the most preferred concentration is 15%. Yes, coconut juice is caproic acid [CH 3 (CH 2 ) 4 COOH], caprylic acid [CH 3 (CH 2 ) 6 COOH], capric acid [CH 3 (CH 2 ) 8 COOH] lauric acid [CH 3 ( CH 2 ) 10 COOH] mytilinic acid [CH 3 (CH 2 ) 12 COOH] etc. 3-20%, most preferred concentration is 10%, citrus peel juice is limonene (C 10 H 16 ) ascorbic acid (C 6 H 8 O 6 ), pantothenic acid (C 9 H 17 NO 5 ) 3-15%, most preferred concentration is 10%.
本発明の天然ミネラルイオン含有植物皮果汁液組成物のミネラルイオン濃度と遊離イソ吉草酸濃度は、Ｋ：５～１５ｇ／ｌ、Ｃａ：０．５～１．５ｇ／ｌ、Ｍｎ：０．１～０．５ｇ／ｌ、Ｆｅ：５～２０ｇ／ｌ、Ａｌ：３～１５ｇ／ｌ、Ｔｉ：０．５～１．５ｇ／ｌ、遊離イソ吉草酸〔（ＣＨ３）２ＣＨＣＨ２ＣＯＯＨ〕：１０～３０ｇ／ｌ、それぞれの好適濃度範囲であれば酸化剤として、溶解する際の促進効果が高い。好適濃度範囲については実施例において具体的に例示する。
The mineral ion concentration and free isovaleric acid concentration of the natural mineral ion-containing plant skin juice composition of the present invention are K: 5 to 15 g / l, Ca: 0.5 to 1.5 g / l, Mn: 0.1 0.5 g / l, Fe: 5-20 g / l, Al: 3-15 g / l, Ti: 0.5-1.5 g / l, free isovaleric acid [(CH 3 ) 2 CHCH 2 COOH]: When the concentration is within a range of 10 to 30 g / l, the oxidant has a high accelerating effect when dissolved. The preferred concentration range is specifically exemplified in the examples.
酸化剤である過酸化水素の好適濃度は、Ｈ２Ｏ２：１０～３０ｇ／ｌ、超微粒子二酸化チタンは、０．１～３ｇ／ｌが好適濃度である。これより低濃度ではアスベスト（二価鉄含有角閃石類）の溶解は容易でなくなる。
The preferred concentration of hydrogen peroxide as the oxidizing agent is H 2 O 2 : 10 to 30 g / l, and that of ultrafine titanium dioxide is 0.1 to 3 g / l. At concentrations lower than this, dissolution of asbestos (divalent iron-containing amphibolite) becomes difficult.
カリミョウバン〔ＫＡｌ（ＳＯ４）・１２Ｈ２Ｏ〕の好適濃度は、５～２０ｇ／ｌで、最も好適濃度は１０ｇ／ｌであり、アスベスト吹付壁材に噴霧吹付け作業の際、発生する悪臭を除去するために有効である。これより低濃度では効果が低く、高濃度では効果は同等である。
The preferred concentration of potash alum [KAl (SO 4 ) · 12H 2 O] is 5 to 20 g / l, the most preferred concentration is 10 g / l, and a bad odor generated during spraying on asbestos spray wall material. It is effective to remove. At lower concentrations than this, the effect is low, and at high concentrations, the effect is equivalent.
実施例により、本発明をさらに詳しく説明する。なお、本実施例は本発明の一実施形態に過ぎず、なんら限定解釈されるものではなく、本発明の範囲内で設計変更可能である。
≪実施例１≫ The examples further illustrate the present invention. In addition, a present Example is only one Embodiment of this invention, is not limitedly interpreted at all, and a design change is possible within the scope of the present invention.
Example 1
≪実施例１≫ The examples further illustrate the present invention. In addition, a present Example is only one Embodiment of this invention, is not limitedly interpreted at all, and a design change is possible within the scope of the present invention.
Example 1
アスベストの蛇紋岩質白石綿クリソタイル〔Ｍｇ６Ｓｉ４Ｏ１０（ＯＨ）８〕原石５０ｇ（粒径３ｍｍφ以下８０％）をオルトリン酸（Ｈ３ＰＯ４、９８％）２０ｇと、植物性有機酸のパイナップル皮果汁液（イソ吉草酸１５％、酪酸１０％）との混合酸２００ｍｌに浸漬し、常温にて３０分間攪拌処理した。
それぞれの成分定性分析の結果、溶解処理液中にマグネシウム（Ｍｇ）を確認した。溶解残渣をＸ線回折の結果、ＳｉＯ２を確認した。
白石綿クリソタイル〔Ｍｇ６Ｓｉ４Ｏ１０（ＯＨ）８〕繊維状針状結晶体は、オルトリン酸と植物性有機酸との混合酸により溶解切断されたことを確認し、溶解残渣のＸ線回折によりＳｉＯ２を確認した。また残渣中にクリソタイルは確認されなかった。
≪実施例２≫ Asbestos serpentinite white asbestos chrysotile [Mg 6 Si 4 O 10 (OH) 8 ] raw stone 50g (particle size 3mmφ or less 80%) and orthophosphoric acid (H 3 PO 4 , 98%) 20g, It was immersed in 200 ml of mixed acid with pineapple peel juice (isovaleric acid 15%, butyric acid 10%) and stirred at room temperature for 30 minutes.
As a result of each component qualitative analysis, magnesium (Mg) was confirmed in the dissolution treatment liquid. As a result of X-ray diffraction of the dissolved residue, SiO 2 was confirmed.
Shiraishi cotton chrysotile [Mg 6 Si 4 O 10 (OH) 8 ] fibrous acicular crystals were confirmed to be dissolved and cut by a mixed acid of orthophosphoric acid and vegetable organic acid, and X-ray diffraction of the dissolved residue Confirmed SiO 2 . Further, no chrysotile was confirmed in the residue.
<< Example 2 >>
それぞれの成分定性分析の結果、溶解処理液中にマグネシウム（Ｍｇ）を確認した。溶解残渣をＸ線回折の結果、ＳｉＯ２を確認した。
白石綿クリソタイル〔Ｍｇ６Ｓｉ４Ｏ１０（ＯＨ）８〕繊維状針状結晶体は、オルトリン酸と植物性有機酸との混合酸により溶解切断されたことを確認し、溶解残渣のＸ線回折によりＳｉＯ２を確認した。また残渣中にクリソタイルは確認されなかった。
≪実施例２≫ Asbestos serpentinite white asbestos chrysotile [Mg 6 Si 4 O 10 (OH) 8 ] raw stone 50g (particle size 3mmφ or less 80%) and orthophosphoric acid (H 3 PO 4 , 98%) 20g, It was immersed in 200 ml of mixed acid with pineapple peel juice (isovaleric acid 15%, butyric acid 10%) and stirred at room temperature for 30 minutes.
As a result of each component qualitative analysis, magnesium (Mg) was confirmed in the dissolution treatment liquid. As a result of X-ray diffraction of the dissolved residue, SiO 2 was confirmed.
Shiraishi cotton chrysotile [Mg 6 Si 4 O 10 (OH) 8 ] fibrous acicular crystals were confirmed to be dissolved and cut by a mixed acid of orthophosphoric acid and vegetable organic acid, and X-ray diffraction of the dissolved residue Confirmed SiO 2 . Further, no chrysotile was confirmed in the residue.
<< Example 2 >>
アスベストの角閃石系茶石綿アモサイト〔（Ｆｅ，Ｍｇ）７Ｓｉ８Ｏ２２（ＯＨ）２〕原石５０ｇ（粒径３ｍｍφ以下８０％）をオルトリン酸（Ｈ３ＰＯ４、９８％）２０ｇと植物性有機酸のパイナップル皮果汁液（イソ吉草酸１５％、酪酸１０％）との混合酸２００ｍｌに、過酸化水素（３５％）５ｇ、超微粒子二酸化チタン５ｇ、カリミョウバン３ｇ、天然ミネラルイオン含有植物皮果汁液組成物２０ｍｌを加えたアスベスト溶解液中に浸漬し、３０分間常温にて攪拌した。これを固液分離した後、溶解処理後液と溶解残渣を得た。
溶解処理後液を定性分析した結果、マグネシウム（Ｍｇ）と三価鉄（Ｆｅ３＋）を確認した。残渣はＸ線回折の結果ＳｉＯ２を確認した。
オルトリン酸（Ｈ３ＰＯ４）２０％溶液のみによる比較テストでは、アモサイトの結晶は、浸漬時間３０分では残渣の中に残留し、浸漬時間３時間でも残渣の中に残留することを確認した。
≪実施例３≫ Asbestos amphibole-based tea asbestos amosite [(Fe, Mg) 7 Si 8 O 22 (OH) 2 ] rough stone 50 g (particle size 3 mmφ or less 80%) and orthophosphoric acid (H 3 PO 4 , 98%) 20 g and plant Organic acid pineapple peel juice (isovaleric acid 15%, butyric acid 10%) mixed acid 200ml, hydrogen peroxide (35%) 5g, ultrafine titanium dioxide 5g, potassium alum 3g, plant skin containing natural mineral ions It was immersed in an asbestos solution added with 20 ml of a fruit juice composition and stirred at room temperature for 30 minutes. This was subjected to solid-liquid separation to obtain a solution after dissolution treatment and a dissolution residue.
As a result of qualitative analysis of the solution after dissolution treatment, magnesium (Mg) and trivalent iron (Fe 3+ ) were confirmed. The residue was confirmed to be SiO 2 as a result of X-ray diffraction.
In a comparative test using only a 20% orthophosphoric acid (H 3 PO 4 ) solution, it was confirmed that amosite crystals remained in the residue at an immersion time of 30 minutes and remained in the residue even at an immersion time of 3 hours.
Example 3
溶解処理後液を定性分析した結果、マグネシウム（Ｍｇ）と三価鉄（Ｆｅ３＋）を確認した。残渣はＸ線回折の結果ＳｉＯ２を確認した。
オルトリン酸（Ｈ３ＰＯ４）２０％溶液のみによる比較テストでは、アモサイトの結晶は、浸漬時間３０分では残渣の中に残留し、浸漬時間３時間でも残渣の中に残留することを確認した。
≪実施例３≫ Asbestos amphibole-based tea asbestos amosite [(Fe, Mg) 7 Si 8 O 22 (OH) 2 ] rough stone 50 g (particle size 3 mmφ or less 80%) and orthophosphoric acid (H 3 PO 4 , 98%) 20 g and plant Organic acid pineapple peel juice (isovaleric acid 15%, butyric acid 10%) mixed acid 200ml, hydrogen peroxide (35%) 5g, ultrafine titanium dioxide 5g, potassium alum 3g, plant skin containing natural mineral ions It was immersed in an asbestos solution added with 20 ml of a fruit juice composition and stirred at room temperature for 30 minutes. This was subjected to solid-liquid separation to obtain a solution after dissolution treatment and a dissolution residue.
As a result of qualitative analysis of the solution after dissolution treatment, magnesium (Mg) and trivalent iron (Fe 3+ ) were confirmed. The residue was confirmed to be SiO 2 as a result of X-ray diffraction.
In a comparative test using only a 20% orthophosphoric acid (H 3 PO 4 ) solution, it was confirmed that amosite crystals remained in the residue at an immersion time of 30 minutes and remained in the residue even at an immersion time of 3 hours.
Example 3
アスベスト含有廃材（粒径５ｍｍφ以下８０％）９０ｇをオルトリン酸（Ｈ３ＰＯ４、９８％）１０ｇと≪実施例２≫に用いたアスベスト溶解液２００ｍｌの中に浸漬し、常温にて３０分間攪拌し溶解処理した。これを固液分離し溶解処理後液と溶解残渣を得た。溶解処理後液の定性分析の結果、マグネシウム（Ｍｇ）と三価鉄（Ｆｅ３＋）を確認した。Ｘ線回折の結果残渣からＳｉＯ２を確認したが、アスベスト組成物のクリソタイル、アモサイト等は確認しなかった。
≪実施例４≫ 90 g of asbestos-containing waste material (particle size of 5 mmφ or less 80%) is immersed in 10 g of orthophosphoric acid (H 3 PO 4 , 98%) and 200 ml of asbestos solution used in << Example 2 >> and stirred at room temperature for 30 minutes And dissolved. This was solid-liquid separated to obtain a solution and a residue after dissolution treatment. As a result of qualitative analysis of the solution after dissolution treatment, magnesium (Mg) and trivalent iron (Fe 3+ ) were confirmed. As a result of X-ray diffraction, SiO 2 was confirmed from the residue, but chrysotile, amosite and the like of the asbestos composition were not confirmed.
Example 4
≪実施例４≫ 90 g of asbestos-containing waste material (particle size of 5 mmφ or less 80%) is immersed in 10 g of orthophosphoric acid (H 3 PO 4 , 98%) and 200 ml of asbestos solution used in << Example 2 >> and stirred at room temperature for 30 minutes And dissolved. This was solid-liquid separated to obtain a solution and a residue after dissolution treatment. As a result of qualitative analysis of the solution after dissolution treatment, magnesium (Mg) and trivalent iron (Fe 3+ ) were confirmed. As a result of X-ray diffraction, SiO 2 was confirmed from the residue, but chrysotile, amosite and the like of the asbestos composition were not confirmed.
Example 4
≪実施例３≫で得た溶解処理後液１００ｍｌの中に溶解性炭酸カルシウム３０ｇ、塩化カルシウム１０ｇ、生石灰（貝殻仮焼ＣａＯ）１０ｇを投入し、水分４０％の固化物８０ｇを得た。この固化物を乾燥後、Ｘ線回析した結果、ＭｇＣＯ３とＭｇ（ＯＨ）２およびＭｇＣｌ２を確認した。
≪実施例５≫ In 100 ml of the solution after dissolution treatment obtained in << Example 3 >>, 30 g of soluble calcium carbonate, 10 g of calcium chloride, and 10 g of quick lime (shell calcined CaO) were added to obtain 80 g of a solidified product having a water content of 40%. As a result of X-ray diffraction after drying this solidified product, MgCO 3 , Mg (OH) 2 and MgCl 2 were confirmed.
Example 5
≪実施例５≫ In 100 ml of the solution after dissolution treatment obtained in << Example 3 >>, 30 g of soluble calcium carbonate, 10 g of calcium chloride, and 10 g of quick lime (shell calcined CaO) were added to obtain 80 g of a solidified product having a water content of 40%. As a result of X-ray diffraction after drying this solidified product, MgCO 3 , Mg (OH) 2 and MgCl 2 were confirmed.
Example 5
アスベスト含有廃棄物処理の概略工程を図１に示す。
Schematic process of asbestos-containing waste treatment is shown in FIG.
本発明は、主成分の植物性有機酸とオルトリン酸（Ｈ３ＰＯ４）に加え天然ミネラルイオン含有植物皮果汁液組成物、過酸化水素、超微粒子二酸化チタン、カリミョウバンからなるアスベスト溶解液を用いて、アスベスト含有廃材を浸漬または噴霧吹付け処理を実施することにより、常温で安全かつ低コストで繊維状針状結晶物を切断、無害化することを可能にしたことは、今後の広範なアスベスト処理対策の推進に多大な貢献をするものと期待される。
The present invention provides an asbestos solution comprising a plant skin juice composition containing natural mineral ions, hydrogen peroxide, ultrafine titanium dioxide, and potassium alum, in addition to the main components of a vegetable organic acid and orthophosphoric acid (H 3 PO 4 ). It was possible to cut and detoxify the fibrous needle-shaped crystals at room temperature safely and at low cost by immersing or spraying asbestos-containing waste materials. It is expected to make a significant contribution to the promotion of asbestos treatment measures.
Claims (8)
- 植物性有機酸とオルトリン酸および天然ミネラルイオン含有植物皮果汁液組成物による混合酸、過酸化水素、超微粒子二酸化チタン、カリミョウバンからなるアスベスト溶解剤。 An asbestos solubilizer composed of a mixed acid, hydrogen peroxide, ultrafine titanium dioxide, and potassium alum by a plant skin juice composition containing plant organic acids, orthophosphoric acid and natural mineral ions.
- 植物性有機酸が、パイナップル皮果汁液およびココナツ果汁液または柑橘皮果汁液の単独ないし複合皮果汁液であることを特徴とする請求項１に記載するアスベスト溶解剤。 The asbestos-dissolving agent according to claim 1, wherein the plant organic acid is pineapple peel juice and coconut juice or citrus peel juice alone or in a complex peel juice.
- 天然ミネラルイオン含有植物皮果汁液組成物が、イソ吉草酸と微少量のカルシウム、カリウム、マンガン、鉄、チタン、ケイ素、リン等の各種ミネラルイオンを含有することを特徴とする請求項１または２に記載するアスベスト溶解剤。 The natural mineral ion-containing plant skin juice composition contains isovaleric acid and a small amount of various mineral ions such as calcium, potassium, manganese, iron, titanium, silicon, and phosphorus. Asbestos solubilizer described in 1.
- アスベストを含有する壁材または吹付耐火材ないし断熱材に対し、前記請求項１から３のいずれか一に記載のアスベスト溶解剤を噴霧吹付けすることを特徴とするアスベスト無害化湿式処理方法。 An asbestos-detoxifying wet-treatment method, characterized in that the asbestos-dissolving agent according to any one of claims 1 to 3 is spray-sprayed on a wall material, sprayed refractory material or heat insulating material containing asbestos.
- アスベストを含有する廃材を、前記請求項１から３のいずれか一に記載のアスベスト溶解剤で溶解する第一工程、第一工程の溶解後液を可溶性炭酸カルシウムを含む、塩化カルシウム、生石灰または消石灰を用いてアスベスト溶解成分を不溶性塩として変換固形化する第二工程を特徴とするアスベスト無害化湿式処理方法。 The first step of dissolving the waste material containing asbestos with the asbestos solubilizer according to any one of claims 1 to 3, calcium chloride, quicklime or slaked lime containing soluble calcium carbonate as a solution after dissolution in the first step Asbestos detoxification wet processing method characterized by the second step of converting and solidifying an asbestos-dissolved component as an insoluble salt by using a sucrose.
- アスベスト組成分の変換固形化物を農業用肥料に利用する請求項５に記載するアスベスト無害化湿式処理方法。 The asbestos-detoxifying wet processing method according to claim 5, wherein the converted solidified component of asbestos composition is used for agricultural fertilizer.
- イソ吉草酸、酪酸、カプロン酸、カプリル酸、カプリン酸、ラウリル酸、ミスチリン酸、リモネン、アスコルビン酸、パントテン酸のいずれか一又は二以上からなる酸、過酸化水素、超微粒子二酸化チタン、カリミョウバンからなるアスベスト溶解剤 Acids consisting of one or more of isovaleric acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristylic acid, limonene, ascorbic acid, pantothenic acid, hydrogen peroxide, ultrafine titanium dioxide, potassium alum Asbestos dissolving agent consisting of
- 請求項５に記載のアスベスト無害化湿式処理方法で得られるアスベスト溶解成分を不溶性塩として変換固形化した生成物からなる農業用肥料。 An agricultural fertilizer comprising a product obtained by converting and solidifying an asbestos-dissolved component obtained by the asbestos-detoxifying wet-treatment method according to claim 5 as an insoluble salt.
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| JP2011025212A (en) * | 2009-07-28 | 2011-02-10 | Sunao Iwatsuki | Asbestos dissolving agent and asbestos detoxifying wet method |
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| JPH02149389A (en) * | 1988-09-22 | 1990-06-07 | Nippon Pillar Packing Co Ltd | Pollution-free treatment of waste asbestos |
| JPH04506165A (en) * | 1989-06-15 | 1992-10-29 | トニー ノサイト インコーポレイティド | Improved methods and products for treating asbestos |
| US5741358A (en) * | 1996-09-27 | 1998-04-21 | W. R. Grace & Co.-Conn. | Corrosion inhibiting composition for treating asbestos containing materials |
| JP2007295943A (en) * | 2006-03-13 | 2007-11-15 | Koichi Takano | Method of detoxification by dissolving asbestos |
| JP2008246445A (en) * | 2007-03-30 | 2008-10-16 | Sumitomo Osaka Cement Co Ltd | Method for treating asbestine detoxification |
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| JP2923181B2 (en) * | 1993-09-20 | 1999-07-26 | フジックス株式会社 | Water-soluble powder containing high concentration of calcium and method for producing the same |
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Patent Citations (5)
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|---|---|---|---|---|
| JPH02149389A (en) * | 1988-09-22 | 1990-06-07 | Nippon Pillar Packing Co Ltd | Pollution-free treatment of waste asbestos |
| JPH04506165A (en) * | 1989-06-15 | 1992-10-29 | トニー ノサイト インコーポレイティド | Improved methods and products for treating asbestos |
| US5741358A (en) * | 1996-09-27 | 1998-04-21 | W. R. Grace & Co.-Conn. | Corrosion inhibiting composition for treating asbestos containing materials |
| JP2007295943A (en) * | 2006-03-13 | 2007-11-15 | Koichi Takano | Method of detoxification by dissolving asbestos |
| JP2008246445A (en) * | 2007-03-30 | 2008-10-16 | Sumitomo Osaka Cement Co Ltd | Method for treating asbestine detoxification |
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| JP2011025212A (en) * | 2009-07-28 | 2011-02-10 | Sunao Iwatsuki | Asbestos dissolving agent and asbestos detoxifying wet method |
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