Method for removing organic fluorine compound from solution containing organic fluorine compound and from deposit, coagulating the removed organic fluorine compound, and method for manufacturing water-soluble organic fluorine compound cleaning agent used therein

Abstract

To provide a water-soluble cleaning agent and a water treatment method capable of effectively neutralizing persistent substances such as organic fluorine compounds in an economical and highly efficient manner.SOLUTION: The method efficiently removes organic fluorine compounds adhering to equipment walls, pipe interiors, structures, and solid objects with high-pressure wash guns, running water, brushes, or sponges by adding a cleaning agent containing abrasives, activated carbon, and surface active agent to the cleaning water, and coagulating the removed organic fluorine compounds. The cleaning agent contains 5 to 30 wt.% of abrasive, 10 to 50 wt.% of activated carbon, and 5 to 30 wt.% of surface active agent. The method for manufacturing an organic fluorine compound cleaning agent for removing organic fluorine compounds and coagulating them is characterized by adding the cleaning agent at 5 to 40 wt.% to the cleaning water, as well as to the wastewater and waste liquid.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for removing organic fluorine compounds from materials containing or deposits containing organic fluorine compounds, and to the production of an organic fluorine compound cleaning agent. [Background technology]

[0002] Until now, methods for treating water containing persistent organic fluorine compounds such as PFOS and PFOA have included (1) combustion methods and (2) high-pressure supercritical methods. These conventional technologies are suitable when the concentration of organic fluorine compounds is high and the amount of wastewater is too small, but they have the problem of being difficult to apply when the amount of wastewater is large.

[0003] The reality is that the concentrations of organic fluorine compounds contained in groundwater, river water, lake water, seawater, etc. are low, yet the volume of such water is enormous.

[0004] Conventional technologies include (1) combustion treatment and (2) high-pressure supercritical treatment, but these are methods for cases where the concentration of organic fluorine compounds is high and the amount of water is insufficient, and when treatment is performed using these conventional technologies, it is not possible to keep running costs and treatment expenses low, making it impossible to treat economically and efficiently.Furthermore, the conventional technologies of (1) combustion and (2) high-pressure supercritical treatment have the problem of high manufacturing, construction, and installation costs for the equipment, facilities, and equipment.

[0005] Thus, there is a problem that there is no treatment technology that can economically, efficiently, and effectively detoxify organofluorine compounds, which are an international environmental issue, safely and without affecting the human body, animals, and plants. [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-121962 [Patent Document 2] Japanese Patent Application Laid-Open No. 2003-334548 [Patent Document 3] Japanese Patent Application Laid-Open No. 2004-321959 [Patent Document 4] Japanese Patent Application Laid-Open No. 2010-22961 Summary of the Invention [Problem to be solved by the invention]

[0006] Therefore, an object of the present invention is to provide a water-soluble cleaning agent and a water treatment method that can economically, highly efficiently, and effectively detoxify persistent substances such as organic fluorine compounds. [Means for solving the problem]

[0007] High-pressure cleaning guns, running water, brushes, and sponges are ideal for efficiently and safely removing and cleaning persistent organic fluorine compounds from equipment walls, pipe interiors, buildings, and solid materials. Adding abrasives, activated carbon, and surfactants to the cleaning water during cleaning with high-pressure cleaning guns, running water, brushes, and sponges can further enhance the effectiveness of organic fluorine compound removal. The wastewater and effluent generated during the removal of organic fluorine compounds contains organic fluorine compounds that are harmful to humans, animals, and plants. These harmful substances in the cleaning water are coagulated with activated carbon, and the organic fluorine compounds are separated from the rest of the wastewater and effluent, making the wastewater and effluent harmless. Furthermore, coagulants are added to the wastewater and effluent generated during cleaning to precipitate and concentrate the solids, which are then filtered. These solids can then be incinerated for safe, efficient, and effective disposal of organic fluorine compounds.

[0008] Cleaning agents added to cleaning water when using a high-pressure washer gun, running water, brushes, or sponges contain abrasives, surfactants, and activated carbon. Among these, abrasives include anhydrous silicic acid, heavy calcium carbonate, calcium hydrogen phosphate, sodium hydrogen phosphate, potassium carbonate, fine glass powder, pearlite, hydroxyapatite, diatomaceous earth, wollastonite, and diamond powder. Of these, glass-based abrasive powders are suitable for cleaning because they are uniform in composition, inexpensive, and have a high hardness of nearly 9H. Particle sizes between 30 and 100 microns are desirable for easy dispersion in water when cleaning with a cleaning gun, running water, brushes, or sponges.

[0009] The appropriate content of abrasive to be added to the cleaning agent is 3 to 30%, but to ensure that the cleaning agent exhibits abrasive properties, 5 to 20% is desirable.

[0010] On the other hand, there are three types of surfactants added to cleaning agents: cationic surfactants, nonionic surfactants, and amphoteric surfactants. Of these, cationic surfactants include aliphatic quaternary ammonium salts and alkylbenzyl ammonium salts.

[0011] Nonionic surfactants include polyoxyethylene alkyl ethers (AE) and polyethylene glycol fatty acid esters.

[0012] Amphoteric surfactants include alkylcarboxybetaine and alkylamino fatty acid salts. Any surfactant can be used, but alkylbenzenesulfonate, a typical anionic surfactant, is preferred. The amount of surfactant added to the detergent is preferably 5 to 15%.

[0013] Activated carbon is available in granular and powder form, and either can be used, but powder form is preferred as it disperses easily in water and efficiently adsorbs and coagulates organic fluorine compounds. Furthermore, the amount of activated carbon added to the cleaning agent should be 5 to 30%, taking into account the adsorption capacity of persistent organic fluorine compounds. [Effects of the Invention]

[0014] When using a high-pressure cleaning gun, running water, brush, or sponge to remove and wash away organic fluorine compounds adhering to the walls of equipment, the inside of pipes, buildings, or solid objects, adding 5 to 30% of the above-mentioned cleaning agent to the cleaning water will allow for efficient and effective removal and washing of the organic fluorine compounds.

[0015] After using a high-pressure cleaning gun, running water, brushes, or sponges to remove and clean the cleaning water to which this detergent has been added, a coagulant is then added to the wastewater and waste liquid that is generated.The solids that have adsorbed and coagulated the organic fluorine compounds are then precipitated and concentrated, and by filtering the solids, the organic fluorine compounds contained in the water can be coagulated, separated, and removed.The filtered solids can then be incinerated, allowing for safe, efficient, and effective detoxification of persistent organic fluorine compounds that have adhered to the walls of equipment, the inner surfaces of pipes, buildings, and solids. [Example] Example 1

[0016] To remove and wash away organic fluorine compounds using a high-pressure cleaning gun while simultaneously coagulating the compounds, prepare the following composition of the cleaning agent to be added to the cleaning water. 1. Abrasive: Glass-based abrasive (average particle size: 45 μm) 10% by weight 2. Surfactant: 10% by weight of sodium dodecylsulfonate ▲3▼ Powdered activated carbon: 15% by weight This prepared cleaning solution is added at a rate of 10% to the cleaning water used with a high-pressure cleaning gun to remove and clean the inside of the pipes where organic fluorine compounds have adhered, while simultaneously coagulating the organic fluorine compounds.The waste liquid generated by this cleaning is collected in a large bucket, and a coagulant is added to allow the solids to settle.The supernatant liquid is then analyzed for organic fluorine compounds: PFOS (perfluorooctane sulfonic acid), PFOA (perfluorooctanoic acid), and fluorine. TIFF2025137310000001.tif27124 Example 2

[0017] To remove and wash away organic fluorine compounds using a high-pressure cleaning gun while simultaneously coagulating the compounds, prepare the following composition of the cleaning agent to be added to the cleaning water. 1. Abrasive: 15% by weight of hydroxyapatite (average particle size: 45 μm) 2. Surfactant: 10% by weight of sodium dodecylsulfonate ▲3▼ Powdered activated carbon: 15% by weight This prepared cleaning solution is added at a rate of 10% to the cleaning water used with a high-pressure cleaning gun to remove and clean the inside of the pipes where organic fluorine compounds have adhered, while simultaneously coagulating the organic fluorine compounds.The waste liquid generated by this cleaning is collected in a large bucket, and a coagulant is added to allow the solids to settle.The supernatant liquid is then analyzed for organic fluorine compounds: PFOS (perfluorooctane sulfonic acid), PFOA (perfluorooctanoic acid), and fluorine. TIFF2025137310000002.tif26124 Example 3

[0018] To remove and wash away organic fluorine compounds using a high-pressure cleaning gun and simultaneously coagulate the organic fluorine compounds, prepare the following composition of the cleaning agent to be added to the cleaning water. 1. Abrasive: 15% by weight of anhydrous silica abrasive (average particle size: 50 μm) 2. Surfactant: 10% by weight of sodium dodecylsulfonate ▲3▼ Powdered activated carbon: 15% by weight This prepared cleaning solution is added at a rate of 10% to the cleaning water used with a high-pressure cleaning gun to remove and clean the inside of the pipes where organic fluorine compounds have adhered, while simultaneously coagulating the organic fluorine compounds.The waste liquid generated by this cleaning is collected in a large bucket, and a coagulant is added to allow the solids to settle.The supernatant liquid is then analyzed for organic fluorine compounds: PFOS (perfluorooctane sulfonic acid), PFOA (perfluorooctanoic acid), and fluorine. TIFF2025137310000003.tif27126 Comparison example-1

[0019] When removing and cleaning organic fluorine compounds using a high-pressure cleaning gun, prepare the following composition of the cleaning agent to be added to the cleaning water. 1. Abrasive: 15% by weight of anhydrous silica abrasive (average particle size: 50 μm) 2. Surfactant: 10% by weight of sodium dodecylsulfonate This prepared cleaning solution is added at 10% to the cleaning water used with a high-pressure cleaning gun to remove and clean the inside of the pipes where organic fluorine compounds have adhered. The waste liquid generated by this cleaning is poured into a large bucket, and a flocculant is added to allow the solids to settle. The supernatant liquid is then analyzed for organic fluorine compounds: PFOS (perfluorooctane sulfonic acid), PFOA (perfluorooctanoic acid), and fluorine. TIFF2025137310000004.tif26128 comparison-2

[0020] To remove and wash away organic fluorine compounds using a high-pressure cleaning gun while simultaneously coagulating the compounds, prepare the following composition of the cleaning agent to be added to the cleaning water. 1. Abrasive: 10% by weight of anhydrous silica abrasive (average particle size: 50 μm) ▲2▼ Powdered activated carbon: 20% by weight This prepared cleaning solution is added at a rate of 10% to the cleaning water used with a high-pressure cleaning gun to remove and clean the inside of the pipes where organic fluorine compounds have adhered, while simultaneously coagulating the organic fluorine compounds.The waste liquid generated by this cleaning is collected in a large bucket, and a coagulant is added to allow the solids to settle.The supernatant liquid is then analyzed for organic fluorine compounds: PFOS (perfluorooctane sulfonic acid), PFOA (perfluorooctanoic acid), and fluorine. TIFF2025137310000005.tif27127 Comparison example-3

[0021] In washing away organic fluorine compounds with a high-pressure washing gun and simultaneously flocculating the organic fluorine compounds, the following composition of a cleaning agent to be added to washing water is prepared. 1. Surfactant: 5% by weight of sodium dodecyl sulfonate ▲2▼ Powdered activated carbon: 20% by weight This prepared cleaning solution is added at 10% to the cleaning water used with a high-pressure cleaning gun to clean the inside of the pipes where organic fluorine compounds have adhered, and at the same time, coagulates the organic fluorine compounds.The waste liquid generated by this cleaning is poured into a large bucket, and a coagulant is added to allow the solids to settle.The supernatant liquid is then analyzed for organic fluorine compounds: PFOS (perfluorooctane sulfonic acid), PFOA (perfluorooctanoic acid), and fluorine. TIFF2025137310000006.tif27128 [Industrial Applicability]

[0022] For the purpose of removing persistent organic fluorine compounds from equipment walls, pipe interiors, buildings, and solid materials, efficient, safe, and effective stripping and cleaning is best achieved using a high-pressure washer gun, running water, brushes, and sponges. When using a high-pressure washer gun, running water, brushes, and sponges, adding abrasives, activated carbon, and surfactants to the cleaning water can efficiently strip and clean organic fluorine compounds, further enhancing the effectiveness of coagulating the organic fluorine compounds. Furthermore, wastewater and effluent generated by cleaning with a high-pressure washer gun, running water, brushes, and sponges contains organic fluorine compounds that are harmful to humans, animals, and plants. Therefore, these harmful compounds in the cleaning water are coagulated with activated carbon to neutralize the wastewater and effluent. Furthermore, adding a coagulant to the wastewater and effluent generated after stripping and cleaning organic fluorine compounds can precipitate and concentrate the solids, filter them, and then incinerate them for safe, efficient, and effective disposal of organic fluorine compounds. [Brief explanation of the drawings]

[0023] none

Claims

1. This method is characterized in that when removing organic fluorine compounds adhering to the wall surfaces of equipment, the inner surfaces of pipes, buildings, solid objects, etc. with a high-pressure cleaning gun, running water, a brush, or a sponge, a cleaning agent containing an abrasive, activated carbon, and a surfactant is added to the cleaning water, thereby efficiently removing the organic fluorine compounds and flocculating the removed organic fluorine compounds.

2. A method for removing organic fluorine compounds and flocculating the removed organic fluorine compounds by adding a cleaning agent containing an abrasive, activated carbon, and a surfactant to wastewater, waste liquid, groundwater, river water, seawater, etc. containing organic fluorine compounds.

3. The method for producing a cleaning agent for organic fluorine compounds for the purpose of removing organic fluorine compounds and agglomerating the removed organic fluorine compounds according to claims 1 and 2, which comprises 5 to 30% by weight of an abrasive, 10 to 50% by weight of activated carbon, and 5 to 30% by weight of a surfactant, and which comprises adding 5 to 40% by weight of the cleaning agent to cleaning water, wastewater, or effluent.

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