WO2016190388A1 - 廃水の処理方法 - Google Patents
廃水の処理方法 Download PDFInfo
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- WO2016190388A1 WO2016190388A1 PCT/JP2016/065576 JP2016065576W WO2016190388A1 WO 2016190388 A1 WO2016190388 A1 WO 2016190388A1 JP 2016065576 W JP2016065576 W JP 2016065576W WO 2016190388 A1 WO2016190388 A1 WO 2016190388A1
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- polymer
- water
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- polymer flocculant
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D3/00—Differential sedimentation
- B03D3/06—Flocculation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
- C02F3/327—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae characterised by animals and plants
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
- C02F2103/327—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters from processes relating to the production of dairy products
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Definitions
- the present invention relates to a method for treating wastewater, particularly organic wastewater.
- This application claims priority based on Japanese Patent Application No. 2015-107637 for which it applied to Japan on May 27, 2015, and uses the content here.
- An activated sludge method is an example of a wastewater treatment method, particularly a treatment method for purifying organic wastewater.
- the activated sludge method is a method of decomposing pollutants into aerobic microorganisms by aeration.
- Good quality treated water can be obtained by appropriately managing the concentration of pollutants and the amount of aeration, and it is widely used for purification treatment of organic wastewater from sewage and organic wastewater discharged from factories.
- livestock organic wastewater containing a large amount of manure and organic wastewater discharged from large-scale factories the load fluctuates greatly. Therefore, the operating conditions for normal operation are complicated, maintenance becomes difficult, and a great deal of labor is required.
- many of the organic wastewaters for livestock production are regarded as problematic in that the BOD and COD in the wastewater are high, the treatment time becomes long, and the operation cost and the construction cost increase due to the increase in the volume of the aeration tank. .
- Wastewater treatment methods other than the activated sludge method especially as a treatment method for purifying organic wastewater, a method for purifying wastewater by injecting organic wastewater into an artificial wetland and purifying the microorganisms and aquatic plants in the wetland Is mentioned.
- Artificial wetlands are artificially constructed wetlands for wastewater treatment, and are isolated from the outside by a water shielding sheet or the like so that the wastewater does not leak outside the wetlands.
- artificial wetlands can easily control the flow rate by installing media such as gravel and pebbles, water gradient, wastewater inflow and outflow pipes, and have better purification capacity per unit area than natural wetlands. ing.
- the underground flow type constructed wetland has a feature that the purification performance per area is higher than the surface flow type because the filtration effect by the filter medium such as gravel packed in the wetland as a filter bed is obtained. Therefore, compared with the activated sludge method, it is becoming popular throughout Europe and other countries as a purification treatment method with a low environmental load and low labor.
- the underground type constructed wetland has a vertical type (hereinafter referred to as “vertical flow”) for aerobic purification treatment and a horizontal type (hereinafter referred to as “horizontal flow”) for anaerobic purification treatment. is there.
- vertical flow vertical type
- horizontal flow horizontal type
- a subsidence type constructed wetland combining a vertical flow and a horizontal flow has been developed and put into practical use as a purification treatment method combining a denitrification effect by anaerobic purification in a horizontal flow wetland.
- a down-flow type constructed wetland connected with a vertical flow wetland has been developed, and has been widely used as a purification method for avoiding clogging of the filter bed due to the circulation of organic wastewater.
- the first and second subsurface flow vertical wetlands are provided with a first subsurface flow vertical wetland, a second subsurface flow vertical wetland, and a subsurface horizontal wetland so that the organic wastewater is circulated sequentially.
- an underflow type constructed wetland system that performs aerobic purification in a flowing wetland and performs anaerobic purification in a downflow horizontal flow wetland (Patent Document 1).
- any of these purification methods using artificial wetlands has a limited concentration application range of organic wastewater, and is difficult to apply to high-concentration organic wastewater.
- organic wastewater with a high content of suspended solids hereinafter referred to as “SS”) is clogged in the filter bed when circulating the wastewater even in a submerged constructed wetland where vertical flow wetlands are connected.
- SS suspended solids
- organic wastewater with high BOD and COD since the load of artificial wetland becomes high, a vast area is needed by the whole installation by the expansion of the required area of a wetland and the increase in the required number of steps. Therefore, the problem that the place and area which can install the equipment of an artificial wetland is limited arises.
- Examples of organic wastewater having a high SS concentration, BOD, and COD include livestock manure wastewater (hereinafter referred to as “livestock manure wastewater”).
- livestock manure wastewater livestock manure wastewater
- regulations on manure disposal have become stricter, and there is concern about an increase in the cost of treating livestock manure.
- the burden per person will increase as the area of the treatment plant increases and the number of employees decreases. It has become a very important issue. Accordingly, there is a strong demand to expand the application range of organic wastewater with high SS concentration, BOD, and COD by a low environmental load and low labor treatment method such as a purification treatment method using a submerged constructed wetland.
- the processing method for removing the solid content of organic wastewater includes a method of coagulating and separating the solid content of organic wastewater using an inorganic coagulant or a polymer flocculant.
- a method of aggregating and separating livestock manure wastewater that is organic wastewater chlorite, hypochlorite, bromate, bromate, hypobromite can be used for livestock manure wastewater.
- a polymer flocculant composed of cationic and / or amphoteric polymers is added.
- Patent Document 2 A method of coagulating and then solid-liquid separation by dehydration with a dehydrator has been proposed (Patent Document 2).
- the present invention improves the reduction in purification performance due to clogging of the filter bed, which is a problem when purifying wastewater with high SS concentration, BOD and COD, particularly organic wastewater, in artificial wetlands.
- a coagulation floc forming step of forming a coagulation floc by adding a polymer flocculant to waste water, a solid-liquid separation step of obtaining the separated water by solid-liquid separation of the coagulation floc, and an artificial wetland A wastewater treatment method comprising a purification step of purifying separated water.
- the polymer flocculant is one or more polymer flocculants selected from the group consisting of an amidine cationic polymer (A), an amphoteric polymer (B), and a non-amidine cationic polymer (C).
- [6] The method for treating wastewater according to [5], wherein the amount of the polymer flocculant added to the wastewater is 100 to 3000 ppm by mass with respect to the mass of the wastewater.
- R 3 is a hydrogen atom or a methyl group
- R 4 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R 6 is an alkyl group having 1 to 4 carbon atoms.
- Y is an oxygen atom or NH
- Z ⁇ is an anion
- n is an integer of 1 to 3.
- R 3 is a hydrogen atom or a methyl group
- R 4 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R 6 is an alkyl group having 1 to 4 carbon atoms.
- Y is an oxygen atom or NH
- Z ⁇ is an anion
- n is an integer of 1 to 3.
- a polymer flocculant is added to the wastewater in advance to form an aggregate floc,
- the aggregated floc can be separated into solid and liquid to obtain separated water, and the obtained separated water can be purified without adversely affecting the microbial flora and aquatic plants in the constructed wetland.
- the application range of purification treatment by artificial wetlands to wastewater particularly organic wastewater with high SS, BOD, and COD, and reduction of the number of necessary stages of artificial wetlands,
- the processing cost can be greatly reduced by reducing the required area.
- the wastewater treatment method of the present invention is a method for reducing BOD and COD from wastewater, particularly organic wastewater, and removing total nitrogen, total phosphorus and the like, and includes the following steps.
- This step is a step of forming a floc floc by adding a polymer flocculant to waste water.
- Aggregating agent means an agent having a function of aggregating water-soluble and water-insoluble contaminants contained in wastewater to form fine flocs and agglomerated flocs.
- Fine floc means a substance that increases the negatively charged BOD and COD insolubilized by charge neutralization and aggregates to form a fine aggregate. A substance or a colloidal substance or the like insoluble in water may be charged neutralized and aggregated to form a fine aggregate.
- Aggregated floc means a fine floc further agglomerated to a floc diameter necessary for agglomeration separation.
- the wastewater to be treated by the wastewater treatment method of the present invention is preferably organic wastewater.
- organic wastewater include livestock manure wastewater generated from livestock facilities, digestive wastewater obtained by subjecting wastewater containing manure to methane fermentation.
- dairy wastewater generated from a processing facility in the dairy industry swine urine wastewater generated from a processing facility in the pig farming industry, and the like can be given.
- wastewater such as sewage including miscellaneous sewage and human waste, wastewater generated from beverage factories and food factories, wastewater generated from chemical factories (dyeing, resin, fiber, chemical products), and other various plant facilities Waste water to be used.
- the organic substances contained in the organic wastewater are water-soluble and water-insoluble organic substances, and the BOD, COD and VTS values can be used as indicators of the organic substance content, and the SS concentration can also be used.
- the wastewater treated by the wastewater treatment method of the present invention may further contain suspended substances, colloidal substances, ionic components, and the like.
- the “ionic component” means a viscous anionic or amphoteric organic polymer component or an anionic component derived from an inorganic salt contained in wastewater.
- BOD means contamination by water-soluble and water-insoluble organic substances contained in wastewater.
- the BOD value means a value measured according to the BOD analysis method described in JIS K 0102: 21 and 32.3.
- the BOD of the wastewater to which the polymer flocculant is added in the aggregation floc forming step described later is preferably 4000 mg / L, more preferably 7000 mg / L, further preferably 10,000 mg / L, and particularly preferably 20000 mg / L. Moreover, 100000 mg / L or less is preferable and 80000 mg / L or less is more preferable.
- the BOD of the wastewater to which the polymer flocculant is added in the aggregation floc forming step is preferably 4000 to 100,000 mg / L, more preferably 7000 to 80000 mg / L, further preferably 10,000 to 80000 mg / L, and 20000 to 80000 mg / L. L is particularly preferred.
- COD means contamination by water-soluble and water-insoluble organic substances contained in wastewater. In the present invention, it is used as an alternative value for BOD.
- the value of COD means a value measured according to the COD (Mn) analysis method described in JIS K 0102: 17.
- the COD of the wastewater to which the polymer flocculant is added in the below-described aggregation floc forming step is preferably 4000 mg / L or more, more preferably 7000 mg / L or more, further preferably 10,000 mg / L or more, and particularly preferably 20000 mg / L or more. Moreover, 100000 mg / L or less is preferable and 80000 mg / L or less is more preferable.
- the COD of the wastewater to which the polymer flocculant is added in the aggregation floc forming step is preferably 4000 to 100,000 mg / L, more preferably 7000 to 80000 mg / L, further preferably 10,000 to 80000 mg / L, and 20000 to 80,000 mg / L. L is particularly preferred.
- VTS means an organic substance contained in wastewater, and the value of VTS means a value specifically measured by the following procedure. (1) 100 ml of waste water is dried at 105 ° C. for 6 hours, and the remaining amount (total solid content) (g) is weighed. (2) Then, it heats at 600 degreeC for 2 hours, and weighs the residual amount (incineration weight) (g) after ashing. (3) The ignition loss (VTS;% / solid content) is calculated
- VTS (% / solid content) ⁇ (total solid content ⁇ incineration weight) / total solid content ⁇ ⁇ 100 (A)
- the VST of the wastewater to which the polymer flocculant is added in the agglomeration floc forming step described below is preferably 40% / solid content or more, more preferably 50% / solid content or more, and further preferably 60% / solid content or more. Moreover, 100% / solid content or less is preferable. If it is in the said range, a favorable coagulation
- the VST of the wastewater to which the polymer flocculant is added in the aggregation floc forming step is preferably 40 to 100% / solid, more preferably 50 to 100% / solid, and further 60 to 100% / solid. preferable.
- SS is a suspended solid content contained in waste water, and means a substance remaining on the filter medium when organic waste water is filtered through a filter medium having a pore diameter of 1 ⁇ m in accordance with JIS K 0102: 2008. Further, “SS concentration” means a value measured using a glass fiber filter having a pore diameter of 1 ⁇ m as a filter medium in accordance with the measurement method described in JIS K 0102: 2008.
- the SS concentration of the wastewater to which the polymer flocculant is added in the aggregation floc forming process described later is preferably 6000 mg / L or more, more preferably 10,000 mg / L or more, and further preferably 20000 mg / L or more.
- the application range concentration can be expanded to a higher concentration range.
- the SS concentration of waste water to which the polymer flocculant is added in the coagulation floc forming step is preferably 6000 to 100,000 mg / L, more preferably 10,000 to 80,000 mg / L, and 20000 to 80,000 mg / L with respect to the total amount of waste water. Is more preferable.
- Total phosphorus means all phosphorus components contained in wastewater.
- the value of total phosphorus is a value measured according to the potassium peroxodisulfate decomposition method and molybdenum blue spectrophotometry described in JIS K 0102: 46.3.1 and JIS K 0102: 46.1.1. Means.
- the total phosphorus in the wastewater to which the polymer flocculant is added in the aggregation floc forming step described later is preferably 10 mg / L or more, more preferably 100 mg / L or more, and even more preferably 200 mg / L or more.
- the total phosphorus in the wastewater to which the polymer flocculant is added in the aggregation floc forming step is preferably 10 to 10,000 mg / L, more preferably 100 to 5000 mg / L, and further preferably 200 to 1000 mg / L.
- the polymer flocculant is at least one selected from the group consisting of an amidine cationic polymer (A), an amphoteric polymer (B), and a non-amidine cationic polymer (C).
- a polymer flocculant can be used.
- group cationic polymer (A) is included as a polymer flocculent.
- an amphoteric polymer (B) is included as a polymer flocculant.
- the non-amidine cationic polymer (C) is contained as the polymer flocculant.
- amidine-based cationic polymer (A) is a polymer containing an amidine structural unit represented by either the general formula (1) or the general formula (2).
- the content of the amidine structural unit with respect to all the structural units is preferably 30 mol% or more with respect to the number of moles of all the structural units of the amidine-based cationic polymer (A), % Or more is more preferable.
- 90 mol% or less is preferable and 80 mol% or less is more preferable.
- the target substances that increase the values of SS, BOD and COD in the flocculation treatment of waste water, especially organic waste water efficiently flocculate, and in the purification treatment of separated water by artificial wetlands, good BOD and The effect of reducing COD can be obtained, and high-quality treated water can be obtained.
- the content of the amidine structural unit with respect to all the structural units in the amidine-based cationic polymer (A) is preferably 30 to 90 mol% with respect to the number of moles of all the structural units of the amidine-based cationic polymer (A). 40 to 80 mol% is more preferable.
- the “structural unit” is a structural unit derived from a monomer molecule formed by polymerization of monomers, or a pendant group of a structural unit derived from a monomer molecule and a pendant group of a structural unit derived from another monomer molecule. It means a structural unit composed of structural units derived from two or more monomer molecules in which pendant groups are linked by reaction. “Polymer” means a compound having a structure composed of a plurality of structural units.
- Examples of the anions in the general formula (1) and the general formula (2) include chloride ions, bromide ions, sulfate ions, hydrogen sulfate ions, nitrate ions, hydrogen nitrate ions, and the like. Bromide ions are preferred, and chloride ions are particularly preferred.
- Examples of the ethylenically unsaturated monomer include CH 2 ⁇ CR 7 —NHCOR 8 (general formula (5): wherein R 7 is a hydrogen atom or a methyl group, and R 8 is a hydrogen atom or a carbon number of 1 to 4).
- An alkyl group is preferable.
- the acylamino group contained in the copolymer is easily converted to an amino group by hydrolysis or alcoholysis. In addition, this amino group reacts with the adjacent cyano group to amidinate.
- N-vinylformamide is particularly preferred.
- the ratio of the ethylenically unsaturated monomer and the nitrile used in the copolymer is usually preferably 20:80 to 80:20, more preferably 40:60 to 60:40 in terms of molar ratio.
- the amidine-based cationic polymer (A) having N-vinylformamide and acrylonitrile as structural units is most typically a copolymer formed by copolymerizing N-vinylformamide and acrylonitrile as described above. It is produced by heating in the presence of hydrochloric acid to form an amidine structural unit from a cyano group adjacent to the amino group formed by hydrolysis. At this time, the amidine-based cationic polymer (A) having various compositions can be obtained by appropriately selecting the molar ratio of N-vinylformamide and acrylonitrile to be used for copolymerization and the amidination conditions of the copolymer.
- the amidine-based cationic polymer (A) may be obtained from a commercially available product.
- the amidine-based cationic polymer (A) two or more kinds of amidine-based cationic polymers (A) can be used in combination.
- the amidine-based cationic polymer (A) is a reduced viscosity at 25 ° C. (hereinafter referred to as “reduced viscosity”) of a 1 mol / L sodium chloride aqueous solution containing 0.1 g / dL of the amidine-based cationic polymer (A).
- reduced viscosity a reduced viscosity at 25 ° C.
- the reduced viscosity of the amidine-based cationic polymer (A) is preferably from 0.1 to 10 dL / g, more preferably from 1 to 5 dL / g.
- the amphoteric polymer (B) is a polymer containing a cationic structural unit represented by the general formula (3).
- the content of the cationic structural unit relative to all the structural units is preferably 20 mol% or more based on the number of moles of all the structural units of the amphoteric polymer (B).
- 80 mol% or less is preferable and 55 mol% or less is more preferable. If it is in the said range, a favorable coagulation
- the content of the cationic structural unit in the amphoteric polymer (B) is preferably 20 to 80 mol%, preferably 20 to 55 mol, based on the number of moles of all the structural units of the amphoteric polymer (B). % Is more preferable.
- anion in the general formula (3) examples include chloride ion, bromide ion, sulfate ion, hydrogen sulfate ion, nitrate ion, hydrogen nitrate ion, and the like, preferably chloride ion and bromide ion, Chloride ions are particularly preferred.
- R 6 in the general formula (3) is preferably an alkyl group having 1 to 4 carbon atoms.
- alkyl group having 1 to 4 carbon atoms in the general formula (3) examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, preferably a methyl group and an ethyl group, Is particularly preferred.
- Examples of the cationic structural unit include a cationic structural unit derived from a mineral salt of a dialkylaminoalkyl (meth) acrylate that is a cationic monomer, or an alkyl chloride quaternary salt, or a mineral of a dialkylaminoalkyl (meth) acrylamide. And a cationic structural unit derived from an acid salt or an alkyl chloride quaternary salt. In particular, dialkylaminoalkyl (meth) acrylate alkyl chloride quaternary salts are preferred.
- a cationic monomer may be used individually by 1 type, and may use 2 or more types together.
- (meth) acrylate is a generic term for acrylate and methacrylate. That is, “(meth) acrylate” means one or both of acrylate and methacrylate. The same applies to (meth) acrylic acid, (meth) acrylamide and the like.
- the amphoteric polymer (B) also contains an anionic structural unit.
- the anionic structural unit include (meth) acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid. Acrylic acid is particularly preferred.
- the content of the anionic structural unit relative to all the structural units is preferably 3 mol% or more, more preferably 5 mol% or more, based on the number of moles of all the structural units of the amphoteric polymer (B). .
- 75 mol% or less is preferable and 30 mol% or less is more preferable.
- the content of the anionic structural unit in the amphoteric polymer (B) is preferably 3 to 75 mol% with respect to the number of moles of all the structural units of the amphoteric polymer (B), and 5 to 30 mol. % Is more preferable.
- the amphoteric polymer (B) contains a nonionic structural unit in addition to the cationic structural unit and the anionic structural unit.
- (Meth) acrylamide is mentioned as a nonionic structural unit.
- the content of nonionic structural units relative to all the structural units is preferably 1 to 80 mol% with respect to the number of moles of all the structural units of the amphoteric polymer (B).
- the method for producing the amphoteric polymer (B) is not particularly limited, but an aqueous monomer solution in which the above monomer is dissolved in water is formed into a uniform sheet, and is irradiated with visible light or ultraviolet light using a photopolymerization initiator.
- a method; an emulsion polymerization method in which an aqueous monomer solution is emulsified in a non-aqueous solvent using an emulsifier and polymerized; and the like can be appropriately selected.
- the polymer is obtained as an aqueous gel. Therefore, it is preferable to pulverize and dry the aqueous gel to form a powder.
- the reduced viscosity of the amphoteric polymer (B) is preferably 0.1 dL / g or more, and more preferably 3.0 dL / g or more. Moreover, it is preferable that it is 10.0 dL / g or less, and it is more preferable that it is 7.5 dL / g or less. If it is in the said range, a favorable coagulation
- the reduced viscosity of the amphoteric polymer (B) is preferably from 0.1 to 10.0 dL / g, more preferably from 3.0 to 7.5 dL / g.
- the method for preparing the amphoteric polymer (B) having the reduced viscosity is not particularly limited, but in consideration of the viscosity of the polymer for producing conditions such as polymerization time, polymerization temperature, and amount of chain transfer agent used in the production process. It can be selected as appropriate.
- the reduced viscosity is preferably adjusted according to the amount of chain transfer agent used.
- the type of chain transfer agent is not particularly limited, and examples thereof include thiol compounds such as mercaptoethanol and mercaptopropionic acid, and reducing inorganic salts such as sodium sulfite, sodium bisulfite, and sodium hypophosphite. Of these, sodium hypophosphite is particularly preferable.
- the amount of the chain transfer agent used is usually 1 to 3000 ppm by mass with respect to the mass of all raw materials monomers.
- Non-amidine cationic polymer (C) is a polymer containing a cationic structural unit represented by the general formula (4).
- the content of the cationic structural unit relative to all the structural units is preferably 10 mol% or more with respect to the number of moles of all the structural units of the non-amidine cationic polymer (C). 20 mol% or more is more preferable, and 40 mol% or more is more preferable. Moreover, 100 mol% or less is preferable.
- the content of the cationic structural unit relative to all the structural units is 10 to 100 moles relative to the number of moles of all the structural units of the non-amidine cationic polymer (C). %, More preferably 20 to 100 mol%, still more preferably 40 to 100 mol%.
- Examples of the anion in the general formula (4) include chloride ion, bromide ion, sulfate ion, hydrogen sulfate ion, nitrate ion, hydrogen nitrate ion, and the like, preferably chloride ion and bromide ion, Chloride ions are particularly preferred.
- R 6 is preferably an alkyl group having 1 to 4 carbon atoms.
- examples of the alkyl group having 1 to 4 carbon atoms in the general formula (4) include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. A methyl group and an ethyl group are preferable, and a methyl group is preferable. Is particularly preferred.
- Examples of the cationic structural unit include a cationic structural unit derived from a mineral salt of a dialkylaminoalkyl (meth) acrylate that is a cationic monomer, or an alkyl chloride quaternary salt, or a mineral of a dialkylaminoalkyl (meth) acrylamide. And a cationic structural unit derived from an acid salt or an alkyl chloride quaternary salt. In particular, dialkylaminoalkyl (meth) acrylate alkyl chloride quaternary salts are preferred.
- a cationic monomer may be used individually by 1 type, and may use 2 or more types together.
- the non-amidine cationic polymer (C) may contain a nonionic structural unit in addition to the cationic structural unit.
- (Meth) acrylamide is mentioned as a nonionic structural unit.
- the inclusion of the nonionic structural unit in all the structural units in the nonamidine cationic polymer (C) The amount is preferably 1 to 90 mol% with respect to the number of moles of all the structural units of the non-amidine cationic polymer (C).
- the method for producing the non-amidine cationic polymer (C) is not particularly limited, and methods such as the aqueous solution photopolymerization method, adiabatic polymerization method, dispersion polymerization method, and emulsion polymerization method can be appropriately selected.
- the polymer is obtained as an aqueous gel. Therefore, it is preferable to pulverize and dry the aqueous gel to form a powder.
- the polymer flocculant used in the wastewater treatment method of the present invention is an amidine-based cationic polymer (A), an amphoteric polymer (B), and a non-amidine-based cation as long as the effects of the present invention are not impaired.
- Other non-amidine cationic polymers other than the functional polymer (C), or amphoteric polymers may be included. These polymers are preferably 0% by mass or more and less than 10% by mass, more preferably 0% by mass or more and less than 5% by mass, and 0% by mass with respect to the total mass of the polymer flocculant. More preferably.
- an anionic polymer (D) may be further added after the addition of the polymer flocculant in the aggregation floc formation step in order to form a better aggregation floc.
- the step of adding the anionic polymer (D) after the addition of the polymer flocculant in the aggregation floc forming step is also referred to as “anionic polymer (D) addition step”.
- the anionic polymer (D) is a polymer containing an anionic structural unit.
- the anionic structural unit include (meth) acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid. Acrylic acid is particularly preferred.
- the content of the anionic structural unit with respect to all the structural units is preferably 5 to 90 mol% with respect to the number of moles of all the structural units of the anionic polymer (D).
- the anionic polymer (D) may contain a nonionic structural unit.
- the nonionic structural unit include (meth) acrylamide.
- the content of nonionic structural units with respect to all structural units is preferably 10 to 95 mol% with respect to the number of moles of all structural units in the anionic polymer (D).
- the method for producing the anionic polymer (D) is not particularly limited, and examples thereof include a precipitation polymerization method, a bulk polymerization method, a dispersion polymerization method, and an aqueous solution polymerization method.
- a known method can be applied as a method for adding the polymer flocculant to the waste water and a method for forming the floc floc.
- the polymer flocculant As a method for adding the polymer flocculant, it is preferable to dissolve the polymer flocculant in water at a concentration of 0.05 to 0.5% by mass and then add it to the waste water.
- the polymer flocculant is composed of two or more kinds of polymers, that is, the amidine-based cationic polymer (A), the amphoteric polymer (B), and the non-amidine-based cationic polymer (C), a one-pack type in which each polymer is mixed. It is preferable to add it as a medicine.
- the polymer flocculant may be added to the waste water in the form of a powder. When adding the polymer flocculant, it is preferable to stir the wastewater.
- stirring time is based also on the quantity of the wastewater to process, it is preferable that it is 30 second or more. Moreover, it is preferable that it is 300 seconds or less, and it is more preferable that it is 120 seconds or less. For example, the stirring time is preferably 30 to 300 seconds, and more preferably 30 to 120 seconds.
- the anionic polymer added after the addition of the polymer flocculant varies depending on the SS concentration of the wastewater added, the concentration and content of suspended substances, colloidal substances, ionic components, etc., BOD, COD, VTS, and total phosphorus.
- the unreacted polymer flocculant can be selected within a range that does not remain excessively in the waste water. As a rough guide, the amount is 1 to 2000 ppm by mass with respect to the mass of wastewater (not including the mass of the added polymer flocculant).
- the addition amount of the polymer flocculant and the anionic polymer (D) added after the addition of the polymer flocculant to the waste water is the mass of the waste water to be added (not including the mass of the added polymer flocculant).
- 1 ppm or more is preferable, 10 ppm or more is more preferable, and 300 ppm or more is more preferable.
- 2000 ppm or less is preferable and 1000 ppm or less is more preferable. If it is in the said range, a favorable coagulation
- the obtained separation water can be purified without adversely affecting the microbial flora and aquatic plants in the artificial wetland.
- the addition amount of the polymer flocculant to the waste water and the addition amount of the anionic polymer (D) added after the addition of the polymer flocculant are the mass of the waste water added (the mass of the added polymer flocculant). 1 to 2000 ppm by mass, more preferably 10 to 1000 ppm by mass, and still more preferably 300 to 1000 ppm by mass.
- the polymer flocculant contains the amidine-based cationic polymer (A). It is preferable. Since the polymer flocculant contains the amidine-based cationic polymer (A), the negatively charged pollutant contained in the wastewater is insolubilized by charge neutralization, and other ionic components, suspended substances, and colloids Substances and the like can be neutralized simultaneously to form fine flocs efficiently. Furthermore, the action of cross-linking adsorption is improved, the fine flocs can be efficiently enlarged, and better aggregated flocs can be formed.
- the anionic polymer (D) further added after the addition of the polymer flocculant
- the amount of addition of) varies depending on the SS concentration of the wastewater to be added, the concentration and content of suspended substances, colloidal substances, ionic components, etc., BOD, COD, VTS, and total phosphorus. It can be selected as long as unreacted polymer flocculant does not remain excessively in the wastewater. As a rough guide, the amount is 1 to 3000 ppm by mass with respect to the mass of wastewater (not including the mass of the added polymer flocculant).
- the addition amount of the polymer flocculant and the anionic polymer (D) added after the addition of the polymer flocculant to the waste water is the mass of the waste water to be added (not including the mass of the added polymer flocculant).
- 1 ppm or more is preferable, 10 ppm or more is more preferable, and 300 ppm or more is more preferable.
- 3000 ppm or less is preferable, 2500 ppm or less is more preferable, and 2000 ppm or less is more preferable. If it is in the said range, a favorable coagulation
- the obtained separation water can be purified without adversely affecting the microbial flora and aquatic plants in the artificial wetland.
- the addition amount of the polymer flocculant to the waste water and the addition amount of the anionic polymer (D) added after the addition of the polymer flocculant are the mass of the waste water added (the mass of the added polymer flocculant). 1 to 3000 ppm by mass, more preferably 10 to 2500 ppm by mass, and even more preferably 300 to 2000 ppm by mass.
- an acidic substance is added to the water when the polymer flocculant is dissolved in water. May be.
- the acidic substance include sulfamic acid and acidic sodium sulfite.
- the addition conditions such as the addition amount of the acidic substance and the timing of addition can be appropriately determined.
- an inorganic coagulant and / or an organic coagulant may be added to the waste water.
- coagulant an inorganic coagulant and / or an organic coagulant
- the inorganic coagulant include sulfuric acid band, polyaluminum chloride, ferric chloride, ferrous sulfate, ferric sulfate, polyiron (polyiron sulfate, polyiron chloride) and the like.
- the organic coagulant examples include polyamine, polydiallyldimethylammonium chloride, alkyl chloride quaternary salt of polydialkylaminoalkyl methacrylate, and a cationic surfactant.
- the addition conditions such as the addition amount of the coagulant and the timing of the addition can be appropriately determined.
- the addition amount of the coagulant is preferably 5 to 3000 parts by mass with respect to 100 parts by mass of the polymer coagulant.
- the timing of adding the coagulant to the waste water is before the polymer coagulant is added to the waste water. It is preferable to add.
- This step is a step of obtaining separated water by solid-liquid separation of the aggregated floc obtained in the previous step.
- “Separated water” means a separated liquid component obtained by solid-liquid separation of the aggregated floc formed in the aggregated floc forming step in the solid-liquid separation step.
- waste water is treated in the coagulation flock formation step and the subsequent solid-liquid separation step to obtain separated water, thereby reducing at least one of SS, BOD, COD, total nitrogen and total phosphorus in the waste water.
- the SS concentration of the separated water obtained in the solid-liquid separation step in the wastewater treatment method of the present invention is preferably as small as possible. For example, it is 1 mg / L or more with respect to the total amount of separated water, and is 10 mg / L or more. Also good.
- the application range concentration can be expanded to a higher concentration range.
- the SS concentration of the separation water obtained in the solid-liquid separation step in the wastewater treatment method of the present invention is preferably 1 to 5000 mg / L, more preferably 10 to 3000 mg / L, relative to the total amount of separation water. 1000 mg / L is more preferable.
- Colloidal value means the amount of negative charge contained in the supernatant water or separated water of wastewater.
- supernatant water of wastewater means a liquid phase obtained by subjecting wastewater to centrifugal separation at 3000 rpm for 5 minutes to perform solid-liquid separation.
- the value of the colloid value means a value specifically measured by the following procedure. (1) Into a 200 mL tall beaker, collect 10 mL of supernatant water or separated water of waste water and add 90 mL of pure water. (2) Further, 2 mL of a 1 / 200N methyl glycol chitosan solution is added and stirred. (3) Add 1-2 drops of toluidine blue as an indicator.
- the colloid value of the separated water means a negative charge amount contained in the separated water, and is an index of the content of the unreacted polymer flocculant remaining in the separated water.
- the colloid value of the separated water is preferably ⁇ 2.00 meq / L or more, more preferably ⁇ 0.50 meq / L or more. Moreover, 0.50 meq / L or less is preferable and 0.10 meq / L or less is more preferable.
- the obtained separation water can be purified without adversely affecting the microbial flora and aquatic plants in the artificial wetland. Furthermore, since the separated water passes through the filter bed of the constructed wetland satisfactorily, the separated water can be efficiently purified.
- the colloid value of the separated water is preferably ⁇ 2.00 to 0.50 meq / L, more preferably ⁇ 0.50 to 0.10 meq / L.
- CST means the time when a predetermined amount of supernatant water or separated water is dripped onto a specific filter paper, the water is sucked by the capillary suction phenomenon, expands in the circumferential direction, and passes between two concentric circles. In addition, it can be used as an index of the amount of mucilage contained in the supernatant water or separated water of wastewater, and can also be used as an index of the content of unreacted polymer flocculant remaining in the separated water. Specifically, the value of CST is the value measured by the procedure described in “Sewerage Test Method 2012, Volume 1, Volume 5, Sludge and Gas Test, Chapter 1, General Sludge Test, Section 15, Dehydration Test, 3. CST Test”. means.
- the CST of the separated water is preferably 5 seconds or more, and more preferably 10 seconds or more. Moreover, 200 seconds or less are preferable and 50 seconds or less are more preferable. If it is in the said range, in the flocculation process of wastewater, especially organic wastewater, a favorable flocculation floc will be formed and solid-liquid separation can be performed efficiently. Moreover, if it is in the said range, the obtained separation water can be purified without adversely affecting the microbial flora and aquatic plants in the artificial wetland. Furthermore, since the separated water passes well through the filter bed of the artificial wetland, the separated water can be efficiently purified. For example, the CST of the separated water is preferably 5 to 200 seconds, more preferably 10 to 200 seconds, and further preferably 10 to 50 seconds.
- the method for solid-liquid separation of the aggregated floc is not particularly limited, and examples thereof include methods such as aggregated precipitation, flotation separation, centrifugation and filtration, and solid-liquid separation is preferably performed by aggregation precipitation and flotation separation.
- the time required for coagulation sedimentation and flotation separation depends on the type and amount of wastewater to be treated, but is preferably 1 minute or more, and more preferably 3 minutes or more. Moreover, it is preferable that it is 60 minutes or less, It is more preferable that it is 30 minutes or less, It is further more preferable that it is 10 minutes or less.
- the agglomerated floc may be separated into solid and liquid using a dehydrating apparatus and dehydrated.
- examples of the dehydrator used for dehydration include a press dehydrator, a centrifugal dehydrator, a screw press dehydrator, a multi-disc dehydrator, a rotary press filter, and a vacuum dehydrator.
- the time required for coagulation sedimentation and flotation separation is preferably 1 to 60 minutes, more preferably 3 to 30 minutes, and further preferably 3 to 10 minutes.
- This step is a step of purifying the separated water obtained in the previous step using an artificial wetland.
- the separated water obtained through the aggregated floc forming step and the subsequent solid-liquid separation step in the wastewater treatment method of the present invention is purified using an artificial wetland.
- “Purification” using an artificial wetland means that separated water is allowed to flow into the artificial wetland to reduce at least one of BOD, COD, total nitrogen, and total phosphorus in the separated water. In particular, it is preferable to reduce the at least one of BOD, COD, total nitrogen, and total phosphorus in the separated water by circulating the separated water through the constructed wetland.
- the COD (Mn) of the treated water at the final wetland outlet located at the most downstream is preferably as small as possible, for example, 1 mg / L with respect to the total amount of treated water. It is above and may be 10 mg / L or more. Moreover, 1000 mg / L or less is preferable and 500 mg / L or less is more preferable. Within the above range, the lower the COD (Mn), the more efficiently the treated water can be discharged into the river without adversely affecting the environment.
- the COD (Mn) of the treated water at the final wetland outlet located at the most downstream is preferably 1 to 1000 mg / L, more preferably 10 to 500 mg / L. preferable.
- the value obtained by dividing the value of COD (Mn) of the waste water in the method for treating waste water of the present invention by the value of COD (Mn) of the treated water at the final wetland outlet (waste water COD (Mn) / final wetland outlet COD (Mn)) Is preferably 8 or more, more preferably 10 or more. Moreover, 10,000 or less are preferable and 5000 or less are more preferable. Within the above range, the higher the value of waste water COD (Mn) / final wetland outlet COD (Mn), the more efficiently the treated water can be discharged into the river without adversely affecting the environment.
- the value obtained by dividing the value of COD (Mn) of waste water in the method for treating waste water of the present invention by the value of COD (Mn) of the treated water at the final wetland outlet (waste water COD (Mn) / final wetland outlet COD (Mn )) Is preferably 8 to 10,000, and more preferably 10 to 5,000.
- the constructed wetland used in the wastewater treatment method of the present invention preferably includes at least one of a vertical flow wetland and a horizontal flow wetland, and is used by installing a vertical flow wetland and a horizontal flow wetland in combination. Is more preferable. Conditions such as the installation order, the number of installation stages, the wetland area, and the wetland volume of each wetland are not particularly limited, and can be appropriately selected and used in consideration of the properties and generation amount of the separated water and the target water quality of the treated water.
- the conditions such as the size, material and filling amount of the filter bed filled in the wetland are not particularly limited, and can be appropriately selected and used in consideration of the properties and generation amount of the separated water and the target water quality of the treated water. it can. Although it does not specifically limit about the kind of aquatic plant, Yoshi, Azege, Casasuge, etc. are mentioned. Among these, reed and sedge are preferable, and sedge is more preferable. If it is maggot, BOD and COD in the separated water can be reduced well. Moreover, maggots are perennials and form a stable community, so the load of wetland maintenance management is saved and a good landscape-forming function can be obtained.
- the conditions such as the amount of aquatic plants are not particularly limited, and can be appropriately selected and used in consideration of the properties and generation amount of separated water and the target water quality of treated water.
- the reduced viscosity was measured with an Ostwald viscometer at 25 ° C. as a 0.1 g / dL polymer solution in a 1 mol / L sodium chloride aqueous solution.
- HPA Sodium hypophosphite
- Polymer A-1 was dissolved in heavy water, and a 13 C-NMR spectrum was measured with an NMR spectrometer (manufactured by JEOL Ltd., 270 MHz). The composition of each structural unit was calculated from the integrated value of the peak corresponding to each repeating unit in the 13 C-NMR spectrum. Content was calculated
- Amidine Amidine hydrochloride structural unit
- NVF N-vinylformamide structural unit
- AN Acrylonitrile structural unit
- VAM Vinylamine hydrochloride structural unit
- the aqueous monomer solution was transferred to a stainless steel reaction vessel, and sprayed with water at 16 ° C. from below the vessel, using a chemical lamp, with an irradiation intensity of 5 W / m 2 from above the vessel and a surface temperature of 40 ° C. Light was irradiated until. After the surface temperature reached 40 ° C., light was irradiated for 30 minutes at an irradiation intensity of 0.3 W / m 2 . Furthermore, in order to reduce the residual amount of monomer, irradiation was performed for 10 minutes at an irradiation intensity of 50 W / m 2 . Thereby, a hydrogel polymer was obtained.
- the obtained hydrogel polymer was taken out from the container, crushed using a small meat chopper, and then dried at a temperature of 60 ° C. for 16 hours. Thereafter, the dried polymer was pulverized using a Willet pulverizer to obtain an amphoteric polymer (B) (polymer B-1).
- Production Example 3 Production Example 4
- the same procedure as in Production Example 2 was carried out except that the amount of each monomer and HPA was adjusted and changed to the proportions shown in Table 2, and the amphoteric polymer (B) (polymer B-2, polymer respectively) B-3) was obtained.
- Waste water VTS was measured by the above-described VTS measurement method.
- Examples 1 to 10 [Waste water]
- organic wastewater having the following characteristics generated from a treatment facility in the dairy industry was used. That is, the pH of the wastewater measured using the analysis method described in the JIS standard is 7.81, the SS concentration is 65000 mg / L, the VTS is 52.8% / solid, and the colloid value of the supernatant water is ⁇ 6.
- Organic wastewater having 50 meq / L, CST of supernatant water for 4180 seconds, BOD of 25000 mg / L, COD of 24000 mg / L, and total phosphorus of 860 mg / L.
- the particle size of pumice A is 20 to 40 mm
- the particle size of pumice B is 5 to 20 mm
- the particle size of gravel is 0.2 to 2 mm
- the particle size of Kuroboku soil is 0.2 to 2 mm.
- the SS concentration, COD and total phosphorus of the separated water after the flocculation treatment were significantly larger than the wastewater used. It was reduced to. Furthermore, by treating the separated water with an artificial wetland, the COD and total phosphorus in the treated water were further reduced, and a high-quality treated water was obtained. In Examples 1 to 10 in which the colloid value of the separation water was -2.00 to 0.50 meq / L, the COD of the treated water was less than 500 mg / L.
- Comparative Example 1 is the result of purifying wastewater that has not been subjected to agglomeration treatment in the wastewater treatment method of the present invention in an artificial wetland, and the SS concentration of separated water, COD, The total phosphorus was high, and the filter bed of the constructed wetland was clogged, so it could not be purified by the constructed wetland.
- Example 11 to 14, Comparative Example 2 [Used organic wastewater]
- organic wastewater having the following characteristics generated from a treatment facility in the pig farming industry was used. That is, the pH of wastewater measured using each analysis method described in JIS standard is 6.66, SS concentration is 16500 mg / L, VTS is 76.0% / solid, and colloid value of supernatant water is -1.
- the particle size of pumice A is 20-40mm
- the particle size of pumice B is 5-20mm
- the particle size of gravel is 0.2-2mm
- the particle size of black soil is 0.2-2mm.
- the SS concentration, COD and total phosphorus of the separated water after the flocculation treatment were significantly higher than the wastewater used. It was reduced to. Further, by purifying the separated water in the artificial wetland, the COD and total phosphorus in the treated water were further reduced, and a high-quality treated water was obtained. Further, in Examples 11 to 14 where the colloid value of the separated water was ⁇ 2.00 to 0.50 meq / L, the COD of the treated water was less than 500 mg / L.
- Comparative Example 2 is a result of purifying wastewater that has not been subjected to agglomeration treatment in the wastewater treatment method of the present invention in an artificial wetland, and the SS concentration of separated water, COD, The total phosphorus was high, and the filter bed of the constructed wetland was clogged, so it could not be purified by the constructed wetland.
- Examples 15 to 22, Comparative Example 3 [Used organic wastewater]
- organic wastewater having the following characteristics generated from a treatment facility in the dairy industry was used. That is, the pH of wastewater measured using each analysis method described in the JIS standard is 7.94, SS concentration is 35800 mg / L, VTS is 66.3% / solid, and the colloid value of supernatant water is ⁇ 12.
- the SS concentration, COD and total phosphorus of the separated water after the flocculation treatment were significantly larger than the wastewater used. It was reduced to. Furthermore, by treating the separated water with an artificial wetland, the COD and total phosphorus in the treated water were further reduced, and a high-quality treated water was obtained. In Examples 15 to 18 and 20 in which the colloid value of the separated water was ⁇ 2.00 to 0.50 meq / L, the COD of the treated water was less than 500 mg / L.
- Comparative Example 3 is the result of purifying wastewater that has not been subjected to agglomeration treatment in the wastewater treatment method of the present invention in an artificial wetland, and the SS concentration of separated water, COD, The total phosphorus was high, and the filter bed of the constructed wetland was clogged, so it could not be purified by the constructed wetland.
- Examples 23 to 25, Comparative Example 4 [Used organic wastewater]
- organic wastewater having the following characteristics generated from a treatment facility in the dairy industry was used. That is, the pH of waste water measured using each analysis method described in JIS standard is 7.85, SS concentration is 35000 mg / L, VTS is 66.0% / solid, and colloid value of supernatant water is ⁇ 12.
- Pumice A has a particle size of 20-40 mm
- Pumice B has a particle size of 5-20 mm
- gravel has a particle size of 0.2-2 mm.
- the SS concentration, COD and total phosphorus of the separated water after the flocculation treatment were significantly larger than the wastewater used. It was reduced to. Furthermore, by treating the separated water with an artificial wetland, the COD and total phosphorus in the treated water were further reduced, and a high-quality treated water was obtained. In Examples 23 to 25 in which the colloid value of the separated water was ⁇ 2.00 to 0.50 meq / L, the COD of the treated water was less than 500 mg / L.
- Comparative Example 4 is a result of purifying wastewater that has not been subjected to agglomeration treatment in the wastewater treatment method of the present invention in an artificial wetland, and the SS concentration of separated water, COD, The total phosphorus was high, and the filter bed of the constructed wetland was clogged, so it could not be purified by the constructed wetland.
- a polymer flocculant is added to the organic wastewater in advance, and the wetland is subjected to the coagulation separation treatment.
- the load of purification treatment by artificial wetlands is reduced, and BOD, COD, total nitrogen, and total phosphorus in treated water are greatly reduced, and high-quality treated water is obtained.
- a method for treating wastewater is provided.
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Abstract
Description
本願は、2015年5月27日に日本に出願された特願2015-107637号に基づき優先権を主張し、その内容をここに援用する。
しかし、糞尿を多く含む畜産系の有機性廃水や、大規模な工場から排出される有機性廃水の処理は、負荷の変動が激しい。そのため、正常に稼動させるための運転条件が複雑であったり、メンテナンスが困難となったり、多大な労力が必要になる。また、畜産系の有機性廃水の多くは、廃水中のBODおよびCODが高く、処理時間が長くなることや、曝気槽の容積増大により運転コストや建設コストが高くなることが問題視されている。
人工湿地には、湿地表面を水が流れる表面流式人工湿地と、湿地内部を水が流れる伏流式人工湿地がある。伏流式の人工湿地は、湿地内に濾床として詰められた砂利等の濾材による濾過効果が得られるため、表面流式に比べて面積当たりの浄化能が高いという特長がある。そのため、活性汚泥法と比較して、低環境負荷かつ低労力な浄化処理方法として、ヨーロッパを始めとして世界中に普及しつつある。
そして、有機性廃水を順次に流通させるように第1の伏流式垂直流湿地と、第2の伏流式垂直流湿地と、伏流式水平流湿地とを備え、第1及び第2の伏流式垂直流湿地において好気的な浄化を行い、伏流式水平流湿地において嫌気的な浄化を行う伏流式人工湿地システムの提案がなされている(特許文献1)。
また、BODおよびCODが高い有機性廃水では、人工湿地の負荷が高くなるため、湿地の必要面積の拡大や必要段数の増加により、設備全体で広大な面積が必要になる。そのため、人工湿地の設備を設置できる場所や地域が限定されるという問題が生じることになる。
[1]廃水に高分子凝集剤を添加して凝集フロックを形成させる凝集フロック形成工程と、前記凝集フロックを固液分離して分離水を得る固液分離工程と、人工湿地を使用して前記分離水を浄化する浄化工程とを含む、廃水の処理方法。
[2]前記凝集フロック形成工程において高分子凝集剤が添加される廃水の浮遊固形分が、前記廃水の総量に対して6000~100000mg/Lである、[1]に記載の廃水の処理方法。
[3]前記凝集フロック形成工程において高分子凝集剤が添加される廃水の全リンの含有量が、前記廃水の総量に対して10~10000mg/Lである、[1]または[2]に記載の廃水の処理方法。
[4]前記高分子凝集剤が、アミジン系カチオン性ポリマー(A)、両性ポリマー(B)、及び非アミジン系カチオン性ポリマー(C)からなる群より選択される一種以上の高分子凝集剤を含む、[1]~[3]のいずれか一項に記載の廃水の処理方法。
[5]前記高分子凝集剤が、アミジン系カチオン性ポリマー(A)を含む、[4]に記載の廃水の処理方法。
[6]前記廃水に対する高分子凝集剤の添加量が、前記廃水の質量に対して100~3000質量ppmである、[5]に記載の廃水の処理方法。
[7]前記高分子凝集剤が、両性ポリマー(B)を含む、[4]に記載の廃水の処理方法。
[8]前記廃水に対する高分子凝集剤の添加量が、前記廃水の質量に対して100~2000質量ppmである、[7]に記載の廃水の処理方法。
[9]前記高分子凝集剤が、非アミジン系カチオン性ポリマー(C)を含む、[4]に記載の廃水の処理方法。
[10]前記廃水に対する高分子凝集剤の添加量が、前記廃水の質量に対して100~2000質量ppmである、[9]に記載の廃水の処理方法。
[11]前記アミジン系カチオン性ポリマー(A)が、一般式(1)又は一般式(2)のいずれかで表されるアミジン構成単位を含むポリマーである、[5]に記載の廃水の処理方法。
(式中、R1及びR2はそれぞれ独立して水素原子又はメチル基であり、X-は陰イオンである。)
(式中、R1及びR2はそれぞれ独立して水素原子又はメチル基であり、X-は陰イオンである。)
[12]前記両性ポリマー(B)が、アニオン性構成単位、非イオン性構成単位、及び一般式(3)で表されるカチオン性構成単位を含むポリマーである、[7]に記載の廃水の処理方法。
(式中、R3は水素原子又はメチル基であり、R4及びR5はそれぞれ独立して水素原子又は炭素数1~4のアルキル基であり、R6は炭素数1~4のアルキル基又はベンジル基であり、Yは酸素原子又はNHであり、Z-は陰イオンであり、nは1~3の整数である。)
[13]前記非アミジン系カチオン性ポリマー(C)が、一般式(4)で表されるカチオン性構成単位を含むポリマーである、[9]に記載の廃水の処理方法。
(式中、R3は水素原子又はメチル基であり、R4及びR5はそれぞれ独立して水素原子又は炭素数1~4のアルキル基であり、R6は炭素数1~4のアルキル基又はベンジル基であり、Yは酸素原子又はNHであり、Z-は陰イオンであり、nは1~3の整数である。)
[14]前記分離水のコロイド値が-2.00~0.50meq/Lである、[1]~[13]のいずれか一項に記載の廃水の処理方法。
[15]前記人工湿地が垂直流湿地と水平流湿地のうちの少なくとも1つを含む、[1]~[14]のいずれか一項に記載の廃水の処理方法。
[16]前記廃水のCOD(Mn)の値を最下流に位置する最終湿地出口の処理水のCOD(Mn)の値で除した値(廃水COD(Mn)/最終湿地出口COD(Mn))が8~10000である、[1]~[15]のいずれか一項に記載の廃水の処理方法。
本発明の廃水の処理方法は、廃水、特に有機性廃水からBOD、CODを低減させ、全窒素、全リン等を除去する方法であり、下記の工程を含むものである。
(1)廃水に高分子凝集剤を添加して凝集フロックを形成させる凝集フロック形成工程;
(2)前記凝集フロックを固液分離して分離水を得る固液分離工程;及び
(3)人工湿地を使用して前記分離水を浄化する浄化工程。
本工程は、廃水に高分子凝集剤を添加して凝集フロックを形成させる工程である。
「微細フロック」は、負に帯電したBOD及びCODの値を増大させる対象物質が荷電中和により不溶化したものが凝集し、微細な集合体を形成したものを意味し、それ以外に、懸濁物質やコロイド状物質等の水に不溶な粒子が荷電中和され凝集し微細な集合体を形成したものを含んでもよい。
「凝集フロック」は、微細フロックがさらに凝集して、凝集分離に必要なフロック径にまで粗大化したものを意味する。
本発明の廃水の処理方法により処理される廃水は、有機性廃水であることが好ましい。有機性廃水として例えば、畜産施設から発生する畜産糞尿廃水や、糞尿を含む廃水に対してメタン醗酵処理を行うことで得られる消化廃水等を挙げることができる。具体的には、酪農産業の処理施設から発生する酪農廃水、養豚産業の処理施設から発生する養豚尿廃水等を挙げることができる。また、雑生活下水やし尿を含む下水等の廃水、飲料工場や食品工場から発生する廃水、化学系工場(染色、樹脂、繊維、化成品)から発生する廃水、その他、様々な工場施設より発生する廃水等が挙げられる。有機性廃水に含まれる有機物は、水溶性及び非水溶性の有機物であり、有機物の含有量の指標としては、BOD、COD及びVTSの値を用いることができ、さらにSS濃度を用いることもできる。本発明の廃水の処理方法で処理される廃水には、さらに懸濁物質、コロイド状物質、イオン性成分等が含まれていてもよい。ここで、「イオン性成分」とは、廃水に含まれる粘質性のアニオン性もしくは両性の有機高分子成分や無機塩由来のアニオン性成分を意味する。
例えば、凝集フロック形成工程において高分子凝集剤が添加される廃水のBODは、4000~100000mg/Lが好ましく、7000~80000mg/Lがより好ましく、10000~80000mg/Lがさらに好ましく、20000~80000mg/Lが特に好ましい。
例えば、凝集フロック形成工程において高分子凝集剤が添加される廃水のCODは、4000~100000mg/Lが好ましく、7000~80000mg/Lがより好ましく、10000~80000mg/Lがさらに好ましく、20000~80000mg/Lが特に好ましい。
(1)廃水100mlを105℃で6時間乾燥し残量(総固形分量)(g)を秤量する。
(2)その後600℃で2時間加熱し、灰化後の残量(焼却重量)(g)を秤量する。
(3)下記式(A)を用いて、強熱減量物(VTS;%/固形分)を求める。
VTS(%/固形分)={(総固形分量-焼却重量)/総固形分量}×100 ・・・(A)
後述の凝集フロック形成工程において高分子凝集剤が添加される廃水のVSTは、40%/固形分以上が好ましく、50%/固形分以上がより好ましく、60%/固形分以上がさらに好ましい。また、100%/固形分以下が好ましい。前記範囲内であれば、廃水、特に有機性廃水の凝集処理にて良好な凝集フロックが形成され、効率よく固液分離を行うことができる。
例えば、凝集フロック形成工程において高分子凝集剤が添加される廃水のVSTは、40~100%/固形分が好ましく、50~100%/固形分がより好ましく、60~100%/固形分がさらに好ましい。
例えば、凝集フロック形成工程において高分子凝集剤が添加される廃水のSS濃度は、廃水の総量に対して、6000~100000mg/Lが好ましく、10000~80000mg/Lがより好ましく、20000~80000mg/Lがさらに好ましい。
例えば、凝集フロック形成工程において高分子凝集剤が添加される廃水の全リンは、10~10000mg/Lが好ましく、100~5000mg/Lがより好ましく、200~1000mg/Lがさらに好ましい。
本発明の廃水の処理方法では、高分子凝集剤として、アミジン系カチオン性ポリマー(A)、両性ポリマー(B)、及び非アミジン系カチオン性ポリマー(C)からなる群より選択される一種以上の高分子凝集剤を用いることができる。
ある態様としては、高分子凝集剤として、アミジン系カチオン性ポリマー(A)を含むことが好ましい。別の態様としては、高分子凝集剤として、両性ポリマー(B)を含むことが好ましい。さらに別の態様としては、高分子凝集剤として、非アミジン系カチオン性ポリマー(C)を含むことが好ましい。
アミジン系カチオン性ポリマー(A)は、前記一般式(1)又は前記一般式(2)のいずれかで表されるアミジン構成単位を含むポリマーである。アミジン系カチオン性ポリマー(A)における、全構成単位に対するアミジン構成単位の含有量は、アミジン系カチオン性ポリマー(A)の全構成単位のモル数に対して、30モル%以上が好ましく、40モル%以上がより好ましい。また、90モル%以下が好ましく、80モル%以下がより好ましい。前記範囲内であれば、廃水、特に有機性廃水の凝集処理にてSS、BOD及びCODの値を増大させる対象物質が効率よく凝集し、人工湿地による分離水の浄化処理において、良好なBOD及びCODの低減の効果が得られ、良質な処理水を得ることができる。
例えば、アミジン系カチオン性ポリマー(A)における、全構成単位に対するアミジン構成単位の含有量は、アミジン系カチオン性ポリマー(A)の全構成単位のモル数に対して、30~90モル%が好ましく、40~80モル%がより好ましい。
なお、アミジン系カチオン性ポリマー(A)として、2種以上のアミジン系カチオン性ポリマー(A)を併用することもできる。
例えば、アミジン系カチオン性ポリマー(A)の還元粘度は、0.1~10dL/gが好ましく、1~5dL/gがより好ましい。
両性ポリマー(B)は、前記一般式(3)で表されるカチオン性構成単位を含むポリマーである。両性ポリマー(B)における、全構成単位に対するカチオン性構成単位の含有量は、両性ポリマー(B)の全構成単位のモル数に対して、20モル%以上が好ましい。また、80モル%以下が好ましく、55モル%以下がより好ましい。前記範囲内であれば、廃水、特に有機性廃水の凝集処理にて良好な凝集フロックが形成され、効率よく固液分離を行うことができる。
例えば、両性ポリマー(B)における、全構成単位に対するカチオン性構成単位の含有量は、両性ポリマー(B)の全構成単位のモル数に対して、20~80モル%が好ましく、20~55モル%がより好ましい。
例えば、両性ポリマー(B)における、全構成単位に対するアニオン性構成単位の含有量は、両性ポリマー(B)の全構成単位のモル数に対して、3~75モル%が好ましく、5~30モル%がさらに好ましい。
例えば、両性ポリマー(B)の還元粘度は、0.1~10.0dL/gが好ましく、3.0~7.5dL/gがより好ましい。
非アミジン系カチオン性ポリマー(C)は、前記一般式(4)で表されるカチオン性構成単位を含むポリマーである。非アミジン系カチオン性ポリマー(C)における、全構成単位に対するカチオン性構成単位の含有量は、非アミジン系カチオン性ポリマー(C)の全構成単位のモル数に対して、10モル%以上が好ましく、20モル%以上がより好ましく、40モル%以上がさらに好ましい。また、100モル%以下が好ましい。前記範囲内であれば、廃水、特に有機性廃水の凝集処理にて、良好な凝集フロックが形成され、効率よく固液分離を行うことができる。また、人工湿地による分離水の浄化処理において、濾床の目詰まりを防止する効果が得られ、人工湿地の浄化性能が安定し、効率よく浄化処理を行うことができ、良質な処理水を得ることができる。
例えば、非アミジン系カチオン性ポリマー(C)における、全構成単位に対するカチオン性構成単位の含有量は、非アミジン系カチオン性ポリマー(C)の全構成単位のモル数に対して、10~100モル%が好ましく、20~100モル%がより好ましく、40~100モル%がさらに好ましい。
本発明の廃水の処理方法で用いられる高分子凝集剤は、本発明の効果を損なわない範囲で、アミジン系カチオン性ポリマー(A)、両性ポリマー(B)、及び非アミジン系カチオン性ポリマー(C)以外の他の非アミジン系カチオン性ポリマー、又は両性ポリマーを含んでいてもよい。これらのポリマーは、高分子凝集剤の全質量に対して、0質量%以上10質量%未満であることが好ましく、0質量%以上5質量%未満であることがより好ましく、0質量%であることがさらに好ましい。
本発明の廃水の処理方法において、より良好な凝集フロックを形成するため、凝集フロック形成工程における高分子凝集剤の添加後に、さらにアニオン性ポリマー(D)を添加してもよい。なお、凝集フロック形成工程における高分子凝集剤の添加後に、さらにアニオン性ポリマー(D)を添加する工程を、「アニオン性ポリマー(D)添加工程」とも言う。
高分子凝集剤を添加する際には、廃水を撹拌することが好ましい。撹拌が弱すぎると、高分子凝集剤が均一に混和されず、撹拌が強すぎると微細フロックが凝集フロックへと成長しにくくなる。したがって、高分子凝集剤を添加する際には、180~3000rpmの回転数で廃水を撹拌することが好ましい。また、撹拌時間は、処理する廃水の量にもよるが、30秒以上であることが好ましい。また、300秒以下であることが好ましく、120秒以下であることがより好ましい。例えば、撹拌時間は、30~300秒が好ましく、30~120秒がより好ましい。
廃水に対する前記高分子凝集剤、及び高分子凝集剤の添加後にさらに添加するアニオン性ポリマー(D)の添加量は、添加される廃水の質量(添加した高分子凝集剤の質量を含まない。)に対して、それぞれ1ppm以上が好ましく、10ppm以上がより好ましく、300ppm以上がさらに好ましい。また、2000ppm以下が好ましく、1000ppm以下がより好ましい。前記範囲内であれば、廃水、特に有機性廃水の凝集処理にて、良好な凝集フロックが形成され、効率よく固液分離を行うことができる。また、前記範囲内であれば、得られた分離水を人工湿地内の微生物菌叢や水生植物に悪影響を与えることなく浄化処理することができる。
例えば、廃水に対する高分子凝集剤の添加量、及び高分子凝集剤の添加後にさらに添加するアニオン性ポリマー(D)の添加量は、添加される廃水の質量(添加した高分子凝集剤の質量を含まない。)に対して、それぞれ1~2000質量ppmが好ましく、10~1000質量ppmがより好ましく、300~1000質量ppmがさらに好ましい。
廃水に対する前記高分子凝集剤、及び高分子凝集剤の添加後にさらに添加するアニオン性ポリマー(D)の添加量は、添加される廃水の質量(添加した高分子凝集剤の質量を含まない。)に対して、それぞれ1ppm以上が好ましく、10ppm以上がより好ましく、300ppm以上がさらに好ましい。また、3000ppm以下が好ましく、2500ppm以下がより好ましく、2000ppm以下がさらに好ましい。前記範囲内であれば、廃水、特に有機性廃水の凝集処理にて、良好な凝集フロックが形成され、効率よく固液分離を行うことができる。また、前記範囲内であれば、得られた分離水を人工湿地内の微生物菌叢や水生植物に悪影響を与えることなく浄化処理することができる。
例えば、廃水に対する高分子凝集剤の添加量、及び高分子凝集剤の添加後にさらに添加するアニオン性ポリマー(D)の添加量は、添加される廃水の質量(添加した高分子凝集剤の質量を含まない。)に対して、それぞれ1~3000質量ppmが好ましく、10~2500質量ppmがより好ましく、300~2000質量ppmがさらに好ましい。
高分子凝集剤の水への溶解性の向上や、高分子凝集剤の水溶液の粘度低下などの劣化防止のために、高分子凝集剤を水に溶解する際に、水に酸性物質を添加してもよい。
酸性物質としては、例えば、スルファミン酸、酸性亜硫酸ナトリウムなどが挙げられる。
その添加の目的、添加する酸性物質の種類に応じて、酸性物質の添加量や添加するタイミング等の添加条件を適宜定めることができる。
高分子凝集剤に加えて、無機凝結剤及び/又は有機凝結剤(以下、まとめて「凝結剤」と言う。)を廃水に添加してもよい。本発明の廃水の処理方法で用いる高分子凝集剤は、凝結剤と併用しても、廃水に対する汚濁物質の低減効果を十分に発揮することができる。
無機凝結剤としては、例えば、硫酸バンド、ポリ塩化アルミニウム、塩化第2鉄、硫酸第1鉄、硫酸第2鉄、ポリ鉄(ポリ硫酸鉄、ポリ塩化鉄)などが挙げられる。有機凝結剤としては、例えば、ポリアミン、ポリジアリルジメチルアンモニウムクロライド、ポリジアルキルアミノアルキルメタクリレートのアルキルクロライド4級塩、カチオン性界面活性剤などが挙げられる。
その添加の目的、添加する凝結剤の種類に応じて、凝結剤の添加量や添加するタイミング等の添加条件を適宜定めることができる。凝結剤の添加量は、高分子凝集剤100質量部に対して5~3000質量部であることが好ましく、凝結剤を廃水に添加するタイミングとしては、高分子凝集剤を廃水に添加する前に添加することが好ましい。
本工程は、前工程にて得た凝集フロックを固液分離して、分離水を得る工程である。
例えば、本発明の廃水の処理方法における固液分離工程で得られる分離水のSS濃度は、分離水の総量に対して1~5000mg/Lが好ましく、10~3000mg/Lがより好ましく、10~1000mg/Lがさらに好ましい。
(1)200mLのトールビーカーに、廃水の上澄み水または分離水10mLを採取し、純水を90mL加える。
(2)さらに1/200Nのメチルグリコールキトサン溶液を2mL加えて撹拌する。
(3)さらに指示薬としてトルイジンブルーを1~2滴加える。
(4)500rpmで撹拌しながら、1/400Nのポリビニル硫酸カリウム水溶液にて滴定し、液の色が青からピンクに変わる滴定量X(mL)を測定する。
(5)同様に純水100mLのみを、(2)~(3)の作業で滴定し、ブランクの滴定量Y(mL)を測定する。
(6)下記式(B)を用いて、コロイド値(meq/L)を求める。
コロイド値(meq/L)=(滴定量X-滴定量Y)/10×1/400×1000 ・・・(B)
分離水のコロイド値は、分離水中に含まれるマイナス荷電量を意味し、分離水中に残留する未反応の高分子凝集剤含有量の指標になる。分離水のコロイド値は-2.00meq/L以上が好ましく、-0.50meq/L以上がより好ましい。また0.50meq/L以下が好ましく、0.10meq/L以下がより好ましい。前記範囲内であれば、廃水、特に有機性廃水の凝集処理において、良好な凝集フロックが形成され、効率よく固液分離を行うことができる。また、前記範囲内であれば、得られた分離水を人工湿地内の微生物菌叢や水生植物に悪影響を与えることなく浄化処理することができる。さらに、分離水は人工湿地の濾床内を良好に通過するため、分離水を効率よく浄化処理することができる。
例えば、分離水のコロイド値は、-2.00~0.50meq/Lが好ましく、-0.50~0.10meq/Lがより好ましい。
例えば、分離水のCSTは、5~200秒が好ましく、10~200秒がより好ましく、10~50秒がさらに好ましい。
例えば、凝集沈殿や浮上分離に要する時間は、1~60分間が好ましく、3~30分間がより好ましく、3~10分間がさらに好ましい。
本工程は、人工湿地を使用して前工程にて得た分離水を浄化する工程である。
本発明の廃水の処理方法における凝集フロック形成工程、それに続く固液分離工程を経て得られた分離水は、人工湿地を使用して浄化される。人工湿地を使用した「浄化」とは、人工湿地に分離水を流入させて分離水中のBOD、COD、全窒素及び全リンのうちの少なくともいずれかを低減させることを意味する。特に、人工湿地に分離水を流通させて分離水中のBOD、COD、全窒素及び全リンのうちの少なくともいずれかを低減させることが好ましい。本発明の廃水の処理方法で用いられる人工湿地のうち、最下流に位置する最終湿地出口の処理水のCOD(Mn)は小さければ小さいほど好ましく、例えば、処理水の総量に対して1mg/L以上であり、10mg/L以上であってもよい。また、1000mg/L以下が好ましく、500mg/L以下がより好ましい。前記範囲内であれば、COD(Mn)が低い程、環境に悪影響を与えることなく河川への処理水の放流を効率的に行うことができる。例えば、本発明の廃水の処理方法で用いられる人工湿地のうち、最下流に位置する最終湿地出口の処理水のCOD(Mn)は、1~1000mg/Lが好ましく、10~500mg/Lがより好ましい。
1mol/Lの塩化ナトリウム水溶液中、0.1g/dLのポリマー溶液として25℃でオストワルド型粘度計により還元粘度を測定した。
[モノマー]
(i)カチオン性モノマー:
(a)N,N-ジメチルアミノエチルアクリレート塩化メチル4級塩(以下、「DME」と言う。)、大阪有機化学工業社製、80質量%水溶液
(b)N,N-ジメチルアミノエチルメタクリレート塩化メチル4級塩(以下、「DMC」と言う。)、大阪有機化学工業社製、80質量%水溶液
(ii)アニオン性モノマー:
(a)アクリル酸(以下、「AA」と言う。)、三菱化学社製、50質量%水溶液
(iii)非イオン性モノマー:
(a)アクリルアミド(以下、「AAM」と言う。)、三菱レイヨン社製、50質量%水溶液
(b)アクリロニトリル(以下、「AN」と言う。)、三菱レイヨン社製、純度99質量%
(c)N-ビニルホルムアミド(以下、「NVF」と言う。)、三菱レイヨン社製、純度91質量%水溶液
(i)2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン(DAROCUR(登録商標)1173)、(以下、「D-1173」と言う。)、Ciba社製
(ii)2,2’-アゾビス(2-アミジノプロパン)2塩酸塩(V-50)(以下、「V-50」と言う。)、和光純薬社製
次亜リン酸ナトリウム(以下、「HPA」と言う。)、和光純薬社製
(製造例1)
攪拌機、窒素導入管、冷却管を備えた内容積50mLの四つ口フラスコにANとNVFの混合物(モル比=55:45)6gと蒸留水34gを入れた。窒素ガス中、攪拌しつつ60℃に昇温し、V-50を0.12g添加し、さらに、60℃で3時間保持し、水中にポリマーが析出した懸濁物を得た。懸濁物に蒸留水を20g添加し、さらに、濃塩酸をポリマーのホルミル基に対し1当量添加し、100℃で4時間保持し、黄色の高粘度液を得た。これを多量のアセトンに添加し、ポリマーを析出させ、得られたポリマーゲルを細断し、60℃で1昼夜乾燥後、粉砕してアミジン系カチオン性ポリマー(A)(ポリマーA-1)を得た。
(製造例2)
DME 632.9g、AA 100.0g、AAM 900.0gを、内容積2000mLの褐色耐熱瓶に投入し、HPA 3.0gと蒸留水を加え、総質量が2000gのモノマー水溶液(DME:AA:AAM=26.9:7.2:65.9(モル%)、モノマー濃度50%)を調製した。さらに、D-1173を、モノマー水溶液の総質量に対して、150ppmとなるように投入し、これに窒素ガスを30分間吹き込みながらモノマー水溶液の温度を20℃に調節した。
製造例2において、各モノマー及びHPAの量を調節し、表2に記載の割合に変更した以外は、製造例2と同様の操作を行い、両性ポリマー(B)(それぞれポリマーB-2、ポリマーB-3)を得た。
(製造例5~製造例9)
製造例2において、各モノマー及びHPAの量を調節し、表2に記載の割合に変更した以外は、製造例2と同様の操作を行い、カチオンポリマー(C)(それぞれポリマーC-1~ポリマーC-5)を得た。
廃水及び分離水のSS濃度は、前記のSS濃度の測定方法によって測定した。
廃水のBODは、前記のBODの測定方法によって測定した。
廃水、分離水及び処理水のCODは、前記のCOD(Mn)の測定方法によって測定した。なお、分離水のBODを表す代替値として分離水のCODの測定結果を用いた。
廃水、分離水及び処理水の全リンは、前記の全リンの測定方法によって測定した。
廃水のVTSは、前記のVTSの測定方法によって測定した。
廃水の上澄み水、分離水のコロイド値は、前記のコロイド値の測定方法によって測定した。
廃水の上澄み水、分離水のコロイド値は、前記のCSTの測定方法によって測定した。
[廃水]
廃水として、酪農産業の処理施設から発生した、下記特性を有する有機性廃水を用いた。即ち、JIS規格に記載された分析方法を用いて測定された廃水のpHが7.81、SS濃度が65000mg/L、VTSが52.8%/固形分、上澄み水のコロイド値が-6.50meq/L、上澄み水のCSTが4180秒、BODが25000mg/L、CODが24000mg/L、全リンが860mg/Lである有機性廃水。
1000Lのオープンタンクに前記有機性廃水の600Lを採取した。次いで、表1及び表2に記載の高分子凝集剤を0.3%になるように水に溶解して高分子凝集剤水溶液を調製し、これを表4に記載の濃度になるよう添加した後、中速型撹拌機で攪拌速度:300rpm、攪拌時間:60秒間の条件で撹拌混合して凝集フロックを形成させた。その後、凝集フロックを5分間沈殿させることで固液分離し、凝集フロックと分離水に分離した。後述の評価結果を表4に示す。
用いた高分子凝集剤を表4に示す通りに変更した以外は、実施例1と同様にして凝集フロックを形成させ、凝集フロックと分離水を分離した。後述の評価結果を表4に示す。
[凝集フロック粒径、濾過性、分離水のSS濃度、CST、コロイド値、COD、全リン]
各実施例と比較例において凝集フロックを形成させた後に攪拌を止め、凝集フロック粒径を目視により測定した。その後、500mlビーカーに、凝集フロックを形成させた廃水を300ml採取し、予め濾布を敷いたヌッチェに移し、濾過性(60秒間の濾過分離水量)を測定した。また、1000Lのオープンタンク内で固液分離して分離水を採取し、分離水のSS濃度、CST、コロイド値、COD、全リンを測定した。
実施例1~10と比較例1において、1000Lのオープンタンク内で固液分離して分離水を採取し、表3に示すような人工湿地に分離水を流入させ、浄化処理を行い、処理水を得た。その後、処理水を採取しCOD、全リンを測定した。処理水のCOD、全リンの測定結果を表4に示す。
[使用有機性廃水]
廃水として、養豚産業の処理施設から発生した、下記特性を有する有機性廃水を用いた。即ち、JIS規格に記載された各分析方法を用いて測定された廃水のpHが6.66、SS濃度が16500mg/L、VTSが76.0%/固形分、上澄み水のコロイド値が-1.80meq/L、上澄み水のCSTが1153秒、BODが18300mg/L、CODが7240mg/L、全リンが2420mg/Lである有機性廃水。
試験に用いた高分子凝集剤を表6に示す通りに変更した以外は、実施例1と同様の凝集試験を実施した。実施例11~14及び比較例2における評価結果を表6に示す。
実施例11~14と比較例2において、1000Lのオープンタンク内で固液分離して分離水を採取し、表5に示すような人工湿地に流入させ、浄化処理を行い、処理水を得た。その後、処理水を採取しCOD及び全リンを測定した。処理水のCOD及び全リンの測定結果を表6に示す。
[使用有機性廃水]
廃水として、酪農産業の処理施設から発生した、下記特性を有する有機性廃水を用いた。即ち、JIS規格に記載された各分析方法を用いて測定された廃水のpHが7.94、SS濃度が35800mg/L、VTSが66.3%/固形分、上澄み水のコロイド値が-12.30meq/L、上澄み水のCSTが3120秒、BODが7480mg/L、CODが12000mg/L、全リン980mg/Lである有機性廃水。
試験に用いた高分子凝集剤を表7に示す通りに変更した以外は、実施例1と同様の凝集試験を実施した。実施例15~22及び比較例3における評価結果を表7に示す。
実施例15~22と比較例3において、1000Lのオープンタンク内で固液分離して分離水を採取し、表3に示すような人工湿地に流入させ、浄化処理を行い、処理水を得た。その後、処理水を採取しCOD及び全リンを測定した。処理水のCOD及び全リンの測定結果を表7に示す。
[使用有機性廃水]
廃水として、酪農産業の処理施設から発生した、下記特性を有する有機性廃水を用いた。即ち、JIS規格に記載された各分析方法を用いて測定された廃水のpHが7.85、SS濃度が35000mg/L、VTSが66.0%/固形分、上澄み水のコロイド値が-12.40meq/L、上澄み水のCSTが3020秒、BODが7200mg/L、CODが11000mg/L、全リン900mg/Lである有機性廃水。
試験に用いた高分子凝集剤を表9に示す通りに変更した以外は、実施例1と同様の凝集試験を実施した。実施例23~25及び比較例4における評価結果を表9に示す。
実施例23~25と比較例4において、1000Lのオープンタンク内で固液分離して分離水を採取し、表8に示すような人工湿地に流入させ、浄化処理を行い、処理水を得た。その後、処理水を採取しCOD及び全リンを測定した。処理水のCOD及び全リンの測定結果を表9に示す。
Claims (16)
- 廃水に高分子凝集剤を添加して凝集フロックを形成させる凝集フロック形成工程と、前記凝集フロックを固液分離して分離水を得る固液分離工程と、人工湿地を使用して前記分離水を浄化する浄化工程とを含む、廃水の処理方法。
- 前記凝集フロック形成工程において高分子凝集剤が添加される廃水の浮遊固形分が、前記廃水の総量に対して6000~100000mg/Lである、請求項1に記載の廃水の処理方法。
- 前記凝集フロック形成工程において高分子凝集剤が添加される廃水の全リンの含有量が、前記廃水の総量に対して10~10000mg/Lである、請求項1または請求項2に記載の廃水の処理方法。
- 前記高分子凝集剤が、アミジン系カチオン性ポリマー(A)、両性ポリマー(B)、及び非アミジン系カチオン性ポリマー(C)からなる群より選択される一種以上の高分子凝集剤を含む、請求項1~請求項3のいずれか一項に記載の廃水の処理方法。
- 前記高分子凝集剤が、アミジン系カチオン性ポリマー(A)を含む、請求項4に記載の廃水の処理方法。
- 前記廃水に対する高分子凝集剤の添加量が、前記廃水の質量に対して100~3000質量ppmである、請求項5に記載の廃水の処理方法。
- 前記高分子凝集剤が、両性ポリマー(B)を含む、請求項4に記載の廃水の処理方法。
- 前記廃水に対する高分子凝集剤の添加量が、前記廃水の質量に対して100~2000質量ppmである、請求項7に記載の廃水の処理方法。
- 前記高分子凝集剤が、非アミジン系カチオン性ポリマー(C)を含む、請求項4に記載の廃水の処理方法。
- 前記廃水に対する高分子凝集剤の添加量が、前記廃水の質量に対して100~2000質量ppmである、請求項9に記載の廃水の処理方法。
- 前記分離水のコロイド値が-2.00~0.50meq/Lである、請求項1~請求項13のいずれか一項に記載の廃水の処理方法。
- 前記人工湿地が垂直流湿地と水平流湿地のうちの少なくとも1つを含む、請求項1~請求項14のいずれか一項に記載の廃水の処理方法。
- 前記廃水のCOD(Mn)の値を最下流に位置する最終湿地出口の処理水のCOD(Mn)の値で除した値(廃水COD(Mn)/最終湿地出口COD(Mn))が8~10000である、請求項1~請求項15のいずれか一項に記載の廃水の処理方法。
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WO2018199330A1 (ja) * | 2017-04-28 | 2018-11-01 | 三菱ケミカル株式会社 | 有機性廃水の処理方法及びその利用 |
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EP3305732A1 (en) | 2018-04-11 |
JPWO2016190388A1 (ja) | 2017-06-15 |
US20180155224A1 (en) | 2018-06-07 |
JP6378342B2 (ja) | 2018-08-22 |
EP3305732A4 (en) | 2019-03-13 |
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