WO2007007569A1 - 難分解性物質含有水の処理方法 - Google Patents
難分解性物質含有水の処理方法 Download PDFInfo
- Publication number
- WO2007007569A1 WO2007007569A1 PCT/JP2006/313113 JP2006313113W WO2007007569A1 WO 2007007569 A1 WO2007007569 A1 WO 2007007569A1 JP 2006313113 W JP2006313113 W JP 2006313113W WO 2007007569 A1 WO2007007569 A1 WO 2007007569A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hardly decomposable
- adsorbent
- membrane
- decomposable substance
- water containing
- Prior art date
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- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- RDVQTQJAUFDLFA-UHFFFAOYSA-N cadmium Chemical compound [Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd] RDVQTQJAUFDLFA-UHFFFAOYSA-N 0.000 description 1
- NZUYJPMKCSBVLS-UHFFFAOYSA-N cadmium;hydrogen peroxide Chemical compound [Cd].OO NZUYJPMKCSBVLS-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 description 1
- 235000019402 calcium peroxide Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910002096 lithium permanganate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229940105296 zinc peroxide Drugs 0.000 description 1
Classifications
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/16—Feed pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/04—Feed pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/58—Multistep processes
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2317/00—Membrane module arrangements within a plant or an apparatus
- B01D2317/02—Elements in series
- B01D2317/025—Permeate series
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2317/00—Membrane module arrangements within a plant or an apparatus
- B01D2317/08—Use of membrane modules of different kinds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/04—Backflushing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
-
- 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
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/305—Endocrine disruptive agents
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
- C02F2101/366—Dioxine; Furan
Definitions
- dioxins can be removed by directly treating the wastewater with ozone, photolysis, or hydrogen peroxide chemistry.
- Decomposition, removal by microorganisms, separation using adsorbents and flocculants, etc. are performed.
- separation / removal technology directly processes the diluted solution, which is not only inefficient but also requires a large capital investment.
- the wastewater is polluted at a high concentration, there are cases where the discharge standards cannot be satisfied.
- a means for detoxifying such a hardly decomposable organic compound for example, as a method for removing dioxins, ozone, photolysis, chemical decomposition with hydrogen peroxide, microorganisms can be used for the dioxins.
- Hands such as disassembly by separation, separation and removal using adsorbent and flocculant The stage is known.
- the treatment is simple because it is easy to operate, and an oxidation agent is added to the dioxins to chemically decompose them to make them harmless.
- an oxidizing agent to chemically decompose the dioxins for example, a technique using a persulfate is provided (for example, Patent Document 1 and Patent Document 2).
- a step of settling the contaminated water a step of filtering through a net having an average pore size of 10 to 100 ⁇ m, and the permeated water is subjected to catalytic decomposition by irradiation with ultraviolet rays in the presence of photocatalyst powder.
- Technology for a wastewater treatment method that performs a step of treating with an ultrafiltration membrane and then a step of treating with an ultrafiltration membrane has been reported (for example, Patent Document 3).
- Sources of wastewater containing persistent materials include chlorinated bleach equipment at Kraft Panorep manufacturing plant, waste PCB (polychlorinated biphenyl) or PCB processed material decomposition equipment, PCB contamination or PCB processed material cleaning equipment, aluminum Also known are waste gas cleaning equipment, wet dust collection equipment, waste pits that discharge sewage, etc. for melting furnaces used for the production of aluminum alloys.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2003-93999
- Patent Document 2 Japanese Patent Laid-Open No. 2003-285043
- Patent Document 3 Japanese Unexamined Patent Publication No. 2003-144857
- Patent Document 4 JP-A-11 347591
- Patent Document 5 Japanese Unexamined Patent Publication No. 2000-354894
- Patent Document 6 Japanese Unexamined Patent Publication No. 2000-189945
- Patent Document 7 JP-A-11 99395
- Non-Patent Document 1 “Directive for Dioxins”, directed by Stephenchi Hirayama, published by CMC, 19 7-205 (1998)
- Patent Document 1 and Patent Document 2 described above when a persulfate is added to a hardly decomposable organic compound and the compound is chemically decomposed, it is difficult. Due to the low decomposition efficiency of degradable organic compounds, it was extremely difficult to cope with high concentrations. On the other hand, as a means for treating such high-concentration organic compounds, the ability to add a metal salt such as ruthenium salt to persulfate is very powerful. It is expensive and not practical from the viewpoint of cost.
- Patent Document 3 The technique as disclosed in Patent Document 3 is a method for metal wastewater with little solids in the decomposition product. Since the film layer of the solid deposit in the decomposition product is not formed on the ash, the solid in the decomposition product of fine particles containing dioxin and the dissolved dioxin permeate the metal mesh, resulting in insufficient processing There was a case.
- an object of the present invention is to concentrate indigestible substances such as dioxins contained in contaminated water (treated raw water) such as incinerator demolition construction wastewater, industrial wastewater from specified facilities, and some soil leachate.
- contaminated water treated raw water
- a wastewater treatment method capable of a closed system capable of effectively decomposing a hardly decomposable substance adsorbed on a solid as it is without performing an operation such as desorption, and a difficult decomposition
- the purpose is to provide a circulation-type on-site treatment method that does not generate waste by recycling the adsorbent used for the adsorption and separation of active substances.
- Adsorbent after decomposition of refractory substances (E) Adsorbent after decomposition of refractory substances (B) Process to return to adsorption process (Adsorbent return process)
- a method for treating water containing a hardly decomposable substance comprising:
- step (E) is a step of solid-liquid separation of water containing the adsorbent after decomposition of the hardly decomposable substance and returning the adsorbent to the (B) adsorption treatment step.
- step (E) the permeate is separated using a filtration membrane, and the adsorbent after decomposition of the hardly decomposable substance is released from the filtration membrane by backwashing the filtration membrane, )
- the adsorbent added in the step (B) is one selected from the group consisting of titanium dioxide, zeolite, acid clay, active clay, diatomaceous earth, metal oxide, metal powder, activated carbon and carbon black.
- the filtration membrane used in the step (C) is composed of an ultrafiltration membrane (UF membrane), a nanofilter membrane (NF membrane), a microfiltration membrane (MF membrane), and a reverse osmosis membrane (R0 membrane).
- UF membrane ultrafiltration membrane
- NF membrane nanofilter membrane
- MF membrane microfiltration membrane
- R0 membrane reverse osmosis membrane
- At least a part of the adsorbent adsorbing the hardly decomposable substance concentrated in the step (A) and Z or the hardly decomposable substance concentrated in the step (C) is treated with water containing the hardly decomposable substance.
- Process (A) or process (C) returned to the process upstream of [1] to [: 13] above
- a second aspect of the present invention provides an apparatus for treating water containing a hardly decomposable substance for carrying out the first aspect of the present invention.
- a membrane filtration processing unit for separating the permeate using a filtration membrane and concentrating the adsorbent adsorbing the hardly decomposable substance
- An apparatus for treating water containing a hardly decomposable substance is provided.
- a reductive substance input unit for introducing a reducible substance that neutralizes free chlorine in the hardly decomposable substance-containing water into the hardly decomposable substance-containing water;
- a membrane concentration treatment unit for separating permeate from water containing a hardly decomposable substance using a reverse osmosis membrane (RO membrane) or a nanofilter membrane (NF membrane) and condensing the hardly decomposable substance,
- RO membrane reverse osmosis membrane
- NF membrane nanofilter membrane
- An adsorbent addition unit for adding an adsorbent to the concentrated hardly decomposable substance, and adsorbing the hardly decomposable substance to the adsorbent;
- a membrane filtration processing unit for separating the permeate using a filtration membrane and concentrating the adsorbent adsorbing the hardly decomposable substance
- a hardly decomposable substance decomposing unit for decomposing the hardly decomposable substance adsorbed on the adsorbent and
- An adsorbent return section for separating the permeate using a filtration membrane and returning the adsorbent after decomposition of the hardly decomposable substance to the adsorbent addition section
- the water-decomposable substance-containing water treatment apparatus comprising:
- a hardly decomposable substance such as dioxin contained in water can be efficiently decomposed and rendered harmless regardless of its concentration.
- chemical decomposition alone with an oxidizing agent, ultraviolet irradiation It is possible to provide a highly reliable treatment system that can efficiently reduce difficult-to-decompose substances contained in water to a lower level by combining photodecomposition alone with water or combining chemical and photolysis. it can.
- the chemical decomposition treatment and / or as described above in which the desorption operation is not performed in the state where the hardly decomposable substance is adsorbed to the solid. Since the adsorbent can be regenerated by photolytic treatment, the adsorbent can be used repeatedly, and the treatment system can be recirculated, and waste is greatly reduced. That power S.
- water containing a hardly decomposable substance can be efficiently and safely treated by a closed system, and the water containing the hardly decomposable substance-containing water is generated. As all treatments are completed, there is no need to transport persistent materials that cause environmental pollution (on-site treatment is possible) and there is no negative impact on the environment.
- FIG. 2 is a flow diagram showing the configuration of a preferred embodiment of the method for treating water containing a hardly decomposable substance according to the present invention.
- FIG. 3 is a flow diagram showing the configuration of one embodiment of the method for treating water containing a hardly decomposable substance of the present invention employing photolysis and chemical decomposition.
- FIG. 4 is a flow diagram showing a configuration of one embodiment of a method for treating water containing a hardly decomposable substance of the present invention employing photolysis.
- FIG. 5 is a schematic diagram of a treatment apparatus for carrying out one embodiment of the method for treating water containing a hardly decomposable substance of the present invention, which employs photolysis and chemical decomposition.
- FIG. 6 is a schematic view of a treatment apparatus for carrying out one embodiment of the method for treating water containing a hardly decomposable substance of the present invention, which employs photolysis.
- FIG. 7 is a schematic diagram showing a configuration of a processing apparatus according to Embodiment 1.
- FIG. 8 is a schematic diagram showing a configuration of a processing apparatus according to a second embodiment.
- FIG. 9 is a schematic diagram illustrating a configuration of a processing apparatus according to a third embodiment.
- FIG. 10 is a schematic view showing a configuration of a processing apparatus according to Embodiment 4.
- FIG. 11 is a schematic view showing a configuration of a processing apparatus according to Embodiment 5.
- FIG. 12 is a schematic view showing a configuration of a processing apparatus according to Embodiment 6.
- the method for treating water containing a hardly decomposable substance which is the first aspect of the present invention (hereinafter referred to as the method of the present invention), comprises the following steps:
- Adsorbent after decomposition of refractory substances (E) Adsorbent after decomposition of refractory substances (B) Process to return to adsorption process (Adsorbent return process)
- the method of the present invention concentrates and removes a hardly decomposable substance contained in water by membrane filtration, and detoxifies it by decomposing the concentrated hardly decomposable substance.
- the decomposition of the hardly decomposable substance is preferably performed by detoxification by chemical decomposition and z or photolysis.
- concentrate the hardly decomposable substance or the adsorbent that has adsorbed the hardly decomposable substance to increase the concentration of the hardly decomposable substance or the adsorbent that has adsorbed the hardly decomposable substance in water containing them.
- Examples of the hardly decomposable substances that can be detoxified by the method of the present invention include dioxins, which are harmful pollutants in the soil and the mouth, and other endocrine disrupting substances and carcinogenic substances. It is done.
- examples of dioxins include halogenated dibenzodioxins and halo.
- halogenated dibenzodioxins include 2, 3, 7, 8 tetrachlorodibenzo_P_dioxin, 1, 2, 3, 7, 8 _pentachlorodibenzomono-P-dioxin, 1, 2 , 3, 4, 7, 8 _Hexachlorodibenzo _P_dioxin, 1, 2, 3, 4, 6, 7, 8 _Heptac mouth Lodibenzo P-dioxin, 1, 2, 3, 4, 6, 7 , 8, 9-Otachlorodibenzo-1-P-dioxin.
- halogenated dibenzofurans examples include 2, 3, 7, 8-tetrachlorodibenzofuran, 1, 2, 3, 7, 8_pentachlorodibenzofuran, 1, 2, 3, 4, 7, 8 _ Hexachlorodibenzofuran, 1,2,3,4,6,7,8-heptachlorodibenzofuran, 1,2,3,4,6,7,8,9-otatachlorodibenzofuran and the like.
- PCBs particularly, cobranner PCBs substituted with a chlorine atom other than the ortho position
- PCBs include 3, 3, 4, 4, 4, 5-tetrachlorobiphenyl, 3, 3 ', 4, 4, 5, 5-pentachlorobiphenyl, 3, 3 ', 4, 4', 5, 5'-hexachlorobiphenyl and the like.
- Endocrine disrupting substances and carcinogenic substances other than dioxins include alkylphenols such as t-ptylphenol, nonylphenol and octylphenol, halogenated phenols such as tetrachlorophenol and pentachlorophenol, and the like.
- 2, 2 Bis (4-hydroxyphenyl) propane (Bisphenol) A 1, 2 Bis (4-hydroxyphenyl) propane (Bisphenol) A, 1-bis) 4-Hydroxyphenyl) Bisphenols such as cyclohexane, benzopyrene, thalylene, benzoanthracene, benzofluoranthene And polycyclic aromatic hydrocarbons such as picene, and phthalic acid esters such as dibutyl phthalate, butyl benzyl phthalate, and di-2-ethylhexyl phthalate.
- the above-mentioned dioxins and PCBs which are difficult to decompose organic halogen compounds such as dichlorobromine, trichloroethane, trichloroethylene, tetrachloroethylene and dichloroethylene, are also photodecomposed or chemically decomposed by the method of the present invention. It can be removed.
- organic halogen compounds such as dichlorobromine, trichloroethane, trichloroethylene, tetrachloroethylene and dichloroethylene
- the method of the present invention includes (B) an adsorption treatment step, (C) a membrane filtration treatment step, (D) a hardly decomposable substance decomposition step, and (E) an adsorbent return step as essential steps.
- A membrane concentration treatment process
- F free chlorine neutralization process
- I volatile substance removal process
- M pre-filtration Step
- N Pre-treatment pH adjustment step
- G Backwash step
- H Solid-liquid separation step
- Permeate neutralization step (ii) Regenerated adsorbent pH adjustment step
- L Two-stage membrane One or more steps selected from the group consisting of filtration treatment steps may be included.
- each of the above steps may be performed only once, or may be performed twice or more. By performing one or more of the above steps a plurality of times, it becomes possible to decompose and remove the hardly decomposable substance to a lower concentration with higher reliability.
- each step will be described with reference to FIG. Further, referring to FIG. 3 which shows a case where photolysis and chemical decomposition are combined, which is a preferred embodiment, and FIG. 4 which shows a case where only photolysis is used, each optional step provided as necessary is also described. explain.
- volatile substances light components with a low boiling point
- they may be adsorbed by the adsorbent and reduce the adsorption efficiency of the persistent substances. This is a process provided to remove this in advance. Therefore, (ii) it is more preferable to remove it before the adsorption process.
- the volatile substance to be removed depends on the water containing the hardly decomposable substance to be treated and is not particularly limited, but generally includes, for example, hydrogen chloride.
- volatile matter for example, distillation, evaporation, publishing with inert gas, or heating (flash) at a temperature at which persistent substances such as dioxins do not volatilize.
- volatile matter is adsorbed on activated carbon or the like and incinerated at a high temperature at which harmful substances can be decomposed.
- This process is provided as necessary to neutralize residual free chlorine in water containing persistent substances. Since residual free chlorine oxidizes and degrades the reverse osmosis membrane, it is desirable to remove it beforehand. Measure the free chlorine concentration with a chlorine concentration meter and add an appropriate amount of reducing substances. Examples of the reducing substance include sodium bisulfite, sodium metabisulfite, sulfur dioxide and the like, and sodium bisulfite is preferable.
- Refractory substance-containing water (treated raw water) or free chlorine after neutralization of free chlorine This is a process provided as needed to adjust the pH of the water. If the pH of water containing persistent substances (treated raw water) or water containing persistent substances after neutralizing free chlorine is low, the filtration membrane used in the subsequent process may be damaged. In order to prevent this, it is preferable to adjust the pH (preferably adjusted to around pH 7) before proceeding to the step of using a filtration membrane.
- the order of pretreatment such as (I) volatile substance removal step, (F) free chlorine neutralization step, (N) pretreatment pH adjustment step and (M) prefiltration step is not particularly limited. Therefore, it should be determined as appropriate according to the water containing raw materials (raw water).
- the (M) pre-filtration step is preferably set immediately before the (A) membrane concentration treatment step, which will be described later, in order to reliably remove solids that may clog the filtration membrane.
- a process that is provided as necessary to separate permeate from water containing persistent substances using reverse osmosis membranes (RO membranes) or nanofilter membranes (NF membranes) and concentrate persistent materials. is there.
- dioxin has a molecular weight of 200 or more and can be separated at the molecular level by a reverse osmosis membrane or a single nanofilter membrane.
- Reverse osmosis membranes and nanofilter membranes do not allow permeation of not only persistent substances but also salts contained in water. Therefore, since the salt is also concentrated at the same time, the osmotic pressure of the concentrated water containing the hardly decomposable substance is increased and the filtration performance is lowered.
- salt includes all kinds of salts contained in water containing persistent substances
- the main salts include sodium salt, sodium metabisulfite or bisulfite, sodium hydrogensulfate and the like. Since sodium chloride is produced when neutralizing residual free chlorine, it is often contained in water containing persistent substances that are to be treated.
- the operating pressure in the membrane concentration treatment with a reverse osmosis membrane is not particularly limited, but is usually a general setting because the higher the operating pressure, the higher the removal rate of persistent substances such as dioxin. It is preferable to operate at a pressure higher than 3 MPa, IMPa or higher, more preferably 1.5 MPa or higher, and 7 MPa or higher when the increase in osmotic pressure due to the above-mentioned salt concentration becomes a problem. Furthermore, in order to operate the reverse osmosis membrane for a long period of time and to prevent a reduction in the removal rate due to the concentration of circulating water, the ratio of the concentrated water to the permeate may be appropriately determined according to the properties of the wastewater. Is in the range of 1:99 to 80:20, preferably 30:70 to 60:40, particularly 50:50.
- the constituent materials of the reverse osmosis membrane include polyamide (including cross-linked polyamide, aromatic polyamide, etc.), aliphatic amine condensate, heterocyclic polymer, cellulose acetate, polyethylene, polyvinyl alcohol Examples thereof include resin materials such as those based on polyether and polyether.
- the membrane form of the reverse osmosis membrane can be an asymmetric membrane or a composite membrane with no particular limitations.
- a flat membrane type As the membrane module, a flat membrane type, a hollow fiber type, a spiral type, a cylindrical (tubular) type, a pre-type, etc. can be appropriately employed.
- Constituent materials of the nanofilter membrane include polyamide-based (including crosslinked polyamide-based aromatic polyamide-based), aliphatic amine condensate-based, heterocyclic polymer-based, acetate cell base Resin materials such as polyethylene, polyvinyl alcohol, and polyether, and inorganic materials such as ceramic.
- the membrane form of the nanofilter membrane is not particularly limited, and can be an asymmetric membrane or a composite membrane, similar to the above-described reverse osmosis membrane.
- a flat membrane type a hollow fiber type, a spiral type, a cylindrical (tubular) type, a pleat type, or the like can be appropriately employed.
- the desalination rate of the reverse osmosis membrane is not particularly limited, but it is preferable to use a salt having a selectivity of approximately 95% or more. If it is a nano filter membrane, It is preferable to use those having a desalination rate of approximately 40% or more. If the salt concentration in the water containing persistent substances is high, a filtration membrane with a low salt rejection (desalting rate) may be selected. Thereby, the concentration of the salt by the circulation treatment can be reduced.
- the liquid (concentrated water) that has not passed through the membrane by the membrane concentration treatment using the reverse osmosis membrane or the nanofilter membrane may be returned to the untreated water containing the hardly decomposable substance.
- the permeate generated in this step can be used as backwash water in the (G) backwash step described later, or can be discharged as discharged water if the concentration of difficult-to-decompose substances is below the discharge standard value.
- the cleaning agent used for cleaning the membrane is not particularly limited, but in general, for example, an aqueous solution of oxalic acid, an aqueous solution of citrate, an aqueous solution of ammonium citrate, an aqueous solution of hydrochloric acid, an aqueous solution of sulfuric acid, a sodium hydroxide solution, an oxidizing agent, Examples thereof include reducing agents and surfactants.
- concentration of the detergent, the adjustment of such P H may be Re be appropriately selected depending on the chemical resistance of the film.
- an adsorbent is added to water containing raw materials that are difficult to decompose (processed raw water) or water concentrated in the step (A), and the hard material is adsorbed to the adsorbent. is there.
- the refractory substance or the water concentrated by the above membrane concentration treatment is used as it is for the (C) membrane filtration treatment step, the amount of the fraction of the filtration membrane relative to the size of the refractory substance such as dioxin will be reduced. Due to its large size, it is impossible to concentrate hardly decomposable substances. For this reason, after adsorbing the adsorbent and adsorbing the fine hardly decomposable substance onto the large adsorbent particles, (C) membrane filtration treatment is performed to concentrate the hardly decomposable substance.
- the adsorbent used in the method of the present invention includes an inorganic porous material and an organic porous material.
- an inorganic porous material such as zeolite, diatomaceous earth, acidic clay, activated clay, carbon black or the like.
- metal oxides such as titanium dioxide
- inorganic adsorbents such as metal powder
- organic porous bodies such as activated carbon and ion exchange resins. These may be used alone or in combination of two or more.
- titanium dioxide having a high adsorption efficiency is particularly preferable among inorganic adsorbents.
- an absorption that can function as a photocatalyst is titanium dioxide.
- the amount of adsorbent added may be appropriately determined in consideration of the type of adsorbent, the adsorption performance, the type and amount of contaminants to be treated, the treatment time and cost, etc., but generally 1 to:! OOOppm 10 ⁇ : OOppm is preferable.
- the amount of the hard-to-decompose substance adsorbed increases as the amount added increases, but the cost increases. Therefore, the amount of titanium dioxide to be added should be selected as appropriate in consideration of the cost, etc., and is usually preferably in the range:! ⁇ 100, OOOppm 10 ⁇ : 1, in the range of OOOppm More preferably.
- an adsorbent having a large specific surface area.
- an X-ray particle size of about 7 nm is preferable.
- the permeate that contains salt but does not substantially contain the hardly decomposable substance is separated by using a filter membrane that does not allow the adsorbent that has adsorbed the hardly decomposable substance to pass but the salt passes, and adsorbs the hardly degradable substance.
- a filter membrane that does not allow the adsorbent that has adsorbed the hardly decomposable substance to pass but the salt passes, and adsorbs the hardly degradable substance
- the type of the membrane used in the membrane filtration treatment is not particularly limited as long as it has the above-mentioned separation performance.
- an ultrafiltration membrane It is preferable to use a UF membrane), a nanofilter membrane (NF membrane), a microfiltration membrane (MF membrane), a reverse osmosis membrane (R0 membrane), or the like.
- an ultrafiltration membrane can sufficiently remove fine adsorbents adsorbing dioxins and the like and fine particles such as dioxin insoluble in water, Good operability and economy.
- Examples of the ultrafiltration membrane (UF membrane) include a porous membrane, an asymmetric membrane, and a composite membrane.
- Constituent materials for the membrane (UF membrane) include resin materials such as cellulose acetate, polyacrylonitrile, polysulfine, and polyethersulfone, and inorganic materials such as ceramic membranes and dynamic membranes.
- a flat membrane type, a hollow fiber type, a spiral type, a cylindrical type, a pleated type and the like can be appropriately employed.
- the molecular weight cutoff of the ultrafiltration membrane is not particularly limited, but a molecular weight of about 3000 to 150000 may be used.
- MF membranes examples include porous membranes, asymmetric membranes, irradiation etching membranes, and ion exchange membranes.
- Constituent materials for microfiltration membranes (MF membranes) include cellulose ester and polyacrylonitrile.
- Resin materials such as polysulfone, polysulfin, and polyethersulfone, and inorganic materials such as ceramic films and metal films.
- a flat membrane, a filter cartridge, a disposer cartridge, a bag filter, etc. may be selected as required.
- the size of the pores (pores) of the microfiltration membrane may be determined as appropriate depending on the particle size of the adsorbent used in the adsorption treatment, but may be about 0.01 to 1 ⁇ .
- RO membrane reverse osmosis membrane
- NF membrane nanofilter membrane
- the filtration membrane used in step (C) is back-washed to release the adsorbent adsorbing the hardly decomposable substance from the filtration membrane.
- the adsorbent that adsorbs the hardly decomposable substance (especially when titanium dioxide is used as the adsorbent) clogs the ultrafiltration membrane.
- the frequency of backwashing may be selected as appropriate. For example, it is preferably about once every 30 to 120 minutes and about 1 to 10 minutes.
- the water to be backwashed is not particularly limited as long as it is clear water that does not contain solid matter. It is economical to use the permeate obtained in the step, (C) the permeate obtained in the membrane filtration step, or the permeate obtained in the (L) two-stage filtration step described later. Especially preferred is (A) Permeate obtained in the membrane concentration treatment step.
- a detergent such as sodium hypochlorite and citrate for washing. It may be added so that the residual free chlorine concentration afterwards falls within the range of 1 to 100 mg / L.
- the water transferred to the (D) difficult decomposable substance decomposing step described later washed out the adsorbent adsorbing the hardly decomposable substance. It is preferable to use only washing wastewater, or if necessary, (A) the hardly decomposable substance concentrated water obtained in the membrane concentration treatment process may be transferred to (D) the hardly decomposable substance decomposing process. Les.
- the force S which is inconvenient to add a flocculant when performing a circulation treatment, may be added when all or part of the adsorbent is discarded as industrial waste.
- an aggregating agent may be added to the liquid containing the adsorbent adsorbing the hardly decomposable substance to promote the aggregation and separation of the adsorbent adsorbing the hardly decomposable substance. More specifically, a flocculant is added to the liquid containing the adsorbent that has adsorbed the hardly decomposable substance concentrated in the step (C) or the backwash waste water obtained in the step (G). By further aggregating the adsorbent adsorbing the degradable substance, an aggregate containing the hardly decomposable substance can be obtained. Aggregates are generally sedimented (sediments), but may also be aggregates that float on the liquid surface (floats).
- The usually the supernatant liquid
- the concentration of persistent substances is below the emission standard value, it may be discharged.
- the flocculant is added in order to shorten the time when the adsorbent that adsorbs the hardly decomposable substance is fine and requires time for solid-liquid separation, and (D) the hardly decomposable substance that follows this. This is done to increase the decomposition efficiency of persistent materials in the decomposition process.
- a flocculant is used, waste will be generated, and it will be difficult to circulate wastewater, so the amount used should be kept to a minimum.
- an inorganic flocculant either an inorganic flocculant or an organic flocculant can be used alone or in combination.
- inorganic flocculants include aluminum sulfate, ferric chloride, ferrous sulfate, polyaluminum chloride, zeolite.
- organic flocculants include various anionic polymer flocculants such as sodium polyacrylate, a copolymer of sodium acrylate and acrylic amide, cationic polymer flocculants and the like, and BRIOZOA as a mixture And silicate polymers.
- the flocculant is not particularly limited as long as it does not adversely affect (D) the decomposition process of the hardly decomposable substance, but it is mainly composed of an inorganic substance capable of obtaining an aggregate having a high bulk density in a small amount. Is preferred.
- the addition amount of the flocculant should be appropriately determined in consideration of the type of flocculant, adsorption performance, cost, etc. 10 to: 1, OOOp pm is preferable. In consideration of reducing the final amount of discharged solids as much as possible, it is preferable that the amount of flocculant is not excessive. To reduce costs, do not use flocculants. Is desirable.
- the adsorbent that has been concentrated in the step (C) and adsorbed the hardly decomposable substance that passed through the photodecomposition step in some cases is solid-liquid separated.
- it is a step provided as necessary in order to increase the chemical decomposition efficiency by reacting the resulting slurry with an oxidizing agent.
- solid-liquid separation means known solid-liquid separation means without particular limitation can be used, and examples thereof include sedimentation of solids, centrifugation, liquid cyclone, filter press and the like.
- the hardly decomposable substance decomposing step includes (D-1) a step of decomposing the hardly decomposable substance adsorbed on the concentrated adsorbent by irradiating with ultraviolet rays (photodecomposition step) and / or (D — 2) It is preferable to carry out a process (chemical decomposition process) in which the hardly decomposable substance adsorbed on the concentrated adsorbent is chemically decomposed with peroxide without desorption from the adsorbent. Yes.
- Detoxification of persistent substances is (D_ l) photolysis process or (D_ 2) chemical decomposition. Only one of the two may be used, but it is preferable to combine the two because it is possible to more stably decompose the hardly decomposable substance to below the emission standard value.
- the water containing the adsorbent adsorbing the hardly decomposable substance is irradiated with ultraviolet rays to decompose the hardly decomposable substance.
- the (D-1) photolysis step can be provided alone as shown in FIG. 4 or in combination with the (D-2) chemical decomposition step as shown in FIG. That is, it decomposes the hardly decomposable substance in water that is not adsorbed by the adsorbent and a part of the hardly decomposable substance adsorbed by the adsorbent.
- the adsorbent used in the present invention is titanium dioxide
- the hardly decomposable substance in water is more efficiently photodegraded by light irradiation (preferably 250 to 380 nm).
- the longer the photolysis is performed the higher the decomposition efficiency.
- a decomposition efficiency of dioxins of about 60 to 70% can be obtained.
- the light used in the photolysis step is preferably ultraviolet light, but it is possible to use a light source such as a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an excimer laser, natural light, or a fluorescent lamp.
- a light source such as a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an excimer laser, natural light, or a fluorescent lamp.
- Adsorbent adsorbing the hardly decomposable substance concentrated in step (C), adsorbent treated in step (D-1), or solid obtained by solid-liquid separation in step (H) (sediment) Or a suspended substance) is a step of chemically degrading a hardly decomposable substance by adding a peroxide.
- the chemical decomposition is performed, the hardly decomposable substance adsorbed by the adsorbent is reacted with the peroxide to the hardly decomposable substance without performing a desorption operation from the adsorbent. Can be decomposed and made harmless without splashing outside.
- the chemical decomposition performed in the step (D-2) refers to decomposition by a general chemical method, and examples thereof include oxidative decomposition and decomposition by free radicals.
- the peroxide that chemically decomposes the hardly decomposable substance may react with the hardly decomposable substance in the form of the compound as it is, or the compound, ion, radical, etc. changed in water. You can react with persistent substances in the form of
- peroxides used as preferred oxidizing agents are permanganate and persulfate.
- persulfate examples include ammonium persulfate, sodium persulfate, potassium persulfate, potassium hydrogen persulfate, lead persulfate, and rubidium persulfate. Particularly preferred are persulfates such as ammonium sulfate, sodium persulfate and potassium persulfate. These can be used alone or in combination of two or more.
- the amount used is preferably 100 times mole or more, more preferably ⁇ 4 to ⁇ 12 times mole, and more preferably based on the number of moles of the hardly decomposable substance adsorbed on the adsorbent. Is selected in the range of 10 7 to: io 1Q times mole.
- the amount of peroxide used was 100 times mol or more of the hardly decomposable substance, it was adsorbed by the adsorbent even if the concentration of the hardly decomposable substance in the water containing the hardly decomposable substance fluctuated.
- Refractory substances can be stably chemically decomposed to below the emission standard value for industrial waste (3,000 pg-TEQ / g).
- the addition method it may be added all at once at the start of the reaction, or it may be added in portions at regular time intervals.
- the amount of peroxide added may be appropriately determined according to the type and concentration of the hardly decomposable organic compound in the material containing the hardly decomposable material, and the type and concentration of the coexisting material.
- Strength When the hardly decomposable substance-containing material is in the form of a solution, it is preferably 100 to 100, OOOppm, particularly preferably 1000 to 50, OOOppm.
- the material containing the hardly decomposable substance is a solid, 0.01 to 100 mass with respect to the material containing the hardly decomposable substance It is particularly preferable to set the ratio to 0.:! To 20% by mass.
- the amount of peroxide added may be determined in consideration of the oxidizing power of persulfuric acid in the case of promoting only the power reaction that varies depending on the pH of the water to be treated.
- peroxide is preferably reacted with a hardly decomposable substance in a dissolved state in water, and other oxidizing agents such as hydrogen peroxide and Let ozone coexist.
- an organic solvent such as hydrocarbons having 2 to 12 carbon atoms such as n-hexane, toluene, xylene, methylphthalene and the like are preferably used.
- an acid such as sulfuric acid may be added in order to generate and react an acid such as excessively acid.
- Persulfate is decomposed by heating to generate a bisulfate ion radical, a sulfate ion radical or a hydroxyl radical, and the ability of this radical to decompose a hardly decomposable substance such as dioxin.
- a hardly decomposable substance such as dioxin.
- there is a limit to stirring which is extremely disadvantageous economically due to the capacity of the decomposition vessel and the viscosity of the slurry. It is preferable to carry out violently as long as it does not occur.
- the reaction temperature at which the hardly decomposable substance adsorbed on the adsorbent is chemically decomposed with peroxide is preferably from room temperature to 100 ° C. More preferably, it is 40 ° C to 100 ° C. Below 40 ° C, decomposition may take a long time.
- the decomposition treatment is preferably performed under the following atmospheric pressure.
- the difficulty of decomposing substances such as dioxin evaporates as the temperature rises as the water evaporates. It is necessary to provide it.
- any heating method such as an electric heating method, a heating water supply method, a steam suction method, a boiler method, etc. can be used.
- care must be taken not to increase the amount of water. If the amount of water becomes too high, the persulfate concentration for the reaction will decrease.
- the chemical decomposition treatment time depends on the treatment temperature and other conditions, and cannot be determined in general, but it is usually about 10 minutes and about 500 hours.
- the regenerated adsorbent returned to the (B) adsorption treatment step is preferably subjected to solid-liquid separation before being returned to the step (B).
- solid-liquid separation By performing solid-liquid separation, the amount of water sent to the step (B) together with the regenerated adsorbent can be reduced.
- the amount of water sent to the step (B) together with the regenerated adsorbent can be reduced.
- the (H) solid-liquid separation step is provided before the (D-2) chemical decomposition step, the amount of water has already been reduced before the decomposition processing of the hardly decomposable substance.
- the solid-liquid separation means that may be returned to the step (B) without performing solid-liquid separation can be any known solid-liquid separation means without particular limitation. Or centrifugal separation, hydrocyclone, filter press, membrane separation, etc., and membrane separation is preferred. Separation unit operation should be selected in view of process economy.
- the water containing the adsorbent after decomposing the difficult-to-decompose substance is subjected to membrane filtration treatment to separate the permeate, and the filtration membrane is backwashed to obtain the free adsorption obtained from the filtration membrane.
- the backwash waste water containing the agent (regenerated adsorbent) is returned to the (B) adsorption treatment step.
- the filtration membrane used in this step should be one that can separate the target adsorbent particles.
- the water containing the adsorbent after chemical decomposition may have a pH of 1 or less, it is preferable to appropriately select a filtration membrane according to the pH.
- the filtration membrane used in this step include an ultrafiltration membrane (UF membrane) and a microfiltration membrane (MF membrane).
- the solid waste containing the adsorbent to be discarded may be extracted and discarded in the process of transferring the adsorbent to the step (B) after the solid-liquid separation in the step).
- This step is provided as necessary to neutralize the permeate separated from the regenerated adsorbent in the step (E).
- the permeate separated in the step (E) may be below pH force due to the oxidant used in the (D-2) chemical decomposition step. Since there is a possibility of adverse effects, neutralization is performed.
- the neutralizing agent used for neutralizing the permeate is not particularly limited as long as it does not adversely affect the environment.
- an aqueous sodium hydroxide solution is preferably used.
- this step is (D-1) only the photolysis step, and is not usually required when (D-2) chemical decomposition step is not provided.
- the pH is adjusted (neutralized) by this step. This is a process provided as necessary to prevent the pH from decreasing cumulatively during the circulation process.
- the pH adjuster used in this step is not particularly limited, but for example, sodium hydroxide aqueous solution A liquid or the like is preferred.
- the discharge standard value is stable. This is a process provided as necessary to reduce the concentration of persistent substances and discharge (release) it to the following.
- the filtration membrane used in this step is preferably a nanofilter membrane (NF membrane).
- NF membrane nanofilter membrane
- the permeate obtained in this step can be discharged as discharged water if it is below the discharge standard value, and can also be used as backwash water used in the (G) backwash step.
- the filtrate collected after separating the permeate in this step is preferably sent to the (B) adsorption treatment step and again subjected to (D) a hardly decomposable substance decomposition step.
- a membrane filtration processing unit for separating the permeate using a filtration membrane and concentrating the adsorbent adsorbing the hardly decomposable substance
- a preferred embodiment of the device of the present invention is:
- a membrane concentration treatment unit for separating permeate from water containing a hardly decomposable substance using a reverse osmosis membrane (RO membrane) or a nanofilter membrane (NF membrane) and condensing the hardly decomposable substance,
- RO membrane reverse osmosis membrane
- NF membrane nanofilter membrane
- An adsorbent addition unit for adding an adsorbent to the concentrated hardly decomposable substance, and adsorbing the hardly decomposable substance to the adsorbent;
- a membrane filtration processing unit for separating the permeate using a filtration membrane and concentrating the adsorbent adsorbing the hardly decomposable substance
- a hardly decomposable substance decomposing unit for decomposing the hardly decomposable substance adsorbed on the adsorbent and
- An adsorbent return section for separating the permeate using a filtration membrane and returning the adsorbent after decomposition of the hardly decomposable substance to the adsorbent addition section
- FIG. 5 shows an example of an apparatus that combines the (D-1) photolysis process and the (D-2) chemical decomposition process.
- Figure 6 shows an example of an apparatus that uses only the (D-1) photolysis process. An example is shown.
- FIG. 5 is a schematic diagram of the treatment apparatus 1 for carrying out one embodiment of the method for treating water containing a hardly decomposable substance according to the present invention, which combines photolysis and chemical decomposition.
- the processing apparatus 1 shown in FIG. 5 includes a membrane concentration processing unit 20, an adsorbent addition unit 30, a membrane filtration processing unit 40, a photolysis processing unit 50, a solid-liquid separation unit 70, a chemical decomposition processing unit 80, and an adsorbent return.
- Part 90 is the basic configuration.
- FIG. 5 further shows a reducing substance input unit 10, a prefilter 13, a volatile substance removal unit 130, an acid neutralization unit 100, a regenerated adsorbent pH adjustment unit 110, and a two-stage membrane filtration treatment provided as necessary.
- Part 120 is listed.
- Water containing hardly decomposable substances such as dioxins is placed in the input tank 11. Free chlorine in the raw water is neutralized by adding sodium bisulfite from the reducing substance supply unit 12 to the charging tank 11 via a pump (not shown). Also, in the input tank 11 The raw water and sodium bisulfite are mixed by stirring means, and the residual free chlorine concentration in the raw water is measured with a chlorine concentration meter (not shown).
- the means for removing volatile substances is not particularly limited, and examples thereof include distillation, evaporation, and publishing with an inert gas.
- Volatile substances removed from water containing persistent substances are adsorbed on an adsorbent such as activated carbon (not shown), and the adsorbent is preferably incinerated at a temperature at which harmful substances decompose.
- an adsorbent such as activated carbon (not shown)
- the water containing the hardly decomposable substance neutralized with sodium bisulfite can pass through the prefilter 13 to remove suspended substances and the like.
- filter membrane material used for the prefilter examples include polypropylene and the like.
- the solid content captured by the prefilter can be discharged to the outside if the content of the hardly decomposable substance is below the emission standard value (300 Opg—TEQ / g). If this is not the case, the pre-filter is back-washed, and the back-wash waste water is introduced into an appropriate step in this process, preferably the photolysis tank 51 or the solid-liquid separation tank 71.
- the water that has passed through the prefilter 13 is sent to the reverse osmosis membrane 22 via a pump (not shown), and membrane treatment is performed by the reverse osmosis membrane 22. Then, it is divided into a permeate that has passed through the reverse osmosis membrane 22 and a liquid (concentrate) that has not passed through the membrane.
- the permeate that has passed through the reverse osmosis membrane 22 can be discharged to the outside if the content of the hardly decomposable substance is equal to or less than the discharge standard value (10 pg_TEQ / L). Further, it can be stored in a backwash water tank 42 of the membrane filtration processing unit 40 described later and used as backwash water for backwashing the ultrafiltration membrane 41.
- the liquid (concentrate) that has not passed through the reverse osmosis membrane 22 is mixed with the water containing the hardly decomposable substance after passing through the prefilter 13. Re Do reverse osmosis membrane treatment.
- the concentrate is retransmitted several times.
- the concentrate that has not passed through the reverse osmosis membrane 22 is sent to the treatment tank 31 disposed in the adsorbent addition section 30. Will follow.
- the adsorbent sent from the adsorbent supply unit 32 via a feeder (not shown) is added to the liquid (concentrate) sent to the processing tank 31.
- the liquid component of the concentrate and the adsorbent are mixed by the stirring means, so that the hardly decomposable substance remaining in the liquid component is efficiently adsorbed to the added adsorbent. It will be.
- titanium dioxide When titanium dioxide is used as the adsorbent, the hardly decomposable substance in the liquid is adsorbed on the adsorbent, and at the same time, the UV lamp is irradiated with ultraviolet rays to photolyze the hardly decomposable substance. You can also. At this time, titanium dioxide as an adsorbent functions as a photocatalyst and promotes photodecomposition of hardly decomposable substances.
- the liquid component (concentrate) to which the adsorbent has been added is subjected to membrane filtration treatment by the ultrafiltration membrane 41 via a pump (not shown) in the membrane filtration treatment unit 40.
- a pump not shown
- the permeate that has passed through the reverse osmosis membrane 22 in the membrane concentration treatment unit 20 may be used as water for backwashing (backwashing water).
- the liquid content of the hardly decomposable substance-containing water to which the adsorbent is added is divided into a permeate and a concentrate (backwash solution).
- the permeate may be discharged to the outside as discharged water or reused as backwash water if the content of the hardly decomposable substance is below the emission standard value (10 pg_TEQ / L).
- UV irradiation unit 50 In the ultraviolet irradiation unit 50, the concentrate (backwash wastewater) that has not passed through the ultrafiltration membrane 41 in the membrane filtration processing unit 40 is sent to the photolysis tank 51, and is stirred by the stirring means while being irradiated by the ultraviolet ray lamp 53. Irradiation may be performed to decompose the hardly decomposable substance. In this ultraviolet irradiation unit 50, hydrogen peroxide solution may be added via a pump (not shown) from the promoter supply unit 52 in order to promote photolysis by ultraviolet rays.
- the adsorbent added in the adsorbent addition section 30 is preferably titanium dioxide that functions as a photocatalyst. By using titanium dioxide, photolytic treatment with high resolution is performed.
- the hardly decomposable substance adsorbed by the adsorbent is solid-liquid separated in the solid-liquid separation tank 71.
- the means for solid-liquid separation is not particularly limited, and any known means may be used. Examples thereof include sedimentation, stretching separation, liquid cyclone, filter press and the like.
- an aggregating agent can be added. However, if a flocculant is added, solid waste is generated, so the amount of flocculant added is small.
- the solid-liquid separation tank 71 is a sedimentation tank, it is preferable to provide a stirring means (not shown) so as not to harden at the bottom and to stir at a gentle rotational speed of about 1 rpm.
- the clear supernatant can be returned to the treatment tank 31 of the adsorbent addition unit 30 or discharged if it is below the emission standard value (10 pg_TEQ / L).
- the clear supernatant can be discharged if it is less than the power returned to the treatment tank 31 of the adsorbent addition unit 30 and the discharge standard value (10pg_TEQZL).
- the adsorbent return section 90 returns the adsorbent after decomposition of the hardly decomposable substance to the adsorbent addition section in order to recycle the adsorbent after decomposition of the hardly decomposable substance (regenerated adsorbent) and circulate the system.
- the permeate is separated using a filtration membrane, and the adsorbent after decomposition of the hardly decomposable substance is washed back by washing the filtration membrane to release the filtration membrane force. At the same time, it is transferred to the adsorbent addition section.
- any filtration membrane may be used as long as it can separate the target adsorbent particles.
- the water containing the adsorbent after chemical decomposition may have a pH of 1 or less, it is preferable to appropriately select a filtration membrane according to the pH.
- the filtration membrane used here include an ultrafiltration membrane (UF membrane) and a microfiltration membrane (MF membrane), and an ultrafiltration membrane (UF membrane) is particularly preferable.
- the pH force S1 of the permeate separated in the adsorbent return unit 90 may be below. Therefore, the permeate is put in the acid neutralization tank 101, the pH of the permeate is measured with a pH measuring device (not shown), and a necessary amount of alkali is supplied from the alkaline supply unit 102 as necessary. Neutralize permeate and discharge as drained water.
- the backwash waste water containing the adsorbent after the permeate is separated may be adjusted to a low pH.
- the backwash effluent placed in a pH adjustment tank 111, shown Shinare by P H measuring device measures the pH of the backwash effluent, if necessary, pH adjusting agent supply unit to pH adjustment Seizai required amount 112, the pH of the backwash wastewater is adjusted, and the backwash wastewater containing the pH-adsorbed adsorbent is returned to the adsorption tank 31.
- the outlet concentration of discharged water after wastewater treatment also changes accordingly, and contains persistent substances at concentrations exceeding the discharge standard value.
- the discharged water may be discharged. However, it takes about one month by the official method and about two weeks by the simplified method to measure the concentration of persistent substances such as dioxin in the discharged water. Really impossible.
- the concentration of the hardly decomposable substance in the raw water varies, the concentration of the hardly decomposable substance in the discharged water is stably kept below the discharge standard value.
- a two-stage membrane filtration treatment unit 120 for membrane filtration treatment of the permeate generated from each step.
- the filtration membrane used here is preferably a nanofilter membrane (NF membrane).
- the environmental standard is such that the concentration of the hardly decomposable substance in the permeate is not more than the emission standard value (10pg-TEQZL) by two or more membrane filtration treatments. It was also confirmed that the value was less than the value (lpg_TEQ / L).
- Table 1 below shows two membrane filtration treatments. Shows the change in the concentration of dioxin in the permeate and the removal rate (%) of dioxin in the permeation solution.
- F membrane F membrane 121, and the permeate can be discharged as discharged water. It is preferable to return the collected material to the adsorption tank 31.
- FIG. 7 shows the configuration of the wastewater treatment apparatus according to Example 1, and details of each process are shown below.
- Contaminated water containing dioxins (dioxin concentration 6500pg-TEQZL) was placed in an adsorption tank with a residence time of 1 hour, diatomaceous earth was added as adsorbent to lOOOppm, and stirred to adsorb dioxins onto diatomaceous earth.
- This decomposition product was filtered through an ultrafiltration membrane (monolith type, molecular weight cut off 150,000). Dioxins concentration transparently liquid at this time was the emission standard value (10 P g_TEQZL) hereinafter in 8Pg_TEQZL.
- the ultrafiltration membrane was backwashed with the permeate in the (C) membrane filtration treatment step to release diatomaceous earth adhering to the ultrafiltration membrane.
- This backwash wastewater is placed in an adsorption tank with a residence time of 1 hour along with contaminated water containing dioxins (treated raw water, dioxin concentration 6500pg—TEQ / L), and (B) adsorption treatment process and (C) membrane filtration treatment process. The same operation was repeated.
- the contaminated water mixed with this adsorbent is filtered through an ultrafiltration membrane (hollow fiber type, molecular weight cut off 150,000), and a part of the liquid that has not passed through the ultrafiltration membrane is hardly decomposed mixed with diatomaceous earth. It was added to contaminated water containing substances and membrane filtration was performed at an operating pressure of 0.3MPA. The concentration of dioxins in the permeate at this time was 3. Opg-TEQ / L, and it was confirmed that the dioxins removal performance almost equivalent to the original could be reproduced.
- Contaminated water containing dioxins (dioxin concentration 6500pg-TEQZL) was placed in an adsorption tank with a residence time of 1 hour, and 15 ppm of titanium dioxide was added as an adsorbent and adsorbed with stirring.
- (C) Membrane filtration process The contaminated water mixed with this adsorbent is filtered through an ultrafiltration membrane (hollow fiber type, molecular weight cut off 150,000), and a part of the liquid that has not passed through the ultrafiltration membrane is hardly decomposed mixed with titanium dioxide. It was added to the contaminated water containing the physical substances, and membrane filtration was performed at an operating pressure of 0.2 MPa. In backwash water of 4 times dioxins concentration had a is less emission standard value (10 P g_TEQ / Hide 8Pg_TEQZL. Ultrafiltration permeate the amount of transmission fluid of this time, 1 minute ultrafiltration membrane Backwash was performed, and this backwash wastewater was used as a concentrate.
- ultrafiltration membrane high fiber type, molecular weight cut off 150,000
- This concentrate was transferred to a photolysis tank (D-1) having a residence time of 24 hours and irradiated with ultraviolet rays (254 ⁇ m).
- the concentration of dioxin in the water and titanium dioxide mixture after irradiation was 500 pg —TEQ / L.
- Contaminated water mixed with this adsorbent is filtered through an ultrafiltration membrane (hollow fiber type, molecular weight cut off 150,000), and a portion of the liquid that has not passed through the ultrafiltration membrane is difficult to mix with titanium dioxide. It was added to contaminated water containing degradable substances, and membrane filtration was performed at an operating pressure of 0.2 MPa. The permeated liquid at this time was 7. Opg-TEQ / L, and it was confirmed that the dioxins removal effect performance was almost the same as the original.
- Contaminated water containing dioxins (dioxin concentration 6500pg-TEQZL) was filtered through a reverse osmosis membrane (spiral type, NaCl rejection 95% by mass). A part of the liquid that does not pass through this reverse osmosis membrane is added to the contaminated water containing persistent substances, and the operating pressure is higher than IMPa. And 2/3 of the raw water amount was used as the permeate. The dioxin concentration in the permeate at this time was lpg-TEQ / L, which was less than the emission standard value (10 pg-TEQ / L). This permeate was combined with the permeate in the (C) membrane filtration treatment step and used as (E) backwash water in the adsorbent return step and (C) backwash water in the membrane filtration treatment step.
- the concentrated solution that was 1/3 of the amount of raw water for membrane concentration treatment in (A) was placed in an adsorption tank having a residence time of 1 hour as in Example 1, and 2000 ppm of activated clay was added as an adsorbent and adsorbed with stirring.
- Example 2 sodium persulfate was added as an oxidizing agent to the slurry of the concentrate containing the activated clay so that the concentration was 10% by mass, and the reaction was carried out at 70 ° C for 7 hours. 950 pg-TEQ / g, which is below the emission standard value (3000 pg-TEQ / g).
- the concentration of dioxins in the liquid part of this decomposition product is 15 pg_TEQZL, which was filtered through an ultrafiltration membrane (monolith type, molecular weight cut off 150,000).
- C The permeate obtained in the membrane filtration process was used as backwash water to release the activated clay adhering to the ultrafiltration membrane.
- B In the adsorption process When the returned activated clay was reused, it was confirmed that almost the same dioxin removal performance could be reproduced.
- Example 4 The configuration of the wastewater treatment apparatus according to Example 4 is shown in FIG. 10, and details of each process are shown below.
- the pretreated dioxin-containing water was filtered through a reverse osmosis membrane (hollow fiber type, NaCl rejection 95 mass%). A portion of the liquid that did not pass through the reverse osmosis membrane was added to contaminated water containing a hardly decomposable substance and filtered at an operating pressure of IMPa or higher. Two-thirds of the raw water was used as the permeate. At this time, the concentration of dioxins in the permeate was 1.3 pg-TEQ / L, which was below the emission standard value (10 pg-TEQ / L).
- the concentrate of contaminated water containing activated clay is filtered through an ultrafiltration membrane (hollow fiber type, 10,000 fraction), and a portion of the liquid that has not passed through the ultrafiltration membrane is mixed with activated clay.
- Membrane filtration was performed at an operating pressure of 0. IMPa.
- the dioxin concentration of the ultrafiltration membrane permeate was 1.8 pg_TEQ / L, which was below the emission standard value (10 pg_TEQ / L).
- a combination of reverse osmosis membrane permeate and ultrafiltration membrane permeate (dioxin concentration is 1.4 P g_TEQZL) is used as the backwash water for the ultrafiltration membrane to limit the solid content attached to the ultrafiltration membrane. Backwash for 4 minutes with the amount of backwash water that is 4 times the amount of the permeated membrane of the outer filtration membrane. Concentrated.
- Example 2 sodium persulfate was added as an oxidizing agent to the concentrated slurry containing the activated clay so that the concentration became 3% by mass (100 mol or more of the hardly decomposable substance). 24 hours, then 3% by weight of sodium persulfate was added and reacted for 24 hours.
- the scale had a dioxin concentration of 350 pg-TEQ / g, which was the emission standard value (3000 pg-TE
- the concentration of dioxins in the liquid part of this decomposition product was 8pg_TEQZL, which was below the emission standard value (10pg – TEQZL).
- Water containing activated clay after chemical decomposition was filtered through an ultrafiltration membrane (monolith type, molecular weight cut off 150,000).
- the permeate from the membrane concentration treatment step and (C) the permeate from the membrane filtration step were combined to form drained water.
- the ultrafiltration membrane was backwashed with a combination of the reverse osmosis membrane permeate and the ultrafiltration membrane permeate to release the activated clay adhering to the ultrafiltration membrane and transferred to the (B) adsorption treatment step.
- B adsorption treatment step.
- the configuration of the wastewater treatment apparatus according to Example 5 is shown in FIG. 11, and details of each process are shown below.
- Contaminated water containing dioxins (dioxin concentration 6500pg—TEQ / L, volatile substance (HC1 150ppm), SS100mg / L), 3% publishing nitrogen gas as inert gas to remove HC1 (process ( I)), and sodium bisulfite as a chemical was stirred and added to 150 mg / L, which is 3 times the amount of free chlorine (step (F)). Since the pH was 4.5, the pH tank (N) was adjusted to pH 7 by adding a 20% by mass sodium hydroxide solution (step (N)). This was passed through a prefilter (tubular type pore diameter 1 ⁇ m) (step (M)).
- Contaminated water containing dioxins that passed through the prefilter was filtered through a reverse osmosis membrane (hollow fiber type, NaCl rejection 95% by mass).
- a reverse osmosis membrane hindered polystyrene membrane
- One portion of the liquid that did not pass through this reverse osmosis membrane Part was added to contaminated water containing dioxins, and filtered at an operating pressure of 2 MPa or higher. 2/3 of the raw water was used as the permeate.
- the dioxin concentration in the permeate at this time was 1.2 pg-TEQ / L, which was less than the emission standard value (10 pg-TEQ / L).
- the concentrate with the amount of raw water of 1Z3 was put into an adsorption tank with a residence time of 1 hour as in Example 1, and diatomaceous earth was added as adsorbent to lOOppm and adsorbed with stirring.
- This concentrate containing diatomaceous earth is filtered through an ultrafiltration membrane (hollow fiber type, 10,000 fraction), and a portion of the liquid that has not passed through the ultrafiltration membrane is contaminated with dioxins mixed with diatomaceous earth. Filtration was carried out at an operating pressure of 0.2 MPa in water.
- the dioxin concentration in the ultrafiltration membrane permeate was 1.5 pg_TEQZL, which was below the emission standard value (lOpg-TEQZL).
- the reverse osmosis membrane permeate and the ultrafiltration membrane permeate were combined into the effluent (dioxin concentration was 1.3 pg—TEQ / L).
- a portion of the discharged water is used as backwash water, and the solid matter adhering to the ultrafiltration membrane is backwashed for 1 minute with a backwash water amount 4 times the amount of the ultrafiltration membrane permeate.
- the concentrate was transferred to a settling tank (H) having a residence time of 12 hours, and the precipitate layer obtained from the bottom was transferred to a chemical decomposition tank. Compared to the case of chemical decomposition without sedimentation, the volume was reduced to 1/10 or less.
- sodium persulfate was added as an oxidizing agent so as to be 5% by mass (100 mol or more of the hardly decomposable substance), and reacted at 70 ° C. for 12 hours.
- the concentration of dioxin in the slurry was 30 pg-TEQ / L including solids.
- the slurry was neutralized to pH 7 with a 20 mass% sodium hydroxide solution in a neutralization tank ti). This was transferred to the adsorption treatment step (B) and reused. When the returned diatomaceous earth was reused, it was confirmed that almost the same dioxin removal performance could be reproduced.
- Example 6 two-stage membrane filtration
- the method of the present invention can be applied to, for example, refractory organic compounds such as dioxins and PCBs contained in industrial wastewater, soil leachate, cleaning wastewater generated in incinerator demolition work, etc. It can be widely used as a treatment method that can be detoxified by chemical decomposition in a closed system and that can stably reduce the concentration of persistent substances in the discharged water below the emission standard value.
- the adsorbent is reused (recycled), it becomes possible to perform a circulating wastewater treatment, and to minimize the amount of waste (discharged solids) generated.
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Abstract
Description
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US11/994,508 US20090223894A1 (en) | 2005-07-14 | 2006-06-30 | Method for treatment of water containing hardly-degradable substance |
CA002611311A CA2611311A1 (en) | 2005-07-14 | 2006-06-30 | Method for treating water containing hardly decomposable substance |
EP06780680A EP1903008A4 (en) | 2005-07-14 | 2006-06-30 | PROCESS FOR TREATING WATER CONTAINING A LOWLY DEGRADABLE SUBSTANCE |
AU2006267697A AU2006267697A1 (en) | 2005-07-14 | 2006-06-30 | Method for treatment of water containing hardly-degradable substance |
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- 2006-06-30 RU RU2008105554/15A patent/RU2008105554A/ru not_active Application Discontinuation
- 2006-06-30 US US11/994,508 patent/US20090223894A1/en not_active Abandoned
- 2006-06-30 KR KR1020087000888A patent/KR20080033260A/ko not_active Application Discontinuation
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Publication number | Priority date | Publication date | Assignee | Title |
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CN104609636A (zh) * | 2015-02-11 | 2015-05-13 | 四川大学 | 一种利用铁锰双相掺杂石墨烯激活单过硫酸盐去除水中内分泌干扰物的方法 |
CN104609636B (zh) * | 2015-02-11 | 2016-05-11 | 四川大学 | 一种利用铁锰双相掺杂石墨烯激活单过硫酸盐去除水中内分泌干扰物的方法 |
Also Published As
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RU2008105554A (ru) | 2009-08-20 |
TW200712006A (en) | 2007-04-01 |
CA2611311A1 (en) | 2007-01-18 |
EP1903008A4 (en) | 2008-09-17 |
EP1903008A1 (en) | 2008-03-26 |
AU2006267697A1 (en) | 2007-01-18 |
CN101223109A (zh) | 2008-07-16 |
JP2007021347A (ja) | 2007-02-01 |
US20090223894A1 (en) | 2009-09-10 |
KR20080033260A (ko) | 2008-04-16 |
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