CN111977833A - Aluminum oxidation wastewater treatment method and method for preparing iron phosphate by using wastewater - Google Patents
Aluminum oxidation wastewater treatment method and method for preparing iron phosphate by using wastewater Download PDFInfo
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- CN111977833A CN111977833A CN201910421185.6A CN201910421185A CN111977833A CN 111977833 A CN111977833 A CN 111977833A CN 201910421185 A CN201910421185 A CN 201910421185A CN 111977833 A CN111977833 A CN 111977833A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 47
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 43
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 40
- 230000003647 oxidation Effects 0.000 title claims abstract description 37
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 17
- 238000004065 wastewater treatment Methods 0.000 title claims description 26
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002505 iron Chemical class 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 13
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 11
- 239000010452 phosphate Substances 0.000 claims abstract description 11
- 239000002699 waste material Substances 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 9
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 6
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 6
- 239000004571 lime Substances 0.000 claims abstract description 6
- 239000008267 milk Substances 0.000 claims abstract description 5
- 210000004080 milk Anatomy 0.000 claims abstract description 5
- 235000013336 milk Nutrition 0.000 claims abstract description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000002244 precipitate Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000005955 Ferric phosphate Substances 0.000 claims description 8
- 229940032958 ferric phosphate Drugs 0.000 claims description 8
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 8
- 238000005273 aeration Methods 0.000 claims description 7
- -1 ferric iron ions Chemical class 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 239000012066 reaction slurry Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 3
- 239000001506 calcium phosphate Substances 0.000 abstract description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 abstract description 2
- 235000011010 calcium phosphates Nutrition 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 239000010802 sludge Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010812 mixed waste Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic 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
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to a method for treating aluminum oxidation wastewater and a method for preparing iron phosphate by using the wastewater, which comprises the steps of taking water from phosphoric acid-containing wastewater which is discharged in a mixed manner in the aluminum oxidation process, adding alkali liquor for neutralization adjustment, setting pH. to be 2.4-3.0, adding a certain amount of iron salt into a next-stage stirring tank, adding an oxidant into the stirring tank, stirring and mixing, and generating iron phosphate precipitation; after separation, the iron phosphate with high purity can be obtained, clear liquid is neutralized by lime milk and is controlled between pH. and 9.5 to 10.5 for secondary precipitation, residual phosphate radical can be precipitated in a calcium phosphate mode, aluminum, fluorine and nickel ions in waste liquid are simultaneously precipitated, mud and water are further separated, the clear liquid is aerated by adding quantitative sodium hypochlorite, ammonia nitrogen in water is blown off after being oxidized, the pH value of effluent falls back to 7 to 9, and finally the effluent can reach the national discharge standard through treatment, and the phosphate is effectively recovered in a precipitation mode.
Description
Technical Field
The invention relates to the field of treatment of aluminum oxidation wastewater, in particular to a method for treating the aluminum oxidation wastewater and a method for preparing iron phosphate by using the aluminum oxidation wastewater.
Background
The existing aluminum oxidation surface treatment process needs to carry out electrolytic polishing and chemical polishing on the surface of the aluminum material, then carries out surface nickel sealing and dyeing, when certain requirements are met on the surface treatment quality, high-concentration phosphoric acid is generally used as a main material and is matched with sulfuric acid and nitric acid for treatment, a large amount of acid liquor is consumed in the whole process due to the active chemical property of aluminum, the waste acid and wastewater amount is large, harmful substances in the wastewater are continuously discharged, the biodegradability of the wastewater is extremely poor, and the overload and collapse of a biochemical system of a subsequent municipal sewage treatment enterprise are caused if the advanced treatment is not thoroughly carried out, so that a serious environmental pollution accident is caused.
The traditional aluminum oxidation wastewater treatment is neutralization with lime powder, coagulation and decoloration. Because of high acidity and high concentration of aluminum ions in the wastewater of the aluminum oxidation process, a large amount of sludge is generated in the traditional method, and the sludge contains heavy metals such as nickel, chromium, copper and the like, so that the sludge must be treated by dangerous solid wastes, the treatment cost is high, and heavy pressure is brought to related enterprises and wastewater treatment. Moreover, with this treatment method, a large amount of high-value phosphoric acid in the wastewater is not effectively utilized.
Disclosure of Invention
The method for treating the aluminum oxidation wastewater and the method for preparing the iron phosphate by using the wastewater effectively solve the problem of treatment of the aluminum oxidation wastewater, and the iron phosphate is prepared by using the phosphoric acid in the wastewater through wastewater treatment, so that waste is changed into valuable. Taking water from the mixed-discharge phosphoric acid-containing wastewater in the aluminum oxidation process, adding waste ammonia water generated in acid mist removal in the aluminum oxidation production process for neutralization regulation, setting pH. to be 2.4-3.0, then adding a fixed amount of ferric salt into a next primary stirring tank, adding an oxidant into the stirring tank, stirring and mixing to generate ferric phosphate precipitate, wherein the precipitate is homogeneous precipitate, the reaction rate is high, other impurities cannot precipitate within the range of pH., after separation, ferric phosphate with higher purity can be obtained, clear liquid is neutralized by lime milk, and is controlled to be pH. -9.5 to 10.5 for secondary precipitation, residual phosphate radical can be precipitated in a calcium phosphate mode, aluminum, fluorine and nickel ions in the waste liquid are synchronously precipitated, further mud and water separation is carried out, the clear liquid is aerated by adding a fixed amount of sodium hypochlorite, ammonia nitrogen in the water is oxidized and then blown off, the pH of the effluent is returned to 7-9, through treatment, the final effluent can reach the national discharge standard, phosphate is effectively recovered in a precipitation mode, the sludge amount containing dangerous solid waste is greatly reduced, the market value of the finally recovered iron phosphate is greatly reduced, the cost of the full-flow wastewater treatment is greatly reduced, and positive benefits can be realized.
The invention comprises the following contents:
an aluminum oxidation wastewater treatment method, comprising the following steps:
step one, leading the waste water containing waste acid liquid from the mixed discharge into a primary neutralization tank, carrying out acid-base neutralization by using alkali liquor, and adjusting the pH value to 2.4-3.5;
step two, introducing the wastewater obtained after neutralization in the step one into a stirring reaction tank, adding ferric salt and an oxidant for catalysis, generating a precipitate, and separating to obtain a supernatant and the precipitate;
step three, introducing the supernatant obtained after neutralization in the step two into a next-stage stirring reaction tank, adding alkali liquor for secondary neutralization, and setting the pH value to be 9.5-10.5; stirring for reaction, and carrying out solid-liquid separation on a reaction product to obtain a precipitate and a supernatant;
adding sodium hypochlorite into the wastewater obtained in the step three to perform ammonia nitrogen removal and COD removal treatment, and performing aeration, wherein the addition amount of the sodium hypochlorite refers to an ammonia nitrogen removal breakpoint chlorination method to perform quantitative addition; the pH of the wastewater after ammonia nitrogen removal falls back to 7.5-9.0.
Preferably, the alkali liquor in the first step of the aluminum oxidation wastewater treatment method is one or more of waste ammonia water, flake caustic soda, soda ash solution, ammonia water or urea which are absorbed by a workshop.
Preferably, in the first step of the aluminum oxidation wastewater treatment method, acid and alkali are used for neutralization, and the pH is adjusted to 2.4-2.8.
Preferably, in the second step of the aluminum oxidation wastewater treatment method, the iron salt is ferrous sulfate, and the oxidant is hydrogen peroxide.
Preferably, in the second-stage neutralization process in the third step of the aluminum oxidation wastewater treatment method, the wastewater is neutralized to pH. value of 5-6 by liquid alkali; then introducing into the next-stage stirring reaction tank, adding lime milk, and setting the pH value to 9.5-10.5.
A method for preparing iron phosphate by adopting the aluminum oxidation wastewater treatment method, wherein the iron salt in the step two is a ferrous salt or a ferric salt;
when ferrous salt is adopted, oxidizing ferrous iron by an oxidant, and generating a precipitate with phosphate radical in the wastewater after the ferrous iron is oxidized into ferric iron ions;
when the ferric salt is adopted, alkali liquor or ammonia water is supplemented in the stage of reaction, and the pH value interval of the reaction is set between 1.8 and 2.2.
Preferably, the ferric salt in the aluminum oxidation wastewater treatment method adopts ferrous salt, the dosage of the ferric salt solution is based on the content of phosphate radicals in wastewater, and the molar ratio of iron to phosphorus is preferably controlled to be 0.8:1-1.2: 1.
Preferably, the oxidizing agent in the aluminum oxidation wastewater treatment method is hydrogen peroxide; the hydrogen peroxide is added in proportion to the amount of the iron salt added, and the molar ratio is (Fe: H)2O2=2: 1-2: 1.5), and the control range is 300mv-500mv by using an ORP meter.
Preferably, an aeration device is adopted to aerate during the second step in the aluminum oxidation wastewater treatment method, part of ferrous iron is oxidized by oxygen in air, and simultaneously, the products of organic matters in the wastewater in the oxidation reaction are blown off.
Preferably, in the separation process of the reaction product in the aluminum oxidation wastewater treatment method, the precipitate is dehydrated by a plate and frame filter press after being pre-concentrated by a sedimentation tank according to the concentration of the precipitated iron phosphate; and (3) for the reaction slurry with higher ferric phosphate content, directly pumping all the slurry obtained by the reaction into a plate-and-frame filter press for mud-water separation without precipitation, and cleaning and drying the obtained mud cake to obtain the ferric phosphate dihydrate.
Detailed Description
The present invention will be described in further detail with reference to examples, which are illustrative of the present invention and are not to be construed as being limited thereto.
Example 1:
1. and introducing the waste water containing the mixed waste acid liquor from the collecting tank into a primary neutralizing tank, performing acid-base neutralization by using alkali liquor and ammonia water, and adjusting pH. -2.4-3.5.
(1) The alkali liquor can be caustic soda flakes, a sodium carbonate solution or alkaline aqueous solutions such as ammonia water and urea, preferably waste ammonia water which absorbs acid mist in a workshop is used for primary neutralization, so that the waste ammonia water is reasonably utilized, and the pollution of volatile ammonia gas to the atmospheric environment is effectively reduced;
(2) the value of the neutralization regulation pH. is set between 2.4 and 3.5, and in order to reduce the precipitation of aluminum ions in the wastewater in the step, pH. is preferably 2.4 to 2.8;
2. and introducing the wastewater after the first-stage neutralization into a stirring reaction tank, adding iron salt and an oxidant for catalysis, thus producing iron phosphate precipitate, separating mud and water to obtain sludge which is high-purity iron phosphate, and greatly reducing the phosphorus content in clear liquid.
(1) The iron salt can be all water-soluble ferrous and ferric salts;
firstly, when ferrous salt is used, adding an oxidant to oxidize the ferrous salt, and generating a precipitate with phosphate radical in the wastewater after the ferrous salt is oxidized into ferric ions;
secondly, when the ferric salt is used, alkali liquor or ammonia water is added in the stage of reaction, and the reaction interval is set between pH. and 1.8-2.2.
In practice, ferrous sulfate is preferably selected, and when the ferrous sulfate is oxidized into ferric sulfate, part of sulfuric acid in the wastewater is also neutralized simultaneously, so that the alkali consumption in subsequent neutralization is reduced;
(2) the filling amount of the iron salt solution is based on the content of phosphate radicals in the wastewater, and the molar ratio of iron to phosphorus is preferably controlled to be 0.8:1-1.2:1 in practice;
(3) the oxidant can be any oxidant capable of oxidizing ferrous iron into ferric iron, and in practice, hydrogen peroxide is preferably used for oxidation catalysis;
firstly, the adding amount of hydrogen peroxide is in direct proportion to the amount of the added iron salt, the molar ratio of the hydrogen peroxide to the iron salt is (Fe: H2O2=2: 1-2: 1.5), and practically, the hydrogen peroxide is controlled by an ORP meter, and the control range is 300mv-500 mv;
and secondly, in the reaction, an optional aeration device is used for aeration, part of ferrous iron is oxidized by using oxygen in the air, and meanwhile, the product of organic matters in the wastewater in the oxidation reaction is blown off, so that the reduction of the concentration of ammonia nitrogen and COD in the wastewater is facilitated.
(4) Performing sludge-water separation, namely performing preconcentration by using a sedimentation tank according to the concentration of the precipitated iron phosphate, and then dehydrating the precipitate by using a plate-and-frame filter press; and (3) for the reaction slurry with higher ferric phosphate content, directly pumping all the slurry obtained by the reaction into a plate-and-frame filter press for mud-water separation without precipitation, and cleaning and drying the obtained mud cake to obtain the ferric phosphate dihydrate. And (5) the clear liquid enters the next stage for treatment.
3. Introducing the dephosphorized clear liquid into a primary stirring reaction tank, adding alkali liquor for secondary neutralization, setting the pH. value to be 9.5-10.5, and precipitating nickel ions, fluorine ions and residual phosphate radicals in the water body;
the two-stage neutralization of the grade can continuously optimize the scheme for reducing the content of the sludge, and the alternatives are as follows: neutralizing the wastewater with liquid caustic soda to pH. value of 5-6; then introducing the mixture into a next-stage stirring reaction tank, adding lime milk, and setting pH. value to 9.5-10.5; the scheme can synchronously precipitate pollutants in the water body and simultaneously reduce inert gypsum precipitates;
and discharging the wastewater after the stirring reaction into a sedimentation tank for sedimentation and solid-liquid separation. And (5) carrying out next denitrification treatment on the clear liquid.
4. And adding sodium hypochlorite into the wastewater neutralized to medium-weak alkalinity for ammonia nitrogen removal and COD removal treatment, and aerating, wherein the addition amount of the sodium hypochlorite in the link needs to be quantitatively added by referring to an ammonia nitrogen removal breakpoint chlorination method. pH. of the waste water after ammonia nitrogen removal falls back to 7.5-9, and a small amount of dissolved aluminum ions in alkaline solution in the water body are synchronously precipitated, so that the aluminum oxidation waste water is subjected to resource recovery and harmless treatment, and the emission can reach the national standard.
In addition, it should be noted that the specific embodiments described in the present specification may differ in the shape of the components, the names of the components, and the like. All equivalent or simple changes of the structure, the characteristics and the principle of the invention which are described in the patent conception of the invention are included in the protection scope of the patent of the invention. Various modifications, additions and substitutions for the specific embodiments described may be made by those skilled in the art without departing from the scope of the invention as defined in the accompanying claims.
Claims (10)
1. A method for treating aluminum oxidation wastewater is characterized by comprising the following steps: the aluminum oxidation wastewater treatment method comprises the following steps:
step one, leading the waste water containing waste acid liquid from the mixed discharge into a primary neutralization tank, carrying out acid-base neutralization by using alkali liquor, and adjusting the pH value to 2.4-3.5;
step two, introducing the wastewater obtained after neutralization in the step one into a stirring reaction tank, adding ferric salt and an oxidant for catalysis, generating a precipitate, and separating to obtain a supernatant and the precipitate;
step three, introducing the supernatant obtained after neutralization in the step two into a next-stage stirring reaction tank, adding alkali liquor for secondary neutralization, and setting the pH value to be 9.5-10.5; stirring for reaction, and carrying out solid-liquid separation on a reaction product to obtain a precipitate and a supernatant;
Adding sodium hypochlorite into the supernatant obtained in the step three to perform ammonia nitrogen removal and COD removal treatment, and performing aeration, wherein the addition amount of the sodium hypochlorite is quantitatively added by referring to an ammonia nitrogen removal breakpoint chlorination method; the pH of the wastewater after ammonia nitrogen removal falls back to 7.5-9.0.
2. The aluminum oxidation wastewater treatment method according to claim 1, characterized in that: and the alkali liquor in the step one is one or more of waste ammonia water, flake caustic soda, soda ash solution, ammonia water or urea for absorbing acid mist in a workshop.
3. The aluminum oxidation wastewater treatment method according to claim 1, characterized in that: neutralizing with acid and alkali in the first step, and adjusting the pH value to 2.4-2.8.
4. The aluminum oxidation wastewater treatment method according to claim 1, characterized in that: in the second step, the ferric salt is ferrous sulfate, and the oxidant is hydrogen peroxide.
5. The aluminum oxidation wastewater treatment method according to claim 1, characterized in that: in the second-stage neutralization process in the third step, the wastewater is neutralized to pH. value of 5-6 by liquid caustic soda; then introducing into the next-stage stirring reaction tank, adding lime milk, and setting the pH value to 9.5-10.5.
6. A method for preparing iron phosphate according to the aluminum oxidation wastewater treatment method of claim 1, characterized in that: the iron salt in the second step is ferrous salt or ferric salt;
When ferrous salt is adopted, oxidizing ferrous iron by an oxidant, generating precipitate with phosphate radical in wastewater after the ferrous iron is oxidized into ferric iron ions, and carrying out solid-liquid separation to obtain an iron phosphate product.
7. The aluminum oxidation wastewater treatment method according to claim 6, characterized in that: the iron salt is ferrous salt, the dosage of the iron salt solution is based on the content of phosphate radicals in the wastewater, and the molar ratio of iron to phosphorus is preferably controlled to be 0.8:1-1.2: 1.
8. The aluminum oxidation wastewater treatment method according to claim 7, characterized in that: the oxidant is hydrogen peroxide; the hydrogen peroxide is added in proportion to the amount of the iron salt added, and the molar ratio is (Fe: H)2O2=2: 1-2: 1.5), and the control range is 300mv-500mv by using an ORP meter.
9. The aluminum oxidation wastewater treatment method according to claim 6, characterized in that: and in the second step, an aeration device is adopted for aeration, part of ferrous iron is oxidized by using oxygen in the air, and meanwhile, products of organic matters in the wastewater in the oxidation reaction are blown off.
10. The aluminum oxidation wastewater treatment method according to claim 6, characterized in that: in the separation process of the reaction product, according to the concentration of the precipitated iron phosphate, the reaction product can be pre-concentrated by using a sedimentation tank, and then the precipitate is dehydrated by using a plate and frame filter press; and (3) for the reaction slurry with higher ferric phosphate content, directly pumping all the slurry obtained by the reaction into a plate-and-frame filter press for mud-water separation without precipitation, and cleaning and drying the obtained mud cake to obtain the ferric phosphate dihydrate.
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