CN116891315A - Method for chromium plating wastewater hazardous waste reduction and chromium mud recycling - Google Patents
Method for chromium plating wastewater hazardous waste reduction and chromium mud recycling Download PDFInfo
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- CN116891315A CN116891315A CN202310851519.XA CN202310851519A CN116891315A CN 116891315 A CN116891315 A CN 116891315A CN 202310851519 A CN202310851519 A CN 202310851519A CN 116891315 A CN116891315 A CN 116891315A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 183
- 239000011651 chromium Substances 0.000 title claims abstract description 131
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 74
- 238000007747 plating Methods 0.000 title claims abstract description 32
- 238000004064 recycling Methods 0.000 title claims abstract description 26
- 230000009467 reduction Effects 0.000 title claims abstract description 24
- 239000002920 hazardous waste Substances 0.000 title claims description 15
- 239000010802 sludge Substances 0.000 claims abstract description 86
- 230000008569 process Effects 0.000 claims abstract description 33
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 29
- 239000002699 waste material Substances 0.000 claims abstract description 19
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 9
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 50
- 238000001914 filtration Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 150000002500 ions Chemical class 0.000 claims description 18
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 15
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 238000004458 analytical method Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 22
- 231100000719 pollutant Toxicity 0.000 abstract description 22
- 238000009713 electroplating Methods 0.000 abstract description 21
- 238000011084 recovery Methods 0.000 abstract description 11
- 239000003403 water pollutant Substances 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 230000009931 harmful effect Effects 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000011027 product recovery Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 11
- 238000003825 pressing Methods 0.000 description 11
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000002910 solid waste Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 5
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000005189 flocculation Methods 0.000 description 5
- 230000016615 flocculation Effects 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-N disulfurous acid Chemical compound OS(=O)S(O)(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000013494 PH determination Methods 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 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
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand 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
- 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
- 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
- C02F1/66—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
- C02F1/70—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
- 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
- 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
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The application relates to a sewageThe method for recycling chromium plating waste water and waste reduction and chromium mud mainly comprises COD degradation, separation and purification of chromium and product recovery, does not need adding of a catalyst ferrous sulfate in the degradation process of organic pollutants in the waste water, has no newly added sludge amount or newly added sludge type in the UV/Fenton treatment process, has no toxic and harmful gas generation, improves the purity of products obtained by recycling the subsequent chromium, and removes Ni from various heavy metal pollutants in the waste water after chromium recovery 2+ The external content can meet the requirements of the water pollutant emission limit value specified in the electroplating pollutant emission standard (GB 21900-2008) Table 2, and the recycling recovery of the heavy metal pollutant chromium is achieved, so that the solid dangerous waste amount in the wastewater treatment process is greatly reduced.
Description
Technical Field
The application relates to the field of sewage treatment and resource recovery, in particular to a method for chromium plating wastewater hazardous waste reduction and chromium mud recycling.
Background
The chromium plating process has wide application, and the chromium plating process mainly has the functions of decoration, corrosion resistance and the like, such as the chromium plating of door handles, logos, grids and the like of automobiles or the chromium plating of plastics and hardware, the chromium plating of the surfaces of mechanical parts is used for improving the wear resistance, the chromium plating of the inner bores of guns and the like is used for improving the wear resistance and the ablation resistance, the chromium plating process can generate chromium electroplating wastewater, and the main heavy metal pollutants in the chromium electroplating wastewater are used for removing Cr according to the difference of plated parts 6+ Cr 3+ Besides Fe 3+ 、Cu 2+ 、Ni 2+ Zn (zinc) 2+ Etc., cr 6+ Is the strongest carcinogen in metal ions. The COD (chemical oxygen demand ) value of wastewater is usually not high, but organic pollutants in wastewater are difficult to degrade due to oxidation resistance.
The common method for chromium removal of chromium plating wastewater is to adopt a reducing agent to remove Cr in the wastewater 6+ Reduction to Cr 3+ And then regulating the pH value of the wastewater to alkaline precipitation. Cr in the wastewater due to the electroplating additive in the chromium plating process 3+ And the rest of heavy metal ions Cu 2+ Even Fe 3+ And the pH value is difficult to be directly reduced to meet the highest emission limit requirement of the heavy metal ions in the ' electroplating pollutant emission standard ' (GB 21900-2008) '. After the reduction and reprecipitation treatment process, a large amount of chromium-containing sludge is formed, the chromium-containing sludge is used as a dangerous waste which is difficult to treat, the treatment cost is high, and enterprises with dangerous waste treatment qualification are generally unwilling to treat.
Another treatment contains Cr 6+ The method of wastewater is to recycle. Cr recovery 6+ The most direct method is to use anion exchange resin for exchange and then recycle the recovered product to electroplating. Years of research prove that the ion exchange resin is due to Cr 6+ Rapid oxidation rejection resulting in recovery of Cr by ion exchange 6+ Is a dead road; another recovery method is to form PbCrO first 4 Or BaCrO 4 After precipitation H is obtained by treatment with sulfuric acid 2 Cr 2 O 7 Or CrO 3 The product recovered by this method is recycled to the plating to seriously affect the quality of the plated product and is not acceptable to the chromium plating manufacturer. The other recycling methods for chromium-containing wastewater are not practical due to high cost or low purity of the recycled product, and the application provides a method for dangerous waste reduction of chromium-containing wastewater and recycling chromium mud to solve the problems.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the application provides a method for chromium plating wastewater hazardous waste reduction and chromium mud recycling, which does not need adding of a catalyst ferrous sulfate in the process of degrading organic pollutants in wastewater, has no newly increased sludge amount or newly increased sludge variety in the UV/Fenton treatment process, has no toxic and harmful gas generation, and obtains the purity of the product obtained by recycling the subsequent chromiumImprove, remove Ni from various heavy metal pollutants in the wastewater after chromium recovery 2+ The external content can meet the requirements of the water pollutant emission limit value specified in the electroplating pollutant emission standard (GB 21900-2008) Table 2, and the recycling recovery of the heavy metal pollutant chromium is achieved, so that the solid dangerous waste amount in the wastewater treatment process is greatly reduced.
(II) technical scheme
In order to achieve the above purpose, the present application provides the following technical solutions: the chromium plating waste water dangerous waste reduction method is characterized by comprising the following steps:
1) Collecting chromium-containing wastewater, analyzing the COD value of the wastewater, and calculating the required hydrogen peroxide amount V according to the measured COD value (g/L) 1 (the unit is L/m 3 Or L/ton);
2) The collected chromium-containing wastewater is discharged into a UV/Fenton treatment system after the COD value is measured, and the pH value of the wastewater in the UV/Fenton treatment system is adjusted 4 The value is adjusted to 3-10 according to V 1 And calculating the volume or weight of the waste water collected by the UV/Fenton treatment system to obtain the required added hydrogen peroxide V (the unit is L), starting a UV lamp of the UV/Fenton treatment system, and adding hydrogen peroxide into the waste water in the UV/Fenton treatment system, wherein the added hydrogen peroxide is V;
3) After the UV lamp is started for a certain time, adding alkali into the UV/Fenton treatment system until the pH value of wastewater in the system is reached 5 Adding a sufficient amount of NaClO into the UV/Fenton treatment system after the alkali addition is finished until the value is between 4 and 13, and then continuously starting the UV lamp for a certain time, wherein the total starting time of the UV lamp is 0.5 to 10 hours;
4) After the UV lamp is turned off, the wastewater in the UV/Fenton treatment system is discharged to the filtering system 1, the wastewater filtered by the filtering system 1 is added with a certain reducing agent SP for reduction, and the pH of the reduced wastewater is adjusted 6 The value is adjusted to be between 5 and 13, and the sludge filtered by the filtering system 1 is additionally treated;
5)pH 6 after the adjustment is completed, the wastewater is discharged to a filter system 2, the concentrated sludge in the filter system 2 is washed for 1 to 10 times by adopting clear water, clear water filtered by the filter system 2 is additionally treated, and the cleaned sewage in the filter system 2The sludge is discharged into a sludge filter pressing system, and the sludge is formed into dry sludge through filter pressing of the sludge filter pressing system.
Preferably, the pH is 6 The preferred value of the value range is between 6 and 9, the pH value 5 The preferred value of the value range is between 8 and 10.
Preferably, the preferred value of the number of times of concentrated sludge cleaning in the filtering system 2 is 2-4, and the sludge press filtration system is a high-pressure diaphragm type plate-and-frame filter press.
Preferably, the COD value analysis method is as follows:
1) Firstly taking a proper amount of chromium-containing wastewater and measuring the pH value of the wastewater 1 Value and Cr 6+ The content a (g/L) is measured, and the total chromium content b (g/L) and the content of other heavy metal ions in the chromium-containing wastewater are measured;
2) Determination of Cr in wastewater 6+ Adding sufficient reducing agent GV according to the proportion after the content;
3) After GV is added, stirring the wastewater until GV is dissolved, and adding a proper amount of acid or alkali into the wastewater to adjust the pH of the wastewater after GV is dissolved 2 Value to proper value, pH 2 After the value adjustment is finished, standing the wastewater for 10-500min;
4) After the standing time is over, adding a proper amount of alkali into the wastewater to adjust the pH value of the wastewater 3 A pH of between 9 and 14 3 After the adjustment is finished, filtering the wastewater;
5) After the wastewater is filtered, the COD value of the wastewater is analyzed and measured.
Preferably, the GV is ferrous sulfate (FeSO 4 ·7H 2 O), the addition amount of the ferrous sulfate is calculated according to the following formula:
m ≥ 5.4 × a (1)
in the formula (1), m is FeSO which needs to be added in each liter of water 4 ·7H 2 The amount of O is given in units of: g/L, V 1 The calculation is carried out according to the following formula:
V 1 ＝ p × COD (2)
the value range of p is 0.5-9.
Preferably, the preferred value of the p value range is between 2.8 and 5.6.
Preferably, the mass percentage content of the sodium hypochlorite is 10%, and the addition amount of the NaClO is calculated according to the following formula:
V 2 ＝ q × (b – a) (3)
in the formula (3), the units of b and a are g/L and V 2 Is L/m 3 I.e. the volume of sodium hypochlorite to be added per cubic meter or ton of water;
in the formula (3), q is a coefficient, and the value range of q is 9-11.
Preferably, the preferred value of the q value range is between 9.3 and 10.2.
The dry sludge prepared by the method can be subjected to chromium sludge recycling treatment, and particularly, the dry sludge filtered by the sludge press filtration system can be finally prepared into different finished products according to different treatment processes.
(III) beneficial effects
Compared with the prior art, the application provides a method for chromium plating wastewater hazardous waste reduction and chromium mud recycling, which has the following beneficial effects:
1. by utilizing the original Fe in the wastewater 3+ As the catalyst in the UV/Fenton treatment process, no additional catalyst is needed in the UV/Fenton treatment process, and no new sludge is added, because of the original Fe in the wastewater 3+ The UV/Fenton reaction speed is high due to the high content, and the reaction can be completed within 30 minutes, so that the equipment investment is low;
2. after UV/NaClO treatment, cr existing in the wastewater 3+ Oxidized to Cr 6+ The method can avoid the loss of chromium in the subsequent treatment process, and for the possibly mixed cyanide in the chromium plating wastewater, the UV/NaClO can realize high-efficiency and rapid cyanide breaking, and most of organic pollutants in the wastewater and the possibly mixed cyanide are removed through the two-stage oxidation of UV/Fenton- & gtUV/NaClO, thereby being beneficial to the subsequent precipitation and removal of Cu in the wastewater 2+ 、Ni 2+ The separation of impurity ions and chromium is realized by the equal heavy metal pollutants, so that the purity of the finally prepared chromium-containing compound is effectively improved;
3. recycling and recovering heavy metal pollutant chromium in wastewater, so that solid dangerous waste generated in the process of treating the chromium electroplating wastewater is reduced by more than 99%, and the sludge disposal cost is reduced;
4. the indexes of various pollutants in the treated wastewater are effectively reduced, and the subsequent treatment or discharge is facilitated.
Drawings
FIG. 1 is a schematic flow chart of the present application.
Detailed Description
The technical solutions of the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Referring to FIG. 1, the application provides a method for reducing chromium plating wastewater hazardous waste, which aims to treat the chromium plating wastewater and reduce various heavy metal pollutants in the chromium plating wastewater, mainly comprises COD degradation and separation and purification of chromium, and in a specific implementation process, firstly, the chromium-containing wastewater needs to be collected and analyzed for COD value, and the required hydrogen peroxide amount V is calculated according to the measured COD value (in g/L) 1 (the unit is L/m 3 Or L/ton), the collected chromium-containing wastewater is discharged into a UV/Fenton treatment system after the COD value is measured, and the pH value of the wastewater in the UV/Fenton treatment system is measured 4 The value is adjusted to 3-10 according to V 1 And calculating the volume or weight of the waste water collected by the UV/Fenton treatment system to obtain the required added hydrogen peroxide quantity V (the unit is L).
The COD value analysis method comprises the following steps:
1) Firstly taking a proper amount of chromium-containing wastewater and measuring the pH value of the wastewater 1 Value and Cr 6+ The content a (g/L) is measured, and the total chromium content b (g/L) and the content of other heavy metal ions in the chromium-containing wastewater are measured;
2) Determination of Cr in wastewater 6+ After the content, adding enough reducing agent GV according to the proportion, wherein GV is a substance which does not or is not easy to interfere with the measurement of COD value;
3) After GV is added, stirring the wastewater until GV is dissolved, and adding a proper amount of acid or alkali into the wastewater to adjust the pH of the wastewater after GV is dissolved 2 Value to proper value, pH 2 After the value adjustment is finished, standing the wastewater for 10-500min;
4) After the standing time is over, adding a proper amount of alkali into the wastewater to adjust the pH value of the wastewater 3 A pH of between 9 and 14 3 After the adjustment is finished, filtering the wastewater;
5) After the wastewater is filtered, the COD value of the wastewater is analyzed and measured.
GV is ferrous sulfate (FeSO) 4 ·7H 2 O), the addition amount of ferrous sulfate is calculated according to the following formula:
m ≥ 5.4 × a (1)
in the formula (1), m is FeSO which needs to be added in each liter of water 4 ·7H 2 The amount of O is given in units of: g/L, V 1 The calculation is carried out according to the following formula:
V 1 ＝ p × COD (2)
the value range of p is between 0.5 and 9, and the preferred value of the value range of p is between 2.8 and 5.6.
After the UV/Fenton treatment system calculates the required added hydrogen peroxide amount V, a UV lamp of the UV/Fenton treatment system is started, hydrogen peroxide is added into the wastewater in the UV/Fenton treatment system, and the added hydrogen peroxide amount is V.
The method for calculating the addition amount of the hydrogen peroxide comprises the following steps:
v 0 ＝ 13.241 × COD × n (4)
in the formula (4), the unit of COD is g/L, n is a coefficient, the value of n is in the range of 0.06-0.4, v in the formula (4) 0 Is L/m 3 Or L/t;
calculating the adding amount of hydrogen peroxide by combining the effective volume in the UV/Fenton treatment system:
V ＝ U × v 0 (5)
the result V calculated by the calculation formula (5) is the volume of hydrogen peroxide to be added in the oxidation pond, and the unit is: l.
After the UV lamp is started for a certain time, the UV lamp is thrown into the UV/Fenton treatment systemAdding alkali until the pH of the wastewater in the system 5 And after the alkali addition is finished, adding a sufficient amount of NaClO into the UV/Fenton treatment system, and then continuously starting the UV lamp for a certain time, wherein the total starting time of the UV lamp is 0.5-10h.
Wherein, the mass percentage content of sodium hypochlorite is 10%, and the addition amount of NaClO is calculated according to the following formula:
V 2 ＝ q × (b – a) (3)
in the formula (3), the units of b and a are g/L and V 2 Is L/m 3 I.e. the volume of sodium hypochlorite to be added per cubic meter or ton of water;
in the formula (3), q is a coefficient, the value range of q is 9-11, and the preferred value of the value range of q is 9.3-10.2.
After the UV lamp is turned off, the wastewater in the UV/Fenton treatment system is discharged to the filtering system 1, the wastewater filtered by the filtering system 1 is added with a certain reducing agent SP for reduction, and the pH of the reduced wastewater is adjusted 6 The value is adjusted to 5-13, and the sludge filtered by the filtering system 1 is additionally treated.
pH 6 After the adjustment is finished, the wastewater is discharged to a filter system 2, concentrated sludge in the filter system 2 is washed for 1-10 times by adopting clear water, clear water filtered by the filter system 2 is additionally treated, the cleaned sludge in the filter system 2 is discharged into a sludge press filtration system, the sludge is press-filtered by the sludge press filtration system to form dry sludge, the optimal value of the times of cleaning the concentrated sludge in the filter system 2 is 2-4, and the sludge press filtration system is a high-pressure diaphragm type plate-and-frame filter press.
During the above treatment, pH 5 The preferred range of (2) is determined through experiments, and experiments are carried out on certain wastewater, wherein the experimental process is as follows: after the UV lamp is started for a certain time, taking a certain volume of wastewater in the UV/Fenton treatment system, and dividing the obtained wastewater in the UV/Fenton treatment system into a plurality of groups; adding alkali into several groups of waste water respectively to regulate pH value of waste water 5 A value; after the pH adjustment of the wastewater of the groups is finished, standing the wastewater of the groups for 10-100min respectively; after the standing time of the wastewater of the groups is over, filtering the wastewater of the groups respectively; after filtering several groups of waste water, respectively measuring heavy metal ion content of several groups of waste waterThe amounts of heavy metal ions in several groups of wastewater are shown in Table 1 below, and pH was determined from the data of the following table 5 Preferred value ranges for the values.
TABLE 1 heavy metal ion content and pH 7 Relation of (2)
Note that: N/A indicates that the detection limit of the instrument is lower (1 mug/L)
pH 5 The preferred value range of (2) is pH at which the content of heavy metal ions other than total chromium is the lowest 6 The pH value was found by comparing the data in Table 1 5 Is preferably in the range of 8-10.
The dry sludge prepared by the method can be subjected to chromium sludge recycling treatment, so that the purpose of recycling the chromium sludge is achieved while the pure chromium-containing compound is obtained by low-cost recovery, and particularly, the dry sludge filtered by the sludge filter pressing system can be finally prepared into different finished products according to different treatment processes, wherein the treatment process can be selected from one of the following:
dissolving the dry sludge by hydrochloric acid, evaporating and crystallizing the solution obtained by dissolving the dry sludge to obtain an industrial product chromium chloride (CrCl) 3 ·6H 2 O)；
The dry sludge is dissolved by nitric acid, and the solution obtained by dissolving the dry sludge is evaporated and crystallized to obtain the industrial product chromium nitrate (Cr (NO) 3 ) 3 ·9H 2 O)；
Calcining the dry sludge at high temperature to obtain chromium oxide solid, and ball-milling the chromium oxide solid to obtain chromium oxide green pigment;
the dry sludge is subjected to sludge drying treatment, and then the anhydrous chromium sludge is directly sold as a product;
dissolving the dry sludge with concentrated sulfuric acid, adding sufficient oxidant to obtain A, and processing according to different purposes to obtain Cr-containing sludge 6+ The product of (C) is directly sold or is reused as a raw material of electroplating hard chromium.
The method is used for degrading organic pollutants in wastewater, the addition of a catalyst ferrous sulfate is not needed in the degradation process, the newly increased sludge amount and the newly increased sludge types are not generated in the UV/Fenton treatment process, toxic and harmful gases are not generated, the COD value is degraded in advance, the precipitation removal of various heavy metal impurity ions in the later stage is facilitated, the method is beneficial to the purification of wastewater pollutants, and the purity of the product obtained by recycling and recycling the subsequent chromium is improved.
Ni is removed from various heavy metal pollutants in wastewater after chromium recovery 2+ The external content can meet the requirements of the discharge limit value of water pollutants specified in the discharge standard of electroplating pollutants (GB 21900-2008) Table 2, the COD value and the content of heavy metal pollutants are reduced, the subsequent treatment of wastewater is facilitated, the purity of the finally recovered chromium compound can meet the requirements of the purity of general chemical raw materials or electroplating raw materials after treatment, and the recycling recovery of the heavy metal pollutants chromium is realized, so that the solid dangerous waste amount in the wastewater treatment process is greatly reduced.
Experimental example 1:
long Fuzhen A certain electroplating wastewater treatment Limited company collects 960m of chromium-containing electroplating wastewater every day 3 The effective volume of the wastewater collection tank is 393.9m 3 The original treatment process adopts the traditional treatment process: waste water collection, acid-base regulation, reduction, acid-base regulation, flocculation precipitation, and Cr-containing after flocculation precipitation 3+ The sludge is subjected to steps such as filter pressing and the like, is subjected to hazardous waste treatment, is subjected to flocculation and precipitation, is subjected to a series of treatment, and is mixed with other electroplating wastewater to be treated after removing heavy metal ions which cannot be removed by conventional treatment and precipitation.
The system is reformed by adopting the method of the application, and two sets of ultrafiltration systems and one set of UV/Fenton treatment system (the treatment capacity is 80 m) 3 ) The sludge filter-pressing system is a set, the other pH meters and the like, and the chromium-containing sludge obtained after sludge reduction and recycling is directly sold according to products after drying.
The specific treatment process is as follows:
(1) The chromium-containing wastewater is collected and analyzed for COD value, and the COD value analysis method comprises the following steps:
A. firstly takingAppropriate amount of chromium-containing wastewater and determination of pH of wastewater 1 Cr 6+ A, determining the total chromium content b and the content of other heavy metal ions in the chromium-containing wastewater;
B. after the wastewater is filtered, the COD value of the wastewater is analyzed and measured according to the method of the application, and the required hydrogen peroxide amount V is calculated according to the measured COD value and b 1 ＝0.53L/m3；
(2) The collected chromium-containing wastewater is discharged into a UV/Fenton treatment system after the COD value is measured, and the wastewater UV/Fenton treatment system collects 80m 3 After the wastewater, the pH value of the wastewater in the UV/Fenton treatment system 4 The value is adjusted to 3-5;
(3) According to V 1 And calculating the quantity V of the hydrogen peroxide required to be added according to the volume of the wastewater collected by the UV/Fenton treatment system;
(4) After the pH value of the wastewater in the UV/Fenton treatment system is regulated, starting a UV lamp of the UV/Fenton treatment system, and adding hydrogen peroxide into the wastewater in the UV/Fenton treatment system after the UV lamp is started, wherein the adding amount of the hydrogen peroxide is 28L;
(5) After the hydrogen peroxide is added for 30min, adding alkali into the UV/Fenton treatment system until the pH value of wastewater in the system is reached 5 A value between 8 and 10;
(6)pH 5 after the adjustment is finished, adding sodium hypochlorite into the wastewater, wherein the adding amount of the sodium hypochlorite is 510L;
(7) After the sodium hypochlorite is added, continuously starting a UV lamp for 30min; after the starting time of the UV lamp is over, the UV lamp is turned off;
(8) After the UV lamp is turned off, discharging the wastewater in the UV/Fenton treatment system to the filtering system 1;
(9) The wastewater filtered by the filtering system 1 is added with a certain amount of pyrosulfurous acid (Na 2 S 2 O 5 ) Reducing, and the pH of the reduced wastewater is adjusted 6 The value is adjusted to be 8-9, and the sludge filtered by the filtering system 1 is additionally treated;
(10)pH 6 after the adjustment is completed, the wastewater is discharged to a filter system 2, the concentrated sludge in the filter system 2 is washed 3 times by clean water, and the washed sludge in the filter system 2 is discharged to a sludge press filtration systemThe clean water filtered by the filtering system is mixed with other electroplating wastewater and then enters the original biochemical system;
(11) And after the dried sludge is subjected to sludge drying treatment, analyzing and testing the content of various components in the sludge.
The raw water pollutant content is shown in the following table 2, the clear water pollutant content after filter pressing is shown in the following table 3, and the impurity content in the chromium mud is shown in the following table 4:
TABLE 2 raw water contaminant content
Wherein:
1 determination of chemical oxygen demand of Water dichromate (HJ 828-2017), determination was performed according to the method described in the patent of the present application;
2 determination of hexavalent chromium in water flow injection-dibenzoyl dihydrazide photometry (HJ 908-2017);
3 calculating the difference between the total chromium content and hexavalent chromium;
4 atomic absorption spectrophotometry for measuring copper, zinc, lead and cadmium in water (GB 7475-1987);
5 determination of Nickel in Water flame atomic absorption Spectrophotometry (GB 11912-1989);
6 flame atomic absorption spectrophotometry for determination of iron and manganese in water (GB 11911-1989).
TABLE 3 clear water contaminant content after pressure filtration
Wherein:
* N/A indicates that the concentration is below the detection limit of the instrument (1. Mu.g/L)；
7 Determination of chromium in Water flame atomic absorption Spectrophotometry (HJ 757-2015).
TABLE 4 impurity content in chromium mud
Wherein:
8 gravimetric determination of solid waste moisture and dry matter content (HJ 1222-2021);
9 determination of solid waste nickel and copper flame atomic absorption spectrophotometry (HJ 751-2015);
10 determination of solid wastes lead, zinc and cadmium flame atomic absorption spectrophotometry (HJ 786-2016).
According to the detection data, the clean water after filter pressing has greatly reduced pollutants and Ni removal 2+ Besides the content, the content of the rest heavy metal ions meets the requirements of the electroplating pollutant emission standard (GB 21900-2008) and the highest emission limit value specified in Table 3, the COD value of the wastewater is reduced to a certain extent, the subsequent treatment is facilitated, the content of various heavy metal pollutants in the anhydrous chromium mud can meet the requirements of general enterprises on recycling purchase, and the anhydrous chromium mud can be directly sold as a product.
In the original sewage treatment process of the company, chromium-containing waste water generates about 200-300 tons of chromium-containing hazardous waste every year, the amount of the hazardous waste generated per year is close to 1 ton after the method is adopted for transformation, the hazardous waste is reduced by more than 99.5 percent before and after transformation, no other solid waste or hazardous waste is newly added in the treatment process, and the reduction and recycling of the hazardous solid waste are realized.
Experimental example 2:
the electroplating wastewater station of a certain industrial limited company of the sand well collects the chromium-containing electroplating wastewater 180m each day 3 The effective volume of the wastewater collection tank is 200m 3 The original treatment process adopts the traditional treatment process: waste water collection, acid-base regulation, reduction, acid-base regulation, flocculation precipitation and flocculationPrecipitated Cr-containing 3+ And finally, carrying out filter pressing and the like on the sludge, carrying out flocculation precipitation on clear water according to dangerous waste treatment, carrying out a series of treatment on the clear water, removing heavy metal ions which cannot be removed by conventional process treatment precipitation, mixing the heavy metal ions with other electroplating wastewater, and then, carrying out treatment on the mixed water in a biochemical system.
The system is reformed by adopting the method of the application, and two sets of ultrafiltration systems and one set of UV/Fenton treatment system (the treatment capacity is 6 m) 3 Each time) and one set of evaporation crystallization equipment, one set of sludge press filtration system, a plurality of other pH meters and the like, and the chromium-containing sludge obtained after sludge reduction and recycling is sold according to chemical products after being treated.
The specific treatment process is as follows:
(1) The chromium-containing wastewater is collected and analyzed for COD value, and the COD value analysis method comprises the following steps:
A. firstly taking a proper amount of chromium-containing wastewater and measuring the pH value of the wastewater 1 Cr 6+ A, determining the total chromium content b and the content of other heavy metal ions in the chromium-containing wastewater;
B. after the wastewater is filtered, the COD value of the wastewater is analyzed and measured according to the method of the application, and the required hydrogen peroxide amount V is calculated according to the measured COD value and b 1 ＝1.456L/m3；
(2) The collected chromium-containing wastewater is discharged into a UV/Fenton treatment system after the COD value is measured, and the wastewater UV/Fenton treatment system collects the wastewater of 5m 3 After the wastewater, the pH value of the wastewater in the UV/Fenton treatment system 4 The value is adjusted to 3-5;
(3) According to V 1 And calculating the quantity V of the hydrogen peroxide required to be added according to the volume of the wastewater collected by the UV/Fenton treatment system;
(4) After the pH value of the wastewater in the UV/Fenton treatment system is regulated, starting a UV lamp of the UV/Fenton treatment system, and adding hydrogen peroxide into the wastewater in the UV/Fenton treatment system after the UV lamp is started, wherein the adding amount of the hydrogen peroxide is 7.28L;
(5) After the UV lamp is started for a certain time, adding alkali into the UV/Fenton treatment system until the pH value of wastewater in the system is reached 5 A value between 9 and 10;
(6) The total time for starting the UV lamp is 40min, and after the starting time of the UV lamp is over, the UV lamp is turned off;
(7) After the UV lamp is turned off, discharging the wastewater in the UV/Fenton treatment system to the filtering system 1;
(8) The wastewater filtered by the filtering system 1 is added with a certain amount of pyrosulfurous acid (Na 2 S 2 O 5 ) Reducing, and the pH of the reduced wastewater is adjusted 6 The value is adjusted to be 8-9, and the sludge filtered by the filtering system 1 is additionally treated;
(9)pH 6 after the adjustment is completed, the wastewater is discharged to the filtering system 2;
(10) The concentrated sludge in the filtering system 2 is washed 3 times by clean water, the washed sludge in the filtering system 2 is discharged into a sludge press filtration system, and the clean water filtered by the filtering system is mixed with other electroplating wastewater and then enters an original biochemical system;
(11) And after the dried sludge is subjected to sludge drying treatment, analyzing and testing the content of various components in the sludge.
The raw water pollutant content is shown in the following table 5, the clear water pollutant content after filter pressing is shown in the following table 6, and the technical indexes of the product after evaporation and crystallization are shown in the following table 7:
TABLE 5 raw water contaminant content
Wherein:
1 determination of chemical oxygen demand of water dichromate (HJ 828-2017), determination method was performed according to the method described in the patent of the application;
2 determination of chromium in water flame atomic absorption spectrophotometry (HJ 757-2015);
3 atomic absorption spectrophotometry for measuring copper, zinc, lead and cadmium in water (GB 7475-1987);
4 determination of Nickel in Water flame atomic absorption Spectrophotometry (GB 11912-1989);
5 determination of flame atomic absorption fraction of water quality iron and manganeseSpectrophotometry (GB 11911-1989).
TABLE 6 clear water contaminant content after pressure filtration
Wherein: * N/A indicates below the detection limit of the instrument (1. Mu.g/L).
TABLE 7 technical indices of products after evaporative crystallization 6
Wherein: 6 industrial chromium chloride (HG/T4311-2012), all technical indicators in the table are tested in the manner or by the method described in the HG/T4311-2012 standard.
According to the detection data, the clean water after filter pressing has greatly reduced pollutants and Ni removal 2+ Besides the content, the content of the rest heavy metal ions meets the highest emission limit regulation specified in the electroplating pollutant emission standard (GB 21900-2008) in Table 3, the COD value of the wastewater is reduced to a certain extent, and the subsequent treatment is facilitated.
The chromium chloride product prepared after evaporation and crystallization meets the technical requirements of first-class products in the table 1 of industrial chromium chloride (HG/T4311-2012), and can be directly sold as a chemical product.
In the original sewage treatment process of the company, chromium-containing waste water generates chromium-containing dangerous waste of approximately 300 tons per year (the water content is approximately 50 percent, and after sludge is dried), the amount of the dangerous waste generated per year is approximately 2 tons (the water content is approximately 50 percent, and after sludge is dried), the dangerous waste is reduced by more than 99.5 percent before and after transformation, and no other solid waste or dangerous waste is newly added in the treatment process, thereby realizing the reduction and recycling of the dangerous solid waste.
Although embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the application, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The chromium plating waste water dangerous waste reduction method is characterized by comprising the following steps:
1) Collecting chromium-containing wastewater, analyzing the COD value of the wastewater, and calculating the required hydrogen peroxide amount V according to the measured COD value (g/L) 1 (the unit is L/m 3 Or L/ton);
2) The collected chromium-containing wastewater is discharged into a UV/Fenton treatment system after the COD value is measured, and the pH value of the wastewater in the UV/Fenton treatment system is adjusted 4 The value is adjusted to 3-10 according to V 1 And calculating the volume or weight of the waste water collected by the UV/Fenton treatment system to obtain the required added hydrogen peroxide V (the unit is L), starting a UV lamp of the UV/Fenton treatment system, and adding hydrogen peroxide into the waste water in the UV/Fenton treatment system, wherein the added hydrogen peroxide is V;
3) After the UV lamp is started for a certain time, adding alkali into the UV/Fenton treatment system until the pH value of wastewater in the system is reached 5 Adding a sufficient amount of NaClO into the UV/Fenton treatment system after the alkali addition is finished until the value is between 4 and 13, and then continuously starting the UV lamp for a certain time, wherein the total starting time of the UV lamp is 0.5 to 10 hours;
4) After the UV lamp is turned off, the wastewater in the UV/Fenton treatment system is discharged to the filtering system 1, the wastewater filtered by the filtering system 1 is added with a certain reducing agent SP for reduction, and the pH of the reduced wastewater is adjusted 6 The value is adjusted to be between 5 and 13, and the sludge filtered by the filtering system 1 is additionally treated;
5)pH 6 after the adjustment is finished, the wastewater is discharged to a filter system 2, the concentrated sludge in the filter system 2 is washed for 1-10 times by adopting clear water, clear water filtered by the filter system 2 is additionally treated, the cleaned sludge in the filter system 2 is discharged to a sludge press filtration system, and the sludge is press-filtered by the sludge press filtration system to form dry sludge.
2. The chromium plating wastewater hazardous waste reduction method according to claim 1, which comprisesCharacterized in that the pH is 6 The preferred value of the value range is between 6 and 9, the pH value 5 The preferred value of the value range is between 8 and 10.
3. The method for reducing the risk of waste chrome plating wastewater according to claim 1, wherein the optimal value of the number of times of concentrated sludge cleaning in the filtering system 2 is 2-4, and the sludge press filtration system is a high-pressure diaphragm type plate-and-frame filter press.
4. The chromium plating wastewater hazardous waste reduction method according to any one of claims 1 to 3, wherein the COD value analysis method is as follows:
1) Firstly taking a proper amount of chromium-containing wastewater and measuring the pH value of the wastewater 1 Value and Cr 6+ The content a (g/L) is measured, and the total chromium content b (g/L) and the content of other heavy metal ions in the chromium-containing wastewater are measured;
2) Determination of Cr in wastewater 6+ Adding sufficient reducing agent GV according to the proportion after the content;
3) After GV is added, stirring the wastewater until GV is dissolved, and adding a proper amount of acid or alkali into the wastewater to adjust the pH of the wastewater after GV is dissolved 2 Value, pH 2 After the value adjustment is finished, standing the wastewater for 10-500min;
4) After the standing time is over, adding a proper amount of alkali into the wastewater to adjust the pH value of the wastewater 3 A pH of between 9 and 14 3 After the adjustment is finished, filtering the wastewater;
5) After the wastewater is filtered, the COD value of the wastewater is analyzed and measured.
5. The method for reducing chromium plating wastewater risk according to claim 4, wherein said GV is ferrous sulfate (FeSO) 4 ·7H 2 O), the addition amount of the ferrous sulfate is calculated according to the following formula:
m ≥ 5.4 × a (1)
in the formula (1), m is FeSO which needs to be added in each liter of water 4 ·7H 2 The amount of O is given in units of: g/L, V 1 The calculation is carried out according to the following formula:
V 1 ＝ p × COD (2)
the value range of p is 0.5-9.
6. The method for reducing chromium plating wastewater risk and waste according to claim 5, wherein the preferable value of the p value range is 2.8-5.6.
7. The method for reducing the risk of chromium plating wastewater according to any one of claims 1 to 3, wherein the mass percentage content of the sodium hypochlorite is 10%, and the addition amount of the NaClO is calculated according to the following formula:
V 2 ＝ q × (b – a) (3)
in the formula (3), the units of b and a are g/L and V 2 Is L/m 3 I.e. the volume of sodium hypochlorite to be added per cubic meter or ton of water;
in the formula (3), q is a coefficient, and the value range of q is 9-11.
8. The method for reducing chromium plating wastewater risk and waste according to claim 7, wherein the q value range is preferably 9.3-10.2.
9. Use of dry sludge produced by the chromium plating wastewater hazardous waste reduction method according to any one of claims 1 to 8 in chromium sludge recycling.
10. The method for recycling chromium sludge by using the dry sludge obtained by the chromium plating wastewater hazardous waste reduction method according to any one of claims 1 to 8, which is characterized in that the dry sludge filtered by the sludge press filtration system can be finally manufactured into different finished products according to different treatment processes.
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