CN113582468A - Stainless steel pickling waste acid liquid treatment system and treatment method - Google Patents
Stainless steel pickling waste acid liquid treatment system and treatment method Download PDFInfo
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- CN113582468A CN113582468A CN202110996167.8A CN202110996167A CN113582468A CN 113582468 A CN113582468 A CN 113582468A CN 202110996167 A CN202110996167 A CN 202110996167A CN 113582468 A CN113582468 A CN 113582468A
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- 239000002699 waste material Substances 0.000 title claims abstract description 75
- 239000002253 acid Substances 0.000 title claims abstract description 69
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 65
- 239000010935 stainless steel Substances 0.000 title claims abstract description 65
- 238000005554 pickling Methods 0.000 title claims abstract description 56
- 239000007788 liquid Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002351 wastewater Substances 0.000 claims abstract description 99
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000010802 sludge Substances 0.000 claims abstract description 79
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 45
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 27
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 24
- 238000010306 acid treatment Methods 0.000 claims abstract description 23
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001556 precipitation Methods 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 238000006115 defluorination reaction Methods 0.000 claims abstract description 16
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000008235 industrial water Substances 0.000 claims abstract description 11
- 229910001385 heavy metal Inorganic materials 0.000 claims description 23
- 238000004062 sedimentation Methods 0.000 claims description 20
- 238000010521 absorption reaction Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000011737 fluorine Substances 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000000108 ultra-filtration Methods 0.000 claims description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 8
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 8
- 239000004571 lime Substances 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 5
- 239000008394 flocculating agent Substances 0.000 claims description 5
- 235000021110 pickles Nutrition 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- -1 fluorine ions Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002912 waste gas Substances 0.000 claims description 3
- 238000010129 solution processing Methods 0.000 claims 2
- 238000004064 recycling Methods 0.000 abstract description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract description 2
- 208000028659 discharge Diseases 0.000 abstract 1
- 230000008569 process Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XWROUVVQGRRRMF-UHFFFAOYSA-N F.O[N+]([O-])=O Chemical compound F.O[N+]([O-])=O XWROUVVQGRRRMF-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
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2001/007—Processes including a sedimentation step
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- 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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- 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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F3/30—Aerobic and anaerobic processes
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Abstract
The invention provides a stainless steel pickling waste acid liquid treatment system and a treatment method, which are used for treating waste acid and waste water generated in a stainless steel pickling production line, wherein the treatment system comprises a waste water treatment subsystem and a waste acid treatment subsystem, and the waste acid treatment subsystem comprises the following steps: the wastewater treatment subsystem comprises a sludge treatment device, and a neutralization device, a precipitation device, a defluorination device, a biological denitrification reaction tank and a reverse osmosis water treatment device which are sequentially communicated, and is used for obtaining produced water, concentrated water and sludge through treatment, wherein the produced water is used as industrial water for recycling, and the concentrated water and the sludge are conveyed to the waste acid treatment subsystem; and the waste acid treatment subsystem comprises a roasting furnace, the roasting furnace comprises an upper section reactor and a lower section reactor which are communicated, the upper section reactor is used for roasting the waste acid and concentrated water to generate solid metal oxide, and the solid metal oxide is conveyed to the lower section reactor, mixed with sludge and roasted to obtain the ferric oxide powder. The invention realizes zero discharge treatment of stainless steel pickling waste acid and wastewater and recycling of resources.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a stainless steel pickling acid pickle treatment system and a treatment method.
Background
The stainless steel has many advantages of acid corrosion resistance, good heat resistance, good high-temperature oxidation resistance and the like, so the stainless steel is widely applied to the fields of petroleum, chemical engineering, power, nuclear engineering, aerospace, medical machinery, light industrial products, personal home decoration, high-grade hotel facilities and the like. During the forming and heat treatment process of stainless steel, a layer of black oxide skin is generated on the surface, the structure of the oxide skin is compact, the aesthetic property of the surface of the steel is damaged, the electrochemical corrosion of the metal surface is accelerated, and the stress corrosion of the surface of the steel is accelerated due to the existing surface stress. The scale on the surface of the stainless steel must be removed before subsequent processing. In engineering, an acid pickling process is often used to remove oxide skin formed on the surface of stainless steel during hot rolling and annealing, and passivation is performed on the surface of stainless steel to make the surface of stainless steel more corrosion resistant.
The stainless steel pickling process actually consists of two processes, namely a pickling process and a passivation process. In the acid cleaning process, sulfuric acid or nitric acid-hydrofluoric acid mixed acid is mainly adopted to remove and strip the iron scale of stainless steel with different materials. According to different pickling processes, the content of free acid and the content of metal ions in the waste acid solution are different.
At present, in the treatment method for recovering acid from mixed acid solution of hydrofluoric and nitric acid, most of waste acid solution treatment needs to adopt a lime neutralization precipitation method to neutralize residual acid in water to form coprecipitation sludge of calcium sulfate or calcium fluoride or metal hydroxide. The method has the advantages of simple process, less equipment investment, better effluent quality and lower salt content. The disadvantages are that partial metal hydroxide is not completely precipitated in the pH range of 6-9, the sludge amount generated by water treatment is large, the precipitate contains a large amount of heavy metals, the management is required according to industrial hazardous waste, and the sludge disposal cost is high.
Meanwhile, the treated wastewater contains sodium nitrate, the total nitrogen content of the discharged water seriously exceeds the standard, the discharged water can reach the standard after further deepening treatment, and the water treatment operation cost is high. The method has the defects of high operation cost, large water resource waste, high salinity of discharged water and serious standard exceeding of total nitrogen in the aspect of water treatment, so the method is difficult to popularize and apply in industrial application.
Disclosure of Invention
The invention aims to provide a stainless steel pickling waste acid liquid treatment system and a treatment method, which have good treatment effect and can not cause secondary pollution, and realize zero emission treatment of stainless steel pickling waste acid and wastewater and recycling of resources.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a stainless steel pickling spent acid solution treatment system for treating spent acid and wastewater generated in a stainless steel pickling line, comprising a wastewater treatment subsystem and a spent acid treatment subsystem, wherein:
the wastewater treatment subsystem is used for treating the wastewater and comprises a sludge treatment device, a neutralization device, a precipitation device, a defluorination device, a biological denitrification reaction tank and a reverse osmosis water treatment device which are sequentially communicated, wherein the neutralization device is used for adjusting the pH value of the wastewater and reacting with heavy metal ions in the wastewater by adding caustic soda liquid to generate heavy metal precipitates, the precipitation device is used for carrying out solid-liquid separation on the wastewater to obtain wastewater clear liquid and sludge, the defluorination device and the biological denitrification reaction tank are used for carrying out defluorination and denitrification on the wastewater clear liquid, the reverse osmosis water treatment device is used for carrying out reverse osmosis treatment on the wastewater clear liquid to obtain produced water and concentrated water, the produced water is reused as industrial water in the stainless steel pickling production line, the concentrated water is conveyed to the waste acid treatment subsystem, and the sludge treatment device is communicated with the precipitation device to receive the sludge, the sludge treatment device is used for concentrating and dehydrating the sludge and then conveying the sludge to a waste acid treatment subsystem;
the waste acid treatment subsystem is used for treating the waste acid and comprises a roasting furnace, the roasting furnace comprises an upper section reactor and a lower section reactor which are communicated, the upper section reactor is used for roasting the waste acid and the concentrated water and generating solid metal oxide, the solid metal oxide is conveyed to the lower section reactor and mixed with the concentrated and dehydrated sludge, and the solid metal oxide is roasted through the lower section reactor to obtain iron oxide powder.
Optionally, the neutralization apparatus includes equalizing basin, first neutralizing tank and the second neutralizing tank that communicates in order, the equalizing basin is used for collecting waste water and adjusting the concentration of waste water, first neutralizing tank is used for adding lime in the waste water and carries out the preneutralization, the second neutralizing tank is used for adding liquid caustic soda in the waste water and heavy metal ion neutralization reaction in the waste water generates heavy metal precipitate.
Optionally, the first neutralization tank controls the pH value of the pre-neutralization reaction to be between 2 and 4, and the second neutralization tank controls the pH value of the neutralization reaction to be between 9 and 10.
Optionally, the sedimentation device comprises a sedimentation tank and a feeding pump, the sedimentation tank is communicated with the neutralization device, and the feeding pump is used for feeding a first flocculating agent into the sedimentation tank so as to perform solid-liquid separation on the wastewater to obtain wastewater clear liquid and sludge.
Optionally, the sludge treatment device includes a sludge concentration tank and a filter press which are communicated with each other, the sludge concentration tank is communicated with the sedimentation device to receive the sludge, and the filter press is used for dehydrating the sludge and conveying the sludge to the lower reactor of the roasting furnace.
Optionally, the defluorination device comprises a fluorine reaction tank and a fluoride precipitation device which are communicated, the fluorine reaction tank is communicated with the precipitation device to receive the wastewater clear liquid, the fluorine reaction tank is used for removing fluorine ions in the wastewater clear liquid by adding polyaluminium chloride and lime, the fluoride precipitation device is used for carrying out solid-liquid separation by adding a second flocculating agent, and the separated sludge is conveyed to the sludge concentration tank.
Optionally, a filtering device is further arranged between the biological denitrification reaction tank and the reverse osmosis water treatment device, and the filtering device is used for further removing suspended matters in the clear wastewater liquid.
Optionally, reverse osmosis water treatment facilities is including ultrafiltration equipment, one-level RO equipment, second grade RO equipment and the tertiary RO equipment that communicates in order, ultrafiltration equipment with filter equipment intercommunication, tertiary RO equipment with upper segment reactor intercommunication, the waste water clear solution warp ultrafiltration equipment gets into after filtering the one-level RO equipment, the clear water after the one-level RO equipment is handled gets into the second grade RO equipment, the one-level RO equipment is handled and the dense water after the second grade RO equipment is handled gets into the tertiary RO equipment, the dense water after the tertiary RO equipment is handled is carried extremely the upper segment reactor, the second grade RO equipment reaches the clear water after the tertiary RO equipment is handled is used for as industrial water the stainless steel pickling production line.
Optionally, the waste acid treatment subsystem further comprises an absorption tower communicated with the roasting furnace, roasting gas enters the absorption tower from the top of the roasting furnace, and the absorption tower absorbs the roasting gas by using washing water to form regenerated acid.
Optionally, the waste acid treatment subsystem further comprises an SCR reactor and a burner, the SCR reactor is communicated with the absorption tower, and the residual waste gas absorbed by the absorption tower is heated by the burner and then enters the SCR reactor together with ammonia water for reaction.
In order to achieve the above object, according to a second aspect of the present invention, there is provided a method for treating a stainless steel pickling waste acid solution, for treating waste acid and wastewater generated in a stainless steel pickling line, comprising the steps of:
adjusting the pH value of the wastewater, and adding liquid alkali to react with heavy metal ions in the wastewater to generate heavy metal precipitates;
carrying out solid-liquid separation on the wastewater to obtain wastewater clear liquid and sludge;
carrying out defluorination and denitrification on the clear wastewater liquid and carrying out concentration and dehydration on the sludge;
carrying out reverse osmosis treatment on the clear wastewater to obtain produced water and concentrated water, wherein the produced water is used as industrial water for the stainless steel pickling production line;
roasting the waste acid and the concentrated water to produce solid metal oxide;
and mixing the solid metal oxide with the concentrated and dehydrated sludge, and roasting to obtain the iron oxide powder.
The invention provides a stainless steel pickling waste acid liquid treatment system and a treatment method, wherein concentrated water and waste acid generated after reverse osmosis concentration treatment are roasted in a roasting furnace together to generate solid metal oxide, sludge containing heavy metal components generated by wastewater treatment enters the lower part of the roasting furnace to be mixed with the solid metal oxide for roasting again to form iron oxide powder which can be used as a stainless steel smelting raw material, so that the resource regeneration treatment of the stainless steel pickling waste acid and wastewater is realized, and the requirements of zero discharge of wastewater and non-leaving factory of solid waste are met.
Drawings
It will be appreciated by those skilled in the art that the drawings are provided for a better understanding of the invention and do not constitute any limitation to the scope of the invention. Wherein:
FIG. 1 is a schematic diagram of a stainless steel pickling pickle liquor treatment system according to an embodiment of the present invention;
FIG. 2 is a diagram illustrating the steps of a method for treating a stainless steel pickling pickle liquor according to an embodiment of the present invention;
in the drawings:
1-a regulating reservoir; 2-a first neutralization tank; 3-a second neutralization tank; 4-a sedimentation tank; 5-sludge concentration tank; 6, a filter press; 7-roasting furnace; 8-fluorine reaction tank; 9-fluoride precipitation means; 10-a biological denitrification reaction tank; 11-a quicksand filter; 12-a multi-media filter; 13-ultrafiltration equipment; 14-a primary RO device; 15-a secondary RO device; 16-a tertiary RO plant; 17-an absorption column; 18-SCR reactor.
Detailed Description
To further clarify the objects, advantages and features of the present invention, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. It is to be noted that the drawings are in greatly simplified form and are not to scale, but are merely intended to facilitate and clarify the explanation of the embodiments of the present invention. Further, the structures illustrated in the drawings are often part of actual structures. In particular, the drawings may have different emphasis points and may sometimes be scaled differently.
As used in this application, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise. As used in this disclosure, the term "or" is generally employed in its sense including "and/or" unless the content clearly dictates otherwise. As used in this disclosure, the term "plurality" is generally employed in its sense including "at least one" unless the content clearly dictates otherwise. As used in this disclosure, the term "at least two" is generally employed in a sense including "two or more" unless the content clearly dictates otherwise. Furthermore, the terms "first", "second", "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, features defined as "first", "second", "third" may explicitly or implicitly include one or at least two of the features.
The embodiment provides a stainless steel pickling waste acid liquid processing system for handle the spent acid and the waste water that stainless steel pickling production line produced, including waste water treatment subsystem and spent acid treatment subsystem, wherein:
the wastewater treatment subsystem is used for treating the wastewater and comprises a sludge treatment device, a neutralization device, a precipitation device, a defluorination device, a biological denitrification reaction tank and a reverse osmosis water treatment device which are sequentially communicated, wherein the neutralization device is used for adjusting the pH value of the wastewater and reacting with heavy metal ions in the wastewater by adding caustic soda liquid to generate heavy metal precipitates, the precipitation device is used for carrying out solid-liquid separation on the wastewater to obtain wastewater clear liquid and sludge, the defluorination device and the biological denitrification reaction tank are used for carrying out defluorination and denitrification on the wastewater clear liquid, the reverse osmosis water treatment device is used for carrying out reverse osmosis treatment on the wastewater clear liquid to obtain produced water and concentrated water, the produced water is reused as industrial water in the stainless steel pickling production line, the concentrated water is conveyed to the waste acid treatment subsystem, and the sludge treatment device is communicated with the precipitation device to receive the sludge, the sludge treatment device is used for concentrating and dehydrating the sludge and then conveying the sludge to a waste acid treatment subsystem;
the waste acid treatment subsystem is used for treating the waste acid and comprises a roasting furnace, the roasting furnace comprises an upper section reactor and a lower section reactor which are communicated, the upper section reactor is used for roasting the waste acid and the concentrated water and generating solid metal oxide, the solid metal oxide is conveyed to the lower section reactor and mixed with the concentrated and dehydrated sludge, and the solid metal oxide is roasted through the lower section reactor to obtain iron oxide powder.
Specifically, the stainless steel pickling waste acid solution treatment system provided by the embodiment is mainly used for treating waste acid and waste water generated in the production process of a stainless steel pickling production line, and the waste acid and the waste water are respectively discharged at different working sections, so that the waste acid and the waste water can be classified, collected, stored and subjected to synergistic treatment. Concentrated water and waste acid generated after reverse osmosis concentration treatment are roasted in a roasting furnace together to generate solid metal oxide, sludge containing heavy metal components generated by wastewater treatment enters the lower part of the roasting furnace to be mixed with the solid metal oxide for roasting again to form ferric oxide powder which can be used as a stainless steel smelting raw material, resource regeneration treatment of stainless steel pickling waste acid and wastewater is realized, and the requirements of zero wastewater discharge and no solid waste delivery are met.
As shown in fig. 1, fig. 1 is a schematic view of a stainless steel pickling waste acid solution treatment system according to an embodiment of the present invention. The neutralization apparatus comprises an adjusting tank 1, a first neutralization tank 2 and a second neutralization tank 3 which are sequentially communicated, the adjusting tank 1 is used for collecting the wastewater and adjusting the concentration of the wastewater, the first neutralization tank 2 is used for adding lime into the wastewater for pre-neutralization, and the second neutralization tank 3 is used for adding liquid alkali into the wastewater to perform neutralization reaction with heavy metal ions in the wastewater to generate heavy metal precipitates. In the process, heavy metal ions such as iron, chromium, nickel, manganese and the like in the wastewater are removed to form metal hydroxide precipitates, and the use amount of the liquid caustic soda can be reduced and the neutralization cost can be reduced by adopting lime for pre-neutralization.
Preferably, the first neutralization tank 2 controls the pH value of the pre-neutralization reaction to be between 2 and 4, and the second neutralization tank 3 controls the pH value of the neutralization reaction to be between 9 and 10.
With reference to fig. 1, the sedimentation device includes a sedimentation tank 4 and a feeding pump, the sedimentation tank 4 is communicated with the second neutralization tank 3 of the neutralization device, and the feeding pump is used for feeding a first flocculating agent into the sedimentation tank 4 to perform solid-liquid separation on the wastewater to obtain wastewater clear liquid and sludge. In this embodiment, the neutralized wastewater automatically flows into the sedimentation tank 4, a certain amount of the first flocculant can be added into the sedimentation tank 4 through the adding pump, so as to realize solid-liquid separation, the wastewater clear liquid enters the fluoride treatment process section for continuous treatment, and the sludge is extracted from the bottom of the sedimentation tank 4 to the sludge concentration tank 5. In this embodiment, the first flocculant is, for example, polyacrylamide, and this application does not limit this.
With reference to fig. 1, the sludge treatment apparatus includes a sludge concentration tank 5 and a filter press 6, which are communicated with each other, the sludge concentration tank 5 is communicated with the sedimentation apparatus to receive the sludge, and the filter press 6 is used for dewatering the sludge and conveying the sludge to the lower reactor of the roasting furnace 7. In this embodiment, the sludge is extracted from the bottom of the sedimentation tank 4 to the sludge concentration tank 5, and the sludge in the sludge concentration tank 5 is dewatered by the extrusion plate and frame filter press and conveyed to the lower reactor of the roasting furnace 7 of the waste acid treatment subsystem for continuous treatment.
Referring to fig. 1 again, the fluorine removal device includes a fluorine reaction tank 8 and a fluoride precipitation device 9 which are communicated with each other, the fluorine reaction tank 8 is communicated with the precipitation device to receive the wastewater clear liquid, the fluorine reaction tank 8 removes fluorine ions in the wastewater clear liquid by adding polyaluminium chloride and lime, the fluoride precipitation device 9 performs solid-liquid separation by adding a second flocculant, and the separated sludge is conveyed to the sludge concentration tank 5. In this embodiment, the second flocculant is, for example, polyacrylamide, and this application does not limit this.
In this embodiment, the clear wastewater after neutralization and defluorination is pumped to the biological denitrification reaction tank 10, the biological denitrification reaction tank 10 adopts an AAAO structure, and the inlet and the third-stage a tank are respectively provided with a cooling tower for cooling the wastewater.
With reference to fig. 1, a filtering device is further disposed between the biological denitrification reaction tank 10 and the reverse osmosis water treatment device, and the filtering device is used for further removing suspended matters in the clear wastewater. In this embodiment, the filtering device includes a quicksand filter 11 and a multi-media filter 12, the clear wastewater liquid after biochemical treatment is filtered by the quicksand filter 11 and enters a clean water tank, at this time, the wastewater reaches the "GB 13456-2012 discharge standard for pollutants in steel industry water", and the wastewater after reaching the standard is treated and is further passed through the multi-media filter 12 to further remove suspended matters in the water.
Referring to fig. 1, the reverse osmosis water treatment device includes an ultrafiltration device 13, a primary RO device 14, a secondary RO device 15, and a tertiary RO device 16, which are sequentially connected, the ultrafiltration device 13 is connected to the filtration device, the tertiary RO device 16 is connected to the upper stage reactor, the wastewater supernatant is filtered by the ultrafiltration device 13 and then enters the primary RO device 14, the clean water treated by the primary RO device 14 enters the secondary RO device 15, the concentrated water treated by the primary RO device 14 and treated by the secondary RO device 15 enters the tertiary RO device 16, the concentrated water treated by the tertiary RO device 16 is delivered to the upper stage reactor, and the clean water treated by the secondary RO device 15 and the tertiary RO device 16 is recycled as industrial water to the stainless steel pickling line.
In the embodiment, after the clear wastewater is treated by the ultrafiltration device 13, the primary RO device 14 and the secondary RO device 15, the reverse osmosis produced water is desalted water (the conductivity is less than or equal to us/cm), and the desalted water can be reused for production of a stainless steel pickling line. And after being collected, the reverse osmosis concentrated water is continuously treated by a three-level RO device 16, the produced water is used as industrial water to be reused in a stainless steel pickling production line, and the rest concentrated water is conveyed to a waste acid treatment subsystem for roasting.
With reference to fig. 1, the waste acid treatment subsystem is configured to treat the waste acid, and includes a roasting furnace 7, where the roasting furnace 7 includes an upper-stage reactor and a lower-stage reactor that are communicated with each other, the upper-stage reactor is configured to roast the waste acid and the concentrated water and generate a solid metal oxide, and the solid metal oxide is transported to the lower-stage reactor, mixed with the concentrated and dehydrated sludge, and roasted by the lower-stage reactor to obtain iron oxide powder.
In this embodiment, the roasting furnace 7 is composed of two sections, the upper section reactor is a cylindrical steel container with a flat bottom, and a stirrer is installed at the upper section of the reactor; the lower reactor was also equipped with a round-bottomed steel vessel having a flat bottom and a stirrer. The upper section reactor and the lower section reactor are directly heated by a burner. The burner in the upper reactor had a temperature of about 550 c and a top temperature of about 200 to 300 c.
Solid metal oxide generated by roasting the upper reactor is conveyed to the lower reactor through an upper stirrer, and is mixed with sludge dehydrated from a wastewater treatment subsystem, and the mixture is continuously heated to about 650 ℃ in the lower reactor, and is discharged through a rotary valve through a lower stirrer, and the obtained iron oxide powder can be used as a stainless steel smelting raw material.
Further, the waste acid treatment subsystem further comprises an absorption tower 17 communicated with the roasting furnace 7, roasting gas enters the absorption tower 17 from the top of the roasting furnace 7, the absorption tower 17 absorbs the roasting gas by using washing water to form regenerated acid, and the regenerated acid can be returned to a stainless steel pickling production line for recycling through a storage and conveying system.
Furthermore, the waste acid treatment subsystem further comprises an SCR reactor 18 and a burner, the SCR reactor 18 is communicated with the absorption tower 17, and residual waste gas absorbed by the absorption tower 17 is heated by the burner and then enters the SCR reactor 18 together with ammonia water for reaction. In this embodiment, the SCR reactor 18 is filled with a honeycomb catalyst, the honeycomb catalyst is a solid metal oxide catalyst, and under the action of the catalyst, the reducing agent ammonia selectively reduces nitrogen monoxide and nitrogen dioxide in the exhaust gas to nitrogen gas and water at 290-.
Based on this, the embodiment further provides a method for treating a stainless steel pickling waste acid solution, and with reference to fig. 2, fig. 2 is a step diagram of the method for treating a stainless steel pickling waste acid solution according to the embodiment of the present invention, where the method for treating a stainless steel pickling waste acid solution includes the following steps:
s1, adjusting the pH value of the wastewater and adding liquid alkali to react with heavy metal ions in the wastewater to generate heavy metal precipitates;
s2, carrying out solid-liquid separation on the wastewater to obtain wastewater clear liquid and sludge;
s3, carrying out defluorination and denitrification on the clear wastewater liquid and carrying out concentration and dehydration on the sludge;
s4, performing reverse osmosis treatment on the clear wastewater to obtain produced water and concentrated water, wherein the produced water is reused as industrial water in the stainless steel pickling production line;
s5, roasting the waste acid and the concentrated water to generate solid metal oxide;
s6, mixing the solid metal oxide with the concentrated and dehydrated sludge, and roasting to obtain the iron oxide powder.
To sum up, the embodiment of the invention provides a stainless steel pickling waste acid solution treatment system and a treatment method, concentrated water generated after reverse osmosis concentration treatment and waste acid are fed into a roasting furnace together for roasting to generate solid metal oxide, sludge containing heavy metal components generated by wastewater treatment is fed into the lower part of the roasting furnace to be mixed with the solid metal oxide for roasting again to form iron oxide powder which can be used as a stainless steel smelting raw material, so that the resource regeneration treatment of stainless steel pickling waste acid and wastewater is realized, and the requirements of zero wastewater discharge and no solid waste delivery are met.
It should be understood, however, that the intention is not to limit the invention to the particular embodiments described. It will be apparent to those skilled in the art from this disclosure that many changes and modifications can be made, or equivalents modified, in the embodiments of the invention without departing from the scope of the invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the protection scope of the technical solution of the present invention, unless the content of the technical solution of the present invention is departed from.
Claims (11)
1. The utility model provides a stainless steel pickling waste acid liquid processing system for handle waste acid and the waste water that stainless steel pickling production line produced, its characterized in that, including waste water treatment subsystem and waste acid treatment subsystem, wherein:
the wastewater treatment subsystem is used for treating the wastewater and comprises a sludge treatment device, a neutralization device, a precipitation device, a defluorination device, a biological denitrification reaction tank and a reverse osmosis water treatment device which are sequentially communicated, wherein the neutralization device is used for adjusting the pH value of the wastewater and reacting with heavy metal ions in the wastewater by adding caustic soda liquid to generate heavy metal precipitates, the precipitation device is used for carrying out solid-liquid separation on the wastewater to obtain wastewater clear liquid and sludge, the defluorination device and the biological denitrification reaction tank are used for carrying out defluorination and denitrification on the wastewater clear liquid, the reverse osmosis water treatment device is used for carrying out reverse osmosis treatment on the wastewater clear liquid to obtain produced water and concentrated water, the produced water is reused as industrial water in the stainless steel pickling production line, the concentrated water is conveyed to the waste acid treatment subsystem, and the sludge treatment device is communicated with the precipitation device to receive the sludge, the sludge treatment device is used for concentrating and dehydrating the sludge and then conveying the sludge to a waste acid treatment subsystem;
the waste acid treatment subsystem is used for treating the waste acid and comprises a roasting furnace, the roasting furnace comprises an upper section reactor and a lower section reactor which are communicated, the upper section reactor is used for roasting the waste acid and the concentrated water and generating solid metal oxide, the solid metal oxide is conveyed to the lower section reactor and mixed with the concentrated and dehydrated sludge, and the solid metal oxide is roasted through the lower section reactor to obtain iron oxide powder.
2. The stainless steel pickling waste acid solution treatment system according to claim 1, wherein the neutralization device comprises a regulating reservoir, a first neutralization tank and a second neutralization tank which are sequentially communicated, wherein the regulating reservoir is used for collecting the wastewater and regulating the concentration of the wastewater, the first neutralization tank is used for adding lime into the wastewater for pre-neutralization, and the second neutralization tank is used for adding liquid alkali into the wastewater to perform a neutralization reaction with heavy metal ions in the wastewater to generate heavy metal precipitates.
3. The stainless steel pickling pickle liquor treatment system of claim 2 wherein said first neutralization tank controls the PH of said pre-neutralization reaction to be between 2 and 4 and said second neutralization tank controls the PH of said neutralization reaction to be between 9 and 10.
4. The stainless steel pickling waste acid solution treatment system according to claim 1, wherein the sedimentation device comprises a sedimentation tank and a feeding pump, the sedimentation tank is communicated with the neutralization device, and the feeding pump is used for feeding a first flocculating agent into the sedimentation tank so as to perform solid-liquid separation on the wastewater to obtain a wastewater clear solution and sludge.
5. The stainless steel pickling pickle liquor treatment system of claim 1, wherein the sludge treatment device comprises a sludge concentration tank and a filter press which are communicated, wherein the sludge concentration tank is communicated with the sedimentation device to receive the sludge, and the filter press is used for dehydrating the sludge and conveying the sludge to the lower reactor of the roasting furnace.
6. The stainless steel pickling waste acid solution treatment system according to claim 5, wherein the defluorination device comprises a fluorine reaction tank and a fluoride precipitation device which are communicated with each other, the fluorine reaction tank is communicated with the precipitation device to receive the wastewater clear solution, the fluorine reaction tank removes fluorine ions in the wastewater clear solution by adding polyaluminium chloride and lime, the fluoride precipitation device performs solid-liquid separation by adding a second flocculating agent, and the separated sludge is conveyed to the sludge concentration tank.
7. The stainless steel pickling waste acid solution treatment system according to claim 1, wherein a filtering device is further arranged between the biological denitrification reaction tank and the reverse osmosis water treatment device, and the filtering device is used for further removing suspended matters in the waste water clear solution.
8. The stainless steel pickling waste acid solution treatment system according to claim 7, wherein the reverse osmosis water treatment device comprises an ultrafiltration device, a primary RO device, a secondary RO device and a tertiary RO device which are sequentially communicated, the ultrafiltration device is communicated with the filtration device, the tertiary RO device is communicated with the upper stage reactor, the clear wastewater solution is filtered by the ultrafiltration device and enters the primary RO device, the clear water treated by the primary RO device enters the secondary RO device, the concentrated water treated by the primary RO device and treated by the secondary RO device enters the tertiary RO device, the concentrated water treated by the tertiary RO device is conveyed to the upper stage reactor, and the clear water treated by the secondary RO device and the tertiary RO device is reused as industrial water in the stainless steel pickling production line.
9. The stainless steel pickling waste acid solution processing system of claim 1, wherein the waste acid processing subsystem further comprises an absorption tower in communication with the roaster, roasting gas enters the absorption tower from the top of the roaster, and the absorption tower uses rinse water to absorb the roasting gas to form regenerated acid.
10. The stainless steel pickling waste acid solution processing system of claim 9, wherein the waste acid processing subsystem further comprises an SCR reactor and a burner, the SCR reactor is communicated with the absorption tower, and waste gas remaining after absorption by the absorption tower is heated by the burner and then enters the SCR reactor together with ammonia water for reaction.
11. A method for treating waste acid liquor generated in stainless steel pickling production line is used for treating waste acid and waste water generated in stainless steel pickling production line, and is characterized by comprising the following steps:
adjusting the pH value of the wastewater, and adding liquid alkali to react with heavy metal ions in the wastewater to generate heavy metal precipitates;
carrying out solid-liquid separation on the wastewater to obtain wastewater clear liquid and sludge;
carrying out defluorination and denitrification on the clear wastewater liquid and carrying out concentration and dehydration on the sludge;
carrying out reverse osmosis treatment on the clear wastewater to obtain produced water and concentrated water, wherein the produced water is used as industrial water for the stainless steel pickling production line;
roasting the waste acid and the concentrated water to produce solid metal oxide;
and mixing the solid metal oxide with the concentrated and dehydrated sludge, and roasting to obtain the iron oxide powder.
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CN114368852A (en) * | 2021-12-14 | 2022-04-19 | 唐山钢铁集团有限责任公司 | Cold rolling acid-containing wastewater treatment system and process |
CN114956393A (en) * | 2022-08-02 | 2022-08-30 | 山东凤鸣桓宇环保有限公司 | Nickel-containing electroplating wastewater treatment process |
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CN114368852A (en) * | 2021-12-14 | 2022-04-19 | 唐山钢铁集团有限责任公司 | Cold rolling acid-containing wastewater treatment system and process |
CN114956393A (en) * | 2022-08-02 | 2022-08-30 | 山东凤鸣桓宇环保有限公司 | Nickel-containing electroplating wastewater treatment process |
CN114956393B (en) * | 2022-08-02 | 2022-10-25 | 山东凤鸣桓宇环保有限公司 | Nickel-containing electroplating wastewater treatment process |
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