CN112125437A - Method for reducing chromium-containing wastewater by using activated carbon acid-making wastewater - Google Patents
Method for reducing chromium-containing wastewater by using activated carbon acid-making wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 125
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 111
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 70
- 239000011651 chromium Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 25
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 7
- 239000010959 steel Substances 0.000 claims abstract description 7
- 239000010802 sludge Substances 0.000 claims abstract description 6
- 239000008394 flocculating agent Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000005097 cold rolling Methods 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000002893 slag Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 229910001385 heavy metal Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000440 bentonite Substances 0.000 claims description 7
- 229910000278 bentonite Inorganic materials 0.000 claims description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000009615 deamination Effects 0.000 claims description 6
- 238000006481 deamination reaction Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000003795 desorption Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003546 flue gas Substances 0.000 claims description 3
- 238000005246 galvanizing Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000001741 organic sulfur group Chemical group 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 238000006479 redox reaction Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 239000013049 sediment Substances 0.000 abstract 2
- 238000005453 pelletization Methods 0.000 abstract 1
- 239000002910 solid waste Substances 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 description 16
- 239000000706 filtrate Substances 0.000 description 10
- 238000002161 passivation Methods 0.000 description 9
- 239000002699 waste material Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 229920002401 polyacrylamide Polymers 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000428 dust Substances 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- CSMWJXBSXGUPGY-UHFFFAOYSA-L sodium dithionate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)S([O-])(=O)=O CSMWJXBSXGUPGY-UHFFFAOYSA-L 0.000 description 1
- 229940075931 sodium dithionate Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
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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
- 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
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/004—Sludge detoxification
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
Abstract
The invention discloses a method for reducing chromium-containing wastewater by using activated carbon acid-making wastewater, which comprises the steps of carrying out acid filtration on the activated carbon acid-making wastewater to obtain sediment and clear liquid, carrying out mixed reaction on the obtained clear liquid and the chromium-containing wastewater, adjusting the pH of the solution to 8-10 by using alkaline liquor after the reaction is finished, adding a heavy catching agent and a flocculating agent to obtain chromium-containing sludge and ammonia nitrogen-containing wastewater, carrying out ammonia nitrogen removal treatment on the ammonia nitrogen-containing wastewater to convert the ammonia nitrogen-containing wastewater into high-salt wastewater without ammonia nitrogen, carrying out solid waste uniform mixing and pelletizing on the chromium-containing sludge and the sediment obtained by acid filtration, and carrying out rotary kiln calcination and further blast furnace treatment to remove. The method fully utilizes the reducibility and acidity of the acid wastewater prepared by the activated carbon, and realizes the low-cost harmless treatment of the chromium-containing wastewater in the steel plant without adding a reducing agent.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a method for reducing chromium-containing wastewater by using wastewater generated in acid preparation by using activated carbon.
Background
In the iron smelting process, a large amount of chromium-containing waste water is generated, particularly in the cold rolling process, such as the cold rolling galvanizing passivation process, in order to improve the corrosion resistance of a galvanized layer, chromate passivation treatment is often carried out on the galvanized layer, and the zinc on the surface of the galvanized layer is converted into zinc chromate by chemical reaction. During operation, a large amount of passivation solution is generated, which contains a high concentration of hexavalent chromium, which is highly toxic. The discharge form and discharge amount of chromium are strictly limited in all countries of the world and cannot be discharged randomly.
Aiming at the treatment of the wastewater containing hexavalent chromium, the hexavalent chromium is reduced to trivalent chromium by a reducing agent, and then neutralization and precipitation are carried out to realize the low-toxicity treatment of the chromium. For example, Chinese patent CN104310650B "method for treating wastewater from cold rolling of chromium-containing stainless steel" utilizes sodium sulfite and sodium dithionate to reduce hexavalent chromium under acidic condition, and removes chromium from the wastewater by neutralization.
After the flue gas of the sintering machine is subjected to desulfurization and denitrification by using the activated carbon, complex desorption gas (SRG gas) containing high-concentration sulfur dioxide, high dust and high salt content can be generated in the high-temperature desorption process of the activated carbon, and the gas is discharged from an outlet of a desorption tower and then is sent to an acid making system to prepare sulfuric acid. In order to ensure the quality of sulfuric acid and the stability of an acid making system, a wet washing method is adopted to wash and remove impurities from SRG gas and simultaneously realize the cooling of the SRG gas. Because the SRG gas contains a large amount of dust (mainly activated carbon powder), the dust can be removed in the washing process and enters the washing liquid, and the content of suspended matters in the washing liquid is increased. Because the washing liquid is for recycling, when the suspended solid volume is more in the washing liquid, can cause the jam of a series of equipment such as spray column nozzle, circulation tank to can not effectively cool down and the edulcoration to SRG gas, very big influence the steady operation of system sour system. Therefore, when the washing liquid is circulated for a certain number of times, the washing liquid needs to be discharged outside, and the washing wastewater of the activated carbon preparation acid is generated. Considering that the washing wastewater of the activated carbon is a strongly acidic reducing solution, if the washing wastewater of the activated carbon is used for treating the chromium-containing wastewater of the cold rolling, the 'treatment of waste by waste' can be realized, the organic integration of internal resources of steel plants can be realized, and the cost can be greatly reduced.
Disclosure of Invention
Aiming at the technical defects, the method for reducing the chromium-containing wastewater by using the wastewater generated in the acid preparation by using the activated carbon can realize the treatment of waste by waste and remove chromium from the wastewater, and has the advantages of simple and convenient operation and low operation cost.
In order to achieve the technical purpose, the invention adopts the following technical scheme: a method for reducing chromium-containing wastewater by using activated carbon acid-making wastewater comprises the following steps:
(1) acid filtration: filtering the activated carbon acid-making wastewater to obtain carbon powder precipitate and clear liquid;
(2) oxidation-reduction reaction: mixing and stirring the clear liquid obtained in the step (1) and chromium-containing wastewater for reaction;
(3) heavy metal capture: after the reaction is finished, adjusting the pH of the solution to 8-10 by using alkaline liquor, and adding a recapture agent and a flocculating agent to obtain metal-containing sludge and clear liquid;
(4) and (3) deamination and nitrogen treatment: adjusting the pH of the clear liquid obtained in the step (3) to 11-14 by using alkali liquor, then transferring the clear liquid into a physical deamination device, and performing ammonia nitrogen removal and ammonia resource recovery to obtain high-salinity wastewater without ammonia nitrogen;
(5) and (3) chromium removal treatment: and (3) mixing the metal-containing sludge obtained in the step (3) with the carbon powder precipitate obtained in the step (1), adding blast furnace dry ash and a binder, transferring the mixed material to a pelletizer to obtain a spherical material, putting the spherical material into a rotary kiln for calcining, and further carrying out blast furnace treatment on the slag obtained after calcining.
Further, the wastewater from the acid production by activated carbon in the step (1) is high-temperature analysis gas generated by an analysis tower in the flue gas purification process by activated carbon, and the wastewater is generated in the purification process by water washing.
Further, the chromium-containing wastewater in the step (2) is wastewater generated by a zinc plating process in a cold rolling plant in the steel industry.
Further, the reaction time of the clear liquid and the chromium-containing wastewater in the step (2) is 10-120min, and the pH value of the mixed solution is controlled to be less than 5.
Further, the alkali liquor in the step (3) is one of sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate.
Further, the heavy metal capturing agent in the step (3) is an organic sulfur type heavy metal capturing agent, and the adding amount of the heavy metal capturing agent is 10-500 mg/L.
Further, the flocculant in the step (3) is PAM, and the addition amount of the PAM is 0.005-1 wt%.
Further, the physical deamination device in the step (4) is one or more of an ammonia still, a stripping tower and a gaseous membrane device.
Further, the binder in the step (5) is bentonite.
Further, the pelletizer in the step (5) is one or more of a pair-roller pelletizer, a disc pelletizer and a cylinder pelletizer.
Further, the further blast furnace treatment in the step (5) is as follows: and collecting the slag, adding the slag into a blast furnace, wherein chromium enters molten iron due to the property of the chromium close to that of iron, and finally realizing the harmless treatment of the chromium.
The invention has the beneficial effects that: the method makes full use of the reducibility and acidity of the acid-making wastewater of the activated carbon, organically integrates the internal resources of the steel plant under the condition of not adding a reducing agent, realizes the cooperative treatment of the chromium-containing wastewater of the steel plant and the acid-making wastewater of the activated carbon, realizes the treatment of waste by waste, and finally realizes the low-cost harmless treatment of the chromium-containing wastewater.
Drawings
FIG. 1 is a schematic view of a process flow for reducing chromium-containing wastewater from acid production with activated carbon according to the present invention;
Detailed Description
In order to make the purpose and technical solution of the embodiments of the present invention clearer, the technical solution of the embodiments of the present invention will be clearly and completely described below with reference to the drawings and the implementation examples of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments.
Example 1
The water quality condition of the wastewater:
activated carbon acid-making wastewater: the pH value is 0.68, the initial SS concentration is 3000mg/L, the total iron is 120mg/L, the sulfite concentration is 830mg/L, and the ammonia nitrogen is 15000 mg/L.
Chromium-containing wastewater generated by cold rolling galvanization passivation: the pH value is 4.5, the total chromium is 2490mg/L, the chloride ion concentration is 34mg/L, and the sulfate ion concentration is 0.016 mg/L.
(II) a method for reducing chromium-containing wastewater by using wastewater generated in acid preparation by using activated carbon, which comprises the following steps:
(1) adding 500mL of activated carbon acid-making wastewater into a vertical precipitation tank, keeping the retention time in the vertical precipitation tank at 4h, and discharging most of carbon powder suspended matters which are relatively high in density and can be precipitated to the bottom of the vertical precipitation tank to obtain carbon powder precipitate and clear liquid.
(2) And (3) mixing 50mL of chromium-containing wastewater with the clear liquid obtained in the step (1), and fully stirring to react for 30min, wherein the pH value of the solution after reaction is 2.8.
(3) And (3) adjusting the pH value of the mixed wastewater in the step (2) to 9.5 by using NaOH with the mass concentration of 15%, observing that a large amount of dark green precipitates are formed in the solution, adding 50mg of TMT-15 and ten-thousandth of nonionic polyacrylamide into the wastewater, and filtering to obtain filtrate and filter residue.
(4) And (3) adjusting the pH value of the filtrate obtained in the step (3) to 11 by using a sodium hydroxide solution, generating a large amount of ammonia gas at the moment, and reacting the solution in a stripping manner in a stripping tower for 2 hours to obtain the high-salinity wastewater with ammonia nitrogen.
(5) Mixing the filter residue obtained in the step (3) with the carbon powder precipitate obtained in the step (1), adding 5g of blast furnace dry ash and bentonite as binders, fully and uniformly mixing, adding into a disc pelletizer to obtain a spherical material, putting the spherical material into a rotary kiln for calcining, and carrying out blast furnace treatment on the slag obtained after calcining.
Example 2
The water quality condition of the wastewater:
activated carbon acid-making wastewater: the pH was 0.68, the initial SS concentration was 3000mg/L, total iron was 120mg/L, sulfite concentration was 830mg/L, and ammonia nitrogen was 15000 mg/L.
Chromium-containing wastewater generated by cold rolling galvanization passivation: the pH value is 4.5, the total chromium is 2490mg/L, the chloride ion concentration is 34mg/L, and the sulfate ion concentration is 0.016 mg/L.
(II) a method for reducing chromium-containing wastewater by using wastewater generated in acid preparation by using activated carbon, which comprises the following steps:
(1) adding 600mL of activated carbon acid-making wastewater into a vertical precipitation tank, keeping the retention time in the vertical precipitation tank at 4h, and discharging most of carbon powder suspended matters which are relatively high in density and can be precipitated to the bottom of the vertical precipitation tank to obtain carbon powder precipitate and clear liquid.
(2) And (3) mixing 50mL of chromium-containing wastewater with the clear liquid obtained in the step (1), and fully stirring to react for 30min, wherein the pH value of the solution after reaction is 2.1.
(3) And (3) adjusting the pH value of the mixed wastewater in the step (2) to 10 by using NaOH with the mass concentration of 15%, observing that a large amount of dark green precipitates can be formed in the solution, adding 50mg of TMT-15 and one ten thousandth of nonionic polyacrylamide into the wastewater, and filtering to obtain filtrate and filter residue.
(4) And (3) adjusting the pH value of the filtrate obtained in the step (3) to 11 by using a sodium hydroxide solution, generating a large amount of ammonia gas at the moment, and reacting the solution in a stripping manner in a stripping tower for 2 hours to obtain the high-salinity wastewater with ammonia nitrogen.
(5) Mixing the filter residue obtained in the step (3) with the carbon powder precipitate obtained in the step (1), adding 5g of blast furnace dry ash and bentonite as binders, fully and uniformly mixing, adding into a disc pelletizer to obtain a spherical material, putting the spherical material into a rotary kiln for calcining, and carrying out blast furnace treatment on the slag obtained after calcining.
Example 3
The water quality condition of the wastewater:
activated carbon acid-making wastewater: the pH was 0.68, the initial SS concentration was 3000mg/L, total iron was 120mg/L, sulfite concentration was 830mg/L, and ammonia nitrogen was 15000 mg/L.
Chromium-containing wastewater generated by cold rolling galvanization passivation: the pH value is 4.5, the total chromium is 2490mg/L, the chloride ion concentration is 34mg/L, and the sulfate ion concentration is 0.016 mg/L.
(II) a method for reducing chromium-containing wastewater by using wastewater generated in acid preparation by using activated carbon, which comprises the following steps:
(1) 1000mL of activated carbon acid-making wastewater is added into a vertical precipitation tank, the standing time in the vertical precipitation tank is kept to be 4h, most of carbon powder suspended matters can be precipitated to the bottom of the vertical precipitation tank due to high density, and the carbon powder suspended matters are discharged to obtain carbon powder precipitate and clear liquid.
(2) And (3) mixing 50mL of chromium-containing wastewater with the clear liquid obtained in the step (1), and fully stirring to react for 30min, wherein the pH value of the solution after reaction is 0.87.
(3) And (3) adjusting the pH value of the mixed wastewater in the step (2) to 9.5 by using NaOH with the mass concentration of 15%, observing that a large amount of dark green precipitates are formed in the solution, adding 50mg of TMT-15 and ten-thousandth of nonionic polyacrylamide into the wastewater, and filtering to obtain filtrate and filter residue.
(4) And (3) adjusting the pH value of the filtrate obtained in the step (3) to 11 by using a sodium hydroxide solution, generating a large amount of ammonia gas at the moment, and reacting the solution in a stripping manner in a stripping tower for 2 hours to obtain the high-salinity wastewater with ammonia nitrogen.
(5) Mixing the filter residue obtained in the step (3) with the carbon powder precipitate obtained in the step (1), adding 5g of blast furnace dry ash and bentonite as binders, fully and uniformly mixing, adding into a disc pelletizer to obtain a spherical material, putting the spherical material into a rotary kiln for calcining, and carrying out blast furnace treatment on the slag obtained after calcining.
Example 4
The water quality condition of the wastewater:
activated carbon acid-making wastewater: the pH was 0.68, the initial SS concentration was 3000mg/L, total iron was 120mg/L, sulfite concentration was 830mg/L, and ammonia nitrogen was 15000 mg/L.
Chromium-containing wastewater generated by cold rolling galvanization passivation: the pH value is 4.5, the total chromium is 2490mg/L, the chloride ion concentration is 34mg/L, and the sulfate ion concentration is 0.016 mg/L.
(II) a method for reducing chromium-containing wastewater by using wastewater generated in acid preparation by using activated carbon, which comprises the following steps:
(1) adding 400mL of activated carbon acid-making wastewater into a vertical precipitation tank, keeping the retention time in the vertical precipitation tank at 4h, and discharging most of carbon powder suspended matters which are larger in density and can be precipitated to the bottom of the vertical precipitation tank to obtain carbon powder precipitate and clear liquid.
(2) And (3) mixing 50mL of chromium-containing wastewater with the clear liquid obtained in the step (1), and fully stirring to react for 30min, wherein the pH value of the solution after reaction is 3.2.
(3) And (3) adjusting the pH value of the mixed wastewater in the step (2) to 9.5 by using NaOH with the mass concentration of 15%, observing that a large amount of dark green precipitates are formed in the solution, adding 50mg of TMT-15 and ten-thousandth of nonionic polyacrylamide into the wastewater, and filtering to obtain filtrate and filter residue.
(4) And (3) adjusting the pH value of the filtrate obtained in the step (3) to 11 by using a sodium hydroxide solution, generating a large amount of ammonia gas at the moment, and reacting the solution in a stripping manner in a stripping tower for 2 hours to obtain the high-salinity wastewater with ammonia nitrogen.
(5) Mixing the filter residue obtained in the step (3) with the carbon powder precipitate obtained in the step (1), adding 5g of blast furnace dry ash and bentonite as binders, fully and uniformly mixing, adding into a disc pelletizer to obtain a spherical material, putting the spherical material into a rotary kiln for calcining, and carrying out blast furnace treatment on the slag obtained after calcining.
Example 5
The water quality condition of the wastewater:
activated carbon acid-making wastewater: the pH was 0.68, the initial SS concentration was 3000mg/L, total iron was 120mg/L, sulfite concentration was 830mg/L, and ammonia nitrogen was 15000 mg/L.
Chromium-containing wastewater generated by cold rolling galvanization passivation: the pH value is 4.5, the total chromium is 2490mg/L, the chloride ion concentration is 34mg/L, and the sulfate ion concentration is 0.016 mg/L.
(II) a method for reducing chromium-containing wastewater by using wastewater generated in acid preparation by using activated carbon, which comprises the following steps:
(1) adding 300mL of activated carbon acid-making wastewater into a vertical precipitation tank, keeping the retention time in the vertical precipitation tank at 4h, and discharging most of carbon powder suspended matters which are relatively high in density and can be precipitated to the bottom of the vertical precipitation tank to obtain carbon powder precipitate and clear liquid.
(2) And (3) mixing 50mL of chromium-containing wastewater with the clear liquid obtained in the step (1), and fully stirring to react for 30min, wherein the pH value of the solution after reaction is 3.7.
(3) And (3) adjusting the pH value of the mixed wastewater in the step (2) to 9.5 by using NaOH with the mass concentration of 15%, observing that a large amount of dark green precipitates are formed in the solution, adding 50mg of TMT-15 and ten-thousandth of nonionic polyacrylamide into the wastewater, and filtering to obtain filtrate and filter residue.
(4) And (3) adjusting the pH value of the filtrate obtained in the step (3) to 11 by using a sodium hydroxide solution, generating a large amount of ammonia gas at the moment, and reacting the solution in a stripping manner in a stripping tower for 2 hours to obtain the high-salinity wastewater with ammonia nitrogen.
(5) Mixing the filter residue obtained in the step (3) with the carbon powder precipitate obtained in the step (1), adding 5g of blast furnace dry ash and bentonite as binders, fully and uniformly mixing, adding into a disc pelletizer to obtain a spherical material, putting the spherical material into a rotary kiln for calcining, and carrying out blast furnace treatment on the slag obtained after calcining.
Examples 1-57 chromium-containing wastewater was treated by the method of "treating waste with waste" of the present invention and then tested for water quality, and the test results were as follows:
the method for reducing the chromium-containing wastewater by using the acid wastewater prepared by the activated carbon can obviously remove the chromium content in the chromium-containing wastewater generated by cold rolling galvanization passivation, and simultaneously obviously remove ammonia nitrogen in the wastewater, and realizes organic integration of internal resources of a steel plant by adopting a waste-to-waste mode, thereby realizing low-cost harmless treatment of the chromium-containing wastewater.
In the description herein, the particular features, structures, materials, or characteristics disclosed may be combined in any suitable manner in any one or more embodiments or examples. Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents, all of which are within the scope of the invention.
Claims (11)
1. A method for reducing chromium-containing wastewater by using activated carbon acid-making wastewater is characterized by comprising the following steps:
(1) acid filtration: filtering the activated carbon acid-making wastewater to obtain carbon powder precipitate and clear liquid;
(2) oxidation-reduction reaction: mixing and stirring the clear liquid obtained in the step (1) and chromium-containing wastewater for reaction;
(3) heavy metal capture: after the reaction is finished, adjusting the pH of the solution to 8-10 by using alkaline liquor, and adding a recapture agent and a flocculating agent to obtain metal-containing sludge and clear liquid;
(4) and (3) deamination and nitrogen treatment: adjusting the pH of the clear liquid obtained in the step (3) to 11-14 by using alkali liquor, then transferring the clear liquid into a physical deamination device, and performing ammonia nitrogen removal and ammonia resource recovery to obtain high-salinity wastewater without ammonia nitrogen;
(5) and (3) chromium removal treatment: and (3) mixing the metal-containing sludge obtained in the step (3) with the carbon powder precipitate obtained in the step (1), adding blast furnace dry ash and a binder, transferring the mixed material to a pelletizer to obtain a spherical material, putting the spherical material into a rotary kiln for calcining, and further carrying out blast furnace treatment on the slag obtained after calcining.
2. The method for reducing chromium-containing wastewater by using activated carbon acid-making wastewater as claimed in claim 1, wherein the activated carbon acid-making wastewater in step (1) is from high-temperature decomposition gas generated by a desorption tower in an activated carbon flue gas purification process, and wastewater generated in a water washing purification process.
3. The method for reducing chromium-containing wastewater from acid production by using activated carbon as claimed in claim 1, wherein the chromium-containing wastewater from step (2) is wastewater from galvanizing process in cold rolling mill in steel industry.
4. The method for reducing chromium-containing wastewater by using activated carbon-made acid wastewater as claimed in claim 1, wherein the reaction time of the clear solution and the chromium-containing wastewater in the step (2) is 10-120min, and the pH of the mixed solution is controlled to be less than 5.
5. The method for reducing chromium-containing wastewater from the production of acid by using activated carbon as claimed in claim 1, wherein the alkali solution in step (3) is one of sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate.
6. The method for reducing chromium-containing wastewater by using activated carbon-to-acid wastewater according to claim 1, wherein the heavy metal capturing agent in the step (3) is an organic sulfur type heavy metal capturing agent, and the addition amount of the heavy metal capturing agent is 10-500 mg/L.
7. The method for reducing chromium-containing wastewater from activated carbon-made acid wastewater according to claim 1, wherein the flocculant in step (3) is PAM, and the addition amount of PAM is 0.005-1 wt%.
8. The method for reducing chromium-containing wastewater by using activated carbon acid-making wastewater as claimed in claim 1, wherein the physical deamination device in the step (4) is one or more of an ammonia still, a stripping tower and a gaseous membrane device.
9. The method for reducing chromium-containing wastewater from activated carbon-made acid wastewater according to claim 1, wherein the binder in the step (5) is bentonite.
10. The method for reducing chromium-containing wastewater by using activated carbon acid-making wastewater as claimed in claim 1, wherein the pelletizer in the step (5) is one or more of a pair-roller pelletizer, a disc pelletizer and a cylinder pelletizer.
11. The method for reducing chromium-containing wastewater from acid production with activated carbon as claimed in claim 1, wherein the slag is collected and added into the blast furnace, and chromium enters molten iron due to its property close to that of iron, so as to realize harmless treatment of chromium.
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| CN108002580A (en) * | 2017-09-22 | 2018-05-08 | 中冶长天国际工程有限责任公司 | A kind of acidic flue gas treatment of waste water from washing and application thereof |
| CN109052711A (en) * | 2018-08-16 | 2018-12-21 | 武汉钢铁有限公司 | The innoxious and resource utilization method of steel and iron industry chromate waste water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108002580A (en) * | 2017-09-22 | 2018-05-08 | 中冶长天国际工程有限责任公司 | A kind of acidic flue gas treatment of waste water from washing and application thereof |
| CN109052711A (en) * | 2018-08-16 | 2018-12-21 | 武汉钢铁有限公司 | The innoxious and resource utilization method of steel and iron industry chromate waste water |
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| CN113976135A (en) * | 2021-11-18 | 2022-01-28 | 国网山东省电力公司电力科学研究院 | Chromium-containing wastewater treatment method, chromium-containing catalyst, preparation method and application |
| CN113976135B (en) * | 2021-11-18 | 2023-09-22 | 国网山东省电力公司电力科学研究院 | Chromium-containing wastewater treatment method, chromium-containing catalyst, preparation method and application |
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