CN112960814A - Harmless treatment method for leachate of electrolytic manganese slag - Google Patents
Harmless treatment method for leachate of electrolytic manganese slag Download PDFInfo
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- CN112960814A CN112960814A CN202110148423.8A CN202110148423A CN112960814A CN 112960814 A CN112960814 A CN 112960814A CN 202110148423 A CN202110148423 A CN 202110148423A CN 112960814 A CN112960814 A CN 112960814A
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- leachate
- electrolytic manganese
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- manganese slag
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000002893 slag Substances 0.000 title claims abstract description 45
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 43
- 239000011572 manganese Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 52
- 239000003607 modifier Substances 0.000 claims abstract description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011593 sulfur Substances 0.000 claims abstract description 31
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 31
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 26
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000292 calcium oxide Substances 0.000 claims abstract description 25
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 238000001179 sorption measurement Methods 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 17
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 239000006228 supernatant Substances 0.000 claims abstract description 17
- 239000010457 zeolite Substances 0.000 claims abstract description 17
- 239000008394 flocculating agent Substances 0.000 claims abstract description 9
- 230000001105 regulatory effect Effects 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000005484 gravity Effects 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000003002 pH adjusting agent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 19
- 239000007789 gas Substances 0.000 abstract description 8
- 229910001437 manganese ion Inorganic materials 0.000 abstract description 6
- 238000002386 leaching Methods 0.000 abstract description 4
- 239000011259 mixed solution Substances 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- 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
-
- 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
- C02F2101/206—Manganese or manganese compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
Abstract
The invention discloses a harmless treatment method for leachate of electrolytic manganese slag, which comprises the following steps: s1: filtering to obtain leachate A; s2: preparing a modifier; s3: pouring the modifier into the percolate A, and uniformly mixing and stirring to obtain a mixture B; s4: adding a PH regulator into the mixture B, and regulating the PH value to 7-10 to obtain a mixture C; s5: adding a flocculating agent into the mixture C; s6: performing pulse electrolysis on the supernatant D to obtain a mixed gas F and a remainder E; s7: and adsorbing the residue E by using electrolytic manganese slag-based zeolite. The modifier is prepared from the sulfur fixation ash and the calcium oxide, so that the adsorption efficiency of manganese ions in the mixed solution can be improved, and the removal capacity of the manganese ions in the leachate can be further improved. By adopting a pulse electrolysis mode, the ammonia nitrogen double salt ore phase with lower solubility in the electrolytic manganese slag can be changed, the ammonia nitrogen leaching period is quickly cut off, and the treatment efficiency of the leachate is improved.
Description
Technical Field
The invention relates to the technical field of electrolytic manganese slag leachate treatment, in particular to a harmless treatment method for leachate of electrolytic manganese slag.
Background
China is the biggest world with the highest production, consumption and export of electrolytic manganese metal, and the electrolytic manganese metal yield in China in 2017 reaches 175 ten thousand tons, which accounts for 98.5 percent of the total global electrolytic manganese yield. The electrolytic manganese slag is a mixture of acid leaching slag, sulfide slag and anode slag generated after acidolysis, neutralization, filter pressing and impurity removal of manganese carbonate ore in the production process of electrolytic manganese metal, and is a key pollutant in the electrolytic manganese industry. The production amount of electrolytic manganese slag reaches 7-11 tons per ton of manganese, the annual production amount is about 2000 ten thousand tons, and the accumulated amount is huge over the years. At present, enterprises do not find a method for properly treating electrolytic manganese slag, and the electrolytic manganese slag is generally transported to a storage yard to be built into a dam for stacking. Under the influence of natural factors such as rain wash and the like, the long-term stacked electrolytic manganese residues seriously pollute the soil, surface water and underground water around the landfill site through surface runoff and percolation. The electrolytic manganese slag leachate has complex components, high concentration and large change, and the main pollutants are total manganese, ammonia nitrogen and heavy metal ions such as lead, cadmium, nickel and the like.
The patent application number is 2016105286998, and the name is a method for harmlessly treating electrolytic manganese slag leachate. Carrying out suction filtration on the electrolytic manganese slag leachate collected from the slag warehouse to obtain clear filtrate; adding saturated clear lime water into a container in which the clear filtrate is placed, and adjusting the pH value of the solution to 7.0-8.0 to obtain a mixture A; adding sodium silicate powder into the mixture A, and stirring for 1-2 hours to obtain a mixture B; the weight to volume ratio (g: mL) of the sodium silicate to the clear filtrate is in the range of 1: 150-1: 200 of a carrier; adding sodium chloride crystals into the mixture B, and stirring to obtain a mixture C; the concentration range of sodium chloride in the mixture C is 200-250 mg/L; 5) and adding a cathode plate and an anode plate on a container in which the mixture C is placed, loading an electric field and stirring, and obtaining the harmlessly treated electrolytic manganese slag leachate after 3-4 hours.
The sodium silicate adopted by the electrolytic manganese slag leachate treatment method is high in cost, and the treatment effect of the electrolytic manganese slag leachate is poor, so that the development of the effective treatment method of the electrolytic manganese slag leachate is of great significance.
Disclosure of Invention
The invention aims to solve the problems of poor treatment effect and high treatment cost of the existing electrolytic manganese slag leachate and provides a harmless treatment method of the leachate of the electrolytic manganese slag.
A method for harmlessly treating percolate of electrolytic manganese residues comprises the following steps:
s1: filtering, namely pouring the manganese slag leachate after electrolysis into a filter, and filtering to obtain a leachate A;
s2: preparing a modifier: mixing the sulfur fixation ash and calcium oxide, and putting the mixture into a ball mill for carrying out ball milling; obtaining a modifier;
s3: pouring the modifier into the percolate A, and uniformly mixing and stirring to obtain a mixture B;
s4: adding a PH regulator into the mixture B, and regulating the PH value to 7-10 to obtain a mixture C;
s5: adding a flocculating agent into the mixture C, and standing and separating to obtain a supernatant D and a precipitate E;
s6: performing pulse electrolysis on the supernatant D to obtain a mixed gas F and a remainder E;
s7: and adsorbing the remainder E by adopting electrolytic manganese slag-based zeolite to obtain system reuse water.
Further, the specific gravity of the solid sulfur ash and the calcium oxide in the S2 is 2: 1.
further, the ball milling time in the step S2 is 45-60 min, and the ball milling rotation speed is 450-525 r/min.
Further, the temperature in the step S3 is controlled to be 35-40 ℃, and the temperature in the step S4 is controlled to be 40-45 ℃.
Further, the PH adjusting agent in step S4 is set to be clear lime water or sodium hydroxide.
Further, the stirring speed in the step S3 and the step S4 is 120 r/min.
Further, the precipitate E in the step S5 is dehydrated and dried, and then collected and stored.
Further, the current density in the step S6 is 70-80 mA/cm ^2, and the pulse frequency is 4500-6000 Hz.
Further, the electrolytic manganese slag-based zeolite in the step S7 is 15-30 g/L, and the adsorption time is 60-80 min.
The invention has the beneficial effects that: 1. the modifier is prepared from the sulfur fixation ash and the calcium oxide, so that the adsorption efficiency of manganese ions in the mixed solution can be improved, and the removal capacity of the manganese ions in the leachate can be further improved. 2. By adopting a pulse electrolysis mode, the ammonia nitrogen double salt ore phase with lower solubility in the electrolytic manganese slag can be changed, the ammonia nitrogen leaching period is quickly cut off, and the treatment efficiency of the leachate is improved.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict.
Example 1:
a method for harmlessly treating percolate of electrolytic manganese residues comprises the following steps:
s1: filtering, namely pouring the manganese slag leachate after electrolysis into a filter, and filtering to obtain a leachate A;
s2: preparing a modifier: mixing the sulfur fixation ash and calcium oxide, and putting the mixture into a ball mill for carrying out ball milling; obtaining a modifier;
s3: pouring the modifier into the percolate A, and uniformly mixing and stirring to obtain a mixture B;
s4: adding a PH regulator into the mixture B, and regulating the PH value to 7-10 to obtain a mixture C;
s5: adding a flocculating agent into the mixture C, and standing and separating to obtain a supernatant D and a precipitate E;
s6: performing pulse electrolysis on the supernatant D to obtain a mixed gas F and a remainder E;
s7: and adsorbing the remainder E by adopting electrolytic manganese slag-based zeolite to obtain system reuse water.
Specifically, the specific gravity of the solid sulfur ash and the calcium oxide in the S2 is 2: 1.
specifically, the ball milling time in the step S2 is 45min, and the ball milling rotation speed is 525 r/min.
Specifically, the temperature in step S3 is controlled to be 35 ℃, and the temperature in step S4 is controlled to be 40 ℃.
Specifically, the PH adjusting agent in step S4 is set to clarify lime water.
Specifically, the stirring speed in the steps S3 and S4 is 120 r/min.
Specifically, the precipitate E in the step S5 is dehydrated and dried, and then collected and stored.
Specifically, the current density in the step S6 is 700mA/cm ^2, and the pulse frequency is 4500 Hz.
Specifically, the electrolytic manganese residue-based zeolite in the step S7 is 15g/L, and the adsorption time is 60 min.
The modifier obtained by mixing and ball milling the solid sulfur ash and calcium oxide increases the unit adsorption capacity of single solid sulfur ash from 5.3mg/g to 27.45mg/g, and the adsorption efficiency is improved from 13.75% to 68.6%.
Compared with the traditional direct current treatment, the efficiency of pulse treatment of ammonia nitrogen is improved by 16.1 percent, energy consumption is saved by 20.72 percent, namely, the ammonia nitrogen solution with the same concentration is treated, and the energy consumption can be reduced by pulse electrolysis.
Example 2:
a method for harmlessly treating percolate of electrolytic manganese residues comprises the following steps:
s1: filtering, namely pouring the manganese slag leachate after electrolysis into a filter, and filtering to obtain a leachate A;
s2: preparing a modifier: mixing the sulfur fixation ash and calcium oxide, and putting the mixture into a ball mill for carrying out ball milling; obtaining a modifier;
s3: pouring the modifier into the percolate A, and uniformly mixing and stirring to obtain a mixture B;
s4: adding a pH regulator into the mixture B, and regulating the pH value to be 10 to obtain a mixture C;
s5: adding a flocculating agent into the mixture C, and standing and separating to obtain a supernatant D and a precipitate E;
s6: performing pulse electrolysis on the supernatant D to obtain a mixed gas F and a remainder E;
s7: and adsorbing the remainder E by adopting electrolytic manganese slag-based zeolite to obtain system reuse water.
Specifically, the specific gravity of the solid sulfur ash and the calcium oxide in the S2 is 2: 1.
specifically, the ball milling time in the step S2 is 60min, and the ball milling rotation speed is 500 r/min.
Specifically, the temperature in step S3 is controlled to be 40 ℃, and the temperature in step S4 is controlled to be 42 ℃.
Specifically, the PH adjusting agent in step S4 is set to clarify lime water.
Specifically, the stirring speed in the steps S3 and S4 is 120 r/min.
Specifically, the precipitate E in the step S5 is dehydrated and dried, and then collected and stored.
Specifically, the current density in the step S6 is 70mA/cm ^2, and the pulse frequency is 5000 Hz.
Specifically, the electrolytic manganese residue-based zeolite in the step S7 is 28g/L, and the adsorption time is 70 min.
The modifier obtained by mixing and ball milling the solid sulfur ash and calcium oxide increases the unit adsorption capacity of single solid sulfur ash from 5.3mg/g to 27.45mg/g, and the adsorption efficiency is improved from 13.75% to 68.6%.
Compared with the traditional direct current treatment, the efficiency of pulse treatment of ammonia nitrogen is improved by 16.1 percent, energy consumption is saved by 20.72 percent, namely, the ammonia nitrogen solution with the same concentration is treated, and the energy consumption can be reduced by pulse electrolysis.
Example 1:
a method for harmlessly treating percolate of electrolytic manganese residues comprises the following steps:
s1: filtering, namely pouring the manganese slag leachate after electrolysis into a filter, and filtering to obtain a leachate A;
s2: preparing a modifier: mixing the sulfur fixation ash and calcium oxide, and putting the mixture into a ball mill for carrying out ball milling; obtaining a modifier;
s3: pouring the modifier into the percolate A, and uniformly mixing and stirring to obtain a mixture B;
s4: adding a pH regulator into the mixture B, and regulating the pH value to be 7 to obtain a mixture C;
s5: adding a flocculating agent into the mixture C, and standing and separating to obtain a supernatant D and a precipitate E;
s6: performing pulse electrolysis on the supernatant D to obtain a mixed gas F and a remainder E;
s7: and adsorbing the remainder E by adopting electrolytic manganese slag-based zeolite to obtain system reuse water.
Specifically, the specific gravity of the solid sulfur ash and the calcium oxide in the S2 is 2: 1.
specifically, the ball milling time in the step S2 is 45min, and the ball milling rotation speed is 525 r/min.
Specifically, the temperature in step S3 is controlled to be 40 ℃, and the temperature in step S4 is controlled to be 45 ℃.
Specifically, the PH adjuster in step S4 is sodium hydroxide.
Specifically, the stirring speed in the steps S3 and S4 is 120 r/min.
Specifically, the precipitate E in the step S5 is dehydrated and dried, and then collected and stored.
Specifically, the current density in the step S6 is 70mA/cm ^2, and the pulse frequency is 6000 Hz.
Specifically, the electrolytic manganese residue-based zeolite in the step S7 is 20g/L, and the adsorption time is 70 min.
The modifier obtained by mixing and ball milling the solid sulfur ash and calcium oxide increases the unit adsorption capacity of single solid sulfur ash from 5.3mg/g to 27.45mg/g, and the adsorption efficiency is improved from 13.75% to 68.6%.
Compared with the traditional direct current treatment, the efficiency of pulse treatment of ammonia nitrogen is improved by 16.1 percent, energy consumption is saved by 20.72 percent, namely, the ammonia nitrogen solution with the same concentration is treated, and the energy consumption can be reduced by pulse electrolysis.
Example 3:
a method for harmlessly treating percolate of electrolytic manganese residues comprises the following steps:
s1: filtering, namely pouring the manganese slag leachate after electrolysis into a filter, and filtering to obtain a leachate A;
s2: preparing a modifier: mixing the sulfur fixation ash and calcium oxide, and putting the mixture into a ball mill for carrying out ball milling; obtaining a modifier;
s3: pouring the modifier into the percolate A, and uniformly mixing and stirring to obtain a mixture B;
s4: adding a pH regulator into the mixture B, and regulating the pH value to be 8 to obtain a mixture C;
s5: adding a flocculating agent into the mixture C, and standing and separating to obtain a supernatant D and a precipitate E;
s6: performing pulse electrolysis on the supernatant D to obtain a mixed gas F and a remainder E;
s7: and adsorbing the remainder E by adopting electrolytic manganese slag-based zeolite to obtain system reuse water.
Specifically, the specific gravity of the solid sulfur ash and the calcium oxide in the S2 is 2: 1.
specifically, the ball milling time in the step S2 is 50min, and the ball milling rotation speed is 525 r/min.
Specifically, the temperature in step S3 is controlled to be 40 ℃, and the temperature in step S4 is controlled to be 45 ℃.
Specifically, the PH adjuster in step S4 is sodium hydroxide.
Specifically, the stirring speed in the steps S3 and S4 is 120 r/min.
Specifically, the precipitate E in the step S5 is dehydrated and dried, and then collected and stored.
Specifically, the current density in the step S6 is 75mA/cm ^2, and the pulse frequency is 6000 Hz.
Specifically, the electrolytic manganese residue-based zeolite in the step S7 is 30g/L, and the adsorption time is 60 min.
The modifier obtained by mixing and ball milling the solid sulfur ash and calcium oxide increases the unit adsorption capacity of single solid sulfur ash from 5.3mg/g to 27.45mg/g, and the adsorption efficiency is improved from 13.75% to 68.6%.
Compared with the traditional direct current treatment, the efficiency of pulse treatment of ammonia nitrogen is improved by 16.1 percent, energy consumption is saved by 20.72 percent, namely, the ammonia nitrogen solution with the same concentration is treated, and the energy consumption can be reduced by pulse electrolysis.
Example 4:
a method for harmlessly treating percolate of electrolytic manganese residues comprises the following steps:
s1: filtering, namely pouring the manganese slag leachate after electrolysis into a filter, and filtering to obtain a leachate A;
s2: preparing a modifier: mixing the sulfur fixation ash and calcium oxide, and putting the mixture into a ball mill for carrying out ball milling; obtaining a modifier;
s3: pouring the modifier into the percolate A, and uniformly mixing and stirring to obtain a mixture B;
s4: adding a pH regulator into the mixture B, and regulating the pH value to be 8 to obtain a mixture C;
s5: adding a flocculating agent into the mixture C, and standing and separating to obtain a supernatant D and a precipitate E;
s6: performing pulse electrolysis on the supernatant D to obtain a mixed gas F and a remainder E;
s7: and adsorbing the remainder E by adopting electrolytic manganese slag-based zeolite to obtain system reuse water.
Specifically, the specific gravity of the solid sulfur ash and the calcium oxide in the S2 is 2: 1.
specifically, the ball milling time in the step S2 is 50min, and the ball milling rotation speed is 500 r/min.
Specifically, the temperature in step S3 is controlled to be 35 ℃, and the temperature in step S4 is controlled to be 40 ℃.
Specifically, the PH adjuster in step S4 is sodium hydroxide.
Specifically, the stirring speed in the steps S3 and S4 is 120 r/min.
Specifically, the precipitate E in the step S5 is dehydrated and dried, and then collected and stored.
Specifically, the current density in the step S6 is 75mA/cm ^2, and the pulse frequency is 5000 Hz.
Specifically, the electrolytic manganese residue-based zeolite in the step S7 is 30g/L, and the adsorption time is 80 min.
The modifier obtained by mixing and ball milling the solid sulfur ash and calcium oxide increases the unit adsorption capacity of single solid sulfur ash from 5.3mg/g to 27.45mg/g, and the adsorption efficiency is improved from 13.75% to 68.6%.
Compared with the traditional direct current treatment, the efficiency of pulse treatment of ammonia nitrogen is improved by 16.1 percent, energy consumption is saved by 20.72 percent, namely, the ammonia nitrogen solution with the same concentration is treated, and the energy consumption can be reduced by pulse electrolysis.
Example 5:
a method for harmlessly treating percolate of electrolytic manganese residues comprises the following steps:
s1: filtering, namely pouring the manganese slag leachate after electrolysis into a filter, and filtering to obtain a leachate A;
s2: preparing a modifier: mixing the sulfur fixation ash and calcium oxide, and putting the mixture into a ball mill for carrying out ball milling; obtaining a modifier;
s3: pouring the modifier into the percolate A, and uniformly mixing and stirring to obtain a mixture B;
s4: adding a pH regulator into the mixture B, and regulating the pH value to be 7 to obtain a mixture C;
s5: adding a flocculating agent into the mixture C, and standing and separating to obtain a supernatant D and a precipitate E;
s6: performing pulse electrolysis on the supernatant D to obtain a mixed gas F and a remainder E;
s7: and adsorbing the remainder E by adopting electrolytic manganese slag-based zeolite to obtain system reuse water.
Specifically, the specific gravity of the solid sulfur ash and the calcium oxide in the S2 is 2: 1.
specifically, the ball milling time in the step S2 is 458min, and the ball milling rotation speed is 480 r/min.
Specifically, the temperature in step S3 is controlled to 38 ℃, and the temperature in step S4 is controlled to 42 ℃.
Specifically, the PH adjusting agent in step S4 is set to be clear lime water or sodium hydroxide.
Specifically, the stirring speed in the steps S3 and S4 is 120 r/min.
Specifically, the precipitate E in the step S5 is dehydrated and dried, and then collected and stored.
Specifically, the current density in the step S6 is 75mA/cm ^2, and the pulse frequency is 5000 Hz.
Specifically, the electrolytic manganese residue-based zeolite in the step S7 is 27g/L, and the adsorption time is 70 min.
The modifier obtained by mixing and ball milling the solid sulfur ash and calcium oxide increases the unit adsorption capacity of single solid sulfur ash from 5.3mg/g to 27.45mg/g, and the adsorption efficiency is improved from 13.75% to 68.6%.
Compared with the traditional direct current treatment, the efficiency of pulse treatment of ammonia nitrogen is improved by 16.1 percent, energy consumption is saved by 20.72 percent, namely, the ammonia nitrogen solution with the same concentration is treated, and the energy consumption can be reduced by pulse electrolysis.
The modifier is prepared from the sulfur fixation ash and the calcium oxide, so that the adsorption efficiency of manganese ions in the mixed solution can be improved, and the removal capacity of the manganese ions in the leachate can be further improved.
By adopting a pulse electrolysis mode, the ammonia nitrogen double salt ore phase with lower solubility in the electrolytic manganese slag can be changed, the ammonia nitrogen leaching period is quickly cut off, and the treatment efficiency of the leachate is improved.
The above-mentioned embodiments only express the specific embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (9)
1. A method for harmlessly treating percolate of electrolytic manganese slag is characterized by comprising the following steps: the method comprises the following steps:
s1: filtering, namely pouring the manganese slag leachate after electrolysis into a filter, and filtering to obtain a leachate A;
s2: preparing a modifier: mixing the sulfur fixation ash and calcium oxide, and putting the mixture into a ball mill for carrying out ball milling; obtaining a modifier;
s3: pouring the modifier into the percolate A, and uniformly mixing and stirring to obtain a mixture B;
s4: adding a PH regulator into the mixture B, and regulating the PH value to 7-10 to obtain a mixture C;
s5: adding a flocculating agent into the mixture C, and standing and separating to obtain a supernatant D and a precipitate E;
s6: performing pulse electrolysis on the supernatant D to obtain a mixed gas F and a remainder E;
s7: and adsorbing the remainder E by adopting electrolytic manganese slag-based zeolite to obtain system reuse water.
2. The method for the innocent treatment of leachate of electrolytic manganese residues according to claim 1, characterized in that: the specific gravity of the solid sulfur ash and the calcium oxide in the S2 is 2: 1.
3. the method for the innocent treatment of leachate of electrolytic manganese residues according to claim 1, characterized in that: the ball milling time in the step S2 is 45-60 min, and the ball milling rotation speed is 450-525 r/min.
4. The method for the innocent treatment of leachate of electrolytic manganese residues according to claim 1, characterized in that: the temperature in the step S3 is controlled to be 35-40 ℃, and the temperature in the step S4 is controlled to be 40-45 ℃.
5. The method for the innocent treatment of leachate of electrolytic manganese residues according to claim 1, characterized in that: the PH adjusting agent in the step S4 is set to be clear lime water or sodium hydroxide.
6. The method for the innocent treatment of leachate of electrolytic manganese residues according to claim 1, characterized in that: the stirring speed in the step S3 and the step S4 was 120 r/min.
7. The method for the innocent treatment of leachate of electrolytic manganese residues according to claim 1, characterized in that: and (4) dehydrating and drying the precipitate E in the step S5, and then collecting and storing the precipitate E.
8. The method for the innocent treatment of leachate of electrolytic manganese residues according to claim 1, characterized in that: the current density in the step S6 is 70-80 mA/cm ^2, and the pulse frequency is 4500-6000 Hz.
9. The method for the innocent treatment of leachate of electrolytic manganese residues according to claim 1, characterized in that: the electrolytic manganese slag-based zeolite in the step S7 is 15-30 g/L, and the adsorption time is 60-80 min.
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Application publication date: 20210615 |