CN112458292A - Classification and recovery process for valuable metals in waste acid - Google Patents
Classification and recovery process for valuable metals in waste acid Download PDFInfo
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- CN112458292A CN112458292A CN202011286129.5A CN202011286129A CN112458292A CN 112458292 A CN112458292 A CN 112458292A CN 202011286129 A CN202011286129 A CN 202011286129A CN 112458292 A CN112458292 A CN 112458292A
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- waste
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- copper sulfide
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- 239000002699 waste material Substances 0.000 title claims abstract description 52
- 239000002253 acid Substances 0.000 title claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 24
- 239000002184 metal Substances 0.000 title claims abstract description 23
- 150000002739 metals Chemical class 0.000 title claims abstract description 18
- 238000011084 recovery Methods 0.000 title abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 40
- 230000008569 process Effects 0.000 claims abstract description 31
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 29
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 239000002912 waste gas Substances 0.000 claims abstract description 17
- 230000001376 precipitating effect Effects 0.000 claims abstract description 15
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 13
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 13
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 13
- 239000004571 lime Substances 0.000 claims abstract description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000007599 discharging Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 6
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 6
- 239000000701 coagulant Substances 0.000 claims abstract description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002351 wastewater Substances 0.000 claims abstract description 6
- 239000011787 zinc oxide Substances 0.000 claims abstract description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 5
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 238000005342 ion exchange Methods 0.000 claims abstract description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 17
- 239000003546 flue gas Substances 0.000 claims description 17
- 239000000706 filtrate Substances 0.000 claims description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 12
- 239000005751 Copper oxide Substances 0.000 claims description 11
- 229910000431 copper oxide Inorganic materials 0.000 claims description 11
- 238000006477 desulfuration reaction Methods 0.000 claims description 8
- 230000023556 desulfurization Effects 0.000 claims description 8
- 238000003837 high-temperature calcination Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000003463 adsorbent Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 6
- 239000011550 stock solution Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical group [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000011162 core material Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 239000004071 soot Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 239000002910 solid waste Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- -1 fluoride ions Chemical class 0.000 abstract 1
- 230000001698 pyrogenic effect Effects 0.000 abstract 1
- 239000000779 smoke Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0002—Preliminary treatment
- C22B15/001—Preliminary treatment with modification of the copper constituent
- C22B15/0013—Preliminary treatment with modification of the copper constituent by roasting
- C22B15/0017—Sulfating or sulfiding roasting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
-
- 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
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a process for classifying and recovering valuable metals in waste acid, which comprises the following steps: precipitating dirty acid raw materials, filtering crystal particles, preparing copper sulfide, reducing copper sulfide, treating waste gas, feeding and filtering, carrying out ion exchange, carrying out cyclone electrolysis and neutralizing and discharging, precipitating and filtering dirty acid to remove impurities in the dirty acid, then adding lime, coagulant, sodium hypochlorite and ferric chloride into the waste acid to obtain copper sulfide and separation liquid, calcining the copper sulfide according to a pyrogenic process to obtain copper, carrying out environment-friendly treatment on the generated waste gas, then adding concentrated sulfuric acid, white smoke ash and zinc oxide into the separation liquid, stirring to obtain a mixed liquid, removing chloride ions and fluoride ions in the mixed liquid by using ion exchange resin, then, the heavy metal zinc is obtained by using the cyclone electrolysis device, valuable metals in the waste acid can be effectively recovered, the method is more efficient and convenient compared with a common recovery method, and the waste gas and the waste water are discharged and treated, so that the method is more environment-friendly.
Description
Technical Field
The invention relates to the field of metal recovery, in particular to a process for classifying and recovering valuable metals in waste acid.
Background
In the acid making process flow of copper smelting, the flue gas of a smelting furnace and a converter after electric dust collection passes through two sections of dynamic wave washers, the generated acid is polluted acid, the polluted acid contains various metal elements with certain content, including zinc, copper and the like, the commonly used polluted acid is mostly discharged and treated through a polluted acid sewage treatment station, although the pollution to the environment is reduced, various valuable metals in the polluted acid cannot be effectively recovered in the treatment process, and unnecessary resource waste is caused.
Disclosure of Invention
The invention mainly aims to provide a process for classifying and recovering valuable metals in waste acid, which can effectively solve the problems in the background technology.
In order to achieve the purpose, the invention adopts the technical scheme that:
a process for classifying and recovering valuable metals in waste acid comprises the following steps:
s1: settling a dirty acid raw material, draining dirty acid into a settling tank for standing and settling to realize primary material separation, settling some solid wastes and impurities in the dirty acid raw material, and taking a stock solution above;
s2: filtering crystal particles, injecting stock solution into a storage tank, filtering by using a filter membrane to realize core material separation, and separating solid particles which are insoluble in water and organic matters with particle sizes larger than 1 micron to obtain filtrate;
s3: preparing copper sulfide, namely injecting filtrate into a reaction tank, adding lime, coagulant, sodium hypochlorite and ferric chloride into the filtrate, stirring to fully react, standing and precipitating again after the reaction is finished to precipitate waste residues to the bottom of the reaction tank, and then performing solid-liquid separation to obtain copper sulfide waste residues and a separation solution;
s4: reducing copper sulfide, cleaning the obtained copper sulfide waste residue, then putting the copper sulfide waste residue into a furnace for high-temperature calcination to obtain copper oxide solid and sulfur dioxide waste gas, and then carrying out high-temperature calcination reaction on the copper oxide and the copper sulfide waste residue to obtain copper;
s5: waste gas treatment, namely carrying out waste gas treatment on the sulfur dioxide pollution gas generated in the calcining process, treating the gas by using a flue gas desulfurization mode, and spraying an adsorbent into the flue gas to remove sulfur dioxide so as to reach the emission standard;
s6: adding materials and filtering, injecting the obtained separation liquid into a reaction kettle, adding concentrated sulfuric acid, then adding white soot, heating and leaching, finally adding zinc oxide to adjust the pH value, stirring, reacting and filtering to obtain a mixed liquid;
s7: ion exchange, namely using ion exchange resin, removing chlorine in the mixed solution by using chloride ion exchange resin, and removing fluorine in the mixed solution by using fluoride ion exchange resin;
s8: performing cyclone electrolysis, namely performing cyclone electrolysis on the mixed solution after ions are removed by using a cyclone electrolysis device so as to remove arsenic in the mixed solution and recover heavy metal zinc in the mixed solution;
s9: and (4) neutralizing and discharging, namely adding lime into the treated residual mixed liquor for neutralization, and finally discharging the wastewater.
Preferably, in the step S1, the standing and precipitating time is not less than 1 h.
Preferably, in the step S3, the stirring time is 10 to 15min, the standing and precipitating time is 2h, the upper separated liquid should be extracted first during solid-liquid separation, and then the bottom copper oxide waste residue is obtained.
Preferably, in the step S5, the flue gas generated during the calcination process should be discharged through a high chimney, and the flue gas desulfurization may be performed by spraying a liquid or powder adsorbent into the flue gas in a wet or dry manner, so as to achieve environment-friendly discharge.
Preferably, in the step S6, concentrated sulfuric acid is added to adjust the acidity to 40-50g/L, the heating temperature needs to reach 80 ℃, and the PH should be adjusted to 3.0 when zinc chloride is added.
Preferably, in the step S9, lime is added to adjust the ph of the residual mixed solution to be close to zero, and the mixed solution is discharged.
Compared with the prior art, the invention has the following beneficial effects:
through deposiing and filtering dirty sour, impurity and granule wherein can effectively be got rid of, conveniently carry out subsequent technology and handle, through add lime in the filtrating, the coagulant, sodium hypochlorite and ferric chloride, obtain the copper oxide residue, obtain copper through pyrometallurgy copper smelting again, through adding concentrated sulfuric acid in the parting liquid, white cigarette ash and zinc oxide, and take out the ion through ion exchange resin, can obtain metallic zinc through whirl electrolysis, through adsorbing and neutralizing waste gas and waste water, effectively reduce the pollution degree of waste material, promote industrial environmental protection degree.
Drawings
FIG. 1 is a process flow chart of the process for classifying and recovering valuable metals in waste acid.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
As shown in fig. 1, a process for classifying and recovering valuable metals in waste acid comprises the following steps:
s1: the method comprises the following steps of (1) precipitating a dirty acid raw material, in order to effectively remove impurities in the dirty acid, draining the dirty acid into a precipitation tank for standing precipitation to realize primary material separation, precipitating solid wastes and impurities in the dirty acid raw material, and taking a stock solution above;
s2: filtering crystal particles, injecting stock solution into a storage tank, filtering by using a filter membrane to realize core material separation, and separating solid particles which are insoluble in water and organic matters with particle sizes larger than 1 micron to obtain filtrate;
s3: preparing copper sulfide, namely injecting filtrate into a reaction tank in order to recover metal copper in waste acid, adding lime, a coagulant, sodium hypochlorite and ferric chloride into the filtrate, stirring to fully react the filtrate, standing and precipitating the filtrate again after the reaction is finished to precipitate waste residues to the bottom of the reaction tank, and then carrying out solid-liquid separation to obtain copper sulfide waste residues and a separation solution;
s4: copper sulfide reduction, namely, in order to recover metal copper from copper sulfide waste residues, cleaning the obtained copper sulfide waste residues, then putting the copper sulfide waste residues into a furnace for high-temperature calcination to obtain copper oxide solids and sulfur dioxide waste gas, and then performing high-temperature calcination reaction on the copper oxide and the copper sulfide waste residues to obtain copper;
s5: waste gas treatment, in order to avoid pollution caused by direct emission of the sulfur dioxide gas generated by calcination into the atmosphere, the waste gas treatment is carried out on the sulfur dioxide pollution gas generated in the calcination process, the treatment is carried out by using a flue gas desulfurization mode, and an adsorbent is sprayed into the flue gas to remove the sulfur dioxide so as to reach the emission standard;
s6: adding materials and filtering, in order to remove ions in the separation liquid and obtain metal zinc, injecting the separation liquid obtained in the previous step into a reaction kettle, adding concentrated sulfuric acid, then adding white soot, heating and leaching, finally adding zinc oxide to adjust the pH value, stirring, reacting and filtering to obtain a mixed liquid;
s7: ion exchange, namely using ion exchange resin, removing chlorine in the mixed solution by using chloride ion exchange resin, and removing fluorine in the mixed solution by using fluoride ion exchange resin;
s8: performing cyclone electrolysis, namely performing cyclone electrolysis on the mixed solution after ions are removed by using a cyclone electrolysis device so as to remove arsenic in the mixed solution and recover heavy metal zinc in the mixed solution;
s9: and (4) neutralizing and discharging, namely adding lime into the treated residual mixed liquid for neutralization in order to avoid pollution caused by discharging residual liquid, and finally discharging waste water.
In the step S1, standing and precipitating for not less than 1h, in the step S3, stirring for 10-15min, standing and precipitating for 2h, extracting upper separation liquid during solid-liquid separation, then obtaining copper oxide waste residue at the bottom, in the step S5, discharging flue gas in the calcining process through a high chimney, spraying liquid or powder adsorbent into the flue gas for desulfurization by using a wet method or a dry method to realize environment-friendly discharge, in the step S6, adding concentrated sulfuric acid to adjust the acidity to 40-50g/L, heating the temperature to 80 ℃, adding zinc chloride to adjust the pH to 3.0, and in the step S9, adding lime to adjust the pH value in the residual mixed liquid to be close to zero and discharging.
The invention is a process for classifying and recovering valuable metals in waste acid, firstly introducing waste acid to be recovered into a precipitation tank, standing and precipitating for more than 1h to make impurities fall to the bottom of the tank, then extracting raw liquid in the tank, putting the raw liquid into a storage tank and performing filtering operation by matching with a filter membrane to realize core material separation, separating solid particles which are insoluble in water and organic matters with particle size larger than 1 micron to obtain filtrate, then extracting and recovering metallic copper in the filtrate, injecting the filtrate into a reaction tank, cleaning and drying the reaction tank to avoid impurities, then adding lime, coagulant, sodium hypochlorite and ferric chloride into the reaction tank, stirring for auxiliary stirring during reaction, stirring for about 15min to make the mixture react fully, standing and precipitating again after the reaction is finished, standing for 2 hours to ensure that waste residues generated in the reaction are completely precipitated to the bottom of a reaction tank, then carrying out solid-liquid separation, firstly extracting a separation liquid in the reaction tank, pumping the separation liquid in the reaction tank by using a pump, then obtaining copper sulfide waste residues at the bottom of the reaction tank, then recovering the obtained copper sulfide waste residues, putting the copper sulfide waste residues into a furnace for calcination to obtain metal copper, firstly cleaning the obtained copper sulfide waste residues, then putting the copper sulfide waste residues into the furnace for high-temperature calcination, discharging waste gas generated in the calcination process by using a high chimney by using a calciner to obtain copper oxide solid and sulfur dioxide waste gas, then carrying out high-temperature calcination reaction on the copper oxide and the copper sulfide waste residues to obtain copper, wherein a certain amount of sulfur dioxide gas is generated in the calcination process, and the sulfur dioxide is a harmful substance and is directly discharged into the atmosphere to seriously pollute the environment, so that the waste gas generated in the calcination process needs to be subjected to, the method comprises the following steps of carrying out desulfurization treatment by using a flue gas desulfurization mode, and spraying a liquid or powdery adsorbent into flue gas to remove sulfur dioxide so as to reach the emission standard and avoid polluting the atmospheric environment; adding materials into the separation liquid, filtering, injecting the separation liquid into a reaction kettle, adding concentrated sulfuric acid, adjusting the acidity to 50g/L, adding white soot, heating to 80 ℃, leaching, adding zinc oxide to adjust the pH to 3.0, stirring, reacting and filtering to obtain a mixed liquid, removing chlorine in the mixed liquid by using chloride ion exchange resin and fluorine in the mixed liquid by using fluorine ion exchange resin, performing cyclone electrolysis on the mixed liquid by using a cyclone electrolysis device to remove arsenic in the mixed liquid and recover heavy metal zinc in the mixed liquid, and directly discharging the residual mixed liquid to pollute soil, thereby adding lime into the residual mixed liquid and measuring the pH value of the mixed liquid, the waste acid recycling process has the advantages that the waste acid recycling process is close to zero and then is discharged, pollution is avoided, valuable metals in waste acid can be effectively recycled according to the process, the waste acid recycling process is more efficient and convenient compared with a common recycling method, waste gas and waste water are discharged and treated, and the waste acid recycling process is more environment-friendly.
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.
Claims (6)
1. A process for classifying and recovering valuable metals in waste acid is characterized by comprising the following steps: the method comprises the following steps:
s1: settling a dirty acid raw material, draining dirty acid into a settling tank for standing and settling to realize primary material separation, settling some solid wastes and impurities in the dirty acid raw material, and taking a stock solution above;
s2: filtering crystal particles, injecting stock solution into a storage tank, filtering by using a filter membrane to realize core material separation, and separating solid particles which are insoluble in water and organic matters with particle sizes larger than 1 micron to obtain filtrate;
s3: preparing copper sulfide, namely injecting filtrate into a reaction tank, adding lime, coagulant, sodium hypochlorite and ferric chloride into the filtrate, stirring to fully react, standing and precipitating again after the reaction is finished to precipitate waste residues to the bottom of the reaction tank, and then performing solid-liquid separation to obtain copper sulfide waste residues and a separation solution;
s4: reducing copper sulfide, cleaning the obtained copper sulfide waste residue, then putting the copper sulfide waste residue into a furnace for high-temperature calcination to obtain copper oxide solid and sulfur dioxide waste gas, and then carrying out high-temperature calcination reaction on the copper oxide and the copper sulfide waste residue to obtain copper;
s5: waste gas treatment, namely carrying out waste gas treatment on the sulfur dioxide pollution gas generated in the calcining process, treating the gas by using a flue gas desulfurization mode, and spraying an adsorbent into the flue gas to remove sulfur dioxide so as to reach the emission standard;
s6: adding materials and filtering, injecting the obtained separation liquid into a reaction kettle, adding concentrated sulfuric acid, then adding white soot, heating and leaching, finally adding zinc oxide to adjust the pH value, stirring, reacting and filtering to obtain a mixed liquid;
s7: ion exchange, namely using ion exchange resin, removing chlorine in the mixed solution by using chloride ion exchange resin, and removing fluorine in the mixed solution by using fluoride ion exchange resin;
s8; performing cyclone electrolysis, namely performing cyclone electrolysis on the mixed solution after ions are removed by using a cyclone electrolysis device so as to remove arsenic in the mixed solution and recover heavy metal zinc in the mixed solution;
s9; and (4) neutralizing and discharging, namely adding lime into the treated residual mixed liquor for neutralization, and finally discharging the wastewater.
2. The process for classifying and recovering valuable metals in waste acid according to claim 1, which is characterized in that: and in the step S1, the standing and precipitating time is not less than 1 h.
3. The process for classifying and recovering valuable metals in waste acid according to claim 1, which is characterized in that: in the step S3, the stirring time is 10-15min, the standing and precipitating time is 2h, the upper separation liquid is firstly extracted during solid-liquid separation, and then the copper oxide waste residue at the bottom is obtained.
4. The process for classifying and recovering valuable metals in waste acid according to claim 1, which is characterized in that: in the step S5, the flue gas in the calcination process should be discharged through a high chimney, and wet or dry flue gas desulfurization may be performed by spraying a liquid or powdery adsorbent into the flue gas to achieve environment-friendly discharge.
5. The process for classifying and recovering valuable metals in waste acid according to claim 1, which is characterized in that: in the step S6, concentrated sulfuric acid is added to adjust the acidity to 40-50g/L, the heating temperature needs to reach 80 ℃, and the pH value is adjusted to 3.0 when zinc chloride is added.
6. The process for classifying and recovering valuable metals in waste acid according to claim 1, which is characterized in that: and in the step S9, lime is added to adjust the pH value of the residual mixed solution to be close to zero and the mixed solution is discharged.
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