CN110451680A - A kind of processing method of nonferrous smelting waste acid - Google Patents
A kind of processing method of nonferrous smelting waste acid Download PDFInfo
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- CN110451680A CN110451680A CN201910685534.5A CN201910685534A CN110451680A CN 110451680 A CN110451680 A CN 110451680A CN 201910685534 A CN201910685534 A CN 201910685534A CN 110451680 A CN110451680 A CN 110451680A
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- Prior art keywords
- waste acid
- gained
- nonferrous smelting
- processing method
- smelting waste
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- Granted
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- 239000002253 acid Substances 0.000 title claims abstract description 63
- 239000002699 waste material Substances 0.000 title claims abstract description 61
- 238000003723 Smelting Methods 0.000 title claims abstract description 48
- 238000003672 processing method Methods 0.000 title claims abstract description 27
- 238000001914 filtration Methods 0.000 claims abstract description 33
- 239000000706 filtrate Substances 0.000 claims abstract description 32
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims abstract description 25
- 239000012528 membrane Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 19
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 17
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 16
- 239000010440 gypsum Substances 0.000 claims abstract description 16
- 238000004073 vulcanization Methods 0.000 claims abstract description 13
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000002893 slag Substances 0.000 claims abstract description 10
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 9
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 9
- 230000001376 precipitating effect Effects 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 5
- 239000010865 sewage Substances 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003546 flue gas Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000006071 cream Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 238000007670 refining Methods 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000012065 filter cake Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 239000007788 liquid Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 8
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 description 8
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 8
- 229910001431 copper ion Inorganic materials 0.000 description 8
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000009867 copper metallurgy Methods 0.000 description 4
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/20—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—Sulfides
-
- 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
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/02—Methods and apparatus for dehydrating gypsum
-
- 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
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Ceramic Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a kind of processing methods of nonferrous smelting waste acid.Nonferrous smelting waste acid is filtered using membrane filter first, obtains lead sulfate filter residue, recycles lead sulfate；Vulcanizing agent is added in gained filtrate, vulcanizes the copper in filtrate and generates copper sulfide precipitation, recycle copper resource after filtering；Then vulcanizing agent is added again in gained filtrate, the vulcanization of the heavy metals such as arsenic is made to generate precipitating removal；Then carbide slag is added in gained filtrate and adjusts its pH value, gypsum is made, be then dehydrated using centrifuge, obtain dehydrated gypsum；Last gained sewage carries out advanced treating, qualified discharge or recycling.Processing method of the present invention can effectively solve the problem that the technical issues of generating a large amount of dangerous waste slags in existing nonferrous smelting waste acid processing technique.
Description
One, technical field:
The invention belongs to nonferrous smelting pollutant abatement technology fields, more particularly, to a kind of processing side of nonferrous smelting waste acid
Method.
Two, background technique:
Waste acid contains contents of many kinds of heavy metal ion in acid water mainly from the dynamic wave flue gas washing of sulfuric acid plant, and
Concentration of heavy metal ion height, complex shape, toxicity are big.With petering out for mineral resources, lead-zinc smelting enterprise is faced with nothing
The situation of stable, single mineral resources, the ingredient in waste acid will be more complicated.Northwest Lead Zinc smeltery handles various schools of thinkers mine all the time,
Its waste acid has the characteristics that peracid, high Hg, high COD, high F, original vulcanization-lime Neutralisation treatment method be difficult to realize Hg,
The stably reaching standard of COD, F；Before 2010, since environmental protection pressure is smaller, and environmental protection itself is without benefit.Therefore, most of lead zinc
Smelting enterprise seldom focuses on the research work of this respect, not only causes the serious pollution of environment in this way, or even also causes the gold such as mercury
The loss of category.
The waste acid generated in Flue Gas of Nonferrous Smelting acid manufacturing processes contains the heavy metals such as a large amount of arsenic, lead, copper, common waste acid
Treatment process is waste acid to be firstly vulcanized to the most heavy metal of removal, then adjust waste acid pH value to neutrality.As Environmental Protection Situation is cured
Hair is severe, and waste acid conventional treatment process is often difficult to meet emission request.Waste acid conventional treatment process by vulcanization by copper, lead with
The heavy metals such as arsenic precipitate filtering together, cause the waste of copper, lead resource；Simultaneously as step vulcanization is difficult to completely remove weight
Metal, part heavy metal enter neutralization step, are reacted into gypsum with carbide slag, influence gypsum qualitt, and the gypsum of generation is
Dangerous waste, it is difficult to recycle.
The processing mode of waste acid is always the problem of Copper making industry, and enterprise is also studying always, exploring and seek in recent years
More efficient, convenient, environmental protection waste acid purification process.
Three, summary of the invention:
The technical problem to be solved by the present invention is the technology according to present in existing nonferrous smelting waste acid processing method is asked
Topic, the present invention provide a kind of processing method of new nonferrous smelting waste acid.Processing method of the present invention can effectively solve the problem that existing dirt
The technical issues of a large amount of dangerous waste slags are generated in sour processing technique.
To solve the above-mentioned problems, the technical solution adopted by the present invention is that:
The present invention provides a kind of processing method of nonferrous smelting waste acid, the treating method comprises following steps:
A, nonferrous smelting waste acid is filtered first using membrane filter, lead sulfate filter residue is obtained after filtering, recycles it
In lead sulfate；
B, vulcanizing agent is added in gained filtrate after step a filtering, control ORP value is 10~50mv, makes the copper in filtrate
Vulcanization generates copper sulfide precipitation, recycles copper resource after filtering；
C, vulcanizing agent is added in gained filtrate again after step b filtering, control ORP value is -20~0mv, makes the weight such as arsenic
Metal vulcanization generates precipitating removal；
D, carbide slag is added in the filtrate obtained by step c and adjusts its pH value to 7~8, gypsum is made, then uses centrifuge
By manufactured gypsum dehydration, dehydrated gypsum is obtained；
E, sewage obtained by step d is subjected to advanced treating, qualified discharge or recycling.
According to the processing method of above-mentioned nonferrous smelting waste acid, nonferrous smelting waste acid described in step a is flue gas during smelting system
Flue gas washing purifies during acid acid waste water containing heavy metal, the processing waste water for being mixed with flue gas and electrolysis system draining
At least one of.
According to the processing method of above-mentioned nonferrous smelting waste acid, the filter membrane mesh number of membrane filter described in step a is 100
~500 mesh.
It is leaded in lead sulfate filter residue described in step a in terms of butt according to the processing method of above-mentioned nonferrous smelting waste acid
Mass percent be 50~70%.
According to the processing method of above-mentioned nonferrous smelting waste acid, vulcanizing agent described in step b be vulcanized sodium, NaHS or
Hydrogen sulfide；In terms of butt, cupric mass percent is 20~28% in gained copper sulfide precipitation.
According to the processing method of above-mentioned nonferrous smelting waste acid, vulcanizing agent described in step c be vulcanized sodium, NaHS or
Hydrogen sulfide.
According to the processing method of above-mentioned nonferrous smelting waste acid, in step d gained dehydrated gypsum in moisture content be reduced to≤
15%；In terms of butt, the mass percent of sulfur acid calcium is 40~60% in gained dehydrated gypsum.
According to the processing method of above-mentioned nonferrous smelting waste acid, the detailed process of advanced treating described in step e are as follows: in step
Nanoscale Iron is added after rapid d centrifuge separation in gained sewage, Nanoscale Iron dosage is 200~500ppm, is carried out after Nanoscale Iron is added
Filtering, gained supernatant qualified discharge or recycling.
Positive beneficial effect of the invention:
1, waste acid is filtered using membrane filter, lead sulfate filter residue is obtained after filtering, nonferrous smelting dirt can be recycled
At least 98% lead in acid.
2, by vulcanizing to two sections of waste acid, in nonferrous smelting waste acid at least 80% copper not only can be recycled, but also can remove at least
95% arsenic and other heavy metals.
3, waste acid by two sections vulcanization after, after obtained vulcanization in liquid heavy metal ion be down to it is extremely low.To liquid after this vulcanization
It is neutralized, obtained gypsum purity is higher, avoids traditional handicraft and generates largely containing the gypsum tailings of heavy metal, effectively returns
With the sulfate radical in waste liquid, and greatly reduce the neutralization medicament additional amount of back segment system neutralisation treatment technique.
4, using technical solution of the present invention, nonferrous smelting waste acid after processing can stably reaching standard discharge.
Four, specific embodiment:
The present invention is further explained with reference to embodiments, but is not intended to limit the range of technical solution of the present invention protection.
Embodiment 1:
It is process object, each main component concentration are as follows: (quality percentage is dense for sulfuric acid 15.3% with the waste acid of certain copper smelting plant
Degree), copper ion 2133.8mg/L, arsenic ion 13420.5mg/L, cadmium ion 374.2mg/L, lead ion 15.9mg/L.
The detailed step for carrying out nonferrous smelting waste acid processing method using technical solution of the present invention is as follows:
A, first by above-mentioned waste acid with pump squeeze into membrane filter be filtered (the filter membrane mesh number of membrane filter be 300
Mesh), obtain lead sulfate filter residue after filtering, lead sulfate filter residue obtained after plate and frame filter press filters containing lead sulfate 62.3% (with
Butt meter) filter cake, lead sulfate filter cake enters lead smelting system and smelted；
B, the sodium sulfide solution that mass percentage concentration is 10% is added in gained filtrate after the filtering of step a membrane filter,
The ORP value for controlling solution is 30mv, vulcanizes the copper in filtrate and generates copper sulfide precipitation, is filtered subsequently into filter press,
Filter cake Containing Sulfur copper 25.7% (in terms of butt) is obtained after filtering, gained filter cake enters copper metallurgy industry and smelted；
C, it is molten that the vulcanized sodium that mass percentage concentration is 10% is added in gained filtrate again after the filtering of step b filter press
Liquid, control ORP value are -10mv, and the vulcanization of the heavy metals such as arsenic is made to generate precipitating；Solution after adjusting is entered filter press to carry out
Filter, the centralized processing of gained filter cake；
D, carbide slag is added in gained filtrate after the filtering of step c filter press and adjusts its pH value to 7.3, gained mixed solution
Into concentrator, concentrator supernatant enters process, thickener underflow and enters centrifuge and separated, and obtaining moisture content is
14.2% land plaster, Centrifuge filtrate are back to concentrator and recycle；
E, supernatant obtained by step d is added to the Nanoscale Iron of 300ppm, gained mixed liquor completes mud in inclined-plate clarifying basin
Water separation, focuses on after bed mud filters pressing；Each main component in clear liquid are as follows: pH value 7.2, copper ion 0.05mg/L, arsenic ion
0.03mg/L, cadmium ion 0.011mg/L, lead ion 0.02mg/L meet " lead, Zn Cr coating pollutant emission standard " and especially discharge
It is required that qualified discharge.
Embodiment 2:
It is process object, each main component concentration are as follows: (quality percentage is dense for sulfuric acid 14.1% with the waste acid of certain copper smelting plant
Degree), copper ion 3765.7mg/L, arsenic ion 15028.6mg/L, cadmium ion 325.1mg/L, lead ion 18.1mg/L.
The detailed step for carrying out nonferrous smelting waste acid processing method using technical solution of the present invention is as follows:
A, first by above-mentioned waste acid with pump squeeze into membrane filter be filtered (the filter membrane mesh number of membrane filter be 350
Mesh), obtain lead sulfate filter residue after filtering, lead sulfate filter residue obtained after plate and frame filter press filters containing lead sulfate 60.8% (with
Butt meter) filter cake, lead sulfate filter cake enters lead smelting system and smelted；
B, the sodium sulfide solution that mass percentage concentration is 10% is added in gained filtrate after the filtering of step a membrane filter,
The ORP value for controlling solution is 35mv, vulcanizes the copper in filtrate and generates copper sulfide precipitation, is filtered subsequently into filter press,
Filter cake Containing Sulfur copper 27.3% (in terms of butt) is obtained after filtering, gained filter cake enters copper metallurgy industry and smelted；
C, it is molten that the vulcanized sodium that mass percentage concentration is 10% is added in gained filtrate again after the filtering of step b filter press
Liquid, control ORP value are -12mv, and the vulcanization of the heavy metals such as arsenic is made to generate precipitating；Solution after adjusting is entered filter press to carry out
Filter, the centralized processing of gained filter cake；
D, carbide slag is added in gained filtrate after the filtering of step c filter press and adjusts its pH value to 7.5, gained mixed solution
Into concentrator, concentrator supernatant enters process, thickener underflow and enters centrifuge and separated, and obtaining moisture content is
14.3% land plaster, Centrifuge filtrate are back to concentrator and recycle；
E, supernatant obtained by step d is added to the Nanoscale Iron of 350ppm, gained mixed liquor completes mud in inclined-plate clarifying basin
Water separation, focuses on after bed mud filters pressing；Each main component in clear liquid are as follows: pH value 7.3, copper ion 0.03mg/L, arsenic ion
0.05mg/L, cadmium ion 0.009mg/L, lead ion 0.017mg/L meet " lead, Zn Cr coating pollutant emission standard " and especially arrange
Put requirement, qualified discharge.
Embodiment 3:
It is process object, each main component concentration are as follows: (quality percentage is dense for sulfuric acid 18.9% with the waste acid of certain copper smelting plant
Degree), copper ion 4568.4mg/L, arsenic ion 9021.6mg/L, cadmium ion 355.3mg/L, lead ion 24.8mg/L.
The detailed step for carrying out nonferrous smelting waste acid processing method using technical solution of the present invention is as follows:
A, first by above-mentioned waste acid with pump squeeze into membrane filter be filtered (the filter membrane mesh number of membrane filter be 300
Mesh), obtain lead sulfate filter residue after filtering, lead sulfate filter residue obtained after plate and frame filter press filters containing lead sulfate 66.1% (with
Butt meter) filter cake, lead sulfate filter cake enters lead smelting system and smelted；
B, the sodium sulfide solution that mass percentage concentration is 10% is added in gained filtrate after the filtering of step a membrane filter,
The ORP value for controlling solution is 29mv, vulcanizes the copper in filtrate and generates copper sulfide precipitation, is filtered subsequently into filter press,
Filter cake Containing Sulfur copper 24.6% (in terms of butt) is obtained after filtering, gained filter cake enters copper metallurgy industry and smelted；
C, it is molten that the vulcanized sodium that mass percentage concentration is 10% is added in gained filtrate again after the filtering of step b filter press
Liquid, control ORP value are -14mv, and the vulcanization of the heavy metals such as arsenic is made to generate precipitating；Solution after adjusting is entered filter press to carry out
Filter, the centralized processing of gained filter cake；
D, carbide slag is added in gained filtrate after the filtering of step c filter press and adjusts its pH value to 7.4, gained mixed solution
Into concentrator, concentrator supernatant enters process, thickener underflow and enters centrifuge and separated, and obtaining moisture content is
14.0% land plaster, Centrifuge filtrate are back to concentrator and recycle；
E, supernatant obtained by step d is added to the Nanoscale Iron of 400ppm, gained mixed liquor completes mud in inclined-plate clarifying basin
Water separation, focuses on after bed mud filters pressing；Each main component in clear liquid are as follows: pH value 7.0, copper ion 0.05mg/L, arsenic ion
0.06mg/L, cadmium ion 0.008mg/L, lead ion 0.016mg/L meet " lead, Zn Cr coating pollutant emission standard " and especially arrange
Put requirement, qualified discharge.
Embodiment 4:
It is process object, each main component concentration are as follows: (quality percentage is dense for sulfuric acid 22.7% with the waste acid of certain copper smelting plant
Degree), copper ion 5711.6mg/L, arsenic ion 18232.4mg/L, cadmium ion 301.8mg/L, lead ion 10.9mg/L.
The detailed step for carrying out nonferrous smelting waste acid processing method using technical solution of the present invention is as follows:
A, first by above-mentioned waste acid with pump squeeze into membrane filter be filtered (the filter membrane mesh number of membrane filter be 400
Mesh), obtain lead sulfate filter residue after filtering, lead sulfate filter residue obtained after plate and frame filter press filters containing lead sulfate 64.2% (with
Butt meter) filter cake, lead sulfate filter cake enters lead smelting system and smelted；
B, the sodium sulfide solution that mass percentage concentration is 10% is added in gained filtrate after the filtering of step a membrane filter,
The ORP value for controlling solution is 27mv, vulcanizes the copper in filtrate and generates copper sulfide precipitation, is filtered subsequently into filter press,
Filter cake Containing Sulfur copper 26.9% (in terms of butt) is obtained after filtering, gained filter cake enters copper metallurgy industry and smelted；
C, it is molten that the vulcanized sodium that mass percentage concentration is 10% is added in gained filtrate again after the filtering of step b filter press
Liquid, control ORP value are -15mv, and the vulcanization of the heavy metals such as arsenic is made to generate precipitating；Solution after adjusting is entered filter press to carry out
Filter, the centralized processing of gained filter cake；
D, carbide slag is added in gained filtrate after the filtering of step c filter press and adjusts its pH value to 7.1, gained mixed solution
Into concentrator, concentrator supernatant enters process, thickener underflow and enters centrifuge and separated, and obtaining moisture content is
13.7% land plaster, Centrifuge filtrate are back to concentrator and recycle；
E, supernatant obtained by step d is added to the Nanoscale Iron of 250ppm, gained mixed liquor completes mud in inclined-plate clarifying basin
Water separation, focuses on after bed mud filters pressing；Each main component in clear liquid are as follows: pH value 7.0, copper ion 0.04mg/L, arsenic ion
0.07mg/L, cadmium ion 0.001mg/L, lead ion 0.015mg/L meet " lead, Zn Cr coating pollutant emission standard " and especially arrange
Put requirement, qualified discharge.
Claims (8)
1. a kind of processing method of nonferrous smelting waste acid, which is characterized in that the treating method comprises following steps:
A, nonferrous smelting waste acid is filtered first using membrane filter, lead sulfate filter residue is obtained after filtering, recycled therein
Lead sulfate；
B, vulcanizing agent is added in gained filtrate after step a filtering, control ORP value is 10~50mv, vulcanizes the copper in filtrate
Copper sulfide precipitation is generated, recycles copper resource after filtering；
C, vulcanizing agent is added in gained filtrate again after step b filtering, control ORP value is -20~0mv, makes the heavy metals such as arsenic
Vulcanization generates precipitating removal；
D, carbide slag is added in the filtrate obtained by step c and adjusts its pH value to 7~8, gypsum is made, will then be made using centrifuge
At gypsum dehydration, obtain dehydrated gypsum；
E, sewage obtained by step d is subjected to advanced treating, qualified discharge or recycling.
2. the processing method of nonferrous smelting waste acid according to claim 1, it is characterised in that: coloured smelting described in step a
Refining waste acid is the acid waste water containing heavy metal that flue gas washing purifies during metallurgical off-gas acid-making, is mixed with the processing of flue gas
At least one of waste water and electrolysis system draining.
3. the processing method of nonferrous smelting waste acid according to claim 1, it is characterised in that: the filtering of film described in step a
The filter membrane mesh number of device is 100~500 mesh.
4. the processing method of nonferrous smelting waste acid according to claim 1, it is characterised in that: in terms of butt, institute in step a
Stating mass percent leaded in lead sulfate filter residue is 50~70%.
5. the processing method of nonferrous smelting waste acid according to claim 1, it is characterised in that: vulcanizing agent described in step b
For vulcanized sodium, NaHS or hydrogen sulfide；In terms of butt, cupric mass percent is 20~28% in gained copper sulfide precipitation.
6. the processing method of nonferrous smelting waste acid according to claim 1, it is characterised in that: vulcanizing agent described in step c
For vulcanized sodium, NaHS or hydrogen sulfide.
7. the processing method of nonferrous smelting waste acid according to claim 1, it is characterised in that: gained is dehydrated stone in step d
Moisture content is reduced to≤15% in cream；In terms of butt, the mass percent of sulfur acid calcium is 40~60% in gained dehydrated gypsum.
8. the processing method of nonferrous smelting waste acid according to claim 1, it is characterised in that: depth described in step e
The detailed process of reason are as follows: Nanoscale Iron is added in gained sewage after step d centrifuge separation, Nanoscale Iron dosage is 200~
500ppm is filtered, gained supernatant qualified discharge or recycling after Nanoscale Iron is added.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112062250A (en) * | 2020-08-14 | 2020-12-11 | 昆明铂锐金属材料有限公司 | Method for treating non-ferrous smelting wastewater by using phosphogypsum reduction product |
| CN113233646A (en) * | 2021-05-17 | 2021-08-10 | 紫金铜业有限公司 | Treatment process of high-concentration arsenic-containing waste acid |
| CN114956390A (en) * | 2022-07-06 | 2022-08-30 | 河南省冶金研究所有限责任公司 | Method for removing heavy metal waste acid and reducing red mud solid waste grade by comprehensively utilizing lead smelting |
| CN115259441A (en) * | 2022-07-05 | 2022-11-01 | 铜陵有色金属集团股份有限公司 | Process for removing arsenic from waste acid |
| CN115677109A (en) * | 2022-11-02 | 2023-02-03 | 清水源（上海）环保科技有限公司 | A method and system for treating sewage acid wastewater from non-ferrous smelting |
| CN115849641A (en) * | 2023-02-20 | 2023-03-28 | 山东恒邦冶炼股份有限公司 | Waste acid vulcanization treatment equipment and method |
| CN117985882A (en) * | 2024-02-03 | 2024-05-07 | 江西铜业铅锌金属有限公司 | A process for treating smelting wastewater with multiple pollutants |
| CN118047512A (en) * | 2024-04-16 | 2024-05-17 | 长春黄金研究院有限公司 | Method for comprehensively utilizing acid mine wastewater |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105567984A (en) * | 2016-01-18 | 2016-05-11 | 中南大学 | Method for potential controlled selection separation of copper refinery ash |
| US20160137524A1 (en) * | 2013-06-17 | 2016-05-19 | Sumitomo Metal Mining Co., Ltd. | Hematite manufacturing process and hematite manufactured by same |
-
2019
- 2019-07-27 CN CN201910685534.5A patent/CN110451680B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160137524A1 (en) * | 2013-06-17 | 2016-05-19 | Sumitomo Metal Mining Co., Ltd. | Hematite manufacturing process and hematite manufactured by same |
| CN105567984A (en) * | 2016-01-18 | 2016-05-11 | 中南大学 | Method for potential controlled selection separation of copper refinery ash |
Non-Patent Citations (3)
| Title |
|---|
| 唐元洪: "《纳米材料导论》", 30 June 2011 * |
| 宋修明: "《炼铜企业管理探索与实践》", 31 January 2012 * |
| 张琦等: "《冶金工业节能减排技术》", 31 October 2013 * |
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| CN112062250A (en) * | 2020-08-14 | 2020-12-11 | 昆明铂锐金属材料有限公司 | Method for treating non-ferrous smelting wastewater by using phosphogypsum reduction product |
| CN113233646A (en) * | 2021-05-17 | 2021-08-10 | 紫金铜业有限公司 | Treatment process of high-concentration arsenic-containing waste acid |
| CN115259441A (en) * | 2022-07-05 | 2022-11-01 | 铜陵有色金属集团股份有限公司 | Process for removing arsenic from waste acid |
| CN115259441B (en) * | 2022-07-05 | 2023-11-24 | 铜陵有色金属集团股份有限公司 | Process for removing arsenic in waste acid |
| CN114956390A (en) * | 2022-07-06 | 2022-08-30 | 河南省冶金研究所有限责任公司 | Method for removing heavy metal waste acid and reducing red mud solid waste grade by comprehensively utilizing lead smelting |
| CN115677109A (en) * | 2022-11-02 | 2023-02-03 | 清水源（上海）环保科技有限公司 | A method and system for treating sewage acid wastewater from non-ferrous smelting |
| CN115849641A (en) * | 2023-02-20 | 2023-03-28 | 山东恒邦冶炼股份有限公司 | Waste acid vulcanization treatment equipment and method |
| CN117985882A (en) * | 2024-02-03 | 2024-05-07 | 江西铜业铅锌金属有限公司 | A process for treating smelting wastewater with multiple pollutants |
| CN118047512A (en) * | 2024-04-16 | 2024-05-17 | 长春黄金研究院有限公司 | Method for comprehensively utilizing acid mine wastewater |
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