CN103495589B - A kind of plating waste residue recoverying and utilizing method - Google Patents
A kind of plating waste residue recoverying and utilizing method Download PDFInfo
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- CN103495589B CN103495589B CN201310428274.6A CN201310428274A CN103495589B CN 103495589 B CN103495589 B CN 103495589B CN 201310428274 A CN201310428274 A CN 201310428274A CN 103495589 B CN103495589 B CN 103495589B
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- 239000002699 waste material Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 58
- 238000007747 plating Methods 0.000 title claims abstract description 52
- 238000001556 precipitation Methods 0.000 claims abstract description 67
- 238000002386 leaching Methods 0.000 claims abstract description 53
- 230000009467 reduction Effects 0.000 claims abstract description 53
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 52
- 230000003647 oxidation Effects 0.000 claims abstract description 44
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 44
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003381 stabilizer Substances 0.000 claims abstract description 30
- 239000002244 precipitate Substances 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 239000003337 fertilizer Substances 0.000 claims abstract description 5
- 230000007613 environmental effect Effects 0.000 claims abstract description 3
- 230000008569 process Effects 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 230000003381 solubilizing effect Effects 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 20
- 230000006641 stabilisation Effects 0.000 claims description 18
- 238000011105 stabilization Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 230000003213 activating effect Effects 0.000 claims description 16
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 14
- 238000005273 aeration Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 10
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 10
- 238000007654 immersion Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- OQNWZSQVHNDLSQ-UHFFFAOYSA-N [Na].S(=O)(=O)(O)C1N(CCNC1)C(=O)O Chemical compound [Na].S(=O)(=O)(O)C1N(CCNC1)C(=O)O OQNWZSQVHNDLSQ-UHFFFAOYSA-N 0.000 claims description 5
- -1 hydroxyl amino dithio formate Chemical compound 0.000 claims description 5
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 4
- 230000002906 microbiologic effect Effects 0.000 claims description 4
- 239000012991 xanthate Substances 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 229940072033 potash Drugs 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 241001417490 Sillaginidae Species 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 238000011017 operating method Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 23
- 239000002184 metal Substances 0.000 abstract description 23
- 239000000706 filtrate Substances 0.000 abstract description 20
- 239000008346 aqueous phase Substances 0.000 abstract description 10
- 238000009713 electroplating Methods 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000010802 sludge Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
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- 239000004566 building material Substances 0.000 abstract 1
- 238000005457 optimization Methods 0.000 abstract 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 34
- 229910052742 iron Inorganic materials 0.000 description 17
- 239000003344 environmental pollutant Substances 0.000 description 16
- 231100000719 pollutant Toxicity 0.000 description 16
- 239000002893 slag Substances 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 11
- 239000002351 wastewater Substances 0.000 description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 9
- 239000010801 sewage sludge Substances 0.000 description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 8
- 239000008394 flocculating agent Substances 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 239000003403 water pollutant Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000010563 solid-state fermentation Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241001062472 Stokellia anisodon Species 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
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- 239000012452 mother liquor Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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- 230000001427 coherent effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
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- 235000021110 pickles Nutrition 0.000 description 1
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- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
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- 235000013619 trace mineral Nutrition 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The present invention relates to a kind of plating waste residue recoverying and utilizing method, its main technological steps is: first electroplating sludge waste residue is carried out Oxidation Leaching, is namely diluted with water to solution and carries out aqueous phase leaching, then by Oxidation Leaching aaerosol solution isolated by filtration, obtains filter mud and filtrate; Reclaim after filter mud reduction is stable and make fertilizer or building materials raw material, filtrate sends into Waste Water Treatment, controls different condition (pH value), carry out fractional precipitation, the compound precipitates obtaining each heavy metal species reclaims respectively, poor metal, then as micro-centralized recovery.After wastewater treatment, recycling, for dilute solution or washing, view, environmental sanitation.It is last that available YHD is stabilizing agent specially used, and to carry out reduction to the residual heavy metal in filter mud and filtrate stable as required, make its no longer with water generation oxidation.The present invention can realize global optimization target and the effect of the cleaner production recycling economy of " zero-emission, pollution-free, complete utilization, increase benefit " of electroplating industry enterprise waste residue.
Description
Technical field
The invention belongs to the processing technology field of industry plating waste residue, be specifically related to a kind of plating waste residue recoverying and utilizing method.
Background technology
Plating waste residue is the discarded object that Electroplate Factory carries out daily production generation, mainly comprise two parts, the plating waste residue that a part has been piled up before being, a part is the waste residue mud of the stylish generation of precipitate and separate in wastewater treatment process, belong to hazardous waste, composition is very complicated, the various heavy metal ion do not waited containing quantity and organic matter, become serious secondary source of pollution again, if directly landfill or air storage, soak oxidation through underground water and rainwater, the pollution of being just without end year in year out, consequence seriously has endless trouble.Bury not all right, fortune difficulty, do not deposit (on a small quantity can remove), much more difficult more than the process of electroplating wastewater, become the maximum disaster of electroplating enterprise and burden.But meanwhile, these heavy metal sewage sludges contain again huge benefit, if recycled, economic worth is high.
At present, the existing treatment technology of recycling electroplating waste residue mainly concentrates on harmless treatment, although some also considers take into account resource and harmless treatment, but ubiquity reclaims not thorough, recovery system is not well established, does not reach efficiency of cycling economy, and cost is high.If ammonia process recovery is leached with Cu, Ni, Zn that ammoniacal liquor will be electroplated in waste residue mud, and be difficult to process iron and chromium stay in solids, and ammonia process processing technological flow is tediously long, ammoniacal liquor leaches and is only separated copper, zinc, nickel, other heavy metal elements cannot leach, and especially ammonia leaching solution is admittedly larger, reach 12:1, cause volume of equipment, add equipment investment, and it is large to leach the quantity of slag, what have accounts for initial mud more than 50%, and the siderochrome in slag also must continue harmless treatment etc.The siderochrome that acid system reclaims in normally leachate removes with co-precipitation, this has easily caused valency heavy metal ion as the co-precipitation such as nickel, zinc for the electroplating sludge of high-load siderochrome thus has reduced its rate of recovery, and siderochrome slags a large amount of on the other hand needs follow-up loaded down with trivial details refinement leaching.Thus practicality is not good enough, therefore is difficult to promote.
Patent 200610050002.7, discloses a kind of method reclaiming valuable metal from electroplating sludge, and its primary sequence step is: with the valuable metal contained in diluted acid leaching electroplating sludge, filter to isolate acid leaching residue and pickle liquor; At high temperature use the copper in sulfide precipitation pickling liquid, filter to isolate copper sulfide and mother liquor of precipitation of ammonium; Add aqueous slkali in mother liquor, control pH5.0-6.0, make the chromium in solution and aluminum precipitation.This invented technology is succinct, but range of applicability is narrow, and the method does not realize comprehensive system recycling plating waste residue, and the mud for plating waste residue does not process utilization further.
Because each heavy metal species be present in sewage is different, stability, oxidisability and reproducibility, affinity, proportion, surface-active etc. under its oxidation state, the compound form existed with different oxidation state, difficulty soluble salt solubilized degree, different condition, also different, this also just reclaims to classification and provides possible condition.
Summary of the invention
The object of the invention is to overcome during existing plating waste residue is recycled that to there is method too single, systematized recycling system can not be formed, narrow application range, reclaim not exclusively not thorough, the waste residue finally obtained still needs the shortcomings such as follow-up harmless treatment, a kind of plating waste residue recoverying and utilizing method realizing efficiency of cycling economy is provided, pass through Oxidation Leaching, isolated by filtration, fractional precipitation, the committed steps such as reduction is stable, plating waste residue after process can realize resource recycling, the filter mud obtained can be used as micro-biological humic composite fertilizer, the harmless silt that waste liquid and Solid state fermentation produce can as the raw material of cement or fragment of brick, fractional precipitation heavy metal compound out can be made into the heavy metal product of high value, also can be used for smeltery and carry out metal smelt.
A kind of plating waste residue recoverying and utilizing method realizing efficiency of cycling economy of the present invention, the foundation realized is: the research and experiment carry out fully different metal different qualities, corresponded to reality, relatively more thorough characteristic and the mechanics grasping each heavy metal, and related data structures, form, according to different metal characteristic, different conditions is set, selects different oxidants, metal deposition catalyst, realize the process of waste residue.The present invention is achieved through the following technical solutions:
A kind of plating waste residue recoverying and utilizing method, its operating procedure comprises: Oxidation Leaching, isolated by filtration, and filter mud reclaims, and filtrate fractional precipitation reclaims precious metal and trace element, and reduction is stable, it is characterized in that:
(1) Oxidation Leaching: will waste residue be electroplated and water carries out immersion 3 ~ 9h according to the ratio of solid-liquid volume 1:5 ~ 10, aeration adds the stirring of redox medicament simultaneously, mixing speed is 200 ~ 1000rmp, make polluter be converted into water soluble compound dissolving and enter aqueous phase, pH value in solubilizing reaction pond controls between 8 ~ 9, in waste residue, heavy metal ion changes into water soluble carbonate and hydroxide, after oxidative leaching process completes in solubilizing reaction pond, obtains Oxidation Leaching slip.
The foundation that above Oxidation Leaching realizes: waste residue Oxidation Leaching quotes the waste water of generation or the solution after processing, after waste residue dissolves in water, under aeration, redox medicament, stirring action, make all contaminants matter wherein existed be converted into water-soluble higher compound, be all dissolved in leaching solution; Implement oxidation in leaching process simultaneously, this oxidation catalysis effect control pH implements under the condition of 8 ~ 9, make all heavy metal ion, transform into water soluble carbonate or hydroxide, Oxidation Leaching is dissolved in solubilizing reaction pond and completes, and makes all elements converting compounds be that solubility enters aqueous phase.
Above-described plating waste residue recoverying and utilizing method, it is characterized in that, described aeration blasts air for utilizing air blast, air velocity is 0.6 ~ 1.5m
3/ min, air enters from dissolving reaction tank bottom air dispenser, discharges from top, solubilizing reaction pond; Described redox medicament is any one in clorox, hydrogen peroxide, and the consumption of redox medicament is 0.5 ~ 3% of plating waste residue weight; Described solubilizing reaction pond is underground device, the direct scraper sewage sludge waste slag of forklift easy to use and feeding intake in reactor, saves labour and power.
(2) isolated by filtration: carry out silt separation to the Oxidation Leaching slip that step 1) obtains, re-use the continuous automatic fitration of horizontal rubber belt filter 1 ~ 3 time, obtain the solution of filter mud and enriching heavy metal, filter mud reclaims, and solution processes.
(3) fractional precipitation: by step 2) in the solution of enriching heavy metal that obtains, be conveyed in solution handling system, by different metal, control ph, drop into flocculant (as aluminium, iron, manganese series), precipitated catalyst, and utilize metallic surface activating agent, each heavy metal species fractional precipitation, obtain compound precipitates at different levels and residual solution.The fractional precipitation reaction time is 1 ~ 3h.
More than realize the foundation of various different element fractional precipitation: coherent element oxidation state, compound form, difficulty soluble salt solubilized degree, affinity, proportion, oxidisability, reproducibility, stability, surface-active etc. are distinguished, select to control suitable pH value and YHD special agent, can ensure when precipitating certain compound, the suitable compound solubility difference of other elements, all more than 2 orders of magnitude, guarantee that precipitation and separation reclaims completely, reclaim and be precipitated compound.
Above-described plating waste residue recoverying and utilizing method, is characterized in that, described flocculant be in aluminum sulfate, aluminium chloride, ferric sulfate, iron chloride one of; Described precipitated catalyst be in N, N-bis-or two sulfo-piperazinecarboxylic acid sodium, hydroxyl amino dithio formate, xanthate one of.
The above fractional precipitation, one-level is precipitated as the AlSnSi alloy adding 0.01 ~ 0.02% in the solution of enriching heavy metal, adds 0.05 ~ 0.08% metallic surface activating agent, adds the precipitated catalyst of 0.005 ~ 0.015%, precipitation 0.5 ~ 1.5h; Two-stage precipitation be add in one-level precipitation solution 0.01 ~ 0.02% iron-based flocculating agent, continue precipitation 0.5 ~ 1.5h, obtain compound precipitates at different levels and residual solution.
(4) reduction is stable: as required, available YHD reduces stabilizing agent to step 2) foreign metal that may remain in filtrate after the precipitation that obtains of the filter mud that obtains and step 3), carry out reduction respectively to stablize, the weight ratio of reduction stabilizing agent and filter mud is 0.01 ~ 0.05:1000, reduction stabilization time is 0.5 ~ 1h, the weight ratio of reduction stabilizing agent and filtrate is 0.005 ~ 0.01:100, and it is 1 ~ 30min that compound precipitates reduces stabilization time.
Above-described reduction stabilizing agent be in sodium carbonate, magnesium carbonate, potash, sodium acid carbonate, saleratus one of.
Above-described plating waste residue recoverying and utilizing method, the method reclaims the filter mud and compound precipitates that obtain, it is characterized in that, described filter mud is used as micro-biological humic composite fertilizer; Described compound precipitates is used as heavy metal and smelts resource; Described residual solution uses as waste residue dissolved water, view environmental sanitation water circulation.
The present invention's one plating waste residue recoverying and utilizing method creates following good result: (1) the present invention electroplates waste residue recoverying and utilizing method will electroplate the improvement of waste residue removal process, instead of a certain heavy metal of single recovery, form the recycling system of complete set, realize the efficiency of cycling economy of plating waste residue, fundamentally solve plating production development waste residue environmentally hazardous " bottleneck ".(2) the Oxidation Leaching solubilizing reaction pond of the employing in the present invention is the underground devices of the single groove of many slurries, the direct scraper sewage sludge waste slag of forklift easy to use and feeding intake in reactor, saves labour and power.(3), after electroplating Solid state fermentation, the innoxious filter mud obtained can be mixed with micro-biological humic composite fertilizer; Fractional precipitation heavy metal compound out can the metallic article of production high value, or becomes metal smelt resource; The siliceous harmless silt that waste liquid and Solid state fermentation produce can as the raw material of cement or fragment of brick; Invention achieves comprehensive utilization of resources.(4) the whole technical process of the present invention can automatic continuously be carried out, and mainly a small amount of medicament, air force and the transport energy of consumption, make the recycling cost of plating waste residue greatly reduce.(5) after Oxidation Leaching and fractional precipitation, effluent monitoring index is all better than in country " plating pollutant emission standard-GB21900-2008 " table 3 " the special emission limit of water pollutant ", wherein COD (COD, mg/L)≤30,50 to the limit value of COD in national standard, suspension (mg/L)≤10, be 30 to suspension limit value in national standard, all heavy metals all remove, realize " zero-emission; complete utilization, pollution-free ", create efficiency of cycling economy.
Accompanying drawing explanation
Fig. 1. a kind of plating waste residue recoverying and utilizing method flow chart.
Detailed description of the invention
Describe the present invention's one plating waste residue recoverying and utilizing method below in conjunction with accompanying drawing 1 and embodiment, plating waste residue handled in embodiment derives from certain enterprise of large-scale Electroplate Factory.
Embodiment 1
(1) Oxidation Leaching: plating waste residue and water are carried out immersion 4 ~ 5h according to the ratio of solid-liquid volume 1:8, aeration adds clorox simultaneously, and air velocity is 0.9m
3/ min, the consumption of clorox is 0.8% of plating waste residue weight, mixing speed is 200rmp, make polluter be converted into water soluble compound dissolving and enter aqueous phase, pH value in solubilizing reaction pond controls between 8 ~ 9, in waste residue, heavy metal ion changes into water soluble carbonate and hydroxide, after oxidative leaching process completes in solubilizing reaction pond, obtains Oxidation Leaching slip.Described solubilizing reaction pond is underground device, the direct scraper sewage sludge waste slag of forklift easy to use and feeding intake in reactor, saves labour and power.
(2) isolated by filtration: carry out silt separation to the Oxidation Leaching slip that step 1) obtains, re-use the continuous automatic fitration of horizontal rubber belt filter 3 times, obtain the solution of filter mud and enriching heavy metal, filter mud reclaims, and solution processes.
(3) fractional precipitation: by step 2) in the solution of enriching heavy metal that obtains, be conveyed in solution handling system, by different metal, control ph drops into flocculant (aluminium, iron, manganese series), precipitated catalyst, and utilizes metallic surface active.Wherein one-level is precipitated as the AlSnSi alloy aluminum sulfate adding 0.01% in the solution of enriching heavy metal, adds 0.06% metallic surface activating agent, adds the precipitated catalyst N of 0.005%, N-bis-or two sulfo-piperazinecarboxylic acid sodium, precipitation 0.5 ~ 1.5h; Two-stage precipitation be add in one-level precipitation solution 0.01 ~ 0.02% iron-based flocculating agent iron chloride, continue precipitation 0.5 ~ 1.5h, obtain compound precipitates at different levels and residual solution.
(4) reduction is stable: as required, available YHD reduces stabilizing agent to step 2) foreign metal that may remain in filtrate after the precipitation that obtains of the filter mud that obtains and step 3), carry out reduction respectively to stablize, the weight ratio of reduction stabilizing agent and filter mud is 0.02:1000, reduction stabilization time is 0.5h, the weight ratio of reduction stabilizing agent and filtrate is 0.008:100, and it is 25min that compound precipitates reduces stabilization time.
The Pollutants in Wastewater content of the generation after the present embodiment process, as table 1, is better than the special emission limit of water pollutant in country " plating pollutant emission standard-GB21900-2008 ".
Embodiment 2
(1) Oxidation Leaching: plating waste residue and water are carried out immersion 3 ~ 4h according to the ratio of solid-liquid volume 1:9, aeration adds redox medicament hydrogen peroxide simultaneously, and air velocity is 0.6m
3/ min, the consumption of hydrogen peroxide is 0.5% of plating waste residue weight, mixing speed is 250rmp, make polluter be converted into water soluble compound dissolving and enter aqueous phase, pH value in solubilizing reaction pond controls between 8 ~ 9, in waste residue, heavy metal ion changes into water soluble carbonate and hydroxide, after oxidative leaching process completes in solubilizing reaction pond, obtains Oxidation Leaching slip.Described solubilizing reaction pond is underground device, the direct scraper sewage sludge waste slag of forklift easy to use and feeding intake in reactor, saves labour and power.
(2) isolated by filtration: carry out silt separation to the Oxidation Leaching slip that step 1) obtains, re-use the continuous automatic fitration of horizontal rubber belt filter 2 times, obtain the solution of filter mud and enriching heavy metal, filter mud reclaims, and solution processes.
(3) fractional precipitation: by step 2) in the solution of enriching heavy metal that obtains, be conveyed in solution handling system, by different metal, control ph drops into flocculant (aluminium, iron, manganese series), metallic surface activating agent, precipitated catalyst.Wherein one-level is precipitated as the AlSnSi alloy aluminium chloride adding 0.02% in the solution of enriching heavy metal, adds 0.05% metallic surface activating agent, adds the precipitated catalyst hydroxyl amino dithio formate of 0.01%, precipitation 0.5 ~ 1.5h; Two-stage precipitation be add in one-level precipitation solution 0.01% iron-based flocculating agent ferric sulfate, continue precipitation 0.5 ~ 1.5h, obtain compound precipitates at different levels and residual solution.
(4) reduction is stable: as required, available YHD reduces stabilizing agent to step 2) foreign metal that may remain in filtrate after the precipitation that obtains of the filter mud that obtains and step 3), carry out reduction respectively to stablize, the weight ratio of reduction stabilizing agent and filter mud is 0.01:1000, reduction stabilization time is 0.6h, the weight ratio of reduction stabilizing agent and filtrate is 0.007:100, and it is 10min that compound precipitates reduces stabilization time.
The Pollutants in Wastewater content of the generation after the present embodiment process, as table 1, is better than the special emission limit of table 3 water pollutant in country " plating pollutant emission standard-GB21900-2008 ".
Embodiment 3
(1) Oxidation Leaching: plating waste residue and water are carried out immersion 4 ~ 5h according to the ratio of solid-liquid volume 1:6, aeration adds redox medicament hydrogen peroxide simultaneously, and air velocity is 0.8m
3/ min, the consumption of redox medicament is 1.2% of plating waste residue weight, mixing speed is 900rmp, make polluter be converted into water soluble compound dissolving and enter aqueous phase, pH value in solubilizing reaction pond controls between 8 ~ 9, in waste residue, heavy metal ion changes into water soluble carbonate and hydroxide, after oxidative leaching process completes in solubilizing reaction pond, obtains Oxidation Leaching slip.Described solubilizing reaction pond is underground device, the direct scraper sewage sludge waste slag of forklift easy to use and feeding intake in reactor, saves labour and power.
(2) isolated by filtration: carry out silt separation to the Oxidation Leaching slip that step 1) obtains, re-use the continuous automatic fitration of horizontal rubber belt filter 1 time, obtain the solution of filter mud and enriching heavy metal, filter mud reclaims, and solution processes.
(3) fractional precipitation: by step 2) in the solution of enriching heavy metal that obtains, be conveyed in solution handling system, by different metal, control ph drops into flocculant (aluminium, iron, manganese series), metallic surface activating agent, precipitated catalyst.Wherein one-level is precipitated as the AlSnSi alloy aluminum sulfate adding 0.01% in the solution of enriching heavy metal, adds 0.06% metallic surface activating agent, adds the precipitated catalyst xanthate of 0.015%, precipitation 0.5 ~ 1.5h; Two-stage precipitation be add in one-level precipitation solution 0.02% iron-based flocculating agent ferric sulfate, continue precipitation 0.5 ~ 1.5h, obtain compound precipitates at different levels and residual solution.
(4) reduction is stable: as required, available YHD reduces stabilizing agent to step 2) foreign metal that may remain in filtrate after the precipitation that obtains of the filter mud that obtains and step 3), carry out reduction respectively to stablize, the weight ratio of reduction stabilizing agent and filter mud is 0.03:1000, reduction stabilization time is 0.7h, the weight ratio of reduction stabilizing agent and filtrate is 0.005:100, and it is 1 ~ 5min that compound precipitates reduces stabilization time.
The Pollutants in Wastewater content of the generation after the present embodiment process, as table 1, is better than the special emission limit of table 3 water pollutant in country " plating pollutant emission standard-GB21900-2008 ".
Embodiment 4
(1) Oxidation Leaching: plating waste residue and water are carried out immersion 6 ~ 7h according to the ratio of solid-liquid volume 1:7, aeration adds redox medicament clorox simultaneously, and air velocity is 1.0m
3/ min, the consumption of clorox is 2.0% of plating waste residue weight, mixing speed is 300rmp, make polluter be converted into water soluble compound dissolving and enter aqueous phase, pH value in solubilizing reaction pond controls between 8 ~ 9, in waste residue, heavy metal ion changes into water soluble carbonate and hydroxide, after oxidative leaching process completes in solubilizing reaction pond, obtains Oxidation Leaching slip.Described solubilizing reaction pond is underground device, the direct scraper sewage sludge waste slag of forklift easy to use and feeding intake in reactor, saves labour and power.
(2) isolated by filtration: carry out silt separation to the Oxidation Leaching slip that step 1) obtains, re-use the continuous automatic fitration of horizontal rubber belt filter 3 times, obtain the solution of filter mud and enriching heavy metal, filter mud reclaims, and solution processes.
(3) fractional precipitation: by step 2) in the solution of enriching heavy metal that obtains, be conveyed in solution handling system, by different metal, control ph drops into flocculant (aluminium, iron, manganese series), metallic surface activating agent, precipitated catalyst.Wherein one-level is precipitated as the AlSnSi alloy aluminium chloride adding 0.015% in the solution of enriching heavy metal, adds 0.08% metallic surface activating agent, adds the precipitated catalyst N of 0.012%, N-bis-or two sulfo-piperazinecarboxylic acid sodium, precipitation 0.5 ~ 1.5h; Two-stage precipitation be add in one-level precipitation solution 0.015% iron-based flocculating agent ferric sulfate, continue precipitation 0.5 ~ 1.5h, obtain compound precipitates at different levels and residual solution.
(4) reduction is stable: as required, available YHD reduces stabilizing agent potash to step 2) foreign metal that may remain in filtrate after the precipitation that obtains of the filter mud that obtains and step 3), carry out reduction respectively to stablize, the weight ratio of reduction stabilizing agent and filter mud is 0.04:1000, reduction stabilization time is 0.8h, the weight ratio of reduction stabilizing agent and filtrate is 0.01:100, and it is 5min that compound precipitates reduces stabilization time.
The Pollutants in Wastewater content of the generation after the present embodiment process, as table 1, is better than the special emission limit of water pollutant in country " plating pollutant emission standard-GB21900-2008 ".
Embodiment 5
(1) Oxidation Leaching: plating waste residue and water are carried out immersion 7 ~ 8h according to the ratio of solid-liquid volume 1:6, aeration adds redox medicament clorox simultaneously, and air velocity is 0.6 ~ 1.5m
3/ min, the consumption of clorox is 1.8% of plating waste residue weight, mixing speed is 300rmp, make polluter be converted into water soluble compound dissolving and enter aqueous phase, pH value in solubilizing reaction pond controls between 8 ~ 9, in waste residue, heavy metal ion changes into water soluble carbonate and hydroxide, after oxidative leaching process completes in solubilizing reaction pond, obtains Oxidation Leaching slip.Described solubilizing reaction pond is underground device, the direct scraper sewage sludge waste slag of forklift easy to use and feeding intake in reactor, saves labour and power.
(2) isolated by filtration: carry out silt separation to the Oxidation Leaching slip that step 1) obtains, re-use the continuous automatic fitration of horizontal rubber belt filter 3 times, obtain the solution of filter mud and enriching heavy metal, filter mud reclaims, and solution processes.
(3) fractional precipitation: by step 2) in the solution of enriching heavy metal that obtains, be conveyed in solution handling system, by different metal, control ph drops into flocculant (aluminium, iron, manganese series), metallic surface activating agent, precipitated catalyst.Wherein one-level is precipitated as the AlSnSi alloy aluminium chloride adding 0.017% in the solution of enriching heavy metal, adds 0.07% metallic surface activating agent, adds the precipitated catalyst N of 0.013%, N-bis-or two sulfo-piperazinecarboxylic acid sodium, precipitation 0.5 ~ 1.5h; Two-stage precipitation be add in one-level precipitation solution 0.018% iron-based flocculating agent ferric sulfate, continue precipitation 0.5 ~ 1.5h, obtain compound precipitates at different levels and residual solution.
(4) reduction is stable: as required, available YHD reduces stabilizing agent sodium acid carbonate to step 2) foreign metal that may remain in filtrate after the precipitation that obtains of the filter mud that obtains and step 3), carry out reduction respectively to stablize, the weight ratio of reduction stabilizing agent and filter mud is 0.05:1000, reduction stabilization time is 0.6h, the weight ratio of reduction stabilizing agent and filtrate is 0.007:100, and it is 15min that compound precipitates reduces stabilization time.
The Pollutants in Wastewater content of the generation after the present embodiment process, as table 1, is better than the special emission limit of water pollutant in country " plating pollutant emission standard-GB21900-2008 ".
Embodiment 6
(1) Oxidation Leaching: plating waste residue and water are carried out immersion 8 ~ 9h according to the ratio of solid-liquid volume 1:8, aeration adds redox medicament hydrogen peroxide simultaneously, and air velocity is 1.5m
3/ min, the consumption of hydrogen peroxide is 3.0% of plating waste residue weight, mixing speed is 500rmp, make polluter be converted into water soluble compound dissolving and enter aqueous phase, pH value in solubilizing reaction pond controls between 8 ~ 9, in waste residue, heavy metal ion changes into water soluble carbonate and hydroxide, after oxidative leaching process completes in solubilizing reaction pond, obtains Oxidation Leaching slip.Described solubilizing reaction pond is underground device, the direct scraper sewage sludge waste slag of forklift easy to use and feeding intake in reactor, saves labour and power.
(2) isolated by filtration: carry out silt separation to the Oxidation Leaching slip that step 1) obtains, re-use the continuous automatic fitration of horizontal rubber belt filter 3 times, obtain the solution of filter mud and enriching heavy metal, filter mud reclaims, and solution processes.
(3) fractional precipitation: by step 2) in the solution of enriching heavy metal that obtains, be conveyed in solution handling system, by different metal, control ph drops into flocculant (aluminium, iron, manganese series), metallic surface activating agent, precipitated catalyst.Wherein one-level is precipitated as the AlSnSi alloy aluminium chloride adding 0.018% in the solution of enriching heavy metal, adds 0.06% metallic surface activating agent, adds the precipitated catalyst hydroxyl amino dithio formate of 0.008%, precipitation 0.5 ~ 1.5h; Two-stage precipitation be add in one-level precipitation solution 0.017% iron-based flocculating agent iron chloride, continue precipitation 0.5 ~ 1.5h, obtain compound precipitates at different levels and residual solution.
(4) reduction is stable: as required, available YHD reduces stabilizing agent to step 2) foreign metal that may remain in filtrate after the precipitation that obtains of the filter mud that obtains and step 3), carry out reduction respectively to stablize, the weight ratio of reduction stabilizing agent and filter mud is 0.01:1000, reduction stabilization time is 0.9h, the weight ratio of reduction stabilizing agent and filtrate is 0.008:100, and it is 20min that compound precipitates reduces stabilization time.
The Pollutants in Wastewater content of the generation after the present embodiment process, as table 1, is better than the special emission limit of water pollutant in country " plating pollutant emission standard-GB21900-2008 ".
Embodiment 7
(1) Oxidation Leaching: plating waste residue and water are carried out immersion 5 ~ 6h according to the ratio of solid-liquid volume 1:10, aeration adds redox medicament clorox simultaneously, and air velocity is 1.5m
3/ min, the consumption of clorox is 2.2% of plating waste residue weight, mixing speed is 500rmp, make polluter be converted into water soluble compound dissolving and enter aqueous phase, pH value in solubilizing reaction pond controls between 8 ~ 9, in waste residue, heavy metal ion changes into water soluble carbonate and hydroxide, after oxidative leaching process completes in solubilizing reaction pond, obtains Oxidation Leaching slip.Described solubilizing reaction pond is underground device, the direct scraper sewage sludge waste slag of forklift easy to use and feeding intake in reactor, saves labour and power.
(2) isolated by filtration: carry out silt separation to the Oxidation Leaching slip that step 1) obtains, re-use the continuous automatic fitration of horizontal rubber belt filter 3 times, obtain the solution of filter mud and enriching heavy metal, filter mud reclaims, and solution processes.
(3) fractional precipitation: by step 2) in the solution of enriching heavy metal that obtains, be conveyed in solution handling system, by different metal, control ph drops into flocculant (aluminium, iron, manganese series), metallic surface activating agent, precipitated catalyst.Wherein one-level is precipitated as the AlSnSi alloy aluminium chloride adding 0.02% in the solution of enriching heavy metal, adds 0.08% metallic surface activating agent, adds the precipitated catalyst xanthate of 0.006%, precipitation 0.5 ~ 1.5h; Two-stage precipitation be add in one-level precipitation solution 0.02% iron-based flocculating agent iron chloride, continue precipitation 0.5 ~ 1.5h, obtain compound precipitates at different levels and residual solution.
(4) reduction is stable: as required, available YHD reduces stabilizing agent to step 2) foreign metal that may remain in filtrate after the precipitation that obtains of the filter mud that obtains and step 3), carry out reduction respectively to stablize, the weight ratio of reduction stabilizing agent and filter mud is 0.05:1000, reduction stabilization time is 0.9h, the weight ratio of reduction stabilizing agent and filtrate is 0.009:100, and it is 30min that compound precipitates reduces stabilization time.
The Pollutants in Wastewater content of the generation after the present embodiment process, as table 1, is better than the special emission limit of water pollutant in country " plating pollutant emission standard-GB21900-2008 ".
Table 1, plating waste residue are recycled and are produced Wastewater Pollutant content overview
Note: "-" representative " not detecting " in table.
Claims (3)
1. electroplate a waste residue recoverying and utilizing method, its operating procedure comprises: Oxidation Leaching, isolated by filtration, and filter mud reclaims, fractional precipitation, and reduction is stable, it is characterized in that:
Step 1) Oxidation Leaching: plating waste residue and water are carried out immersion 3 ~ 9h according to the ratio of solid-liquid volume 1:5 ~ 10, aeration adds redox medicament simultaneously, mixing speed is 200 ~ 1000rmp, pH value in solubilizing reaction pond controls between 8 ~ 9, after oxidative leaching process completes in solubilizing reaction pond, obtain Oxidation Leaching slip;
Step 2) isolated by filtration: to step 1) the Oxidation Leaching slip that obtains carries out silt separation, re-use the continuous automatic fitration of horizontal rubber belt filter 1 ~ 3 time, obtain the solution of filter mud and enriching heavy metal, filter mud reclaims, and solution processes;
Step 3) fractional precipitation: by step 2) in the solution of enriching heavy metal that obtains, be conveyed in solution handling system, control ph, drop into flocculant, precipitated catalyst, and utilize metallic surface activating agent, each heavy metal species fractional precipitation, obtain compound precipitates at different levels and residual solution, the fractional precipitation reaction time is 1 ~ 3h;
Step 4) reduction is stable: utilize reduction stabilizing agent to step 2) filter mud that obtains and step 3) residual solution after fractional precipitation, carry out reduction respectively to stablize, the weight ratio of reduction stabilizing agent and filter mud is 0.01 ~ 0.05:1000, reduction stabilization time is 0.5 ~ 1h, the weight ratio of reduction stabilizing agent and residual solution is 0.005 ~ 0.01:100, and it is 1 ~ 30min that compound precipitates reduces stabilization time;
Described flocculant be in aluminum sulfate, aluminium chloride, ferric sulfate, iron chloride one of; Described precipitated catalyst be in N, N-bis-or two sulfo-piperazinecarboxylic acid sodium, hydroxyl amino dithio formate, xanthate one of; Described reduction stabilizing agent be in sodium carbonate, magnesium carbonate, potash, sodium acid carbonate, saleratus one of.
2. one plating waste residue recoverying and utilizing method according to claim 1, it is characterized in that, described aeration blasts air for utilizing air blast, and air enters from dissolving reaction tank bottom air dispenser, discharges from top, solubilizing reaction pond; Described redox medicament is any one in clorox, hydrogen peroxide, and the consumption of redox medicament is 0.5 ~ 3% of plating waste residue weight; Described solubilizing reaction pond is underground device.
3., according to claim 1 ~ 2 arbitrary described one plating waste residue recoverying and utilizing method, the method reclaims the filter mud and compound precipitates that obtain, it is characterized in that, described filter mud is used as micro-biological humic composite fertilizer; Described compound precipitates is used as heavy metal and smelts resource; Described residual solution uses as waste residue dissolved water, view environmental sanitation water circulation.
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| CN105833985B (en) * | 2016-03-24 | 2018-05-11 | 清华大学 | A kind of industrial solid waste residue Selective Separation and recoverying and utilizing method |
| CN107857389B (en) * | 2017-11-06 | 2020-06-09 | 广州超邦化工有限公司 | Method for treating alkaline zinc-nickel alloy electroplating wastewater |
| CN110237481A (en) * | 2018-07-10 | 2019-09-17 | 华东理工大学 | A kind of abraum salt method for innocent treatment |
| CN111870862A (en) * | 2020-07-29 | 2020-11-03 | 沈阳有研矿物化工有限公司 | Harmless treatment method for waste salt in production of alkylxanthate beneficiation reagent |
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