CN109706319A - Method low cost recycling metal from electroplating sludge and produce refined sulfuric acid nickel - Google Patents
Method low cost recycling metal from electroplating sludge and produce refined sulfuric acid nickel Download PDFInfo
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Abstract
The present invention relates to methods low cost recycling metal from electroplating sludge and produce refined sulfuric acid nickel, including following technical process: by electroplating sludge pulp and weeding out sundries, sulfuric acid leaching, E.Z, which is carried out, with alkali removes iron, extracting copper prepares copper products, and extracting copper extraction raffinate depth removes aluminium, chromium, abstraction impurity removal matter calcium, magnesium, copper, manganese and zinc and output solution of zinc sulfate, extracting and enriching nickel prepares refined sulfuric acid nickel, environment-friendly solidified ferrochrome slag and sewage treatment.The present invention stays in chromium in slag, and all Product recycling is made by extraction process respectively in copper, zinc, nickel, and Heavy Metals element casting yield is high.Raw material, auxiliary material are easy to get cheaply, and cost advantage is obvious.It avoids fluorine ion from being added, mitigates environmental pressure.Integrated treatment is at low cost, can largely handle electroplating sludge, reduces dangerous waste discharge, and social benefit is obvious.
Description
Technical field
The present invention relates to methods low cost recycling metal from electroplating sludge and produce refined sulfuric acid nickel, are particularly suitable for
In electroplating sludge in the low-grade situation of heavy metal chromium, copper, nickel, zinc, carries out low-cost separation synthetical recovery metal and produce essence
The nickel sulfate of system.
Background technique
Electroplating industry is the main basic processing industry in China, and the electroplating sludge that plating process generates belongs to China
Environmentally friendly dangerous waste register HW17.It generates 3~10 kilograms of sludge quantities with electroplating wastewater per ton to calculate, document estimates Chinese festiva electroplating sludge
10,000,000 tons of total amount or so.
The heavy metal being enriched in electroplating wastewater in electroplating sludge, physicochemical characteristics: belonging to alkaline matter, and universal aqueous 75
~90%；When airing is to 60%, composition containing various metals in mixing sludge, wherein based on chromium, copper, nickel, zinc heavy metal.It is right
" electroplating sludge " entry, carrying out Chinese patent search so far from 2000 can find 300 multinomial patents.Currently, China is electroplated
The universal small scale of enterprise, electroplating sludge associated contamination Frequent Accidents, the innoxious of electroplating sludge, recycling, synthetical recovery processing
It is still difficult point hot spot.
Currently, processing disposition electroplating sludge method have very much, generally there are two types of, that is, be divided into solidification and stabilization and resource
Change two kinds of recycling.Wherein solidification and stabilization, present mainstream are to mix cement processed, pitch bonding, burning glass.Patent
CN201510700010.0 thinks that solidification electroplating sludge consumption amount is little, also fails to solve secondary pollution and resource regeneration
The problems such as.And resource recycling is first carried out, resolidification stabilizes, and reduces sludge total amount, and realize economic value, becomes mainstream
Research and develop research direction.
Currently, electric plating sludge resource recycles, and it is divided into pyrogenic attack and two kinds of wet-treating.Wherein pyrogenic attack
Electroplating sludge, copper and mickel often have an emphasis.Copper is extracted using pyrogenic process and first makes ice copper as emphasis, then the blister copper that blows, blister copper
80% or more cupric, in addition other substances, accommodate nickel amount very little；Using nickel as emphasis, nickel (nickel matte) first is made ice, nickel-copper ratio 2~
2.5 preferably；Nickel-copper ratio 22:31 in electroplating sludge physicochemical property；The loss of pyrogenic attack casting yield is larger.The high moisture content of electroplating sludge,
Low content, multielement (there are also chromium and zinc etc.), also make the selective advantage of wet-treating.
Currently, wet processing process is generally: leaching one deposition of a purification.It is to leach first, leaching method mainly has:
Ore Leaching, ammonia leach, bioanalysis leaches.Bioanalysis leaching is bioleaching, and Spawn incubation domestication is slow, bacteria live environmental condition
It is invariable, and electroplating sludge source is unstable, is still difficult to industrialize now；Ammonia leaching process, the originally environmentally friendly limiting emission of ammonia
Object, processing cost is high, and low concentration ammonia leaching rate is low, and high strength ammonia is related to high-tension apparatus, and equipment material leads to high production cost；Cause
This common sulfuric acid, salt Ore Leaching have larger cost advantage.
Currently, how Cost Competition point is realizing copper extraction with after sulfuric acid or salt Ore Leaching electroplating sludge in wet-treating,
I.e. how high casting yield, low cost production higher value copper products.Firstly, iron is added in displacement copper, post processing cost is high, sponge
Copper value is not high to be excluded；Secondly ammonium hydroxide, sodium carbonate, sodium hydroxide and vulcanized sodium cement copper, product purity low value are low；Again
Secondary, low concentration cupric electrolysis directly extracts how at high cost copper loss electricity is, and high pressure hydrogen reduction low concentration Copper Processing Industry is difficult to carry out.Realizing copper
In several patents of extraction, CN200910184773.9 liquid-solid ratio takes 8:1, and casting yield and wastewater flow rate are exactly hang-up.
It is not low with import extractant M5640 and Lix984 cost after CN201510445046.9 pretreatment；CN201710528952.4 is used
The electroplating sludge of the strip solution blending low copper containing of high cupric, without mixing ratio, no comparativity, electroplating sludge, which adds to be not added, does not know
Road；The environmental protection of the Dong Jiang CN200910190516.6 uses P507 extracting copper, and saponification and pickling are at high cost；CN201310124563.7 is yellow
Extracting copper after natrojarosite, difficulties are that extraction split-phase is not resolved, and production continuity is not strong.
Currently, deferrization process in wet-treating, mainly has hydrolysis except iron, sodium jarosite are except iron, iron precipitation by goethite process and red iron
Mine removes iron.It wherein hydrolyzes except iron strainability is poor, precipitating entrainment weight, other metal casting yields are low；Yellow modumite method needs higher
Temperature, 90~95 DEG C；75~85 DEG C of goethite process reaction temperature；Hematite process is to generate di-iron trioxide at high temperature under high pressure
(iron oxide red).In contrast goethite and sodium jarosite have comparativity, and goethite process cost is lower.E.Z is removed except iron dust in goethite
Iron method.
Currently, extracting copper, after iron operation, the removal of impurity calcium, magnesium is a competition spot again, i.e., whether takes present warp
The sodium fluoride deliming of allusion quotation, magnesium technique.Sodium fluoride deliming, magnesium, joined environmental pollution object fluorine, and 90 DEG C of reaction process temperature or more,
Feed liquid will be down to room temperature after reaction, precipitate and be easy colloidization, and current environmental protection fluorine removal does not have cost effective method.So being removed using extraction
Calcium, magnesium are advantageous.
Currently, nickel and zinc separate and extract high purity product, extraction has a clear superiority.It is preferred that extractant be mainly P204,
P507, C272 etc., wherein C272 is more expensive.Related patents CN201410317878.8 use fractional extraction, language it is unknown, purport is not
Bright, output is almost mixture, needs to extract separation again.Without Depth Study removing calcium with solvent extraction, magnesium, then calcium, magnesium addition meeting
It is enriched with jointly with nickel, manufacture refined sulfuric acid nickel difficulty increases.
Currently, the chromium in electroplating sludge, extremely low with pyrogenic attack volatility, the rate of recovery is high.
Summary of the invention
The present invention current electroplating sludge processing especially wet-treating electroplating sludge there are aiming at the problem that, provide it is a kind of from
Method low cost recycling metal in electroplating sludge and produce refined sulfuric acid nickel.
The method that technical solution of the present invention: low cost recycling metal from electroplating sludge and produces refined sulfuric acid nickel, packet
Include following steps:
Step 1, by electroplating sludge and water with liquid-solid ratio (1~2): 1 carries out pulp, removes sundries in slurry with sieve；Tightly
Then, sulfuric acid is added to slurry, the pH value of control reaction end slurry is 0.5~3.5；
Step 2, the hydrogen peroxide that mass percent is 28~35% is added into step 1 terminal slurry, it just will be in slurry
Ferrous oxidation become ferric iron, as material A；Another configuration aqueous slkali is material B；Preparation bottom water (starts to use in reactive tank
Tap water, last reaction leaves a part of slurry and does not have to pump filtering in later period production, and amount just contacts stirring blade
Bottom) it is used as material C；E.Z is carried out except iron operates: opening stirring, material A and material B are added in material C simultaneously, control mixing
System material A+material B+ material C temperature is at 75~85 DEG C, Fe3+Less than 1g/L, pH stable is 3.0~3.5, A to be added
Separation of solid and liquid filtering is carried out after material, obtains filter residue and filtrate；
E.Z is carried out except iron key reaction equation is as follows:
2Fe2++H2O2+2H+=2Fe3++2H2O
Fe3++2H2O=FeOOH+3H+
Cr3++3H2O=Cr (OH)3+3H+
H++ NaOH=Na++H2O
2H++Na2CO3=2Na++H2O+CO2；
Step 3, step 2 obtains filtrate reuse except organic and pretreatment before extracting copper the dedicated extractant of copper into
The operation of row extracting copper, obtains two materials: first is that high copper-containing solution, prepares tough cathode into electro deposited copper, second is that copper raffinate；It is main
Want reaction equation as follows:
2RH+Cu2+→R2Cu+2H+Extraction reaction, acidity pH1.0~4.5；
R2Cu+2H+→2RH+Cu2+Back extraction reaction, 2~5mol/L of acidity；
Step 4, a part of return step 1 of the copper raffinate that step 3 obtains is added anti-as production recycle-water, another part
Answer slot, by adding aqueous slkali, control reaction system solution ph 4.5~5.0, further precipitation and purification chromium therein, aluminium,
Iron, after precipitation and purification, filtering is separated by solid-liquid separation, and obtains filtrate and filter residue, and wherein filter residue return step 1 is when raw material use；It is main
Want reaction equation:
Fe3++3H2O=Fe (OH)3+3H+
Cr3++3H2O=Cr (OH)3+3H+
Al3++3H2O=Al (OH)3+3H+
H++ NaOH=Na++H2O
2H++Na2CO3=2Na++H2O+CO2；
Step 5, the pH value of filtrate is obtained with a small amount of sulfuric acid regulating step 4 3.0~4.0, carries out two stages in order
Extraction processing；First stage is abstraction impurity removal matter, using p507-kerosene system, retain nickel extraction remove calcium in filtrate,
Magnesium, copper, manganese, zinc impurity, while solution of zinc sulfate is made in composition zinc therein；Second stage is called extracting and enriching, with first
It is raw material that stage raffinate, which is called liquid after extracting impurities, extraction of nickel, and then backwash promotes the nickel concentration of nickel backwash liquor, further
Impurity in secondary purification nickel solution, obtains nickel sulfate solution；First stage generates a small amount of impure waste water, the nickeliferous impurity that removes
Raffinate, solution of zinc sulfate；Second stage output nickel sulfate solution and raffinate waste water；
Extraction process key reaction equation:
NaOH+H2A2→Na(HA2)+H2O
Na(HA2)+H+→H2A2+Na+
M2++2NaHA2→M(HA2)2+2Na+
M(HA2)2+2H+→2H2A2+M2+
M represents Ca, Mg, Cu, Zn, Mn, Ni element in equation；H2A2、HA2Represent organic P507 or P204；P204 extraction
Metal sequence: Fe3+> Zn2+> Ca2+> Cu2+> Mn2+> Co2+> Mg2+> Ni2+；P507 extracting metals sequence: Fe3+> Zn2+
> Mn2+> Cu2+> Ca2+> Co2+> Mg2+> Ni2+；
Step 6, by solution of zinc sulfate and the resulting nickel sulfate solution of step 5 second stage obtained by the first stage in step 5,
Sulfuric acid zinc product and refined sulfuric acid nickel is made in evaporative crystallization respectively；
Step 7, filter residue step 2 obtained washs, filtering, obtains filter residue and filtrate, filtrate return step 1 is as life
Produce recycle-water, filter residue solidification disposition；
First stage in step 5 is generated into waste water, is pre-processed with alkali precipitation, is filtered, filter residue solidification disposition, filtrate is as life
It produces sewage and enters sewage treatment process；Second stage in step 5 is generated into waste water and other production wastes, carries out sewage treatment.
The electroplating sludge includes the composition of following all or part of mass percent: Cr2O3: 0.01~20, CuO:0.3
~20, NiO:0.3~20, ZnO:0.3~20, Fe2O3: 0.01~5.0, FeO:0.01~8.0, Al2O3: 0.01~5.0,
SiO2: 0.01~5.0, CaO:0.01~40, MgO:0.01~10, H2O:0.0~90. also respectively the PbO containing (0.01~1.0),
SnO2、MnO2。
Preferred: the water that step 1 pulp uses is tap water or production recycle-water, and the production recycle-water includes step
The filtrate being obtained by filtration after copper raffinate, step 7 washery slag in 3；20~50 DEG C of slurrying temperature, slurry time 1~3 hour；Slurry
10~30% that sulfuric acid amount is electroplating sludge quality are added after change into slurry.
It is preferred: material B in step 2 are as follows: sodium hydroxide or sodium carbonate aqueous slkali, aqueous slkali mass percent concentration are 10
~20%.
Preferred: except organic and pretreated feed liquid enters the preceding organic concentrations≤5mg/L of extraction in step 3, feed liquid is clear
It is bright transparent；The dedicated extractant of copper in step 3 are as follows: AD -100 or N902, kerosene include: aviation kerosine, 260# kerosene；Copper is dedicated
Extractant and kerosene percent by volume 10~20%, extraction equipment is mixing -- clarifier, using multistage cascade extraction；Organic phase
With volume flow ratio mL/mL:1/4~4/1 of water phase, 10~40 DEG C of extraction temperature；Copper extraction process: extraction-washing-back extraction,
Extraction tandem series is respectively: 2~3 grades of extractions, 1~2 grade of washing, 2~5 grades of back extraction；Liquid copper 20~30g/L copper before being stripped, instead
Liquid copper 20~60g/L copper after extraction.
Preferred: the aqueous slkali that reactive tank is added in step 4 is sodium hydroxide or sodium carbonate liquor, and concentration is 10~20%
Mass percent.
It is preferred: extractant P507-kerosene system of first stage to be extracted in step 5, wherein kerosene includes sulfonated coal
Oil, 260# kerosene, aviation kerosine, common kerosene, P507 percentage by volume in kerosene is 5~25%, and extraction equipment is mixed
Close -- clarifier, using multistage cascade extraction；Organic phase carries out saponification process, saponification sodium hydroxide or sodium carbonate alkali soluble in advance
Liquid, aqueous slkali mass percent are 10~50%, saponification rate 10~60%, the volume flow ratio mL/mL:1/8 of organic phase and water phase
~8/1,10~40 DEG C of extraction temperature；Extraction process: saponification-, which extract-washes nickel-and washes calcium, magnesium, copper, manganese-and wash zinc-regeneration, to be had
Machine；
Extract tandem series: 1~3 grade of saponification extracts 5~20 grades, washes 3~10 grades of nickel, wash calcium, magnesium, copper, 3~10 grades of manganese,
3~10 grades of zinc are washed, regenerates organic 3~10 grades；It washes acid: washing nickel, hydrochloric acid or nitric acid, 0.1~1.0mol/L of acid concentration；Wash calcium, magnesium,
Copper, manganese, hydrochloric acid or nitric acid, 2~4mol/L of acid concentration；Wash zinc, sulfuric acid, 2~6mol/L of acid concentration；Regenerate organic, concentration of hydrochloric acid
3.5~8mol/L.
It is preferred: the extractant of second stage to be extracted in step 5 are as follows: P507-kerosene system or P204-kerosene system；
Wherein kerosene includes sulfonated kerosene, 260# kerosene, aviation kerosine, common kerosene, P507 or the P204 percentage by volume in kerosene
It is 5~30%, extraction equipment is mixing -- clarifier, using multistage cascade extraction；Organic phase carries out saponification process in advance, saponification
With sodium hydroxide or sodium carbonate aqueous slkali, aqueous slkali mass percent is 10~50%, saponification rate 10~70%, organic phase and water
Volume flow ratio mL/mL:1/8~8/1 of phase, 10~40 DEG C of extraction temperature；Extraction process: saponification-extraction of nickel-washing-back extraction
Nickel-regeneration is organic；Extract tandem series: 1~3 grade of saponification, 3~10 grades of extraction, 3~10 grades of washing, 3~10 grades of nickel of back extraction, then
Raw organic 3~8 grades；Wash acid: washing, sulfuric acid, 0.1~1.0mol/L of acid concentration；It is stripped nickel, sulfuric acid, 2~6mol/L of acid concentration；
Regenerate organic, 3.5~8mol/L of concentration of hydrochloric acid.
It is preferred: step 6 solution of zinc sulfate 60~120g/L containing zinc, the nickeliferous 60~110g/L of nickel sulfate solution.
It is preferred: be (2~5) to the liquid-solid ratio of residue washing in step 7: 1, filtering uses filter press；At filter residue solidification
Reason uses cement solidification or glass solidification；Sewage treatment uses sodium hydroxide or sodium carbonate with alkali.
The content being not described in detail is the prior art (such as except organic etc.).
The present invention stays in chromium in slag, and all Product recycling is made by extraction process respectively in copper, zinc, nickel, a main huge sum of money
It is high to belong to element casting yield.Using leaching agent sulfuric acid, E.Z removes iron, the dedicated extractant extracting copper of copper, with extraction removing calcium and magnesium, extraction
Method prepares zinc sulfate and refined sulfuric acid nickel, and raw material, auxiliary material are easy to get cheaply, and cost advantage is obvious.Fluorine ion is avoided to be added,
Mitigate environmental pressure.Integrated treatment of the present invention is at low cost, can largely handle electroplating sludge, reduces dangerous waste discharge, and social benefit is bright
It is aobvious.
Detailed description of the invention
Fig. 1 is flow chart of the invention.
Specific embodiment
Below in conjunction with example of the invention, clear and complete description is carried out to technical solution of the present invention.Obviously, it is retouched
The example stated is only a part of the embodiments of the present invention, rather than whole embodiments, and ability field those of ordinary skill is not having
Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.
Flow diagram according to Fig. 1, process main line is: pulp-leaching-E.Z removes iron-pretreatment-extraction
Copper-deep iron removal, aluminium, chromium-extracting impurities and output solution of zinc sulfate-extraction of nickel output nickel sulfate solution-evaporation system production
Product-sewage treatment, the solidification disposition of ferrochrome slag.
Embodiment 1
The mass percentage (%) of electroplating sludge main matter: CuO 1.70, NiO 1.44, ZnO 0.74, Cr2O3
0.57,H2O 65.3。
Tap water is added by liquid-solid ratio 2:1 in electroplating sludge material by step (1)；30 DEG C of temperature, strong stirring is opened, is mixed
It closes slurrying 2 hours, weeds out sundries (sack, wood, plastics etc.), it is also possible to pulper slurrying material.Material is pumped into another after pulp
The concentrated sulfuric acid, control solution endpoint pH to 1.5~2.5 is added in reactive tank under agitation.
Step (1) is regulated endpoint pH to 1.5~2.5 slurry, measures ferrous content, oxidation is added by step (2)
Theoretical amount hydrogen peroxide (hydrogen peroxide mass percent 28~35%), it is standby to make material A by ferrous oxidation at ferric iron；Configuration quality
20% aqueous sodium carbonate of percentage is standby to make material B；Prepare tap water in reactive tank for material C is made.Progress E.Z is operated except iron,
So that material C is just contacted stirring blade bottom makes stirring power that tap water be driven to turn over, and material C is heated to 85 DEG C or so, is opened
Stirring is opened, material A and material B are added in material C simultaneously, control the mixed system of A+B+C, keeps pH value 3.0~3.5, three
Valence concentration of iron is less than 1g/L, and 75~85 DEG C of temperature, until material A adds or reactive tank is fuller, elementary reaction terminates.To being starched
Material is filtered, and is separated by solid-liquid separation, and filter residue and filtrate are obtained.
Step (3) pre-processes the filtrate that step (2) is last before carrying out extracting copper, mainly remove organic and pretreatment,
The last filtrate of the step of obtaining (2) is transferred to pH value needed for extracting copper again, large trough is stood later, and refined filtration removes solid slag, oil removing
Device oil removing, makes feed liquid enter organic concentrations≤5mg/L before extraction, and solution is clear and transparent；Reuse dedicated extractant AD -100 of copper
Adding aviation kerosine, 100 concentration of AD-is percentage by volume 15%, 25 DEG C of temperature, the volume flow ratio (mL/mL) of organic phase and water phase
Between 1/4~4/1, using " mixing ----clarifier " equipment, multistage cascade extraction operation is carried out, extraction process: " 2 grades of extractions
Take --- -2 grades of washings --- -5 grades of back extraction copper ", acid arrange: the pH value 3.0~3.5 of raw material is extracted, cleaning solution selects tap water,
It is stripped copper and uses 2~5mol/L sulfuric acid；Extracting and washing water is incorporated in material liquid by raffinate outlet, is stripped copper liquid and is entered production
Electrodeposition copper products, liquid is returned to again as back extraction copper liquid after electrodeposition, and circulation carries out.Copper extracts extraction raffinate discharge.
Step (4), step (3) copper extraction extraction raffinate are divided to two trends, and one is moved towards return step (1) as production reuse
Water；Another trend enters reactive tank, and measurement is ferrous, and ferrous oxidation at ferric iron, is passed through addition quality by supplement hydrogen peroxide
15% sodium carbonate liquor of percentage adjusts the pH value 4.5~5.0 of reaction system solution, the pH value 4.0 of precipitated iron；Precipitate chromium
PH value 4.5；The pH value 5.0 of precipitation of aluminium.After the reaction was completed, it is separated by solid-liquid separation, obtains filter residue and filtrate.Filter residue return step
(1) when raw material uses.
Step (5), by filtrate in step (4), first checked for impurities Ca, Mg, Cu, Zn, Mn content, with a small amount of sulfuric acid tune filtrate
PH value 3.0~4.0 between, into " P507-aviation kerosine " extraction system, P507 concentration is percent by volume 20%, saponification
With the sodium hydroxide of 30% mass percent, saponification rate selects 50%；25 DEG C of temperature, the volume flow ratio (mL/ of organic phase and water phase
ML) between 1/4~4/1, " mixing-clarifier " equipment is used, using multistage cascade extraction.Extraction process uses: " soap
Change ----extraction--- wash nickel--- it is organic to wash calcium, magnesium, copper, manganese--- washing zinc--- regeneration ", extract stage number selection: " saponification 1
Grade, extraction select 8 grades, wash nickel and select 5 grades, wash calcium, magnesium, copper, manganese and select 7 grades, wash zinc and select 5 grades, regeneration is organic to select 3 grades ".Use acidity:
Nickel 0.5mol/L hydrochloric acid is washed, calcium, magnesium, copper, mangaic acid degree 2.5mol/L hydrochloric acid are washed, washes zinc 5.5mol/L sulfuric acid, is regenerated organic
5.0mol/L hydrochloric acid.First stage enters material liquid, washing acid, saponification caustic, extraction raffinate after output extracting impurities, wash calcium, magnesium, copper,
Solution after manganese, solution of zinc sulfate, regeneration have machine washing acid.
The second stage of step (5), with the raffinate of first stage (or liquid after making extraction miscellaneous), using " P507-aviation
Kerosene " extraction system, P507 concentration are percent by volume 25%, are saponified the sodium hydroxide of 30% mass percent, saponification rate
Select 70%；It 25 DEG C of temperature, between organic phase and the volume flow ratio (mL/mL) 1/6~6/1 of water phase, uses " mixing-clarifier "
Equipment, using multistage cascade extraction.Extraction process uses: " --- -- regeneration has for washing--- back extraction--- for-extraction-for saponification
Machine ", extraction stage number selection: " 1 grade of saponification, extraction select 8 grades, and washing selects 5 grades, and back extraction selects 5 grades, and regeneration is organic to select 3 grades ".It uses
Acidity: washing 0.5mol/L sulfuric acid is stripped 5.5mol/L sulfuric acid, regenerates organic 6mol/L hydrochloric acid, and configuration second stage acid is molten
Water used in liquid is deionized water or distilled water.Second stage enters extraction raffinate after the extracting impurities of first stage output, washing acid, instead
Extraction acid, regenerates organic acid.Output: extraction extraction raffinate, nickel sulfate solution, regeneration have machine washing acid.
Step (6), by the solution of zinc sulfate of first stage output in step (5), zinc 110g/L；By step (5) second-order
The nickel sulfate solution of section back extraction output, nickel 105g/L；The two distinguishes evaporative crystallization, process industry level zinc sulfate and refined sulfuric acid
Nickel product.
Step (7), the filter residue that step (2) is obtained add tap water, and liquid-solid ratio 3:1 is washed twice, and use filter press mistake
Filter realizes and is separated by solid-liquid separation that output filter residue carries out pyrogenic process solidification, and cement mixes cement baking by 5% mass ratio；Filtrate is returned
Step (1) is gone back to use as production recycle-water；
The waste water that the first stage generates in step (5), with 20% sodium carbonate liquor precipitation process, copper, manganese heavy metal exist
7.0 preformed precipitate of pH value pretreatment, then drains into production waste and is jointly processed by；
Second stage waste water and first stage are merged with the pretreated waste water of sodium carbonate in step (5), are carried out at environmental protection
Reason, technique thinking is: 30~35% sodium hydroxide solutions precipitating, adjust high ph-values oxidation to harness emulsion precipitating, readjustment pH value 6~7 from
Sub- exchange adsorption, biological treatment COD.
Embodiment 2
Embodiment 2 compared with Example 1, in addition to following difference, the other the same as in Example 1:
Production recycle-water is added by liquid-solid ratio 1.2:1 in electroplating sludge object in step (1), and extracting copper raffinate is used for pulp.
E.Z is selected in embodiment 1 produced by step (2) except pre-prepd material C in the reactive tank of iron in step (2)
E.Z remove iron rear material, do not carry out being separated by solid-liquid separation preceding slurry.
Step (5) first stage extract stage number selection: " saponification 1 grade, extraction select 7 grades, wash nickel and select 4 grades, wash calcium, magnesium, copper,
Manganese selects 4 grades, washes zinc and selects 4 grades, regeneration is organic to select 3 grades ".It uses acidity: washing nickel 0.6mol/L hydrochloric acid, wash calcium, magnesium, copper, mangaic acid degree
2.0mol/L hydrochloric acid washes zinc 4mol/L sulfuric acid, regenerates organic 6.0mol/L hydrochloric acid；
Step (5) second stage extractant selects " P507---- sulfonated kerosene " system, uses acidity: washing 0.6mol/L
Sulfuric acid is stripped 5.0mol/L sulfuric acid, regenerates organic 6mol/L hydrochloric acid.
Embodiment 3
Embodiment 3 compared with Example 1, in addition to following difference, the other the same as in Example 1:
Production recycle-water is added by solid-to-liquid ratio 1.1:1 in electroplating sludge in step (1), the slag washing water of step (7) in embodiment 2
As production recycle-water.
Step (2) is the same as embodiment 2.E.Z removes the material C of iron, using E.Z in embodiment 2 except slurry after iron.
The dedicated extractant of step (3) copper selects " N902---- aviation kerosine " system.
Step (5) saponification first stage and second stage select 20% sodium carbonate liquor of mass percent.First stage
Extract stage number selection: " 2 grades of saponification, extraction select 11 grades, wash nickel and select 4 grades, wash calcium, magnesium, copper, manganese and select 6 grades, wash zinc and select 5 grades, regeneration
It is organic to select 4 grades ".Second stage stage number selection: " 1 grade of saponification, extraction select 6 grades, and washing selects 5 grades, and back extraction selects 6 grades, regenerates organic
Select 4 grades "；Use acidity: washing 0.2mol/L sulfuric acid is stripped 5.0mol/L sulfuric acid, regenerates organic 5mol/L hydrochloric acid.
Embodiment 4
Embodiment 4 compared with Example 1, in addition to following difference, the other the same as in Example 1:
The mass percentage (%) of electroplating sludge Heavy Metals: CuO 1.59, NiO 1.03, ZnO 0.62, Cr2O3
2.13,H2O 69.0。
Step (1) electroplating sludge is added production recycle-water by solid-to-liquid ratio 1:1 and extracts copper extraction raffinate, carries out pulp.
Step (2) E.Z removes the material C of iron, using embodiment 3 E.Z except after iron it is useless be separated by solid-liquid separation before slurry.
The extraction of step (3) copper: extraction process: " 3 grades of extractions --- -1 grade of washing --- -5 grades of back extraction copper ",
Step (5) first stage extract stage number selection: " saponification 2 grades, extraction select 14 grades, wash nickel and select 8 grades, wash calcium, magnesium, copper,
Manganese selects 9 grades, washes zinc and selects 6 grades, regeneration is organic to select 5 grades ".
Step (5) second stage extractant selects " P507---- sulfonated kerosene " system, and saponification rate selects 50%, extracts series
It selects: " 2 grades of saponification, extraction select 10 grades, and washing selects 8 grades, and back extraction selects 6 grades, and regeneration is organic to select 3 grades ".
Embodiment 5
Embodiment 5 compared with Example 1, in addition to following difference, the other the same as in Example 1:
The mass percentage (%) of electroplating sludge Heavy Metals: CuO 1.59, NiO 1.03, ZnO 0.62, Cr2O3
2.13,H2O 69.0。
Step (1), step (2) are the same as above embodiments 4.
Step (3) extractant is using " AD -100 and 260# kerosene " system, extractant percentage by volume 20%.
Step (5) first stage extract stage number selection: " saponification 1 grade, extraction select 16 grades, wash nickel and select 9 grades, wash calcium, magnesium, copper,
Manganese selects 9 grades, washes zinc and selects 7 grades, regeneration is organic to select 5 grades "；It uses acidity: washing nickel 0.7mol/L hydrochloric acid, wash calcium, magnesium, copper, mangaic acid degree
4.0mol/L hydrochloric acid washes zinc 5.0mol/L sulfuric acid, regenerates organic 6.0mol/L hydrochloric acid.
Embodiment 6
Embodiment 6 compared with Example 1, in addition to following difference, the other the same as in Example 1:
The mass percentage (%) of electroplating sludge Heavy Metals: CuO 1.59, NiO 1.03, ZnO 0.62, Cr2O3
2.13,H2O 69.0。
Step (1), step (2) are the same as above embodiments 4.
Step (3) extractant is using " AD -100 and 260# kerosene " system, extractant percentage by volume 20%；Extract work
Skill: " 2 grades of extractions --- -1 grade of washing --- -3 grades of back extraction copper ".
15% sodium hydroxide solution is added in step (4), adjusts solution ph 4.5~4.7.
Step (5) first stage extract stage number selection: " saponification 1 grade, extraction select 18 grades, wash nickel and select 5 grades, wash calcium, magnesium, copper,
Manganese selects 7 grades, washes zinc and selects 6 grades, regeneration is organic to select 4 grades "；It uses acidity: washing nickel 0.7mol/L hydrochloric acid, wash calcium, magnesium, copper, mangaic acid degree
3.0mol/L hydrochloric acid washes zinc 5.0mol/L sulfuric acid, regenerates organic 7.0mol/L hydrochloric acid.
Step (5) second stage extracts stage number selection: " 1 grade of saponification, extraction select 7 grades, and washing selects 6 grades, and back extraction selects 5 grades,
It regenerates and organic selects 3 grades ".Use acidity: washing 0.3mol/L sulfuric acid is stripped 5.5mol/L sulfuric acid, regenerates organic 5mol/L salt
Acid.
The filter residue that step (7) is obtained with step (2) adds tap water, and liquid-solid ratio 3:1 is washed twice, and uses squeezer mistake
Filter is realized and is separated by solid-liquid separation, then output filter residue carries out pyrogenic process solidification, selects method for vitrification, 1100 DEG C of nature of glass fired above.
Claims (10)
1. method low cost recycling metal from electroplating sludge and produce refined sulfuric acid nickel, characterized in that the following steps are included:
Step 1, by electroplating sludge and water with liquid-solid ratio (1~2): 1 carries out pulp, removes sundries in slurry with sieve；And then,
Sulfuric acid is added to slurry, the pH value of control reaction end slurry is 0.5~3.5；
Step 2, the hydrogen peroxide that mass percent is 28~35% is added into step 1 terminal slurry, just by the Asia in slurry
Iron is oxidized into ferric iron, as material A；Another configuration aqueous slkali is material B；Preparation bottom water is as material C in reactive tank；Into
Row E.Z is operated except iron: opening stirring, material A and material B are added in material C simultaneously, control mixed system material A+material B+ object
Expect the temperature of C at 75~85 DEG C, Fe3+Less than 1g/L, pH stable is separated by solid-liquid separation after adding A material 3.0~3.5
Filtering, obtains filter residue and filtrate；
E.Z is carried out except iron key reaction equation is as follows:
2Fe2++H2O2+2H+=2Fe3++2H2O
Fe3++2H2O=FeOOH+3H+
Cr3++3H2O=Cr (OH)3+3H+
H++ NaOH=Na++H2O
2H++Na2CO3=2Na++H2O+CO2；
Step 3, the filtrate that step 2 obtains removes organic and pretreatment before carrying out extracting copper, reuses the dedicated extractant of copper and is extracted
It takes copper to operate, obtains two materials: first is that high copper-containing solution, prepares tough cathode into electro deposited copper, second is that copper raffinate；It is main anti-
Answer equation as follows:
2RH+Cu2+→R2Cu+2H+Extraction reaction, acidity pH1.0~4.5；
R2Cu+2H+→2RH+Cu2+Back extraction reaction, 2~5mol/L of acidity；
Step 4, reaction is added as production recycle-water, another part in a part of return step 1 of the copper raffinate that step 3 obtains
Slot controls reaction system solution ph 4.5~5.0 by adding aqueous slkali, further precipitation and purification chromium therein, aluminium,
Iron, after precipitation and purification, filtering is separated by solid-liquid separation, and obtains filtrate and filter residue, and wherein filter residue return step 1 is when raw material use；It is main
Want reaction equation:
Fe3++3H2O=Fe (OH)3+3H+
Cr3++3H2O=Cr (OH)3+3H+
Al3++3H2O=Al (OH)3+3H+
H++ NaOH=Na++H2O
2H++Na2CO3=2Na++H2O+CO2；
Step 5, the pH value of filtrate is obtained with a small amount of sulfuric acid regulating step 4 3.0~4.0, carries out the extraction in two stages in order
Take processing；First stage is abstraction impurity removal matter, using p507-kerosene system, retain nickel extraction remove calcium in filtrate, magnesium,
Copper, manganese, zinc impurity, while solution of zinc sulfate is made in composition zinc therein；Second stage is called extracting and enriching, with the first stage
It is raw material that raffinate, which is called liquid after extracting impurities, extraction of nickel, and then backwash promotes the nickel concentration of nickel backwash liquor, again only
Change the impurity in nickel solution, obtains nickel sulfate solution；First stage generates a small amount of impure waste water, the nickeliferous raffinate for removing impurity
Liquid, solution of zinc sulfate；Second stage output nickel sulfate solution and raffinate waste water；
Extraction process key reaction equation:
NaOH+H2A2→Na(HA2)+H2O
Na(HA2)+H+→H2A2+Na+
M2++2NaHA2→M(HA2)2+2Na+
M(HA2)2+2H+→2H2A2+M2+
M represents Ca, Mg, Cu, Zn, Mn, Ni element in equation；H2A2、HA2Represent organic P507 or P204；P204 extracting metals
Sequentially: Fe3+> Zn2+> Ca2+> Cu2+> Mn2+> Co2+> Mg2+> Ni2+；P507 extracting metals sequence: Fe3+> Zn2+> Mn2 +> Cu2+> Ca2+> Co2+> Mg2+> Ni2+；
Step 6, by solution of zinc sulfate obtained by the first stage in step 5 and the resulting nickel sulfate solution of step 5 second stage, respectively
Sulfuric acid zinc product and refined sulfuric acid nickel is made in evaporative crystallization；
Step 7, filter residue step 2 obtained washs, filtering, obtains filter residue and filtrate, and filtrate return step 1 is used as and produces back
With water, filter residue solidification disposition；
First stage in step 5 is generated into waste water, is pre-processed with alkali precipitation, is filtered, filter residue solidification disposition, filtrate is used as production dirty
Water enters sewage treatment process；Second stage in step 5 is generated into waste water and other production wastes, carries out sewage treatment.
2. the method according to claim 1 low cost recycling metal from electroplating sludge and produce refined sulfuric acid nickel,
Be characterized in: the water that step 1 pulp uses is tap water or production recycle-water, and the production recycle-water includes the copper in step 3
The filtrate being obtained by filtration after raffinate, step 7 washery slag；20~50 DEG C of slurrying temperature, slurry time 1~3 hour；To slurry after pulp
10~30% that sulfuric acid amount is electroplating sludge quality are added in material.
3. the method according to claim 1 low cost recycling metal from electroplating sludge and produce refined sulfuric acid nickel,
It is characterized in: material B in step 2 are as follows: sodium hydroxide or sodium carbonate aqueous slkali, aqueous slkali mass percent concentration are 10~20%.
4. the method according to claim 1 low cost recycling metal from electroplating sludge and produce refined sulfuric acid nickel,
Be characterized in: except organic and pretreated feed liquid enters the preceding organic concentrations≤5mg/L of extraction in step 3, feed liquid is clear and transparent；Step
The dedicated extractant of copper in rapid 3 are as follows: AD -100 or N902, kerosene include: aviation kerosine, 260# kerosene；The dedicated extractant of copper and coal
Oil volume percentage 10~20%, extraction equipment is mixing -- clarifier, using multistage cascade extraction；The body of organic phase and water phase
Product stream is than mL/mL:1/4~4/1, and 10~40 DEG C of extraction temperature；Copper extraction process: extraction-washing-back extraction extracts tandem grade
Number is respectively: 2~3 grades of extractions, 1~2 grade of washing, 2~5 grades of back extraction；Liquid copper 20~30g/L copper, liquid copper 20 after back extraction before being stripped
~60g/L copper.
5. the method according to claim 1 low cost recycling metal from electroplating sludge and produce refined sulfuric acid nickel,
Be characterized in: the aqueous slkali that reactive tank is added in step 4 is sodium hydroxide or sodium carbonate liquor, and concentration is 10~20% mass percentages
Number.
6. the method according to claim 1 low cost recycling metal from electroplating sludge and produce refined sulfuric acid nickel,
It is characterized in: extracts extractant P507-kerosene system of first stage in step 5, wherein kerosene includes sulfonated kerosene, 260# coal
Oil, aviation kerosine, common kerosene, P507 percentage by volume in kerosene is 5~25%, and extraction equipment is mixing -- clarifier,
Using multistage cascade extraction；Organic phase carries out saponification process, saponification sodium hydroxide or sodium carbonate aqueous slkali, aqueous slkali matter in advance
Measuring percentage is 10~50%, saponification rate 10~60%, volume flow ratio mL/mL:1/8~8/1 of organic phase and water phase, extraction temperature
10~40 DEG C of degree；Extraction process: saponification-extract-washes nickel-and washes calcium, magnesium, copper, manganese-to wash zinc-regeneration organic；
Extract tandem series: 1~3 grade of saponification extracts 5~20 grades, washes 3~10 grades of nickel, wash calcium, magnesium, copper, 3~10 grades of manganese, wash zinc
3~10 grades, regenerate organic 3~10 grades；It washes acid: washing nickel, hydrochloric acid or nitric acid, 0.1~1.0mol/L of acid concentration；Wash calcium, magnesium, copper,
Manganese, hydrochloric acid or nitric acid, 2~4mol/L of acid concentration；Wash zinc, sulfuric acid, 2~6mol/L of acid concentration；Regenerate organic, concentration of hydrochloric acid 3.5
~8mol/L.
7. the method according to claim 1 low cost recycling metal from electroplating sludge and produce refined sulfuric acid nickel,
It is characterized in: extracts the extractant of second stage in step 5 are as follows: P507-kerosene system or P204-kerosene system；Wherein kerosene
Including sulfonated kerosene, 260# kerosene, aviation kerosine, common kerosene, P507 or the P204 percentage by volume in kerosene is 5~
30%, extraction equipment is mixing -- clarifier, using multistage cascade extraction；Organic phase carries out saponification process in advance, and hydrogen is used in saponification
Sodium oxide molybdena or sodium carbonate aqueous slkali, aqueous slkali mass percent are 10~50%, saponification rate 10~70%, organic phase and water phase
Volume flow ratio mL/mL:1/8~8/1,10~40 DEG C of extraction temperature；Extraction process: saponification-extraction of nickel-washing-back extraction nickel-
It regenerates organic；Extract tandem series: 1~3 grade of saponification extracts 3~10 grades, washs 3~10 grades, is stripped 3~10 grades of nickel, regeneration has
3~8 grades of machine；Wash acid: washing, sulfuric acid, 0.1~1.0mol/L of acid concentration；It is stripped nickel, sulfuric acid, 2~6mol/L of acid concentration；Regeneration
It is organic, 3.5~8mol/L of concentration of hydrochloric acid.
8. the method according to claim 1 low cost recycling metal from electroplating sludge and produce refined sulfuric acid nickel,
It is characterized in: step 6 solution of zinc sulfate 60~120g/L containing zinc, the nickeliferous 60~110g/L of nickel sulfate solution.
9. the method according to claim 1 low cost recycling metal from electroplating sludge and produce refined sulfuric acid nickel,
It is characterized in: is (2~5) to the liquid-solid ratio of residue washing in step 7: 1, filtering uses filter press；Filter residue curing process uses water
Mud solidification or glass solidification；Sewage treatment uses sodium hydroxide or sodium carbonate with alkali.
10. the method according to claim 1 low cost recycling metal from electroplating sludge and produce refined sulfuric acid nickel,
Be characterized in: the electroplating sludge includes the composition of following all or part of mass percent: Cr2O3: 0.01~20, CuO:0.3~
20, NiO:0.3~20, ZnO:0.3~20, Fe2O3: 0.01~5.0, FeO:0.01~8.0, Al2O3: 0.01~5.0, SiO2:
0.01~5.0, CaO:0.01~40, MgO:0.01~10, H2O:0.0~90. also contain PbO, the SnO of (0.01~1.0) respectively2、
MnO2。
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