CN107460341A - The method that recovery prepares cupric sulfate purified from copper containing scrap - Google Patents
The method that recovery prepares cupric sulfate purified from copper containing scrap Download PDFInfo
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- CN107460341A CN107460341A CN201710661379.4A CN201710661379A CN107460341A CN 107460341 A CN107460341 A CN 107460341A CN 201710661379 A CN201710661379 A CN 201710661379A CN 107460341 A CN107460341 A CN 107460341A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0086—Treating solutions by physical methods
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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Abstract
The present invention relates to scrap metal to recycle technical field, more particularly to the method that recovery prepares cupric sulfate purified from copper containing scrap, leached including dissolving, abstraction impurity removal, ultrasonic oil removing, resin adsorption purifies, evaporative crystallization, fluidized drying process, using copper containing scrap as raw material, metal is oxidized into metal ion through acidleach to be dissolved in leachate, press filtration separation after from filtrate extracting copper, tentatively cleaned, then carry out resin adsorbing separation, clean again, obtain refined sulfuric acid copper solution, finally to refined sulfuric acid copper solution evaporative crystallization, fluidized drying, obtain electroplating primes or even electroplate the copper sulphate of high-class product.The method for preparing cupric sulfate purified of the recovery from copper containing scrap of the present invention, this method preparation technology is simple, reliable, cleanliness without any pollution, and it is higher to reclaim the copper sulphate purity being prepared, and can be directly used for electroplating, has good economic and social benefit.
Description
Technical field
The present invention relates to scrap metal to recycle technical field, more particularly to recovery prepares electricity from copper containing scrap
The method for plating grade bluestone.
Background technology
Copper sulphate exists typically in the form of containing five crystallizations water, and copper sulphate is important Inorganic Chemicals, main to use
In the mordant of cotton and silk goods printing and dyeing, insecticide, the bactericide of water, the preservation of timber against decay agent, while also it is largely used to prepare ripple
Your more liquid, copper electroplating liquid, is also largely used to that non-ferrous metal ore industry, marine paints are industrial and the manufacture of other industrial chemicals.
With the rapid development of high-tech electronic component, integrated circuit, printed wiring board and relevant enterprise at home, the city of copper sulphate
Field demand increases substantially at an unprecedented rate, at the same time also proposes higher requirement to the quality of copper sulphate.By
Inevitably contain different degrees of organic impurities, various metals and nonmetallic inclusion, these impurity in technical grade sulfuric acid copper
The quality of electronic product will be directly affected without removing.Such as during the electronic component such as printed circuit board progress electroless plating, plating
Liquid is to impurity with regard to very sensitive；Organic and nonmetallic inclusion can reduce the activity of plating solution, cause chemical plating prompt drop low and plating leakage, sternly
Chemical plating process is also resulted in during weight completely to stop；And various metal impurities also result in the reduction of chemical plating speed and plating leakage etc. now
The appearance of elephant, and coating can be caused to shade, deposition of the metal impurities on coating, it can also cause coating unstable, make coating
Roughening, therefore, the purity and cleanliness factor of copper sulphate have particularly significant to the yield rate of electroplated product, electrical property and reliability
Influence.
The raw material of production cupric sulfate purified and method have at present, using copper sponge as raw material, oxidation, the method production of catalysis
Cupric sulfate purified；So that containing copper mine, as raw material, method production cupric sulfate purified of acid dissolving etc., not only condition is severe for these methods
Carve, production cost height, and it is seriously polluted, it is difficult to promote.In PCB production processes, substantial amounts of acidic etching waste liquid is generated, this
The copper content of a little waste liquids is very high；Electroplating sludge is a kind of dangerous solid waste of output during electroplating wastewater processing, its into
Divide complexity, contain substantial amounts of heavy metal copper, nickel, chromium etc.；In the waste materials such as copper dead catalyst, copper oxidized sludge and waste product copper there is also
Substantial amounts of metallic copper.If these waste materials containing metal will result in serious environmental disruption and great resource without dealing carefully with
Waste.
In order to fully recycle these waste and old resources, at present using these waste and old resources as raw material, prepared to reclaim
Copper sulphate, conventional method have ammonia leaching process, catalytic oxidation, acid-base neutralization method.These methods can be from copper containing scrap
Middle recovery prepares copper sulphate, but reclaims preparation technology complexity, easily causes secondary pollution, and the copper sulphate impurity being prepared contains
Amount is higher, it is impossible to is directly used in plating.
The content of the invention
In view of this, it is an object of the invention to provide from copper containing scrap recovery prepare the side of cupric sulfate purified
Method, this method preparation technology is simple, reliable, cleanliness without any pollution, and it is higher to reclaim the copper sulphate purity being prepared, and can be directly used for
Plating, has good economic and social benefit.
The present invention solves above-mentioned technical problem by following technological means：
The method that recovery prepares cupric sulfate purified from copper containing scrap, the copper containing scrap include copper plating groove
Slag and sludge, copper sulphate copper plating wastewater sludge, copper regeneration sludge, copper dead catalyst, copper facing sludge, copper etchant solution sludge, copper oxygen
Change sludge, including following process：
S1. dissolving is leached, and deionized water is added into copper containing scrap and carries out dissolving pulp, is then pumped into dissolving tank
In, sulfuric acid is added into dissolving tank and is stirred, oxygen-enriched air is blasted and reacts 2~3h, be transferred to press filtration in plate and frame filter press and separate
To filtrate A and filter residue A.
S2. abstraction impurity removal, including extracting copper and back extraction, extracting copper, filtrate A are transferred in extraction tank, add copper extraction
Agent AD-100 and 260# solvent naphtha is extracted, and obtains cupric organic phase；Back extraction, 1.8mol/L is added into cupric organic phase
Sulfuric acid solution be stripped, obtain being stripped organic phase and strip liquor, back extraction organic phase is reclaimed for extracting copper step.
S3. ultrasonic oil removing, strip liquor obtain rough copper-bath and oil after supersonic gas vibrating and air supporting tower oil removing
Phase, oil phase are recovered in strip stage.
S4. resin adsorption purify, by rough copper-bath with 3BV/h~5BV/h flow velocity be passed through large porous strong acid sun from
Sub-exchange resin post carries out Cu2+Absorption, after resin adsorption saturation, with 6mol/L~8mol/L sulfuric acid solution with 3BV/h~
5BV/h flow velocity backwash desorption, obtains refined sulfuric acid copper solution.
S5. evaporative crystallization, it is dense that refined sulfuric acid copper solution is transferred to progress technique in three-effect countercurrent evaporation in three-effect evaporation and condensation device
Contracting, it is 150g/L~180g/L copper sulphate concentrates to obtain concentration, and copper sulphate concentrate is cold in -5 DEG C~-3 DEG C progress of temperature
Freeze brilliant 1.5h~2h, be transferred to centrifugal dehydration in centrifuge, obtain supernatant and crystal settling.
S6. fluidized drying, crystal settling is put into Vibratingfluidbeddrier and carries out fluidized drying, that is, obtains electroplating level
Copper sulphate.
Further, dissolved in the S1 processes leaching temperature be 43 DEG C~60 DEG C, mixing speed be 600r/min~
800r/min。
Further, the flow of the oxygen-enriched air is 0.3m3/ h~0.5m3/ h, pressure in dissolving tank for 0.5MPa~
0.8MPa。
Further, after the filter residue A that the S1 processes obtain carries out countercurrent washing twice with 1.8mol/L sulfuric acid solution, obtain
To washery slag Water Sproading be used for dissolving tank in, the waste residue after washing is as fixed-end forces.
Further, the S2 processes extracting copper step carries out Pyatyi circulated in countercurrent extraction, the copper extractant to filtrate A
AD-100 and 260# solvent naphthas by volume 1:5 compounding mixing, filtrate A flow direction and copper extractant AD-100 and 260# are molten
The flow direction of agent oil is opposite.
Further, the S2 processes strip stage carries out Pyatyi circulated in countercurrent back extraction to cupric organic phase, and cupric has
The flow direction of machine phase is opposite with the flow direction of sulfuric acid solution.
Further, the S3 processes supersonic gas vibrating parameter is frequency 22kHz~25kHz, power 450W, 35 DEG C of temperature~
45℃。
Further, in the S4 processes macroporous strong-acid cation-exchange resin in D001MB, D001FC, D001 one
Kind.
Further, the temperature of the first evaporator of the S4 processes technique in three-effect countercurrent evaporation concentration is 110 DEG C~120 DEG C,
The temperature of second level evaporator is 95 DEG C~100 DEG C, and the temperature of third evaporator is 75 DEG C~85 DEG C, refined sulfuric acid copper solution
Flow velocity be 1.5m/s~1.8m/s.
Copper containing scrap is first added water slurry, then acid adding to leach by the present invention, and being stirred in leaching process makes its mixing, is passed through
The air of certain flow simultaneously controls the pressure in dissolving tank, is advantageous to the copper in scrap metal and leaches completely as much as possible, improves
Copper recovery.Copper extractant extracting copper is added into leachate and enters organic phase, copper is then stripped again, obtains strip liquor, will
Strip liquor carries out deoiling treatment, and to remove organic impurities, obtained rough copper-bath, the process realizes metallic copper and its
The initial gross separation of its metal impurities, then rough copper-bath is subjected to Cu with macroporous strong-acid cation-exchange resin2+Absorption, satisfy
With it is rear, eluted with sulfuric acid, just obtained the less copper-bath of impurity content, copper-bath is finally evaporated crystallization
And fluidized drying, copper sulphate is just obtained, is operated more than, obtained copper sulphate purity is high, meets plating primes, or even electricity
Plate the standard of high-class product.
The present invention leaches the filter residue A that process obtains to dissolving and carries out countercurrent washing twice, and washery slag Water Sproading is used to dissolve
Leach process；It is stripped isolated back extraction organic phase to reclaim for extracting copper step, the oil phase recovery that ultrasonic oil removing obtains
It in strip stage, so on the one hand make use of existing resource to carry out Efficient Cycle utilization, reduce cost and environmental pollution, reach
Energy-saving and emission-reduction, the purpose of high-efficiency environment friendly；On the other hand the loss of copper is avoided, copper has been reclaimed to greatest extent, to a certain degree
On, improve recovery utilization rate.
Embodiment
Below with reference to specific embodiment, the present invention is described in detail：
The copper containing scrap of the present invention refers to copper plating groove slag and sludge, copper sulphate copper plating wastewater sludge, copper regeneration dirt
The scrap metals such as mud, copper dead catalyst, copper facing sludge, copper etchant solution sludge, copper oxidized sludge, containing big in these scrap metals
The metallic copper of amount, plating level sulfuric acid will be prepared to be reclaimed to the present invention from copper containing scrap by specific embodiment below
The method of copper is described in detail.
Embodiment one
The method that the recovery from copper containing scrap of the present embodiment prepares cupric sulfate purified, including following process：
S1. dissolving is leached, and copper containing scrap is added in the deionized water of 3 times of volumes and carries out dissolving pulp, then pump
Enter in dissolving tank, 8mol/L sulfuric acid solution is added into dissolving tank, dissolving is stirred with 600r/min mixing speeds, simultaneously
With flow 0.3m3/ h blasts oxygen-enriched air, and it is 0.5MPa to control the pressure in dissolving tank, and temperature is 60 DEG C, dissolving reaction 3h,
The isolated filtrate A1 and filter residue A1 of press filtration in plate and frame filter press is transferred to, filter residue A1 is dried up with compressed air after press filtration, makes filter
Slag A1 water content reduces as far as possible.In order to improve the rate of recovery of copper, concentration is used to enter for 1.8mol/L sulfuric acid solution to filter residue A1
Row countercurrent washing twice, fully to wash away the soluble valuable metal carried secretly in filter residue, the washery slag Water Sproading of second of washing is used
Washed in first time filter residue A1, wash obtained washery slag Water Sproading for the first time and be used in dissolving tank, by the metal ion in material
Reclaim as far as possible, the filter residue A1 after washing twice is as fixed-end forces.
The main chemical reactions occurred in the process are as follows：MeO+H2SO4=MeSO4+H2O, Me therein are soluble gold
Category, predominantly Cu, Ni, Fe, Mn, Ca, Mg.Dissolving can produce a small amount of sulfuric acid mist during leaching, and can pass through
Air draft system enters alkali spray absorber and absorbs rear high altitude discharge up to standard.
S2. abstraction impurity removal, including extracting copper and back extraction.Extracting copper, using 260# solvent naphthas as the diluent of extractant,
Copper extractant AD-100 and 260# solvent naphtha by volume 1:5 carry out compounding mixing, and filtrate A is transferred in extraction tank, add copper
Extractant AD-100 and 260# solvent naphtha carry out Pyatyi circulated in countercurrent extraction, filtrate A flow direction and copper extractant AD-100
Flow direction with 260# solvent naphthas is on the contrary, be obtained by extraction cupric organic phase；Back extraction, is added into cupric organic phase
1.8mol/L sulfuric acid solution carries out Pyatyi circulated in countercurrent back extraction, the flow direction of cupric organic phase and the flowing of sulfuric acid solution
In the opposite direction, obtain being stripped organic phase and strip liquor, back extraction organic phase is reclaimed for extracting copper step.
S3. ultrasonic oil removing, by strip liquor in frequency 25kHz, power 450W, supersonic gas vibrating is carried out under the conditions of 35 DEG C of temperature
Oil removing, then after being transferred to air supporting tower oil removal by air bubbling, rough copper-bath and oil phase are obtained, oil phase is reclaimed for strip stage.
S4. resin adsorption purifies, and resin D001MB dress posts is exchanged from macroporous strong-acid cation, by rough copper-bath
Macroporous strong-acid cation exchange resin post is passed through with 3BV/h flow velocity Cu is carried out under normal temperature2+Absorption, after resin adsorption saturation,
Desorbed with 8mol/L sulfuric acid solution with 3BV/h flow velocity backwash, obtain refined sulfuric acid copper solution.Strong-acid cation after desorption
Exchange resin and carry out immersion regeneration with 3mol/L hydrochloric acid solution, resin is switched to Hydrogen resin, be then converted to before putting into operation
Sodium-ion type cation resin uses.
S5. evaporative crystallization, refined sulfuric acid copper solution is transferred in three-effect evaporation and condensation device and carried out with 1.8m/s flow velocity
Technique in three-effect countercurrent evaporation concentrates, and the temperature of the first evaporator of triple effect enrichment facility is 120 DEG C, and the temperature of second level evaporator is
95 DEG C, the temperature of third evaporator is 75 DEG C, and it is 150g/L copper sulphate concentrates that evaporation, which obtains concentration, by copper sulphate concentrate
In -3 DEG C of progress freezing and crystallizing 2h of temperature, it is transferred to centrifuge and centrifugal dehydration is carried out with middle 3500r/min, obtain supernatant and crystal
Precipitation, supernatant is recyclable to be used to dissolve leaching process.
S6. fluidized drying, crystal settling is put into Vibratingfluidbeddrier and carries out fluidized drying, that is, obtains electroplating level
Copper sulphate.
The copper sulphate that the present embodiment is prepared is tested and analyzed, and is contrasted with national standard, as a result such as table
1：
| Content/% | Electroplate high-class product | Electroplate primes | Sulfuric acid copper products |
| Copper | ≥98 | ≥98 | 98.5 |
| Water-insoluble | ≤0.005 | ≤0.01 | 0.0031 |
| Chloride | ≤0.002 | ≤0.01 | 0.0025 |
| Iron | ≤0.002 | ≤0.005 | 0.0013 |
| Zinc | ≤0.001 | ≤0.005 | 0.0027 |
| Nickel | ≤0.0005 | ≤0.005 | 0.00041 |
| Arsenic | ≤0.0005 | ≤0.0005 | 0.00038 |
| Cadmium | ≤0.0025 | ≤0.0025 | 0.0022 |
| Lead | ≤0.001 | ≤0.005 | 0.00089 |
Table 1
By data above analysis shows, the copper sulphate that the present embodiment is prepared meets the requirement of plating primes, can be straight
Scoop out in electroplating industry.
Embodiment two
The method that the recovery from copper containing scrap of the present embodiment prepares cupric sulfate purified, including following process：
S1. dissolving is leached, and copper containing scrap is added in the deionized water of 2 times of volumes and carries out dissolving pulp, then pump
Enter in dissolving tank, 8mol/L sulfuric acid solution is added into dissolving tank, dissolving is stirred with 800r/min mixing speeds, simultaneously
With flow 0.5m3/ h blasts oxygen-enriched air, and it is 0.8MPa to control the pressure in dissolving tank, and temperature is 43 DEG C, dissolving reaction 2h,
The isolated filtrate A2 and filter residue A2 of press filtration in plate and frame filter press is transferred to, filter residue A2 is dried up with compressed air after press filtration, makes filter
Slag A2 water content reduces as far as possible.In order to improve the rate of recovery of copper, concentration is used to enter for 1.8mol/L sulfuric acid solution to filter residue A2
Row countercurrent washing twice, fully to wash away the soluble valuable metal carried secretly in filter residue, the washery slag Water Sproading of second of washing is used
Washed in first time filter residue A2, wash obtained washery slag Water Sproading for the first time and be used in dissolving tank, by the metal ion in material
Reclaim as far as possible, the filter residue A2 after washing twice is as fixed-end forces.Dissolving can produce a small amount of sulfuric acid during leaching
Mist, alkali spray absorber can be entered by air draft system and absorbs rear high altitude discharge up to standard.
S2. abstraction impurity removal, including extracting copper and back extraction.Extracting copper, using 260# solvent naphthas as the diluent of extractant,
Copper extractant AD-100 and 260# solvent naphtha by volume 1:5 carry out compounding mixing, and filtrate A2 is transferred in extraction tank, add copper
Extractant AD-100 and 260# solvent naphtha carry out Pyatyi circulated in countercurrent extraction, filtrate A2 flow direction and copper extractant AD-100
Flow direction with 260# solvent naphthas is on the contrary, be obtained by extraction cupric organic phase；Back extraction, is added into cupric organic phase
1.8mol/L sulfuric acid solution carries out Pyatyi circulated in countercurrent back extraction, the flow direction of cupric organic phase and the flowing of sulfuric acid solution
In the opposite direction, obtain being stripped organic phase and strip liquor, back extraction organic phase is reclaimed for extracting copper step.
S3. ultrasonic oil removing, by strip liquor in frequency 22kHz, power 450W, supersonic gas vibrating is carried out under the conditions of temperature 45 C
Oil removing, then after being transferred to air supporting tower oil removal by air bubbling, rough copper-bath and oil phase are obtained, oil phase is reclaimed for strip stage.
S4. resin adsorption purifies, and resin D001FC dress posts is exchanged from macroporous strong-acid cation, by rough copper-bath
Macroporous strong-acid cation exchange resin post is passed through with 5BV/h flow velocity Cu is carried out under normal temperature2+Absorption, after resin adsorption saturation,
Desorbed with 6mol/L sulfuric acid solution with 3BV/h flow velocity backwash, obtain refined sulfuric acid copper solution.Strong-acid cation after desorption
Exchange resin and carry out immersion regeneration with 3mol/L hydrochloric acid solution, resin is switched to Hydrogen resin, be then converted to before putting into operation
Sodium-ion type cation resin uses.
S5. evaporative crystallization, refined sulfuric acid copper solution is transferred in three-effect evaporation and condensation device and carried out with 1.5m/s flow velocity
Technique in three-effect countercurrent evaporation concentrates, and the temperature of the first evaporator of triple effect enrichment facility is 110 DEG C, and the temperature of second level evaporator is
100 DEG C, the temperature of third evaporator is 85 DEG C, and it is 180g/L copper sulphate concentrates that evaporation, which obtains concentration, and copper sulphate is concentrated
Liquid is transferred to centrifuge and carries out centrifugal dehydration with middle 3800r/min in -5 DEG C of temperature progress freezing and crystallizing 1.5h, obtain supernatant and
Crystal settling, supernatant is recyclable to be used to dissolve leaching process.
S6. fluidized drying, crystal settling is put into Vibratingfluidbeddrier and carries out fluidized drying, that is, obtains electroplating level
Copper sulphate.
The copper sulphate that the present embodiment is prepared is tested and analyzed, and is contrasted with national standard, as a result such as table
2：
| Content/% | Electroplate high-class product | Electroplate primes | Sulfuric acid copper products |
| Copper | ≥98 | ≥98 | 99.1 |
| Water-insoluble | ≤0.005 | ≤0.01 | 0.0034 |
| Chloride | ≤0.002 | ≤0.01 | 0.0017 |
| Iron | ≤0.002 | ≤0.005 | 0.0011 |
| Zinc | ≤0.001 | ≤0.005 | 0.0008 |
| Nickel | ≤0.0005 | ≤0.005 | 0.00026 |
| Arsenic | ≤0.0005 | ≤0.0005 | 0.00035 |
| Cadmium | ≤0.0025 | ≤0.0025 | 0.0019 |
| Lead | ≤0.001 | ≤0.005 | 0.00078 |
Table 2
By data above analysis shows, the copper sulphate that the present embodiment is prepared meets the requirement of plating high-class product, can be straight
Scoop out in electroplating industry.
Embodiment three
The method that the recovery from copper containing scrap of the present embodiment prepares cupric sulfate purified, including following process：
S1. dissolving is leached, and copper containing scrap is added in the deionized water of 2.5 times of volumes and carries out dissolving pulp, then
It is pumped into dissolving tank, 8mol/L sulfuric acid solution is added into dissolving tank, dissolving is stirred with 700r/min mixing speeds, together
When with flow 0.4m3/ h blasts oxygen-enriched air, and it is 0.7MPa to control the pressure in dissolving tank, and temperature is 50 DEG C, dissolving reaction
2.5h, the isolated filtrate A3 and filter residue A3 of press filtration in plate and frame filter press is transferred to, is dried up filter residue A3 with compressed air after press filtration,
Filter residue A3 water content is set to reduce as far as possible.In order to improve the rate of recovery of copper, it is 1.8mol/L sulfuric acid solution to filter residue to use concentration
A3 carries out countercurrent washing twice, and fully to wash away the soluble valuable metal carried secretly in filter residue, the slag washing water of second of washing returns
Receive and washed for first time filter residue A3, wash obtained washery slag Water Sproading for the first time and be used in dissolving tank, by the metal in material
Ion reclaims as far as possible, and the filter residue A3 after washing twice is as fixed-end forces.Dissolving can produce a small amount of during leaching
Sulfuric acid mist, alkali spray absorber can be entered by air draft system and absorbs rear high altitude discharge up to standard.
S2. abstraction impurity removal, including extracting copper and back extraction.Extracting copper, using 260# solvent naphthas as the diluent of extractant,
Copper extractant AD-100 and 260# solvent naphtha by volume 1:5 carry out compounding mixing, and filtrate A3 is transferred in extraction tank, add copper
Extractant AD-100 and 260# solvent naphtha carry out Pyatyi circulated in countercurrent extraction, filtrate A3 flow direction and copper extractant AD-100
Flow direction with 260# solvent naphthas is on the contrary, be obtained by extraction cupric organic phase；Back extraction, is added into cupric organic phase
1.8mol/L sulfuric acid solution carries out Pyatyi circulated in countercurrent back extraction, the flow direction of cupric organic phase and the flowing of sulfuric acid solution
In the opposite direction, obtain being stripped organic phase and strip liquor, back extraction organic phase is reclaimed for extracting copper step.
S3. ultrasonic oil removing, by strip liquor in frequency 23kHz, power 450W, supersonic gas vibrating is carried out under the conditions of 40 DEG C of temperature
Oil removing, then after being transferred to air supporting tower oil removal by air bubbling, rough copper-bath and oil phase are obtained, oil phase is reclaimed for strip stage.
S4. resin adsorption is purified, and resin D001 dress post is exchanged from macroporous strong-acid cation, by rough copper-bath with
4BV/h flow velocity is passed through macroporous strong-acid cation exchange resin post and Cu is carried out under normal temperature2+Absorption, after resin adsorption saturation, use
7mol/L sulfuric acid solution is desorbed with 4BV/h flow velocity backwash, obtains refined sulfuric acid copper solution.Strong-acid cation after desorption is handed over
Change resin and carry out immersion regeneration with 3mol/L hydrochloric acid solution, resin is switched to Hydrogen resin, sodium is then converted to before putting into operation
Ionic cation resin uses.
S5. evaporative crystallization, refined sulfuric acid copper solution is transferred in three-effect evaporation and condensation device and carried out with 1.6m/s flow velocity
Technique in three-effect countercurrent evaporation concentrates, and the temperature of the first evaporator of triple effect enrichment facility is 115 DEG C, and the temperature of second level evaporator is
98 DEG C, the temperature of third evaporator is 80 DEG C, and it is 160g/L copper sulphate concentrates that evaporation, which obtains concentration, by copper sulphate concentrate
In -4 DEG C of progress freezing and crystallizing 1.6h of temperature, it is transferred to centrifuge and centrifugal dehydration is carried out with middle 4000r/min, obtain supernatant and crystalline substance
Body is precipitated, and supernatant is recyclable to be used to dissolve leaching process.
S6. fluidized drying, crystal settling is put into Vibratingfluidbeddrier and carries out fluidized drying, that is, obtains electroplating level
Copper sulphate.
The copper sulphate that the present embodiment is prepared is tested and analyzed, and is contrasted with national standard, as a result such as table
3：
| Content/% | Electroplate high-class product | Electroplate primes | Sulfuric acid copper products |
| Copper | ≥98 | ≥98 | 98.9 |
| Water-insoluble | ≤0.005 | ≤0.01 | 0.0030 |
| Chloride | ≤0.002 | ≤0.01 | 0.0014 |
| Iron | ≤0.002 | ≤0.005 | 0.0011 |
| Zinc | ≤0.001 | ≤0.005 | 0.0009 |
| Nickel | ≤0.0005 | ≤0.005 | 0.00045 |
| Arsenic | ≤0.0005 | ≤0.0005 | 0.00029 |
| Cadmium | ≤0.0025 | ≤0.0025 | 0.0017 |
| Lead | ≤0.001 | ≤0.005 | 0.00091 |
Table 3
By data above analysis shows, the copper sulphate that the present embodiment is prepared meets the requirement of plating high-class product, can be straight
Scoop out in electroplating industry.
Example IV
The method that the recovery from copper containing scrap of the present embodiment prepares cupric sulfate purified, including following process：
S1. dissolving is leached, and copper containing scrap is added in the deionized water of 3 times of volumes and carries out dissolving pulp, then pump
Enter in dissolving tank, 8mol/L sulfuric acid solution is added into dissolving tank, dissolving is stirred with 750r/min mixing speeds, simultaneously
With flow 0.5m3/ h blasts oxygen-enriched air, and it is 0.7MPa to control the pressure in dissolving tank, and temperature is 45 DEG C, dissolving reaction 3h,
The isolated filtrate A4 and filter residue A4 of press filtration in plate and frame filter press is transferred to, filter residue A4 is dried up with compressed air after press filtration, makes filter
Slag A4 water content reduces as far as possible.In order to improve the rate of recovery of copper, concentration is used to enter for 1.8mol/L sulfuric acid solution to filter residue A4
Row countercurrent washing twice, fully to wash away the soluble valuable metal carried secretly in filter residue, the washery slag Water Sproading of second of washing is used
Washed in first time filter residue A4, wash obtained washery slag Water Sproading for the first time and be used in dissolving tank, by the metal ion in material
Reclaim as far as possible, the filter residue A4 after washing twice is as fixed-end forces.Dissolving can produce a small amount of sulfuric acid during leaching
Mist, alkali spray absorber can be entered by air draft system and absorbs rear high altitude discharge up to standard.
S2. abstraction impurity removal, including extracting copper and back extraction.Extracting copper, using 260# solvent naphthas as the diluent of extractant,
Copper extractant AD-100 and 260# solvent naphtha by volume 1:5 carry out compounding mixing, and filtrate A4 is transferred in extraction tank, add copper
Extractant AD-100 and 260# solvent naphtha carry out Pyatyi circulated in countercurrent extraction, filtrate A4 flow direction and copper extractant AD-100
Flow direction with 260# solvent naphthas is on the contrary, be obtained by extraction cupric organic phase；Back extraction, is added into cupric organic phase
1.8mol/L sulfuric acid solution carries out Pyatyi circulated in countercurrent back extraction, the flow direction of cupric organic phase and the flowing of sulfuric acid solution
In the opposite direction, obtain being stripped organic phase and strip liquor, back extraction organic phase is reclaimed for extracting copper step.
S3. ultrasonic oil removing, by strip liquor in frequency 24kHz, power 450W, supersonic gas vibrating is carried out under the conditions of 40 DEG C of temperature
Oil removing, then after being transferred to air supporting tower oil removal by air bubbling, rough copper-bath and oil phase are obtained, oil phase is reclaimed for strip stage.
S4. resin adsorption purifies, and resin D001MB dress posts is exchanged from macroporous strong-acid cation, by rough copper-bath
Macroporous strong-acid cation exchange resin post is passed through with 5BV/h flow velocity Cu is carried out under normal temperature2+Absorption, after resin adsorption saturation,
Desorbed with 6mol/L sulfuric acid solution with 5BV/h flow velocity backwash, obtain refined sulfuric acid copper solution.Strong-acid cation after desorption
Exchange resin and carry out immersion regeneration with 3mol/L hydrochloric acid solution, resin is switched to Hydrogen resin, be then converted to before putting into operation
Sodium-ion type cation resin uses.
S5. evaporative crystallization, refined sulfuric acid copper solution is transferred in three-effect evaporation and condensation device and carried out with 1.6m/s flow velocity
Technique in three-effect countercurrent evaporation concentrates, and the temperature of the first evaporator of triple effect enrichment facility is 120 DEG C, and the temperature of second level evaporator is
95 DEG C, the temperature of third evaporator is 85 DEG C, and it is 170g/L copper sulphate concentrates that evaporation, which obtains concentration, by copper sulphate concentrate
In -5 DEG C of progress freezing and crystallizing 1.5h of temperature, it is transferred to centrifuge and centrifugal dehydration is carried out with middle 3500r/min, obtain supernatant and crystalline substance
Body is precipitated, and supernatant is recyclable to be used to dissolve leaching process.
S6. fluidized drying, crystal settling is put into Vibratingfluidbeddrier and carries out fluidized drying, that is, obtains electroplating level
Copper sulphate.
The copper sulphate that the present embodiment is prepared is tested and analyzed, and is contrasted with national standard, as a result such as table
4：
| Content/% | Electroplate high-class product | Electroplate primes | Sulfuric acid copper products |
| Copper | ≥98 | ≥98 | 99.4 |
| Water-insoluble | ≤0.005 | ≤0.01 | 0.0014 |
| Chloride | ≤0.002 | ≤0.01 | 0.0011 |
| Iron | ≤0.002 | ≤0.005 | 0.0008 |
| Zinc | ≤0.001 | ≤0.005 | 0.0007 |
| Nickel | ≤0.0005 | ≤0.005 | 0.00020 |
| Arsenic | ≤0.0005 | ≤0.0005 | 0.00031 |
| Cadmium | ≤0.0025 | ≤0.0025 | 0.0016 |
| Lead | ≤0.001 | ≤0.005 | 0.00074 |
Table 4
By data above analysis shows, the copper sulphate that the present embodiment is prepared meets the requirement of plating high-class product, can be straight
Scoop out in electroplating industry.
The above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to preferred embodiment to this hair
It is bright to be described in detail, it will be understood by those within the art that, technical scheme can be modified
Or equivalent substitution, without departing from the objective and scope of technical solution of the present invention, it all should cover the claim in the present invention
Among scope.The present invention be not described in detail technology, shape, construction part be known technology.
Claims (9)
1. the method that recovery prepares cupric sulfate purified from copper containing scrap, it is characterised in that including following process：
S1. dissolving is leached, and to being pumped into after copper containing scrap plus water slurry in dissolving tank, sulfuric acid is added into dissolving tank and is stirred
Mix, blast oxygen-enriched air reaction 2h~3h, be transferred to the isolated filtrate A and filter residue A of press filtration in plate and frame filter press；
S2. abstraction impurity removal, including extracting copper and back extraction, extracting copper, filtrate A are transferred in extraction tank, add copper extractant AD-
100 and 260# solvent naphthas are extracted, and obtain cupric organic phase；Back extraction, 1.8mol/L sulphur is added into cupric organic phase
Acid solution is stripped, and obtains being stripped organic phase and strip liquor, back extraction organic phase is reclaimed for extracting copper step；
S3. ultrasonic oil removing, strip liquor obtain rough copper-bath and oil phase after supersonic gas vibrating and air supporting tower oil removing, oil
Mutually it is recovered in strip stage；
S4. resin adsorption purifies, and rough copper-bath is passed through into macroporous strong-acid cation with 3BV/h~5BV/h flow velocity hands over
Change resin column and carry out Cu2+Adsorb, after resin adsorption saturation, with 6mol/L~8mol/L sulfuric acid solution with 3BV/h~5BV/h's
Flow velocity backwash desorbs, and obtains refined sulfuric acid copper solution；
S5. evaporative crystallization, refined sulfuric acid copper solution is transferred to progress technique in three-effect countercurrent evaporation concentration in three-effect evaporation and condensation device, obtained
It is 150g/L~180g/L copper sulphate concentrates to concentration, by copper sulphate concentrate in -5 DEG C~-3 DEG C progress freezing and crystallizings of temperature
1.5h~2h, centrifugal dehydration in centrifuge is transferred to, obtains supernatant and crystal settling；
S6. fluidized drying, crystal settling is put into Vibratingfluidbeddrier and carries out fluidized drying, that is, obtains electroplating level sulfuric acid
Copper.
2. the method that the recovery according to claim 1 from copper containing scrap prepares cupric sulfate purified, its feature exist
In the temperature that leaching is dissolved in the S1 processes is 43 DEG C~60 DEG C, and mixing speed is 600r/min~800r/min.
3. the method that the recovery according to claim 2 from copper containing scrap prepares cupric sulfate purified, its feature exist
In the flow of the oxygen-enriched air is 0.3m3/ h~0.5m3/ h, the pressure in dissolving tank is 0.5MPa~0.8MPa.
4. the method that the recovery according to claim 3 from copper containing scrap prepares cupric sulfate purified, its feature exist
In after the filter residue A that the S1 processes obtain carries out countercurrent washing twice with 1.8mol/L sulfuric acid solution, obtained slag washing water returns
Receive in dissolving tank, the waste residue after washing to be as fixed-end forces.
5. the method that the recovery according to claim 4 from copper containing scrap prepares cupric sulfate purified, its feature exist
In the S2 processes extracting copper step carries out Pyatyi circulated in countercurrent extraction to filtrate A, and the copper extractant AD-100 and 260# is molten
Agent oil by volume 1:5 compounding mixing, filtrate A flow direction and the flow direction of copper extractant AD-100 and 260# solvent naphtha
Conversely.
6. the method that the recovery according to claim 5 from copper containing scrap prepares cupric sulfate purified, its feature exist
In the S2 processes strip stage carries out Pyatyi circulated in countercurrent back extraction, the flowing side of cupric organic phase to cupric organic phase
To opposite with the flow direction of sulfuric acid solution.
7. the method that the recovery according to claim 6 from copper containing scrap prepares cupric sulfate purified, its feature exist
In, the S3 processes supersonic gas vibrating parameter be frequency 22kHz~25kHz, power 450W, 35 DEG C~45 DEG C of temperature.
8. the method that the recovery according to claim 7 from copper containing scrap prepares cupric sulfate purified, its feature exist
In the one kind of macroporous strong-acid cation-exchange resin in D001MB, D001FC, D001 in the S4 processes.
9. the method that the recovery according to claim 8 from copper containing scrap prepares cupric sulfate purified, its feature exist
In the temperature of the first evaporator of the S4 processes triple effect enrichment facility is 110 DEG C~120 DEG C, the temperature of second level evaporator
Spend for 95 DEG C~100 DEG C, the temperature of third evaporator is 75 DEG C~85 DEG C, the flow velocity of refined sulfuric acid copper solution for 1.5m/s~
1.8m/s。
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| CN110923456A (en) * | 2019-12-13 | 2020-03-27 | 陕西易莱德新材料科技有限公司 | Method for preparing high-purity copper and copper sulfate by adsorption from copper-plating sludge |
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