CN109161895A - Acid copper chloride etching liquid copper reclaiming system and reclaiming method - Google Patents
Acid copper chloride etching liquid copper reclaiming system and reclaiming method Download PDFInfo
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- CN109161895A CN109161895A CN201810979851.3A CN201810979851A CN109161895A CN 109161895 A CN109161895 A CN 109161895A CN 201810979851 A CN201810979851 A CN 201810979851A CN 109161895 A CN109161895 A CN 109161895A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/08—Apparatus, e.g. for photomechanical printing surfaces
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
- C25C7/08—Separating of deposited metals from the cathode
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Abstract
The present invention provides a kind of acid copper chloride etching liquid copper reclaiming system and reclaiming method, is related to etching solution recycling technical field.Acid copper chloride etching liquid copper reclaiming system of the present invention includes etching solution regenerative system and the exhaust treatment system positioned at etching solution regenerative system downstream, further includes molten iron washing liquid treating system；The problems such as high energy consumption, low reclamation rate, tough cathode impurity content that acid copper chloride etching liquid copper reclaiming method of the present invention effectively solves existing acid copper chloride etching liquid regeneration cycle be more, chlorine secondary pollution environment provide technical support to the overall application of acid copper chloride etching liquid electrolytic regeneration circulating technology.
Description
Technical field
The present invention relates to etching solution recycling technical fields, and in particular to a kind of recycling of acid copper chloride etching liquid copper is again
Raw system and reclaiming method.
Background technique
Printed circuit board is the basic components of various electronic products, and the important ring in production process is to use chemical attack
Method etches away copper extra except copper foil on-board circuitry needs (generally in 60-70%).Acidic copper chloride and alkaline copper chloride
Etching solution is current most commonly used etchant, and wherein acid copper chloride etching liquid is particularly suitable for because having the characteristics that lateral erosion is small
The demanding printed circuit panel products of etching precision, are used more and more by a large amount of printed circuit board factory.Etching and processing
The chemical reaction of Shi Fasheng is that a metallic copper atoms on copper foil plate are generated two by a bivalent cupric ion in etching solution
A univalent copper ion.Therefore with the progress of etching, total copper and univalent copper ion concentration increase in etching solution, it will cause etch capabilities
It is gradually reduced.To keep ideal etching power, it is common practice that carry out chemical regeneration to a part of etching solution, i.e., to etching solution
Monovalence copper is oxidized to cupric by middle addition chemical oxidizing agent.Etching solution after chemical regeneration is reused, and another part is not
Regenerated etching solution becomes etching waste liquor.It is 100- that one square metre of printed circuit board of every lithography, which about generates 2-2.5L copper content,
150g.L-1Etching waste liquor.
The copper waste etching solution generated in printed circuit board factory will generally be sent to liquid waste processing station-service neutralization precipitation method, displacement
The chemical methodes such as method, extraction processing recycling copper.But the copper that these processing methods are recycled from waste liquid be in the form of compound,
Value of the product is low, and a large amount of chemical agents are consumed in treatment process.In addition, due to the Technical Board of each chemical recycling itself
Limit, has quite a few copper not recycled, but is discharged into environment, causes environmental pollution.
Currently, the unit of research and development chlorination copper etchant solution electrolytic recovery copper is many both at home and abroad, the equipment researched and developed exists
Occur different problems in use process, leads to that industry use cannot be put into, such as: etching solution can not be recycled after electrolysis mentions copper
It utilizes, it is not single to be polluted to environment, also lead to the waste of chemical raw material；Another technical problem is in electrolytic process Anodic
Chlorine precipitation is had, according to theoretical calculation, every electrolytic deposition goes out the copper of 100kg, accordingly can be in the chlorine of anode precipitation 111.6kg
Gas, the volume under standard state is about 35.26m3, a large amount of chlorine and remaining waste for how dealing carefully with generation are without right
Environment causes secondary pollution, can undoubtedly make increased costs and the device is complicated change.
Therefore, a kind of recycling of acid copper chloride etching liquid copper reclaiming system and reclaiming method for copper is developed
It recycles particularly important.
Summary of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of acid copper chloride etching liquid copper reclaiming system and recycling again
Generation method.
In order to achieve the above object, technical solution of the present invention is achieved by the following technical programs:
A kind of acid copper chloride etching liquid copper reclaiming system, the acid copper chloride etching liquid copper reclaiming system
Exhaust treatment system including etching solution regenerative system and positioned at etching solution regenerative system downstream further includes at molten iron cleaning solution
Reason system, the etching solution regenerative system include sequentially connected etching production line, waste liquid storage barrel, electrolytic cell, regenerated liquid storage
Bucket is deposited, the downstream of the regenerated liquid storage barrel is connect with etching production line, and the anode region of the electrolytic cell and solution absorption cylinder connect
Logical, fluidic device, etching production line are sequentially communicated；
The molten iron washing liquid treating system includes sequentially connected molten iron cylinder, molten iron absorption cylinder, molten iron scrubbing tower；
There is environment exhaust column, the environment exhaust column passes through pipeline and the exhaust-gas treatment system on the etching production line
System connection,
The exhaust treatment system includes sequentially connected solution absorption cylinder, molten iron absorption cylinder, molten iron scrubbing tower, lye suction
Tower, exhaust outlet are received, the exhaust treatment system upstream connects with anode electrolytic cell area, electric tank cathode area, environment exhaust column respectively
It connects, the anode electrolytic cell area is connect with the solution absorption cylinder, and (gas in anode electrolytic cell area is sequentially entered molten by pipeline
Solution absorbs cylinder, molten iron absorbs cylinder, molten iron scrubbing tower, lye absorption tower, exhaust outlet, completes exhaust-gas treatment)；The electric tank cathode
Area connect with the molten iron scrubbing tower (gas in electric tank cathode area by pipeline sequentially enter molten iron scrubbing tower, lye absorb
Tower, exhaust outlet complete exhaust-gas treatment)；The environment exhaust column is connect with the lye absorption tower.
Further, the reclaiming method includes etching solution regeneration, chlorine treatment, the processing of molten iron cleaning solution, exhaust gas
Processing；The etching solution regeneration are as follows: by etching waste liquor, it is introduced into electrolytic cell and is electrolysed as electrolyte, under electrolysis,
When electrolyte is electrolysed, metallic copper is generated on cathode plate, chlorine is generated on anode plate, copper ion is in cathode quilt in etching waste liquor
It is reduced to copper powder simple substance and reduces copper ion concentration, while under the oxidation of anode strong oxidizing property product chlorine, ORP liter
Height so that etching waste liquid regeneration reaches effective etching solution standard, and then regenerated etching solution is introduced on etching production line, is followed
Ring uses.
Further, content of copper ion control in the electric tank cathode area is in 30-70g/L, the electrolysis electricity of the electrolytic cell
Stream is 1000-3000A, the copper ion mass concentration of electric tank cathode area electrolyte always < copper of anode region electrolyte from
Protonatomic mass concentration.
Further, every content of copper ion of four hour sampling analyses in the electric tank cathode area, was normally electrolysed
Content of copper ion is controlled in 30-50g/L in journey, the Faradaic current of the electrolytic cell is 1800-2400A, as copper ion < 30g/
When L, etching waste liquor is added.
Further, the inside of the electrolytic cell is equipped with electrolyte membrane.
Further, the chlorine treatment are as follows: the oxidizing gas chlorine that anode chamber generates enters solution absorption cylinder, then passes through
Fluidic device reuse reaches circular regeneration to production line is etched, with this.
Further, the molten iron cleaning solution process flow is successively are as follows: molten iron cylinder-molten iron absorbs cylinder-molten iron absorption tower, institute
It states and contains ferrous chloride, fe, hydrogen chloride in molten iron cylinder；It is the ferrous chloride containing impurity in cylinder that the molten iron, which absorbs,；Institute
It states in molten iron absorption tower as pure ferrous chloride.
Further, the exhaust-gas treatment process are as follows: anode electrolytic cell gas-solution absorption cylinder-molten iron absorbs cylinder-molten iron
Absorption tower-alkali liquid washing tower-discharge；Electric tank cathode gas-molten iron absorbs cylinder-molten iron absorption tower-alkali liquid washing tower-discharge；
Environment exhaust column-alkali liquid washing tower-discharge.
The present invention provides a kind of acid copper chloride etching liquid copper reclaiming system and reclaiming method, with the prior art
It is compared to advantage:
Acid copper chloride etching liquid copper reclaiming system and reclaiming method of the present invention effectively solve existing acid chlorine
The problems such as changing the more high energy consumption of copper etchant solution regeneration cycle, low reclamation rate, tough cathode impurity content, chlorine secondary pollution environment,
Technical support is provided to the overall application of acid copper chloride etching liquid electrolytic regeneration circulating technology；
Faradaic current of the invention is high-efficient, can be effectively saved production cost, energy saving, raising copper recovery efficiency,
Make entire reclaiming technique stability with higher, safety and higher economic benefit；Acidic copper chloride erosion of the present invention
It carves liquid copper reclaiming system and reclaiming method guarantees that etching and electrolysis can swimmingly be run simultaneously.In addition, using machine
Device collects the beginning and stopping for being electrolysed resulting metallic copper and automatically controlling electrolysis automatically, and the integrated automation degree of technique is high,
Human input is reduced.The chlorine generated in electrolysis can be used as oxidant, univalent copper ion in oxidation electrolyte and it is ferrous from
Son, to save the use for etching liquid oxidizer in sub- liquid regenerative process；
The purity is high for the copper that acid copper chloride etching liquid copper reclaiming system and reclaiming method of the present invention are recycled,
Further purification processes are not needed, so that it may directly recycle；Acid copper chloride etching liquid copper reclaiming system of the present invention
And reclaiming method process can effectively absorb and consume the chlorine that electrolysis generates, electrolytically generated most of chlorine can be stood
Quarter is consumed by the redox reaction of electrolyte, and remaining fraction chlorine can be quickly soluble in electrolyte, subsequent
Process in be reused as oxidant；Waste gas treatment process can effectively avoid poisonous fume from polluting environment, ensure that
The safety of whole process.
Detailed description of the invention
Fig. 1 is etching solution regeneration technology flow chart of the present invention；
Fig. 2 is chlorine treatment flow chart of the present invention；
Fig. 3 is molten iron cleaning solution process flow diagram of the present invention；
Fig. 4 is exhaust-gas treatment process figure of the present invention.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below with reference to the embodiment of the present invention pair
Technical solution in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is a part of the invention
Embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making wound
Every other embodiment obtained under the premise of the property made labour, shall fall within the protection scope of the present invention.
In embodiment, the addition time of etching waste liquor is controlled, makes electric tank cathode area Cu2+Concentration is controlled in 30-70g/L；
Points for attention: unsuitable open high-current when copper ion is lower is easy to generate copper thorn easy to fall off, is unfavorable for collecting and influence
The quality of copper；Electric current should be turned when shutdown down to 500A or so, can just be shut down, to protect anode plate and fiery ox；System is temporary in short-term
When stoppage in transit row, electric current need to be turned down to 500A or so, with reduce solution analysis copper speed and protect tough cathode not to be etched liquid is counter to be lost,
Electrolysis is unable to backlash current after opening, in order to avoid the copper being electrolysed is lost by counter；System is not run for a long time, will be electric by drug row pipe
Etching waste liquor drains into waste liquid storage barrel in solution slot, and cleans electrolytic cell with clear water, reduces corruption of the etching waste liquor to equipment and pole plate
Erosion；When cathodic region copper ion, which is higher than 50g/L, is lower than 70g/L, etching solution liquid feeding pump is closed, extremely with 2400-3000A current electroanalysis
Start feed liquor again after state modulator range；When higher than 70g/L, regenerated liquid or water is added to reduce copper ion；When system, some position goes out
When now abnormal, it should be stopped urgently corresponding " automatic " Kai Guan ﹙ and be such as in an emergency, " emergency stop switch " ﹚ should be pressed immediately.
Electrolytic tank electrolysis maintenance and copper:
Cylinder is opened in electrolysis
Electrolytic cell side's copper, titanium tabula rasa copper bar contact point are scrubbed with 1% dilute sulfuric acid, prevent conductive bad and hair
Heat；It is put into titanium tabula rasa, checks that titanium tabula rasa plate face has non-oxidation (black obfuscation) when being put into, will be polished at oxidation with wire brush wheel
Fall, tighten the screw of titanium tabula rasa and copper bar, and whether vertically downward to check titanium tabula rasa, positive copper bar bending arc need to be twisted when offsetting
Degree；It opens waste liquid and adds Ball valve of pipeline and pumping, after the amount for adding about 1/4-1/3 volume of electrolytic cell, close waste drains pump, addition
Regenerated liquid or water supply liquid level and (open cathode circulation pump during addition medical fluid for cathode chamber medical fluid and be pumped into electrolytic cell, pay attention to yin
Pole room liquid level prevents circulation pump depletion)；Cathode circulation pump is opened, acidity degree copper brightener is added；After opening tail gas absorption equipment,
Be then turned on rectifier, be first electrolysed 1-2H with 1000-1500A, guarantee that bottom copper is combined with cathode plate, analysis be electrolysed buried copper from
Sub- content adjusts electric current further according to copper ion concentration, and whether uniformly (clears up titanium plate when current unevenness with split-core type meter measurement electric current
With square copper contact point)；
It is safeguarded in electrolytic process
Electrolytic process middle-jiao yang, function of the spleen and stomach pole room constantly has regeneration etching solution outflow, pays attention to cathode chamber liquid level at any time, prevents cathode circulation
Pump depletion opens regenerated liquid addition pump and adds liquid level when liquid level is low；Every four hours sampling analysis in cathode circulation cylinder is primary
Content of copper ion, and electric current is adjusted according to copper, content of copper ion is controlled in 30-50g/L in normal electrolytic process, works as copper
When ion is less than 30g/L, waste liquid is added；Per tour will extract one piece of copper sheet, check that copper situation is tied on copper sheet surface, if copper sheet surface at
Powder, current control are excessively high；The long copper thorn in copper sheet surface is serious, increases copper plating additive amount；After electrolysis one day, per tour must use PP rod
Stick knocks out copper thorn on cathode plate, in case copper thorn top wears anode diaphragm or causes anode and cathode short-circuit；Per tour will be in electrolytic process
Analysis and detection data perform record, and every batch of cathode plate is electrolysed 4-7 days, and every copper sheet weighs 10-15KG, can copper；
Electrolyzing copper
It needs to stop addition waste liquid on the day before copper, existing medical fluid copper ion is reduced to 5g/L hereinafter, in order to discharge
It to waste water station processing, prevents etching solution from expanding, when copper content, which is electrolysed, to be reduced, pays attention to adjusting electric current；When cathode chamber copper ion
When lower than 5g/L, cathode circulation pump is closed, electric current is adjusted to 500A or closes rectifier, will be etched in electrolytic cell by drug row pipe
Liquid drains into regenerated liquid bucket or Sewage Disposal (liquid medicine must shut off rectifier when draining into half)；Opening electro bath-lid water will be negative
Pole plate and anode cassette are rinsed once, prevent a large amount of hydrochloric acid smog；Cathode plate is removed, cathode plate two sides copper sheet is removed, is put
It is impregnated one day to washing in copper cylinder；Copper sheet in copper cylinder will be washed to pull out, neatly discharged on snap-gauge, cross and claim after water is drained.
Molten iron absorbs cylinder and opens cylinder and replacement:
Molten iron cylinder, molten iron absorption cylinder is clean；
The operating point newly to burst at the seams need to use the brewed FeCl2 solution of iron: adding water 1/2 in molten iron cylinder, iron and hydrochloric acid, hydrochloric acid control is added
The concentration in 1-2N is made, iron is constantly added to molten iron cylinder, keeps there is iron in molten iron cylinder always, brewed about 3-4 days, in solution
20-50g/L of Fe2+ content；
Will iron inhale in cylinder plus 2/3 water, the solution of molten iron cylinder and iron are absorbed into cylinder circulation, water supplement and salt when liquid level declines
Acid, controlling pH is in 0.3-0.8N concentration；
It opens iron and absorbs cylinder jet pump, be then turned on electrolytic cell, when iron the water is just on the boil cylinder should be electrolysed with low current, then be gradually increased
It is up to standard to notice whether detection tail gas is handled at any time for electric current；
Notice adding iron (to have remained iron in molten iron cylinder) and hydrochloric acid that (controlling pH is in 0.3- in molten iron cyclic process
0.8), when specific gravity reaches 1.5, molten iron need to be replaced.
Molten iron washs fluid exchange: when hot metal ratio weighs to 1.5, molten iron cleaning solution being discharged 80%, then by 7.1 to 7.5
Step is prepared, and notices that molten iron need to be discharged into environmentally friendly pond or dedicated storage tank.
Embodiment 1:
The present embodiment acid copper chloride etching liquid copper reclaiming system include etching solution regenerative system and be located at etching
The exhaust treatment system in liquid regenerative system downstream, further includes molten iron washing liquid treating system, and etching solution regenerative system includes successively
Etching production line, waste liquid storage barrel, electrolytic cell, the regenerated liquid storage barrel of connection, the downstream of regenerated liquid storage barrel and etching produce
Line connection, the anode region of electrolytic cell is connected to solution absorption cylinder, fluidic device, etching production line are sequentially communicated；
Molten iron washing liquid treating system includes sequentially connected molten iron cylinder, molten iron absorption cylinder, molten iron scrubbing tower；
Etching has environment exhaust column on production line, environment exhaust column is connect by pipeline with exhaust treatment system,
Exhaust treatment system includes sequentially connected solution absorption cylinder, molten iron absorption cylinder, molten iron scrubbing tower, lye absorption
Tower, exhaust outlet, exhaust treatment system upstream are connect with anode electrolytic cell area, electric tank cathode area, environment exhaust column respectively, electrolysis
Slot anode region is connect with cylinder is dissolved and absorbed, and (gas in anode electrolytic cell area is sequentially entered by pipeline and dissolves and absorbs cylinder, molten iron is inhaled
Cylinder, molten iron scrubbing tower, lye absorption tower, exhaust outlet are received, exhaust-gas treatment is completed)；Electric tank cathode area is connect with molten iron scrubbing tower
(gas in electric tank cathode area sequentially enters molten iron scrubbing tower, lye absorption tower, exhaust outlet by pipeline, completes at exhaust gas
Reason)；Environment exhaust column is connect with lye absorption tower；
The reclaiming method of the present embodiment acid copper chloride etching liquid copper includes etching solution regeneration, chlorine treatment, molten iron
Cleaning solution processing, exhaust-gas treatment；The etching solution regeneration are as follows: by etching waste liquor, be introduced into electrolytic cell and carry out electricity as electrolyte
Solution, under electrolysis, when electrolyte is electrolysed, generates metallic copper, chlorine, etching waste liquor is generated on anode plate on cathode plate
Middle copper ion is reduced to copper powder simple substance in cathode and reduces copper ion concentration, while in anode strong oxidizing property product chlorine
Under oxidation, ORP is increased, so that etching waste liquid regeneration reaches effective etching solution standard, and then regenerated etching solution is introduced
Onto etching production line, it is recycled.
The every content of copper ion of four hour sampling analyses in electric tank cathode area contains copper ion in normal electrolytic process
Amount control is 2400-3000A, the copper ion of electric tank cathode area electrolyte in 50-70g/L, the Faradaic current of the electrolytic cell
Mass concentration always < the copper ion mass concentration of anode region electrolyte；The inside of electrolytic cell is equipped with electrolyte membrane；
Chlorine treatment are as follows: the oxidizing gas chlorine that anode chamber generates enters solution absorption cylinder, then through fluidic device reuse
To etching production line, circular regeneration is reached with this；Molten iron cleaning solution process flow is successively are as follows: molten iron cylinder-molten iron absorbs cylinder-molten iron
Absorption tower, the molten iron cylinder is interior to contain ferrous chloride, fe, hydrogen chloride；The molten iron absorbs in cylinder for two containing impurity
Iron chloride；It is pure ferrous chloride in the molten iron absorption tower；Exhaust-gas treatment process are as follows: anode electrolytic cell gas-dissolution is inhaled
It receives cylinder-molten iron and absorbs cylinder-molten iron absorption tower-alkali liquid washing tower-discharge；Electric tank cathode gas-molten iron absorbs cylinder-molten iron and absorbs
Tower-alkali liquid washing tower-discharge；Environment exhaust column-alkali liquid washing tower-discharge.
Embodiment 2:
The present embodiment acid copper chloride etching liquid copper reclaiming system include etching solution regenerative system and be located at etching
The exhaust treatment system in liquid regenerative system downstream, further includes molten iron washing liquid treating system, and etching solution regenerative system includes successively
Etching production line, waste liquid storage barrel, electrolytic cell, the regenerated liquid storage barrel of connection, the downstream of regenerated liquid storage barrel and etching produce
Line connection, the anode region of electrolytic cell is connected to solution absorption cylinder, fluidic device, etching production line are sequentially communicated；
Molten iron washing liquid treating system includes sequentially connected molten iron cylinder, molten iron absorption cylinder, molten iron scrubbing tower；
Etching has environment exhaust column on production line, environment exhaust column is connect by pipeline with exhaust treatment system,
Exhaust treatment system includes sequentially connected solution absorption cylinder, molten iron absorption cylinder, molten iron scrubbing tower, lye absorption
Tower, exhaust outlet, exhaust treatment system upstream are connect with anode electrolytic cell area, electric tank cathode area, environment exhaust column respectively, electrolysis
Slot anode region is connect with cylinder is dissolved and absorbed, and (gas in anode electrolytic cell area is sequentially entered by pipeline and dissolves and absorbs cylinder, molten iron is inhaled
Cylinder, molten iron scrubbing tower, lye absorption tower, exhaust outlet are received, exhaust-gas treatment is completed)；Electric tank cathode area is connect with molten iron scrubbing tower
(gas in electric tank cathode area sequentially enters molten iron scrubbing tower, lye absorption tower, exhaust outlet by pipeline, completes at exhaust gas
Reason)；Environment exhaust column is connect with lye absorption tower；
The reclaiming method of the present embodiment acid copper chloride etching liquid copper includes etching solution regeneration, chlorine treatment, molten iron
Cleaning solution processing, exhaust-gas treatment；The etching solution regeneration are as follows: by etching waste liquor, be introduced into electrolytic cell and carry out electricity as electrolyte
Solution, under electrolysis, when electrolyte is electrolysed, generates metallic copper, chlorine, etching waste liquor is generated on anode plate on cathode plate
Middle copper ion is reduced to copper powder simple substance in cathode and reduces copper ion concentration, while in anode strong oxidizing property product chlorine
Under oxidation, ORP is increased, so that etching waste liquid regeneration reaches effective etching solution standard, and then regenerated etching solution is introduced
Onto etching production line, it is recycled.
The every content of copper ion of four hour sampling analyses in electric tank cathode area contains copper ion in normal electrolytic process
In 30-50g/L, the Faradaic current of the electrolytic cell is for amount control
1800-2400A, the copper ion mass concentration of electric tank cathode area electrolyte always < copper of anode region electrolyte from
Protonatomic mass concentration；The inside of electrolytic cell is equipped with electrolyte membrane；
Chlorine treatment are as follows: the oxidizing gas chlorine that anode chamber generates enters solution absorption cylinder, then through fluidic device reuse
To etching production line, circular regeneration is reached with this；Molten iron cleaning solution process flow is successively are as follows: molten iron cylinder-molten iron absorbs cylinder-molten iron
Absorption tower, the molten iron cylinder is interior to contain ferrous chloride, fe, hydrogen chloride；The molten iron absorbs in cylinder for two containing impurity
Iron chloride；It is pure ferrous chloride in the molten iron absorption tower；Exhaust-gas treatment process are as follows: anode electrolytic cell gas-dissolution is inhaled
It receives cylinder-molten iron and absorbs cylinder-molten iron absorption tower-alkali liquid washing tower-discharge；Electric tank cathode gas-molten iron absorbs cylinder-molten iron and absorbs
Tower-alkali liquid washing tower-discharge；Environment exhaust column-alkali liquid washing tower-discharge.
Embodiment 3:
The present embodiment acid copper chloride etching liquid copper reclaiming system include etching solution regenerative system and be located at etching
The exhaust treatment system in liquid regenerative system downstream, further includes molten iron washing liquid treating system, and etching solution regenerative system includes successively
Etching production line, waste liquid storage barrel, electrolytic cell, the regenerated liquid storage barrel of connection, the downstream of regenerated liquid storage barrel and etching produce
Line connection, the anode region of electrolytic cell is connected to solution absorption cylinder, fluidic device, etching production line are sequentially communicated；
Molten iron washing liquid treating system includes sequentially connected molten iron cylinder, molten iron absorption cylinder, molten iron scrubbing tower；
Etching has environment exhaust column on production line, environment exhaust column is connect by pipeline with exhaust treatment system,
Exhaust treatment system includes sequentially connected solution absorption cylinder, molten iron absorption cylinder, molten iron scrubbing tower, lye absorption
Tower, exhaust outlet, exhaust treatment system upstream are connect with anode electrolytic cell area, electric tank cathode area, environment exhaust column respectively, electrolysis
Slot anode region is connect with cylinder is dissolved and absorbed, and (gas in anode electrolytic cell area is sequentially entered by pipeline and dissolves and absorbs cylinder, molten iron is inhaled
Cylinder, molten iron scrubbing tower, lye absorption tower, exhaust outlet are received, exhaust-gas treatment is completed)；Electric tank cathode area is connect with molten iron scrubbing tower
(gas in electric tank cathode area sequentially enters molten iron scrubbing tower, lye absorption tower, exhaust outlet by pipeline, completes at exhaust gas
Reason)；Environment exhaust column is connect with lye absorption tower；
The reclaiming method of the present embodiment acid copper chloride etching liquid copper includes etching solution regeneration, chlorine treatment, molten iron
Cleaning solution processing, exhaust-gas treatment；The etching solution regeneration are as follows: by etching waste liquor, be introduced into electrolytic cell and carry out electricity as electrolyte
Solution, under electrolysis, when electrolyte is electrolysed, generates metallic copper, chlorine, etching waste liquor is generated on anode plate on cathode plate
Middle copper ion is reduced to copper powder simple substance in cathode and reduces copper ion concentration, while in anode strong oxidizing property product chlorine
Under oxidation, ORP is increased, so that etching waste liquid regeneration reaches effective etching solution standard, and then regenerated etching solution is introduced
Onto etching production line, it is recycled.
The every content of copper ion of four hour sampling analyses in electric tank cathode area contains copper ion in normal electrolytic process
Amount control is 1000-1800A, the copper ion of electric tank cathode area electrolyte in 15-30g/L, the Faradaic current of the electrolytic cell
Mass concentration always < the copper ion mass concentration of anode region electrolyte；The inside of electrolytic cell is equipped with electrolyte membrane；
Chlorine treatment are as follows: the oxidizing gas chlorine that anode chamber generates enters solution absorption cylinder, then through fluidic device reuse
To etching production line, circular regeneration is reached with this；Molten iron cleaning solution process flow is successively are as follows: molten iron cylinder-molten iron absorbs cylinder-molten iron
Absorption tower, the molten iron cylinder is interior to contain ferrous chloride, fe, hydrogen chloride；The molten iron absorbs in cylinder for two containing impurity
Iron chloride；It is pure ferrous chloride in the molten iron absorption tower；Exhaust-gas treatment process are as follows: anode electrolytic cell gas-dissolution is inhaled
It receives cylinder-molten iron and absorbs cylinder-molten iron absorption tower-alkali liquid washing tower-discharge；Electric tank cathode gas-molten iron absorbs cylinder-molten iron and absorbs
Tower-alkali liquid washing tower-discharge；Environment exhaust column-alkali liquid washing tower-discharge.
It should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although ginseng
According to previous embodiment, invention is explained in detail, those skilled in the art should understand that: it still can be with
It modifies the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；And
These are modified or replaceed, the spirit and model of technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution
It encloses.
Claims (8)
1. a kind of acid copper chloride etching liquid copper reclaiming system, which is characterized in that the acid copper chloride etching liquid copper returns
Receiving regenerative system includes etching solution regenerative system and the exhaust treatment system positioned at etching solution regenerative system downstream, further includes iron
Water washing liquor processing system, the etching solution regenerative system include sequentially connected etching production line, waste liquid storage barrel, electrolysis
Slot, regenerated liquid storage barrel, the downstream of the regenerated liquid storage barrel are connect with etching production line, the anode region of the electrolytic cell with it is molten
Solution absorption cylinder connection, fluidic device, etching production line are sequentially communicated；
The molten iron washing liquid treating system includes sequentially connected molten iron cylinder, molten iron absorption cylinder, molten iron scrubbing tower；
There is environment exhaust column, the environment exhaust column is connected by pipeline and the exhaust treatment system on the etching production line
It connects,
The exhaust treatment system includes sequentially connected solution absorption cylinder, molten iron absorption cylinder, molten iron scrubbing tower, lye absorption
Tower, exhaust outlet, the upstream of the exhaust treatment system connect with anode electrolytic cell area, electric tank cathode area, environment exhaust column respectively
It connecing, the anode electrolytic cell area is connect with the solution absorption cylinder, and the electric tank cathode area is connect with the molten iron scrubbing tower,
The environment exhaust column is connect with the lye absorption tower.
2. using the reclaiming method of acid copper chloride etching liquid copper reclaiming system described in claim 1, feature exists
In the reclaiming method includes etching solution regeneration, chlorine treatment, the processing of molten iron cleaning solution, exhaust-gas treatment；The etching solution
Regeneration are as follows: by etching waste liquor, be introduced into electrolytic cell and be electrolysed as electrolyte, under electrolysis, electrolyte is electrolysed
When, metallic copper is generated on cathode plate, chlorine is generated on anode plate, copper ion is reduced to copper powder simple substance in cathode in etching waste liquor
And reducing copper ion concentration, while under the oxidation of anode strong oxidizing property product chlorine, ORP is increased, so that etching is useless
Liquid regeneration reaches effective etching solution standard, and then regenerated etching solution is introduced on etching production line, is recycled.
3. reclaiming method according to claim 2, which is characterized in that the electric tank cathode area content of copper ion control
System is 1000-3000A, the copper ion of electric tank cathode area electrolyte in 30-70g/L, the Faradaic current of the electrolytic cell
Mass concentration always < the copper ion mass concentration of anode region electrolyte.
4. reclaiming method according to claim 3, which is characterized in that electric tank cathode area every four hours take
Sample analyzes a content of copper ion, controls content of copper ion in 30-50g/L, the electricity of the electrolytic cell in normal electrolytic process
Solution electric current is that 1800-2400A adds etching waste liquor as copper ion < 30g/L.
5. reclaiming method according to claim 2, it is characterised in that: the inside of the electrolytic cell be equipped with electrolysis every
Film.
6. reclaiming method according to claim 2, which is characterized in that the chlorine treatment are as follows: what anode chamber generated
Oxidizing gas chlorine enters solution absorption cylinder, then through fluidic device reuse to production line is etched, reaches circular regeneration with this.
7. reclaiming method according to claim 2, which is characterized in that the molten iron cleaning solution process flow is successively
Are as follows: molten iron cylinder-molten iron absorbs cylinder-molten iron absorption tower, contains ferrous chloride, fe, hydrogen chloride in the molten iron cylinder；The iron
It is the ferrous chloride containing impurity in cylinder that water, which absorbs,；It is pure ferrous chloride in the molten iron absorption tower.
8. reclaiming method according to claim 2, which is characterized in that the exhaust-gas treatment process are as follows: electrolytic cell sun
Pole gas-solution absorption cylinder-molten iron absorbs cylinder-molten iron absorption tower-alkali liquid washing tower-discharge；Electric tank cathode gas-molten iron is inhaled
Receive cylinder-molten iron absorption tower-alkali liquid washing tower-discharge；Environment exhaust column-alkali liquid washing tower-discharge.
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| CN113088722A (en) * | 2021-03-17 | 2021-07-09 | 磨名言 | Method for electrolytically recovering copper from copper sulfide ore |
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