CN108914129A - A kind of alkaline etching liquid indirect regeneration and its method - Google Patents
A kind of alkaline etching liquid indirect regeneration and its method Download PDFInfo
- Publication number
- CN108914129A CN108914129A CN201810972310.8A CN201810972310A CN108914129A CN 108914129 A CN108914129 A CN 108914129A CN 201810972310 A CN201810972310 A CN 201810972310A CN 108914129 A CN108914129 A CN 108914129A
- Authority
- CN
- China
- Prior art keywords
- copper
- cylinder
- liquid
- etching
- extractant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Abstract
The invention discloses a kind of alkaline etching liquid circulation regeneration methods, include the following steps：(1) etching waste liquor generates；(2) it extracts：Etching waste liquor is mixed with extractant, and copper ion is separated from etching waste liquor, forms supported copper oil phase, and regenerated liquid is stored in regenerated liquid bucket；(3) composition regulation：Cu is carried out to regenerated liquid2+、NH4 +、Cl‑It is chemically examined with pH value, the amount of the ammonia and ammonium chloride that are added needed for being determined according to result of laboratory test, then is back to etching production line；(4) it washes together：Supported copper oil is mutually washed together, isolates water phase and supported copper oil phase；(5) it is stripped：Supported copper oil is mutually transferred in strip liquor, the loaded extractant and H in supported copper oil phase2SO4Solution haptoreaction, copper ion are separated from extractant, generate CuSO4Solution enters in water phase；(6) electrodeposition：By CuSO4Solution is added in electrolyte, by electrolyte to CuSO4Solution is electrolysed, and cathode deposits blister copper, and anode generates oxygen, and by CuSO4Liquid flows back into back extraction cylinder after electrodeposition.
Description
Technical field
The present invention relates to etching technique field more particularly to a kind of alkaline etching liquid indirect regeneration and its methods.
Background technique
In the past 20 years, Chinese PCB industry is always maintained at the annual growth rate of 10-00%, and there are many PCB of scale at present
More than 3500 families of enterprise, monthly output reach 1.2 hundred million square metres.Etching is the biggish process of liquid medicine amount to be consumed in PCB production, and generate
Waste liquid and the maximum process of waste water, it is however generally that, the dual platen of every one square metre of normal thickness (18 μm) of production consumes etching solution
About 2-3 liter, and generate spent etching solution 2-3 liter.China's PCB industry monthly consumes 60,000 ton/month of refined copper or more, the copper etching of output
Total amount of copper causes seriously the society's especially water resource of PCB factory surrounding area and soil in 50,000 tons/month or more in waste liquid
Pollution.
Copper is that one kind is present in soil and the intracorporal heavy metal element of people and animals, in soil content generally in 0.2ppm or so,
With people and animals' intracorporal enzyme precipitating/complex reaction can occur for excessive copper, and poisoning by enzyme occurs and loses physiological function.In nature
Copper is transferred in people and animals' body by water body, plant etc., is made one to raise intracorporal Equilibrium of Trace Elements and be destroyed, heavy metal is caused to exist
Intracorporal abnormal accumulation generates the results such as denaturation, carcinogenicity of causing a disease.
The monitor control index of copper is 0.5ppm, drinking water standard 0.03ppm, America and Europe in the industrial wastewater discharge standard of China
Relevant criterion it is then more severe.Since cupric is tens supreme hundred grams per liters in copper scrap etching solution, and have containing a large amount of others
Machine and inorganic pathogenic denaturing compounds, therefore, PCB copper scrap etching solution (useless copper etching liquor) is positioned as dangerous liquid by State Environmental Protection Administration
Body waste (HazardousWaste) is, it is specified that treatment in situ, forbids transboundary movement.
The clearer production technology for exploring copper etching process eliminates copper waste etching solution in process of production, and realization follows online
Ring regeneration, thoroughly to prevent pollution sources and its contamination, realizes watershed management truly, is both environmental protection department
The first choice and PCB industry for forcing law enforcement reduce production cost, walk the inevitable choice of Sustainable Development Road.
Therefore, occurred the relevant technologies of spent etching solution recycling on the market, however, current technology,
Still there is the phenomenon that discharging of waste liquid in each process, can not accomplish the complete recycling and reusing of whole system, the effect of zero-emission.
Summary of the invention
In view of the above deficiencies, the purpose of the present invention is to provide a kind of alkaline etching liquid indirect regeneration and its method,
The etching waste liquor of failure is set effectively to be recycled and be recycled, devil liquor recovery utilization rate 100%, copper recovery 100%, technique
Process realizes the closed cycle of each material, enables not generating new pollution sources while etching solution reuse, reduces and be produced into
This, achievees the purpose that energy-saving.
The technical scheme adopted by the invention to achieve the purpose is as follows：
A kind of alkaline etching liquid circulation regeneration method, which is characterized in that include the following steps：
(1) etching waste liquor generates：It is stored in waste liquid barrel by the etching waste liquor that etching production line generates, the erosion in waste liquid barrel
Waste liquid is carved to be added in extraction cylinder；
(2) it extracts：The extractant hybrid reaction in etching waste liquor and extraction cylinder being added in extraction cylinder, extractant concentration
For 40-60%, it is comparably O/A=2, most copper ion is separated from etching waste liquor, and generation load extraction is reacted with extractant
Agent is taken, then clarification layering, water-oil separating forms supported copper oil phase, and is containing the regenerated liquid that copper concentration is reduced to 25-35g/L
Water phase is stored in regenerated liquid bucket；
(3) composition regulation：Cu is carried out to the regenerated liquid in regenerated liquid bucket2+、NH4 +, Cl- and pH value chemically examine, tied according to chemical examination
The amount of ammonia and ammonium chloride that fruit is added needed for determining, makes the etching regenerated liquid to be formed meet etch requirements, then is back to etching life
It is used in producing line, simultaneously executes step (4)；
(4) it washes together：Supported copper oil is mutually carried out washing together, is further separated out water phase and supported copper oil phase；
(5) it is stripped：The supported copper oil that step (4) is isolated mutually is transferred in back extraction cylinder, and is added into back extraction cylinder
Enter the H that concentration is 2.5-3.5mol/L2SO4Loaded extractant and H of the solution as strip liquor, in supported copper oil phase2SO4Solution
Reaction is come into full contact with, separates copper ion from extractant, then clarification layering, water-oil separating generates CuSO4Solution into
Enter in water phase, and isolate the extractant after copper ion and restore extraction function, in the extraction process in step (2)；
(6) electrodeposition：Copper containing 12-45g/L is added into Winning cell, 180-220g/L sulfuric acid, is less than 0-1g/L iron and 0-
The electrolyte of 10g/L oil, by the CuSO in step (5) water phase4Solution is added in electrolyte, is 100- by Winning cell medium spacing
The CuSO that the anode and anode of 120mm obtains back extraction4Solution is electrolysed, electrolyte flow rate 0.1-0.2m3/m2.h, electric
Current density is 100-240A/m2, then blister copper is deposited in cathode, generates oxygen in anode, while regenerating H2SO4Solution, and will
Containing H2SO4The remaining CuSO of solution4Liquid flows back into back extraction cylinder after electrodeposition.
As a further improvement of the present invention, in the step (6), the oxygen generated in anode is passed through spray column
In, and the alkaline foam containing sodium hydroxide solution is sprayed in spray column, and keep the pH value of solution in spray column in 8-13 model
In enclosing, then the foam of oxygen carries sulfuric acid mist and sodium hydroxide solution neutralizes, then pure oxygen is given off from spray column.
As a further improvement of the present invention, the step (5) is further comprising the steps of：It is isolated using step (4)
Water phase carries out two washings to the extractant after copper ion is isolated in back extraction cylinder, isolate pure extractant and point
From the water phase after extractant, and by the absolute extract agent of acquisition, in the extraction process in step (2).
As a further improvement of the present invention, the step (5) is further comprising the steps of：To what is isolated after two washings
Water phase carries out RO film process and pH value adjustment, then is back in one of washing step of step (4).
As a further improvement of the present invention, further comprising the steps of：
(7) copper is refined：It is the copper-bath of 0.4-0.6mol/L as electroplate liquid that concentration is added into electroplating bath, and is added
Entering concentration is the triethanolamine of 0.5-1.5g/L as additive, and the cathode that blister copper is deposited in step (6) is put into plating
It is used as anode in slot, and a clean copper plates are put into electroplating bath as cathode, is 450-550A/m in current density2The case where
Lower plating, the blister copper on anode dissolve and pass through cathode deposition, smooth refined copper is obtained on cathode.
Implement the alkaline etching liquid indirect regeneration of the above method, which is characterized in that including being connected to etching production line
A waste liquid barrel, the extraction cylinder for being connected to waste liquid barrel, the oil expeller for being connected to extraction cylinder, be connected to a regeneration of oil expeller
Liquid bucket, the water washing cylinder together for being connected to extraction cylinder, connects the composition regulation cylinder for being connected to regenerated liquid bucket and etching production line
It is connected to a back extraction cylinder of one of water washing cylinder, a Winning cell of back extraction cylinder is connected to and is connected to an electroplating bath of Winning cell,
To form closed cycle, wherein be respectively arranged at a propeller in the extraction cylinder and back extraction cylinder.
It as a further improvement of the present invention, further include being connected to one of water washing cylinder, back extraction cylinder and extraction cylinder
Two water washing cylinders.
It as a further improvement of the present invention, further include being connected to two water washing cylinders and together the RO film between water washing cylinder
Treatment trough and it is connected to RO film process slot and together the PH regulating tank between water washing cylinder.
It as a further improvement of the present invention, further include the spray column for being connected to Winning cell, which includes a tower
It body, the demister for being set to the intracorporal spraying mechanism of tower, being set in tower body and being located above spraying mechanism and is set to
An extraction sector outside tower body, wherein be provided with an admission line on the tower body and on the downside of spraying mechanism, and at this
An outlet pipe is provided in tower body, which is located in tower body and extends to above demister；The extraction sector
Including being connected to a pumping chamber of outlet pipe other end end and being connected to a pumping blower of pumping chamber, in the pumping chamber
It is upper that there is an exhaust outlet, and an oxygen filter screen is provided in the pumping chamber；In the tower body side, bottom offers a blowdown
Mouthful.
As a further improvement of the present invention, the spraying mechanism include be set to the intracorporal several spray assemblies of tower and
It is set to outside tower body and is connected to a purification return-flow structure of sewage draining exit, wherein the spray assemblies include being horizontally placed in tower body
And be located at the spray tube below demister and several solid-cone (type) nozzles for being set to below spray tube, the spray tube one end by
An import end flanges on tower body outer wall protrude into tower body, and the spray tube other end is inserted and fixed in one on tower body outer wall
It supports in end flanges；The purification return-flow structure includes the liquid storage cylinder being connected with sewage draining exit, is set to liquid storage cylinder inlet end
A filter, be connected to spray tube a return pipe, be connected to a circulating pump of return pipe and be set in liquid storage cylinder and electricity
It is connected to a floating ball type liquid-level meter of circulating pump.
Beneficial effects of the present invention are：
(1) solvent extraction-film process-electrodeposition reduction method is used, the recovering copper from the etching waste liquor of failure leads to simultaneously
Overfill adding medicine makes the etching waste liquor of failure effectively be recycled and be recycled, devil liquor recovery utilization rate 100%, copper recycling
Rate 100% realizes the closed cycle of etching solution, the closed cycle of electrolyte, the closed cycle of extractant and oily phase wash water
The closed cycle of each material is realized in closed cycle by process flow, enables not generating new pollution while etching solution reuse
Source；Entire technique has many advantages, such as that operation can continuous and automatic, equipment novelty, at low cost；
(2) copper is recycled using lossless separating technology, does not destroy the original composition of etching solution, keep etching solution complete
Reuse makes to etch clean manufacturing line of the production line as waste zero-emission；
(3) extraction process is compensated using multistage staggered floor, occupation area of equipment is small, high-efficient；
(4) efficient extractant is selected, extraction process balancing speed is fast, good separating effect, treating capacity are big, at low cost, operation
Easy continuous and automatic and safe ready；
(5) alkaline etching solution recycling system is recycled by fully closed road, the container of each process is subjected to closed cycle company
It connects, is provided safeguard for the closed cycle of each material of entire process, enable not generating new dirt while etching solution reuse
Dye source, while to needing solvent recovery to be used to recycle, primary be added is recycled for multiple times, and reduces production cost, reaches
Energy-saving purpose.
Above-mentioned is the general introduction of inventive technique scheme, below in conjunction with attached drawing and specific embodiment, is done further to the present invention
Explanation.
Detailed description of the invention
Fig. 1 is flow chart of the invention；
Fig. 2 is overall structure block diagram of the invention；
Fig. 3 is the structural schematic diagram of spray column of the present invention.
Specific embodiment
Further to illustrate the present invention to reach the technical means and efficacy that predetermined purpose is taken, below in conjunction with attached drawing
And preferred embodiment, detailed description of specific embodiments of the present invention.
Embodiment one：
Fig. 1 is please referred to, the present embodiment provides a kind of alkaline etching liquid circulation regeneration methods, include the following steps：
(1) etching waste liquor generates：It is stored in waste liquid barrel by the etching waste liquor that etching production line generates, the erosion in waste liquid barrel
Waste liquid is carved to be added in extraction cylinder；
(2) it extracts：The extractant hybrid reaction in etching waste liquor and extraction cylinder being added in extraction cylinder, extractant concentration
It is 40%, is comparably O/A=2, most copper ion is separated from etching waste liquor, and reacts generation load extraction with extractant
Agent, then clarification layering, water-oil separating forms supported copper oil phase, and deposits containing the regenerated liquid that copper concentration is reduced to 25g/L for water phase
In regenerated liquid bucket；
(3) composition regulation：Cu is carried out to the regenerated liquid in regenerated liquid bucket2+、NH4 +, Cl- and pH value chemically examine, tied according to chemical examination
The amount of ammonia and ammonium chloride that fruit is added needed for determining, makes the etching regenerated liquid to be formed meet etch requirements, then is back to etching life
It is used in producing line, simultaneously executes step (4)；
(4) it washes together：Supported copper oil is mutually carried out washing together, is further separated out water phase and supported copper oil phase；
(5) it is stripped：The supported copper oil that step (4) is isolated mutually is transferred in back extraction cylinder, and is added into back extraction cylinder
Enter the H that concentration is 2.5mol/L2SO4Loaded extractant and H of the solution as strip liquor, in supported copper oil phase2SO4Solution is abundant
Haptoreaction separates copper ion from extractant, then clarification layering, and water-oil separating generates CuSO4Solution enters water
Xiang Zhong, and isolate the extractant after copper ion and restore extraction function, in the extraction process in step (2)；
(6) electrodeposition：Copper containing 12g/L, 180g/L sulfuric acid are added into Winning cell, less than the electrolysis of 0.5g/L iron and 5g/L oil
Liquid, by the CuSO in step (5) water phase4Solution is added in electrolyte, the anode and anode for being 100mm by Winning cell medium spacing
The CuSO that back extraction is obtained4Solution is electrolysed, electrolyte flow rate 0.1m3/m2.h, current density 100A/m2, then exist
Cathode deposits blister copper, generates oxygen in anode, while regenerating H2SO4Solution, and H will be contained2SO4The remaining CuSO of solution4Electricity
Liquid flows back into back extraction cylinder after product.
Embodiment two：
The present embodiment provides a kind of alkaline etching liquid circulation regeneration methods, include the following steps：
(1) etching waste liquor generates：It is stored in waste liquid barrel by the etching waste liquor that etching production line generates, the erosion in waste liquid barrel
Waste liquid is carved to be added in extraction cylinder；
(2) it extracts：The extractant hybrid reaction in etching waste liquor and extraction cylinder being added in extraction cylinder, extractant concentration
It is 60%, is comparably O/A=2, most copper ion is separated from etching waste liquor, and reacts generation load extraction with extractant
Agent, then clarification layering, water-oil separating forms supported copper oil phase, and deposits containing the regenerated liquid that copper concentration is reduced to 35g/L for water phase
In regenerated liquid bucket；
(3) composition regulation：Cu is carried out to the regenerated liquid in regenerated liquid bucket2+、NH4 +、Cl-It chemically examines with pH value, is tied according to chemical examination
The amount of ammonia and ammonium chloride that fruit is added needed for determining, makes the etching regenerated liquid to be formed meet etch requirements, then is back to etching life
It is used in producing line, simultaneously executes step (4)；
(4) it washes together：Supported copper oil is mutually carried out washing together, is further separated out water phase and supported copper oil phase；
(5) it is stripped：The supported copper oil that step (4) is isolated mutually is transferred in back extraction cylinder, and is added into back extraction cylinder
Enter the H that concentration is 3.5mol/L2SO4Loaded extractant and H of the solution as strip liquor, in supported copper oil phase2SO4Solution is abundant
Haptoreaction separates copper ion from extractant, then clarification layering, and water-oil separating generates CuSO4Solution enters water
Xiang Zhong, and isolate the extractant after copper ion and restore extraction function, in the extraction process in step (2)；
(6) electrodeposition：Copper containing 45g/L, 220g/L sulfuric acid are added into Winning cell, less than the electrolysis of 1g/L iron and 10g/L oil
Liquid, by the CuSO in step (5) water phase4Solution is added in electrolyte, the anode and anode for being 120mm by Winning cell medium spacing
The CuSO that back extraction is obtained4Solution is electrolysed, electrolyte flow rate 0.2m3/m2.h, current density 240A/m2, then exist
Cathode deposits blister copper, generates oxygen in anode, while regenerating H2SO4Solution, and H will be contained2SO4The remaining CuSO of solution4Electricity
Liquid flows back into back extraction cylinder after product.
Embodiment three：
The present embodiment provides a kind of alkaline etching liquid circulation regeneration methods, include the following steps：
(1) etching waste liquor generates：It is stored in waste liquid barrel by the etching waste liquor that etching production line generates, the erosion in waste liquid barrel
Waste liquid is carved to be added in extraction cylinder；
(2) it extracts：The extractant hybrid reaction in etching waste liquor and extraction cylinder being added in extraction cylinder, extractant concentration
It is 50%, is comparably O/A=2, most copper ion is separated from etching waste liquor, and reacts generation load extraction with extractant
Agent, then clarification layering, water-oil separating forms supported copper oil phase, and deposits containing the regenerated liquid that copper concentration is reduced to 30g/L for water phase
In regenerated liquid bucket；
(3) composition regulation：Cu is carried out to the regenerated liquid in regenerated liquid bucket2+、NH4 +、Cl-It chemically examines with pH value, is tied according to chemical examination
The amount of ammonia and ammonium chloride that fruit is added needed for determining, makes the etching regenerated liquid to be formed meet etch requirements, then is back to etching life
It is used in producing line, simultaneously executes step (4)；
(4) it washes together：Supported copper oil is mutually carried out washing together, is further separated out water phase and supported copper oil phase；
(5) it is stripped：The supported copper oil that step (4) is isolated mutually is transferred in back extraction cylinder, and is added into back extraction cylinder
Enter the H that concentration is 3.0mol/L2SO4Loaded extractant and H of the solution as strip liquor, in supported copper oil phase2SO4Solution is abundant
Haptoreaction separates copper ion from extractant, then clarification layering, and water-oil separating generates CuSO4Solution enters water
Xiang Zhong, and isolate the extractant after copper ion and restore extraction function, in the extraction process in step (2)；
(6) electrodeposition：Copper containing 29g/L, 200g/L sulfuric acid are added into Winning cell, less than the electrolysis of 0.8g/L iron and 8g/L oil
Liquid, by the CuSO in step (5) water phase4Solution is added in electrolyte, the anode and anode for being 110mm by Winning cell medium spacing
The CuSO that back extraction is obtained4Solution is electrolysed, electrolyte flow rate 0.15m3/m2.h, current density 170A/m2, then exist
Cathode deposits blister copper, generates oxygen in anode, while regenerating H2SO4Solution, and H will be contained2SO4The remaining CuSO of solution4Electricity
Liquid flows back into back extraction cylinder after product.
In above-described embodiment one and embodiment three, each process principle is as follows：
It is different from the distribution ratio in etching waste liquor in extractant using copper ion in above-mentioned steps (2), pass through extractant
It is mixed with etching waste liquor, the copper in etching waste liquor is made to be transferred to extractant, to achieve the purpose that separate copper.The extraction that the present embodiment uses
Taking agent is CP-150 extractant.
Extracting key reaction is：2RH+Cu2+=CuR2+2H+(RH indicates extractant)
The dissociation of copper complex ion is reacted：CuLm=Cu2++ Ml (L NH3Or Cl-)
In above-mentioned steps (3), etching waste liquor is after solvent selection extracts copper, subsequently into allocation process.Although extraction
Taking process is selectivity extraction copper, remaining ingredient is unchanged in spent etching solution, but the etching waste liquor ingredient after etching process removes
Outside the variation of copper, there are also more or less ammonia, chlorine and etching salt, the reduction for etching additive, and therefore, raffinate etching waste liquor also needs
Ingredient is deployed, meets the requirement etched on production line to restore its etch functions.
In order to reach the accurate control of etching component, it is both needed to the Cu to regenerated liquid every time2+、NH4+、Cl-Plasma and PH
Value is chemically examined, and the amount of the ammonia, ammonium chloride that add needed for being determined according to result of laboratory test reaches the etching performance of etching solution most
It is excellent.
In above-mentioned steps (5), with containing H2SO4Copper sulphate electrodeposition after liquid and by washing loaded extractant sufficiently connect
Touching, is transferred to copper in water phase from extractant (oily phase), while the extractant after unloading restores extraction function, and can be used for step
(2) in the extraction process in.
It is stripped key reaction：CuR2+2H2SO4=CuSO4+ 2RH (RH indicates extractant)
In above-mentioned steps (6), make anode with titanium active coating plate respectively, copper sheet makees anode, to the resulting sulphur of back extraction
Sour copper solution is electrolysed, and cathode blister copper is obtained, and realizes the recycling of copper metal.
Electrode reaction is as follows：
Anode reaction：4OH-=O2+2H2O+4e
Cathode reaction：Cu2++ 2e=Cu
Example IV：
The present embodiment and the main distinction of embodiment one to embodiment three are：
In the step (6), the oxygen generated in anode is passed through in spray column, and spray contains hydrogen-oxygen in spray column
The alkaline foam for changing sodium solution, and keeps the pH value of solution in spray column within the scope of 8-13, then the sulfuric acid mist that oxygen carries with
The foam of sodium hydroxide solution neutralizes, then pure oxygen is given off from spray column.
Anode generates oxygen when CuSO4 solution electrodeposition, may carry part of sulfuric acid mist, it can be removed by alkaline foam
Acid mist final vacuum.The present embodiment passes to oxygen in spray column, and the foam containing sodium hydroxide in sulfuric acid mist and spray column neutralizes,
Comply with standard the gas of discharge.Water management pH value in spray column is within 8~13, when sulfuric acid mist and sodium hydroxide neutralize
When, the pH value of shower water constantly reduces, and when pH value drops to 8, adjusts pH value with sodium hydroxide and is constantly recycled to 13.
Embodiment five：
The present embodiment and the main distinction of embodiment one to example IV are：
The step (5) is further comprising the steps of：The water phase isolated using step (4) is separated in back extraction cylinder
The extractant after copper ion carries out two washings out, isolates pure extractant and has separated the water phase after extractant, and will
The absolute extract agent of acquisition, in the extraction process in step (2).
It is stripped the extractant obtained after process by step (5), is returning it into step (2) extraction process before use, adopting
The aqueous solution isolated carries out two washings to extractant after being washed together with step (4), obtains the extractant of cleaning, and by its
Return step (2) repeats to reuse, and to ensure that extractant is restored to optimum performance, reaches extractant and is constantly recycled back to aqueous solution
Receive the purpose recycled.
Embodiment six：
The present embodiment and the main distinction of embodiment one to embodiment five are：
The step (5) is further comprising the steps of：RO film process and pH value are carried out to the water phase isolated after two washings
It adjusts, then is back in one of washing step of step (4).
By washing together and the water phase (aqueous solution) after two washings, performance can be influenced, and the present embodiment passes through
RO film process and pH value adjustment are carried out to the water phase (aqueous solution) isolated after two washings, enabling that treated, aqueous solution restores
It to initial performance, returns to washing together and uses, to achieve the purpose that the continuous circulation and stress of aqueous solution recycles.
Embodiment seven：
The present embodiment and the main distinction of embodiment one to embodiment six are：
It is further comprising the steps of：
(7) copper is refined：It is the copper-bath of 0.4-0.6mol/L as electroplate liquid that concentration is added into electroplating bath, and is added
Entering concentration is the triethanolamine of 0.5-1.5g/L as additive, and the cathode that blister copper is deposited in step (6) is put into plating
It is used as anode in slot, and a clean copper plates are put into electroplating bath as cathode, is 450-550A/m in current density2The case where
Lower plating, the blister copper on anode dissolve and pass through cathode deposition, smooth refined copper is obtained on cathode.
In electrodeposition process, the copper deposited on cathode is blister copper, contains a certain amount of impurity.The present embodiment is with electrification
Blister copper preparation is in refined copper by mode.It is specifically limited by the progress to each parameters such as current density, each solution composition concentration, with
Obtain bright smooth pure layers of copper.
Referring to figure 2., the embodiment of the invention also provides a kind of alkaline etching liquid circular regeneration systems for implementing the above method
System, including being connected to a waste liquid barrel of etching production line, being connected to the one of the waste liquid barrel oil removing for extracting cylinder, being connected to extraction cylinder
Device, the regenerated liquid bucket for being connected to oil expeller, be connected to regenerated liquid bucket with etch production line a composition regulation cylinder, connect
In extraction cylinder one of water washing cylinder, be connected to one of water washing cylinder one back extraction cylinder, be connected to back extraction cylinder a Winning cell and
It is connected to an electroplating bath of Winning cell, to form closed cycle, wherein be respectively arranged at one in the extraction cylinder and back extraction cylinder
Propeller.
It is stored in waste liquid barrel by the etching waste liquor that etching production line generates, by the extractant in extraction cylinder to etching waste liquor
Extraction process is carried out, it is different from the distribution ratio in etching waste liquor in extractant using copper ion, pass through extractant and etching waste liquor
Mixing, makes the copper in etching waste liquor be transferred to extractant, to achieve the purpose that separate copper.
Etching waste liquor is introduced into oil expeller and carries out oil removing, subsequently into composition regulation cylinder after solvent selection extracts copper
Component allotment is carried out, so that regenerated liquid restores its etch functions and meets the requirement etched on production line, it is final to realize etching liquid-tight
The purpose of road circulation.
Meanwhile the supported copper oil that extraction and separation go out mutually carries out after washing together into one of water washing cylinder, enters back into back extraction
By containing H in cylinder2SO4Copper sulphate electrodeposition after liquid carry out back extraction process, be transferred to copper in water phase from extractant (oily phase), formed
CuSO4Solution, while the extractant after unloading restores extraction function, returns to extraction cylinder use；Then it will be transferred in water phase
CuSO4Solution is transferred in Winning cell and is electrolysed, and to obtain blister copper, and liquid flows back after remaining copper sulphate electrodeposition in Winning cell
Into back extraction cylinder；Last blister copper enters electroplating bath and carries out the bright smooth pure layers of copper of plating acquisition.Whole process realizes
The closed cycle of extractant and electrolyte.
In the present embodiment, alkaline etching liquid indirect regeneration further includes being connected to one of water washing cylinder, back extraction
Cylinder and extraction bis- water washing cylinder of Gang.The extractant that obtains in back extraction cylinder, return it into extraction cylinder before use, using
The aqueous solution isolated in one of water washing cylinder carries out two washings to extractant, obtains clean extractant, and return it into extraction
It takes cylinder to repeat to reuse, to ensure that extractant is restored to optimum performance, reaches extractant closed cycle.
In the present embodiment, alkaline etching liquid indirect regeneration further includes being connected to two water washing cylinders and water washing cylinder together
Between a RO film process slot and be connected to RO film process slot and together the PH regulating tank between water washing cylinder.By one of water
Water phase (aqueous solution) after washing bis- water washing cylinder of Gang Yu, performance can be influenced, it is therefore desirable to after Jiang Dui bis- is washed respectively
The water phase (aqueous solution) isolated is passed through in RO film process slot and PH regulating tank, is carried out RO film process and pH value adjustment, is made to handle
Aqueous solution afterwards can be restored to initial performance, return to one of water washing cylinder and use, sharp again to reach the oily continuous circulation and stress of phase wash water
Purpose.
Referring to figure 3., alkaline etching liquid indirect regeneration further includes the spray column 1 for being connected to Winning cell, for pair
The oxygen generated in Winning cell carries out acid-mist-removing processing.Specifically, the spray column 1 includes a tower body 11, is set to tower body 11
An interior spraying mechanism 12, the demister 13 for being set in tower body 11 and being located at 12 top of spraying mechanism and it is set to tower body
An extraction sector 14 outside 11, wherein be provided with an admission line on the tower body 11 and on the downside of spraying mechanism 12
111, and an outlet pipe 112 is provided in the tower body 11, which, which is located in tower body 11 and extends to, removes
13 top of foam device；The extraction sector 14 includes being connected to a pumping chamber 141 of 112 other end end of outlet pipe and being connected to
One pumping blower 142 of pumping chamber 141, has an exhaust outlet 1411, and set in the pumping chamber 141 on the pumping chamber 141
It is equipped with an oxygen filter screen 143；A sewage draining exit is offered in the 11 side bottom of tower body.
Oxygen is entered in tower body 11 by admission line 111, and extend upward through the injection of spraying mechanism 12 containing hydroxide
The alkaline foam of sodium solution, neutralizes sulfuric acid mist, and then, the oxygen after acid-mist-removing passes through demister 13, finally by extraction sector
14 induced effect draws outside from outlet pipe 112, before this, is first filtered, is made to oxygen by oxygen filter screen 143
Pure oxygen is finally discharged.
In the present embodiment, specifically, the spraying mechanism 12 includes several spray assemblies being set in tower body 11
It 121 and is set to the outside of tower body 11 and is connected to a purification return-flow structure 122 of sewage draining exit, wherein the spray assemblies 121 packet
It includes the spray tube 1211 for being horizontally placed in tower body 11 and being located at 13 lower section of demister and is set to the several of 1211 lower section of spray tube
Solid-cone (type) nozzle 1212,1211 one end of spray tube are protruded into tower body 11 by the import end flanges 1213 on 11 outer wall of tower body,
And 1211 other end of spray tube is inserted and fixed in the support end flanges 1214 on 11 outer wall of tower body.The present embodiment will spray
Shower pipe 1211 is fixed in tower body 11 by import end flanges 1213 and support end flanges 1214 respectively, is being needed to spray tube
1211 when being cleaned or being replaced, and only need to extract spray tube 1211 from import end flanges 1213 out, and does not have to enter tower body
11 constructions.
Meanwhile the present embodiment purification return-flow structure 122 includes the liquid storage cylinder 1221 being connected with sewage draining exit, is set to storage
One filter 1222 at 1221 inlet end of fluid cylinder, is connected to return pipe at the return pipe 1223 for being connected to spray tube 1211
1223 circulating pump 1224 and the floating ball type liquid-level meter for being set in liquid storage cylinder 1221 and being electrically connected to circulating pump 1224
1225。
The alkaline solution containing sodium hydroxide sprayed out by spraying mechanism 12 after contacting with oxygen, drops onto tower body 11
Bottom is entered in liquid storage cylinder 1221 by sewage draining exit, and is filtered by the filter 1222 in liquid storage cylinder 1221 to solution, filtering
Fall acid mist and impurity；And liquid level inspection is carried out to liquid level of solution filtered in liquid storage cylinder 1221 by floating ball type liquid-level meter 1225 in real time
It surveys, when liquid level reaches certain value, circulating pump 1224 starts, and treated solution by return pipe 1223 is flowed back into spray tube
On 1211, as spray solution, to reach the closed cycle of spray liquid, achieve the purpose that circulation and stress recycles.
The above described is only a preferred embodiment of the present invention, be not intended to limit the scope of the present invention,
Therefore technical characteristic same as or similar to the above embodiments of the present invention is used, and obtained other structures, in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of alkaline etching liquid circulation regeneration method, which is characterized in that include the following steps：
(1) etching waste liquor generates：It is stored in waste liquid barrel by the etching waste liquor that etching production line generates, the etching in waste liquid barrel is useless
Liquid is added in extraction cylinder；
(2) it extracts：The extractant hybrid reaction in etching waste liquor and extraction cylinder being added in extraction cylinder, extractant concentration are
40-60% is comparably O/A=2, and most copper ion is separated from etching waste liquor, and generation load extraction is reacted with extractant
Agent, then clarification layering, water-oil separating form supported copper oil phase, and are water containing the regenerated liquid that copper concentration is reduced to 25-35g/L
It is mutually stored in regenerated liquid bucket；
(3) composition regulation：Cu is carried out to the regenerated liquid in regenerated liquid bucket2+、NH4 +、Cl-It is chemically examined with pH value, it is true according to result of laboratory test
The amount of the ammonia and ammonium chloride that add needed for fixed, makes the etching regenerated liquid to be formed meet etch requirements, then be back to etching production line
Middle use simultaneously executes step (4)；
(4) it washes together：Supported copper oil is mutually carried out washing together, is further separated out water phase and supported copper oil phase；
(5) it is stripped：Supported copper that step (4) is isolated oil is mutually transferred in back extraction cylinder, and toward be stripped in cylinder be added it is dense
Degree is the H of 2.5-3.5mol/L2SO4Loaded extractant and H of the solution as strip liquor, in supported copper oil phase2SO4Solution is abundant
Haptoreaction separates copper ion from extractant, then clarification layering, and water-oil separating generates CuSO4Solution enters water
Xiang Zhong, and isolate the extractant after copper ion and restore extraction function, in the extraction process in step (2)；
(6) electrodeposition：Copper containing 12-45g/L, 180-220g/L sulfuric acid are added into Winning cell, is less than 0-1g/L iron and 0-10g/L oil
Electrolyte, by the CuSO in step (5) water phase4Solution is added in electrolyte, is 100-120mm's by Winning cell medium spacing
The CuSO that anode and anode obtain back extraction4Solution is electrolysed, electrolyte flow rate 0.1-0.2m3/m2.h, current density
For 100-240A/m2, then blister copper is deposited in cathode, generates oxygen in anode, while regenerating H2SO4Solution, and H will be contained2SO4
The remaining CuSO of solution4Liquid flows back into back extraction cylinder after electrodeposition.
2. alkaline etching liquid circulation regeneration method according to claim 1, which is characterized in that, will in the step (6)
It is passed through in spray column in the oxygen that anode generates, and sprays the alkaline foam containing sodium hydroxide solution in spray column, and keep
The pH value of solution is within the scope of 8-13 in spray column, then the foam of oxygen carries sulfuric acid mist and sodium hydroxide solution neutralizes, then
Pure oxygen is given off from spray column.
3. alkaline etching liquid circulation regeneration method according to claim 1, which is characterized in that the step (5) further includes
Following steps：The water phase isolated using step (4) carries out two to the extractant after copper ion is isolated in back extraction cylinder
Washing, isolates pure extractant and has separated the water phase after extractant, and by the absolute extract agent of acquisition, is used for step
(2) in the extraction process in.
4. alkaline etching liquid circulation regeneration method according to claim 3, which is characterized in that the step (5) further includes
Following steps：RO film process and pH value adjustment are carried out to the water phase isolated after two washings, then are back to one of step (4)
In washing step.
5. alkaline etching liquid circulation regeneration method according to claim 1, which is characterized in that further comprising the steps of：
(7) copper is refined：It is the copper-bath of 0.4-0.6mol/L as electroplate liquid that concentration is added into electroplating bath, and is added dense
Degree is the triethanolamine of 0.5-1.5g/L as additive, and the cathode that blister copper is deposited in step (6) is put into electroplating bath
It is put into electroplating bath as anode, and by a clean copper plates as cathode, is 450-550A/m in current density2In the case where electricity
It plates, the blister copper on anode dissolves and pass through cathode deposition, and smooth refined copper is obtained on cathode.
6. implementing the alkaline etching liquid indirect regeneration of any the method in claim 1 to 5, which is characterized in that including
An extraction cylinder, the oil expeller for being connected to extraction cylinder, connection for being connected to a waste liquid barrel of etching production line, being connected to waste liquid barrel
In oil expeller a regenerated liquid bucket, be connected to regenerated liquid bucket and etch production line a composition regulation cylinder, be connected to extraction
One of water washing cylinder of cylinder, is connected to a Winning cell of back extraction cylinder and is connected to the back extraction cylinder for being connected to one of water washing cylinder
One electroplating bath of Winning cell, to form closed cycle, wherein be respectively arranged at a spiral in the extraction cylinder and back extraction cylinder and stir
Mix paddle.
7. alkaline etching liquid indirect regeneration according to claim 6, which is characterized in that further include being connected to one
Road water washing cylinder, back extraction cylinder and extraction bis- water washing cylinder of Gang.
8. alkaline etching liquid indirect regeneration according to claim 6, which is characterized in that further include being connected to Er Daoshui
The RO film process slot washed between cylinder and together water washing cylinder and it is connected to RO film process slot and together the PH tune between water washing cylinder
Save slot.
9. alkaline etching liquid indirect regeneration according to claim 6, which is characterized in that further include being connected to Winning cell
A spray column, which includes a tower body, is set to the intracorporal spraying mechanism of tower, is set in tower body and be located at spray
A demister above mechanism and the extraction sector being set to outside tower body, wherein on the tower body and be located at spraying mechanism
Downside is provided with an admission line, and an outlet pipe is provided in the tower body, the outlet pipe one end be located in tower body and
It extends to above demister；The extraction sector includes being connected to a pumping chamber of outlet pipe other end end and being connected to pumping
One pumping blower of air cavity, has an exhaust outlet, and an oxygen filter screen is provided in the pumping chamber on the pumping chamber；?
The tower body side bottom offers a sewage draining exit.
10. alkaline etching liquid indirect regeneration according to claim 9, which is characterized in that the spraying mechanism includes
It is set to the intracorporal several spray assemblies of tower and is set to outside tower body and is connected to a purification return-flow structure of sewage draining exit,
In, which includes the spray tube being horizontally placed in tower body and below demister and is set to below spray tube
Several solid-cone (type) nozzles, which is protruded into tower body by the import end flanges on tower body outer wall, and the spray tube is another
One end is inserted and fixed in the support end flanges on tower body outer wall；The purification return-flow structure includes being connected with sewage draining exit
One liquid storage cylinder, the return pipe for being connected to spray tube, is connected to return pipe at the filter for being set to liquid storage cylinder inlet end
One circulating pump and the floating ball type liquid-level meter for being set in liquid storage cylinder and being electrically connected to circulating pump.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810972310.8A CN108914129A (en) | 2018-08-24 | 2018-08-24 | A kind of alkaline etching liquid indirect regeneration and its method |
| CN201910034200.1A CN109440111A (en) | 2018-08-24 | 2019-01-15 | A kind of alkaline etching liquid indirect regeneration and its method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810972310.8A CN108914129A (en) | 2018-08-24 | 2018-08-24 | A kind of alkaline etching liquid indirect regeneration and its method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108914129A true CN108914129A (en) | 2018-11-30 |
Family
ID=64406182
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810972310.8A Pending CN108914129A (en) | 2018-08-24 | 2018-08-24 | A kind of alkaline etching liquid indirect regeneration and its method |
| CN201910034200.1A Pending CN109440111A (en) | 2018-08-24 | 2019-01-15 | A kind of alkaline etching liquid indirect regeneration and its method |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910034200.1A Pending CN109440111A (en) | 2018-08-24 | 2019-01-15 | A kind of alkaline etching liquid indirect regeneration and its method |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN108914129A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110042251A (en) * | 2019-05-27 | 2019-07-23 | 深圳市祺鑫天正环保科技有限公司 | The recovery method and recovery system of copper in alkaline etching waste liquid for producing |
| CN110144590A (en) * | 2019-05-31 | 2019-08-20 | 深圳市泓达环境科技有限公司 | Alkaline copper-containing etching waste solution regeneration and the ammonia nitrogen waste water circulatory system |
| CN110172727A (en) * | 2019-05-09 | 2019-08-27 | 刘景亮 | A kind of electroplating technology of circuit board |
| CN112376049A (en) * | 2020-11-09 | 2021-02-19 | 江苏净拓环保科技有限公司 | Method for recovering acidic etching solution |
| CN112831787A (en) * | 2020-12-30 | 2021-05-25 | 江苏净拓环保科技有限公司 | Cyclic regeneration method of alkaline etching solution |
| CN114752940B (en) * | 2022-04-21 | 2024-02-06 | 盛隆资源再生（无锡）有限公司 | Method for recycling alkaline copper-containing etching waste liquid |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110042425A (en) * | 2019-04-23 | 2019-07-23 | 博罗县华盈科技有限公司 | A kind of heavy process for copper of alkaline etching waste liquid for producing direct electrowinning |
-
2018
- 2018-08-24 CN CN201810972310.8A patent/CN108914129A/en active Pending
-
2019
- 2019-01-15 CN CN201910034200.1A patent/CN109440111A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110172727A (en) * | 2019-05-09 | 2019-08-27 | 刘景亮 | A kind of electroplating technology of circuit board |
| CN110042251A (en) * | 2019-05-27 | 2019-07-23 | 深圳市祺鑫天正环保科技有限公司 | The recovery method and recovery system of copper in alkaline etching waste liquid for producing |
| CN110144590A (en) * | 2019-05-31 | 2019-08-20 | 深圳市泓达环境科技有限公司 | Alkaline copper-containing etching waste solution regeneration and the ammonia nitrogen waste water circulatory system |
| CN112376049A (en) * | 2020-11-09 | 2021-02-19 | 江苏净拓环保科技有限公司 | Method for recovering acidic etching solution |
| CN112831787A (en) * | 2020-12-30 | 2021-05-25 | 江苏净拓环保科技有限公司 | Cyclic regeneration method of alkaline etching solution |
| CN114752940B (en) * | 2022-04-21 | 2024-02-06 | 盛隆资源再生（无锡）有限公司 | Method for recycling alkaline copper-containing etching waste liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109440111A (en) | 2019-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109440111A (en) | A kind of alkaline etching liquid indirect regeneration and its method | |
| CN104909508B (en) | Electroplating chromium-containing wastewater treatment method and device | |
| CN203999825U (en) | The device that regenerating alkaline etching liquid circulation and copper reclaim | |
| CN106929857A (en) | Cupric acidity etching liquid recycling equipment for reclaiming and method | |
| CN105039989B (en) | A kind of acid chlorization system copper-containing etching waste solution electrodeposition decopper(ing) and regeneration method | |
| CN105483707B (en) | A kind of method that alkaline copper chloride etching waste liquid proposes copper reuse | |
| CN102321908A (en) | Recycling and regenerating process method and metal copper recovery system of acid chloride etching solution | |
| CN202272954U (en) | System for acid chloride etching liquid cycle regeneration and metallic copper recycling | |
| CN109252168A (en) | A kind of devices and methods therefor of efficient activated acid etching solution | |
| CN107059010A (en) | Cupric alkaline etching liquid circular regeneration equipment for reclaiming and method | |
| CN103789769A (en) | Method for recycling and regenerating PCB (Printed Circuit Board) acidic and alkaline etching waste liquid | |
| CN209555372U (en) | A kind of alkaline etching liquid indirect regeneration | |
| CN106367792A (en) | Aluminum pretreatment alkaline three-in-one online recycling system for demolding alkaline liquor for extruding mold aluminum material heads and aluminum hydroxide | |
| US1970973A (en) | Electrolyzing process with the use of a mercury cathode | |
| CN110144590A (en) | Alkaline copper-containing etching waste solution regeneration and the ammonia nitrogen waste water circulatory system | |
| CN100413999C (en) | Method for regenerating etching solutions containing iron for the use in etching or pickling copper or copper alloys and an apparatus for carrying out said method | |
| KR100264446B1 (en) | Method of recycling waste ething solution | |
| CN106011929A (en) | Method for recycling copper extracted from alkaline copper chloride etching waste liquid | |
| CN106587459A (en) | Online recycling method for electroplating washing wastewater | |
| CN104060270A (en) | Circuit board etching and etching solution regeneration complete plant | |
| CN101003396A (en) | System and method for treating wastewater of containing copper from microetching printed circuit board | |
| CN218403896U (en) | Discharge wastewater recycling treatment device and waste lithium battery treatment system | |
| CN204162793U (en) | A kind of circuit board etching and etching solution regeneration complete equipment | |
| CN106757268A (en) | The aluminium pre-treatment three-in-one and alkali liquid regeneration of alkalescence and aluminium hydroxide online recycling technique | |
| CN106367791B (en) | Aluminium pre-treatment and aluminium hydroxide online recycling and the three-in-one frosting technology of alkalinity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181130 |
|
| WD01 | Invention patent application deemed withdrawn after publication |