CN107385470A - Cupric spent etching solution recovery method - Google Patents
Cupric spent etching solution recovery method Download PDFInfo
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- CN107385470A CN107385470A CN201610351348.4A CN201610351348A CN107385470A CN 107385470 A CN107385470 A CN 107385470A CN 201610351348 A CN201610351348 A CN 201610351348A CN 107385470 A CN107385470 A CN 107385470A
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- 238000005530 etching Methods 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000011084 recovery Methods 0.000 title claims abstract description 22
- 238000000605 extraction Methods 0.000 claims abstract description 79
- 239000007788 liquid Substances 0.000 claims abstract description 63
- 239000000243 solution Substances 0.000 claims abstract description 60
- 239000012074 organic phase Substances 0.000 claims abstract description 35
- 238000005406 washing Methods 0.000 claims abstract description 27
- 238000010790 dilution Methods 0.000 claims abstract description 26
- 239000012895 dilution Substances 0.000 claims abstract description 26
- 230000033228 biological regulation Effects 0.000 claims abstract description 25
- 239000002699 waste material Substances 0.000 claims abstract description 24
- 238000003860 storage Methods 0.000 claims abstract description 22
- 239000008346 aqueous phase Substances 0.000 claims abstract description 20
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- 239000012071 phase Substances 0.000 claims abstract description 14
- 230000002378 acidificating effect Effects 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000003350 kerosene Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 81
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 19
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910001431 copper ion Inorganic materials 0.000 claims description 13
- 239000002351 wastewater Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 239000012047 saturated solution Substances 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 7
- 238000011069 regeneration method Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000010865 sewage Substances 0.000 claims description 4
- 239000010802 sludge Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 241000370738 Chlorion Species 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000029219 regulation of pH Effects 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a kind of cupric spent etching solution recovery method, it is comprised the following steps：(1) it is sent into after cupric spent etching solution is filtered and neutralizes dilution trap, adjusts pH to 2.6~3.5；The cupric spent etching solution comprises at least cupric acidic waste etching liquid；(2) mixing liquid neutralized in dilution trap is sent into multi-stage counter current extraction component via the first regulation liquid storage tank, and multi-stage counter current extraction is carried out after adding extractant and kerosene into multi-stage counter current extraction component；(3) load organic phases that multi-stage counter current extraction obtains in step (2) are subjected to multistage washing, obtain washing aqueous phase and organic phase；(4) organic phase that step (3) obtains is stripped, obtains strip aqueous and back extraction organic phase；(5) aqueous phase and oil phase are obtained after the strip aqueous that step (4) obtains being carried out into water-oil separating；(6) aqueous phase that step (5) obtains is electrolysed via electrolyte circulating slot to electrolytic cell；Electrolysis obtains electrolysis waste solution and tough cathode.
Description
Technical field
The present invention relates to the recoverying and utilizing method of cupric spent etching solution, specifically for by acid cupric spent etching solution recovery
Negative electrode copper products are prepared after reason.
Background technology
As China constantly increases to the demand of electronic product, promote the printed wiring board in China, referred to as (PCB) is raw
Production rapidly develops, and has driven local economic development, the production, life style to the mankind bring deep change.PCB lifes simultaneously
There are various heavy waste water and organic wastewater discharge during production, complicated, intractability is larger.Printed circuit board is in difference
Production phase can produce different waste water, and the component difference of various waste water is very big, and existing forms are also not quite similar, and handles work
Process is also just different, and this just constitutes the uniqueness of printed circuit board Wastewater Treatment.
In actual production, three classes are can be largely classified into i.e.：Organic wastewater, plating or etching waste water and sanitary wastewater, have
Machine waste water is mainly demoulding development waste-water, and it is mainly produced by the making wire pattern technique in printed circuit board preparation process
, feature is that content of organics is higher, and pH is higher, complicated component, and water quality and quantity fluctuation is big, and intractability is big.Etch waste water
It is low to be mainly characterized by pH, certain tenor is high, the stronger recycling value of tool.
Etching solution is divided into two kinds of acidic etching liquid and alkaline etching liquid, and wherein acidic etching waste liquid is exactly that a kind of cupric gives up
Water, is caused a kind of industrial wastewater in PCB Production, mainly with stannous chloride, chlorine in HCl-CuCl2 acidic etching waste liquids
Change copper, hydrochloride form is present.Generally, acidic etching liquid cupric is in 100~120g/L.This is due to etching process
Progress, molten amount of copper is continuously increased, and Cu2+ is gradually converted into Cu+ in etching solution, and in etching solution it is maximum to move closer to its for cupric
Capacity is etched, though still having certain etch capabilities, first mate declines its etching speed, and solution is extremely unstable, easily forms pureed
Precipitation, it can no longer meet that PCB industry produces etching work procedure requirement, now etching solution turns into waste liquid and gone out of use, palpus in etching groove
The etching solution more renewed.
Substantial amounts of cupric acidic etching waste liquid, its copper content can be produced in printed circuit board (PCB) production process after etched process
Up to 100~120g/L, simultaneously containing a large amount of chlorine roots, if mishandling, easily cause the serious wasting of resources and environment
Pollution.
In the prior art, for cupric acidic etching waste liquid (also referred to as acid cupric spent etching solution), be by with alkali
Property etching solution neutralize after carry out simultaneously handle recovery (referring to Chinese patent 201210192292.4)；Which causes acid cupric
The recovery of spent etching solution can not be handled individually, reclaim the processing that will also result in acid cupric spent etching solution simultaneously with alkaline etching liquid
Not thoroughly, whole prior art can not realize thorough, the efficient and high environmental benefit recycling of acid cupric spent etching solution
Processing.
The content of the invention
Given up in view of the above-mentioned deficiencies in the prior art, the technical problem to be solved by the present invention is that disclosing a kind of cupric
Etching solution recovery method, acid cupric spent etching solution can be carried out recycling treatment, negative electrode copper products are made by it.
In order to achieve the above object, the present invention is achieved using following technical scheme：
Cupric spent etching solution recovery method, is comprised the following steps：
(1) it is sent into after cupric spent etching solution is filtered and neutralizes dilution trap, adjusts pH to 2.6~3.5；The useless etching of the cupric
Liquid comprises at least cupric acidic waste etching liquid；
(2) mixing liquid neutralized in dilution trap is sent into multi-stage counter current extraction component via the first regulation liquid storage tank, and
Multi-stage counter current extraction is carried out after adding extractant and kerosene into multi-stage counter current extraction component；
(3) multi-stage counter current extraction obtains in step (2) load organic phases are subjected to multistage washing, obtain washing aqueous phase and
Organic phase；
(4) organic phase that step (3) obtains is stripped, obtains strip aqueous and back extraction organic phase；
(5) aqueous phase and oil phase are obtained after the strip aqueous that step (4) obtains being carried out into water-oil separating；
(6) aqueous phase that step (5) obtains is electrolysed via electrolyte circulating slot to electrolytic cell；It is useless that electrolysis obtains electrolysis
Liquid and tough cathode.
The preferred embodiment of the present invention and further improvement are as follows：
First, it is and described also comprising after filtering low copper containing waste liquid and Copper-Containing Mine Acid Water respectively in the step (1)
Cupric spent etching solution is sent into the step of neutralizing dilution trap simultaneously, also include in the step (1) by copper-contained sludge be sent into it is described in
With the step in dilution trap；The step of bag filter contains using copper content detection is carried out after filter impurity screening.
2nd, the step (3) is that the load organic phases that multi-stage counter current extraction obtains in the step (2) are carried out into three-level to wash
Wash, control is in a ratio of O/A=1: 1, washes the chlorion of load organic phases entrainment off；Obtain washing aqueous phase and organic phase；It is described to wash
Wash an aqueous phase part and be sent into the second regulation liquid storage tank, another part, which is sent into, neutralizes dilution trap.
3rd, also include and adjust the pH of the described second regulation liquid storage tank liquid to 6.5~7.0, be used for after press filtration removal of impurities
The step of reclaiming sodium chloride；Also it is included as adding the step of deionized water is diluted in the second regulation liquid storage tank.
4th, also comprising configuration sodium hydroxide solution the step of；The step of configuration sodium hydroxide solution is by water and hydrogen
Sodium oxide molybdena is sent into sodium hydroxide regulating tank and is well mixed, then sodium hydroxide solution storage is sent into after the filtering of bitubular drumfilter
The step of groove；The sodium hydroxide solution storage tank provides alkaline solution for the neutralization dilution trap.
5th, also comprising the step of electrolysis waste solution is recycled into electrolyte circulating slot in the step (6)；The step (6)
In also include by the electrolyte circulation fluid of the electrolyte circulating slot be used for the step (4) in stripping process in.
6th, the back extraction in the step (4) is O/A=2: 1 compared to control；The step (6) also includes and obtains step (5)
During the oil phase arrived is via reuse to the multitple extraction of the step (2) after regeneration filtration step；The step (5) also includes
The back extraction organic phase that the step (4) is obtained carries out one-level washing, washes the sulfate radical of back extraction organic phase entrainment, one-level washing off
Wash water afterwards performs sewage treatment step, and the oil phase after one-level washing is via reuse after regeneration filtration step to the step (2)
Multitple extraction process.
7th, the multi-stage counter current extraction of the step (2) is using level Four extraction step：
S100：The copper ion concentration that one-level extraction adjusts mixing liquid jointly with sodium carbonate solid and waste water is 68~75g/
L, 3~3.5, the flow-rate ratio of extractant and mixing liquid is 3: 1 for pH value control；
S200：Two level extraction sodium hydroxide saturated solution regulation one-level raffinate copper ion concentration is 33~40g/L, pH
3.8~4.0, control is in a ratio of 3: 1 for value control；
S300：Medicinal sodium hydroxide saturated solution regulation two level raffinate is adjusted in three-level extraction, and pH value is adjusted to 5.0~6.0,
Content of copper ion≤2g/L of raffinate；
S400：Medicinal sodium hydroxide saturated solution regulation three-level raffinate, the content of copper ion of raffinate are adjusted in level Four extraction
≤ 100mg/L, raffinate pH value are 0.8~2.0.
It is further：Also include the raffinate in the step S400 via being sent into after No. four raffinate regulating tanks
The step of filter filters, the filter residue obtained after performing the step of the filtering are sent into the neutralization dilution trap reuse, obtained filter
Liquid performs evaporative crystallization steps.
It is further：Also include and collect the part raffinate in the step S100, step S200 and step S300
The step of pH is adjusted in 1~No. 3 raffinate regulating tank, and the raffinate after regulation pH is adjusted via 1~No. 3 raffinate
Liquid storage tank is sent into the step of reuse in the multi-stage counter current extraction of the step (2).
Present invention has the advantages that：
Acidic waste etching liquid is carried out pH regulations, made by cupric spent etching solution recovery method disclosed by the invention, its step (1)
Obtain the progress that extractive reaction can be relatively reliable；Dilution trap is neutralized to can aid in subsequently as the pH adjusting positions of starting stage
Recyclable liquid reuse；
Mixing liquid after neutralization is carried out multitple extraction by the step (2) of the present invention, realizes more preferable effect of extracting；Most
Whole load organic phases (extraction organic phase) have obtained reliably being more suitable for the organic of back extraction after performing the multistage washing of step (3)
Phase；After the back extraction for performing step (4), the strip aqueous that can carry out tough cathode preparation by electrolytic cell be electrolysed instead
Should, tough cathode is made；Electrolyte circulating slot recycles transfer position as electrolyte, can be sent into electrolysis cycle liquid anti-
Extraction process performs back extraction, and electrolysis waste solution can also recycle in electrolysis cycle groove.
In a word, the present invention can reliably, efficiently realize the recycling of acidic waste etching liquid.
Brief description of the drawings
Fig. 1 is a kind of flow chart of embodiment of the present invention.
Embodiment
Embodiments of the present invention are illustrated by particular specific embodiment below, those skilled in the art can be by this explanation
Content disclosed by book understands other advantages and effect of the present invention easily.
As shown in figure 1, it illustrates the embodiment of the present invention, as illustrated, the useless erosion of cupric disclosed by the invention
Liquid recovery method is carved, is comprised the following steps：
(1) it is sent into after cupric spent etching solution is filtered and neutralizes dilution trap, adjusts pH to 2.6~3.5；The useless etching of the cupric
Liquid comprises at least cupric acidic waste etching liquid；Extractant to containing copper etchant solution pH value require it is higher, according to copper in etching solution from
The difference of sub- concentration is different from extraction series, and regulation pH value is 2.6~3.5 or so, contributes to follow-up liquid to be extracted (i.e. following
" mixing liquid ") carry out multitple extraction, the copper sulphate back extraction in organic copper extractant electricity consumption solution groove after extraction, into electrolysis
Groove is electrolysed.In actual production, we are specifically respectively adjusted pH by the way that pH value to have been carried out to the operations of three kinds of specific embodiments
For 2.6,3.0 and 3.5；When pH is adjusted to 3.5, the removal process of whole embodiment being capable of more preferable continuous and steady operation.
(2) mixing liquid neutralized in dilution trap is sent into multi-stage counter current extraction component via the first regulation liquid storage tank, and
Multi-stage counter current extraction is carried out after adding extractant and kerosene into multi-stage counter current extraction component；
(3) multi-stage counter current extraction obtains in step (2) load organic phases are subjected to multistage washing, obtain washing aqueous phase and
Organic phase；
(4) organic phase that step (3) obtains is stripped, obtains strip aqueous and back extraction organic phase；
(5) aqueous phase and oil phase are obtained after the strip aqueous that step (4) obtains being carried out into water-oil separating；
(6) aqueous phase that step (5) obtains is electrolysed via electrolyte circulating slot to electrolytic cell；It is useless that electrolysis obtains electrolysis
Liquid and tough cathode.
The general principle of the extraction of the present invention is as follows：
Extract principle：
Extract absorbed portion：2RH+Cu2+=2RCu+2H+
Organic copper extractant copper ion copper-rich extractant
It is stripped part：2RCu+2H+=2RH+Cu2+
The organic copper extractant of copper-rich extractant sulfuric acid
In some preferred embodiments, also included low copper containing waste liquid and Copper-Containing Mine Acid Water in the step (1)
After filtering respectively, the step of neutralizing dilution trap is sent into simultaneously with the cupric spent etching solution, also being included in the step (1) to contain
Copper sludge is sent into the step neutralized in dilution trap；The bag filter contains using progress copper content inspection after filter impurity screening
The step of survey.The present embodiment is tested for a long time according to us, finds the processing procedure of whole acid cupric spent etching solution, can
Very outstanding resource is still realized in the case where adding low copper containing waste liquid and mine acidity contained waste liquid and copper-contained sludge
Change utilizes process, so just causes the accommodation increase of whole recovery method.
In some preferred embodiments, the step (3) is by multi-stage counter current extraction obtains in the step (2) load
Organic phase carries out three-level washing, and control is in a ratio of O/A=1: 1, washes the chlorion of load organic phases entrainment off；Obtain washing aqueous phase
And organic phase；The washing aqueous phase part is sent into the second regulation liquid storage tank, and another part, which is sent into, neutralizes dilution trap.The present embodiment
Washing aqueous phase has been subjected to reuse process, has reduced waste and disposal of pollutants.
In some preferred embodiments, also include the pH of the described second regulation liquid storage tank liquid is adjusted to 6.5~
7.0, the step of being used to reclaim sodium chloride after press filtration removal of impurities；Addition deionized water in the second regulation liquid storage tank is also included as to enter
The step of row dilution.The present embodiment, the process that washing aqueous phase has been carried out reclaiming sodium chloride, enriches the money in whole recovery method
Sourceization utilizes project, improves environmental benefit.
In some preferred embodiments, also comprising configuration sodium hydroxide solution the step of；The configuration sodium hydroxide solution
The step of be that water and sodium hydroxide are sent into sodium hydroxide regulating tank to be well mixed, then sent after the filtering of bitubular drumfilter
The step of entering sodium hydroxide solution storage tank；The sodium hydroxide solution storage tank provides alkaline solution for the neutralization dilution trap.This
Embodiment is capable of the sodium hydroxide solution of centralized configuration better quality, eventually for links, especially neutralizes in dilution trap
Alkaline solution addition.
In some preferred embodiments, also included in the step (6) and electrolysis waste solution is recycled to electrolyte circulating slot
Step；Also included in the step (6) by the electrolyte circulation fluid of the electrolyte circulating slot for anti-in the step (4)
During extraction.
In some preferred embodiments, the back extraction in the step (4) is O/A=2: 1 compared to control；The step (6)
Also include the oil phase that step (5) obtains via after regeneration filtration step during reuse to the multitple extraction of the step (2)；
The step (5) also includes the back extraction organic phase for obtaining the step (4) and carries out one-level washing, washes back extraction organic phase entrainment off
Sulfate radical, one-level washing after wash water perform sewage treatment step, one-level washing after oil phase via regeneration filtration step after
Reuse to the step (2) multitple extraction process.Reuse after the present embodiment filters oil phase by regeneration, reduce waste and dirt
Dye discharge, the organic phase after back extraction is subjected to one-level washing, goes after sulfate radical wash water carrying out sewage disposal so that discharge reaches
Mark.
In some preferred embodiments, the multi-stage counter current extraction of the step (2) is using level Four extraction step：
S100：The copper ion concentration that one-level extraction adjusts mixing liquid jointly with sodium carbonate solid and waste water is 68~75g/
L, 3~3.5, the flow-rate ratio of extractant and mixing liquid is 3: 1 for pH value control；
S200：Two level extraction sodium hydroxide saturated solution regulation one-level raffinate copper ion concentration is 33~40g/L, pH
3.8~4.0, control is in a ratio of 3: 1 for value control；
S300：Medicinal sodium hydroxide saturated solution regulation two level raffinate is adjusted in three-level extraction, and pH value is adjusted to 5.0~6.0,
Content of copper ion≤2g/L of raffinate；
S400：Medicinal sodium hydroxide saturated solution regulation three-level raffinate, the content of copper ion of raffinate are adjusted in level Four extraction
≤ 100mg/L, raffinate pH value are 0.8~2.0.Present embodiment discloses level Four to extract structure, and effect of extracting is thorough, can be most
The load organic phases (extraction organic phase) for obtaining more high copper of limits；Also contribute to targetedly utilize raffinate simultaneously
Liquid.
In some preferred embodiments, also include the raffinate in the step S400 via No. four raffinate regulating tanks
The step of being sent into filter filtering afterwards, the filter residue obtained after performing the step of the filtering are sent into the neutralization dilution trap reuse,
Obtained filtrate performs evaporative crystallization steps.The present embodiment the raffinate after level Four extracts is filtered after it is detailed-oriented
Processing, realizes more excellent environmental benefit, reduces disposal of pollutants.
In some preferred embodiments, also include and extract the part in the step S100, step S200 and step S300
Extraction raffinate is collected to the step of adjusting pH in 1~No. 3 raffinate regulating tank, and will adjust the raffinate after pH via 1~No. 3 extraction
The step of extraction raffinate regulation liquid storage tank is sent into reuse in the multi-stage counter current extraction of the step (2).The present embodiment targetedly by 1~
Raffinate reuse in 3 grades of extractions realizes more thorough effect of extracting, contributes to the company of extraction process into multistage extraction process
It is continuous to perform.
The preferred embodiment for the present invention is explained in detail above in conjunction with accompanying drawing, but the invention is not restricted to above-mentioned implementation
Mode, can also be on the premise of present inventive concept not be departed from those of ordinary skill in the art's possessed knowledge
Make a variety of changes, these changes are related to correlation technique well-known to those skilled in the art, and these both fall within patent of the present invention
Protection domain.
Many other changes and remodeling can be made by not departing from the spirit and scope of the present invention.It should be appreciated that the present invention is not
It is limited to specific embodiment, the scope of the present invention is defined by the following claims.
Claims (10)
1. cupric spent etching solution recovery method, it is characterised in that comprise the following steps：
(1) it is sent into after cupric spent etching solution is filtered and neutralizes dilution trap, adjusts pH to 2.6~3.5；The cupric spent etching solution is extremely
Cupric acidic waste etching liquid is included less；
(2) mixing liquid neutralized in dilution trap is sent into multi-stage counter current extraction component via the first regulation liquid storage tank, and to more
Multi-stage counter current extraction is carried out after adding extractant and kerosene in stage countercurrent extraction module；
(3) multi-stage counter current extraction obtains in step (2) load organic phases are subjected to multistage washing, obtain washing aqueous phase and organic
Phase；
(4) organic phase that step (3) obtains is stripped, obtains strip aqueous and back extraction organic phase；
(5) aqueous phase and oil phase are obtained after the strip aqueous that step (4) obtains being carried out into water-oil separating；
(6) aqueous phase that step (5) obtains is electrolysed via electrolyte circulating slot to electrolytic cell；Electrolysis obtain electrolysis waste solution and
Tough cathode.
2. cupric spent etching solution recovery method as claimed in claim 1, it is characterised in that also being included in the step (1) will
After low copper containing waste liquid and Copper-Containing Mine Acid Water filter respectively, it is sent into simultaneously with the cupric spent etching solution and neutralizes dilution trap
Step, the step that copper-contained sludge is sent into the neutralization dilution trap is also included in the step (1)；The bag filter is containing use
The step of copper content detection is carried out after filter impurity screening.
3. cupric spent etching solution recovery method as claimed in claim 1, it is characterised in that the step (3) is by the step
Suddenly the load organic phases that multi-stage counter current extraction obtains in (2) carry out three-level washing, and control is in a ratio of O/A=1: 1, washes off and be loaded with
The chlorion that machine is mutually carried secretly；Obtain washing aqueous phase and organic phase；The washing aqueous phase part is sent into the second regulation liquid storage tank, separately
A part, which is sent into, neutralizes dilution trap.
4. cupric spent etching solution recovery method as claimed in claim 3, it is characterised in that also include and adjust liquid by described second
The pH of storage tank liquid is adjusted to 6.5~7.0, for the step of reclaiming sodium chloride after press filtration removal of impurities；Also it is included as described second
The step of deionized water is diluted is added in regulation liquid storage tank.
5. cupric spent etching solution recovery method as claimed in claim 1, it is characterised in that：Also comprising configuration sodium hydroxide solution
The step of；The step of configuration sodium hydroxide solution is that water and sodium hydroxide are sent into sodium hydroxide regulating tank to be well mixed,
The step of being sent into sodium hydroxide solution storage tank after the filtering of bitubular drumfilter again；The sodium hydroxide solution storage tank is institute
State and dilution trap offer alkaline solution is provided.
6. cupric spent etching solution recovery method as claimed in claim 1, it is characterised in that also being included in the step (6) will
Electrolysis waste solution is recycled to the step of electrolyte circulating slot；Also included the electrolysis of the electrolyte circulating slot in the step (6)
Liquid circulation fluid is used in the stripping process in the step (4).
7. cupric spent etching solution recovery method as claimed in claim 1, it is characterised in that the back extraction phase in the step (4)
It is O/A=2: 1 than control；The step (6) also include by the oil phase that step (5) obtains via regeneration filtration step after reuse extremely
During the multitple extraction of the step (2)；The step (5) also includes to enter the back extraction organic phase that the step (4) obtains
Row one-level is washed, and washes the sulfate radical of back extraction organic phase entrainment off, and the wash water after one-level washing performs sewage treatment step, and one-level is washed
Oil phase after washing via reuse after regeneration filtration step to the step (2) multitple extraction process.
8. the cupric spent etching solution recovery method as described in claim 1~7 is any, it is characterised in that the step (2) it is more
Stage countercurrent extraction is using level Four extraction step：
S100：The copper ion concentration that one-level extraction adjusts mixing liquid jointly with sodium carbonate solid and waste water is 68~75g/L, pH
3~3.5, the flow-rate ratio of extractant and mixing liquid is 3: 1 for value control；
S200：Two level extraction sodium hydroxide saturated solution regulation one-level raffinate copper ion concentration is 33~40g/L, pH value control
For system 3.8~4.0, control is in a ratio of 3: 1；
S300：Medicinal sodium hydroxide saturated solution regulation two level raffinate is adjusted in three-level extraction, and pH value is adjusted to 5.0~6.0, raffinate
Content of copper ion≤2g/L of liquid；
S400：Medicinal sodium hydroxide saturated solution regulation three-level raffinate is adjusted in level Four extraction, and the content of copper ion of raffinate≤
100mg/L, raffinate pH value are 0.8~2.0.
9. cupric spent etching solution recovery method as claimed in claim 8, it is characterised in that also include in the step S400
Raffinate via filter filtering is sent into after No. four raffinate regulating tanks the step of, obtained after performing the step of the filtering
Filter residue is sent into the neutralization dilution trap reuse, and obtained filtrate performs evaporative crystallization steps.
10. cupric spent etching solution recovery method as claimed in claim 8, it is characterised in that also include by the step S100,
Part raffinate in step S200 and step S300 is collected to the step of adjusting pH in 1~No. 3 raffinate regulating tank, and will
Adjust the raffinate after pH and be sent into reuse in the multi-stage counter current extraction of the step (2) via 1~No. 3 raffinate regulation liquid storage tank
The step of.
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| CN112647096A (en) * | 2020-12-01 | 2021-04-13 | 苏州美源达环保科技股份有限公司 | Method for recovering copper ions in acidic etching solution |
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Application publication date: 20171124 |