CN106884185A - The technique and system and device of copper in a kind of recovery acidic etching liquid - Google Patents
The technique and system and device of copper in a kind of recovery acidic etching liquid Download PDFInfo
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- CN106884185A CN106884185A CN201710190837.0A CN201710190837A CN106884185A CN 106884185 A CN106884185 A CN 106884185A CN 201710190837 A CN201710190837 A CN 201710190837A CN 106884185 A CN106884185 A CN 106884185A
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- copper
- waste liquid
- iron
- acidic etching
- electrolysis
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- 239000007788 liquid Substances 0.000 title claims abstract description 79
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000010949 copper Substances 0.000 title claims abstract description 65
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 64
- 238000005530 etching Methods 0.000 title claims abstract description 58
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000011084 recovery Methods 0.000 title description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 123
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 64
- 229910052742 iron Inorganic materials 0.000 claims abstract description 62
- 239000002699 waste material Substances 0.000 claims abstract description 55
- 238000006073 displacement reaction Methods 0.000 claims abstract description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010936 titanium Substances 0.000 claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 19
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000005684 electric field Effects 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 7
- 239000006227 byproduct Substances 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 238000006722 reduction reaction Methods 0.000 claims abstract description 5
- 239000003381 stabilizer Substances 0.000 claims abstract description 5
- 230000007646 directional migration Effects 0.000 claims abstract description 4
- 230000006698 induction Effects 0.000 claims abstract description 4
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 3
- 238000009833 condensation Methods 0.000 claims abstract description 3
- 230000005494 condensation Effects 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 230000033228 biological regulation Effects 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 3
- -1 polydithio-dipropyl Polymers 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005553 drilling Methods 0.000 claims description 2
- 229910001447 ferric ion Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000011549 displacement method Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
-
- 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)
- Inorganic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Electrolytic Production Of Metals (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention belongs to contained waste liquid resource and nonferrous metals recycling field, more particularly to a kind of technique and system and device for reclaiming copper in acidic etching liquid.Wherein, iron displacement copper electrolysis cells include anode titanium frame and negative electrode copper sheet, scrap iron is put into anode frame, negative electrode copper sheet is in a cell, under the conditions of applying direct current electric field, there is reduction reaction on the minus plate in copper ion directional migration to electrolytic cell in induction acidic etching waste liquid, it is copper coin and sponge copper products to be electrolysed；And scrap iron is oxidized to divalence ferrous ion in anode titanium frame；After waste liquid after treatment is aoxidized through diaphragm cell, it is added thereto to polymerization stabilizer and polymerisation occurs with polymeric oxygen agent, the basicity of polymer in mixed liquor is finally adjusted with hydrochloric acid or alkali, finally prepares byproduct condensation chlorination ferric flocculant.The present invention can completely reclaim the copper in acidic etching waste liquid, and waste liquid is completely converted into byproduct flocculant, high financial profit, no pollution.
Description
Technical field
It is more particularly to a kind of to reclaim acidic etching liquid the invention belongs to contained waste liquid resource and nonferrous metals recycling field
The technique and system and device of middle copper.
Background technology
Printed circuit board is the basis of electronics and information industry, and modern high technology product all be unable to do without printed circuit board.From
At the beginning of 2009, printed circuit board produces the first big country, printed circuit board for China（PCB）Substantial amounts of acidity is consumed in etching process
Etching solution, copper ion concentration Cu in acidic etching waste liquid2+It is 110g/L~140g/L, most of production high accuracy multilayer circuit boards
（2~3mil of line width）Circuit board enterprise can select for the company that etching waste liquor is sold to special disposal waste liquid to go treatment, with new
Etch sub- liquid and do plate, to ensure to do plate quality requirement, therefore company is reclaimed for liquid medicine, pending acidic etching waste liquid amount is huge
Greatly, how heavy metal pollution in acidic etching waste liquid is rationally reclaimed, urgently solved in heavy metal wastewater thereby recycling
Technical problem certainly.
The acid etching liquid processing method of current disclosed disclosure have iron displacement method, Extraction electrodeposition method, diaphragm process,
Neutralize sedimentation etc.：
（1）Iron displacement method（China Patent Publication No. CN 1062930A）Reproducibility i.e. using iron is higher than copper, and oxytropism etching is useless
The copper in iron displacement acidic etching liquid is added in liquid, it is the big reproducibility iron of specific surface area that the method requirement adds the iron in waste liquid
Powder or iron plate, and displacement reaction produces copper sponge to be wrapped in iron surface directly in the surface generation of iron, causes iron consumption
Greatly, copper products purity only has 70% or so, added value of product not high, and displacement reaction late phase reaction is slow, reaction terminate after still
The copper ion of 1g/L or so is remained in waste liquid, and discharge is polluted and the wasting of resources.
（2）Extraction electrodeposition method（China Patent Publication No. CN 101125719A, China Patent Publication No. CN 202164354
U, China Patent Publication No. CN 101550488A, the A of China Patent Publication No. CN 101693997）Utilize organic copper extractant
Copper ion in extraction etching solution, it is copper-bath to be then stripped with sulfuric acid, and electrolysis is copper coin, the work in entering back into electrolytic cell
Although skill can reclaim high-purity copper coin, also there are shortcomings：Acidic etching waste liquid needs to use alkali（Ammoniacal liquor, NaOH, carbon
Sour sodium etc.）Regulation pH value is easily lost to desirable value is extracted, it is necessary to consume substantial amounts of alkali, and extractant is expensive by acidity
Carving the factors such as liquid oxidation, loss in cyclic process causes the method processing cost huge, and has reclaimed the waste water of copper products and contain
Substantial amounts of ammonium ion and chlorion, discharge cause huge secondary pollution.
（3）Diaphragm process（The A of China Patent Publication No. CN 102286746, China Patent Publication No. CN 102732888
A, the A of China Patent Publication No. CN 102321908）Electrolytic cell is divided into independent anode region and negative electrode using ionic membrane
There is the half-reaction of analysis copper and reclaim copper products in area, cathodic region, anode region improves the redox value of acidic etching waste liquid；It is acid every
The advantage of membrane electrolysis can be the copper in Recycling of waste liquid, while it is new etching solution to allow spent solution regeneration, but method regeneration erosion
Carve liquid and need to add substantial amounts of acid and be can be only achieved with oxidant and be etched back to requiring, the electricity low, treating capacity of effect is small, while, barrier film is electric
Solution groove anode can occur analysis chlorine reaction, cause secondary pollution（Put sulfuric acid or copper sulphate and can avoid analysing chlorine, but cathodic region in anode region
Acid waste liquid changes the increase of cylinder frequency, and dilatation is big）, and diaphragm electrolysis equipment be suitable only for production single sided board, dual platen or
Person's etching required precision circuit board enterprise not high, the circuit board high to etching required precision, method regeneration etching solution cannot be protected
The quality of plate is done in card etching, and diaphragm process equipment investment is high.
（4）Neutralize sedimentation（The A of China Patent Publication No. CN 101654275, China Patent Publication No. CN 101654276
A）Alkali or alkaline etching liquid are added i.e. in acidic etching liquid, basic copper chloride and Kocide SD is first precipitated, it is then molten with acid
Solution directly obtains copper sulphate or dinectly bruning obtains cupric oxide.The added value of product that method treatment acidic etching liquid is obtained is not
Height, and technique is cumbersome can produce a large amount of chloride and ammonia nitrogen waste waters.
There are various different drawbacks in the method that the nonacid etching solution of four kinds of the above reclaims copper, it is impossible to the extensive acid erosion for the treatment of
Carve liquid.
The content of the invention
In order to solve the problems, such as above-mentioned technology, the present invention provides a kind of method for reclaiming copper in acidic etching liquid and is
System equipment, is particularly well-suited to large-scale acidic etching waste liquid treatment company.Using technology disclosed in this invention, acidity can be reduced
Etching waste liquor processing cost, no pollution discharge is realized, valuable resource is reclaimed, is improved acidic etching liquid treating capacity and copper products and add
Value.
The solve the above problems scheme of use of the present invention is：
The system and device of copper in a kind of recovery acidic etching liquid, including two circulating slots, at least two iron displacement copper electrolysis cells, every
Membrane electrolysis cells, polymer reactor；The circulating slot, iron displacement copper electrolysis cells, diaphragm cell, polymer reactor are contacted successively,
Waste liquid buffer container is set each other, and the iron replaces copper electrolysis cells built-in anode and negative electrode；The diaphragm cell is by one
Plant anionic membrane and be divided into multiple anode chambers and cathode chamber, the anionic membrane is a kind of height for allowing anion to be directed through
Molecule resin membrane material.
, using copper sheet as negative electrode, titanium frame is used as anode for the iron displacement copper electrolysis cells.
The anode is arranged in a crossed manner with cathode separation 6cm-8cm.
The anode titanium frame is the titanium sheet or the closed-in construction that is welded into of titanium net of surface drilling, and the solution in electrolytic cell can be with
The hole on anode titanium frame is passed freely through, wherein being placed with scrap iron.
The diaphragm cell anode chamber is placed with noble coatings titanium sheet, and cathode chamber is put into titanium sheet.
Under the conditions of applying direct current electric field, the negative electrode in copper ion directional migration to electrolytic cell in induction acidic etching liquid
There is reduction reaction on plate, obtain copper powder product, scrap iron is oxidized to divalence ferrous ion in anode titanium frame；Contain after wherein processing
Iron waste liquid is processed through diaphragm electrolysis equipment, and divalence ferrous iron is oxidized to iron ion, greatlys save the consumption of polymeric oxygen agent.
The present invention also provides a kind of technique for reclaiming copper in acidic etching liquid, and specific steps include：
S1. by acidic etching waste liquid by circulating slot pump into iron displacement copper electrolysis cells in, add electrolysis additive A, open direct current
Source is electrolysed, and open the circulation pump, acidic etching waste liquid is circulated in circulating slot and iron displacement copper electrolysis cells；
S2. under the conditions of applying direct current electric field, the copper ion directional migration in induction acidic etching liquid replaces copper electrolysis cells to iron
In minus plate on there is reduction reaction, obtain copper products, scrap iron is oxidized to divalence ferrous ion in anode titanium frame；
S3. the iron content waste liquid after the recovered copper of acidic etching waste liquid is aoxidized into diaphragm cell, adds electrolysis additive B, two
Valency ferrous ion is oxidized to ferric ion；
S4. pumped into polymer reactor through the iron content waste liquid after diaphragm electrolysis, add polymerization stabilizer to occur with polymeric oxygen agent
Reaction, then adjusts the basicity of polymer in mixed liquor with acid or alkali, finally prepares byproduct condensation chlorination ferric flocculant.
The applying direct current field action is that two half-reactions for inducing iron displacement copper reaction replace cupric electrolysis in iron respectively
Minus plate in groove and reaction in anode frame.
Circulating slot is respectively provided with two groups with iron displacement copper electrolysis cells, is divided into high current density electrolysis group and low current density electricity
The system of solutions, waste liquid is introduced into high current density electrolysis group, the cyclic electrolysis in this group of circulating slot and iron displacement copper electrolysis cells；Copper ion
When content is high, first high current density electrolysis, current density is 400A/ ㎡~700A/ ㎡；As copper ion concentration≤20g/ in waste liquid
During L, waste liquid is transferred to the circulating slot of low current density electrolysis group and iron replaces copper electrolysis cells cyclic electrolysis, adjusts cathode-current density
For low current density is electrolysed, the current density of electrolysis is 100A/ ㎡~400A/ ㎡；As copper ion concentration≤0.1g/L, waste liquid
Input diaphragm cell electrolysis, is input into polymer reactor afterwards, and the temperature of acidic etching waste liquid should be maintained at 20 DEG C~35 DEG C.
By weight adding, its addition is the 0.01%~0.03% of acidic etching waste liquid amount to the electrolysis additive.
The polymerization stabilizer be sodium phosphate, ammonium phosphate, dibastic sodium phosphate in one or two, the polymeric oxygen agent be chlorine
Sour sodium.
The electrolysis additive A is sodium polydithio-dipropyl sulfonate（SPS）, polyethylene glycol (PEG) mixture, reduction lures
The bath voltage of iron displacement copper reaction is led, electrolysis electricity effect is improved and is improved electrolysis copper products flatness and brightness
The electrolysis additive B main components are thiocarbamide, improve electricity effect, prevent diaphragm cell anode chamber from analysis chlorine occurring and react.
The acid is hydrochloric acid, and alkali is NaOH, and the basicity is 8-30%.
The diaphragm cell current density is adjusted to 500A/ ㎡~1000A/ ㎡.
Compared with prior art, beneficial effects of the present invention are as follows：
（1）Extra electric field can induce acceleration iron displacement copper reaction speed；
（2）Extra electric field can make iron replace copper reaction not in iron surface generation, reclaim high-purity copper product；
（3）Extra electric field iron displacement process for copper septation electrolysis installation can be greatlyd save and prepare oxidation during poly-ferric chloride
The consumption of agent.
（4）Extra electric field induces iron displacement process for copper to have, and acidic etching waste liquid treating capacity is big, processing cost is low, waste liquid is complete
Portion's resource talks about the outstanding advantages such as recovery, zero-emission.
Brief description of the drawings
Fig. 1 is present invention process flow chart.
Fig. 2 is present invention process schematic diagram.
Specific embodiment
So that day processes 30 tons of acidic etching waste liquids as an example, by content of copper ion for the acid etching of 110g/L~140g/L is given up
Liquid pump enters in iron displacement copper electrolysis cells, and electrolysis additive is added by weight proportion, and the addition of electrolysis additive is acid etching
The 0.01%~0.03% of waste liquid amount, opens the electrolysis of dc source low current density, and open the circulation pump；
Appropriate scrap iron is added in anode frame to iron displacement copper electrolysis cells, the content of copper ion according to acidic etching waste liquid is first high
Current density electrolysis, current density is 400A/ ㎡~700A/ ㎡, when copper ion concentration is reduced to 20g/L or so, by waste liquid
Another iron displacement copper electrolysis cells are pumped into, regulation cathode-current density is electrolysed for low current density, and the current density of electrolysis is
100A/ ㎡~400A/ ㎡.Copper ion concentration≤0.1g/L into acidic etching waste liquid.
The low current density of the high current density electrolysis of iron displacement copper electrolysis cells keeps acid etching to give up in electrolytic process
Liquid is circulated in iron displacement copper electrolysis cells with circulating slot, improves electricity effect, reduces the iron displacement copper reaction time, and acidic etching waste liquid exists
It is 500L/h~3000L/h that iron replaces copper electrolysis cells with the circular flow in circulating slot.
Iron content waste liquid after electrolysis is pumped into diaphragm cell, by weight proportion add electrolysis additive B, regulation enter every
The flow of iron content waste liquid in membrane electrolysis cells, the flow of acidic etching liquid is 2000L/h~3000L/h, barrier film in diaphragm cell
The addition of electrolysis additive is 0.1%~0.2% in electrolytic cell, the current density of diaphragm cell be adjusted to 500A/ ㎡~
1000A/ ㎡, the redox value of iron content waste liquid is promoted to after 500mv~1000mv in pumping into polymer reactor, diaphragm cell
In iron content waste liquid 60%~80% divalence ferrous ion can be aoxidized, the consumption of polymeric oxygen agent is saved.
Pumped into polymer reactor through the iron content waste liquid after diaphragm electrolysis, appropriate polymerization-stable is added by weight proportion
Agent, polymeric oxygen agent, polymerisation for a period of time, add acid or alkali to adjust the basicity of poly-ferric chloride, obtain byproduct
Poly ferric chloride flocculant agent.
Claims (10)
1. it is a kind of reclaim acidic etching liquid in copper technique, it is characterised in that specific steps include：
S1. by acidic etching waste liquid by circulating slot pump into iron displacement copper electrolysis cells in, add electrolysis additive A, open direct current
Source is electrolysed, and open the circulation pump, acidic etching waste liquid is circulated in circulating slot and iron displacement copper electrolysis cells；
S2. under the conditions of applying direct current electric field, the copper ion directional migration in induction acidic etching liquid replaces copper electrolysis cells to iron
In minus plate on there is reduction reaction, obtain copper products, scrap iron is oxidized to divalence ferrous ion in anode titanium frame；
S3. the iron content waste liquid after the recovered copper of acidic etching waste liquid is aoxidized into diaphragm cell, adds electrolysis additive B, two
Valency ferrous ion is oxidized to ferric ion；
S4. pumped into polymer reactor through the iron content waste liquid after diaphragm electrolysis, add polymerization stabilizer to occur with polymeric oxygen agent
Reaction, then adjusts the basicity of polymer in mixed liquor with acid or alkali, finally prepares byproduct condensation chlorination ferric flocculant.
2. technique according to claim 1, it is characterised in that the current density of the dc source is according to acidic etching waste liquid
Content of copper ion determine, when content of copper ion is high, first high current density electrolysis, current density be 400A/ ㎡~700A/ ㎡；
When copper ion concentration is reduced to 20g/L or so, regulation cathode-current density is electrolysed for low current density, the current density of electrolysis
It is 100A/ ㎡~400A/ ㎡, copper ion concentration≤0.1g/L into acidic etching waste liquid；The temperature of acidic etching waste liquid should be protected
Hold at 20 DEG C~35 DEG C.
3. technique according to claim 1, it is characterised in that the polymerization stabilizer is sodium phosphate, ammonium phosphate, dibastic sodium phosphate
In one or two, the polymeric oxygen agent be sodium chlorate.
4. technique according to claim 1, it is characterised in that the electrolysis additive A is sodium polydithio-dipropyl sulfonate
（SPS）, polyethylene glycol (PEG) mixture, by weight add, its addition for acidic etching waste liquid amount 0.01%~
0.03%；The electrolysis additive B main components are thiocarbamide.
5. technique according to claim 1, it is characterised in that the diaphragm cell current density be adjusted to 500A/ ㎡~
1000A/㎡。
6. the system and device of technique described in claim 1, it is characterised in that including two circulating slots, at least two iron displacement copper
Electrolytic cell, diaphragm cell, polymer reactor；The circulating slot, iron displacement copper electrolysis cells, diaphragm cell, polymer reactor
Contact successively, middle setting waste liquid buffer container, the iron replaces copper electrolysis cells built-in anode and negative electrode；The diaphragm cell
Multiple anode chambers and cathode chamber are divided into by a kind of anionic membrane.
7. system and device according to claim 6, it is characterised in that the iron displacement copper electrolysis cells are using copper sheet as the moon
Pole, titanium frame is used as anode.
8. system and device according to claim 7, it is characterised in that the anode is arranged in a crossed manner with cathode separation 6cm-8cm.
9. system and device according to claim 7, it is characterised in that the anode titanium frame is the titanium sheet or titanium net of surface drilling
The closed-in construction being welded into, the solution in electrolytic cell can pass freely through the hole on anode titanium frame, wherein being placed with scrap iron.
10. system and device according to claim 6, it is characterised in that the diaphragm cell anode chamber is placed with noble metal
Coating titanium sheet, cathode chamber is put into titanium sheet.
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| CN114606537A (en) * | 2022-03-01 | 2022-06-10 | 大连崇达电子有限公司 | Method for extracting copper from organic acid super-coarsening waste liquid through electrolysis |
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Application publication date: 20170623 Assignee: Xuzhou Dongqi electromechanical Co.,Ltd. Assignor: XUZHOU GEILI MAGNETIC INDUSTRY CO.,LTD. Contract record no.: X2022320000015 Denomination of invention: A process and system device for recovering copper from acid etching solution Granted publication date: 20180821 License type: Exclusive License Record date: 20220118 |