CN107245580A - It is a kind of to clean the effective method that copper, tin and iron are separated and recovered from from spent acidic etching solution - Google Patents
It is a kind of to clean the effective method that copper, tin and iron are separated and recovered from from spent acidic etching solution Download PDFInfo
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- CN107245580A CN107245580A CN201710316396.4A CN201710316396A CN107245580A CN 107245580 A CN107245580 A CN 107245580A CN 201710316396 A CN201710316396 A CN 201710316396A CN 107245580 A CN107245580 A CN 107245580A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
-
- 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
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- 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
Abstract
It is a kind of to clean the effective method that copper, tin and iron are separated and recovered from from spent acidic etching solution, belong to heavy metal processing and separation and recovery field.Multistage MFCs is made up of three MFCs units, multistage MFCs anode electrode attachment electro-chemical activity biomembrane；Anode water inlet is the mixed solution containing organic carbon source and microbial nutrient solution.Spent acidic etching solution containing Sn (II), Fe (II) and Cu (II) is by except tin and except iron MFCs unit bottoms generate stannous hydroxide and/or stannic hydroxide and ferric hydroxide precipitate is able to reclaim and separated, and Cu (II) is reduced recovery on copper removal MFCs negative electrodes.The present invention proposes the organic sewages such as a kind of spent acidic etching solution and municipal administration of the processing simultaneously containing Sn (II), Fe (II) and Cu (II) and separates and recovers the new method of heavy metal therein and energy, has expanded multistage MFCs application field and has used scope；While process by-product electric energy, clean environment firendly.
Description
Technical field
The invention belongs to heavy metal processing and separation and recovery field, more particularly to multistage microbiological fuel cell is from spent acidic
Step is separated and recovered from tin, iron and copper in printed substrate etching solution.
Background technology
Production with the improvement of people ' s living standards with a large amount of electronic products, use and regenerate, generate and largely contain
Sn (II), Fe (II) and Cu (II) acidic etching waste liquid.These discharging of waste liquid cause serious environment into environment, not only
Pollution, and result in the significant wastage of metals resources.Therefore, the processing of such waste liquid is asked with reclaiming not only solution environmental pollution
Topic, and the recycling of price product is realized, have environment, economic and social benefit (Hydrometallurgy 70 concurrently
(2003)23-29；Green Chem 17(2015)3979-3991；Green Chem 17(2015)4418-4431；Environment work
Journey 22 (2004) 75-77).Currently, the processing of acidic waste etching liquid is mainly chemical, physically or electrically chemical with metal recovery processes
It is combined method, such as metal replacement method (CN91100122.0；CN201010189919.1；Plating and 9 (1989) 44- of environmental protection
46), solvent extraction (CN201310174581.6；CN201510335589.5；CN201410016262.7), electrolysis
(CN201310554271.7；CN201610639169.0；CN201510293669.9；CN201410530489.3), interior crystallization
(CN201510815459.1), pyrolysismethod (CN201310554271.7) and the precipitation method (CN201020658781.0；
CN200910030842.0；New Technologies 1 (1993) 41-42) etc..These methods not only there is reagent to consume big, energy consumption
The shortcomings of height, secondary pollution, and the single metallic copper in useless etching solution has only been reclaimed, other metals such as tin, iron are not made
Consider.Although (Green Chem 17 (2015) 3979-3991 such as Swain；Green Chem17 (2015) 4418-4431) profit
Reclaim (the Resour Conserv Recy 20 such as indium metal in spent etching solution, molybdenum, tin and copper, Scott step by step with liquid-liquid extraction
(1997) 43-55) according to chemistry-electrochemical principle by aqua oxidation tin precipitate, electrochemistry separate and reclaim step by step tin, copper and
Lead, but these processes need to consume a large amount of organic solvents, or a large amount of highly basic are consumed, cause secondary pollution；Meanwhile, process power consumption
High, cumbersome complexity.Therefore, seek effective cleaning, the low energy consumption separation from spent acidic etching solution and reclaim tin, iron
And copper technology, as focus of concern.
Microbiological fuel cell (Microbial Fuel CElls, MFCs) rise, will have using microorganism in recent years
Chemical energy in machine sewage is converted into electric energy and/or generates the new technology of reproducibility product simultaneously, with clean environment firendly, simply easily
The characteristics of row and efficient stable.MFCs is main by anode chamber, anode electrode, cathode chamber, cathode electrode, PEM and extrernal resistance
Constitute (Fig. 2).Currently, people carried out extensively single MFCs, apply the single microorganism electrolytic cell of external pressure, multistage MFCs, with
And MFCs and microorganism electrolysis cell combination research, for recovery metal include Cu (II), Ag (I), Zn (II), Hg (II), Cd
(II), the single metal such as Cr (VI) and Cd (II) (CN201310345579, Environ Sci Technol 44 (2010)
4376-4381；Appl Energy 112(2013)1337-1341；Bioresour Technol 102(2011)6304-
6307；J PowerSources 273(2015)1103-1113)；Inter J Hydrogen Energy 41(2016)
13368-13379) and hybrid metal Cu (II) and Ni (II) (FrontEnvironSciEng 9 (2015) 522-527), Cu
And Cd (II) (CN201410669734.9 (II)；Bioresour Technol 200(2016)565-571)、Cu(II)、Co
And Li (I) (SepPurifTechnol 147 (2015) 114-124), Cr (VI), Cu (II) and Cd (II) (Environ (II)
Sci Technol 49(2015):9914-9924), Pb (II), Zn (II), Cu (II) and Ni (II) (J HazardMater
235-236 (2012) 291-297) etc..However, these bio-electrochemical process for reclaiming metal are the oxygen using different metal
Change reduction potential difference deposited metal on electrode could reclaim metal, it is necessary to scrape electrode, so add subsequent treatment into
This.In addition, when hybrid metal material sequentially enters multistage reactor unit, with the solution chemistry such as pH and electricity of reactor unit
The change of conductance etc., different metal component is different in the deposition of same unit, so that different reactor unit is to same
The separation efficiency of metal is different.Accordingly, optimize and regulate and control sedimentary condition (pH, time of the different metal component in same unit
Deng), high effective deposition and the separation of hybrid metal can be achieved.According to the thought, the processing of waste water is etched with returning with reference to current acid
The state of the art is received, overcomes above-mentioned multi-stage biological electrochemical reactor to separate and recover the technical bottleneck of metal, will be expected to develop one
Plant the multistage MFCs technologies that efficient process separates and recovers tin, iron and copper in acid etching waste water with step.
The technical principle of the present invention is as follows：Air cathode MFCs by electron acceptor of oxygen occurs instead in acid condition
Answer (formula 1), catholyte pH is constantly raised；And Sn (OH)2、Sn(OH)4Solubility product be respectively 1.4 × 10-28With 1.0 × 10-56, generation Sn (OH) under acid etching wastewater conditions2With Sn (OH)4The pH that precipitation needs is 0.79-2.45, is existed less than Fe (II)
Reacted in air cathode MFCs (formula 5) and generate Fe (OH)3The pH 3.10 needed for (formula 6) is precipitated, more below Cu (II) is raw
Into Cu (OH)2PH5.68 needed for precipitation.Therefore, the Sn (II) and Fe (II) in acid etching waste water can respectively using oxygen as
In the MFCs cathode chambers of electron acceptor, by differential responses time/residence time to control continuous elevated catholyte pH, finally
With Sn (OH)2Or Sn (OH)4(formula 2-4) and Fe (OH)3The mode of (formula 5-6) precipitation is reclaimed in different reactor unit bottom.
For Cu (II), because the pH value of solution for removing Sn (II) and Fe (II) is up to 5.14, generation Cu (OH) is still below2Precipitation institute
The pH 5.68 needed, but reclaimed in formula (7) mode in cathodic reduction.Due to reclaiming different metal in different reactor unit,
So that three kinds of metals are able to step separation.
O2+4H++4e﹣=2H2O Eθ=+1.229VSHE (1)
Sn2++2H2O=Sn (OH)2↓+2H+ Ksp=1.4 × 10﹣ 28 (2)
2Sn2++O2+4H+=2Sn4++2H2O (3)
Sn4++4H2O=Sn (OH)4↓+4H+Ksp=1.0 × 10﹣ 56 (4)
4Fe2++4H++O2=4Fe3++2H2O (5)
Fe3++3OH﹣=Fe (OH)3↓ Ksp=2.8 × 10﹣ 39 (6)
Cu2++2e﹣=Cu (s) Eθ=+0.340VSHE(7)
The content of the invention
The invention provides one kind, using multistage MFCs, the step from spent acidic etching solution separates and reclaimed tin, iron and copper
Method.The chemical conversion of Sn (II) and Fe (II) in air cathode MFCs and different pH responsiveness are utilized, are existed respectively
Different air cathode MFCs unit bottoms are with Sn (OH)2And/or Sn (OH)4Precipitation, Fe (OH)3Precipitation separation and recovery tin and iron；
And Cu (II) is then reduced recovery in anaerobism MFCs negative electrodes, so as to realize separation and the recovery step by step from spent acidic etching solution
The purpose of tin, iron and copper.
Technical scheme：
Spent acidic etching solution containing Sn (II), Fe (II) and Cu (II) initially enters one-level MFCs cathode chambers, one-level
MFCs copper removals or tin；First-stage reactor water outlet is pumped into two grades of MFCs cathode chambers, and two grades of MFCs remove tin, iron or copper；Second reactor
Water outlet is pumped into three-level MFCs cathode chambers, and three-level MFCs removes iron or copper.The multistage MFCs combinations built accordingly have three kinds：Remove
Copper-except tin-- removes iron-copper removal and except tin-copper removal-except iron, except tin and removes iron (Fig. 1).Each MFCs units include anode chamber,
Anode electrode, cathode chamber, cathode electrode, amberplex and extrernal resistance, each MFCs units are through external resistance and Data Collection system
System is connected；Described amberplex is anion-exchange membrane.The anode electrode of each MFCs units is carbon-point, carbon cloth, carbon
The carbon material such as grain or carbon felt, for except tin, except iron MFCs negative electrode is carbon cloth material, polytetrafluoroethyl-ne to be scribbled towards the side of air
Alkene allows a certain amount of air to enter while preventing water from revealing, and scribbles carbon dust towards the side of solution, cathode electrode passes through
Titanium wire is exported；Cathode electrode for copper removal MFCs is the carbon materials such as carbon-point, carbon cloth, carbon granules, carbon felt or stainless (steel) wire, titanium sheet etc.
Metal material.All MFCs units are connected through extrernal resistance with data gathering system.Multistage MFCs catholyte water inlet composition be containing
Sn (II), Fe (II) and Cu (II) spent acidic etching solution, each tenor are 1~50000mg/L；Initial pH value is 0.0
~2.0；Catholyte electrical conductivity is 0.8~20.0mS/cm；Cathode potential is -0.10~0.60V.By organic carbon source and microorganism
Nutrient solution injection multistage MFCs all anode chambers, the initial pH of anode chamber is 7.0~8.0, and electrical conductivity is 1.0~2.0mS/
Cm, COD is 100~1000mg/L；Anode potential is -0.30~0.00V.
Described external resistance is 1~1000 Ω.
The composition of MFCs anolytes is：12.0mM sodium acetates；2.9mM(NH4)2SO4；0.1mM KH2PO4；Mineral element：
12.5mL/L composition is MgSO4:3.0g/L、MnSO4·H2O:0.5g/L、NaCl:1.0g/L、FeSO4·7H2O:0.1g/L、
CaCl2·2H2O:0.1g/L、CoCl2·6H2O:0.1g/L、ZnCl2:0.13g/L、CuSO4·5H2O:0.01g/L、KAl
(SO4)2·12H2O:0.01g/L、H3BO3:0.01g/L、NiCl2·6H2O:0.024g/L and Na2WO4·2H2O:0.024g/L；
Vitamin:12.5mL/L composition is vitamin B1:5.0g/L, vitamin B2:5.0g/L, vitamin B3:5.0g/L, vitamin
B5:5.0g/L, vitamin B6:10.0g/L, vitamin B11:2.0g/L, biotin:2.0g/L, p-aminobenzoic acid:5.0g/
L, lipoic acid:5.0g/L and aminotriacetic acid:1.5g/L.
Anode chamber's inoculation sewage treatment plant's depositing reservoir sludge is used as the bacterium source for taming electro-chemical activity microorganism.It is described
The pH of depositing reservoir sludge is 7.0~8.0；Electrical conductivity is 1.0~2.0mS/cm；Suspension solid content is 10~20g/L；Chemistry is needed
Oxygen amount is 100~1000mg/L.
The anode chamber of all MFCs units and copper removal MFCs cathode chamber of the present invention needs to keep anaerobic in the process of running
Environment, can be passed through nitrogen to realize anaerobic condition；And except tin MFCs and except in iron MFCs cathode chambers, air passes through polytetrafluoroethyl-ne
Alkene layer enters naturally, also can actively be aerated supply air.
The present invention system operation flow be：Organic matter in anolyte, by microbiological oxidation, is delivered in anode chamber
The electronics of anode electrode imports cathode electrode by external circuit, in except tin reactor, and oxygen is as in electron acceptor and solution
Proton and electron reaction generation water (formula 1), pH value of solution is constantly raised, and Sn (II) and oxidized Sn (IV) (formula 3) are generated
Stannous hydroxide and stannic hydroxide precipitation (formula 2 and 4) are simultaneously deposited on reactor bottom.Iron is removed except the water outlet of tin reactor negative electrode enters
Reactor cathode chamber, Fe (II) is oxidized to Fe (III) (formula 5), and generates ferric hydroxide precipitate (formula 6) with the rise of pH value
And it is deposited on reactor bottom.Except the water outlet of iron reactor negative electrode enters the copper-stripping reaction device cathode chamber of anaerobism, Cu (II) is in electrode
Surface reduction reclaims (formula 7).Due to reclaiming different metal in different reactor unit so that three kinds of metals are able to step point
From.Meanwhile, bottom deposit tin and iron except tin and except iron cathode room also functions to sedimentation basin effect, reduce follow-up separation behaviour
Make.The process while by-product electric energy, reach recycling reclaim and step Separation of Tin, iron and copper effect, with environment and
Ecological, society and economic multiple benefits.
Brief description of the drawings
Fig. 1 is that the recovery of the present invention separates the multistage MFCs process charts of tin, iron and copper in acidic etching solution.
Fig. 2 be the present invention except tin-remove iron-copper removal mode under recovery separation acidic etching solution in tin, iron and copper
Multistage MFCs structural representations.
Fig. 3 is the multistage MFCs of embodiment 1 tin, iron and copper removal rate.
Fig. 4 is the multistage MFCs of embodiment 1 tin, iron and copper separation.
Fig. 5 is the multistage MFCs of embodiment 1 negative electrode water inlet and water outlet pH.
Fig. 6 is the water inlet of multistage MFCs negative electrodes and the water outlet conductivity of embodiment 1.
Fig. 7 is the multistage MFCs average currents of embodiment 1.
Fig. 8 is the multistage MFCs anode potentials and cathode potential of embodiment 1.
In figure：1 anode chamber；2 reference electrodes；3 anode carbon electrodes；4 anion-exchange membranes；
5 external resistances；The acidic etching liquid water inlet of 6 stanniferous, iron and copper；7 peristaltic pumps；8 negative electrode carbon cloth electrodes；
9 anode carbon felt electrodes；10 cathode chambers；11 sample points；12 nitrogen；13 negative carbon electrodes；
14 water outlets.
Embodiment
Below in conjunction with accompanying drawing and technical scheme, the embodiment of the present invention is further illustrated.
Embodiment 1
Step one：Three MFCs reactor units are built, as shown in Figure 2：MFCs anode chambers and cathode chamber are organic glass
Glass material, anode chamber's effective volume is 13mL, and cathode chamber effective volume is 25mL, with anion-exchange membrane (AEM-7000)
Separate.
Step 2：Carbon felt 9 is placed in each reactor anode chamber；By carbon-point 3 and 13 be placed in each reactor anode chamber and
Copper removal MFCs cathode chambers, respectively as respective anode electrode and cathode electrode；Carbon cloth 8 is coated into four stratas towards air side
Tetrafluoroethene, the opposite side of carbon cloth 8 scribbles carbon dust, and respectively as except tin, except iron MFCs negative electrodes, its effective area is 7.1cm2,
Wire is used as using titanium silk.Anode carbon felt is 1.0cm × 1.0cm × 1.0cm fritter；Carbon-point size is0.8cm×L:7cm。
Reference electrode 2 is accessed in each reactor anode chamber, the dispatch from foreign news agency of each MFCs units is collected by computer and data collecting system
The voltage and calculating current of resistance 5；The anode and cathode potential of each MFCs unit are collected according to reference electrode.
Step 3：Deionized water is added in cathode chamber.
Step 4：Anodic dissolution is prepared, it is constituted as described in previous technique scheme.Anolyte is exposed into 15~20min of nitrogen
After access each reactor anode chamber, while be inoculated with sewage treatment plant depositing reservoir sludge 10g after seal.
Step 5：Device is placed under room temperature (20~25 DEG C) and tames and runs.When electric current drops to below 0.01mA,
A cycle is completed, and adds above-mentioned medium component.When continuous three cycle output voltage stabilizations are in similar value, show
Anode electrochemical active bacteria is tamed and started successfully.
Step 6：Solution is configured with copper chloride, stannous chloride and frerrous chloride, makes wherein Sn (II), Fe (II) and Cu
(II) concentration is respectively 80mg/L, 40mg/L and 60mg/L；Regulation electrical conductivity of solution is 4.0mS/cm, and pH is 2.0.
Step 7：Copper removal MFCs cathode chambers are pumped into after step 6 solution is exposed into 15~20min of nitrogen, are transported in copper removal MFCs
Row 12h；Copper removal MFCs cathode chamber water outlets are pumped into except tin MFCs cathode chambers, 4h is run in except tin MFCs；Tin MFCs will be removed
Cathode chamber water outlet is pumped into except iron MFCs cathode chambers, and 8h is run in except iron MFCs.
Step 8：Step 6 solution is pumped into except tin MFCs cathode chambers, 4h is run in except tin MFCs；XiMFCsYin will be removed
Pole room water outlet is pumped into except iron MFCs cathode chambers, and 8h is run in except iron MFCs；Nitrogen 15 will be exposed except the water outlet of iron MFCs cathode chambers
Copper removal MFCs cathode chambers are pumped into after~20min, 12h is run in copper removal MFCs.
Step 9：Step 6 solution is pumped into except tin MFCs cathode chambers, 4h is run in except tin MFCs；XiMFCsYin will be removed
Pole room water outlet is pumped into copper removal MFCs cathode chambers after exposing 15~20min of nitrogen, and 12h is run in copper removal MFCs；By copper removal MFCs
Cathode chamber water outlet is pumped into except iron MFCs cathode chambers, and 8h is run in except iron MFCs.
Step 10：Respectively the solution of determination step six and Step 7: in eight and nine MFCs units at different levels catholyte water outlet
Total copper, tin and concentration of iron, respectively calculate except tin MFCs, except the tin clearance (α in iron MFCs and copper removal MFCsSn,Sn、αFe,Sn、
αCu,Sn, %), iron clearance (αSn,Fe、αFe,Fe、αCu,Fe, %), copper removal rate (αSn,Cu、αFe,Cu、αCu,Cu, %), and each reaction
Device unit removes separation (ε of the metal target relative to other metalsCu、εSn、εFe)。
This example implements multistage MFCs and reclaims tin, iron and the copper separated in spent acidic etching solution.Due to each reactor list
PH, electrical conductivity, concentration of metal ions and the reaction time of first catholyte are different, therefore equal to the recovery separating effect of tin, iron and copper
It is different.αSn,Cu、αSn,Sn、αSn,Fe、αFe,Cu、αFe,Sn、αFe,Fe、αCu,Cu、αCu,Sn、αCu,FeAnd εCu、εSn、εFeCalculating such as formula (8)-
(19) shown in.
In formula：CSn,Cu,0With CSn,Cu,f、CSn,Sn,0With CSn,Sn,fAnd CSn,Fe,0With CSn,Fe,f：Respectively except tin MFCs is mono-
Member water inlet and the total copper of water outlet, total tin and total concentration of iron (g/L)；CFe,Cu,0With CFe,Cu,f、CFe,Sn,0With CFe,Sn,fAnd CFe,Fe,0With
CFe,Fe,f：Respectively except the water inlet of iron MFCs units and the total copper of water outlet, total tin and total concentration of iron (g/L)；CCu,Cu,0With CCu,Cu,f、
CCu,Sn,0With CCu,Sn,fAnd CCu,Fe,0With CCu,Fe,f：The respectively water inlet of copper removal MFCs units and the total copper of water outlet, total tin and total iron
Concentration (g/L).
As a result：In multistage MFCs three kinds of combinations, copper can reach to be removed and reclaims completely.The removal of tin and iron
It is respectively 90.2 ± 0.1% and 78.9 ± 0.4% (Fig. 3) that rate is in (the first) copper removal to be removed under iron order-except tin-；(second
Kind) except tin-except iron-copper removal order under be respectively 87.4 ± 0.1% and 76.1 ± 0.2% (Fig. 3)；(the third) except tin-
Copper removal-except respectively 90.1 ± 0.1% and 77.1 ± 1.3% (Fig. 3) under the order of iron.Correspondingly, tin is in above-mentioned three kinds combinations
Under the conditions of separation be respectively 0.87 ± 0.05,47.02 ± 4.74 and 48.18 ± 5.42；And the separation of iron and copper
Respectively 0.84 ± 0.02,3.76 ± 0.18 and 0.70 ± 0.06 and 7.38 ± 0.29 ,+∞ (copper is kept completely separate) and 3.92
± 0.21 (Fig. 4).Initial inlet flow-patterm under three kinds of combinations is 2.00 ± 0.03, under above-mentioned first way, water outlet pH
Rise to 2.33 ± 0.02,4.05 ± 0.03 and 5.82 ± 0.01 (Fig. 5) successively, electrical conductivity drops to 3.08 ± 0.02 successively,
1.76 ± 0.04 and 1.08 ± 0.01mS/cm (Fig. 6)；Under the above-mentioned second way, water outlet pH rises to 2.83 ± 0.02 successively,
4.94 ± 0.01 and 5.40 ± 0.01 (Fig. 5), electrical conductivity drops to 2.93 ± 0.05,2.01 ± 0.04 and 1.13 successively ±
0.06mS/cm (Fig. 6)；Under the third above-mentioned mode, water outlet pH rises to 2.83 ± 0.02,3.14 ± 0.01 and 5.60 successively ±
0.01 (Fig. 5), electrical conductivity drops to 2.92 ± 0.02,1.56 ± 0.04 and 1.09 ± 0.06mS/cm (Fig. 6) successively.Three kinds of groups
Each reactor unit anode potential under conjunction mode is stablized at -0.20 ± 0.02V (Fig. 8).Under first way, each unit
Current density is followed successively by 0.25 ± 0.01A/m2、0.38±0.02A/m2With 0.25 ± 0.02A/m2(Fig. 7), cathode potential difference
For -0.03 ± 0.02V, 0.10 ± 0.01V and 0.07 ± 0.01V (Fig. 8)；Under the second way, the current density of each unit according to
Secondary is 0.53 ± 0.04A/m2、0.42±0.07A/m2With 0.15 ± 0.00A/m2(Fig. 7), cathode potential is respectively 0.18 ±
0.04V, 0.09 ± 0.05V and -0.11 ± 0.00V (Fig. 8)；Under the third mode, the current density of each unit is followed successively by 0.53
±0.00A/m2、0.20±0.00A/m2With 0.28 ± 0.03A/m2(Fig. 7), cathode potential is respectively 0.18 ± 0.05V, -0.09
± 0.00V and 0.07 ± 0.01V (Fig. 8).
Test result indicates that：1) except tin-except the multistage MFCs units combination of iron-copper removal is more conducive to the ladders of three kinds of metals
Level separation is with reclaiming (Fig. 4)；2) with the progress of reaction, due to oxygen and electronics and hydrogen ion reaction (formula 1), solution is caused
PH constantly rise (Fig. 5), steeply rising for pH provides advantage for the hydrolytic precipitation of tin and iron, makes Sn (II) and Fe
(II) (formula 2,4 and 6) is precipitated with stannous hydroxide, stannic hydroxide and iron hydroxide form, so that under electrical conductivity of solution is continuous
Drop (Fig. 6)；3) except tin and except the current density and cathode potential of iron MFCs units are apparently higher than copper removal MFCs units (Fig. 7 and 8),
Show that the former aerobic conditions are more conducive to the electric energy output of respective reaction device unit than the anaerobic condition of the latter；4) with reaction
Carry out, current density and cathode potential are (Fig. 7 and 8) on a declining curve, and main cause is the progress with reaction, electrical conductivity of solution
Decline (Fig. 6), system internal resistance rises, cause current density and cathode potential to decline.
To sum up, effectively step separates and reclaimed spent acidic etching solution to multistage MFCs systems under conditions of by-product electric energy
In tin, iron and copper, only the processing of spent acidic etching solution and recycling do not provide effective ways, and have expanded multistage
MFCs application field and use scope.Whole process cleanliness without any pollution, has environment and ecological benefits, social benefit and economy concurrently
Benefit.
Claims (10)
1. a kind of clean the effective method that copper, tin and iron are separated and recovered from from spent acidic etching solution, it is characterised in that step
It is rapid as follows：
Described method uses multistage MFCs combinations, and specially three MFCs units are completed jointly, and each MFCs units are equal
Including anode chamber, anode electrode, cathode chamber, cathode electrode, amberplex and extrernal resistance, each MFCs units through external resistance with
Data gathering system is connected；Described amberplex is anion-exchange membrane；
The spent acidic etching solution that Sn (II), Fe (II) and Cu (II) will be contained passes through the moon that intake pump injects one-level MFCs units
Pole room, one-level MFCs units copper removal or tin；First-stage reactor water outlet enters two grades of MFCs cathode chambers, two grades of MFCs units except tin,
Iron or copper；Second reactor water outlet enters three-level MFCs cathode chambers, and three-level MFCs units remove iron or copper；The multistage built accordingly
MFCs combinations have three kinds：Copper removal-except tin-- removes iron-copper removal and except tin-copper removal-except iron, except tin and removes iron, gone according to above-mentioned
Except MFCs units at different levels of sequentially arranging；The anode electrode of all MFCs units is carbon material；Except tin and except the MFCs negative electrodes of iron
Electrode is carbon cloth material, and polytetrafluoroethylene (PTFE) is scribbled towards the side of air, and carbon dust is scribbled towards the side of solution, and cathode electrode leads to
Cross titanium wire export；The MFCs cathode electrodes of copper removal are carbon material or metal material；
The described spent acidic etching solution containing Sn (II), Fe (II) and Cu (II), Sn (II), Fe (II) and Cu (II) are in acid
Property useless etching solution in concentration be 1~50000mg/L；Initial pH value is 0~2.0；Catholyte electrical conductivity be 0.8~
20.0mS/cm；Cathode electrode potential is -0.10~0.60V；Anode electrode potential is -0.30~0.00V；
Organic carbon source and microbial nutrient solution are injected to the anode chamber of multistage MFCs units, the initial pH for controlling anode chamber is 7.0
~8.0, electrical conductivity is 1.0~2.0mS/cm, and COD is 100~1000mg/L；Anode potential is -0.30~0.00V.
2. the effective side that copper, tin and iron are separated and recovered from from spent acidic etching solution of cleaning according to claim 1
Method, it is characterised in that multistage MFCs all anode chambers and the cathode chamber of copper removal MFCs units keep anaerobic in the process of running
Environment, is passed through nitrogen to realize anaerobic condition；In the cathode chamber except tin and except iron MFCs units, air passes through polytetrafluoroethylene (PTFE)
Layer enters naturally or actively aeration supplies air.
3. cleaning according to claim 1 or 2 is effectively separated and recovered from copper, tin and iron from spent acidic etching solution
Method, it is characterised in that described carbon material is carbon-point, carbon cloth, carbon granules or carbon felt；Described metal material be stainless (steel) wire or
Titanium sheet.
4. cleaning according to claim 1 or 2 is effectively separated and recovered from copper, tin and iron from spent acidic etching solution
Method, it is characterised in that the resistance of described external resistance is 1~1000 Ω.
5. the effective side that copper, tin and iron are separated and recovered from from spent acidic etching solution of cleaning according to claim 3
Method, it is characterised in that the resistance of described external resistance is 1~1000 Ω.
6. the cleaning according to claim 1,2 or 5 is effectively separated and recovered from copper, tin and iron from spent acidic etching solution
Method, it is characterised in that the composition of microbial nutrient solution is in described anode chamber：12.0mM sodium acetates；2.9mM(NH4)2SO4；0.1mM KH2PO4；Mineral element：12.5mL/L composition is MgSO4:3.0g/L、MnSO4·H2O:0.5g/L、NaCl:
1.0g/L、FeSO4·7H2O:0.1g/L、CaCl2·2H2O:0.1g/L、CoCl2·6H2O:0.1g/L、ZnCl2:0.13g/L、
CuSO4·5H2O:0.01g/L、KAl(SO4)2·12H2O:0.01g/L、H3BO3:0.01g/L、NiCl2·6H2O:0.024g/L
And Na2WO4·2H2O:0.024g/L；Vitamin:12.5mL/L composition is vitamin B1:5.0g/L, vitamin B2:5.0g/L、
Vitamin B3:5.0g/L, vitamin B5:5.0g/L, vitamin B6:10.0g/L, vitamin B11:2.0g/L, biotin:2.0g/
L, p-aminobenzoic acid:5.0g/L, lipoic acid:5.0g/L and aminotriacetic acid:1.5g/L.
7. the effective side that copper, tin and iron are separated and recovered from from spent acidic etching solution of cleaning according to claim 3
Method, it is characterised in that the composition of microbial nutrient solution is in described anode chamber：12.0mM sodium acetates；2.9mM(NH4)2SO4；
0.1mM KH2PO4；Mineral element：12.5mL/L composition is MgSO4:3.0g/L、MnSO4·H2O:0.5g/L、NaCl:1.0g/
L、FeSO4·7H2O:0.1g/L、CaCl2·2H2O:0.1g/L、CoCl2·6H2O:0.1g/L、ZnCl2:0.13g/L、CuSO4·
5H2O:0.01g/L、KAl(SO4)2·12H2O:0.01g/L、H3BO3:0.01g/L、NiCl2·6H2O:0.024g/L and
Na2WO4·2H2O:0.024g/L；Vitamin:12.5mL/L composition is vitamin B1:5.0g/L, vitamin B2:5.0g/L, dimension
Raw element B3:5.0g/L, vitamin B5:5.0g/L, vitamin B6:10.0g/L, vitamin B11:2.0g/L, biotin:2.0g/L、
P-aminobenzoic acid:5.0g/L, lipoic acid:5.0g/L and aminotriacetic acid:1.5g/L.
8. the effective side that copper, tin and iron are separated and recovered from from spent acidic etching solution of cleaning according to claim 4
Method, it is characterised in that the composition of microbial nutrient solution is in described anode chamber：12.0mM sodium acetates；2.9mM(NH4)2SO4；
0.1mM KH2PO4；Mineral element：12.5mL/L composition is MgSO4:3.0g/L、MnSO4·H2O:0.5g/L、NaCl:1.0g/
L、FeSO4·7H2O:0.1g/L、CaCl2·2H2O:0.1g/L、CoCl2·6H2O:0.1g/L、ZnCl2:0.13g/L、CuSO4·
5H2O:0.01g/L、KAl(SO4)2·12H2O:0.01g/L、H3BO3:0.01g/L、NiCl2·6H2O:0.024g/L and
Na2WO4·2H2O:0.024g/L；Vitamin:12.5mL/L composition is vitamin B1:5.0g/L, vitamin B2:5.0g/L, dimension
Raw element B3:5.0g/L, vitamin B5:5.0g/L, vitamin B6:10.0g/L, vitamin B11:2.0g/L, biotin:2.0g/L、
P-aminobenzoic acid:5.0g/L, lipoic acid:5.0g/L and aminotriacetic acid:1.5g/L.
9. the cleaning according to claim 1,2,5,7 or 8 is effectively separated and recovered from copper, tin from spent acidic etching solution
With the method for iron, it is characterised in that described anode chamber's inoculation sewage treatment plant's depositing reservoir sludge is used as domestication electro-chemical activity
The bacterium source of microorganism；The pH of described depositing reservoir sludge is 7.0~8.0；Electrical conductivity is 1.0~2.0mS/cm；Suspension solid
Thing:10~20g/L；COD is 100~1000mg/L.
10. the effective side that copper, tin and iron are separated and recovered from from spent acidic etching solution of cleaning according to claim 6
Method, it is characterised in that described anode chamber's inoculation sewage treatment plant's depositing reservoir sludge is used as domestication electro-chemical activity microorganism
Bacterium source；The pH of described depositing reservoir sludge is 7.0~8.0；Electrical conductivity is 1.0~2.0mS/cm；Suspension solid content:10~
20g/L；COD is 100~1000mg/L.
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