CN105624408A - Method for separating and recovering tin, copper and iron from waste tinned copper-clad iron pins - Google Patents

Method for separating and recovering tin, copper and iron from waste tinned copper-clad iron pins Download PDF

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CN105624408A
CN105624408A CN201610212724.1A CN201610212724A CN105624408A CN 105624408 A CN105624408 A CN 105624408A CN 201610212724 A CN201610212724 A CN 201610212724A CN 105624408 A CN105624408 A CN 105624408A
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copper
tin
anode
iron
concentration
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CN105624408B (en
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杨建广
陈冰
李树超
史伟强
吕元录
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Central South University
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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
    • C22B7/007—Wet processes by acid leaching
    • 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
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C22B15/0069—Leaching or slurrying with acids or salts thereof containing halogen
    • 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
    • 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
    • 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
    • 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
    • C25C1/14—Electrolytic production, recovery or refining of metals by electrolysis of solutions of tin
    • 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
    • C25C7/04—Diaphragms; Spacing elements
    • 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

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Abstract

The invention discloses a method for separating and recovering tin, copper and iron from waste tinned copper-clad iron pins. The method can implement clean high-efficiency full-dose recovery on abundant waste tinned copper-clad iron pins produced by electronic processing industry, implements technical-process closed circulation, well solves the common problems of high energy consumption, low metal recovery rate, difficulty in comprehensive recovery of valuable metals, heavy pollution and the like in the traditional waste tinned copper-clad iron pin process, and has the outstanding advantages of simple process, high metal recovery rate, high cleanness and environment friendliness.

Description

The method of a kind of Separation and Recovery tin, copper, iron from useless zinc-plated bag copper iron pin
Technical field
The present invention relates to the method for a kind of Separation and Recovery tin, copper, iron from useless zinc-plated bag copper iron pin, belong to resource recovery field.
Background technology
In the electronics industry, tin is plated in copper surface and can play a very good protection, and meanwhile, can strengthen the welding property of plated body, and therefore, the consumption of tin constantly increases, and just creates large amounts of zinc-plated copper junk in production and application end. In addition, the industry development such as electronics and communication, automobile, electric wire is swift and violent in recent years, and in production process, the zinc-plated waste material of zinc-plated leftover bits and model change output increases day by day, every year this kind of waste material nearly 60��700,000 t. Useless zinc-plated copper pin is generally containing copper 91.0%��96.5%, tin 1.5%��3.0%. In recent years, for reducing the consumption of copper in zinc-plated copper product further, the copper core in original zinc-plated copper pin is replaced by iron in a large number, forms the three-decker of tin bag copper-Bao Tie, usually containing tin 3.0%��6.5%, copper 4.5%��7.5%, iron 85%��92%.
Not yet have at present and realize wherein tin, copper and iron for useless zinc-plated bag copper iron pin and entirely measure the report of recovery. The method of existing open report mainly concentrates in the process of useless zinc-plated copper pin, and the technique of report mainly contains fire method electrolytic process, electrochemical process and chemical method etc. Fire method electrolytic process does not reclaim tin in advance, but zinc-plated waste cupron is used as a kind of copper junk, add copper anode furnace, oxidation-reduction smelting be cast into positive plate, cathode copper is produced through electrorefining, this technique fails to realize the efficient recovery of tin because a large amount of tin enters slag, when furnace charge is containing tin height, and by the tin in positive plate except to being less than 0.2% to meet the needs of electrorefining, energy consumption is big, production cost height. Electrochemical process can not corrode Copper substrate, and can reclaim spongy tin, and after washing, melting removal of impurities can obtain the tin of 99.9%. Chemical method is that zinc-plated waste cupron is placed in acidic solution, utilizes the oxygenant separating copper such as copper sulfate or hydrogen peroxide, tin, reaches the effect reclaiming copper. Electrochemical process and chemical method can realize the efficient recovery of tin, but the waste cupron after detin can only be worked as copper scap and sold or enter after copper anode furnace pyrorefining electrorefining again; In addition, in order to the tin in high efficiente callback waste material and copper, now mostly adopt detin in advance, then reclaim the method for copper. Such as, Chinese patent 01132612.3 provides one " method of separate recovery of copper and tin from electroplated copper wastes and anodic drum device ", take sulfuric acid as electrolytic solution, control certain electrolytic condition, control anode roller rotating speed, realizing being separated of tin and copper, this kind of method shortcoming is detin overlong time, all wants a few hours; The fused salt lixiviation process of " on Copper and its alloy product surface the recovery of slicker solder " that Chinese patent ZL91110456 provides, adopt a certain proportion of NaCl and KCl mixing salt composition molten salt system, 5-15 minute is soaked at the temperature of 720-830 DEG C, can directly reclaiming tin slab, but this method is higher to ingredient requirement, raw material is required dry, simultaneously, energy consumption is higher, and cost is relatively big, and the receipts rate of tin is lower; Chinese patent CN201310418151.4 discloses a kind of method reclaiming tin and copper from useless zinc-plated copper pin: a certain amount of sulfuric acid and water are made into certain density solution, adds a certain amount of useless zinc-plated copper pin; Be heated to required temperature, start drip add hydrogen peroxide; Tin and hydrogen peroxide are obtained by reacting stannic oxide, and stannic oxide and sulfuric acid reaction obtain tin sulphate, and tin sulphate hydrolysis obtains the precipitation of stannic hydroxide; After filtration, filter residue copper wire and tin mud, copper wire is for regenerating Copper making, and tin mud is used for the tin metallurgy of tin smeltery, etc.
Being worth being pointed out that, aforesaid method is all useless zinc-plated copper pin material, because of not iron content in such material, so acid system can be adopted during wet processing to reclaim copper and tin etc. adopting. Or adopt and copper metallurgy material matching during pyrometallurgical smelting, can be it can be used as to drop into copper metallurgy industry recovery copper. And the useless zinc-plated bag copper-Bao Tiezhen of method process according to existing wet method, then owing to wherein iron level is usually above 90%, a large amount of iron will enter solution, bring serious hindrance to the recovery of tin, copper, iron; And the method process according to fire method, then owing to the reason of its iron high-content cannot add copper metallurgy industry. Therefore, the useless zinc-plated copper pin recovery method of existing open report is not all suitable for the useless zinc-plated bag copper iron pin of high Fe content in process present patent application. In view of the electronic waste generation of the three-decker of tin bag copper-Bao Tie increases year by year, the cleaning full amount separation and recovery method developing this type of material a kind of is significant.
Summary of the invention
The problem of the useless zinc-plated bag copper iron pin of process high Fe content all it is not suitable for for the open useless zinc-plated copper pin recovery method reported existing in prior art, it is an object of the invention to be to provide the method for a kind of, making high-efficiency comprehensive Separation and Recovery tin, copper, iron cleaning from useless zinc-plated bag copper iron pin, the method has tin, copper, iron recovery height, technical process is short, simple to operate, cost is low, the advantage of non-environmental-pollution.
The present invention provides the technique of a kind of Separation and Recovery tin, copper, iron from useless zinc-plated bag copper iron pin, and this technique comprises the following steps: the method for a kind of Separation and Recovery tin, copper, iron from useless zinc-plated bag copper iron pin, it is characterised in that, comprise the following steps:
Step one: Selectively leaching tin
Useless zinc-plated bag copper iron pin is placed in SnCl4After carrying out Selectively leaching tin in-HCl-additive system, filtering separation, obtains containing SnCl2Leach liquor and copper Bao Tiezhen leach slag;
Step 2: electricity strengthens reduction and purification
To step one gained containing SnCl2Leach liquor undertaken by anode of tin plate " sacrifice " anode electricity strengthen reduction purification, be purified liquid;
Step 3: outfield coupling barrier film galvanic deposit tin
The scavenging solution obtained using step 2, as electrolytic solution, take noble electrode as negative electrode and anode, and anionic membrane is barrier film, carries out outfield coupling barrier film galvanic deposit tin; After electrolytic deposition completes, obtain electrolysis tin from negative electrode, obtain from anolyte compartment returning the Selectively leaching tin process of step one as oxygenant containing stannic solution containing stannic solution;
Step 4: pulsed electrical field " anode electricity molten-cathode electrodeposition " copper
The copper Bao Tiezhen that step one obtained leaches slag and loads in anode frame, take noble electrode as anode, carries out pulsed electrical field " anode electricity molten-cathode electrodeposition " copper in ammonia system; After pulse electrodeposition completes, obtain negative electrode electricity copper from negative electrode, in anode frame, then obtain de-copper iron pin;
Wherein, additive described in step one is alcamines and the mixture of derivative and nitrogen azole and derivative thereof thereof;
Described anionic membrane is with tetramethoxy-silicane and N-trimethoxy silicon propyl group-N, and N, N-trimethyl ammonium chloride is presoma, is prepared by sol-gel method.
The method of a kind of useless zinc-plated bag copper iron pin Separation and Recovery tin of the present invention, copper, iron also comprises following preferred version:
In preferred scheme, alcamines material be selected from trolamine, tri-isopropanolamine, di-alcohol monoisopropanolamine, monoethanolamine diisopropanolamine (DIPA) or its derivative one or more; Nitrogen azole material is selected from ribavirin, triazole and derivative, imidazoles (1,3-diazole) and pyrazoles (1,2-diazole), 2-mercaptobenzimidazole, 2-amino benzoglyoxaline, 2-tolimidazole, benzoglyoxaline, benzotriazole, mercaptobenzothiazole, 3-ammonia-1, one or more in 2,4-triazole or its derivative.
In preferred scheme, the interpolation concentration of alcamines material or its derivative is 0.1wt%��5.0wt%.
In preferred scheme, the interpolation concentration of nitrogen azole material or its derivative is 0.1wt%��5.0wt%.
In preferred scheme, described ammonia system is NH3-NH4Cl-H2O��NH3-(NH4)2SO4-H2O��NH3-NH4NO3-H2O or NH3-NH4Cl-(NH4)2SO4-H2O, in ammonia system, NH3Concentration is 1��5mol/L, NH4 +Concentration is 2��9mol/L, Cu in system2+Concentration is 3��10g/L.
In preferred scheme, the processing condition of Selectively leaching tin process are: extraction temperature is 25��90 DEG C.
In preferred scheme, the processing condition of Selectively leaching tin process are: in hydrochloric acid system, concentration of hydrochloric acid is 1��8mol L-1��
In preferred scheme, the processing condition of Selectively leaching tin process are: SnCl4Content be that the tin in useless zinc-plated bag copper iron pin is all oxidized to SnCl21��4 times of required theoretical molar amount.
In preferred scheme, current density when electricity strengthens reduction and purification is 1��50A/m2; Reduction temperature is 20��60 DEG C, and solution ph is 0.5��3.
In preferred scheme, anode when electricity strengthens reduction and purification is tin plate, and negative electrode is noble electrode, and anode is 1��10:1 with negative electrode useful area ratio.
In preferred scheme, during the coupling barrier film galvanic deposit tin of outfield, described anionic membrane is that N, N-trimethyl ammonium chloride is presoma, is prepared by sol-gel method with tetramethoxy-silicane and N-trimethoxy silicon propyl group-N;
In preferred scheme, during the coupling barrier film galvanic deposit tin of outfield, outfield is that be coupled common electric field, ultrasonic wave field coupled pulse electric field, pulsed electrical field of ultrasonic wave field is coupled common electric field or single pulsed electrical field.
The ultrasonic frequency of ultrasonic wave field is 10KHz��150KHz.
The pulse-repetition of pulsed electrical field is 50��2000Hz, and dutycycle is 50%��80%, and average pulse current density is 200��600A/m2��
The current density of common electric field is 10A/m2��700A/m2��
In preferred scheme, during the coupling barrier film galvanic deposit tin of outfield, tin concentration 10��150g/L in described electrolytic solution, electrodeposition temperature 0��90 DEG C, pole is apart from 1��10cm.
In preferred scheme, during pulsed electrical field " anode electricity molten-cathode electrodeposition " copper, the pulse-repetition of pulsed electrical field is 50��1500Hz, and dutycycle is 50%��90%, and average pulse current density is 100��800A/m2��
Further in preferred scheme, the extraction time of Selectively leaching tin is 10min��180min.
Further in preferred scheme, in the leaching process of Selectively leaching tin, liquid-solid volume mass ratio is 1��10mL:1g.
Further in preferred scheme, it is react 10min��180min when temperature is 20��60 DEG C that electricity strengthens reduction reaction.
Further in preferred scheme, the time of pulsed electrical field " anode electricity molten-cathode electrodeposition " copper is 1��240min.
In preferred scheme, purifying treatment carries out purifying treatment 1��120min when temperature is 20 DEG C��140 DEG C.
In preferred scheme, noble electrode is graphite cake, titanium plate, plating ruthenium titanium plate or platinum plate.
The advantage of hinge structure of the present invention and the Advantageous Effects brought:
Advantage in the technology of the present invention is: first at SnCl4-HCl system carries out selective oxidation and leaches tin, control specific reaction conditions, it is possible to fully the tin in useless zinc-plated bag copper iron pin is optionally leached, and it is not leached by copper, the iron of its parcel. Combine electricity afterwards again and strengthen reduction and purification techniques, it is possible to by copper a small amount of in solution, plumbous plasma high efficiency separation, and simultaneously by Sn unnecessary in solution4+It is reduced to Sn2+, then realize pole plate tin electrodeposition long-time, big in chloride system further combined with outfield coupling diaphragm electrodeposition method, obtain high purity metal tin. And galvanic deposit by-product containing SnCl4Solution then returns oxidation leaching stage as oxygenant, recycles. And the first stage leaches in slag loading anode frame by the copper Bao Tiezhen that Selectively leaching obtains, take noble electrode as anode, ammonia system carries out pulsed electrical field " anode electricity molten-cathode electrodeposition " copper, by controlling specific condition, the copper that can realize in antianode frame on copper Bao Tiezhen realizes optionally dissolving, and iron does not dissolve; Meanwhile, under specific condition, the copper in pass into solution-ammonia complexing ion optionally can precipitate out at negative electrode, obtains cathode copper. After pulse electrodeposition completes, obtain negative electrode electricity copper from negative electrode, in anode frame, then obtain de-copper iron pin, it is achieved that cleaning, the making high-efficiency comprehensive Separation and Recovery of tin, copper, iron in useless zinc-plated bag copper iron pin.
The method of the present invention can realize the amount resource utilization recycling cleaning, efficient, complete of a large amount of useless zinc-plated bag copper iron pin realization to electronics processing industry output, accomplish technical process closed cycle, solve the useless zinc-plated bag copper iron pin recovery method of tradition preferably and generally have that energy consumption height, metal recovery rate are low, valuable metal synthetical recovery difficulty, pollute the problem such as heavily, have that flow process is simple, the outstanding advantage of metal recovery rate height, clean environment firendly.
In order to obtain the effect of the present invention, inventors performed a large amount of tests and explore, paid a large amount of time and efforts; Each step coordinated in the present invention, has all carried out efficient recycling by the tin in useless zinc-plated bag copper iron pin, copper, iron, and the recycling tool for resource has very great significance.
In the present invention, the rate of recovery of tin, copper, iron three kinds of elements is all very high, and the current efficiency height of the present invention.
Specific embodiment
Following examples are intended to illustrate further content of the present invention, instead of the protection domain of restriction the claims in the present invention.
Embodiment 1
The useless zinc-plated bag copper iron pin composition that Guangdong company provides is: Sn6.2%, Cu6.4%, Pb0.2%, Fe86.2%.
The anionic membrane used in embodiment is with tetramethoxy-silicane and N-trimethoxy silicon propyl group-N, and N, N-trimethyl ammonium chloride is presoma, is prepared by sol-gel method.
One example of concrete preparation process is: get the tetramethoxy-silicane of 30g and the N-trimethoxy silicon propyl group-N of 45g, N, N-trimethyl ammonium chloride, the toluene adding 90g is solvent, stirs after evenly, add triisobutyl aluminium 3g, react 6h when 25 DEG C, obtain tetramethoxy-silicane and N-trimethoxy silicon propyl group-N, N, the polymerization colloidal sol of N-trimethyl ammonium chloride, is coated on glasscloth upholder. Put it into afterwards in vacuum drying oven, after 30 DEG C of dry 12h, obtain anionic membrane.
Get above-mentioned useless zinc-plated bag copper iron pin 100g, it is 5mol L at salt acidacidity-1��SnCl4Add-on (counting so that the tin in useless zinc-plated bag copper iron pin is all leached) as 2 times of theoretical amount, liquid-solid ratio is 4mL:1g, 2-mercaptobenzimidazole 0.03wt.%, tri-isopropanolamine 0.5wt.%, after extraction temperature leaches 2h when being 50 DEG C, filtering separation, washing lotion merges with filtrate, and filter residue dries scale weight. Analyzing the content of tin, copper, iron in filtrate and filter residue, the leaching yield obtaining tin is 97.1% (liquid meter)/98.4% (slag meter), and the leaching yield of copper is 0.8%, and the leaching yield of iron is 0.02%, Cu in solution2+��Fe2+Ionic concn is respectively 0.11g/L and 0.08g/L.
Analyze the impurity component in filtrate and Cu2+��Pb2+��Sn4+Content, taking tin plate as anode, negative electrode is graphite, and anode and negative electrode useful area, than being 4:1, are 20A/m in current density2, temperature is 30 DEG C, and when solution ph is 2.5, electricity strengthens reduction 50min. After electricity reinforcement reduction and purification terminate, Cu in solution2+��Pb2+��Sn4+Ionic concn all reaches below 0.01g/L.
Anionic membrane is adopted to carry out ultrasonic wave field coupled pulse electric field diaphragm electrodeposition, ultrasonic frequency 125KHz, pulse-repetition 1500Hz, dutycycle 70%, average pulse current density 250A/m2, pole is apart from 6cm, and temperature 35 DEG C, cathode material is that titanium plate, anode material are graphite cake, after 10 hours electrodeposition time, obtains fine and close tin plate. Current efficiency 99.7%, by analysis, more than 95% is converted into SnCl to the solution in anolyte compartment4��
After getting detin, the copper Bao Tiezhen 50g of gained loads with the anode frame that titanium net makes, at NH3-NH4Cl-H2Carrying out the anode electrodeposition-negative electrode electrodeposition under pulsed electrical field in O system, anode material is graphite cake, and cathode material is plating ruthenium titanium plate, NH in electrolytic solution3Concentration is 1.5mol/L, NH4 +Concentration is 2mol/L, Cu2+Concentration is 5g/L.
The pulse-repetition of pulsed electrical field is 500Hz, and dutycycle is 80%, and average pulse current density is 300A/m2, after reaction times 120min, take out the iron pin analysis in anode frame and contain copper 0.11%, iron level 98.8%; Cathode copper surfacing is fine and close, copper content 99.1%, cathode efficiency 89.4%.
Embodiment 2
The useless zinc-plated bag copper iron pin composition that Hunan company provides is: Sn4.4%, Cu8.9%, Fe86.1%.
Get above-mentioned useless zinc-plated bag copper iron pin 1500g, be 5mL:1g, salt acidacidity in liquid-solid ratio it is 4mol L-1��SnCl4Add-on (counting so that the tin in useless zinc-plated bag copper iron pin is all leached) as 1.3 times of (oxygenant SnCl of theoretical amount4From the SnCl repeatedly repeating anolyte compartment's regeneration of pulse diaphragm electrodeposition test gained in embodiment 14Solution), monoethanolamine diisopropanolamine (DIPA) 1.0wt.%, 2-tolimidazole 0.05wt.%, extraction temperature is after the lower leaching 90min of 40 DEG C of conditions, filtering separation, and washing lotion merges with filtrate, and filter residue dries scale weight. Analyze the content of tin, copper, iron in filtrate and filter residue, the leaching yield obtaining tin be 96.7% (liquid meter)/97.9% (slag meter), copper leaching yield be 0.08%, the leaching yield of iron is 0.01%. .
Analyze the impurity component in filtrate and Cu2+��Sn4+Content, taking tin plate as anode, negative electrode is titanium plate, and anode and negative electrode useful area, than being 3:1, are 40A/m in current density2, temperature is 40 DEG C, and when solution ph is 1.5, electricity strengthens reduction 60min. After electricity reinforcement reduction and purification terminate, Cu in solution2+��Sn4+Ionic concn all reaches below 0.01g/L.
Anionic membrane is adopted to carry out ultrasonic wave field coupled pulse electric field diaphragm electrodeposition, ultrasonic frequency 100KHz, DC current density 200A/m2, pole is apart from 5cm, and temperature 40 DEG C, cathode and anode material is plating ruthenium titanium plate, after 8 hours electrodeposition time, obtains fine and close tin plate. Current efficiency 98.5%, by analysis, more than 94% is converted into SnCl to the solution in anolyte compartment4��
After getting detin, the copper Bao Tiezhen 500g of gained loads with the anode frame that titanium net makes, at NH3-(NH4)2SO4-H2Carrying out the anode electrodeposition-negative electrode electrodeposition under pulsed electrical field in O system, anode material is titanium plate, and cathode material is plating ruthenium titanium plate, NH in electrolytic solution3Concentration is 2.5mol/L, NH4 +Concentration is 3.5mol/L, Cu2+Concentration is 6g/L, and the pulse-repetition of pulsed electrical field is 1000Hz, and dutycycle is 60%, and average pulse current density is 400A/m2, after reaction times 100min, take out remaining iron pin analysis in anode frame and contain copper 0.10%, iron level 98.4%; Cathode copper surfacing is fine and close, copper content 99.8%, cathode efficiency 90.2%.
Embodiment 3
The useless zinc-plated bag copper iron pin composition that Hunan company provides is: Sn5.1%, Pb0.5%, Cu4.9%, Fe89.2%.
Get above-mentioned useless zinc-plated bag copper iron pin 10Kg, be 6mL:1g, salt acidacidity in liquid-solid ratio it is 6mol L-1��SnCl4Add-on (counting so that the tin in useless zinc-plated bag copper iron pin is all leached) as 2.5 times of (oxygenant SnCl of theoretical amount4From the SnCl repeatedly repeating anolyte compartment's regeneration of pulse diaphragm electrodeposition test gained in embodiment 24Solution), trolamine 2wt.%, 3-ammonia-1,2,4-triazole 1.0wt.%, after leaching 60min when extraction temperature is 50 DEG C, filtering separation, washing lotion merges with filtrate, and filter residue dries scale weight. Analyze the content of tin, copper, iron in filtrate and filter residue, the leaching yield obtaining tin be 98.1% (liquid meter)/98.9% (slag meter), copper leaching yield be 0.12%, the leaching yield of iron is 0.07%.
Analyze the impurity component in filtrate and Cu2+��Pb2+��Sn4+Content, taking tin plate as anode, negative electrode is titanium plate, and anode and negative electrode useful area, than being 4:1, are 10A/m in current density2, temperature is 30 DEG C, and when solution ph is 2, electricity strengthens reduction 90min. After electricity reinforcement reduction and purification terminate, Cu in solution2+��Pb2+��Sn4+Ionic concn all reaches below 0.01g/L.
Adopting anionic membrane to carry out pulsed electrical field diaphragm electrodeposition, the pulse-repetition of pulsed electrical field is 1000Hz, and dutycycle is 55%, and average pulse current density is 400A/m2, pole is apart from 4cm, and temperature 30 DEG C, cathode and anode material is plating ruthenium titanium plate, after 8 hours electrodeposition time, obtains fine and close tin plate. Current efficiency 97.9%, by analysis, more than 95% is converted into SnCl to the solution in anolyte compartment4��
After getting detin, the copper Bao Tiezhen 5Kg of gained loads with the anode frame that titanium net makes, at NH3-NH4Cl-(NH4)2SO4-H2Carrying out the anode electrodeposition-negative electrode electrodeposition under pulsed electrical field in O system, anode material is titanium plate, and cathode material is plating ruthenium titanium plate, NH in electrolytic solution3Concentration is 1.5mol/L, NH4 +Concentration is 3.0mol/L, Cu2+Concentration is 8g/L, and the pulse-repetition of pulsed electrical field is 500Hz, and dutycycle is 80%, and average pulse current density is 500A/m2, after reaction times 120min, take out remaining iron pin analysis in anode frame and contain copper 0.09%, iron level 99.0%; Cathode copper surfacing is fine and close, copper content 99.2%, cathode efficiency 94.0%.
Comparative example 1
Get the useless zinc-plated bag copper iron pin 100g that in above-described embodiment 1, Guangdong company provides, it is 5mol L at salt acidacidity-1��SnCl4Add-on (counting so that the tin in useless zinc-plated bag copper iron pin is all leached) as 2 times of theoretical amount, liquid-solid ratio is 4mL:1g, add 2-mercaptobenzimidazole 0.05wt.%, tri-isopropanolamine 0.05wt.%, after extraction temperature leaches 2h when being 50 DEG C, filtering separation, washing lotion merges with filtrate, and filter residue dries scale weight. Analyzing the content of tin, copper, iron in filtrate and filter residue, the leaching yield obtaining tin is for being only 59.5% (liquid meter)/58.1% (slag meter), and the leaching yield of copper is 32.8%, and the leaching yield of iron is 41.2%, Cu in solution2+��Fe2+Ionic concn is respectively 3.39g/L and 5.43g/L.
Analyze the impurity component in filtrate and Cu2+��Fe2+��Pb2+��Sn4+Content, taking tin plate as anode, negative electrode is graphite, and anode and negative electrode useful area, than being 4:1, are 20A/m in current density2, temperature is 30 DEG C, and when solution ph is 2.5, electricity strengthens reduction 50min. After electricity reinforcement reduction and purification terminate, Cu in solution2+��Pb2+��Sn4+Ionic concn all reaches below 0.01g/L, Fe2+Ionic concn 5.45g/L.
Anionic membrane is adopted to carry out ultrasonic wave field coupled pulse electric field diaphragm electrodeposition, ultrasonic frequency 125KHz, pulse-repetition 1500Hz, dutycycle 70%, average pulse current density 250A/m2, pole apart from 6cm, temperature 35 DEG C, cathode material is that titanium plate, anode material are graphite cake, electrodeposition after 1.5 hours negative electrode just start to occur a large amount of " whisker " and powdered product, after 2 hours, electrolytic deposition process almost cannot be carried out down, current efficiency only 51.3%.
Comparative example 2
Get the useless zinc-plated bag copper iron pin 100g that in above-described embodiment 1, Guangdong company provides, it is 5mol L at salt acidacidity-1��SnCl4Add-on (counting so that the tin in useless zinc-plated bag copper iron pin is all leached) as 2 times of theoretical amount, liquid-solid ratio is 4mL:1g, add 2-mercaptobenzimidazole 7wt.%, tri-isopropanolamine 12wt.%, after extraction temperature leaches 2h when being 50 DEG C, filtering separation, washing lotion merges with filtrate, and filter residue dries scale weight. Analyzing the content of tin, copper, iron in filtrate and filter residue, the leaching yield obtaining tin is for being only 69.5% (liquid meter)/71.8% (slag meter), and the leaching yield of copper is 0.3%, and the leaching yield of iron is 0.01%, Cu in solution2+��Fe2+Ionic concn is respectively 0.10g/L and 0.07g/L. 2-mercaptobenzimidazole and tri-isopropanolamine define more serious parcel on zinc-plated bag copper pin surface, reduce Sn4+Active with the redox reaction of Sn, cause moving back tin rate far below embodiment 1 moves back tin rate.
Analyze the impurity component in filtrate and Cu2+��Fe2+��Pb2+��Sn4+Content, taking tin plate as anode, negative electrode is graphite, and anode and negative electrode useful area, than being 4:1, are 20A/m in current density2, temperature is 30 DEG C, and when solution ph is 2.5, electricity strengthens reduction 50min. After electricity reinforcement reduction and purification terminate, Cu in solution2+��Pb2+��Sn4+Ionic concn all reaches below 0.01g/L.
Anionic membrane is adopted to carry out ultrasonic wave field coupled pulse electric field diaphragm electrodeposition, ultrasonic frequency 125KHz, pulse-repetition 1500Hz, dutycycle 70%, average pulse current density 250A/m2, pole is apart from 6cm, and temperature 35 DEG C, cathode material is that titanium plate, anode material are graphite cake, after 10 hours electrodeposition time, obtains the tin plate of surface porosity, polyoma shape. Current efficiency 74.2%, by analysis, 65% is converted into SnCl to the solution in anolyte compartment4. The phenomenons such as electrodeposition Xi Shixi crystal segregation increase the weight of, and have impact on the oxidation activity of stannous ion in anolyte compartment.
Comparative example 3
After getting detin described in above-described embodiment 2, the copper Bao Tiezhen 500g of gained loads with the anode frame that titanium net makes, at NH3-(NH4)2SO4-H2Carrying out the anode electrodeposition-negative electrode electrodeposition of conventional DC voltage-stabilizing power supply in O system, anode material is titanium plate, and cathode material is plating ruthenium titanium plate, NH in electrolytic solution3Concentration is 2.5mol/L, NH4 +Concentration is 3.5mol/L, Cu2+Concentration is 6g/L, and current density is 400A/m2, after reaction times 100min, take out remaining iron pin analysis in anode frame and contain copper 15.20%, iron level 84.7%; Fail to obtain compacted cathode copper coin, only obtain one layer of copper sponge and be loosely attached to cathode surface, cathode efficiency 41.6%.
Comparative example 4
After getting detin, the copper Bao Tiezhen 5Kg of gained loads the anode frame that titanium net makes, at NH3-NH4Cl-(NH4)2SO4-H2Carrying out the anode electrodeposition-negative electrode electrodeposition under pulsed electrical field in O system, anode material is titanium plate, and cathode material is plating ruthenium titanium plate, NH in electrolytic solution3Concentration is 1.5mol/L, NH4 +Concentration is 3.0mol/L, Cu2+Concentration is 8g/L, and the pulse-repetition of pulsed electrical field is 20Hz, and dutycycle is 30%, and average pulse current density is 500A/m2, after reaction times 120min, take out remaining iron pin analysis in anode frame and contain copper 20.1%, iron level 79.6%; Fail to obtain compacted cathode copper coin, only obtain one layer of copper sponge and be loosely attached to cathode surface, cathode efficiency 53.1%.
Comparative example 5
After getting detin, the copper Bao Tiezhen 5Kg of gained loads the anode frame that titanium net makes, at NH3-NH4Cl-(NH4)2SO4-H2Carrying out the anode electrodeposition-negative electrode electrodeposition under pulsed electrical field in O system, anode material is titanium plate, and cathode material is plating ruthenium titanium plate, NH in electrolytic solution3Concentration is 1.5mol/L, NH4 +Concentration is 3.0mol/L, Cu2+Concentration is 8g/L, and the pulse-repetition of pulsed electrical field is 2000Hz, and dutycycle is 40%, and average pulse current density is 900A/m2, after reaction times 120min, take out remaining iron pin analysis in anode frame and contain copper 00.1%, iron level 99.6%; Fail to obtain compacted cathode copper coin, only obtain one layer of copper sponge and be loosely attached to cathode surface, cathode efficiency 43.2%, copper content 93.2% in copper sponge, iron content 5.6%.

Claims (10)

1. the method for Separation and Recovery tin, copper, iron from a useless zinc-plated bag copper iron pin, it is characterised in that, comprise the following steps:
Step one: Selectively leaching tin
Useless zinc-plated bag copper iron pin is placed in SnCl4After carrying out Selectively leaching tin in-HCl-additive system, filtering separation, obtains containing SnCl2Leach liquor and copper Bao Tiezhen leach slag;
Step 2: electricity strengthens reduction and purification
To step one gained containing SnCl2Leach liquor undertaken by anode of tin plate " sacrifice " anode electricity strengthen reduction purification, be purified liquid;
Step 3: outfield coupling barrier film galvanic deposit tin
The scavenging solution obtained using step 2, as electrolytic solution, take noble electrode as negative electrode and anode, and anionic membrane is barrier film, carries out outfield coupling barrier film galvanic deposit tin; After electrolytic deposition completes, obtain electrolysis tin from negative electrode, obtain from anolyte compartment returning the Selectively leaching tin process of step one as oxygenant containing stannic solution containing stannic solution;
Step 4: pulsed electrical field " anode electricity molten-cathode electrodeposition " copper
The copper Bao Tiezhen that step one obtained leaches slag and loads in anode frame, take noble electrode as anode, carries out pulsed electrical field " anode electricity molten-cathode electrodeposition " copper in ammonia system; After pulse electrodeposition completes, obtain negative electrode electricity copper from negative electrode, in anode frame, then obtain de-copper iron pin;
Wherein, additive described in step one is alcamines and the mixture of derivative and nitrogen azole and derivative thereof thereof;
Described anionic membrane is with tetramethoxy-silicane and N-trimethoxy silicon propyl group-N, and N, N-trimethyl ammonium chloride is presoma, is prepared by sol-gel method.
2. technique according to claim 1, it is characterised in that, alcamines material be selected from trolamine, tri-isopropanolamine, di-alcohol monoisopropanolamine, monoethanolamine diisopropanolamine (DIPA) or its derivative one or more; Nitrogen azole material is selected from ribavirin, triazole and derivative, imidazoles (1,3-diazole) and pyrazoles (1,2-diazole), 2-mercaptobenzimidazole, 2-amino benzoglyoxaline, 2-tolimidazole, benzoglyoxaline, benzotriazole, mercaptobenzothiazole, 3-ammonia-1, one or more in 2,4-triazole or its derivative.
3. technique according to claim 1 and 2, it is characterised in that, the interpolation concentration of alcamines material or its derivative is 0.1wt%��5.0wt%.
4. technique according to claim 1 and 2, it is characterised in that, the interpolation concentration of nitrogen azole material or its derivative is 0.1wt%��5.0wt%.
5. technique according to claim 1, it is characterised in that, described ammonia system is NH3-NH4Cl-H2O��NH3-(NH4)2SO4-H2O��NH3-NH4NO3-H2O or NH3-NH4Cl-(NH4)2SO4-H2O, in ammonia system, NH3Concentration is 1��5mol/L, NH4 +Concentration is 2��9mol/L, Cu in system2+Concentration is 3��10g/L.
6. technique according to claim 1, it is characterised in that, the processing condition of Selectively leaching tin process are: extraction temperature is 25��90 DEG C; In hydrochloric acid system, concentration of hydrochloric acid is 1��8mol L-1; SnCl4Content be that the tin in useless zinc-plated bag copper iron pin is all oxidized to SnCl21��4 times of required theoretical molar amount.
7. technique according to claim 1, it is characterised in that, when described electricity strengthens reduction and purification, current density is 1��50A/m2; Reduction temperature is 20��60 DEG C, and solution ph is 0.5��3; Anode is tin plate, and negative electrode is noble electrode, and anode is 1��10:1 with negative electrode useful area ratio, and it is 10min��180min that electricity strengthens the reduction reaction time. .
8. technique according to claim 1, it is characterised in that, during the coupling barrier film galvanic deposit tin of outfield, described outfield is that be coupled common electric field, ultrasonic wave field coupled pulse electric field, pulsed electrical field of ultrasonic wave field is coupled common electric field or single pulsed electrical field; The ultrasonic frequency of ultrasonic wave field is 10KHz��150KHz; The pulse-repetition of pulsed electrical field is 50��2000Hz, and dutycycle is 50%��80%, and average pulse current density is 200��600A/m2; The current density of common electric field is 10A/m2��700A/m2; Tin concentration 10��150g/L in described electrolytic solution, electrodeposition temperature 0��90 DEG C, pole is apart from 1��10cm.
9. technique according to claim 1, it is characterised in that, during described pulsed electrical field " anode electricity molten-cathode electrodeposition " copper, the pulse-repetition of pulsed electrical field is 50��1500Hz, and dutycycle is 50%��90%, and average pulse current density is 100��800A/m2, the reaction times is 1��240min.
10. technique according to claim 1, it is characterised in that, in Selectively leaching tin process, liquid-solid volume mass ratio is 1��10mL:1g.
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CN106978538A (en) * 2017-04-13 2017-07-25 中南大学 Treatment method of high-bismuth lead anode mud or bismuth slag
CN116493386A (en) * 2023-06-05 2023-07-28 清远市金运再生资源有限公司 Environment-friendly recycling process for crushing, sorting and recycling copper and tin from waste circuit boards

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CN101962776A (en) * 2010-09-01 2011-02-02 济南德锡科技有限公司 Solder stripping agent and preparation method thereof
CN103741142A (en) * 2014-01-10 2014-04-23 中南大学 Method for recycling tin from waste tin-stripping solution based on tin-stripping solution of hydrochloric acid-tin salt system
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CN105969992A (en) * 2016-07-04 2016-09-28 中节能（汕头）循环经济有限公司 Method for recycling fine tin from waste circuit board
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