CN104131177B - A kind of method reclaiming zinc-plated refined tin from eleetrotinplate mud - Google Patents
A kind of method reclaiming zinc-plated refined tin from eleetrotinplate mud Download PDFInfo
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- CN104131177B CN104131177B CN201410372932.9A CN201410372932A CN104131177B CN 104131177 B CN104131177 B CN 104131177B CN 201410372932 A CN201410372932 A CN 201410372932A CN 104131177 B CN104131177 B CN 104131177B
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Abstract
From eleetrotinplate mud, reclaim a method for zinc-plated refined tin, belong to tin recovery method technical field, for reclaiming zinc-plated refined tin from eleetrotinplate mud.Its technical scheme is: it takes following removal process: eleetrotinplate mud dehydrates after acidleach; With appropriate reductive agent mix after oxidizing roasting; At lower reduction temperature, under the shorter recovery time, carry out protective atmosphere reduction; The thick tin obtained obtains zinc-plated refined tin after electrorefining remelting.The present invention removes the harmful elements such as Bi, As, Sb by the mode of acidleach, roasting; Reductive agent low price, to be easy to get; Reductive condition easily controls, and recovery time more traditional retailoring reduces greatly; The refined tin impurity obtained is few, meets plating completely with requiring.Recovery method of the present invention not only obtains eleetrotinplate refined tin, alleviates the problem of a large amount of loss of tin in electroplating process, also solves the problem that tin mud is difficult, easily cause environmental pollution, has dual economic benefit and environmental benefit.
Description
Technical field
The present invention relates to a kind of method reclaiming zinc-plated refined tin from eleetrotinplate mud, belong to tin recovery method technical field.
Background technology
Applying maximum in current method of electric tinning is the zinc-plated method of Fu Luositan (PSA), and early stage PSA type tin plating solution adopts the tin anode of solubility to carry out electrolysis, but easily produces the problem that plating solution surplus arranges outward.In order to fundamentally solve this problem, in present zinc-plated process, mostly using insoluble anode, in electroplating process, supplementing tin ion externally in solution.Current molten tin process mostly adopts the method for the molten tin of logical oxygen, molten tin process completes usually in tin dissolving tank, there is tin grain container the top of tin dissolving tank, open tin grain and drop into valve, quantitative tin grain is put into molten molten tin bath, then the electroplate liquid in plating cycle groove is squeezed into a certain amount of to dissolving tank by solution feed pump, open oxygen valve again, supply a certain amount of oxygen, then metallic tin grain reacts in groove, generates Sn
2+, its reaction equation: 2Sn+4H
++ O
2=2Sn
2++ 2H
2o, the solution dissolved through overflow port in settling bath, through three grades of sediment overflow to circulation groove, with supplementary Sn
2+.
Because molten tin process need leads to oxygen, and oxygen can make the Sn that generated
2+continue oxidation and generate Sn
4+, Sn
4+metastannic acid is generated after hydrolysis.Conversion process is:
Sn
2+→ Sn
4+→ 5SnO
2h
2the acid of O(alpha tin) → (SnO
2h
2o)
5(β-stannic acid)
Sn
4+the alpha tin acid that hydrolysis generates is thermodynamics metastable phase, the strong trend that oriented β-stannic acid changes, and β-stannic acid has stable structure, is insoluble to acid, and in colloidal, dispersion makes it muddy, with Sn in the plating solution
4+complex reaction forms yellow mercury oxide, is referred to as tin mud.The generation of tin mud not only makes tin lose but also affects the quality of coating, takes the mode of filtration under normal circumstances or regularly manually remove for the tin mud in plating solution.For the tin mud filtered out, belong to the solid waste of metallurgy industry, deal with improperly and easily affect environment, cause environmental pollution.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method reclaiming zinc-plated refined tin from eleetrotinplate mud, adopt and can carry out reprocessing to the tin mud produced in insoluble anode eleetrotinplate process in this way, plating refined tin is reclaimed from eleetrotinplate mud, not only save resource, also reduce the pollution to environment.
The technical scheme solved the problems of the technologies described above is:
A kind of method reclaiming zinc-plated refined tin from eleetrotinplate mud; it takes following removal process: eleetrotinplate mud dehydrates after acidleach; with appropriate reductive agent mix after oxidizing roasting; at lower reduction temperature, under the shorter recovery time, carry out protective atmosphere reduction; the thick tin obtained obtains zinc-plated refined tin after electrorefining remelting, and concrete steps are as follows:
1. get tin mud from eleetrotinplate factory, add leaching agent hydrochloric acid, carry out heating in water bath, suction filtration obtains filter residue;
2. pair filter residue carries out roasting, is broken for particle stand-by after roasting;
3. filter residue particle is placed in crucible, take be crushed to particle coal as reductive agent, be fully uniformly mixed, be positioned in protective atmosphere process furnace;
4. before heating, logical protective atmosphere replaces oxygen in stove, opens process furnace and carries out protective atmosphere reduction reaction, and heating stops follow-up continuous protective atmosphere to be down to room temperature-232 DEG C to temperature;
5. reaction product crosses 0.5mm sieve, obtains thick tin after screen overflow remelting;
6. thick tin electrolysis in the electrolytic solution, after electrolysis terminates, scrapes remelting by negative electrode tin and obtains refined tin.
The above-mentioned method reclaiming zinc-plated refined tin from eleetrotinplate mud, the water ratio of the described tin mud obtained from eleetrotinplate factory is 20-50%, and stanniferous amount is 20-40%, the concentration of leaching agent hydrochloric acid is 22-25%, extraction temperature is 90-95 DEG C, leaching agent consumption 100-120kg/t, extraction time 1-2h.
The above-mentioned method reclaiming zinc-plated refined tin from eleetrotinplate mud, described maturing temperature is 550-850 DEG C, roasting time 1-2h, and after roasting, particle diameter is for being less than 2mm.
The above-mentioned method reclaiming zinc-plated refined tin from eleetrotinplate mud, described reductive agent is coking coal, and being crushed to particle diameter is 40 orders, and carbon content is 80-90%, and mix tin mud is 8-12:1 with the ratio of reductive agent consumption.
The above-mentioned method reclaiming zinc-plated refined tin from eleetrotinplate mud, described protective atmosphere is industrial nitrogen, and under protective atmosphere, reduction temperature is 800-900 DEG C, and the recovery time is 30-60min, is cooled to room temperature-232 DEG C under protective atmosphere.
The above-mentioned method reclaiming zinc-plated refined tin from eleetrotinplate mud, described electrolytic solution is stannous sulfate+sulfuric acid electrolyte, thick tin in the electrolytic solution electrolysis time, current density is 100-110A/m
2, bath voltage is 0.2-0.4V, and electrolyte temperature is 35-45 DEG C.
The invention has the beneficial effects as follows:
Eleetrotinplate mud can remove the harmful elements such as Bi, As, Sb by the mode of hydrochloric acid acidleach, oxidizing roasting before reduction, reduced impurity element to the impact in sequential reduction operation; Reductive agent is common coking coal, and low price, source are easy to get, and reduction effect is good; Reductive condition easily controls, and recovery time more traditional retailoring reduces greatly; The refined tin impurity obtained is few, meets plating completely with requiring.Recovery method of the present invention not only obtains eleetrotinplate refined tin, alleviates the problem of a large amount of loss of tin in electroplating process, also solves the problem that tin mud is difficult, easily cause environmental pollution, has dual economic benefit and environmental benefit.
Embodiment
The present invention is a kind of method reclaiming zinc-plated refined tin from eleetrotinplate mud, and it takes following removal process: first dehydrated after acidleach by eleetrotinplate mud; Again after oxidizing roasting with appropriate reductive agent mix; Mix carries out protective atmosphere reduction in protective atmosphere process furnace; Finally the thick tin obtained is obtained zinc-plated refined tin after electrorefining remelting.
Concrete steps of the present invention are as follows:
1. get tin mud from eleetrotinplate factory, add leaching agent hydrochloric acid, carry out heating in water bath, suction filtration obtains filter residue.The water ratio of the tin mud obtained from eleetrotinplate factory is 20-50%, and stanniferous amount is 20-40%, and the concentration of leaching agent hydrochloric acid is 22-25%, and extraction temperature is 90-95 DEG C, leaching agent consumption 100-120kg/t, extraction time 1-2h.
2. pair filter residue carries out roasting, is broken for particle stand-by after roasting.Maturing temperature is 550-850 DEG C, roasting time 1-2h, and after roasting, particle diameter is less than 2mm.
3. filter residue particle is placed in crucible, take be crushed to particle coal as reductive agent, be fully uniformly mixed, be positioned in protective atmosphere process furnace.It is 40 orders that coal reductant is crushed to particle diameter, and carbon content is 80-90%, and mix tin mud is 8-12:1 with the ratio of reductive agent consumption.
4. before heating, logical protective atmosphere replaces oxygen in stove, opens process furnace and carries out protection reduction reaction, and heating stops follow-up continuous protective atmosphere to be down to room temperature-232 DEG C to temperature.Protective atmosphere is industrial nitrogen, and under protective atmosphere, reduction temperature is 800-900 DEG C, and the recovery time is 30-60min, is cooled to room temperature-232 DEG C under protective atmosphere.
5. reaction product crosses 0.5mm sieve, obtains thick tin after screen overflow remelting.
6. thick tin electrolysis in the electrolytic solution, after electrolysis terminates, scrapes remelting by negative electrode tin and obtains refined tin.Electrolytic solution is stannous sulfate+sulfuric acid electrolyte, thick tin in the electrolytic solution electrolysis time, current density is 100-110A/m2, and bath voltage is 0.2-0.4V, and electrolyte temperature is 35-45 DEG C.
Several embodiments of the present invention are as follows
Embodiment 1
The preprocessing process of tin mud comprises acidleach, oxidizing roasting.Get tin mud 500g from eleetrotinplate factory, add the hydrochloric acid 50g that concentration is 22%, acidleach 60min at utilizing the mode of heating in water bath to maintain the temperature at 90 DEG C.Suction filtration obtains filter residue 300g, and calculating tin mud water ratio is 40%.Filter residue is roasting 2h at 600 DEG C, is crushed to particle diameter stand-by at about 1mm, and fluorescence spectrum test analysis Theil indices is 62.4%.
Get the good tin mud 200g of pre-treatment in crucible, take and be crushed to particle diameter 40 object reduction coal 20g and be fully uniformly mixed, be positioned in protective atmosphere process furnace.Oxygen in logical industrial nitrogen displacement stove before heating, open reduction temperature 900 DEG C, insulation 40min, heating stops follow-up continuous protective atmosphere to be down to 232 DEG C to temperature.Reaction product crosses 0.5mm sieve, obtains thick tin and is about 80g, electrolysis in stannous sulfate-sulfuric acid electrolyte after screen overflow remelting, and current density is 100A/m
2, bath voltage is 0.4V, and electrolyte temperature is about 35 DEG C, after electrolysis terminates, and negative electrode tin is scraped remelting and obtains refined tin, and analytical results shows, and in refined tin, stanniferous amount is 99.86%, meets the requirement of eleetrotinplate station-service tin.
Embodiment 2
The preprocessing process of tin mud comprises acidleach, oxidizing roasting.Get tin mud 1000g from eleetrotinplate factory, add the hydrochloric acid 100g that concentration is 22%, acidleach 60min at utilizing the mode of heating in water bath to maintain the temperature at 90 DEG C.Suction filtration obtains filter residue 620g, and calculating tin mud water ratio is 38%.Filter residue is roasting 2h at 600 DEG C, is crushed to particle diameter stand-by at about 1mm, and fluorescence spectrum test analysis Theil indices is 58.9%.
Get the good tin mud 500g of pre-treatment in crucible, take and be crushed to particle diameter 40 object reduction coal 55g and be fully uniformly mixed, be positioned in protective atmosphere process furnace.Oxygen in logical industrial nitrogen displacement stove before heating, open reduction temperature 900 DEG C, insulation 40min, heating stops follow-up continuous protective atmosphere to be down to 150 DEG C to temperature.Reaction product crosses 0.5mm sieve, obtains thick tin and is about 230g, electrolysis in stannous sulfate-sulfuric acid electrolyte after screen overflow remelting, and current density is 100A/m
2, bath voltage is 0.4V, and electrolyte temperature is about 35 DEG C, after electrolysis terminates, and negative electrode tin is scraped remelting and obtains refined tin, and analytical results shows, and in refined tin, stanniferous amount is 99.91%, meets the requirement of eleetrotinplate station-service tin.
Embodiment 3
The preprocessing process of tin mud comprises acidleach, oxidizing roasting.Get tin mud 2000g from eleetrotinplate factory, add the hydrochloric acid 200g that concentration is 22%, acidleach 60min at utilizing the mode of heating in water bath to maintain the temperature at 90 DEG C.Suction filtration obtains filter residue 1160g, and calculating tin mud water ratio is 42%.Filter residue is roasting 2h at 600 DEG C, is crushed to particle diameter stand-by at about 1mm, and fluorescence spectrum test analysis Theil indices is 61.8%.
Get the good tin mud 1000g of pre-treatment in crucible, take and be crushed to particle diameter 40 object reduction coal 115g and be fully uniformly mixed, be positioned in protective atmosphere process furnace.Oxygen in logical industrial nitrogen displacement stove before heating, open reduction temperature 900 DEG C, insulation 60min, heating stops follow-up continuous protective atmosphere to be down to 30 DEG C to temperature.Reaction product crosses 0.5mm sieve, obtains thick tin and is about 460g, electrolysis in stannous sulfate-sulfuric acid electrolyte after screen overflow remelting, and current density is 100A/m
2, bath voltage is 0.4V, and electrolyte temperature is about 35 DEG C, after electrolysis terminates, and negative electrode tin is scraped remelting and obtains refined tin, and analytical results shows, and in refined tin, stanniferous amount is 99.89%, meets the requirement of eleetrotinplate station-service tin.
Claims (5)
1. from eleetrotinplate mud, reclaim a method for zinc-plated refined tin, it is characterized in that: it takes following removal process: eleetrotinplate mud dehydrates after acidleach; With appropriate reductive agent mix after oxidizing roasting; Reduction temperature be 800-900 DEG C, the recovery time be 30-60min condition under carry out protective atmosphere reduction; The thick tin obtained obtains zinc-plated refined tin after electrorefining remelting, and concrete steps are as follows:
(1) get tin mud from eleetrotinplate factory, add leaching agent hydrochloric acid, carry out heating in water bath, suction filtration obtains filter residue;
(2) roasting is carried out to filter residue, be broken for particle after roasting stand-by;
(3) filter residue particle is placed in crucible, take be crushed to particle coal as reductive agent, be fully uniformly mixed, be positioned in protective atmosphere process furnace;
(4) before heating, logical protective atmosphere replaces oxygen in stove, opens process furnace and carries out protection reduction reaction, and heating stops follow-up continuous protective atmosphere to be down to room temperature ~ 232 DEG C to temperature;
(5) reaction product crosses 0.5mm sieve, obtains thick tin after screen overflow remelting;
(6) thick tin electrolysis in the electrolytic solution, after electrolysis terminates, scrapes remelting by negative electrode tin and obtains refined tin;
The water ratio of the described tin mud obtained from eleetrotinplate factory is 20-50%, and stanniferous amount is 20-40%, and the concentration of leaching agent hydrochloric acid is 22-25%, and extraction temperature is 90-95 DEG C, leaching agent consumption 100-120kg/t, extraction time 1-2h.
2. the method reclaiming zinc-plated refined tin from eleetrotinplate mud according to claim 1, is characterized in that: described maturing temperature is 550-850 DEG C, roasting time 1-2h, particle diameter < 2mm after roasting.
3. the method reclaiming zinc-plated refined tin from eleetrotinplate mud according to claim 2, is characterized in that: described reductive agent is coking coal, and being crushed to particle diameter is 40 orders, and carbon content is 80-90%, and mix tin mud is 8-12:1 with the ratio of reductive agent consumption.
4. the method reclaiming zinc-plated refined tin from eleetrotinplate mud according to claim 3, is characterized in that: described protective atmosphere is industrial nitrogen, is cooled to room temperature ~ 232 DEG C under protective atmosphere.
5. the method reclaiming zinc-plated refined tin from eleetrotinplate mud according to claim 4, is characterized in that: described electrolytic solution is stannous sulfate+sulfuric acid electrolyte, thick tin in the electrolytic solution electrolysis time, current density is 100-110A/m
2, bath voltage is 0.2-0.4V, and electrolyte temperature is 35-45 DEG C.
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| CN104843770B (en) * | 2015-03-30 | 2017-09-26 | 中国钢研科技集团有限公司 | A kind of method that tin mud resource is utilized |
| CN106636659A (en) * | 2016-10-17 | 2017-05-10 | 中国有色集团（广西）平桂飞碟股份有限公司 | Method for smelting tin from tin smelting powder residue |
| CN107675209A (en) * | 2017-10-18 | 2018-02-09 | 江西理工大学 | A kind of green tin electrorefining electrolyte |
| CN108426923B (en) * | 2018-02-24 | 2020-10-27 | 东北大学 | Method for preparing formaldehyde gas-sensitive material based on tin mud modification in tin plating process and application |
| CN108802117B (en) * | 2018-06-15 | 2020-10-27 | 东北大学 | Method for preparing alcohol gas-sensitive material based on tin mud modification and application |
| CN111500877A (en) * | 2020-06-10 | 2020-08-07 | 广东汉合有色金属有限公司 | Process method for recovering and regenerating refined tin from tin foil ash of tin foil sacrificial offerings |
| CN114635038A (en) * | 2022-02-18 | 2022-06-17 | 永兴长隆环保科技有限公司 | Method for recovering and preparing refined tin from tin-containing waste residues |
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