CN104711431A - Method for producing copper sulfate from copper scum - Google Patents
Method for producing copper sulfate from copper scum Download PDFInfo
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- CN104711431A CN104711431A CN201510138832.4A CN201510138832A CN104711431A CN 104711431 A CN104711431 A CN 104711431A CN 201510138832 A CN201510138832 A CN 201510138832A CN 104711431 A CN104711431 A CN 104711431A
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Abstract
The invention discloses a method for producing copper sulfate from copper scum, which comprises the steps of pretreatment, leaching, iron removal, calcium/magnesium removal, and crystallization and concentration. The method specifically comprises the following steps: crushing and grinding the raw material copper scum, adding a sulfuric acid solution, introducing oxygen or oxygen-enriched air to react, filtering, adding oxydol into the leach solution to react, concentrating, regulating the pH value to 2-4, carrying out hydrolysis reaction to obtain a ferric hydroxide precipitate, carrying out pressure filtration to obtain a filtrate a and a filter residue b, heating the filtrate a, concentrating, cooling, and filtering to obtain a filtrate c and a filter residue d; and concentrating and crystallizing the filtrate c, and carrying out vacuum centrifugal separation to obtain the target substance. The method overcomes the defect of comprehensive recovery in the existing copper scum treatment process. According to the method, the raw material copper scum containing 10-40% of copper and 30-50% of bismuth is subjected to oxygen pressure leaching by the dilute sulfuric acid solution, the obtained leach solution is subjected to iron/calcium/magnesium removal, and the concentrated crystal is dried to obtain the YS/t94-2007 top-grade chalcanthite product.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of method that copper dross slag produces copper sulfate.
Background technology
Copper dross slag is that lead bullion melts the product of analysing copper removal, its cupric 3 ~ 15%, plumbous 75 ~ 85%, and zinc 1 ~ 2%, antimony 1 ~ 2%, silver 300 ~ 2000g/t and other elements (iron, calcium, magnesium, sulphur etc.).Different with equipment owing to dragging for slag mode, copper dross slag form is also different, and common have the forms such as loose fine particulate, bulk.
The treatment process of known employing copper dross slag has can be divided into Blast Furnace Method, reflection oven process, electric furnace process, revolution oven process, pickling process, ammonia leaching process etc.Blast furnace process copper dross slag, Cu/Pb lower (nearly 2 ~ 3) in copper matte regulus, the rate of recovery of copper is low, and a large amount of copper is stayed in lead bullion, causes copper, arsenic and precious metal to circulate during the course.Reflection furnace process labor condition is poor, thermo-efficiency is low and the blowing-ouf of lines fast, maintenance is frequent, is classified as time limit by country and eliminates technique.There is the high (power consumption 330 ~ 370kwh/t of power consumption in electric furnace process
lead bullion, coke 40 ~ 45kg/t
lead bullion), the shortcomings such as operation cost is high, are difficult in the area of power tense realize.Revolution oven process (also known as rotary furnace method) processes copper dross slag and there is diesel consumption comparatively greatly, the shortcoming that cost is higher.There is the shortcomings such as water loss is large, wastewater treatment expense is high in pickling process, ammonia leaching process.
The method of useful converter process copper dross slag, is copper dross slag, soda ash, iron filings or sulfurous iron ore and hard coal are prepared burden according to a certain percentage, adds retailoring in converter.Control temperature 700 ~ 800 DEG C, smelts 1.5 ~ 2 hours; Metal form in copper dross slag lead is separated with copper, then improves temperature to slag temperature of superheat 1100 ~ 1250 DEG C, smelt 2.5 ~ 3 hours, make plumbous compound reduction generate metallic lead, copper then enters matte and achieves asunder copper and lead.Scum silica frost on matte and lead bullion is pulled out, obtains matte and lead bullion.The method is with coal as reductive agent, do fuel with diesel oil, and production cost is higher, and tail gas is difficult.
Also having the smelting process of copper dross slag, is by copper dross slag oxidation blowing output silver-bearing copper bismuth alloy, flue dust and oxidation sludge; Silver-bearing copper bismuth alloy electrolysis output cathode copper and copper anode mud, copper anode mud leaches, and leach liquor first heavy bismuth obtains chlorine oxygen bismuth, and chlorine oxygen bismuth is through the thick bismuth of retailoring output, more heavy copper obtains copper hydroxide, the thick silver of leached mud rotary kiln melting output, flue dust and oxidation sludge; Thick silver-colored electrolysis output finished product silver and silver anode slime, reclaim Au, Pt, Pd from silver anode slime; Two kinds of oxidation sludge retailoring of blast furnace obtain lead antimony alloy, flue dust and slag, and lead antimony alloy reverberatory smelting obtains lead bullion and flue dust; Flue dust reverberatory smelting output lead bullion and weisspiessglanz, weisspiessglanz retailoring output needle antimony; Plumbous and the lead anode slurry of lead bullion and lead bullion electrolysis output, reclaims gold and silver from lead anode slurry.The reverberatory furnace that the method adopts, blast furnace belong to highly energy-consuming stove, the complex process taked, and the intermediate material of output is many.
Also have and be separated the plumbous method of producing copper and silver in copper dross slag of refining, be that refining lead is produced copper dross slag solid materials, under being placed in vacuum condition, after repeatedly heating up, being incubated, collect volatile matter, condensation obtains pb-ag alloy, and remaining solid is slough copper alloy that is plumbous and silver; Again pb-ag alloy is entered conventional plumbous smelting procedure or electrorefining operation as raw material, silver is enriched in the anode sludge, is namely recycled silver; Slough plumbous and silver-colored copper alloy directly as raw material, be namely recycled metallic copper in conventional manner.But the method does not have effective separation that can realize lead bronze.
Also also have copper dross slag side-blown melting to produce the method for lead bullion in addition, be that copper dross slag, soda ash, sulfurous iron ore and hard coal are prepared burden according to a certain percentage, add melting in side-blown.Control temperature 600 ~ 800 DEG C, smelts 1 ~ 2 hour; Metal form in copper dross slag lead is separated with copper, then improves temperature to slag temperature of superheat 1100 ~ 1200 DEG C, smelt 2 ~ 3 hours, make plumbous compound reduction generate metallic lead, copper then enters matte and achieves asunder copper and lead.Scum silica frost on matte and lead bullion is pulled out, obtains matte and lead bullion.The method is with hard coal as reductive agent and fuel, and tail gas is difficult, and copper is not fully utilized.Therefore, develop a kind of processing method that can solve the problem to be very important.
Summary of the invention
A kind of copper dross slag is the object of the present invention is to provide to produce the method for copper sulfate.
The object of the present invention is achieved like this, comprises pre-treatment, leaching, deironing, calcium-magnesium removing, co-crystallization and washing step, specifically comprise:
A, pre-treatment: by for subsequent use for raw copper scum silica frost pulverizing and jevigating;
B, leaching: the copper dross slag after pre-treatment is inserted reactor, add the sulphuric acid soln of solid-liquid volume ratio 4 ~ 10 times, passes into oxygen or oxygen-rich air reaction 2 ~ 6h, filter and obtain leach liquor and leached mud at pressure 0.6 ~ 2.0MPa, temperature 60 ~ 90 DEG C;
C, deironing: add hydrogen peroxide reaction 1 ~ 2h in leach liquor, being concentrated into proportion is 1 ~ 3, and adjust ph is 1 ~ 5, and hydrolysis reaction 0.5 ~ 1h obtains ferric hydroxide precipitate, and press filtration is carried out solid-liquor separation and obtained filtrate a and filter residue b;
D, calcium-magnesium removing: the filtrate a obtained after step C deironing is heated to 70 ~ 90 DEG C, being concentrated into proportion is 1.1 ~ 1.6, is cooled to 65 ~ 80 DEG C, filters and obtains filtrate c and filter residue d;
E, co-crystallization: by filtrate c co-crystallization, solid-liquor separation obtains copper sulfate crystal and mother liquor;
F, washing: the copper sulfate crystal obtained is carried out 2 ~ 4 grades of washings, first step clear water washs, and liquid-solid ratio is 0.5 ~ 2.0m
3/ t, its rear stage of the washing before last step washs the copper/saturated copper sulphate solution of generation as washings, and liquid-solid ratio is 1 ~ 3m
3/ t, the washing of every one-level be first by copper sulfate crystal with washings mixing post-heating to 70 ~ 95 DEG C, crystallisation by cooling again after dissolving completely in copper sulfate, solid-liquor separation goes out copper sulfate crystal and washings, the copper sulfate crystal of last step washings gained, utilize vacuum centrifuge to be separated, crystal enters dryer, through drying and being packaged to be target compound.
The present invention overcomes existing copper scum treatment method and there is the deficiency of synthetical recovery and the shortcoming of complex process, with the copper dross slag of cupric 3 ~ 15%, lead 75 ~ 85% for raw material, dilution heat of sulfuric acid is adopted to carry out oxygen leaching, after the leach liquor obtained carries out deironing calcium magnesium, then carry out co-crystallization, comprise crystallisation by cooling and salting-out crystallization, the copper sulfate crystal obtained carries out multistage washing again, last vacuum separation post-drying, obtains the above cupric sulfate pentahydrate product of YS/t94-2007 top grade product.
Accompanying drawing explanation
Fig. 1 is present invention process schematic flow sheet.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is further illustrated, but limited the present invention never in any form, and any conversion done based on training centre of the present invention or replacement, all belong to protection scope of the present invention.
Copper dross slag of the present invention produces the method for copper sulfate, comprises pre-treatment, leaching, deironing, calcium-magnesium removing, co-crystallization and washing step, specifically comprises:
A, pre-treatment: by for subsequent use for raw copper scum silica frost pulverizing and jevigating;
B, leaching: the copper dross slag after pre-treatment is inserted reactor, add the sulphuric acid soln of solid-liquid volume ratio 4 ~ 10 times, passes into oxygen and/or oxygen-rich air reaction 2 ~ 6h, filter and obtain leach liquor and leached mud at pressure 0.6 ~ 2.0MPa, temperature 60 ~ 90 DEG C;
C, deironing: add hydrogen peroxide reaction 1 ~ 2h in leach liquor, being concentrated into proportion is 1 ~ 3, and adjust ph is 1 ~ 5, and hydrolysis reaction 0.5 ~ 1h obtains ferric hydroxide precipitate, and press filtration is carried out solid-liquor separation and obtained filtrate a and filter residue b;
D, calcium-magnesium removing: the filtrate a obtained after step C deironing is heated to 70 ~ 90 DEG C, being concentrated into proportion is 1.1 ~ 1.6, is cooled to 65 ~ 80 DEG C, filters and obtains filtrate c and filter residue d;
E, co-crystallization: by filtrate c co-crystallization, solid-liquor separation obtains copper sulfate crystal and mother liquor;
F, washing: the copper sulfate crystal obtained is carried out 2 ~ 4 grades of washings, first step clear water washs, and liquid-solid ratio is 0.5 ~ 2.0m
3/ t, its rear stage of the washing before last step washs the copper/saturated copper sulphate solution of generation as washings, and liquid-solid ratio is 1 ~ 3m
3/ t, the washing of every one-level be first by copper sulfate crystal with washings mixing post-heating to 70 ~ 95 DEG C, crystallisation by cooling again after dissolving completely in copper sulfate, solid-liquor separation goes out copper sulfate crystal and washings, the copper sulfate crystal of last step washings gained, utilize vacuum centrifuge to be separated, crystal enters dryer, through drying and being packaged to be target compound.
Levigate granularity described in step A is 200 ~ 500 orders.
Sulphuric acid soln concentration described in step B is 100 ~ 200g/L.
The dividing potential drop passing into oxygen and/or oxygen-rich air described in step B is 0.2 ~ 0.8MPa.
Step B controls reaction end pH value after also comprising Leaching reaction be 2 ~ 4.
Filtration described in step B is filtered at 80 ~ 95 DEG C.
Hydrogen peroxide concentration described in step C is 2 ~ 4%.
Concentrated described in step C passes into be steam heated to 70 ~ 90 DEG C and to concentrate in reaction solution.
Concentrated described in D step takes to concentrate while the mode of fluid infusion concentrates; Described filtration is vacuum filtration.
Co-crystallization described in E step is that filtrate c is cooled to 10 ~ 30 DEG C of crystallization 1 ~ 2h, and the sulfuric acid adding volumetric concentration 98% makes to carry out salting-out crystallization containing after acid 100 ~ 300g/L.
The present invention includes following concrete implementation step:
(1) ball milling of copper dross slag: by levigate for copper dross slag ball mill good for fragmentation, granularity 200 ~ 500, loads hopper and uses in order to leaching.
(2) oxygen leaching: the dilution heat of sulfuric acid of acid 100 ~ 200g/l that sulfur acid is begun and copper dross slag powder, according to liquid-solid ratio (4 ~ 10): 1 mixing, blast oxygen and oxygen-rich air, at temperature 60 ~ 90 DEG C, oxygen partial pressure 0.2 ~ 0.8MPa, total pressure 0.6 ~ 2.0MPa, extraction time 2 ~ 6 hours, and control terminal pH value 2 ~ 4, obtain leaching feed liquid, at 80 ~ 95 DEG C, leaching feed liquid is filtered, obtain leach liquor and leached mud respectively, leaching yield 90 ~ 99%, slag rate 85 ~ 98%;
(3) be hydrolyzed deironing: in copper dross slag, iron level is 0.2 ~ 1.0%, mainly exist with FeO form, in sulfuric acid leaching copper process, iron and sulfuric acid reaction generate FeSO
4enter leach liquor.The hydrogen peroxide reaction 1 ~ 2h of 2 ~ 4% is first added by Fe wherein in copper-bath leach liquor
2+be oxidized to Fe
3+, then solution is passed into steam heating 70 ~ 90 DEG C and be concentrated into proportion 1 ~ 3, then regulate pH value to 1 ~ 5 with lime, hydrolysis reaction 0.5 ~ 1h makes Fe
3+hydrolysis becomes ferric hydroxide precipitate completely, and then carries out solid-liquor separation by pressure filter press filtration and iron is removed, slag rate 3 ~ 10%.
(4) concentrated calcium-magnesium removing: under copper-bath after deironing being heated to 70 ~ 90 DEG C of conditions, take to concentrate while enter the mode of (benefit) liquid, when concentrated proportion 1.1 ~ 1.6, cool to 65 ~ 80 DEG C of vacuum filtrations, oversaturated calcium sulfate and magnesium sulfate are filtered removing, slag rate 1 ~ 5%.
(5) co-crystallization: by the filtered liquid crystallisation by cooling of step (4) gained, add after 98% vitriol oil makes it contain acid 100 ~ 300g/l and carry out salting-out crystallization, solid-liquor separation obtains copper sulfate crystal and mother liquor;
(6) multistage washing: the copper sulfate crystal of step (5) gained is carried out 2 ~ 4 grades of washings, first step clear water washs, and liquid-solid ratio is 0.5 ~ 2.0m
3/ t, its rear stage of the washing before last step washs the copper/saturated copper sulphate solution of generation as washings, and liquid-solid ratio is 1 ~ 3m
3/ t, the washing of every one-level be first by copper sulfate crystal with washings mixing post-heating to 70 ~ 95 DEG C, crystallisation by cooling again after waiting copper sulfate to dissolve completely, solid-liquor separation goes out copper sulfate crystal and washings.The copper sulfate crystal of last step washings gained, utilize vacuum centrifuge to be separated, crystal enters dryer, through drying and being packaged to be the above cupric sulfate pentahydrate product of YS/t94-2007 top grade product.The purity of gained cupric sulfate pentahydrate product is: Cu
2sO
4.5H
2o 99.10%, Zn0.001%, Cd0.0002%, Co0.0005%, Ni0.0002%, Fe0.001%, As0.0003%, Sb < 0.001%, Ca0.0007%, Pb < 0.001%, Bi < 0.001%, Cl < 0.001%, water-insoluble 0.004%.Reach the requirement of YS/T94-2007 top grade quality.
Described step (2) gained leached mud returns plumbous smelting flow process, waits valuable metal for reclaiming plumbous silver.
Described step (3) gained iron dross removing is stored up or is returned fuming furnace batching, for adjusting slag type.
Fuming furnace batching is deposited or returned to described step (4) gained calcium-magnesium removing slag muck, for adjusting slag type.
Described step (5) crystallisation by cooling and salting-out crystallization terminal temperature are 0 ~ 40 DEG C.
The mother liquid obtained step (2) that returns of described step (5) recycles as leaching agent.
Described step (6) the 1st grade washing gained copper/saturated copper sulphate washings returns step (2) and recycles as leaching agent.
Tool of the present invention has the following advantages and effect:
1, copper dross slag is without the need to high melt, without the need to adding reductive agent, oxygenant, flux or catalyzer, adopts oxygen leaching to realize directly leaching the object of copper dross slag, leaching yield more than 90%.
2, without the need to adding cleaner, product purity is high, can reach the above requirement of YS/T94-2007 top grade product.
Embodiment 1
(1) 1t copper dross slag (Cu15.0wt%, Pb75.0 wt %) good for fragmentation is levigate with ball mill, granularity 200, loads hopper and uses in order to leaching.
(2) begin the copper dross slag powder of step (1) gained and sulfur acid the dilution heat of sulfuric acid of sour 130g/l, mix according to liquid-solid ratio 5:1, blast oxygen, at temperature 65 DEG C, oxygen partial pressure 0.3MPa, total pressure 0.8MPa, extraction time 3 hours, and control terminal pH value 2, obtain leaching feed liquid, at 80 DEG C, leaching feed liquid is filtered, obtain leach liquor and leached mud respectively, leaching yield 92%, slag rate 85%;
(3) the hydrogen peroxide reaction 2h of 2% will first be added in the copper-bath leach liquor of step (2) gained by Fe wherein
2+be oxidized to Fe
3+, then solution is passed into steam heating 80 DEG C and be concentrated into proportion 1.5, then regulate pH value to 2 with lime, hydrolysis reaction 1h makes Fe
3+hydrolysis becomes ferric hydroxide precipitate completely, and then carries out solid-liquor separation by pressure filter press filtration and iron is removed, slag rate 15%.
(4) by under after the deironing of step (3) gained, copper-bath is heated to 80 DEG C of conditions, take to concentrate while enter the mode of (benefit) liquid, during concentrated proportion 1.3, cool to 70 DEG C of vacuum filtrations, oversaturated calcium sulfate and magnesium sulfate are filtered removing, slag rate 3%.
(5) co-crystallization: by the filtered liquid crystallisation by cooling of step (4) gained, add after 98% vitriol oil makes it contain sour 200g/l and carry out salting-out crystallization, solid-liquor separation obtains copper sulfate crystal and mother liquor;
(6) multistage washing: the copper sulfate crystal of step (5) gained is carried out 4 grades of washings, first step clear water washs, and liquid-solid ratio is 1.0m
3/ t, its rear stage of the washing before last step washs the copper/saturated copper sulphate solution of generation as washings, and liquid-solid ratio is 1.5m
3/ t, the washing of every one-level be first by copper sulfate crystal with washings mixing post-heating to 75 DEG C, crystallisation by cooling again after waiting copper sulfate to dissolve completely, solid-liquor separation goes out copper sulfate crystal and washings.The copper sulfate crystal of last step washings gained, utilize vacuum centrifuge to be separated, crystal enters dryer, through drying and being packaged to be the above cupric sulfate pentahydrate product of YS/t94-2007 top grade product.The purity of gained cupric sulfate pentahydrate product is: Cu
2sO
4.5H
2o 99.10%, Zn0.001%, Cd0.0002%, Co0.0005%, Ni0.0002%, Fe0.001%, As0.0003%, Sb < 0.001%, Ca0.0007%, Pb < 0.001%, Bi < 0.001%, Cl < 0.001%, water-insoluble 0.004%.Reach the requirement of YS/T94-2007 top grade quality.
Embodiment 2
(1) 200g copper dross slag (Cu10.0wt%, Pb80.0 wt %) good for fragmentation is levigate with ball mill, granularity 400, loads hopper and uses in order to leaching.
(2) begin the copper dross slag powder of step (1) gained and sulfur acid the dilution heat of sulfuric acid of sour 130g/l, mix according to liquid-solid ratio 7:1, blast oxygen, at temperature 75 DEG C, oxygen partial pressure 0.6MPa, total pressure 1.5MPa, extraction time 3 hours, and control terminal pH value 2.5, obtain leaching feed liquid, at 85 DEG C, leaching feed liquid is filtered, obtain leach liquor and leached mud respectively, leaching yield 95%, slag rate 96%;
(3) the hydrogen peroxide reaction 1h of volume ratio 3% will first be added in the copper-bath leach liquor of step (2) gained by Fe wherein
2+be oxidized to Fe
3+, then solution is passed into steam heating 85 DEG C and be concentrated into proportion 2, then regulate pH value to 3 with lime, hydrolysis reaction 0.5h makes Fe
3+hydrolysis becomes ferric hydroxide precipitate completely, and then carries out solid-liquor separation by pressure filter press filtration and iron is removed, slag rate 8%.
(4) by under after the deironing of step (3) gained, copper-bath is heated to 85 DEG C of conditions, take to concentrate while enter the mode of (benefit) liquid, during concentrated proportion 1.3, cool to 75 DEG C of vacuum filtrations, oversaturated calcium sulfate and magnesium sulfate are filtered removing, slag rate 2.0%.
(5) co-crystallization: by the filtered liquid crystallisation by cooling of step (4) gained, add after 98% vitriol oil makes it contain sour 100g/l and carry out salting-out crystallization, solid-liquor separation obtains copper sulfate crystal and mother liquor;
(6) multistage washing: the copper sulfate crystal of step (5) gained is carried out 3 grades of washings, first step clear water washs, and liquid-solid ratio is 2.0m
3/ t, its rear stage of the washing before last step washs the copper/saturated copper sulphate solution of generation as washings, and liquid-solid ratio is 2.0m
3/ t, the washing of every one-level be first by copper sulfate crystal with washings mixing post-heating to 75 DEG C, crystallisation by cooling again after waiting copper sulfate to dissolve completely, solid-liquor separation goes out copper sulfate crystal and washings.The copper sulfate crystal of last step washings gained, utilize vacuum centrifuge to be separated, crystal enters dryer, through drying and being packaged to be the above cupric sulfate pentahydrate product of YS/t94-2007 top grade product.The purity of gained cupric sulfate pentahydrate product is: Cu
2sO
4.5H
2o 99.10%, Zn0.001%, Cd0.0002%, Co0.0005%, Ni0.0002%, Fe0.001%, As0.0003%, Sb < 0.001%, Ca0.0007%, Pb < 0.001%, Bi < 0.001%, Cl < 0.001%, water-insoluble 0.004%.Reach the requirement of YS/T94-2007 top grade quality.
Embodiment 3
(1) 20g copper dross slag (Cu3.0wt%, Pb85.0 wt %) good for fragmentation is levigate with ball mill, granularity 200, loads hopper and uses in order to leaching.
(2) begin the copper dross slag powder of step (1) gained and sulfur acid the dilution heat of sulfuric acid of sour 200g/l, mix according to liquid-solid ratio 10:1, blast oxygen, at temperature 85 DEG C, oxygen partial pressure 0.8MPa, total pressure 2.0MPa, extraction time 3 hours, and control terminal pH value 3, obtain leaching feed liquid, at 80 DEG C, leaching feed liquid is filtered, obtain leach liquor and leached mud respectively, leaching yield 96%, slag rate 97%;
(3) volume ratio 4% hydrogen peroxide reaction 1h will first be added in the copper-bath leach liquor of step (2) gained by Fe wherein
2+be oxidized to Fe
3+, then solution is passed into steam heating 85 DEG C and be concentrated into proportion 2, then regulate pH value to 3 with lime, hydrolysis reaction 0.5h makes Fe
3+hydrolysis becomes ferric hydroxide precipitate completely, and then carries out solid-liquor separation by pressure filter press filtration and iron is removed, slag rate 5%.
(4) by under after the deironing of step (3) gained, copper-bath is heated to 95 DEG C of conditions, take to concentrate while enter the mode of (benefit) liquid, during concentrated proportion 1.6, cool to 70 DEG C of vacuum filtrations, oversaturated calcium sulfate and magnesium sulfate are filtered removing, slag rate 1.5%.
(5) co-crystallization: by the filtered liquid crystallisation by cooling of step (4) gained, add after 98% vitriol oil makes it contain sour 300g/l and carry out salting-out crystallization, solid-liquor separation obtains copper sulfate crystal and mother liquor;
(6) multistage washing: the copper sulfate crystal of step (5) gained is carried out 6 grades of washings, first step clear water washs, and liquid-solid ratio is 1.5m
3/ t, its rear stage of the washing before last step washs the copper/saturated copper sulphate solution of generation as washings, and liquid-solid ratio is 2.5m
3/ t, the washing of every one-level be first by copper sulfate crystal with washings mixing post-heating to 85 DEG C, crystallisation by cooling again after waiting copper sulfate to dissolve completely, solid-liquor separation goes out copper sulfate crystal and washings.The copper sulfate crystal of last step washings gained, utilize vacuum centrifuge to be separated, crystal enters dryer, through drying and being packaged to be the above cupric sulfate pentahydrate product of YS/t94-2007 top grade product.The purity of gained cupric sulfate pentahydrate product is: Cu
2sO
4.5H
2o 99.10%, Zn0.001%, Cd0.0002%, Co0.0005%, Ni0.0002%, Fe0.001%, As0.0003%, Sb < 0.001%, Ca0.0007%, Pb < 0.001%, Bi < 0.001%, Cl < 0.001%, water-insoluble 0.004%.Reach the requirement of YS/T94-2007 top grade quality.
Claims (10)
1. copper dross slag produces a method for copper sulfate, it is characterized in that comprising pre-treatment, leaching, deironing, calcium-magnesium removing, co-crystallization and washing step, specifically comprises:
A, pre-treatment: by for subsequent use for raw copper scum silica frost pulverizing and jevigating;
B, leaching: the copper dross slag after pre-treatment is inserted reactor, add the sulphuric acid soln of solid-liquid volume ratio 4 ~ 10 times, passes into oxygen and/or oxygen-rich air reaction 2 ~ 6h, filter and obtain leach liquor and leached mud at pressure 0.6 ~ 2.0MPa, temperature 60 ~ 90 DEG C;
C, deironing: add hydrogen peroxide reaction 1 ~ 2h in leach liquor, being concentrated into proportion is 1 ~ 3, and adjust ph is 1 ~ 5, and hydrolysis reaction 0.5 ~ 1h obtains ferric hydroxide precipitate, and press filtration is carried out solid-liquor separation and obtained filtrate a and filter residue b;
D, calcium-magnesium removing: the filtrate a obtained after step C deironing is heated to 70 ~ 90 DEG C, being concentrated into proportion is 1.1 ~ 1.6, is cooled to 65 ~ 80 DEG C, filters and obtains filtrate c and filter residue d;
E, co-crystallization: by filtrate c co-crystallization, solid-liquor separation obtains copper sulfate crystal and mother liquor;
F, washing: the copper sulfate crystal obtained is carried out 2 ~ 4 grades of washings, first step clear water washs, and liquid-solid ratio is 0.5 ~ 2.0m
3/ t, its rear stage of the washing before last step washs the copper/saturated copper sulphate solution of generation as washings, and liquid-solid ratio is 1 ~ 3m
3/ t, the washing of every one-level be first by copper sulfate crystal with washings mixing post-heating to 70 ~ 95 DEG C, crystallisation by cooling again after dissolving completely in copper sulfate, solid-liquor separation goes out copper sulfate crystal and washings, the copper sulfate crystal of last step washings gained, utilize vacuum centrifuge to be separated, crystal enters dryer, through drying and being packaged to be target compound.
2. copper dross slag according to claim 1 produces the method for copper sulfate, it is characterized in that the levigate granularity described in step A is 200 ~ 500 orders.
3. copper dross slag according to claim 1 produces the method for copper sulfate, it is characterized in that the sulphuric acid soln concentration described in step B is 100 ~ 200g/L.
4. copper dross slag according to claim 1 produces the method for copper sulfate, it is characterized in that the dividing potential drop passing into oxygen and/or oxygen-rich air described in step B is 0.2 ~ 0.8MPa.
5. copper dross slag according to claim 1 produces the method for copper sulfate, it is characterized in that controlling reaction end pH value after step B also comprises Leaching reaction is 2 ~ 4.
6. copper dross slag according to claim 1 produces the method for copper sulfate, it is characterized in that the filtration described in step B is filtered at 80 ~ 95 DEG C.
7. copper dross slag according to claim 1 produces the method for copper sulfate, it is characterized in that the hydrogen peroxide concentration described in step C is 2 ~ 4%.
8. copper dross slag according to claim 1 produces the method for copper sulfate, and to it is characterized in that described in step C concentrated is pass into be steam heated to 70 ~ 90 DEG C and to concentrate in reaction solution.
9. copper dross slag according to claim 1 produces the method for copper sulfate, and it is characterized in that described in D step concentrated is take to concentrate while the mode of fluid infusion concentrates; Described filtration is vacuum filtration.
10. copper dross slag according to claim 1 produces the method for copper sulfate, it is characterized in that the co-crystallization described in E step is that filtrate c is cooled to 10 ~ 30 DEG C of crystallization 1 ~ 2h, the sulfuric acid adding volumetric concentration 98% makes to carry out salting-out crystallization containing after acid 100 ~ 300g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510138832.4A CN104711431B (en) | 2015-03-27 | 2015-03-27 | A kind of method that copper dross slag produces copper sulphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510138832.4A CN104711431B (en) | 2015-03-27 | 2015-03-27 | A kind of method that copper dross slag produces copper sulphate |
Publications (2)
| Publication Number | Publication Date |
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| CN104711431A true CN104711431A (en) | 2015-06-17 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114107670A (en) * | 2021-11-24 | 2022-03-01 | 白银有色集团股份有限公司 | Method for recovering copper sulfate crystals from waste copper slag |
| CN115807166A (en) * | 2022-11-30 | 2023-03-17 | 郴州雄风环保科技有限公司 | Wet-fire combined treatment process for copper dross |
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| CN101538646A (en) * | 2009-04-28 | 2009-09-23 | 云南驰宏锌锗股份有限公司 | Process method for producing copper sulfate by intensified leaching of copper-containing materials |
| CN102517455A (en) * | 2011-12-29 | 2012-06-27 | 株洲冶炼集团股份有限公司 | Method for recovering cadmium from copper cadmium residues |
| CN103074499A (en) * | 2013-01-31 | 2013-05-01 | 云南驰宏锌锗股份有限公司 | Method for producing high-quality copper sulfate through low-pressure oxygen leaching of copper slag |
| CN104404262A (en) * | 2014-12-25 | 2015-03-11 | 昆明冶金研究院 | Copper scum treatment technique |
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| CN101538646A (en) * | 2009-04-28 | 2009-09-23 | 云南驰宏锌锗股份有限公司 | Process method for producing copper sulfate by intensified leaching of copper-containing materials |
| CN102517455A (en) * | 2011-12-29 | 2012-06-27 | 株洲冶炼集团股份有限公司 | Method for recovering cadmium from copper cadmium residues |
| CN103074499A (en) * | 2013-01-31 | 2013-05-01 | 云南驰宏锌锗股份有限公司 | Method for producing high-quality copper sulfate through low-pressure oxygen leaching of copper slag |
| CN104404262A (en) * | 2014-12-25 | 2015-03-11 | 昆明冶金研究院 | Copper scum treatment technique |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114107670A (en) * | 2021-11-24 | 2022-03-01 | 白银有色集团股份有限公司 | Method for recovering copper sulfate crystals from waste copper slag |
| CN115807166A (en) * | 2022-11-30 | 2023-03-17 | 郴州雄风环保科技有限公司 | Wet-fire combined treatment process for copper dross |
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