CN104711431B - A kind of method that copper dross slag produces copper sulphate - Google Patents
A kind of method that copper dross slag produces copper sulphate Download PDFInfo
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Abstract
The invention discloses a kind of copper dross slag produce copper sulphate method, including pre-treatment, leaching, except iron, removing calcium and magnesium and concentration crystallization step, specifically include：By raw material copper dross slag pulverizing and jevigating, sulfuric acid solution is added, oxygen or oxygen-enriched air reaction is passed through, filtering, hydrogen peroxide reaction is added in leachate, concentration, regulation pH value is 2~4, hydrolysis obtains ferric hydroxide precipitate, press filtration obtains filtrate a and filter residue b, filtrate a heating, concentration, cooling, is filtrated to get filtrate c and filter residue d；Filtrate c condensing crystallizings, the isolated object of traditional vacuum.The present invention overcomes the shortcomings of that existing copper scum treatment method has synthetical recovery, using cupric 10~40%, bismuth 30~50% copper dross slag as raw material, oxygen leaching is carried out using dilution heat of sulfuric acid, obtained leachate remove after iron calcium and magnesium, the crystal of condensing crystallizing obtains the top grade product above cupric sulfate pentahydrate products of YS/t94 2007 by drying.
Description
Technical field
The invention belongs to chemical technology field, and in particular to a kind of method that copper dross slag produces copper sulphate.
Background technology
Copper dross slag is the product that lead bullion melts analysis copper removal, its cupric 3~15%, lead 75~85%, zinc 1~2%, antimony 1~2%, silver
300~2000g/t and other elements（Iron, calcium, magnesium, sulphur etc.）.It is different with equipment due to dragging for slag mode, copper dross slag form also it is each not
It is identical, it is common to have the forms such as loose fine particulate, bulk.
The handling process of known use copper dross slag, which has, can be divided into Blast Furnace Method, reflection oven process, electric furnace process, rotary furnace
Method, the acid-hatching of young eggs, ammonia leaching process etc..Cu/Pb is than relatively low in blast furnace processing copper dross slag, copper matte regulus（Nearly 2~3）, the rate of recovery of copper is low, greatly
The copper of amount is stayed in lead bullion, causes copper, arsenic and noble metal to circulate in the process.Reflection furnace process working condition is poor, the thermal efficiency
The low and blowing-ouf of lines is fast, maintenance is frequent, and being classified as time limit by country eliminates technique.It is high to there is power consumption in electric furnace process（Power consumption 330~
370kwh/tLead bullion, 40~45kg/t of cokeLead bullion）, the shortcomings of operation cost is high be difficult in the area of power tense.Rotary furnace
Method（Also known as rotary furnace method）Processing copper dross slag has that diesel consumption is larger, the higher shortcoming of cost.There is water consumption in the acid-hatching of young eggs, ammonia leaching process
The shortcomings of amount is big, wastewater treatment is costly.
The method that useful converter handles copper dross slag, is according to certain by copper dross slag, soda ash, iron filings or troilite and anthracite
Ratio dispensing, adds reduction melting in converter.700~800 DEG C of temperature is controlled, is smelted 1.5~2 hours；Make the gold in copper dross slag
Category form lead is separated with copper, then improves temperature to 1100~1250 DEG C of slag overtemperature, smelting 2.5~3 hours makes the change of lead
Compound reduction generation metallic lead, copper then realizes asunder copper and lead into matte.Scum silica frost on matte and lead bullion is pulled out, obtained
Matte and lead bullion.This method with coal as reducing agent, fuel is done with diesel oil, production cost is higher, and tail gas is difficult.
Also there is the smelting process of copper dross slag, be by copper dross slag oxidation blowing output silver-bearing copper bismuth alloy, flue dust and oxidizing slag；Silver
Guillaume metal is electrolysed output tough cathode and copper anode mud, and copper anode mud is leached, and first heavy bismuth obtains chlorine oxygen bismuth, chlorine oxygen bismuth warp to leachate
The thick bismuth of reduction melting output, then heavy copper obtain Kocide SD, the thick silver of leached mud rotary furnace melting output, flue dust and oxidizing slag；Slightly
Silver electrolysis output finished product silver and silver anode slime, reclaim Au, Pt, Pd from silver anode slime；Two kinds of oxidizing slag retailoring of blast furnace are obtained
To lead-antimony alloy, flue dust and clinker, lead-antimony alloy reverberatory smelting obtains lead bullion and flue dust；Flue dust reverberatory smelting output lead bullion
And antimony oxide, antimony oxide reduction melting output needle antimony；Lead bullion and lead bullion electrolysis output lead and lead anode slurry, are returned from lead anode slurry
Receive gold and silver.Reverberatory furnace, the blast furnace of this method use belong to highly energy-consuming stove, the complex process taken, the intermediate material of output
It is many.
The method of copper and silver also in separation refining lead production copper dross slag, is, by refining lead production copper dross slag solid material, to be placed in vacuum
Under the conditions of, after repeatedly heating, insulation, volatile matter is collected, pb-ag alloy is condensed to obtain, remaining solid is the copper for sloughing lead and silver
Alloy；Enter conventional lead smelting procedure or electrorefining process using pb-ag alloy as raw material again, silver is enriched in the earth of positive pole, i.e.,
It is recycled silver；The copper alloy of lead and silver is sloughed directly as raw material, metallic copper is recycled in conventional manner.But this method
It is no to realize efficiently separating for lead bronze.
Also there is the method that the side-blown melting of copper dross slag produces lead bullion in addition, be by copper dross slag, soda ash, troilite and anthracite
Dispensing, adds side-blown interior melting according to a certain percentage.600~800 DEG C of temperature is controlled, is smelted 1~2 hour；Make in copper dross slag
Metal form lead is separated with copper, is then improved temperature to 1100~1200 DEG C of slag overtemperature, is smelted 2~3 hours, make the change of lead
Compound reduction generation metallic lead, copper then realizes asunder copper and lead into matte.Scum silica frost on matte and lead bullion is pulled out, obtained
Matte and lead bullion.This method is with anthracite as reducing agent and fuel, and tail gas is difficult, and copper is not comprehensively utilized.Therefore,
A kind of process that can be solved the above problems of exploitation is very important.
The content of the invention
It is an object of the invention to provide a kind of method that copper dross slag produces copper sulphate.
The object of the present invention is achieved like this, including pre-treatment, leaching, except iron, removing calcium and magnesium, co-crystallization and purge step
Suddenly, specifically include：
A, pre-treatment：Raw material copper dross slag pulverizing and jevigating is standby；
B, leaching：Copper dross slag after pre-treatment is inserted into reactor, the sulfuric acid solution of 4~10 times of solid-liquid volume ratio is added,
React 2~6h in being passed through oxygen or oxygen-enriched air at 0.6~2.0MPa of pressure, 60~90 DEG C of temperature, be filtrated to get leachate and
Leached mud；
C, except iron：Hydrogen peroxide is added in leachate and reacts 1~2h, it is 1~3 to be concentrated into proportion, regulation pH value is 1~5, water
0.5~1h of solution reaction obtains ferric hydroxide precipitate, and press filtration carries out solid-liquor separation and obtains filtrate a and filter residue b；
D, removing calcium and magnesium：Step C is removed to the filtrate a obtained after iron and is heated to 70~90 DEG C, it is 1.1~1.6 to be concentrated into proportion,
65~80 DEG C are cooled to, filtrate c and filter residue d is filtrated to get；
E, co-crystallization：By filtrate c co-crystallizations, solid-liquor separation obtains copper sulfate crystal and mother liquor；
F, washing：Obtained copper sulfate crystal is subjected to 2~4 grades of washings, the first order is washed with clear water, and liquid-solid ratio value is
0.5~2.0m3Washing before/t, afterbody washs the copper/saturated copper sulphate solution produced with its rear stage as cleaning solution,
Liquid-solid ratio value is 1~3m3/ t, the washing per one-level is that 70~95 DEG C are heated to after first copper sulfate crystal is mixed with cleaning solution,
Crystallisation by cooling again after being completely dissolved Deng copper sulphate, solid-liquor separation goes out copper sulfate crystal and cleaning solution, obtained by afterbody cleaning solution
Copper sulfate crystal, separated using vacuum centrifuge, crystal enters dryer, by drying and being packaged to be object.
The present invention overcomes the shortcomings of that existing copper scum treatment method haves the shortcomings that synthetical recovery and complex process, with cupric
3~15%, the copper dross slag of lead 75~85% is raw material, and oxygen leaching is carried out using dilution heat of sulfuric acid, and obtained leachate is removed
After iron calcium and magnesium, co-crystallization, including crystallisation by cooling and salting-out crystallization are then carried out, obtained copper sulfate crystal carries out multistage and washed again
Wash, dried after last vacuum separation, obtain YS/t94-2007 top grade product above cupric sulfate pentahydrate products.
Brief description of the drawings
Fig. 1 is present invention process schematic flow sheet.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is further illustrated, but the present invention is not subject in any way
Limitation, based on present invention teach that any conversion or replacement made, belong to protection scope of the present invention.
The method that copper dross slag of the present invention produces copper sulphate, including pre-treatment, leachings, tie except iron, removing calcium and magnesium, joint
Brilliant and washing step, is specifically included：
A, pre-treatment：Raw material copper dross slag pulverizing and jevigating is standby；
B, leaching：Copper dross slag after pre-treatment is inserted into reactor, the sulfuric acid solution of 4~10 times of solid-liquid volume ratio is added,
In being passed through oxygen and/or oxygen-enriched air 2~6h of reaction at 0.6~2.0MPa of pressure, 60~90 DEG C of temperature, leachate is filtrated to get
And leached mud；
C, except iron：Hydrogen peroxide is added in leachate and reacts 1~2h, it is 1~3 to be concentrated into proportion, regulation pH value is 1~5, water
0.5~1h of solution reaction obtains ferric hydroxide precipitate, and press filtration carries out solid-liquor separation and obtains filtrate a and filter residue b；
D, removing calcium and magnesium：Step C is removed to the filtrate a obtained after iron and is heated to 70~90 DEG C, it is 1.1~1.6 to be concentrated into proportion,
65~80 DEG C are cooled to, filtrate c and filter residue d is filtrated to get；
E, co-crystallization：By filtrate c co-crystallizations, solid-liquor separation obtains copper sulfate crystal and mother liquor；
F, washing：Obtained copper sulfate crystal is subjected to 2~4 grades of washings, the first order is washed with clear water, and liquid-solid ratio value is
0.5~2.0m3Washing before/t, afterbody washs the copper/saturated copper sulphate solution produced with its rear stage as cleaning solution,
Liquid-solid ratio value is 1~3m3/ t, the washing per one-level is that 70~95 DEG C are heated to after first copper sulfate crystal is mixed with cleaning solution,
Crystallisation by cooling again after being completely dissolved Deng copper sulphate, solid-liquor separation goes out copper sulfate crystal and cleaning solution, obtained by afterbody cleaning solution
Copper sulfate crystal, separated using vacuum centrifuge, crystal enters dryer, by drying and being packaged to be object.
Levigate granularity described in step A is 200~500 mesh.
Sulfuric acid solution concentration described in step B is 100~200g/L.
Be passed through oxygen and/or the partial pressure of oxygen-enriched air described in step B are 0.2~0.8MPa.
Step B also includes controlling reaction end pH value to be 2~4 after Leach reaction.
Filtering described in step B is filtered at 80~95 DEG C.
Hydrogen peroxide concentration described in step C is 2~4%.
Concentration described in step C is to be passed through to be steam heated to 70~90 DEG C of concentrations in reaction solution.
Concentration described in D steps is that the mode for taking the fluid infusion in concentration is concentrated；Described filtering is vacuum mistake
Filter.
Co-crystallization described in E steps is that filtrate c is cooled into 10~30 DEG C of 1~2h of crystallization, adds volumetric concentration 98%
Sulfuric acid make 100~300g/L containing acid after carry out salting-out crystallization.
The present invention includes implementation steps in detail below：
（1）The ball milling of copper dross slag：The copper dross slag crushed is levigate with ball mill, granularity 200~500, load hopper with
Standby leach is used.
（2）Oxygen leaching：By sulfur acid beginning 100~200g/l of acid dilution heat of sulfuric acid and copper dross slag powder, according to liquid-solid ratio
（4~10）:1 mixing, blasts oxygen and oxygen-enriched air, in 60~90 DEG C of temperature, 0.2~0.8MPa of oxygen partial pressure, gross pressure 0.6
~2.0MPa, extraction time 2~6 hours, and terminal pH value 2~4 is controlled, obtain leaching feed liquid, to leaching at 80~95 DEG C
Feed liquid is filtered, and respectively obtains leachate and leached mud, leaching rate 90~99%, slag rate 85~98%；
（3）Hydrolysis removes iron：Iron content mainly exists 0.2~1.0% in FeO forms in copper dross slag, and copper mistake is soaked in sulfuric acid
Cheng Zhong, iron generates FeSO with sulfuric acid reaction4Into leachate.First added in copper-bath leachate 2~4% hydrogen peroxide
1~2h is reacted by Fe therein2+It is oxidized to Fe3+, solution is then passed through 70~90 DEG C of steam heating and is concentrated into proportion 1~3,
PH values are adjusted to 1~5 with lime again, and 0.5~1h of hydrolysis makes Fe3+Hydrolysis goes completely into ferric hydroxide precipitate, then leads to again
Cross filter press press filtration to carry out solid-liquor separation and remove iron, slag rate 3~10%.
（4）Concentrate removing calcium and magnesium：Copper-bath after iron will be removed to be heated under the conditions of 70~90 DEG C, take and enter in concentration
（Mend）The mode of liquid, during concentration proportion 1.1~1.6, cools to 65~80 DEG C of vacuum filters, oversaturated calcium sulfate and magnesium sulfate
It is filtered to remove, slag rate 1~5%.
（5）Co-crystallization：By step（4）The filtered fluid crystallisation by cooling of gained, add 98% concentrated sulfuric acid make its containing acid 100~
Salting-out crystallization is carried out after 300g/l, solid-liquor separation obtains copper sulfate crystal and mother liquor；
（6）Multistage washing：By step（5）The copper sulfate crystal of gained carries out 2~4 grades of washings, and the first order is washed with clear water,
Liquid-solid ratio value is 0.5~2.0m3Washing before/t, afterbody is washed the copper/saturated copper sulphate solution produced with its rear stage and made
For cleaning solution, liquid-solid ratio value is 1~3m3/ t, the washing per one-level is heated to after first copper sulfate crystal is mixed with cleaning solution
70~95 DEG C, wait copper sulphate be completely dissolved after crystallisation by cooling again, solid-liquor separation goes out copper sulfate crystal and cleaning solution.Afterbody is washed
The copper sulfate crystal obtained by liquid is washed, is separated using vacuum centrifuge, crystal enters dryer, by drying and being packaged to be YS/
T94-2007 top grade product above cupric sulfate pentahydrate products.The purity of gained cupric sulfate pentahydrate product is：Cu2SO4.5H2O
99.10%th, 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 YS/T94-2007 top grades
Quality requirement.
The step（2）Gained leached mud returns to lead and smelts flow, for reclaiming the valuable metals such as lead silver.
The step（3）Fuming furnace dispensing is stored up or returned to gained iron dross removing, for adjusting slag type.
The step（4）Fuming furnace dispensing is deposited or returned to gained removing calcium and magnesium slag muck, for adjusting slag type.
The step（5）Crystallisation by cooling and salting-out crystallization outlet temperature are 0~40 DEG C.
The step（5）Mother liquid obtained return to step（2）Recycled as leaching agent.
The step（6）1st grade of washing gained copper/saturated copper sulphate cleaning solution return to step（2）Make as leaching agent circulation
With.
The invention has the advantages that and effect：
1st, copper dross slag is without high melt, without adding reducing agent, oxidant, flux or catalyst, using oxygen leaching
Realize the purpose for directly leaching copper dross slag, leaching rate more than 90%.
2nd, cleaner need not be added, product purity is high, can reach YS/T94-2007 top grade product requirements above.
Embodiment 1
（1）By the 1t copper dross slags crushed（Cu15.0wt%, Pb75.0 wt %）It is levigate with ball mill, granularity 200, dress
Material bin is used in case leaching.
（2）By step（1）The dilution heat of sulfuric acid of the copper dross slag powder of gained and sulfur acid beginning acid 130g/l, according to liquid-solid ratio 5:
1 mixing, blasts oxygen, in 65 DEG C of temperature, oxygen partial pressure 0.3MPa, gross pressure 0.8MPa, extraction time 3 hours, and controls end
Point pH value 2, obtains leaching feed liquid, to leaching feed liquid filtering at 80 DEG C, respectively obtains leachate and leached mud, leaching rate 92%,
Slag rate 85%；
（3）By step（2）The hydrogen peroxide that 2% is first added in the copper-bath leachate of gained reacts 2h by Fe therein2+
It is oxidized to Fe3+, solution is then passed through 80 DEG C of steam heating and is concentrated into proportion 1.5, then pH values are adjusted to 2 with lime, hydrolysis is anti-
1h is answered to make Fe3+Hydrolysis goes completely into ferric hydroxide precipitate, then carries out solid-liquor separation by filter press press filtration again and removes iron,
Slag rate 15%.
（4）By step（3）The copper-bath after iron that removes of gained is heated under the conditions of 80 DEG C, is taken and is entered in concentration（Mend）
The mode of liquid, during concentration proportion 1.3, cools to 70 DEG C of vacuum filters, oversaturated calcium sulfate and magnesium sulfate are filtered to remove, slag
Rate 3%.
（5）Co-crystallization：By step（4）The filtered fluid crystallisation by cooling of gained, adding 98% concentrated sulfuric acid makes its 200g/l containing acid
After carry out salting-out crystallization, solid-liquor separation obtains copper sulfate crystal and mother liquor；
（6）Multistage washing：By step（5）The copper sulfate crystal of gained carries out 4 grades of washings, and the first order is washed with clear water, liquid
Gu ratio is 1.0m3Washing before/t, afterbody washs the copper/saturated copper sulphate solution produced with its rear stage as washing
Liquid, liquid-solid ratio value is 1.5m3/ t, the washing per one-level is that 75 DEG C are heated to after first copper sulfate crystal is mixed with cleaning solution, etc.
Crystallisation by cooling again after copper sulphate is completely dissolved, solid-liquor separation goes out copper sulfate crystal and cleaning solution.Obtained by afterbody cleaning solution
Copper sulfate crystal, is separated using vacuum centrifuge, and crystal enters dryer, excellent by drying and being packaged to be YS/t94-2007
Level product above cupric sulfate pentahydrate product.The purity of gained cupric sulfate pentahydrate product is：Cu2SO4.5H2O 99.10%、Zn0.001%、
Cd0.0002%, Co0.0005%, Ni0.0002%, Fe0.001%, As0.0003%, Sb ＜ 0.001%, Ca0.0007%, Pb ＜
0.001%th, Bi ＜ 0.001%, Cl ＜ 0.001%, water-insoluble 0.004%.Reach the requirement of YS/T94-2007 top grades quality.
Embodiment 2
（1）By the 200g copper dross slags crushed（Cu10.0wt%, Pb80.0 wt %）It is levigate with ball mill, granularity 400,
Load hopper and used in case leaching.
（2）By step（1）The dilution heat of sulfuric acid of the copper dross slag powder of gained and sulfur acid beginning acid 130g/l, according to liquid-solid ratio 7:
1 mixing, blasts oxygen, in 75 DEG C of temperature, oxygen partial pressure 0.6MPa, gross pressure 1.5MPa, extraction time 3 hours, and controls end
Point pH value 2.5, obtains leaching feed liquid, to leaching feed liquid filtering at 85 DEG C, respectively obtains leachate and leached mud, leaching rate
95%, slag rate 96%；
（3）By step（2）First added in the copper-bath leachate of gained volume ratio 3% hydrogen peroxide reaction 1h by its
In Fe2+It is oxidized to Fe3+, solution is then passed through 85 DEG C of steam heating and is concentrated into proportion 2, then pH values are adjusted to 3 with lime,
Hydrolysis 0.5h makes Fe3+Hydrolysis goes completely into ferric hydroxide precipitate, then again by filter press press filtration progress solid-liquor separation
Remove iron, slag rate 8%.
（4）By step（3）The copper-bath after iron that removes of gained is heated under the conditions of 85 DEG C, is taken and is entered in concentration（Mend）
The mode of liquid, during concentration proportion 1.3, cools to 75 DEG C of vacuum filters, oversaturated calcium sulfate and magnesium sulfate are filtered to remove, slag
Rate 2.0%.
（5）Co-crystallization：By step（4）The filtered fluid crystallisation by cooling of gained, adding 98% concentrated sulfuric acid makes its 100g/l containing acid
After carry out salting-out crystallization, solid-liquor separation obtains copper sulfate crystal and mother liquor；
（6）Multistage washing：By step（5）The copper sulfate crystal of gained carries out 3 grades of washings, and the first order is washed with clear water, liquid
Gu ratio is 2.0m3Washing before/t, afterbody washs the copper/saturated copper sulphate solution produced with its rear stage as washing
Liquid, liquid-solid ratio value is 2.0m3/ t, the washing per one-level is that 75 DEG C are heated to after first copper sulfate crystal is mixed with cleaning solution, etc.
Crystallisation by cooling again after copper sulphate is completely dissolved, solid-liquor separation goes out copper sulfate crystal and cleaning solution.Obtained by afterbody cleaning solution
Copper sulfate crystal, is separated using vacuum centrifuge, and crystal enters dryer, excellent by drying and being packaged to be YS/t94-2007
Level product above cupric sulfate pentahydrate product.The purity of gained cupric sulfate pentahydrate product is：Cu2SO4.5H2O 99.10%、Zn0.001%、
Cd0.0002%, Co0.0005%, Ni0.0002%, Fe0.001%, As0.0003%, Sb ＜ 0.001%, Ca0.0007%, Pb ＜
0.001%th, Bi ＜ 0.001%, Cl ＜ 0.001%, water-insoluble 0.004%.Reach the requirement of YS/T94-2007 top grades quality.
Embodiment 3
（1）By the 20g copper dross slags crushed（Cu3.0wt%, Pb85.0 wt %）It is levigate with ball mill, granularity 200, dress
Material bin is used in case leaching.
（2）By step（1）The dilution heat of sulfuric acid of the copper dross slag powder of gained and sulfur acid beginning acid 200g/l, according to liquid-solid ratio
10:1 mixing, blasts oxygen, in 85 DEG C of temperature, oxygen partial pressure 0.8MPa, gross pressure 2.0MPa, extraction time 3 hours, and controls
Terminal pH value 3, obtains leaching feed liquid, to leaching feed liquid filtering at 80 DEG C, respectively obtains leachate and leached mud, leaching rate
96%, slag rate 97%；
（3）By step（2）The hydrogen peroxide of volume ratio 4% reaction 1h is first added in the copper-bath leachate of gained will wherein
Fe2+It is oxidized to Fe3+, solution is then passed through 85 DEG C of steam heating and is concentrated into proportion 2, then pH values are adjusted to 3, water with lime
Solution reaction 0.5h makes Fe3+Hydrolysis goes completely into ferric hydroxide precipitate, then carries out solid-liquor separation by filter press press filtration again and makes
Iron is removed, slag rate 5%.
（4）By step（3）The copper-bath after iron that removes of gained is heated under the conditions of 95 DEG C, is taken and is entered in concentration（Mend）
The mode of liquid, during concentration proportion 1.6, cools to 70 DEG C of vacuum filters, oversaturated calcium sulfate and magnesium sulfate are filtered to remove, slag
Rate 1.5%.
（5）Co-crystallization：By step（4）The filtered fluid crystallisation by cooling of gained, adding 98% concentrated sulfuric acid makes its 300g/l containing acid
After carry out salting-out crystallization, solid-liquor separation obtains copper sulfate crystal and mother liquor；
（6）Multistage washing：By step（5）The copper sulfate crystal of gained carries out 6 grades of washings, and the first order is washed with clear water, liquid
Gu ratio is 1.5m3Washing before/t, afterbody washs the copper/saturated copper sulphate solution produced with its rear stage as washing
Liquid, liquid-solid ratio value is 2.5m3/ t, the washing per one-level is that 85 DEG C are heated to after first copper sulfate crystal is mixed with cleaning solution, etc.
Crystallisation by cooling again after copper sulphate is completely dissolved, solid-liquor separation goes out copper sulfate crystal and cleaning solution.Obtained by afterbody cleaning solution
Copper sulfate crystal, is separated using vacuum centrifuge, and crystal enters dryer, excellent by drying and being packaged to be YS/t94-2007
Level product above cupric sulfate pentahydrate product.The purity of gained cupric sulfate pentahydrate product is：Cu2SO4.5H2O 99.10%、Zn0.001%、
Cd0.0002%, Co0.0005%, Ni0.0002%, Fe0.001%, As0.0003%, Sb ＜ 0.001%, Ca0.0007%, Pb ＜
0.001%th, Bi ＜ 0.001%, Cl ＜ 0.001%, water-insoluble 0.004%.Reach the requirement of YS/T94-2007 top grades quality.
Claims (6)
1. a kind of method that copper dross slag produces copper sulphate, it is characterised in that including pre-treatment, leaching, except iron, removing calcium and magnesium, joint knot
Brilliant and washing step, is specifically included：
A, pre-treatment：Raw material copper dross slag pulverizing and jevigating is standby, and copper dross slag is the product that lead bullion melts analysis copper removal；
B, leaching：Copper dross slag after pre-treatment is inserted into reactor, the sulfuric acid solution that concentration is 130 ~ 200g/L, solid-liquid is added
Product compares 1:7 ~ 10,3 ~ 6h is reacted in being passed through oxygen and/or oxygen-enriched air at 1.5 ~ 2.0MPa of pressure, 75 ~ 90 DEG C of temperature, reaction
Endpoint pH is 2 ~ 4, and leachate and leached mud are filtrated to get at 80 ~ 95 DEG C；
C, except iron：Hydrogen peroxide is added in leachate and reacts 1 ~ 2h, it is 1 ~ 3 to be concentrated into proportion, regulation pH value is 1 ~ 5, hydrolysis
0.5 ~ 1h obtains ferric hydroxide precipitate, and press filtration carries out solid-liquor separation and obtains filtrate a and filter residue b；
D, removing calcium and magnesium：Step C is removed to the filtrate a obtained after iron and is heated to 70 ~ 90 DEG C, it is 1.1 ~ 1.6 to be concentrated into proportion, is cooled to
65 ~ 80 DEG C, it is filtrated to get filtrate c and filter residue d；
E, co-crystallization：By filtrate c co-crystallizations, co-crystallization is that filtrate c is cooled into 10 ~ 30 DEG C of 1 ~ 2h of crystallization, adds body
The sulfuric acid of product concentration 98% carries out salting-out crystallization after making 100 ~ 300g/L containing acid, and solid-liquor separation obtains copper sulfate crystal and mother liquor；
F, washing：Obtained copper sulfate crystal being subjected to 2 ~ 4 grades of washings, the first order washed with clear water, liquid-solid ratio value is 0.5 ~
2.0m3Washing before/t, afterbody washs the copper/saturated copper sulphate solution produced with its rear stage as cleaning solution, liquid-solid ratio
It is worth for 1 ~ 3m3/ t, the washing per one-level is that 70 ~ 95 DEG C are heated to after first copper sulfate crystal is mixed with cleaning solution, waits copper sulphate
Crystallisation by cooling again after being completely dissolved, solid-liquor separation goes out copper sulfate crystal and cleaning solution, the copper sulphate obtained by afterbody cleaning solution
Crystal, is separated using vacuum centrifuge, and crystal enters dryer, by drying and being packaged to be object.
2. the method that copper dross slag according to claim 1 produces copper sulphate, it is characterised in that levigate granularity described in step A
For 200 ~ 500 mesh.
3. the method that copper dross slag according to claim 1 produces copper sulphate, it is characterised in that oxygen is passed through described in step B
And/or the partial pressure of oxygen-enriched air is 0.2 ~ 0.8MPa.
4. the method that copper dross slag according to claim 1 produces copper sulphate, it is characterised in that hydrogen peroxide concentration described in step C
For 2 ~ 4%.
5. the method that copper dross slag according to claim 1 produces copper sulphate, it is characterised in that concentration is anti-described in step C
Answer to be passed through in liquid and be steam heated to 70 ~ 90 DEG C of concentrations.
6. the method that copper dross slag according to claim 1 produces copper sulphate, it is characterised in that concentration is to take described in D steps
In concentration, the mode of fluid infusion is concentrated；Described filtering is vacuum filter.
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| 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 |
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