CN104384169B - The separation and recovery method of pyrite cinder - Google Patents
The separation and recovery method of pyrite cinder Download PDFInfo
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- CN104384169B CN104384169B CN201410529726.4A CN201410529726A CN104384169B CN 104384169 B CN104384169 B CN 104384169B CN 201410529726 A CN201410529726 A CN 201410529726A CN 104384169 B CN104384169 B CN 104384169B
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Abstract
The separation and recovery method of pyrite cinder.It belongs to inorganic chemical technology field.Present invention aqueous suspension separates calcium hydroxide, magnesium hydroxide and aluminium hydroxide, then dissolves the di-iron trioxide/ferrous oxide in pyrite cinder with SPA, and the sulphur immiscible with SPA, silica and trace meter simple substance mixture are separated by filtration；Separation and recovery di-iron trioxide/ferrous oxide, aluminium hydroxide, calcium carbonate/magnesium carbonate or calcium sulfate/magnesium sulfate, sulfuric acid, sodium metasilicate/potassium silicate and micro copper, lead, zinc, cobalt, the metal simple-substance mixture of Jin Heyin.Separating product is used for industrial raw materials and construction material.
Description
Art：
The present invention relates to the separation and recovery method of inorganic chemical technology field, particularly pyrite cinder.
Background technology：
Troilite produces sulfuric acid, and often producing 1 ton of sulfuric acid will produce 0.8-0.9 tons of pyrite cinder (sulfate slag), China
Annual pyrite cinder discharge capacity is up to 3,000,000 tons, and waste residue yield is huge.Because China's troilite is mostly lean ore, sulfate slag
Middle sulfur content is too high, iron oxide and ferrous oxide content are most below 50%, and the impurity content such as silica is too high, so often
The sulfate slag that year directly recycles only has 1,000,000 tons or so, causes the serious wasting of resources, environmental pollution and land seizure
Waste, so from resources conservation, the angle of effectively utilization and environmental protection, waste residue separation and recovery is significant.Troilite is produced
The main component of waste residue of sulfuric acid (sulfate slag) has：Di-iron trioxide is iron oxide and ferrous oxide, accounts for waste residue 20%--60%, sulphur
Ferrous oxide content seldom, silica, accounts for waste residue 15%--55% in acid sludge, aluminum oxide, accounts for waste residue 10%, calcium oxide, accounts for
Waste residue 5%, magnesia, accounts for waste residue below 5%, and sulphur, accounts for waste residue 1%-2%；In addition with micro copper, lead, zinc, cobalt, gold
With the trace meter simple substance such as silver.In the prior art also without inexpensive, simple efficient real separation and recovery method, serious system
Yue Liao China troilite produces the development of sulfuric acid industry, had not only wasted resource but also had compromised environment.Existing isolation technics, uses salt
Acid or sulfuric acid chemical reaction, this is clearly to talk about stratagems on paper.
Chemically reacted with hydrochloric acid or sulfuric acid, both changed di-iron trioxide, ferrous oxide, aluminum oxide, calcium oxide in waste residue
With the hyle form of magnesia, substantial amounts of hydrochloric acid or sulfuric acid are also consumes, drastically increase waste residue separation costs, while
The water soluble salt mixture for being difficult to separate is generated again；Particularly with sulfuric acid reaction, troilite production sulfuric acid produces waste residue, and is
Separating waste residues again fall sulfuric acid consumption, and pyrite slag amount is too big, lose to come as the sulfuric acid of essential industry raw material
Source.Due to technical bottleneck, China's sulfuric acid industry is faced with awkward predicament：Produced with troilite, waste residue is difficult to separate and recover；With sulphur
(S) ore deposit production, resource-constrained, it is impossible to meet the growth requirement of China's sulfuric acid industry.
The content of the invention：
Inventive principle：
According to existing knowledge, iron oxide and/or ferrous oxide are dissolved in acid, and phosphoric acid is middle strong acid or weak acid, and it is almost
Without oxidisability, so only liquid SPA (80%-85%) could dissolve iron oxide and/or ferrous oxide and in short-term
It is interior not chemically reacted with iron oxide and/or ferrous oxide.Under the conditions of long-time of the SPA only more than 24 hours is placed,
Just with di-iron trioxide and/or ferrous oxide slow reaction；And in the phosphoric acid,diluted aqueous solution below 50%, iron oxide and/or
Ferrous oxide is then immediately disconnected precipitation；Combined with water because phosphoric acid is soluble in water, water is polar molecule, hydrone separates and broken
The polar attraction between iron oxide and/or ferrous oxide molecule and phosphoric acid molecules is broken, and makes iron oxide and/or ferrous oxide point
Son departs from phosphoric acid molecules, free aggregate and precipitate.The present invention only dissolves iron oxide and/or ferrous oxide using SPA, without with
Chemical reaction, the property of Precipitation di-iron trioxide and/or ferrous oxide realizes pyrite in the phosphoric acid,diluted aqueous solution
The separation and recovery of (useless) slag.
The trace meter simple substance such as silica, sulphur and copper, lead, zinc, cobalt, gold and silver does not dissolve in SPA.
To the trace meter simple substance mixture such as silica, sulphur and micro copper, lead, zinc, cobalt, gold and silver, it is also possible to use
Carbon disulfide or carbon tetrachloride or benzene dissolving sulphur, precipitate and separate silica and micro copper, lead, zinc, cobalt, gold and silver etc. are micro-
Amount metal simple-substance mixture；Vacuum pump-down is evaporated, and separates and recovers carbon disulfide or carbon tetrachloride or benzene, while separating and recovering sulphur.
According to existing knowledge, the fusing point of phosphoric acid is 21 DEG C, this be conducive to phosphoric acid from its dilute aqueous solution cryoprecipitation separate,
Dehydration is reclaimed.
It is of the invention to be iron oxide and ferrous oxide waste residue containing di-iron trioxide, add water dilution phosphorus with SPA dissolving
Acid, Precipitation separation and recovery di-iron trioxide are that the method for iron oxide and ferrous oxide is that core technology of the invention is innovated
Essential features.
Technical scheme：
One, is sulfate slag with enough water immersion pyrite cinders, and is stirred, 50 turns -200 revs/min of rotating speed, mixing time
1-2 hours, the aluminum oxide in sulfate slag, calcium oxide, magnesia is set to be separately converted to aluminium hydroxide, calcium hydroxide, magnesium hydroxide
And turn into suspension emulsion, stand, make di-iron trioxide or/and ferrous oxide, silica, sulphur and micro copper, lead, zinc,
Cobalt, gold and silver metal simple substance mixture precipitate and separate immediately；Simultaneous separation of hydrogen aluminum oxide, calcium hydroxide, magnesium hydroxide suspend newborn
Turbid liquid；
Two, in aluminium hydroxide, calcium hydroxide, the magnesium hydroxide suspension emulsion of above-mentioned (one) to adding enough titanium dioxides
Carbon CO2Or air, stirring, 50 turns -200 revs/min of rotating speed, 2-8 hours stirring reaction time, make calcium hydroxide, magnesium hydroxide point
Calcium carbonate and magnesium carbonate or basic magnesium carbonate and immediately precipitate and separate are not converted into, then are precipitated from suspending aluminum hydroxide emulsion
Or aluminium hydroxide is separated by filtration, reclaim aluminium hydroxide, water circulation use；
Three, by the di-iron trioxide or/and ferrous oxide of above-mentioned (one), silica, sulphur and micro copper, lead, zinc,
Cobalt, gold and silver metal simple substance mixture stack nature draining, or by it at 25 DEG C -- 100 DEG C, the condition of pressure 25pa--100pa
Under, it is stirred under vacuum dehydration；Remove excessive moisture；Need not definitely be completely dried；
Four, in the calcium carbonate and magnesium carbonate or basic carbonate magnesium compound of above-mentioned (two) to adding enough dilute sulfuric acids water-soluble
Liquid, stirring makes calcium carbonate and magnesium carbonate or basic magnesium carbonate generation gypsum calcium sulfate and magnesium sulfate solution, staticly settles separation
Gypsum calcium sulfate is reclaimed, and magnesium sulfate solution vacuum dehydration is dried, pressure 25pa--100pa, 25 DEG C of temperature -- 100 DEG C,
- 24 hours 8 hours drying time, separate and recover magnesium sulfate；This step can also be omitted, and by calcium carbonate and magnesium carbonate or basic carbonate
Magnesium compound is directly used as construction material；
Five, at normal temperatures, di-iron trioxide or/and ferrous oxide, silica, sulphur above-mentioned (three) and micro
In the mixture of copper, lead, zinc, cobalt, gold and silver metal simple substance, the SPA of excessive 80%--85%, SPA and three are added
Aoxidize the body of two iron or/and ferrous oxide, silica, sulphur and micro copper, lead, zinc, cobalt, gold and silver metal simple substance mixture
Product is than being that 4-6: 1 i.e. 4 to 6 compare 1；SPA consumption need not be excessive, sub- can be completely dissolved di-iron trioxide or/and oxidation
Iron simultaneously can filter out SPA and be defined with the solution of di-iron trioxide or/and ferrous oxide；Di-iron trioxide or/and oxidation
Ferrous iron, silica, sulphur and micro copper, lead, zinc, cobalt, the mixture of gold and silver metal simple substance need several times or continuous even
Speed adds SPA stirring and dissolving；Stirring, 50 turns -200 revs/min of rotating speed, mixing time 10-60 minutes, make di-iron trioxide or/
After being dissolved completely in SPA with ferrous oxide, filter under stress immediately, separate silica, sulphur and micro copper, lead,
Zinc, cobalt, gold and silver metal simple substance mixture；And with appropriate water agitator treating silica, sulphur and micro copper, lead, zinc,
Cobalt, gold and silver metal simple substance mixture, a small amount of phosphate aqueous solution containing a small amount of phosphoric acid are recycled in following (six)；This step
It is exothermic dissolution that SPA dissolves di-iron trioxide or/and ferrous oxide, if solution temperature is too high, with cold in course of dissolution
Gas or less than 25 DEG C of air cooling are lowered the temperature or/and outside dissolution vessel with cooling water temperature, SPA solution temperature is existed
25℃--50℃；Dissolution time is within 1 hour；
The solution of the di-iron trioxide of above-mentioned (five) or/and ferrous oxide and SPA is added water to dilute by six, immediately, is made
Phosphoric acid mass content in phosphate aqueous solution drops to 30%--50%, stirs, and stands, and makes di-iron trioxide or/and oxygen
Precipitation is separated immediately from the phosphoric acid,diluted aqueous solution to change ferrous iron, reclaims di-iron trioxide or/and ferrous oxide；
The phosphoric acid,diluted aqueous solution of above-mentioned (six) is concentrated in vacuo dehydration, 40 DEG C -100 DEG C of heating-up temperature, pressure 25pa-- by seven,
100pa, time 8-24 hours, makes phosphoric acid quality content in 80%--85%, and phosphoric acid circulation is utilized；Or above-mentioned phosphoric acid,diluted is water-soluble
Liquid is cooled to 1 DEG C -15 DEG C, makes phosphoric acid in crystal gel shape Precipitation, takes out moisture more than phosphoric acid precipitates layer, phosphoric acid and water
Recycle respectively；Aluminium hydroxide do not dissolve in SPA, can aluminium hydroxide, silica, sulphur and micro copper, lead, zinc,
Appropriate water is added in cobalt, gold and silver metal simple substance mixture, is stirred, stood, suspended, precipitate or be separated by filtration aluminium hydroxide,
Water circulation use；
Eight, are by the silica SiO of above-mentioned (five)2, sulphur and micro copper, lead, zinc, cobalt, gold and the mixing of silver metal simple substance
Thing, adds enough oxygen O2Burning, makes sulphur S generate sulfur trioxide SO3, and with enough Water Sproading sulfur trioxides, obtain sulphur
Acid, reclaims sulfuric acid；Separate the mixing of silica and micro copper, lead, zinc, cobalt, gold and silver metal simple substance or its oxide
Thing；
Nine, are by the silica and micro copper of above-mentioned (eight), lead, zinc, cobalt, gold and silver metal simple substance or its oxide
Mixture, adds enough NaOH or potassium hydroxide aqueous solution, and stirring reaction makes silica generate sodium metasilicate/silicic acid
Aqueous solutions of potassium；
SiO2+ 2NaOH=Na2SiO3+H2O, SiO2+ 2KOH=K2SiO3+H2O；
Precipitation separates micro copper, lead, zinc, cobalt, gold and silver metal simple substance or its hopcalite；By silicic acid
Sodium or potassium silicate aqueous solution vacuum concentration are dehydrated, and pressure 25pa--100pa time 8-24 hours, reclaims sodium metasilicate or silicon
Sour potassium；
Ten, reclaim the micro copper of above-mentioned (nine), lead, zinc, cobalt, gold and silver metal simple substance or its hopcalite
Recycle.
The present invention, is not particularly illustrated, and is normal temperature and normal pressure.
Beneficial effect：
1. the present invention has greatly saved waste residue stacking soil.
2. the present invention saves and is effectively utilized the natural resources of preciousness.
3. the present invention protects water environment and water resource.
4. the present invention opens the new wide of the raw material such as di-iron trioxide i.e. iron oxide and ferrous oxide, aluminium hydroxide
Raw material sources, saved the energy.
5. present invention safety in production, prevents inflammable, toxic gas discharge.
Optimal technical scheme of the present invention：
One, is sulfate slag with enough water immersion pyrite cinders, and is stirred, 50 turns -200 revs/min of rotating speed, mixing time
1-2 hours, the aluminum oxide in sulfate slag, calcium oxide, magnesia is set to be separately converted to aluminium hydroxide, calcium hydroxide, magnesium hydroxide
And turn into suspension emulsion, stand, make di-iron trioxide or/and ferrous oxide, silica, sulphur and micro copper, lead, zinc,
Cobalt, gold and silver metal simple substance mixture precipitate and separate immediately；Simultaneous separation of hydrogen aluminum oxide, calcium hydroxide, magnesium hydroxide suspend newborn
Turbid liquid；
Two, in aluminium hydroxide, calcium hydroxide, the magnesium hydroxide suspension emulsion of above-mentioned (one) to adding enough titanium dioxides
Carbon CO2Or air, stirring, 50 turns -200 revs/min of rotating speed, 2-8 hours stirring reaction time, make calcium hydroxide, magnesium hydroxide point
Calcium carbonate and magnesium carbonate or basic magnesium carbonate and immediately precipitate and separate are not converted into, then are precipitated from suspending aluminum hydroxide emulsion
Or aluminium hydroxide is separated by filtration, reclaim aluminium hydroxide, water circulation use；
Three, by the di-iron trioxide or/and ferrous oxide of above-mentioned (one), silica, sulphur and micro copper, lead, zinc,
Cobalt, gold and silver metal simple substance mixture stack nature draining, or by it at 25 DEG C -- 100 DEG C, the condition of pressure 25pa--100pa
Under, it is stirred under vacuum dehydration；Remove excessive moisture；Need not definitely be completely dried；
Four, in the calcium carbonate and magnesium carbonate or basic carbonate magnesium compound of above-mentioned (two) to adding enough dilute sulfuric acids water-soluble
Liquid, stirring makes calcium carbonate and magnesium carbonate or basic magnesium carbonate generation gypsum calcium sulfate and magnesium sulfate solution, staticly settles separation
Gypsum calcium sulfate is reclaimed, and magnesium sulfate solution vacuum dehydration is dried, pressure 25pa--100pa, 25 DEG C of temperature -- 100 DEG C,
- 24 hours 8 hours drying time, separate and recover magnesium sulfate；
Five, at normal temperatures, di-iron trioxide or/and ferrous oxide, silica, sulphur above-mentioned (three) and micro
In the mixture of copper, lead, zinc, cobalt, gold and silver metal simple substance, the SPA of excessive 80%--85%, SPA and three are added
Aoxidize the body of two iron or/and ferrous oxide, silica, sulphur and micro copper, lead, zinc, cobalt, gold and silver metal simple substance mixture
Product is than being 4-6: 1；SPA consumption need not be excessive, can be completely dissolved di-iron trioxide or/and ferrous oxide and being capable of mistake
SPA is leached to be defined with the solution of di-iron trioxide or/and ferrous oxide；Di-iron trioxide or/and ferrous oxide, titanium dioxide
Silicon, sulphur and micro copper, lead, zinc, cobalt, the mixture of gold and silver metal simple substance needs several times or continuously and smoothly adds SPA
Stirring and dissolving；Stirring, 50 turns -200 revs/min of rotating speed mixing time 10-60 minutes, makes di-iron trioxide or/and ferrous oxide complete
CL is filtered under stress immediately in after SPA, separates silica, sulphur and micro copper, lead, zinc, cobalt, gold and silver gold
Category simple substance mixture；And with appropriate water agitator treating silica, sulphur and micro copper, lead, zinc, cobalt, gold and silver metal list
Matter mixture, a small amount of phosphate aqueous solution containing a small amount of phosphoric acid is recycled in following (six)；This step SPA dissolves three oxygen
It is exothermic dissolution to change two iron or/and ferrous oxide, if solution temperature is too high, with cold air or less than 25 DEG C in course of dissolution
Air cooling is lowered the temperature or/and outside dissolution vessel with cooling water temperature, makes SPA solution temperature at 25 DEG C -- and 50 DEG C；Dissolving
Time is within 1 hour；
The solution of the di-iron trioxide of above-mentioned (five) or/and ferrous oxide and SPA is added water to dilute by six, immediately, is made
Phosphoric acid mass content in phosphate aqueous solution drops to 30%--50%, stirs, and stands, and makes di-iron trioxide or/and oxygen
Precipitation is separated immediately from the phosphoric acid,diluted aqueous solution to change ferrous iron, reclaims di-iron trioxide or/and ferrous oxide；
The phosphoric acid,diluted aqueous solution of above-mentioned (six) is concentrated in vacuo dehydration, 40 DEG C -100 DEG C of heating-up temperature, pressure 25pa-- by seven,
100pa, time 8-24 hours, makes phosphoric acid quality content in 80%--85%, and phosphoric acid circulation is utilized；
Eight, are by the silica SiO of above-mentioned (five)2, sulphur and micro copper, lead, zinc, cobalt, gold and the mixing of silver metal simple substance
Thing, adds enough oxygen O2Burning, makes sulphur S generate sulfur trioxide SO3, and with enough Water Sproading sulfur trioxides, obtain sulphur
Acid, reclaims sulfuric acid；Separate the mixing of silica and micro copper, lead, zinc, cobalt, gold and silver metal simple substance or its oxide
Thing；
Nine, are by the silica and micro copper of above-mentioned (eight), lead, zinc, cobalt, gold and silver metal simple substance or its oxide
Mixture, adds enough sodium hydrate aqueous solutions, and stirring reaction makes silica generate sodium silicate aqueous solution；
SiO2+ 2NaOH=Na2SiO3+H2O；
Precipitation separates micro copper, lead, zinc, cobalt, gold and silver metal simple substance or its hopcalite；By silicic acid
Sodium water solution vacuum concentration is dehydrated, pressure 25pa--100pa, time 8-24 hours, reclaims sodium metasilicate；
Ten, reclaim the micro copper of above-mentioned (nine), lead, zinc, cobalt, gold and silver metal simple substance or its hopcalite
Recycle.
Specific embodiment：
Embodiment：
One, is sulfate slag with enough water immersion pyrite cinders, and is stirred, 50 turns -200 revs/min of rotating speed, mixing time
1-2 hours, the aluminum oxide in sulfate slag, calcium oxide, magnesia is set to be separately converted to aluminium hydroxide, calcium hydroxide, magnesium hydroxide
And turn into suspension emulsion, stand, make di-iron trioxide or/and ferrous oxide, silica, sulphur and micro copper, lead, zinc,
Cobalt, gold and silver metal simple substance mixture precipitate and separate immediately；Simultaneous separation of hydrogen aluminum oxide, calcium hydroxide, magnesium hydroxide suspend newborn
Turbid liquid；
Two, in aluminium hydroxide, calcium hydroxide, the magnesium hydroxide suspension emulsion of above-mentioned (one) to adding enough titanium dioxides
Carbon CO2Or air, stirring, 50 turns -200 revs/min of rotating speed, 2-8 hours stirring reaction time, make calcium hydroxide, magnesium hydroxide point
Calcium carbonate and magnesium carbonate or basic magnesium carbonate and immediately precipitate and separate are not converted into, then are precipitated from suspending aluminum hydroxide emulsion
Or aluminium hydroxide is separated by filtration, reclaim aluminium hydroxide, water circulation use；
Three, by the di-iron trioxide or/and ferrous oxide of above-mentioned (one), silica, sulphur and micro copper, lead, zinc,
Cobalt, gold and silver metal simple substance mixture stack nature draining, or by it at 25 DEG C -- 100 DEG C, the condition of pressure 25pa--100pa
Under, it is stirred under vacuum dehydration；Remove excessive moisture；Need not definitely be completely dried；
The calcium carbonate and magnesium carbonate or basic carbonate magnesium compound of above-mentioned (two) are directly used as construction material by four,；
Five, at normal temperatures, di-iron trioxide or/and ferrous oxide, silica, sulphur above-mentioned (three) and micro
In the mixture of copper, lead, zinc, cobalt, gold and silver metal simple substance, the SPA of excessive 80%--85%, SPA and three are added
Aoxidize the body of two iron or/and ferrous oxide, silica, sulphur and micro copper, lead, zinc, cobalt, gold and silver metal simple substance mixture
Product is than being 4-6: 1；SPA consumption need not be excessive, can be completely dissolved di-iron trioxide or/and ferrous oxide and being capable of mistake
SPA is leached to be defined with the solution of di-iron trioxide or/and ferrous oxide；Di-iron trioxide or/and ferrous oxide, titanium dioxide
Silicon, sulphur and micro copper, lead, zinc, cobalt, the mixture of gold and silver metal simple substance needs several times or continuously and smoothly adds SPA
Stirring and dissolving；Stirring, 50 turns -200 revs/min of rotating speed mixing time 10-60 minutes, makes di-iron trioxide or/and ferrous oxide complete
CL is filtered under stress immediately in after SPA, separates silica, sulphur and micro copper, lead, zinc, cobalt, gold and silver gold
Category simple substance mixture；And with appropriate water agitator treating silica, sulphur and micro copper, lead, zinc, cobalt, gold and silver metal list
Matter mixture, a small amount of phosphate aqueous solution containing a small amount of phosphoric acid is recycled in following (six)；This step SPA dissolves three oxygen
It is exothermic dissolution to change two iron or/and ferrous oxide, if solution temperature is too high, with cold air or less than 25 DEG C in course of dissolution
Air cooling is lowered the temperature or/and outside dissolution vessel with cooling water temperature, makes SPA solution temperature at 25 DEG C -- and 50 DEG C；Dissolving
Time is within 1 hour；
The solution of the di-iron trioxide of above-mentioned (five) or/and ferrous oxide and SPA is added water to dilute by six, immediately, is made
Phosphoric acid mass content in phosphate aqueous solution drops to 30%--50%, stirs, and stands, and makes di-iron trioxide or/and oxygen
Precipitation is separated immediately from the phosphoric acid,diluted aqueous solution to change ferrous iron, reclaims di-iron trioxide or/and ferrous oxide；
The phosphoric acid,diluted aqueous solution of above-mentioned (six) is cooled to 1 DEG C -15 DEG C by seven, makes phosphoric acid in crystal gel shape Precipitation,
Moisture more than phosphoric acid precipitates layer is taken out, phosphoric acid quality content is recycled respectively in 80%--85%, phosphoric acid and water；Hydrogen-oxygen
Change aluminium and do not dissolve in SPA, can be mixed in aluminium hydroxide, silica, sulphur and micro copper, lead, zinc, cobalt, gold and silver metal simple substance
Appropriate water is added in compound, is stirred, stood, suspended, precipitate or be separated by filtration aluminium hydroxide, water circulation use；
Eight, are by the silica SiO of above-mentioned (five)2, sulphur and micro copper, lead, zinc, cobalt, gold and the mixing of silver metal simple substance
Thing, adds enough oxygen O2Burning, makes sulphur S generate sulfur trioxide SO3, and with enough Water Sproading sulfur trioxides, obtain sulphur
Acid, reclaims sulfuric acid；Separate the mixing of silica and micro copper, lead, zinc, cobalt, gold and silver metal simple substance or its oxide
Thing；
Nine, are by the silica and micro copper of above-mentioned (eight), lead, zinc, cobalt, gold and silver metal simple substance or its oxide
Mixture, adds enough potassium hydroxide aqueous solutions, and stirring reaction makes silica generate potassium silicate aqueous solution；
SiO2+ 2KOH=K2SiO3+H2O；
Precipitation separates micro copper, lead, zinc, cobalt, gold and silver metal simple substance or its hopcalite；By silicic acid
Aqueous solutions of potassium vacuum concentration is dehydrated, pressure 25pa--100pa, time 8-24 hours, reclaims sodium metasilicate or potassium silicate；
Ten, reclaim the micro copper of above-mentioned (nine), lead, zinc, cobalt, gold and silver metal simple substance or its hopcalite
Recycle.
Claims (1)
1. the separation and recovery method of pyrite cinder, which is mainly characterized in that：
One, is sulfate slag with enough water immersion pyrite cinders, and is stirred, 50 turns -200 revs/min of rotating speed, mixing time 1-2
Hour, the aluminum oxide in sulfate slag, calcium oxide, magnesia is separately converted to aluminium hydroxide, calcium hydroxide, magnesium hydroxide and form
It is suspension emulsion, stands, makes di-iron trioxide or/and ferrous oxide, silica, sulphur and micro copper, lead, zinc, cobalt, gold
With silver metal simple substance mixture precipitate and separate immediately；Simultaneous separation of hydrogen aluminum oxide, calcium hydroxide, magnesium hydroxide suspension emulsion；
Two, in aluminium hydroxide, calcium hydroxide, the magnesium hydroxide suspension emulsion of above-mentioned (one) to adding enough carbon dioxide CO2
Or air, stirring, 50 turns -200 revs/min of rotating speed, makes calcium hydroxide, magnesium hydroxide convert respectively at 2-8 hours stirring reaction time
The precipitate and separate immediately for calcium carbonate and magnesium carbonate or basic magnesium carbonate, then precipitate or filter from suspending aluminum hydroxide emulsion
Aluminium hydroxide is separated, aluminium hydroxide, water circulation use is reclaimed；
Three, are by the di-iron trioxide or/and ferrous oxide of above-mentioned (one), silica, sulphur and micro copper, lead, zinc, cobalt, gold
Nature draining is stacked with silver metal simple substance mixture, or by it at 25 DEG C -- 100 DEG C, under conditions of pressure 25pa--100pa, very
Sky stirring dehydration；Remove excessive moisture；Need not definitely be completely dried；
Four, to adding enough dilute sulfuric acid aqueous solutions in the calcium carbonate and magnesium carbonate or basic carbonate magnesium compound of above-mentioned (two),
Stirring, makes calcium carbonate and magnesium carbonate or basic magnesium carbonate generation gypsum calcium sulfate and magnesium sulfate solution, staticly settles and separates back
Gypsum calcium sulfate is received, and magnesium sulfate solution vacuum dehydration is dried, pressure 25pa--100pa, 25 DEG C of temperature -- 100 DEG C, do
- 24 hours 8 hours dry time, separate and recover magnesium sulfate；Or directly use calcium carbonate and magnesium carbonate or basic carbonate magnesium compound
Make construction material；
Five, at normal temperatures, di-iron trioxide or/and ferrous oxide, silica, sulphur and micro copper, lead above-mentioned (three),
In the mixture of zinc, cobalt, gold and silver metal simple substance, the SPA of excessive 80%--85%, SPA and three oxidations two are added
Iron or/and ferrous oxide, silica, sulphur and micro copper, lead, zinc, cobalt, the volume ratio of gold and silver metal simple substance mixture are
Compare 1 in 4-6: 1 i.e. 4 to 6；SPA consumption need not be excessive, can be completely dissolved di-iron trioxide or/and ferrous oxide and energy
SPA is enough filtered out to be defined with the solution of di-iron trioxide or/and ferrous oxide；Di-iron trioxide or/and ferrous oxide, two
Silica, sulphur and micro copper, lead, zinc, cobalt, the mixture of gold and silver metal simple substance need several times or continuously and smoothly add it is dense
Phosphoric acid stirring and dissolving；Stirring, 50 turns -200 revs/min of rotating speed mixing time 10-60 minutes, makes di-iron trioxide or/and oxidation sub-
After iron is dissolved completely in SPA, filter under stress immediately, separate silica, sulphur and micro copper, lead, zinc, cobalt, Jin He
Silver metal simple substance mixture；And it is golden with appropriate water agitator treating silica, sulphur and micro copper, lead, zinc, cobalt, gold and silver
Category simple substance mixture, a small amount of phosphate aqueous solution containing a small amount of phosphoric acid is recycled in following (six)；This step SPA dissolves
Di-iron trioxide or/and ferrous oxide are exothermic dissolutions, if solution temperature is too high, in course of dissolution with cold air or 25 DEG C with
Under air cooling cooling or/and outside dissolution vessel with cooling water temperature, make SPA solution temperature at 25 DEG C -- 50 DEG C；
Dissolution time is within 1 hour；
The solution of the di-iron trioxide of above-mentioned (five) or/and ferrous oxide and SPA is added water to dilute by six, immediately, makes phosphoric acid
Mass content drops to 30%--50% in phosphate aqueous solution, stirs, and stands, and makes di-iron trioxide or/and oxidation sub-
Precipitation is separated iron immediately from the phosphoric acid,diluted aqueous solution, reclaims di-iron trioxide or/and ferrous oxide；
The phosphoric acid,diluted aqueous solution of above-mentioned (six) is concentrated in vacuo dehydration, 40 DEG C -100 DEG C of heating-up temperature, pressure 25pa-- by seven,
100pa, time 8-24 hours, makes phosphoric acid quality content in 80%--85%, and phosphoric acid circulation is utilized；Or above-mentioned phosphoric acid,diluted is water-soluble
Liquid is cooled to 1 DEG C -15 DEG C, makes phosphoric acid in crystal gel shape Precipitation, takes out moisture more than phosphoric acid precipitates layer, phosphoric acid and water
Recycle respectively；
Eight, are by the silica SiO of above-mentioned (five)2, sulphur and micro copper, lead, zinc, cobalt, gold and silver metal simple substance mixture, plus
Enter enough oxygen O2Burning, makes sulphur S generate sulfur trioxide SO3, and with enough Water Sproading sulfur trioxides, sulfuric acid is obtained, reclaim
Sulfuric acid；Separate silica and micro copper, lead, zinc, cobalt, gold and silver metal simple substance or its hopcalite；
Nine, are by the mixing of the silica and micro copper of above-mentioned (eight), lead, zinc, cobalt, gold and silver metal simple substance or its oxide
Thing, adds enough NaOH or potassium hydroxide aqueous solution, and stirring reaction makes silica generate sodium metasilicate/potassium silicate water
Solution；
SiO2+ 2NaOH=Na2SiO3+H2O, SiO2+ 2KOH=K2SiO3+H2O；
Precipitation separates micro copper, lead, zinc, cobalt, gold and silver metal simple substance or its hopcalite；By sodium metasilicate or
Potassium silicate aqueous solution vacuum concentration is dehydrated, pressure 25pa--100pa, time 8-24 hours, reclaims sodium metasilicate or potassium silicate；
The micro copper of above-mentioned (nine), lead, zinc, cobalt, gold and silver metal simple substance or its hopcalite are reclaimed profit again by ten,
With.
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| CN201410529726.4A CN104384169B (en) | 2014-09-22 | 2014-09-22 | The separation and recovery method of pyrite cinder |
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| CN109368610B (en) * | 2018-10-09 | 2020-10-27 | 湖南雅城新材料有限公司 | Method for preparing iron phosphate with high iron-phosphorus ratio by using pyrite cinder |
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| JPS523024A (en) * | 1975-06-27 | 1977-01-11 | Toyama Chem Co Ltd | Method of preparing metal salts of 2-chloroethylhydrogen 2-chloroethylphosphonate |
| CN1161872A (en) * | 1996-04-05 | 1997-10-15 | 兰州炼油化工总厂三星公司 | Technology for recovering industrial waste sulphuric acid residue containing oil etc. organic substance |
| CN1730679A (en) * | 2005-08-25 | 2006-02-08 | 吴乾城 | Method for flotation concentrate from sulfuric-acid residue |
| RU2332371C1 (en) * | 2007-01-17 | 2008-08-27 | Юлия Алексеевна Щепочкина | Raw mix for cement manufacturing |
| CN102534187B (en) * | 2011-12-12 | 2014-04-16 | 师兆忠 | Method for treating pyrite cinder by combining acidic leaching with alkaline dissolving |
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