CN104384171A - Resource recycling method for pyritic cinders - Google Patents
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- CN104384171A CN104384171A CN201410572846.2A CN201410572846A CN104384171A CN 104384171 A CN104384171 A CN 104384171A CN 201410572846 A CN201410572846 A CN 201410572846A CN 104384171 A CN104384171 A CN 104384171A
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Abstract
The invention discloses a resource recycling method for pyritic cinders and relates to the technical field of inorganic chemical industries. The resource recycling method mainly comprises the following steps: separating aluminium hydroxide and calcium hydroxide from pyritic cinders in an aqueous suspension manner, reacting the pyritic cinders with carbon dioxide, sodium hydroxide or potassium hydroxide in water, and separating and recycling calcium carbonate or calcium hydroxide, and aluminium hydroxide or sodium aluminate, and potassium aluminate; dissolving with ammonium bicarbonate or ammonium sulfate/ammonium chloride or phosphoric acid to separate magnesium oxide; adopting sodium hydroxide or potassium hydroxide to process waste residues of iron sesquioxide or/and ferrous oxide, silicon dioxide and sulfur, and dissolving to separate silicon dioxide and sulfur; recycling iron sesquioxide or/and ferrous oxide, silicic acid, sylvite or sodium salt, and sulfur. The resource recycling method is used for separating and recycling pyritic cinders.
Description
Art:
The present invention relates to inorganic chemical technology field, particularly the resource recoverying and utilizing method of pyrite cinder.
Background technology:
Troilite produces sulfuric acid, and often produce 1 ton of sulfuric acid and will produce 0.8-0.9 ton pyrite cinder (sulfate slag), the annual pyrite cinder discharge capacity of China is up to 3,000,000 tons, and waste residue output is huge.Because China's troilite is lean ore mostly; in sulfate slag, too high, the iron oxide of sulfur content and ferrous oxide content are mostly below 50%; the impurity contents such as silica are too high; so the annual sulfate slag directly recycled only has about 1,000,000 tons; cause the serious wasting of resources, environmental pollution and land seizure waste; so to utilize and the angle of environmental protection from resources conservation, effectively, waste residue separation and recovery is significant.The main component that troilite produces waste residue of sulfuric acid (sulfate slag) has: di-iron trioxide and iron oxide and ferrous oxide, to account for ferrous oxide content in waste residue 20%--60%, sulfate slag less, silica, account for waste residue 15%--55%, aluminium oxide, account for waste residue 10%, calcium oxide, account for waste residue 5%, magnesia, account for waste residue less than 5%, and sulphur (element sulphur), account for waste residue 0.5%-2%; In addition the copper of trace, lead, zinc, cobalt, gold and the trace meter simple substance such as silver-colored is also had.Also there is no low cost, simple real efficiently separation and recovery method in prior art, seriously constrain the development that China's troilite produces sulfuric acid industry, not only waste resource but also compromise environment.Existing isolation technics, with hydrochloric acid or sulfuric acid chemical reaction, this is obviously talk about stratagems on paper.
With hydrochloric acid or sulfuric acid chemical reaction, both di-iron trioxide in waste residue, ferrous oxide, aluminium oxide, calcium oxide and magnesian hyle form had been changed, also consumes a large amount of hydrochloric acid or sulfuric acid, drastically increase waste residue separation costs, create again the water soluble salt mixture being difficult to be separated simultaneously; Particularly with sulfuric acid reaction, troilite is produced sulfuric acid and is produced waste residue, and has been fallen by sulfuric acid consumption in order to separating waste residues, and pyrite slag amount is too large, and the sulfuric acid as essential industry raw material loses source.Existing isolation technics also changes into the carbonate of iron, then high temperature reduction is di-iron trioxide or ferrous oxide, the consumption of chemical raw material and waste excessive, and energy waste is excessive, and separation costs is too high.Due to technical bottleneck, China's sulfuric acid industry is faced with awkward predicament: produce with troilite, waste residue is difficult to separation and recovery; Produce with sulphur (S) ore deposit, resource-constrained, can not meet the growth requirement of China's sulfuric acid industry.
Summary of the invention:
Inventive principle:
According to prior art and knowledge:
1. aluminium oxide, calcium oxide respectively hydration become hydrated alumina, calcium hydroxide suspension emulsion; Magnesia is dissolved in ammonium salt aqueous solution, di-iron trioxide or/and ferrous oxide, silica and sulphur are insoluble to ammonium salt aqueous solution, and by magnesia with di-iron trioxide or/and ferrous oxide, silica and sulphur mixture are separated; Sl. sol. calcium hydroxide aqueous solution again can with carbon dioxide CO
2the insoluble lime deposit of water generation reaction.Carbonic hydroammonium is the ammonium salt of weak acid and weak base, and the aqueous solution is in alkalescence, and carbonic acid is very weak acid, and carbonic hydroammonium can not react with magnesia and generate magnesium salts, and its aqueous solution can only dissolved oxygen magnesium.
2. silica, sulphur all react with the highly basic NaOH of heat or potassium hydroxide aqueous solution, generate water miscible material, are thus separated nonreactive di-iron trioxide or/and ferrous oxide.
3. aluminium oxide is amphoteric compound, and heating can be reacted with highly basic NaOH or potassium hydroxide, generates water miscible aluminate.Industrial Bayer process, aluminium oxide adds the principles of science of thermal response with highly basic NaOH or potassium hydroxide, reaction equation:
AL
2o
3+ 3H
2o+2NaOH heating=2NaAL (OH)
4,
AL
2o
3+ 3H
2o+2KOH heating=2KAL (OH)
4.
4. copper sulfide is insoluble to dilute sulfuric acid, removes hydrogen sulfide.
5. NaOH or potassium hydroxide not with di-iron trioxide or/and ferrous oxide reacts.
6. sulfur dioxide SO
2with hydrosulphuric acid H
2s reacts, and generates sulphur S and water.
7. silicic acid is that a class has [SiO
x(OH)
4-2x]
nthe compound of general formula, can be produced by soluble silicate and acid reaction;
Simple silicic acid is as metasilicic acid H
2siO
3, two silicic acid H
2si
2o
5with orthosilicic acid H
4siO
4deng detecting in weak solution; Metasilicic acid can only about 0 DEG C existence, and be condensed into two silicic acid during room temperature, two silicic acid resolve into water and silica 150 DEG C time;
The silicate of solubility, adds any weak acid, can obtain silicic acid; Free unimolecule silicic acid out, water soluble, but it associates gradually in the solution and forms bimolecular, three molecules, and finally form undissolved polymolecular polymer, the colloid of gained is called " silica sol "; If silicate solution concentration is comparatively large, then directly forms silicic acid jelly after acid adding, after dehydration, obtain silicic acid gel.
8. carbonic hydroammonium starts to be decomposed into ammonia, carbon dioxide and water more than 30 DEG C.
9. ammonium chloride, ammonium sulfate and the magnesia ionic equation of reacting:
MgO+2NH
4 +＝Mg
2++2NH
3↑+H
2O。Recyclable magnesium chloride or magnesium sulfate and an ammoniacal liquor (hydration ammonia NH
3h
2the O aqueous solution).
10., according to existing knowledge, iron oxide and/or ferrous oxide are dissolved in acid, and magnesia is also dissolved in acid; Magnesia can hydration be magnesium hydroxide, but iron oxide or ferrous oxide can not hydration be iron hydroxide or ferrous hydroxide, visible magnesian chemism and molecular polarity than iron oxide or ferrous oxide much better than; And phosphoric acid is middle strong acid or weak acid, it has oxidisability hardly, phosphoric acid to the dissolving power of metal oxide and phosphate aqueous solution mass concentration proportional; Under same phosphate aqueous solution mass concentration, phosphoric acid to the dissolving power of metal oxide and the chemism of metal oxide and molecular polarity size proportional, polar molecule is dissolved in polar molecule; Only have liquid SPA ability dissolved oxygen iron and/or the ferrous oxide of the mass ratio 80%-85% aqueous solution; The phosphate aqueous solution of mass ratio 65%-70% then can only dissolved oxygen magnesium, can not dissolved oxygen iron and/or ferrous oxide; At normal temperatures, at short notice, the phosphate aqueous solution of mass ratio 65%-70% not with magnesia chemical reaction; Because magnesia water solubility is very low, phosphoric acid has oxidisability again hardly, under the phosphate aqueous solution of the mass ratio 65%-70% long-time placement condition only more than 24 hours, just and magnesia slow reaction; And in the phosphoric acid,diluted aqueous solution of mass ratio less than 50%, magnesia immediately precipitation and separation is separated out; Be combined with water because phosphoric acid is soluble in water, water is polar molecule, the polar attraction that hydrone is separated and destroyed between magnesia molecule and phosphoric acid molecules, and makes magnesia molecule depart from phosphoric acid molecules, free aggregate and precipitate.With phosphoric acid and concentration difference separation of oxygenated magnesium thereof, magnesian hyle form can be kept.
11. according to existing knowledge, and hydrogen peroxide (hydrogen peroxide) and sulfuration (Asia) iron react:
(1).H
2O
2+FeS
2+H
2O＝H
2O+Fe(OH)
2+2S；
(2).7H
2O
2+FeS
2＝6H
2O+FeSO
4+H
2SO
4；
(3).15H
2O
2+2FeS
2＝14H
2O+Fe
2(SO
4)
3+H
2SO
4。Sulfuration (Asia) iron can be removed.
Pyrite cinder is divided into aluminium oxide, calcium oxide by the present invention, magnesia, and di-iron trioxide is or/and ferrous oxide, and silica, this four part of sulphur; Directly obtain di-iron trioxide or/and ferrous oxide; Again to hydrated alumina, calcium hydroxide, magnesia, and silica, sulphur conversion yield carry out the method for separation and recovery respectively and combination is that namely core technology of the present invention innovates essential features.
Technical scheme of the present invention:
One. with enough water soaking pyrite cinders and sulfate slag, and stir, rotating speed 30 turns-50 revs/min, mixing time 1-2 hour, make the aluminium oxide in sulfate slag, calcium oxide is separately converted to hydrated alumina, calcium hydroxide, and become suspension emulsion, leave standstill, make di-iron trioxide or/and the copper of ferrous oxide, magnesia, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture precipitate and separate immediately such as silver-colored; Be separated hydrated alumina, calcium hydroxide suspension emulsion simultaneously;
Two. in the hydrated alumina, calcium hydroxide suspension emulsion of above-mentioned (one), add enough carbon dioxide CO
2or air, stir, rotating speed 50 turns-200 revs/min, stirring reaction time 2-8 hour, leaves standstill, and makes calcium hydroxide be converted into calcium carbonate and precipitate and separate immediately, precipitation or isolated by filtration aluminium oxide from hydrated alumina suspension emulsion, reclaim aluminium oxide, water circulation use again;
Or enough NaOH or potassium hydroxide is added in the hydrated alumina, calcium hydroxide suspension emulsion of above-mentioned (one), add thermal response, stirring reaction time 1-2 hour, hydrated alumina is made to change into water miscible sodium aluminate or the potassium aluminate aqueous solution, leave standstill, then precipitate or isolated by filtration recovery calcium hydroxide; Sodium aluminate or potassium aluminate aqueous solution Vacuum Concentration are dehydrated, reclaims sodium aluminate or potassium aluminate;
Reaction equation: AL
2o
3+ 3H
2o+2NaOH heating=2NaAL (OH)
4,
AL
2o
3+ 3H
2o+2KOH heating=2KAL (OH)
4;
Or enough sulfuric acid neutralization reactions are added in the hydrated alumina, calcium hydroxide suspension emulsion of above-mentioned (one), add thermal response, generate water miscible aluminum sulfate aqueous solution, Vacuum Concentration dehydrates, separation and recovery aluminum sulfate; The simultaneously gypsum calcium sulfate that generates of precipitate and separate sulfuric acid and calcium hydroxide reaction;
Three. by the di-iron trioxide of above-mentioned () or/and the copper of ferrous oxide, magnesia, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored, below 28 DEG C, add enough ammonium bicarbonate aqueous solutions, and stir, rotating speed 30 turns-50 revs/min, mixing time 1-2 hour, makes magnesia be dissolved in ammonium bicarbonate aqueous solution; Precipitate and separate di-iron trioxide is or/and the copper of ferrous oxide, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored; Obtain carbonic hydroammonium and the magnesian aqueous solution simultaneously;
Again in airtight container, by carbonic hydroammonium and the magnesian aqueous solution, be heated to 35 DEG C--60 DEG C, make ammonium bicarbonate breaks down, magnesium oxide precipitation is separated out, reclaim magnesia; Reclaim ammonia NH with vacuum simultaneously
3or a hydration ammonia (NH
3h
2o) aqueous solution, in airtight container below 28 DEG C again by ammonia NH
3or a hydration ammonia (NH
3h
2o) aqueous solution and carbon dioxide CO
2reactant aqueous solution, obtains ammonium bicarbonate aqueous solution, recycles;
At this, also can with the aqueous dissolution di-iron trioxide of ammonium chloride or ammonium sulfate or/and magnesia in the copper of ferrous oxide, magnesia, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored, and stir, rotating speed 30 turns-50 revs/min, mixing time 1-2 hour, precipitate and separate di-iron trioxide is or/and the copper of ferrous oxide, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored; Obtain the aqueous solution of magnesium chloride or magnesium sulfate, Vacuum Concentration dehydrates simultaneously, pressure 25pa--100pa, time 8-24 hour, reclaims magnesium chloride or magnesium sulfate; And reclaim ammoniacal liquor;
Or dissolve di-iron trioxide with the phosphate aqueous solution of mass ratio 65%-70% or/and magnesia in the copper of ferrous oxide, magnesia, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored, and stir, rotating speed 30 turns-50 revs/min, mixing time 1-2 hour, precipitate and separate di-iron trioxide is or/and the copper of ferrous oxide, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored; Obtain phosphoric acid and the magnesian aqueous solution; Again phosphoric acid and the magnesian aqueous solution are added water to dilute, make phosphoric acid quality in phosphate aqueous solution than below 50%, make magnesia precipitation and separation precipitation immediately, reclaim magnesia; Again by the phosphoric acid,diluted aqueous solution of this mass ratio less than 50%, Vacuum Concentration dehydration, to the phosphate aqueous solution of mass ratio 65%-70%, recycles;
Four. by the di-iron trioxide of above-mentioned (three) or/and add in the copper of ferrous oxide, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored and react excessive a little NaOH or potassium hydroxide relative to silica, sulfur chemistry, and suppress sodium metasilicate or potassium silicate hydrolysis, to ensure di-iron trioxide or/and the high-purity of ferrous oxide; Add thermal response, stirring reaction, reaction time 2-8 hour;
Reaction equation: SiO
2+ 2NaOH heating=Na
2siO
3+ H
2o,
SiO
2+ 2KOH heating=K
2siO
3+ H
2o;
3S+6NaOH heating=2Na
2s+Na
2sO
3+ 3H
2o;
3S+6KOH heating=2K
2s+K
2sO
3+ 3H
2o;
Obtain the aqueous solution of sodium metasilicate, vulcanized sodium and sodium sulfite or potassium silicate, potassium sulfide and potassium sulfite;
Be separated simultaneously and obtain di-iron trioxide or/and the copper of ferrous oxide and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored;
Five. add enough sulfuric acid, stirring reaction by the aqueous solution of the sodium metasilicate of above-mentioned (four), vulcanized sodium and sodium sulfite or potassium silicate, potassium sulfide and potassium sulfite,
Reaction time 0.5-1 hour, reaction equation:
Na
2SiO
3+H
2SO
4＝H
2SiO
3+Na
2SO
4
K
2SiO
3+H
2SO
4＝H
2SiO
3+K
2SO
4
Na
2sO
3+ H
2sO
4=H
2sO
3+ Na
2sO
4; H
2sO
3general with SO
2exist with water;
K
2sO
3+ H
2sO
4=H
2sO
3+ K
2sO
4; H
2sO
3general with SO
2exist with water;
Na
2S+H
2SO
4＝H
2S↑+Na
2SO
4
K
2S+H
2SO
4＝H
2S↑+K
2SO
4；
Obtain the aqueous solution of silicic acid, sulfurous acid, hydrosulphuric acid, sodium sulphate or potassium sulfate, sulfurous acid H
2sO
3or sulfur dioxide SO
2with hydrosulphuric acid H
2the content of S in its aqueous solution is little; This walks reaction, also can replace sulfuric acid, because hydrochloric acid HL or nitric acid HNO with hydrochloric acid or nitric acid
3acidity all than sulfuric acid H
2sO
4by force, sodium chloride or sodium nitrate or potassium chloride or potassium nitrate and silicic acid, sulfurous acid, hydrosulphuric acid is obtained; This walks reaction, and also can replace sulfuric acid with the more highly acid organic acid such as citric acid, the acid of fixedness generates volatile acid and weak acid, adds thermal response, and obtains its corresponding Organic Sodium Salt or sylvite and silicic acid, sulfurous acid, hydrosulphuric acid; This walks reaction, also can replace sulfuric acid with phosphoric acid, and the acid of fixedness generates volatile acid and weak acid, adds thermal response, obtains sodium ascorbyl phosphate or potassium phosphate and silicic acid, sulfurous acid, hydrosulphuric acid;
Six. by the reacting solution of above-mentioned (five), precipitation or isolated by filtration silicic acid H
2siO
3hydrate is (former) silicic acid namely just; Also be the undissolved polymolecular polymer " silica sol " of water;
Seven. by the aqueous solution of above-mentioned (six), add enough copper sulphate CuSO
4, stirring reaction, makes hydrogen sulfide H
2s reaction generates copper sulfide CuS precipitation, reaction equation:
CuSO
4+ H
2s=CuS ↓+H
2sO
4; CuS is insoluble to dilute sulfuric acid; Precipitation or isolated by filtration copper sulfide CuS; Copper sulphate CuSO
4weak acid do not react with sulfurous acid or sulfur dioxide, because can not generate strong acid; When the aqueous solution of sodium metasilicate, vulcanized sodium and sodium sulfite or potassium silicate, potassium sulfide and potassium sulfite is with hydrochloric acid or nitric acid reaction, CuSO here
4with H
2the sulfuric acid that S reaction generates, available enough calcium hydroxide reactions, generate gypsum calcium sulfate and remove recovery; Remove the sulphur of 2/3rds;
Or by the aqueous solution of above-mentioned (six), according to
3S+6NaOH heating=2Na
2s+Na
2sO
3+ 3H
2o,
3S+6KOH heating=2K
2s+K
2sO
3+ 3H
2o reaction and
Na
2SO
3+H
2SO
4＝H
2SO
3+Na
2SO
4，
K
2SO
3+H
2SO
4＝H
2SO
3+K
2SO
4，
Na
2S+H
2SO
4＝H
2S+Na
2SO
4，
K
2s+H
2sO
4=H
2s+K
2sO
4the sulfur dioxide that reaction generates and hydrogen sulfide molecular number or mole ratio are 1: 2 (1 to 2), then according to sulfur dioxide SO
2with hydrosulphuric acid H
2s reacts, by SO
2and H
2s reaction is converted into sulphur S and water, precipitation or the whole sulphur S of isolated by filtration; Reaction equation: SO
2+ 2H
2s=3S+2H
2o; In airtight container, stirring reaction or heating stirring reaction, temperature 25 DEG C--100 DEG C; Reaction time 0.5-1 hour; The present invention also can first separate sulfur S at this, the more undissolved polymolecular polymer " silica sol " of water in precipitation or isolated by filtration above-mentioned (five);
Eight. by the sodium sulphate Na of above-mentioned (seven)
2sO
4or potassium sulfate K
2sO
4the aqueous solution, Vacuum Concentration dehydrates, pressure 25pa--100pa, time 8-24 hour, reclaim sulfuric acid sodium Na
2sO
4or potassium sulfate K
2sO
4.
The present invention, is not particularly illustrated, and is normal temperature and normal pressure; Produce at convention stir with in leaving standstill.Each chemical reactant need by detection level and calculating.
Due to the imperfect combustion of troilite, di-iron trioxide or/and in the copper of ferrous oxide and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored also containing have an appointment 1% iron sulfide FeS
2, so use hydrogen peroxide (hydrogen peroxide) and sulfuration (Asia) iron to react again, reaction equation:
(1).7H
2O
2+FeS
2＝6H
2O+FeSO
4+H
2SO
4；
Or (2) .15H
2o
2+ 2FeS
2=14H
2o+Fe
2(SO
4)
3+ H
2sO
4; Required hydrogen peroxide water dilution will be reacted, be mixed with the aqueous solution of 3%--10%; Spray into continuously containing a small amount of iron sulfide FeS
2di-iron trioxide or/and in the copper of ferrous oxide and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored, stirring reaction, rotating speed 30 turns-50 revs/min, mixing time 1-2 hour; After, then add appropriate water, as above-mentioned stirring at low speed washing ferrous sulfate and sulfuric acid or ferric sulfate and sulfuric acid; Separation and recovery ferrous sulfate and sulfuric acid or ferric sulfate and sulphur aqueous acid; Obtain di-iron trioxide or/and the mixture of the copper of ferrous oxide and trace, lead, zinc, cobalt, gold and the trace meter simple substance such as silver-colored.
Beneficial effect:
1. the present invention has saved waste residue stacking soil greatly.
2. saving of the present invention and effectively make use of valuable natural resources.
3. the present invention protects water environment and water resource.
4. the present invention opens raw-material wide raw material sources newly such as di-iron trioxide and iron oxide and ferrous oxide, aluminium hydroxide etc., has saved the energy.
5. the present invention's safety in production, stops inflammable, toxic gas discharge.
6. the present invention is simple to operate, and production equipment is simple, small investment of production equipment, and production capacity is large, and production cost is low; Be separated completely, do not produce new waste residue; Each separate substance purity such as di-iron trioxide is all more than 98%; In di-iron trioxide, combined sulfur S constituent content is at 0--0.15%, and not containing element silicon and elemental sulfur, the development for the high-end steel alloy of China and stainless steel industry provides the technical support that raw material are produced.
The preferred version of technical solution of the present invention:
One. with enough water soaking pyrite cinders and sulfate slag, and stir, rotating speed 30 turns-50 revs/min, mixing time 1-2 hour, make the aluminium oxide in sulfate slag, calcium oxide is separately converted to hydrated alumina, calcium hydroxide, and become suspension emulsion, leave standstill, make di-iron trioxide or/and the copper of ferrous oxide, magnesia, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture precipitate and separate immediately such as silver-colored; Be separated hydrated alumina, calcium hydroxide suspension emulsion simultaneously;
Two. in the hydrated alumina, calcium hydroxide suspension emulsion of above-mentioned (one), add enough NaOH, add thermal response, stirring reaction time 1-2 hour, make hydrated alumina change into water miscible sodium aluminate aqueous solution, leave standstill, then precipitate or isolated by filtration recovery calcium hydroxide; Sodium aluminate aqueous solution Vacuum Concentration is dehydrated, reclaims sodium aluminate;
Reaction equation: AL
2o
3+ 3H
2o+2NaOH heating=2NaAL (OH)
4;
Three. by the di-iron trioxide of above-mentioned () or/and the copper of ferrous oxide, magnesia, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored, below 28 DEG C, add enough ammonium bicarbonate aqueous solutions, and stir, rotating speed 30 turns-50 revs/min, mixing time 1-2 hour, makes magnesia be dissolved in ammonium bicarbonate aqueous solution; Precipitate and separate di-iron trioxide is or/and the copper of ferrous oxide, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored; Obtain carbonic hydroammonium and the magnesian aqueous solution simultaneously;
Again in airtight container, by carbonic hydroammonium and the magnesian aqueous solution, be heated to 35 DEG C--60 DEG C, make ammonium bicarbonate breaks down, magnesium oxide precipitation is separated out, reclaim magnesia; Reclaim ammonia NH with vacuum simultaneously
3or a hydration ammonia (NH
3.H
2o) aqueous solution, in airtight container below 28 DEG C again by ammonia NH
3or a hydration ammonia (NH
3.H
2o) aqueous solution and carbon dioxide CO
2reactant aqueous solution, obtains ammonium bicarbonate aqueous solution, recycles;
Four. by the di-iron trioxide of above-mentioned (three) or/and add relative to reacting NaOH excessive a little with silica, sulfur chemistry in the copper of ferrous oxide, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored, and suppress sodium metasilicate to be hydrolyzed, to ensure di-iron trioxide or/and the high-purity of ferrous oxide; Add thermal response, stirring reaction, reaction time 2-8 hour;
Reaction equation: SiO
2+ 2NaOH heating=Na
2siO
3+ H
2o,
3S+6NaOH heating=2Na
2s+Na
2sO
3+ 3H
2o;
Obtain the aqueous solution of sodium metasilicate, vulcanized sodium and sodium sulfite;
Be separated simultaneously and obtain di-iron trioxide or/and the copper of ferrous oxide and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored;
Five. add enough sulfuric acid, stirring reaction by the aqueous solution of the sodium metasilicate of above-mentioned (four), vulcanized sodium and sodium sulfite,
Reaction time 0.5-1 hour, reaction equation:
Na
2SiO
3+H
2SO
4＝H
2SiO
3+Na
2SO
4；
Na
2sO
3+ H
2sO
4=H
2sO
3+ Na
2sO
4; H
2sO
3general with SO
2exist with water;
Na
2S+H
2SO
4＝H
2S+Na
2SO
4
Obtain the aqueous solution of silicic acid, sulfurous acid, hydrosulphuric acid, sodium sulphate, sulfurous acid H
2sO
3or sulfur dioxide SO
2with hydrosulphuric acid H
2the content of S in its aqueous solution is little;
Six. by the reacting solution of above-mentioned (five), precipitation or isolated by filtration silicic acid H
2siO
3hydrate is (former) silicic acid namely just; Also be the undissolved polymolecular polymer " silica sol " of water;
Seven. by the aqueous solution of above-mentioned (six), according to
3S+6NaOH heating=2Na
2s+Na
2sO
3+ 3H
2the reaction of O and
Na
2SO
3+H
2SO
4＝H
2SO
3+Na
2SO
4，
Na
2s+H
2sO
4=H
2s+Na
2sO
4the sulfur dioxide that generates of reaction and the molecular number of hydrogen sulfide or mole ratio be 1: 2, then according to sulfur dioxide SO
2with hydrosulphuric acid H
2s reacts, by SO
2and H
2s reaction is converted into sulphur S and water, precipitation or the whole sulphur S of isolated by filtration; Reaction equation: SO
2+ 2H
2s=3S+2H
2o; In airtight container, stirring reaction or heating stirring reaction, temperature 25 DEG C--100 DEG C; Reaction time 0.5-1 hour;
Eight. by the sodium sulphate Na of above-mentioned (seven)
2sO
4the aqueous solution, Vacuum Concentration dehydrates, pressure 25pa--100pa, time 8-24 hour, reclaim sulfuric acid sodium Na
2sO
4.
The present invention, is not particularly illustrated, and is normal temperature and normal pressure; Produce at convention stir with in leaving standstill.Each chemical reactant need by detection level and calculating.
Detailed description of the invention:
Embodiment:
One. with enough water soaking pyrite cinders and sulfate slag, and stir, rotating speed 30 turns-50 revs/min, mixing time 1-2 hour, make the aluminium oxide in sulfate slag, calcium oxide is separately converted to hydrated alumina, calcium hydroxide, and become suspension emulsion, leave standstill, make di-iron trioxide or/and the copper of ferrous oxide, magnesia, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture precipitate and separate immediately such as silver-colored; Be separated hydrated alumina, calcium hydroxide suspension emulsion simultaneously;
Two. in the hydrated alumina, calcium hydroxide suspension emulsion of above-mentioned (one), add enough carbon dioxide CO
2or air, stir, rotating speed 50 turns-200 revs/min, stirring reaction time 2-8 hour, leaves standstill, and makes calcium hydroxide be converted into calcium carbonate and precipitate and separate immediately, precipitation or isolated by filtration aluminium oxide from hydrated alumina suspension emulsion, reclaim aluminium oxide, water circulation use again; Carbon dioxide does not react with aluminium oxide;
Or enough potassium hydroxide is added in the hydrated alumina, calcium hydroxide suspension emulsion of above-mentioned (one), add thermal response, stirring reaction time 1-2 hour, make hydrated alumina change into the water miscible potassium aluminate aqueous solution, leave standstill, then precipitate or isolated by filtration recovery calcium hydroxide; Potassium aluminate aqueous solution Vacuum Concentration is dehydrated, reclaims potassium aluminate;
Reaction equation: AL
2o
3+ 3H
2o+2KOH heating=2KAL (OH)
4;
Or enough sulfuric acid neutralization reactions are added in the hydrated alumina, calcium hydroxide suspension emulsion of above-mentioned (one), add thermal response, generate water miscible aluminum sulfate aqueous solution, Vacuum Concentration dehydrates, separation and recovery aluminum sulfate; The simultaneously gypsum calcium sulfate that generates of precipitate and separate sulfuric acid and calcium hydroxide reaction;
Three. by the di-iron trioxide of above-mentioned () or/and ferrous oxide, magnesia, silica, the copper of sulphur and trace, plumbous, zinc, cobalt, the trace meter simple substance mixtures such as gold and silver, add enough ammonium chloride or the aqueous solution of ammonium sulfate, dissolve di-iron trioxide or/and ferrous oxide, magnesia, silica, the copper of sulphur and trace, plumbous, zinc, cobalt, magnesia in the trace meter simple substance mixtures such as gold and silver, and stir, rotating speed 30 turns-50 revs/min, mixing time 1-2 hour, precipitate and separate di-iron trioxide is or/and ferrous oxide, silica, the copper of sulphur and trace, plumbous, zinc, cobalt, the trace meter simple substance mixtures such as gold and silver, obtain the aqueous solution of magnesium chloride or magnesium sulfate, Vacuum Concentration dehydrates simultaneously, pressure 25pa--100pa, time 8-24 hour, reclaims magnesium chloride or magnesium sulfate, and reclaim ammonia or ammoniacal liquor,
Or dissolve di-iron trioxide with the phosphate aqueous solution of mass ratio 65%-70% or/and magnesia in the copper of ferrous oxide, magnesia, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored, and stir, rotating speed 30 turns-50 revs/min, mixing time 1-2 hour, precipitate and separate di-iron trioxide is or/and the copper of ferrous oxide, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored; Obtain phosphoric acid and the magnesian aqueous solution; Again phosphoric acid and the magnesian aqueous solution are added water to dilute, make phosphoric acid quality in phosphate aqueous solution than below 50%, make magnesia precipitation and separation precipitation immediately, reclaim magnesia; Again by the phosphoric acid,diluted aqueous solution of this mass ratio less than 50%, Vacuum Concentration dehydration, to the phosphate aqueous solution of mass ratio 65%-70%, recycles;
Four. by the di-iron trioxide of above-mentioned (three) or/and add relative to reacting potassium hydroxide excessive a little with silica, sulfur chemistry in the copper of ferrous oxide, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored, and suppress potassium silicate to be hydrolyzed, to ensure di-iron trioxide or/and the high-purity of ferrous oxide; Add thermal response, stirring reaction, reaction time 2-8 hour;
Reaction equation: SiO
2+ 2KOH heating=K
2siO
3+ H
2o;
3S+6KOH heating=2K
2s+K
2sO
3+ 3H
2o;
Obtain the aqueous solution of potassium silicate, potassium sulfide and potassium sulfite;
Be separated simultaneously and obtain di-iron trioxide or/and the copper of ferrous oxide and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored;
Five. add enough sulfuric acid, stirring reaction by the aqueous solution of the potassium silicate of above-mentioned (four), potassium sulfide and potassium sulfite,
Reaction time 0.5-1 hour, reaction equation:
K
2SiO
3+H
2SO
4＝H
2SiO
3+K
2SO
4，
K
2sO
3+ H
2sO
4=H
2sO
3+ K
2sO
4, H
2sO
3general with SO
2exist with water;
K
2S+H
2SO
4＝H
2S+K
2SO
4；
Obtain the aqueous solution of silicic acid, sulfurous acid, hydrosulphuric acid, potassium sulfate, sulfurous acid H
2sO
3or sulfur dioxide SO
2with hydrosulphuric acid H
2the content of S in its aqueous solution is little; This walks reaction, also can replace sulfuric acid, because hydrochloric acid HL or nitric acid HNO with hydrochloric acid or nitric acid
3acidity all than sulfuric acid H
2sO
4by force, potassium chloride or potassium nitrate and silicic acid, sulfurous acid, hydrosulphuric acid is obtained; This walks reaction, and also can replace sulfuric acid with more highly acid organic acids such as citric acids, the acid of fixedness generates volatile acid and more weak acid, adds thermal response, and obtains its corresponding potassium salt and silicic acid, sulfurous acid, hydrosulphuric acid; This walks reaction, also can replace sulfuric acid with phosphoric acid, and the acid of fixedness generates volatile acid and more weak acid, adds thermal response, obtains potassium phosphate and silicic acid, sulfurous acid, hydrosulphuric acid;
Six. by the reacting solution of above-mentioned (five), precipitation or isolated by filtration silicic acid H
2siO
3hydrate is (former) silicic acid namely just; Also be the undissolved polymolecular polymer " silica sol " of water;
Seven. by the aqueous solution of above-mentioned (six), add enough copper sulphate CuSO
4, stirring reaction, makes hydrogen sulfide H
2s reaction generates copper sulfide CuS precipitation, reaction equation:
CuSO
4+ H
2s=CuS+H
2sO
4; CuS is insoluble to dilute sulfuric acid; Precipitation or isolated by filtration copper sulfide CuS; Copper sulphate CuSO
4weak acid do not react with sulfurous acid or sulfur dioxide, because can not generate strong acid; When the aqueous solution of potassium silicate, potassium sulfide and potassium sulfite is with hydrochloric acid or nitric acid reaction, CuSO here
4with H
2the sulfuric acid that S reaction generates, available enough calcium hydroxide reactions, generate gypsum calcium sulfate and remove recovery; Remove the sulphur of 2/3rds;
Or by the aqueous solution of above-mentioned (six), according to
3S+6KOH heating=2K
2s+K
2sO
3+ 3H
2o reaction and
K
2SO
3+H
2SO
4＝H
2SO
3+K
2SO
4，
K
2s+H
2sO
4=H
2s+K
2sO
4molecular number or the mole ratio of the sulfur dioxide that reaction generates and hydrogen sulfide are 1: 2, then according to sulfur dioxide SO
2with hydrosulphuric acid H
2s reacts, by SO
2and H
2s reaction is converted into sulphur S and water, precipitation or the whole sulphur S of isolated by filtration; Reaction equation: SO
2+ 2H
2s=3S+2H
2o; In airtight container, stirring reaction or heating stirring reaction, temperature 25 DEG C--100 DEG C; Reaction time 0.5-1 hour; The present invention also can first separate sulfur S at this, the more undissolved polymolecular polymer " silica sol " of water in precipitation or isolated by filtration above-mentioned (five);
Eight. by the potassium sulfate K of above-mentioned (seven)
2sO
4the aqueous solution, Vacuum Concentration dehydrates, pressure 25pa--100pa, time 8-24 hour, reclaim sulfuric acid potassium K
2sO
4.
For saving the length of description, the embodiment of the present invention is not done the repetition of simply apparent refinement more and is repeated.
Claims (2)
1. the resource recoverying and utilizing method of pyrite cinder, its feature is mainly:
One. with enough water soaking pyrite cinders and sulfate slag, and stir, rotating speed 30 turns-50 revs/min, mixing time 1-2 hour, make the aluminium oxide in sulfate slag, calcium oxide is separately converted to hydrated alumina, calcium hydroxide, and become suspension emulsion, leave standstill, make di-iron trioxide or/and the copper of ferrous oxide, magnesia, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture precipitate and separate immediately such as silver-colored; Be separated hydrated alumina, calcium hydroxide suspension emulsion simultaneously;
Two. in the hydrated alumina, calcium hydroxide suspension emulsion of above-mentioned (one), add enough carbon dioxide CO
2or air, stir, rotating speed 50 turns-200 revs/min, stirring reaction time 2-8 hour, leaves standstill, and makes calcium hydroxide be converted into calcium carbonate and precipitate and separate immediately, precipitation or isolated by filtration aluminium oxide from hydrated alumina suspension emulsion, reclaim aluminium oxide, water circulation use again;
Or enough NaOH or potassium hydroxide is added in the hydrated alumina, calcium hydroxide suspension emulsion of above-mentioned (one), add thermal response, stirring reaction time 1-2 hour, hydrated alumina is made to change into water miscible sodium aluminate or the potassium aluminate aqueous solution, leave standstill, then precipitate or isolated by filtration recovery calcium hydroxide; Sodium aluminate or potassium aluminate aqueous solution Vacuum Concentration are dehydrated, reclaims sodium aluminate or potassium aluminate;
Reaction equation: AL
2o
3+ 3H
2o+2NaOH heating=2NaAL (OH)
4,
AL
2o
3+ 3H
2o+2KOH heating=2KAL (OH)
4;
Or enough sulfuric acid neutralization reactions are added in the hydrated alumina, calcium hydroxide suspension emulsion of above-mentioned (one), add thermal response, generate water miscible aluminum sulfate aqueous solution, Vacuum Concentration dehydrates, separation and recovery aluminum sulfate; The simultaneously gypsum calcium sulfate that generates of precipitate and separate sulfuric acid and calcium hydroxide reaction;
Three. by the di-iron trioxide of above-mentioned () or/and the copper of ferrous oxide, magnesia, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored, below 28 DEG C, add enough ammonium bicarbonate aqueous solutions, and stir, rotating speed 30 turns-50 revs/min, mixing time 1-2 hour, makes magnesia be dissolved in ammonium bicarbonate aqueous solution; Precipitate and separate di-iron trioxide is or/and the copper of ferrous oxide, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored; Obtain carbonic hydroammonium and the magnesian aqueous solution simultaneously;
Again in airtight container, by carbonic hydroammonium and the magnesian aqueous solution, be heated to 35 DEG C--60 DEG C, make ammonium bicarbonate breaks down, magnesium oxide precipitation is separated out, reclaim magnesia; Reclaim ammonia NH with vacuum simultaneously
3or a hydration ammonia NH
3h
2the O aqueous solution, in airtight container below 28 DEG C again by ammonia NH
3or a hydration ammonia NH
3h
2the O aqueous solution and carbon dioxide CO
2reactant aqueous solution, obtains ammonium bicarbonate aqueous solution, recycles;
Or with the aqueous dissolution di-iron trioxide of ammonium chloride or ammonium sulfate or/and magnesia in the copper of ferrous oxide, magnesia, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored, and stir, rotating speed 30 turns-50 revs/min, mixing time 1-2 hour, precipitate and separate di-iron trioxide is or/and the copper of ferrous oxide, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored; Obtain the aqueous solution of magnesium chloride or magnesium sulfate, Vacuum Concentration dehydrates simultaneously, pressure 25pa--100pa, time 8-24 hour, reclaims magnesium chloride or magnesium sulfate; And reclaim ammoniacal liquor;
Or dissolve di-iron trioxide with the phosphate aqueous solution of mass ratio 65%-70% or/and magnesia in the copper of ferrous oxide, magnesia, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored, and stir, rotating speed 30 turns-50 revs/min, mixing time 1-2 hour, precipitate and separate di-iron trioxide is or/and the copper of ferrous oxide, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored; Obtain phosphoric acid and the magnesian aqueous solution; Again phosphoric acid and the magnesian aqueous solution are added water to dilute, make phosphoric acid quality in phosphate aqueous solution than below 50%, make magnesia precipitation and separation precipitation immediately, reclaim magnesia; Again by the phosphoric acid,diluted aqueous solution of this mass ratio less than 50%, Vacuum Concentration dehydration, to the phosphate aqueous solution of mass ratio 65%-70%, recycles;
Four. by the di-iron trioxide of above-mentioned (three) or/and add in the copper of ferrous oxide, silica, sulphur and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored and react excessive a little NaOH or potassium hydroxide relative to silica, sulfur chemistry, and suppress sodium metasilicate or potassium silicate hydrolysis, to ensure di-iron trioxide or/and the high-purity of ferrous oxide; Add thermal response, stirring reaction, reaction time 2-8 hour;
Reaction equation: SiO
2+ 2NaOH heating=Na
2siO
3+ H
2o,
SiO
2+ 2KOH heating=K
2siO
3+ H
2o;
3S+6NaOH heating=2Na
2s+Na
2sO
3+ 3H
2o;
3S+6KOH heating=2K
2s+K
2sO
3+ 3H
2o;
Obtain the aqueous solution of sodium metasilicate, vulcanized sodium and sodium sulfite or potassium silicate, potassium sulfide and potassium sulfite;
Be separated simultaneously and obtain di-iron trioxide or/and the copper of ferrous oxide and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored;
Five. add enough sulfuric acid, stirring reaction by the aqueous solution of the sodium metasilicate of above-mentioned (four), vulcanized sodium and sodium sulfite or potassium silicate, potassium sulfide and potassium sulfite,
Reaction time 0.5-1 hour, reaction equation:
Na
2SiO
3+H
2SO
4＝H
2SiO
3+Na
2SO
4
K
2SiO
3+H
2SO
4＝H
2SiO
3+K
2SO
4
Na
2sO
3+ H
2sO
4=H
2sO
3+ Na
2sO
4; H
2sO
3general with SO
2exist with water;
K
2sO
3+ H
2sO
4=H
2sO
3+ K
2sO
4; H
2sO
3general with SO
2exist with water;
Na
2S+H
2SO
4＝H
2S+Na
2SO
4
K
2S+H
2SO
4＝H
2S+K
2SO
4；
Obtain the aqueous solution of silicic acid, sulfurous acid, hydrosulphuric acid, sodium sulphate or potassium sulfate, sulfurous acid H
2sO
3or sulfur dioxide SO
2with hydrosulphuric acid H
2the content of S in its aqueous solution is little; This walks reaction, also can replace sulfuric acid with hydrochloric acid or nitric acid, and obtains sodium chloride or sodium nitrate or potassium chloride or potassium nitrate and silicic acid, sulfurous acid, hydrosulphuric acid; This walks reaction, also can replace sulfuric acid with citric acid, add thermal response, and obtains its corresponding Organic Sodium Salt or sylvite and silicic acid, sulfurous acid, hydrosulphuric acid; This walks reaction, also can replace sulfuric acid with phosphoric acid, add thermal response, obtains sodium ascorbyl phosphate or potassium phosphate and silicic acid, sulfurous acid, hydrosulphuric acid;
Six. by the reacting solution of above-mentioned (five), precipitation or isolated by filtration silicic acid H
2siO
3hydrate and positive silicic acid; Also be the undissolved polymolecular polymer " silica sol " of water;
Seven. by the aqueous solution of above-mentioned (six), add enough copper sulphate CuSO
4, stirring reaction, makes hydrogen sulfide H
2s reaction generates copper sulfide CuS precipitation, reaction equation:
CuSO
4+ H
2s=CuS+H
2sO
4; Precipitation or isolated by filtration copper sulfide CuS; When the aqueous solution of sodium metasilicate, vulcanized sodium and sodium sulfite or potassium silicate, potassium sulfide and potassium sulfite is with hydrochloric acid or nitric acid reaction, CuSO here
4with H
2the sulfuric acid that S reaction generates, available enough calcium hydroxide reactions, generate gypsum calcium sulfate and remove recovery; Remove the sulphur of 2/3rds;
Or by the aqueous solution of above-mentioned (six), according to
3S+6NaOH heating=2Na
2s+Na
2sO
3+ 3H
2o,
3S+6KOH heating=2K
2s+K
2sO
3+ 3H
2o reaction and
Na
2SO
3+H
2SO
4＝H
2SO
3+Na
2SO
4，
K
2SO
3+H
2SO
4＝H
2SO
3+K
2SO
4，
Na
2S+H
2SO
4＝H
2S+Na
2SO
4，
K
2s+H
2sO
4=H
2s+K
2sO
4molecular number or the mole ratio of the sulfur dioxide that reaction generates and hydrogen sulfide are 1: 2, then according to sulfur dioxide SO
2with hydrosulphuric acid H
2s reacts, by SO
2and H
2s reaction is converted into sulphur S and water, precipitation or the whole sulphur S of isolated by filtration; Reaction equation: SO
2+ 2H
2s=3S+2H
2o; In airtight container, stirring reaction or heating stirring reaction, temperature 25 DEG C--100 DEG C; Reaction time 0.5-1 hour; The present invention also can first separate sulfur S at this, the more undissolved polymolecular polymer " silica sol " of water in precipitation or isolated by filtration above-mentioned (five);
Eight. by the sodium sulphate Na of above-mentioned (seven)
2sO
4or potassium sulfate K
2sO
4the aqueous solution, Vacuum Concentration dehydrates, pressure 25pa--100pa, time 8-24 hour, reclaim sulfuric acid sodium Na
2sO
4or potassium sulfate K
2sO
4.
2. according to claim 1, di-iron trioxide or/and also contain in the copper of ferrous oxide and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored about 1% iron sulfide FeS
2separation method:
React with hydrogen peroxide and hydrogen peroxide and iron sulfide, reaction equation:
(1).7H
2O
2+FeS
2＝6H
2O+FeSO
4+H2SO
4；
Or (2) .15H
2o
2+ 2FeS
2=14H
2o+Fe
2(SO
4)
3+ H
2sO
4;
Required hydrogen peroxide water dilution will be reacted, be mixed with the aqueous solution of 3%--10%; Spray into continuously containing a small amount of iron sulfide FeS
2di-iron trioxide or/and in the copper of ferrous oxide and trace, lead, zinc, cobalt, gold and the trace meter simple substance mixture such as silver-colored, stirring reaction, rotating speed 30 turns-50 revs/min, mixing time 1-2 hour; After, then add appropriate water, as above-mentioned stirring at low speed washing ferrous sulfate and sulfuric acid or ferric sulfate and sulfuric acid; Separation and recovery ferrous sulfate and sulfuric acid or ferric sulfate and sulphur aqueous acid; Obtain di-iron trioxide or/and the mixture of the copper of ferrous oxide and trace, lead, zinc, cobalt, gold and the trace meter simple substance such as silver-colored.
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| CN108706562A (en) * | 2018-08-14 | 2018-10-26 | 武汉轻工大学 | A method of preparing ferric phosphate using pyrite cinder |
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| CN115069274A (en) * | 2022-07-27 | 2022-09-20 | 广西民族大学 | Iron sulfide @ molybdenum disulfide composite catalyst and preparation method and application thereof |
| CN115106103A (en) * | 2022-07-27 | 2022-09-27 | 广西民族大学 | Composite catalyst for flue gas treatment and preparation method and application thereof |
| CN115155620A (en) * | 2022-07-27 | 2022-10-11 | 广西民族大学 | Desulfurization composite catalyst and preparation method and application thereof |
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