CN100489126C - Method of reclaiming chemical industry products by using industrial slag containing vanadium, chromium, iron and phosphorous - Google Patents
Method of reclaiming chemical industry products by using industrial slag containing vanadium, chromium, iron and phosphorous Download PDFInfo
- Publication number
- CN100489126C CN100489126C CNB2007100113936A CN200710011393A CN100489126C CN 100489126 C CN100489126 C CN 100489126C CN B2007100113936 A CNB2007100113936 A CN B2007100113936A CN 200710011393 A CN200710011393 A CN 200710011393A CN 100489126 C CN100489126 C CN 100489126C
- Authority
- CN
- China
- Prior art keywords
- chromium
- solution
- vanadium
- phosphorus
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a recovering chemical product method with a V, Cr, Fe and P industrial muck in the chemistry field, which comprises the following steps: roasting raw materials; heating and leaching the clinkers; separating ferric oxide from the solution containing V, Cr, Fe and P; crystallizing the solution in order to removing to P; removing P deeply; removing Si; adjusting the acidity of the solution containing V and Cr; extracting V; extracting V reversely; settling V; roasting metammonium vanadate; reducing Cr; settling chromic hydroxide; separating chromic hydroxide from sodium sulfate; removing NH3; getting sodium sulfate crystallization; purifying sodium sulfate mother liquor; adsorbing V, Cr, tertiary sodium phosphate solution with rough tertiary sodium phosphate refining resin and reacting with phosphoric acid; drying and roasting sodium tripolyphosphate; getting V, Cr, Fe and P from the industrial muck containing V, Cr, Fe and P and separating the secondary product of ammoniacal liquor and sodium sulfate in the heat exchange procedure. The invention saves the energy, which adapts to an industrial appliance.
Description
Technical field
What the present invention proposed is that chemical industry, environmental protection field utilize the industrial slag that contains vanadium, chromium, iron and phosphorus to reclaim the method for Chemicals.
Background technology
Vanadium, chromium, phosphorus and iron all are important non-renewable strategic resources, and especially vanadium and chromium are widely used in production scientific research fields such as special steel, steel alloy, military project, space flight, medicine and catalyzer.China's iron and steel ultimate production broke through 34,000 ten thousand tons in 2005, became world steel first big country.
Industrial slag when the industrial slag that contains vanadium and chromium is mainly derived from ferrophosphorus slag that phophatic fertilizer production process produces and special steel smelt additive production removal of impurities.China's Panzhihua Iron and Chengde Iron ﹠ Steel Corp. are to be the large-size enterprise group of raw material production iron and steel with vanadium, titanomagnetite, the industrial slag that annual output contains vanadium, chromium all reaches 200,000 tons/year, the production of phosphate fertilizer enterprise of the U.S. can produce the ferrophosphorus slag hundreds of thousands of ton/year that contains vanadium, chromium every year, and the special steel smelt additive production in Russia and South Africa also produces the hundreds of thousands of ton at least and contains vanadium, chromium waste residue.
Because vanadium, chromium separate this worldwide technological puzzle and do not solve so far in the same solution, a large amount of vanadium, chromium industrial slag antiseepage landfills or expend the energy and be melt into the ferrophosphorus slag behind the reduction and detoxication simply that contain.Not only annually need expend a large amount of funds, and simple toxicide waste residue threatening environment constantly also.From the industrial slag that contains vanadium, chromium, phosphorus and iron, reclaim the purpose that Vanadium Pentoxide in FLAKES, chromium hydroxide, phosphoric acid salt and ferric oxide can be realized environmental protection and increase economic benefit.
Summary of the invention
Reclaim useful vanadium, chromium, iron and phosphorus and by-product Chemicals thereof in order to extract from contain vanadium, chromium, iron and phosphorus industrial residue, the present invention proposes the method that a kind of utilization contains the industrial slag recovery Chemicals of vanadium, chromium, iron and phosphorus.This method transforms by continuous process in same solution and abstraction process solves the technical problem of extracting vanadium, chromium, iron and phosphorus product and isolate the recycle of ammoniacal liquor, sodium sulfate and water, heat simultaneously from the industrial slag that contains vanadium, chromium, iron and phosphorus.
The present invention solves the scheme that its technical problem takes:
1, raw material calcining process
Broken the sieving of ground-slag that will contain vanadium, chromium, iron and phosphorus mixed the back roasting with yellow soda ash, with wherein vanadium, chromium and phosphorus transform into water-soluble grog.
2, the grog lixiviate operation of heating
To join in the hot water through the grog of roasting, water miscible vanadium, chromium and phosphorus are dissolved in the water.
3, ferric oxide and contain vanadium, chromium and phosphorus solution separation circuit
To separate with the aqueous solution that is dissolved with vanadium, chromium and phosphorus compound through the grog solid of lixiviate by filtering, solid part is a ferric oxide, and solution is as the stock liquid that extracts vanadium, chromium and phosphorus.
4, the pre-dephosphorization operation of stock liquid crystallization
To contain the stock liquid cooling of vanadium, chromium and phosphorus, the phosphorus that is dissolved in the stock liquid is separated out from stock liquid in tertiary sodium phosphate crystalline mode, gained raw phosphoric acid trisodium, and make phosphorus content reduction in the stock liquid, reach the purpose of pre-dephosphorization.
5, deep phosphorous removal and desiliconization process
To remove in advance and separate after phosphorus solution adds sulfuric acid and calcium sulfate reacts, with isolating phosphorus slag and lysate after the ferrous sulfate detoxifcation, lysate input desiliconization still is isolated white residue, and gained dephosphorization and desiliconization liquid enter and extract vanadium and chromium cpd operation.
6, contain vanadium and chromium solution potential of hydrogen and adjust operation
In stock liquid, add sulfuric acid, adjust the potential of hydrogen of solution through dephosphorization and desiliconization.
7, extracting vanadium and chromium separation circuit
In extraction reactor, in the dephosphorization of passing through the adjustment potential of hydrogen and desiliconization stock liquid, add extraction agent and sulfuric acid, form rich vanadium organism and chromium-containing solution.
Extraction agent by main extraction agent primary amine and thinner sulfonated kerosene and properties-correcting agent by 13～18: 80～85: 10～5 volume ratios are mixed and are formed.
8, reextraction vanadium operation
Add reverse-extraction agent in rich vanadium organism, form the rich vanadium aqueous solution and extraction agent, extraction agent recycles.
Strippant is by 0.3～0.7mol/L Na
2SO
4Form with 1.2～1.8mol/L NaOH mixed solution.
9, vanadium precipitation operation
In rich vanadium solution, add ammonium sulfate, make the reaction of vanadium and ammonium sulfate generate ammonium meta-vanadate and precipitation supernatant liquor.
10, ammonium meta-vanadate calcining process
The ammonium meta-vanadate that precipitates and isolates is carried out roasting, ammonium is overflowed with the form of ammonia send into ammonia absorber, obtain the Vanadium Pentoxide in FLAKES product simultaneously.
11, chromium reduction operation
Add S-WAT and sulfuric acid in passing through the separating obtained chromium-containing solution of vanadium and chromium, making hexavalent chrome reduction is trivalent chromium.
12, chromium hydroxide precipitation operation
In through the reductive chromium-containing solution, add sodium hydroxide, make chromium form chromium hydroxide precipitation.
13, chromium hydroxide and sodium sulfate separation circuit
Contain sodium sulfate in the solution after adding sulfuric acid and S-WAT, sodium hydroxide and precipitating chromium hydroxide, chromium hydroxide is separated with metabisulfite solution, obtain the mother liquor of chromium hydroxide product and contains sodium sulfate by filtration.
14, deamination operation
In the precipitation supernatant liquor, add sodium hydroxide, make ammonium be transformed into ammonia that gaseous ammonia and roasting ammonium meta-vanadate overflowed and absorbed by water together and become the ammoniacal liquor product.
15, sulfate crystal separation circuit
The mother liquor of the mother liquor of the contains sodium sulfate that will produce through the precipitation chromium hydroxide and the contains sodium sulfate that produces through precipitation vanadium and deamination merges the contains sodium sulfate solution cooling that forms to be handled, and makes sulfate crystal separate out Na
2SO
410H
2O forms the sodium sulfate product that contains crystal water.
16, sodium sulfate separates the mother liquor purification operation
To realize the water purification processing through the separation mother liquor behind the sulfate crystal through reverse osmosis membrane processing, continue on for water of productive use.
17, vanadium and chromium operation are made with extra care-separated to the raw phosphoric acid trisodium
With the pre-dephosphorization operation of the stock liquid crystallization isolated Na that cools
3PO
412H
2The O crystal is by adding 0.7～1.0m per ton
3Deionized water or steam condensate make solution, be input in the ion exchange resin column with pump, vanadium in the solution and chromium ion are attracted on the resin, resolve with sodium hydroxide solution saturated back, regenerates with sulphuric acid soln.Vanadium that parses and chromium solution enter extracting vanadium and chromium separation circuit.
18, trisodium phosphate solution and phosphatase reaction operation
In through the isolated pure trisodium phosphate solution of resin column, add phosphoric acid, generate Na
2HPO
4: NaH
2PO
4The solution of=2:1 with the spray-dried tower oven dry of this solution, gets Na
2HPO
4And NaH
2PO
4Mixture.
19, the calcining process of tripoly phosphate sodium STPP
With Na
2HPO
4And NaH
2PO
4Mixture in rotary kiln, carry out calcination process, obtain the tripoly phosphate sodium STPP product.
20, heat exchange operation
Each section baking flue gas by waste heat exchange heating purifying treatment water, is used for producing and uses hot water.
The inventive method is a raw material with the industrial slag that contains vanadium, chromium, iron and phosphorus, obtain Vanadium Pentoxide in FLAKES by continuous extraction and separation circuit, chromium hydroxide, ferric oxide and tripoly phosphate sodium STPP product, isolate ammoniacal liquor and sodium sulfate byproduct simultaneously, and realize that making full use of with water purification of heat energy recycles, have the characteristics of sharp useless, energy-saving and environmental protection and recycling economy.Suit to contain vanadium, chromium, iron and phosphorus industrial slag and extract useful Chemicals production application.
Description of drawings
Fig. 1 is a process flow chart of the present invention
Among the figure, 1. raw material calcining process, 2. the grog lixiviate operation of heating, ferric oxide with contain vanadium, chromium and phosphorus solution separation circuit, 4. the pre-dephosphorization operation of solution crystallization, 5. deep phosphorous removal and desiliconization process, 6. contain vanadium and chromium solution potential of hydrogen and adjust operation, 7. extracting vanadium and chromium separation circuit, 8. reextraction vanadium operation, 9. vanadium precipitates operation, 10. ammonium meta-vanadate calcining process, 11. chromium reduction operation, 12. chromium hydroxide precipitation operations, 13. chromium hydroxide and sodium sulfate separation circuit, 14. the deamination operation, 15. sulfate crystal separation circuits, 16. sodium sulfate separate the mother liquor purification operation, 17. refining resin absorption vanadium of raw phosphoric acid trisodium and chromium operation, 18. trisodium phosphate solution and phosphatase reaction operation, 19. tripoly phosphate sodium STPP drying and roasting operations, 20. heat exchange operations.
Embodiment
According to shown in Figure 1, its abstraction process and process are:
1. grog calcining process
To contain broken mistake 80～120 mesh sieves of ground-slag of vanadium, chromium, iron and phosphorus, and mix with yellow soda ash according to the amount that contains vanadium, chromium, iron and phosphorus, roasting under 800～1050 ℃ of conditions is with wherein vanadium, chromium and phosphorus transform into grog soluble in water.
2, the grog lixiviate operation of heating
To join through the grog of roasting in the hot water, water temperature stirs under 80 ℃ condition carried out lixiviate in 60～90 minutes, and water miscible vanadium, chromium and phosphorus are dissolved in the water.
Ferric oxide with contain vanadium, chromium and phosphorus solution separation circuit
To separate with the aqueous solution that is dissolved with vanadium, chromium and phosphorus compound through the grog solid of lixiviate by filtering, solid part is a ferric oxide, and solution is as the stock liquid that extracts vanadium, chromium and phosphorus.
4. the pre-dephosphorization operation of solution crystallization
After will containing the stock liquid cooling of vanadium, chromium and phosphorus, the phosphorus that is dissolved in the stock liquid is separated out from stock liquid in tertiary sodium phosphate crystalline mode, this crystal is the raw phosphoric acid trisodium, and makes phosphorus content reduction in the stock liquid, reaches the purpose of pre-dephosphorization.
Phosphorus in the leach liquor in solution mainly with Na
3PO
4Form exist.Present method is with Na
3PO
412H
2O crystalline mode is separated phosphorus.
1. water for cooling: adopt water cooling tower-pump-solution crystallization jar chuck and inner coil pipe polyphone, with water is cold carrier, pump is a power, makes the aqueous solution carry out heat exchange by tank skin and coil pipe outer wall under whipped state, makes the temperature of solution carry out solid-liquid separation after reducing to 30～35 ℃.Solid is Na
3PO
412H
2O goes treating process.
2. chilled brine cooling: will be through the solution after the water for cooling solid-liquid separation with pump delivery to the brine freezing jar, forcing under the stirring condition,-5～-10 ℃ salt solution carries out heat exchange through the chuck inwall of jar and inner coil pipe outer wall and solution, when the solids content in the solution reaches 30～40%, carry out solid-liquid separation, solid Na
3PO
412H
2O goes treating process; Solution continues to cool to-1～2 ℃, carries out the solid-liquid body and separates solid Na
3PO
412H
2O goes treating process, and the liquid input has in the basin of heat-exchanger rig.
5. deep phosphorous removal and desiliconization process
Will be in advance remove phosphorus solution and heat up through heat exchange and stir under 60～80 ℃ of conditions and added sulfuric acid and calcium sulfate reaction 2～3 hours, when the P in the solution＜0.5g/L, carry out solid-liquid separation, the filter residue countercurrent washing is again with isolating phosphorus slag after the ferrous sulfate detoxifcation.
Liquid input desiliconization still after the dephosphorization, stirring and the powdered reaction of adding sodium aluminate are 1～1.5 hour under 50～70 ℃ condition, when the Si in the solution＜0.005g/L, be cooled to 20～30 ℃ through quiescent setting, carry out solid-liquid separation, with isolating white residue after the ferrous sulfate detoxifcation, liquid is used to extract vanadium and chromium product again in the filter residue countercurrent washing.
6. contain vanadium and chromium solution potential of hydrogen and adjust operation
In stock liquid, add sulfuric acid, adjust the potential of hydrogen of solution, make the pH value between 7～8.0 through dephosphorization and desiliconization.
7. extracting vanadium and chromium separation circuit
Deep phosphorous removal and desiliconization and the solution of adjusting the pH value are imported extractor with volume pump, and temperature is controlled at 20～30 ℃, through counter-current extraction. and vanadium enters extraction agent and forms rich vanadium organism, and chromium is stayed in the aqueous solution.
Extraction agent is mixed by 13～18:80～85:10～5 volume ratios by main extraction agent primary amine and thinner sulfonated kerosene and properties-correcting agent and forms.
8, reextraction vanadium operation
Rich vanadium organism and strippant interact in stripper with the volume ratio of 3:1.2～8, under 40～50 ℃, the condition of pH value 8～9, and through fully stirring 10～20 minutes, the vanadium rich vanadium aqueous solution of formation that is dissolved in the water, vanadium concentration reaches 30～40g/L.Extraction agent by the reextraction gained can be reused.
Strippant is by 0.3～0.7mol/L Na
2SO
4Form with 1.2～1.8mol/L NaOH mixed solution.
9, vanadium precipitation operation
In rich vanadium solution, add ammonium sulfate, make the reaction of vanadium and ammonium sulfate generate ammonium meta-vanadate.
10. ammonium meta-vanadate calcining process
The ammonium meta-vanadate that precipitates and isolates is carried out roasting, make the form evaporation of ammonium, obtain the Vanadium Pentoxide in FLAKES product simultaneously with ammonia.
11. chromium reduction operation
Add S-WAT and sulfuric acid in passing through the separating obtained chromium-containing solution of vanadium and chromium, making hexavalent chrome reduction is trivalent chromium.
12. chromium hydroxide precipitation operation
In through the reductive chromium-containing solution, add sodium hydroxide, make chromium form chromium hydroxide precipitation.
13. chromium hydroxide and sodium sulfate separation circuit
Contain sodium sulfate in the solution after adding sulfuric acid and S-WAT, oxygen sodium oxide and precipitating chromium hydroxide, chromium hydroxide is separated with metabisulfite solution, obtain the mother liquor of chromium hydroxide product and contains sodium sulfate by filtration.
14. deamination operation
In the precipitation supernatant liquor, add sodium hydroxide, make ammonium be transformed into ammonia that gaseous ammonia and roasting ammonium meta-vanadate overflowed and absorbed by water together and become the ammoniacal liquor product.
15. sulfate crystal separation circuit
The mother liquor of the mother liquor of the contains sodium sulfate that will produce through the precipitation chromium hydroxide and the contains sodium sulfate that produces through precipitation vanadium and deamination merges the contains sodium sulfate solution cooling that forms to be handled, and makes sulfate crystal separate out Na
2SO
410H
2O forms the sodium sulfate product that contains crystal water.
16. sodium sulfate separates the mother liquor purification operation
To realize the water purification processing through the separation mother liquor behind the sulfate crystal through reverse osmosis membrane processing, continue on for water of productive use.
17. vanadium and chromium operation are made with extra care-separated to the raw phosphoric acid trisodium
With the pre-dephosphorization operation of the stock liquid crystallization isolated Na that cools
3PO
412H
2The O crystal is by adding 0.7～1.0m per ton
3Deionized water or steam condensate make solution, be input in the ion exchange resin column with pump, vanadium in the solution and chromium ion are attracted on the resin, resolve with sodium hydroxide solution saturated back, regenerates with sulphuric acid soln.Vanadium that parses and chromium solution enter extracting vanadium and chromium separation circuit.
18. trisodium phosphate solution and phosphatase reaction operation
In through the isolated pure trisodium phosphate solution of resin column, add phosphoric acid, generate Na
2HPO
4: NaH
2PO
4The solution of=2:1 with the spray-dried tower oven dry of this solution, gets Na
2HPO
4And NaH
2PO
4Mixture.
19. the calcining process of tripoly phosphate sodium STPP
With Na
2HPO
4And NaH
2PO
4Mixture in rotary kiln, carry out calcination process, obtain the tripoly phosphate sodium STPP product.
20. heat exchange operation
Each section baking flue gas by waste heat exchange heating purifying treatment water, is used for producing and uses hot water.
Sulfuric acid in each reactions steps is the 1:1 aqueous sulfuric acid.
The chemical substance cooperation ratio of each reaction process is carried out the adaptability adding and is adjusted according to the mole number of generation material concentration.
The waste heat that is produced in each operation is used for producing by the heat exchanger heat exchange uses thermal source, has realized making full use of of heat energy, has reached energy-conservation effect.
The water that is produced in the production process is handled through ion permeable membrane, changes recycled purifying waste water into.
The present invention has utilized the industrial slag production that contains vanadium, chromium, iron and phosphorus to be up to state standards and adaptable ferric oxide and tripoly phosphate sodium STPP, chromium hydroxide, the important Chemicals of Vanadium Pentoxide in FLAKES, the phosphorus white residue of also isolating useful ammoniacal liquor and sodium sulfate product simultaneously and can reusing has been realized the cyclic utilization of waste.
The present invention in same solution by continuous extraction and the method for separating with the severe contamination ring The valuable industrial slag resource in border changes utilizable industrial chemicals into, and has realized heat energy Take full advantage of and water circuit uses, reached environmental protection, energy-conservation, zero-emission, pollution-free Effect.
Claims (4)
1, utilize the industrial slag that contains vanadium, chromium, iron and phosphorus to reclaim the method for Chemicals, it is characterized in that:
Its abstraction process and process are:
(1), raw material calcining process
To contain broken mistake 80～120 mesh sieves of ground-slag of vanadium, chromium, iron and phosphorus, and mix with yellow soda ash according to the amount that contains vanadium, chromium, iron and phosphorus, roasting under 800～1050 ℃ of conditions is with wherein vanadium, chromium and phosphorus transform into grog soluble in water;
(2), the grog lixiviate operation of heating
To join through the grog of roasting in the hot water, water temperature stirs under 80 ℃ condition carried out lixiviate in 60～90 minutes, and water miscible vanadium, chromium and phosphorus are dissolved in the water;
(3), ferric oxide and contain vanadium, chromium and phosphorus solution separation circuit
To separate with the aqueous solution that is dissolved with vanadium, chromium and phosphorus compound through the grog solid of lixiviate by filtering, solid part is an iron oxide product, and solution is as the stock liquid that extracts vanadium, chromium and phosphorus;
(4), the pre-dephosphorization operation of solution crystallization
After will containing the stock liquid cooling of vanadium, chromium and phosphorus, the phosphorus that is dissolved in the stock liquid is separated out from stock liquid in tertiary sodium phosphate crystalline mode, this crystal is the raw phosphoric acid trisodium, and makes phosphorus content reduction in the stock liquid, reaches the purpose of pre-dephosphorization;
1. water for cooling: adopt water cooling tower-pump-solution crystallization jar chuck and inner coil pipe polyphone, with water is cold carrier, and pump is a power, makes the aqueous solution carry out heat exchange by tank skin and coil pipe outer wall under whipped state, make the temperature of solution carry out solid-liquid separation after reducing to 30～35 ℃, solid is Na
3PO
412H
2O goes treating process;
2. chilled brine cooling: will be through the solution after the water for cooling solid-liquid separation with pump delivery to the brine freezing jar, forcing under the stirring condition,-5～-10 ℃ salt solution carries out heat exchange through the chuck inwall of jar and inner coil pipe outer wall and solution, when the solids content in the solution reaches 30～40%, carry out solid-liquid separation, solid Na
3PO
412H
2O goes treating process; Solution continues to cool to-1～2 ℃, carries out the solid-liquid body and separates solid Na
3PO
412H
2O goes to make with extra care, and the liquid input has in the basin of heat-exchanger rig;
(5), deep phosphorous removal and desiliconization process
Will be in advance remove phosphorus solution and heat up through heat exchange and stir under 60～80 ℃ of conditions and added sulfuric acid and calcium sulfate reaction 2～3 hours, when the P in the solution＜0.5g/L, carry out solid-liquid separation, the filter residue countercurrent washing is again with isolating phosphorus slag after the ferrous sulfate detoxifcation;
Liquid input desiliconization still after the dephosphorization, stirring and the powdered reaction of adding sodium aluminate are 1～1.5 hour under 50～70 ℃ condition, when the Si in the solution＜0.005g/L, be cooled to 20～30 ℃ through quiescent setting, carry out solid-liquid separation, with isolating white residue after the ferrous sulfate detoxifcation, liquid is used to extract vanadium and chromium product again in the filter residue countercurrent washing;
(6), contain vanadium and chromium solution potential of hydrogen and adjust operation
In stock liquid, add sulfuric acid, adjust the potential of hydrogen of solution, make the pH value between 7～8.0 through dephosphorization and desiliconization;
(7), extracting vanadium and chromium separation circuit
With in the volume pump input extractor, temperature is controlled at 20～30 ℃ with deep phosphorous removal and desiliconization and the solution of adjusting the pH value, and through counter-current extraction, vanadium enters extraction agent and forms rich vanadium organism, and chromium is stayed in the aqueous solution;
(8), reextraction vanadium operation
Rich vanadium organism and strippant interact in stripper with the volume ratio of 3:1.2～8, under 40～50 ℃, the condition of pH value 8～9, and through fully stirring 10～20 minutes, the vanadium rich vanadium aqueous solution of formation that is dissolved in the water, vanadium concentration reaches 30～40g/L;
(9), vanadium precipitation operation
In rich vanadium solution, add ammonium sulfate, make the reaction of vanadium and ammonium sulfate generate ammonium meta-vanadate;
(10), ammonium meta-vanadate calcining process
The ammonium meta-vanadate that precipitates and isolates is carried out roasting, make the form evaporation of ammonium, obtain the Vanadium Pentoxide in FLAKES product simultaneously with ammonia;
(11), chromium reduction operation
Add S-WAT and sulfuric acid in passing through the separating obtained chromium-containing solution of vanadium and chromium, making hexavalent chrome reduction is trivalent chromium;
(12), chromium hydroxide precipitation operation
In through the reductive chromium-containing solution, add sodium hydroxide, make chromium form chromium hydroxide precipitation;
(13), chromium hydroxide and sodium sulfate separation circuit
Contain sodium sulfate in the solution after adding sulfuric acid and S-WAT, sodium hydroxide and precipitating chromium hydroxide, chromium hydroxide is separated with metabisulfite solution, obtain the mother liquor of chromium hydroxide product and contains sodium sulfate by filtration;
(14), deamination operation
In the precipitation supernatant liquor, add sodium hydroxide, make ammonium be transformed into ammonia that gaseous ammonia and roasting ammonium meta-vanadate overflowed and absorbed by water together and become the ammoniacal liquor product;
(15), sulfate crystal separation circuit
The mother liquor of the mother liquor of the contains sodium sulfate that will produce through the precipitation chromium hydroxide and the contains sodium sulfate that produces through precipitation vanadium and deamination merges the contains sodium sulfate solution cooling that forms to be handled, and makes sulfate crystal separate out Na
2SO
410H
2O forms the sodium sulfate product that contains crystal water;
(16), sodium sulfate separates the mother liquor purification operation
To realize the water purification processing through the separation mother liquor behind the sulfate crystal through reverse osmosis membrane processing, continue on for water of productive use;
(17), vanadium and chromium operation are made with extra care-separated to the raw phosphoric acid trisodium
With the pre-dephosphorization operation of the stock liquid crystallization isolated Na that cools
3PO
412H
2The O crystal is by adding 0.7～1.0m per ton
3Deionized water or steam condensate make solution, be input in the ion exchange resin column with pump, vanadium in the solution and chromium ion are attracted on the resin, and resolve with sodium hydroxide solution saturated back, with sulphuric acid soln regeneration, vanadium that parses and chromium solution enter extracting vanadium and chromium separation circuit;
(18), trisodium phosphate solution and phosphatase reaction operation
In through the isolated pure trisodium phosphate solution of resin column, add phosphoric acid, generate Na
2HPO
4: NaH
2PO
4The solution of=2:1 with the spray-dried tower oven dry of this solution, gets Na
2HPO
4And NaH
2PO
4Mixture;
(19), the calcining process of tripoly phosphate sodium STPP
With Na
2HPO
4And NaH
2PO
4Mixture in rotary kiln, carry out calcination process, obtain the tripoly phosphate sodium STPP product;
(20), heat exchange operation
Each section baking flue gas by waste heat exchange heating purifying treatment water, is used for producing and uses hot water;
2, method according to claim 1 is characterized in that: the sulfuric acid in each reactions steps is the 1:1 aqueous sulfuric acid.
3, method according to claim 1 is characterized in that: extraction agent by main extraction agent primary amine and thinner sulfonated kerosene and properties-correcting agent by 13～18: 80～85: 10～5 volume ratios are mixed and are formed.
4, method according to claim 1 is characterized in that: strippant is by 0.3～0.7mol/L Na
2SO
4Form with 1.2～1.8mol/L NaOH mixed solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100113936A CN100489126C (en) | 2007-05-18 | 2007-05-18 | Method of reclaiming chemical industry products by using industrial slag containing vanadium, chromium, iron and phosphorous |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100113936A CN100489126C (en) | 2007-05-18 | 2007-05-18 | Method of reclaiming chemical industry products by using industrial slag containing vanadium, chromium, iron and phosphorous |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101058853A CN101058853A (en) | 2007-10-24 |
| CN100489126C true CN100489126C (en) | 2009-05-20 |
Family
ID=38865158
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100113936A Active CN100489126C (en) | 2007-05-18 | 2007-05-18 | Method of reclaiming chemical industry products by using industrial slag containing vanadium, chromium, iron and phosphorous |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100489126C (en) |
Families Citing this family (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI392652B (en) * | 2009-08-24 | 2013-04-11 | Method for extracting vanadium from an vanadium/phosphorus containing iron | |
| CN102191374B (en) * | 2010-03-10 | 2012-11-21 | 中国科学院过程工程研究所 | Method for recycling traditional chromium residue |
| CN102061397B (en) * | 2010-06-02 | 2012-10-03 | 四川龙蟒矿冶有限责任公司 | Method for recycling vanadium, chromium, titanium and iron from vanadium-titanium magnetite ore |
| CN101948122B (en) * | 2010-09-25 | 2012-07-25 | 攀钢集团钢铁钒钛股份有限公司 | Treatment method of crystalline material obtained through evaporation and concentration of vanadium oxide production wastewater |
| CN102041377B (en) * | 2010-11-11 | 2012-04-18 | 武钢集团昆明钢铁股份有限公司 | Method for recovering iron, vanadium and chromium in vanadium-titanium magnetite concentrate |
| CN102477493B (en) * | 2010-11-29 | 2014-06-18 | 攀钢集团钢铁钒钛股份有限公司 | Silicon-removing phosphorus-removing purifying method of sodium-modified vanadium-extraction leachate |
| CN102220498B (en) * | 2011-04-01 | 2013-10-16 | 中国恩菲工程技术有限公司 | Method for preparing fine vanadium slag |
| CN102337411A (en) * | 2011-10-19 | 2012-02-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recycling vanadium and chromium from high-chromium low-vanadium vanadium precipitation wastewater |
| CN102876899B (en) * | 2012-10-30 | 2013-09-11 | 重庆大学 | Method for effectively separating and extracting vanadium and chromium from vanadium-leaching wastewater |
| CN103352124A (en) * | 2012-12-06 | 2013-10-16 | 全喆 | Method for separating and recovering V and Cr from V-Cr waste material |
| CN103288457B (en) * | 2013-06-26 | 2015-07-01 | 长沙理工大学 | Application treatment method of metal skin of recovered waste chromium-electroplated ABS (Acrylonitrile Butadiene Styrene) plastic |
| CN103740934B (en) * | 2013-12-23 | 2015-11-04 | 葫芦岛辉宏有色金属有限公司 | The industrial slag containing vanadium, chromium, phosphorus and calcium is utilized to reclaim chemical substance method |
| CN103966467A (en) * | 2014-03-27 | 2014-08-06 | 湖南大学 | Chloride-free vanadium extraction process |
| CN103937998B (en) * | 2014-04-21 | 2016-02-10 | 中国科学院过程工程研究所 | A kind of method from preparing low silicon Vanadium Pentoxide in FLAKES containing vanadium chrome-silicon solution |
| CN103966438B (en) * | 2014-05-14 | 2016-06-08 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method of vanadium and chromium in electrolytic separation containing vanadium and chromium solution |
| CN104018011B (en) * | 2014-06-23 | 2015-05-27 | 攀钢集团攀枝花钢铁研究院有限公司 | Production method of vanadic oxide |
| CN104357671B (en) * | 2014-12-01 | 2016-07-06 | 重庆大学 | A kind of method separating and recovering vanadium and chromium from vanadium chromium slag |
| CN105063379B (en) * | 2015-07-28 | 2017-06-06 | 四川理工学院 | A kind of method of extracting vanadium from vanadium-containing ferrophosphor |
| CN106381394A (en) * | 2016-10-08 | 2017-02-08 | 河钢股份有限公司承德分公司 | Method for extracting chromium from high-chromium-content calcium-chromium slag |
| CN106399694A (en) * | 2016-10-08 | 2017-02-15 | 河钢股份有限公司承德分公司 | Method for synchronously extracting vanadium and aluminum from waste vanadium oxide smelter refractory brick |
| CN106978542A (en) * | 2017-03-31 | 2017-07-25 | 江苏省冶金设计院有限公司 | The system and method for handling converter vanadium chromium slag |
| CN106834727A (en) * | 2017-03-31 | 2017-06-13 | 江苏省冶金设计院有限公司 | The system and method for processing converter vanadium chromium slag |
| CN108359815B (en) * | 2017-04-26 | 2020-11-03 | 中国科学院过程工程研究所 | Comprehensive utilization method of silicon-removing waste residues of vanadium-containing leaching solution |
| CN108754185B (en) * | 2018-05-25 | 2021-02-02 | 中国科学院过程工程研究所 | Method for purifying silicon, phosphorus and arsenic in vanadium-containing solution |
| CN109970135A (en) * | 2019-04-09 | 2019-07-05 | 中南大学 | The application of the TOC of calcium sulfate and/or calcium phosphate in removal hydrometallurgy raffinate |
| CN110425870A (en) * | 2019-08-30 | 2019-11-08 | 贵州遵义金山磨料有限公司 | A kind of bauxite Brown Alundum calcining-desiliconization integration tunnel oven |
| CN113493244B (en) * | 2020-03-20 | 2022-05-27 | 四川大学 | Method for reducing hexavalent chromium in wastewater by using ferrophosphorus slag |
| CN114480883B (en) * | 2021-12-16 | 2023-11-21 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing high-purity vanadium pentoxide by removing silicon and chromium in vanadium solution through nickel ion cooperation |
| CN114632509B (en) * | 2022-03-25 | 2023-04-21 | 昆明理工大学 | Preparation of Cr-Al by using aluminium-chromium slag 2 O 3 Method for preparing mesoporous catalytic material and application thereof |
| CN114835097A (en) * | 2022-05-09 | 2022-08-02 | 四川大学 | Method for treating pentavalent vanadium in wastewater by using ferrophosphorus slag |
| CN115259103B (en) * | 2022-08-17 | 2023-11-10 | 四川省银河化学股份有限公司 | Acid-base preparation process for chromium-containing sodium sulfate solution |
| CN116334414B (en) * | 2023-03-16 | 2024-07-19 | 核工业北京化工冶金研究院 | Method for selectively separating vanadium and chromium from vanadium-chromium solution |
| CN117305592B (en) * | 2023-08-16 | 2024-06-28 | 永新县稀贵矿业冶化有限责任公司 | Method for extracting vanadium from vanadium-containing alkaline residue and synergistic harmless utilization of vanadium-containing alkaline residue and secondary aluminum ash |
-
2007
- 2007-05-18 CN CNB2007100113936A patent/CN100489126C/en active Active
Non-Patent Citations (2)
| Title |
|---|
| 从含钒钢渣中富集钒的研究. 张鹏科.中国优秀博硕士学位论文全文数据库（硕士），第1期. 2007 |
| 从含钒钢渣中富集钒的研究. 张鹏科.中国优秀博硕士学位论文全文数据库（硕士），第1期. 2007 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101058853A (en) | 2007-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100489126C (en) | Method of reclaiming chemical industry products by using industrial slag containing vanadium, chromium, iron and phosphorous | |
| CN102329964B (en) | Method for separating and recovering vanadium and chromium from vanadium-chromium reduced waste residue | |
| CN101812593B (en) | Method for depositing vanadium wastewater by utilizing vanadium-extraction tailings and acid ammonium salt | |
| CN103602819B (en) | Comprehensive recovery method of vanadate-chromate-containing solution | |
| CN102689930B (en) | Hydrochloric acid pickling waste liquid resource integrated utilization method for preparing iron oxide and ammonium sulfate | |
| CN102586612A (en) | Method for recovering vanadium and chromium from vanadium and chromium-containing slag | |
| CN104831075A (en) | Method for separating and purifying vanadium and molybdenum of waste vanadium-molybdenum SCR (selective catalytic reduction) catalyst | |
| CN104628035A (en) | Resourceful utilization method of waste catalyst | |
| CN108396158A (en) | A kind of processing method of the complex salt crystal object of electrolytic manganese process | |
| CN113045060B (en) | Comprehensive utilization method of seawater resources | |
| CN103011537A (en) | Method for treating sludge containing trivalent chromium and recovering heavy metal | |
| CN109385531B (en) | Resource utilization method of vanadium extraction tailings of aluminum-based vanadium-containing waste catalyst | |
| CN109022806A (en) | A method of utilizing the vanadium liquid removal of impurities clay standby vanadic anhydride of vanadium | |
| CN105923877A (en) | Wastewater treatment process for wet-process chromium metallurgy | |
| CN109336177B (en) | Method for cleanly producing high-purity vanadium pentoxide by using hydrogen peroxide and ammonia water | |
| CN102154559A (en) | Process for extracting vanadium from vanadium slag containing phosphorus at low temperature | |
| CN102220499A (en) | Roasting-leaching method of fine vanadium slags | |
| CN104086032A (en) | Method for recycling vanadium precipitating wastewater | |
| CN113293297B (en) | Multi-element recycling of residual oil hydrogenation waste catalyst | |
| CN108947012A (en) | A method of separating and recovering ammonia from ammonia nitrogen waste water | |
| CN110564979B (en) | Method for recovering vanadium and chromium from vanadium and chromium containing mud | |
| CN110408790A (en) | A kind of method that pressure leaching v-bearing steel slag produces vanadium product | |
| CN102220495B (en) | Method for purifying vanadium-precipitating mother liquor | |
| CN115974123B (en) | Method for recycling sulfuric acid and valuable metals in titanium white waste acid | |
| CN116924472A (en) | Comprehensive utilization method of tungsten-containing magnesium ammonium phosphate slag |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP03 | Change of name, title or address |
Address after: 125017 Huludao province Liaoning City Nanpiao District Lo Hong Zhen Kao Shan Cun Qian pan Cun Xian (South Village Road) Patentee after: Liaoning Hong Kong Industrial Co., Ltd. Address before: 125017 Liaoning province Huludao city lianshanqu Lo Hong Xian Zhen Kao Shan Industrial Park Patentee before: Huludao Huihong Non-ferrous Metal Co., Ltd. |