CN104086032A - Method for recycling vanadium precipitating wastewater - Google Patents
Method for recycling vanadium precipitating wastewater Download PDFInfo
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Abstract
The invention provides a method for recycling vanadium precipitating wastewater. The method comprises the following steps: (a) adding a reducing agent into the vanadium precipitating wastewater to perform reduction reaction, and reducing hexavalent chromium in the vanadium precipitating wastewater into trivalent chromium to obtain a first solution; (b) adding alkaline liquor into the first solution to obtain a mixed solution, heating the mixed solution at 60-90 DEG C, stirring at the same time, and filtering after complete reaction to obtain chromium slag and a second solution; (c) adding roasting clinker into the second solution, uniformly stirring, and performing solid-liquid separation to obtain a vanadium-containing leaching solution and tailings; (d) adding a phosphorus removal agent and activated carbon into the vanadium-containing leaching solution, performing impurity removal and purification on the vanadium-containing leaching solution, and filtering to obtain vanadium-containing qualified liquid; and (e) adding ammonium sulfate and sulfuric acid into the vanadium-containing qualified liquid, and performing vanadium precipitation operation to obtain ammonium polyorthovanadate. According to the method provided by the invention, the vanadium precipitating wastewater can be furthest used, and the treatment quantity and treatment cost of the vanadium precipitating wastewater can be reduced.
Description
Technical field
The present invention relates to a kind of method of vanadium wastewater recycle, more particularly, the present invention relates to a kind of method of vanadium wastewater recycle of the leaching operation that pretreated vanadium wastewater is applied to roasting grog.
Background technology
Ammonium poly-vanadate is the raw material of preparing vanadium oxide, when preparing ammonium poly-vanadate, vanadium slag need to be carried out after pre-treatment to oxidizing roasting, obtain roasting grog, roasting grog obtains, containing vanadium leachate, containing vanadium leachate, obtaining ammonium poly-vanadate again after purification, precipitation through leaching operation.In whole production process, except obtaining ammonium poly-vanadate, also produced a large amount of vanadium wastewater, its main component has ammonium sulfate, sodium sulfate, vanadium, chromium and tiny ammonium poly-vanadate suspended substance etc.
Along with the intensification of the whole people to environmental awareness, environmental issue has become the important indicator that enterprise produces.At present, vanadium corporate boss will adopt waste water evaporating and concentrating process to process vanadium wastewater, vanadium wastewater enters evaporation concentration system after reduction, neutralization, filtration, after evaporation concentration, crystallisation by cooling, obtain solid sodium sulfate and water of condensation, wherein, water of condensation and sodium sulfate recoverable, realized the zero release of waste water.Yet the problems such as this vanadium wastewater treatment process exists that vanadium recovery is low, ammonium sulfate and sodium sulfate mixing salt inferior separating effect.In addition,, because vanadium wastewater treatment capacity is large, cause evaporation concentration system fouling corrosion serious, and vanadium wastewater processing cost is high.
Publication number is the treatment process that the Chinese patent application of CN102795721A discloses a kind of acid waste water for depositing vanadium, in the method acid waste water for depositing vanadium is carried out to twice reduction except after vanadium chromium, neutralization, precipitation, press filtration, gained filtrate qualified discharge.Although this method is easy, do not consider sodium sulfate in waste water, the impact of ammonium sulfate on environment.
Publication number is that the Chinese patent application of CN102051486A discloses a kind of method of utilizing vanadium wastewater to produce low-phosphorous vanadium liquid, leaching agent using vanadium wastewater as vanadium bearing slag in the method, utilize its contained ammonium radical ion and phosphate anion and magnesium ion to form complex precipitate, add again dephosphorization agent to carry out deep phosphorous removal, thereby produce low-phosphorous vanadium liquid.Realized the recycling of vanadium wastewater, but in leaching process, the enrichment of sodium, potassium, chromium etc. will cause disadvantageous effect to precipitation process.
Publication number is a kind of method that the Chinese patent application of CN102838233A discloses acid waste water for depositing vanadium recycle, adopt in the method milk of lime adjustment of acidity vanadium wastewater to carry out solid-liquid separation to alkalescence, obtain basic solution and gypsum tailings, then in basic solution, add decalcifying agent to carry out decalcification, carry out again obtaining supernatant liquid and decalcification slag after solid-liquid separation, return after finally the pH value of supernatant liquid being adjusted to 3～7 with sulfuric acid and leach operation and carry out recycle.Although the method can effectively be controlled the calcium ion concn returning in the solution that leaches operation, the vanadium wastewater in the method is mainly for the vanadium wastewater of calcification baking process for extracting vanadium.
Summary of the invention
One object of the present invention is to provide the method for the vanadium wastewater recycle of at least one technical problem in a kind of can solving the problems of the technologies described above.
The object of the present invention is to provide a kind of method of vanadium wastewater recycle, the method according to this invention, can make vanadium wastewater be maximally utilised, and reduces treatment capacity and the processing costs of vanadium wastewater.
According to the method for a kind of vanadium wastewater recycle of the present invention, comprise the following steps: (a) in described vanadium wastewater, add reductive agent to carry out reduction reaction, making the hexavalent chrome reduction in vanadium wastewater is trivalent chromium, obtains the first solution; (b) in the first solution, add alkali lye to obtain mixing solutions, mixing solutions is heated, Heating temperature is 60 ℃～90 ℃, in heating, stirs, and after complete reaction, filters, and obtains chromium slag and the second solution; (c) in the second solution, add roasting grog, after stirring, carry out solid-liquid separation and obtain containing vanadium leachate and tailings; (d), to adding dephosphorization agent, gac containing in vanadium leachate, to carrying out impurity and purification containing vanadium leachate, after filtration, obtain containing vanadium qualifying liquid; (e) to adding ammonium sulfate, sulfuric acid containing in vanadium qualifying liquid, carry out precipitation operation, obtain ammonium poly-vanadate and the first vanadium wastewater.
According to an aspect of the present invention, the reductive agent in described step (a) comprises sulfurous acid or Sodium Pyrosulfite, and the mol ratio of sulfurous acid or Sodium Pyrosulfite and chromium is 1～2.5:1.
According to an aspect of the present invention, in step (a), add after reductive agent, at 40 ℃～60 ℃, carry out reduction reaction, the reaction times is 10min～30min.
According to an aspect of the present invention, described in step (b), alkali lye comprises production water of condensation, and the ratio that is 0.5～3:1 by volume by the first solution and production water of condensation is mixed to get mixing solutions, wherein, the pH value of producing water of condensation is 8～11, and the pH value of mixing solutions is 6～8.
According to an aspect of the present invention, in step (b), utilize pressurized air to stir, churning time is 10min～40min.
According to an aspect of the present invention, in step (c), the mass ratio of the second solution and roasting grog is 1～2:1, and the second solution and roasting grog are stirred to 5min～20min at 80 ℃～90 ℃, carries out solid-liquid separation and obtains containing vanadium leachate and tailings.
According to an aspect of the present invention, impurity and purification in step (d) comprise to adding dephosphorization agent and react 10min～15min and carry out dephosphorization at 70 ℃～85 ℃ containing in vanadium leachate, after adding again gac to stir, purify, wherein, dephosphorization agent comprises calcium chloride or magnesium chloride, calcium chloride or magnesium chloride and be 2～4:1 containing the mol ratio of the phosphorus in vanadium leachate are 1～3g/L to the amount of the gac containing adding in vanadium leachate.
According to an aspect of the present invention, in step (e), containing adding sulfuric acid to neutralize in vanadium qualifying liquid, solution is heated, when pH value is 4～6, temperature is while being 40 ℃～50 ℃ simultaneously, add ammonium sulfate, add sulfuric acid that pH value is adjusted to 2～2.5 again, and solution is heated to 85 ℃～95 ℃, crystallization goes out ammonium poly-vanadate, wherein, the quality of ammonium sulfate is 1.0～2.5:1 with the mass ratio that contains the vanadium in vanadium qualifying liquid.
According to an aspect of the present invention, described method also comprises that the first vanadium wastewater making in step (e) is back in step (a).
According to an aspect of the present invention, when the concentration that the concentration of the sodium ion in the first vanadium wastewater in step (e) is less than 50g/L and potassium ion is less than 0.6g/L, the first vanadium wastewater is back in step (a).
According to the present invention, can make vanadium wastewater be maximally utilised, reduce treatment capacity and the processing costs of vanadium wastewater.
Accompanying drawing explanation
By the detailed description of carrying out below in conjunction with accompanying drawing, above and other objects of the present invention, feature and advantage will become apparent, wherein:
Fig. 1 shows the schema of vanadium wastewater recycle according to an exemplary embodiment of the present invention.
Embodiment
Hereinafter, exemplary embodiment of the present invention is described with reference to the accompanying drawings more fully.Yet they can be implemented with different forms, and should not be construed as the embodiment that is confined to set forth here.On the contrary, providing these embodiment to make the disclosure will be thoroughly with complete, and the scope of example embodiment will be conveyed to those skilled in the art fully.
Hereinafter, will describe according to the method for a kind of vanadium wastewater recycle of exemplary embodiment of the present invention.
Fig. 1 shows the schema of vanadium wastewater recycle according to an exemplary embodiment of the present invention.
With reference to Fig. 1, a kind of according to an exemplary embodiment of the present invention method of vanadium wastewater recycle comprises the following steps: (a) in vanadium wastewater, add reductive agent to carry out reduction reaction, making the hexavalent chrome reduction in vanadium wastewater is trivalent chromium, obtains the first solution; (b) in the first solution, add alkali lye to obtain mixing solutions, mixing solutions is heated, Heating temperature is 60 ℃～90 ℃, in heating, stirs, and after complete reaction, filters, and obtains chromium slag and the second solution; (c) in the second solution, add roasting grog, after stirring, carry out solid-liquid separation and obtain containing vanadium leachate and tailings; (d), to adding dephosphorization agent, gac containing in vanadium leachate, to carrying out impurity and purification containing vanadium leachate, after filtration, obtain containing vanadium qualifying liquid; (e) to adding ammonium sulfate, sulfuric acid containing in vanadium qualifying liquid, carry out precipitation operation, obtain ammonium poly-vanadate and the first vanadium wastewater.
In step (a), in vanadium wastewater, add reductive agent to carry out reduction reaction.Vanadium wastewater can be the vanadium wastewater that contains ammonium salt of acidity, and particularly, vanadium wastewater can comprise ammonium sulfate, sodium sulfate, vanadium, chromium and tiny ammonium poly-vanadate suspended substance etc.Reductive agent can be chromic reductive agent for making hexavalent chrome reduction.In order to improve the reduction effect of vanadium wastewater, avoid introducing new foreign ion in vanadium wastewater simultaneously, preferably, reductive agent can be sulfurous acid or Sodium Pyrosulfite, but the invention is not restricted to this, and reductive agent can also comprise S-WAT and V-Brite B.When reductive agent is sulfurous acid or Sodium Pyrosulfite, the mol ratio of sulfurous acid or Sodium Pyrosulfite and chromium can be 1～2.5:1.After reductive agent is joined in vanadium wastewater, reductive agent and vanadium wastewater can be carried out reduction reaction to take hexavalent chrome reduction be trivalent chromium at 40 ℃～60 ℃, thereby obtain the first solution, and the reaction times can be 10min～30min.If reduction reaction rate is slow lower than 40 ℃ for reduction reaction temperature; If reduction reaction temperature is higher than 60 ℃, in solution sulfurous acid etc. minute separate the part sulfurous gas that produces can along with steam disperse out, operating environment is worsened, also can cause the waste of material simultaneously.And if the reaction times is less than 10min, what reduction reaction was carried out is not thorough; If the reaction times, more than 30min, is caused the waste of the energy.
Then, in the first solution, add alkali lye to obtain mixing solutions, alkali lye can be in chemical formula, contain hydroxide radical or water-soluble after be alkaline solution, alkali lye can comprise production water of condensation according to an exemplary embodiment of the present invention, producing water of condensation and be the water that the steam that produces in process of production forms after condensation, for example, can be the production water of condensation producing in wastewater treatment operation.Owing to producing in water of condensation, contain a large amount of ammonium ions, therefore produce water of condensation and be alkalescence, particularly, the pH value of producing water of condensation can be 8～11.But the invention is not restricted to this, alkali lye can also be for example ammoniacal liquor.When alkali lye is while producing water of condensation, the ratio that is 0.5～3:1 by volume with production water of condensation by the first solution is mixed, and obtains mixing solutions, and the pH value of mixing solutions is 6～8.Then, mixing solutions is heated, Heating temperature is 60 ℃～90 ℃, in heating, stir, trivalent chromium in mixing solutions can be combined with hydroxide radical and be formed chromium hydroxide precipitation, after complete reaction, filters, and obtains chromium slag (being chromium hydroxide precipitation) and the second solution.If Heating temperature lower than 60 ℃, is unfavorable for forming chromium slag; If Heating temperature, higher than 90 ℃, can cause the waste of the energy.
According to exemplary embodiment of the present invention, in step (b), in heating, can utilize pressurized air to stir, churning time is 10min～40min.Utilize pressurized air to stir not only and can improve stirring velocity, remaining sulfurous acid or Sodium Pyrosulfite that while can be utilized air to drive out and by step (a), be brought in mixing solutions decompose the sulfur dioxide gas obtaining, and the Heating temperature of 60 ℃～90 ℃ is also conducive to drive sulfurous gas.
Then, in the second solution, add roasting grog, roasting grog is that vanadium slag is heated under oxidizing atmosphere, makes it to react the many vanadic acid sodiums that are dissolvable in water water that generate with sodium salt after oxidation.Roasting grog is joined in the second solution, thereby the many vanadic acid sodiums of the solubility in roasting grog can be dissolved in the second solution.According to exemplary embodiment of the present invention, the mass ratio of the second solution and roasting grog can be 1～2:1, the second solution and roasting grog are stirred to 5min～20min at 80 ℃～90 ℃, alr mode can be to utilize pressurized air to stir, then carry out solid-liquid separation, obtain containing vanadium leachate and tailings.When tailings can comprise production roasting grog, unreacted is vanadium slag completely.Any solid-liquid separating method can be adopted, to carrying out solid-liquid separation containing vanadium leachate and tailings, preferably, the solid-liquid separating method of vacuum filtration can be adopted.
To adding dephosphorization agent and react 10min～15min and remove phosphorus reaction at 70 ℃～85 ℃ containing in vanadium leachate, and then to containing vanadium leachate, purify after adding gac to stir, then filter and obtain containing vanadium qualifying liquid.Why need carrying out impurity and purification containing vanadium leachate, because be dissolved in the process of the second solution at many vanadic acid sodiums, some impurity also will be along with many vanadic acid sodiums enter into solution together, follow-up precipitation operation and the quality of product will be affected, therefore to carrying out impurity and purification containing vanadium leachate.Dephosphorization agent can comprise any dephosphorization agent that can remove containing the phosphorus in vanadium leachate, preferably, dephosphorization agent can comprise calcium chloride or magnesium chloride, when dephosphorization agent is calcium chloride or magnesium chloride, and calcium chloride or magnesium chloride and be 2～4:1 containing the mol ratio of the phosphorus in vanadium leachate.When calcium chloride or magnesium chloride and containing the mol ratio of the phosphorus in vanadium leachate, during higher than 2～4:1, can generate vanadic acid calcium or vanadic acid magnesium precipitate, cause the loss of vanadium.Amount to the gac containing adding in vanadium leachate is 1～3g/L.
To containing in vanadium qualifying liquid, add sulfuric acid to carry out neutralization reaction to regulate the acid or alkali environment that is applicable to ammonium sulfate and the reaction of many vanadic acid sodiums, solution is heated simultaneously, when pH value is 4～6, temperature is while being 40～50 ℃, add ammonium sulfate, the quality of ammonium sulfate is 1.0～2.5:1 with the mass ratio that contains the vanadium in vanadium qualifying liquid.After adding ammonium sulfate, add again sulfuric acid that pH value is adjusted to 2～2.5, and solution is heated to 85～95 ℃, under solution is acid condition, additional ammonium sulfate and the ammonium sulfate entering in vanadium wastewater containing vanadium qualifying liquid react with the many vanadic acid sodiums containing vanadium qualifying liquid, crystallization goes out ammonium poly-vanadate, produces the first vanadium wastewater simultaneously.
The method of vanadium wastewater recycle also comprises the first vanadium wastewater is back in step (a) and carries out recycle according to an exemplary embodiment of the present invention.Preferably, when the concentration that the concentration of the sodium ion in the first vanadium wastewater is less than 50g/L and potassium ion is less than 0.6g/L, the first vanadium wastewater is back in step (a) and carries out recycle.When not meeting this condition, the first vanadium wastewater is passed into wastewater treatment operation and processes.
Example 1
In 10L vanadium wastewater, add 110g Sodium Pyrosulfite, be then heated to after 50 ℃, stirring reaction 10min obtains the first solution; In the first solution, add production water of condensation (pH value is 10) to obtain mixing solutions, the first solution with produce water of condensation by volume for 1:1 mixes, the pH value of mixing solutions is 7.0, mixing solutions is heated to after 85 ℃, opening pressurized air stirs mixing solutions, stir after 15min, filter and obtain the second solution and chromium slag; In the second solution, add 20kg roasting grog (wherein, in roasting grog, the content of TV is 5.50%, the content of SV (solvable vanadium) is 4.26%), the second solution and roasting grog are stirred to 8min at 85 ℃, then utilize vacuum filtration to carry out solid-liquid separation, obtain containing vanadium leachate and tailings, wherein, the leaching yield of vanadium (the solvable vanadium in roasting grog enters into the ratio of leach liquor) is 95.8%; To adding 27g calcium chloride containing in vanadium leachate, at 80 ℃, react 10min, add gac 36g, after stirring, filter and obtain containing vanadium qualifying liquid; To containing adding sulfuric acid in vanadium qualifying liquid and to its heating, when pH value is 4～6, temperature is while being 40～50 ℃, add ammonium sulfate, the quality of ammonium sulfate is 1.8:1 with the mass ratio that contains the vanadium in vanadium qualifying liquid, add again sulfuric acid by pH value be adjusted to 2.5, heated solution to 85～95 ℃, crystallization goes out ammonium poly-vanadate.
Wherein, vanadium wastewater, containing vanadium leachate, as shown in table 1 containing pH value and the main component of vanadium qualifying liquid, the composition of ammonium poly-vanadate is as shown in table 2.
Example 2
Sulfurous acid to the 1180mL of the sulfurous gas that to add containing massfraction in 10L vanadium wastewater be 6%, is then heated to after 60 ℃, and stirring reaction 20min obtains the first solution; In the first solution, add production water of condensation (pH value is 9.5) to obtain mixing solutions, the first solution with produce water of condensation by volume for 0.5:1 mixes, the pH value of mixing solutions is 7.5, mixing solutions is heated to after 85 ℃, opening pressurized air stirs mixing solutions, stir after 15min, filter and obtain the second solution and chromium slag; In the second solution, add 20kg roasting grog (wherein, in roasting grog, the content of TV is 5.63%, the content of SV (solvable vanadium) is 4.31%), the second solution and roasting grog are stirred to 8min at 85 ℃, then utilize vacuum filtration to carry out solid-liquid separation, obtain containing vanadium leachate and tailings, wherein, the leaching yield of vanadium (the solvable vanadium in roasting grog enters into the ratio of leach liquor) is 96.4%; To adding 16g magnesium chloride containing in vanadium leachate, at 80 ℃, react 15min, add gac 28g, after stirring, filter and obtain containing vanadium qualifying liquid; To containing adding sulfuric acid in vanadium qualifying liquid and to its heating, when pH value is 4～6, temperature is while being 40～50 ℃, add ammonium sulfate, the quality of ammonium sulfate is 2.2:1 with the mass ratio that contains the vanadium in vanadium qualifying liquid, add again sulfuric acid by pH value be adjusted to 2.0, heated solution to 85～95 ℃, crystallization goes out ammonium poly-vanadate.
Wherein, vanadium wastewater, containing vanadium leachate, as shown in table 1 containing pH value and the main component of vanadium qualifying liquid, the composition of ammonium poly-vanadate is as shown in table 2.
Example 3
In 10L vanadium wastewater, add 138g Sodium Pyrosulfite, be then heated to after 45 ℃, stirring reaction 15min obtains the first solution; In the first solution, add production water of condensation (pH value is 10.5) to obtain mixing solutions, the first solution with produce water of condensation by volume for 2:1 mixes, the pH value of mixing solutions is 6.6, mixing solutions is heated to after 80 ℃, opening pressurized air stirs mixing solutions, stir after 30min, filter and obtain the second solution and chromium slag; In the second solution, add 12kg roasting grog (wherein, in roasting grog, the content of TV is 5.73%, the content of SV (solvable vanadium) is 4.41%), the second solution and roasting grog are stirred to 8min at 85 ℃, then utilize vacuum filtration to carry out solid-liquid separation, obtain containing vanadium leachate and tailings, wherein, the leaching yield of vanadium (the solvable vanadium in roasting grog enters into the ratio of leach liquor) is 94.5%; To adding 25.5g magnesium chloride containing in vanadium leachate, at 80 ℃, react 10min, add gac 18g, after stirring, filter and obtain containing vanadium qualifying liquid; To containing adding sulfuric acid in vanadium qualifying liquid and to its heating, when pH value is 4～6, temperature is while being 40～50 ℃, add ammonium sulfate, the quality of ammonium sulfate is 1.8:1 with the mass ratio that contains the vanadium in vanadium qualifying liquid, add again sulfuric acid by pH value be adjusted to 2.2, heated solution to 85～95 ℃, crystallization goes out ammonium poly-vanadate.
Wherein, vanadium wastewater, containing vanadium leachate, as shown in table 1 containing pH value and the main component of vanadium qualifying liquid, the composition of ammonium poly-vanadate is as shown in table 2.
Example 4
Sulfurous acid to the 720mL of the sulfurous gas that to add containing massfraction in 10L vanadium wastewater be 6%, is then heated to after 45 ℃, and stirring reaction 15min obtains the first solution; In the first solution, add production water of condensation (pH value is 11) to obtain mixing solutions, the first solution with produce water of condensation by volume for 3:1 mixes, the pH value of mixing solutions is 6.4, mixing solutions is heated to after 85 ℃, opening pressurized air stirs mixing solutions, stir after 15min, filter and obtain the second solution and chromium slag; In the second solution, add 12kg roasting grog (wherein, in roasting grog, the content of TV is 5.29%, the content of SV (solvable vanadium) is 4.17%), the second solution and roasting grog are stirred to 8min at 85 ℃, then utilize vacuum filtration to carry out solid-liquid separation, obtain containing vanadium leachate and tailings, wherein, the leaching yield of vanadium (the solvable vanadium in roasting grog enters into the ratio of leach liquor) is 95.1%; To adding 43g magnesium chloride containing in vanadium leachate, at 80 ℃, react 15min, add gac 10g, after stirring, filter and obtain containing vanadium qualifying liquid; To containing adding sulfuric acid in vanadium qualifying liquid and to its heating, when pH value is 4～6, temperature is while being 40～50 ℃, add ammonium sulfate, the quality of ammonium sulfate is 2:1 with the mass ratio that contains the vanadium in vanadium qualifying liquid, add again sulfuric acid by pH value be adjusted to 2.5, heated solution to 85～95 ℃, crystallization goes out ammonium poly-vanadate.
Wherein, vanadium wastewater, containing vanadium leachate, as shown in table 1 containing pH value and the main component of vanadium qualifying liquid, the composition of ammonium poly-vanadate is as shown in table 2.
Table 1 shows pH value and the main component of vanadium wastewater, leach liquor and qualifying liquid in example 1-4, and table 2 shows the main component of ammonium poly-vanadate in example 1-4.
Table 1
As shown in Table 1, the method for vanadium wastewater recycle according to an exemplary embodiment of the present invention, is applied to vanadium wastewater the leaching operation of roasting grog, and the chromium content containing in vanadium qualifying liquid obtaining is starkly lower than the chromium content in vanadium wastewater.This is because before leaching, the chromium in vanadium wastewater has been carried out to reduction and precipitation process, thus containing vanadium leachate with containing the chromium in vanadium qualifying liquid, be the sexavalent chrome in roasting grog, not because using vanadium wastewater that enrichment occurs.
Table 2
| Composition | TV(wt％) | S(wt％) |
| Example 1 | 49.18 | 0.139 |
| Example 2 | 49.29 | 0.158 |
| Example 3 | 49.07 | 0.041 |
| Example 4 | 48.95 | 0.159 |
As shown in Table 2, vanadium wastewater is applied to the leaching operation of roasting grog, TV content in the ammonium poly-vanadate product obtaining all higher than 48.5%, S content all lower than 0.25% (being higher than 48.5% to the content requirement of TV in ammonium poly-vanadate product, is lower than 0.25% to the requirement of S content).
According to the method for a kind of vanadium wastewater recycle of the present invention, by vanadium wastewater is carried out after pre-treatment, be applied to the leaching operation of roasting grog, can make vanadium wastewater be maximally utilised, reduce treatment capacity and the processing costs of vanadium wastewater.
Although described some embodiments of the present invention with reference to the accompanying drawings, it should be appreciated by those skilled in the art that in the situation that do not depart from principle of the present invention and the spirit that is limited its scope by claim and equivalent thereof, can modify to these embodiment.
Claims (10)
1. a method for vanadium wastewater recycle, is characterized in that, said method comprising the steps of:
(a) in described vanadium wastewater, add reductive agent to carry out reduction reaction, making the hexavalent chrome reduction in vanadium wastewater is trivalent chromium, obtains the first solution;
(b) in the first solution, add alkali lye to obtain mixing solutions, mixing solutions is heated, Heating temperature is 60 ℃～90 ℃, in heating, stirs, and after complete reaction, filters, and obtains chromium slag and the second solution;
(c) in the second solution, add roasting grog, after stirring, carry out solid-liquid separation and obtain containing vanadium leachate and tailings;
(d), to adding dephosphorization agent, gac containing in vanadium leachate, to carrying out impurity and purification containing vanadium leachate, after filtration, obtain containing vanadium qualifying liquid;
(e) to adding ammonium sulfate, sulfuric acid containing in vanadium qualifying liquid, carry out precipitation operation, obtain ammonium poly-vanadate and the first vanadium wastewater.
2. method according to claim 1, is characterized in that, the reductive agent in described step (a) comprises sulfurous acid or Sodium Pyrosulfite, and the mol ratio of sulfurous acid or Sodium Pyrosulfite and chromium is 1～2.5:1.
3. method according to claim 1, is characterized in that, in step (a), adds after reductive agent, at 40 ℃～60 ℃, carries out reduction reaction, and the reaction times is 10min～30min.
4. method according to claim 1, it is characterized in that, described in step (b), alkali lye comprises production water of condensation, the ratio that is 0.5～3:1 by volume by the first solution and production water of condensation is mixed to get mixing solutions, wherein, the pH value of producing water of condensation is 8～11, and the pH value of mixing solutions is 6～8.
5. method according to claim 1, is characterized in that, in step (b), utilizes pressurized air to stir, and churning time is 10min～40min.
6. method according to claim 1, it is characterized in that, in step (c), the mass ratio of the second solution and roasting grog is 1～2:1, and the second solution and roasting grog are stirred to 5min～20min at 80 ℃～90 ℃, carries out solid-liquid separation and obtains containing vanadium leachate and tailings.
7. method according to claim 1, it is characterized in that, impurity and purification in step (d) comprise to adding dephosphorization agent and react 10min～15min and carry out dephosphorization at 70 ℃～85 ℃ containing in vanadium leachate, after adding again gac to stir, purify, wherein, dephosphorization agent comprises calcium chloride or magnesium chloride, and calcium chloride or magnesium chloride and be 2～4:1 containing the mol ratio of the phosphorus in vanadium leachate are 1～3g/L to the amount of the gac containing adding in vanadium leachate.
8. method according to claim 1, it is characterized in that, in step (e), containing in vanadium qualifying liquid, adding sulfuric acid to neutralize, solution is heated simultaneously, when pH value is 4～6, temperature is while being 40 ℃～50 ℃, add ammonium sulfate, then add sulfuric acid that pH value is adjusted to 2～2.5, and solution is heated to 85 ℃～95 ℃, crystallization goes out ammonium poly-vanadate, and wherein, the quality of ammonium sulfate is 1.0～2.5:1 with the mass ratio that contains the vanadium in vanadium qualifying liquid.
9. method according to claim 1, is characterized in that, described method also comprises that the first vanadium wastewater making in step (e) is back in step (a).
10. method according to claim 9, is characterized in that, when the concentration that the concentration of the sodium ion in the first vanadium wastewater in step (e) is less than 50g/L and potassium ion is less than 0.6g/L, the first vanadium wastewater is back in step (a).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105087940A (en) * | 2015-08-27 | 2015-11-25 | 河北钢铁股份有限公司承德分公司 | Method for producing vanadium oxide achieving waste water zero discharge in sodium salt roasting process |
| CN114293034A (en) * | 2021-11-29 | 2022-04-08 | 攀钢集团研究院有限公司 | Method for extracting vanadium from sodium-modified vanadium-containing clinker by using vanadium precipitation wastewater |
| CN114350955A (en) * | 2021-12-29 | 2022-04-15 | 四川省绵阳市华意达化工有限公司 | Treatment method for high-valued treatment of each element in vanadium precipitation wastewater |
| CN114349028A (en) * | 2021-11-29 | 2022-04-15 | 攀钢集团研究院有限公司 | Method for resource utilization of vanadium precipitation wastewater |
| CN115594361A (en) * | 2022-11-11 | 2023-01-13 | 攀钢集团攀枝花钢铁研究院有限公司（Cn） | Method for cooperatively treating coal gas desulfurization waste residue and sodium-modified vanadium precipitation wastewater |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812593A (en) * | 2010-04-22 | 2010-08-25 | 攀钢集团钢铁钒钛股份有限公司 | Method for depositing vanadium wastewater by utilizing vanadium-extraction tailings and acid ammonium salt |
| CN102627366A (en) * | 2012-04-19 | 2012-08-08 | 波鹰(厦门)科技有限公司 | Method for treating vanadium pentoxide wastewater and circularly utilizing resources |
-
2014
- 2014-07-30 CN CN201410370471.1A patent/CN104086032B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812593A (en) * | 2010-04-22 | 2010-08-25 | 攀钢集团钢铁钒钛股份有限公司 | Method for depositing vanadium wastewater by utilizing vanadium-extraction tailings and acid ammonium salt |
| CN102627366A (en) * | 2012-04-19 | 2012-08-08 | 波鹰(厦门)科技有限公司 | Method for treating vanadium pentoxide wastewater and circularly utilizing resources |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105087940A (en) * | 2015-08-27 | 2015-11-25 | 河北钢铁股份有限公司承德分公司 | Method for producing vanadium oxide achieving waste water zero discharge in sodium salt roasting process |
| CN105087940B (en) * | 2015-08-27 | 2017-12-08 | 河北钢铁股份有限公司承德分公司 | A kind of method of sodium roasting flow wastewater zero discharge production barium oxide |
| CN114293034A (en) * | 2021-11-29 | 2022-04-08 | 攀钢集团研究院有限公司 | Method for extracting vanadium from sodium-modified vanadium-containing clinker by using vanadium precipitation wastewater |
| CN114349028A (en) * | 2021-11-29 | 2022-04-15 | 攀钢集团研究院有限公司 | Method for resource utilization of vanadium precipitation wastewater |
| CN114293034B (en) * | 2021-11-29 | 2023-09-05 | 攀钢集团研究院有限公司 | Method for extracting vanadium from sodium-modified vanadium-containing clinker by utilizing vanadium precipitation wastewater |
| CN114350955A (en) * | 2021-12-29 | 2022-04-15 | 四川省绵阳市华意达化工有限公司 | Treatment method for high-valued treatment of each element in vanadium precipitation wastewater |
| CN114350955B (en) * | 2021-12-29 | 2024-04-23 | 四川省绵阳市华意达化工有限公司 | Treatment method for high value of each element in vanadium precipitation wastewater |
| CN115594361A (en) * | 2022-11-11 | 2023-01-13 | 攀钢集团攀枝花钢铁研究院有限公司（Cn） | Method for cooperatively treating coal gas desulfurization waste residue and sodium-modified vanadium precipitation wastewater |
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