CN104086032B - A kind of method of vanadium wastewater recycle - Google Patents
A kind of method of vanadium wastewater recycle Download PDFInfo
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Abstract
The invention provides a kind of method of vanadium wastewater recycle, said method comprising the steps of: (a) adds reductive agent and carry out reduction reaction in vanadium wastewater, makes the hexavalent chrome reduction in vanadium wastewater be trivalent chromium, obtains the first solution; B () adds alkali lye and obtains mixing solutions in the first solution, heat, stir simultaneously mixing solutions at 60 DEG C ~ 90 DEG C, when filtering after complete reaction, obtains chromium slag and the second solution; C () adds roasting grog in the second solution, carry out solid-liquid separation and obtain containing vanadium leachate and tailings after stirring; D () adds dephosphorization agent, gac to containing in vanadium leachate, carry out impurity and purification to containing vanadium leachate, obtains containing vanadium qualifying liquid after filtration; E () adds ammonium sulfate, sulfuric acid to containing in vanadium qualifying liquid, carry out precipitation operation, obtain ammonium poly-vanadate.According to the present invention, vanadium wastewater can be made to be maximally utilised, reduce treatment capacity and the processing costs of vanadium wastewater.
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 pretreated vanadium wastewater being applied to the vanadium wastewater recycle of the leaching operation of roasting grog.
Background technology
Ammonium poly-vanadate is the raw material preparing vanadium oxide, when preparing ammonium poly-vanadate, needing vanadium slag to carry out oxidizing roasting after pre-treatment, obtaining roasting grog, roasting grog obtains, containing vanadium leachate, obtaining ammonium poly-vanadate again containing vanadium leachate after purification, precipitation through leaching operation.In whole production process, except obtaining ammonium poly-vanadate, also create 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 whole people are to the intensification of 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 process vanadium wastewater, vanadium wastewater enters evaporation concentration system after reduction, neutralization, filtration, solid sodium sulfate and water of condensation is obtained after evaporation concentration, crystallisation by cooling, wherein, water of condensation and sodium sulfate recoverable, achieve the zero release of waste water.But this vanadium wastewater treatment process also exists that vanadium recovery is low, the problem such as 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 twice reduction except after vanadium chromium, neutralization, precipitation, press filtration, gained filtrate qualified discharge.Although this method is easy, do not consider the impact on environment of sodium sulfate in waste water, ammonium sulfate.
Publication number is that the Chinese patent application of CN102051486A discloses a kind of method utilizing vanadium wastewater to produce low-phosphorous vanadium liquid, in the method using the leaching agent of vanadium wastewater as vanadium bearing slag, ammonium radical ion contained by it and phosphate anion and magnesium ion is utilized to form complex precipitate, add dephosphorization agent again and carry out deep phosphorous removal, thus produce low-phosphorous vanadium liquid.Achieve 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, solid-liquid separation is carried out after adopting milk of lime adjustment of acidity vanadium wastewater to alkalescence in the method, obtain basic solution and gypsum tailings, then in basic solution, add decalcifying agent carry out decalcification, obtain supernatant liquid and decalcification slag after carrying out solid-liquid separation again, return leaching operation after finally the pH value of supernatant liquid being adjusted to 3 ~ 7 with sulfuric acid and carry out recycle.Although the method can effectively control to return the calcium ion concn in the solution leaching 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 the method for the vanadium wastewater recycle of at least one technical problem provided 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, according to method of the present invention, vanadium wastewater can be made to be maximally utilised, reduce treatment capacity and the processing costs of vanadium wastewater.
Method according to a kind of vanadium wastewater recycle of the present invention comprises the following steps: (a) adds reductive agent and carry out reduction reaction in described vanadium wastewater, makes the hexavalent chrome reduction in vanadium wastewater be trivalent chromium, obtains the first solution; B () adds alkali lye and obtains mixing solutions in the first solution, heat mixing solutions, and Heating temperature is 60 DEG C ~ 90 DEG C, stirring, when filtering after complete reaction, obtaining chromium slag and the second solution while heating; C () adds roasting grog in the second solution, carry out solid-liquid separation and obtain containing vanadium leachate and tailings after stirring; D () adds dephosphorization agent, gac to containing in vanadium leachate, carry out impurity and purification to containing vanadium leachate, obtains containing vanadium qualifying liquid after filtration; E () adds ammonium sulfate, sulfuric acid to 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, add reductive agent in step (a) after, at 40 DEG C ~ 60 DEG C, carry out reduction reaction, the reaction times is 10min ~ 30min.
According to an aspect of the present invention, alkali lye described in step (b) comprises production water of condensation, and the ratio being 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, utilize pressurized air to stir in step (b), 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 5min ~ 20min at 80 DEG C ~ 90 DEG C, 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 carries out dephosphorization to containing adding dephosphorization agent and react 10min ~ 15min at 70 DEG C ~ 85 DEG C in vanadium leachate, add again after gac stirs and purify, wherein, dephosphorization agent comprises calcium chloride or magnesium chloride, calcium chloride or magnesium chloride and the mol ratio containing the phosphorus in vanadium leachate are 2 ~ 4:1, are 1 ~ 3g/L to the amount containing the gac added in vanadium leachate.
According to an aspect of the present invention, in step (e), containing add in vanadium qualifying liquid sulfuric acid carry out in and, solution is heated simultaneously, when pH value be 4 ~ 6, temperature be 40 DEG C ~ 50 DEG C time, add ammonium sulfate, add sulfuric acid again and pH value is adjusted to 2 ~ 2.5, and solution is heated to 85 DEG C ~ 95 DEG C, crystallization goes out ammonium poly-vanadate, wherein, the quality of ammonium sulfate is 1.0 ~ 2.5:1 with the mass ratio containing the vanadium in vanadium qualifying liquid.
According to an aspect of the present invention, described method also comprises the first vanadium wastewater in step (e) is back in step (a).
According to an aspect of the present invention, when the concentration of the sodium ion in the first vanadium wastewater in step (e) is less than 50g/L and the concentration of potassium ion is less than 0.6g/L, the first vanadium wastewater is back in step (a).
According to the present invention, vanadium wastewater can be made to 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, with reference to the accompanying drawings exemplary embodiment of the present invention is described more fully.But they can be implemented in different forms, and should not be construed as the embodiment being confined to set forth here.On the contrary, provide these embodiments to make the disclosure to be thoroughly with complete, and the scope example embodiment is conveyed to those skilled in the art fully.
Hereinafter, the method according to a kind of vanadium wastewater recycle of exemplary embodiment of the present invention will be described.
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) adds reductive agent and carry out reduction reaction in vanadium wastewater, make the hexavalent chrome reduction in vanadium wastewater be trivalent chromium, obtain the first solution; B () adds alkali lye and obtains mixing solutions in the first solution, heat mixing solutions, and Heating temperature is 60 DEG C ~ 90 DEG C, stirring, when filtering after complete reaction, obtaining chromium slag and the second solution while heating; C () adds roasting grog in the second solution, carry out solid-liquid separation and obtain containing vanadium leachate and tailings after stirring; D () adds dephosphorization agent, gac to containing in vanadium leachate, carry out impurity and purification to containing vanadium leachate, obtains containing vanadium qualifying liquid after filtration; E () adds ammonium sulfate, sulfuric acid to 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 carry out reduction reaction.Vanadium wastewater can be the acid vanadium wastewater containing ammonium salt, and particularly, vanadium wastewater can comprise ammonium sulfate, sodium sulfate, vanadium, chromium and tiny ammonium poly-vanadate suspended substance etc.Reductive agent can for can make hexavalent chrome reduction be chromic reductive agent.In order to improve the reduction effect of vanadium wastewater, avoid in vanadium wastewater, introduce new foreign ion, preferably, reductive agent can be sulfurous acid or Sodium Pyrosulfite, but the present invention is not limited thereto, and reductive agent can also comprise S-WAT and V-Brite B simultaneously.When reductive agent be sulfurous acid or Sodium Pyrosulfite time, the mol ratio of sulfurous acid or Sodium Pyrosulfite and chromium can be 1 ~ 2.5:1.Reductive agent is joined after in vanadium wastewater, reductive agent and vanadium wastewater can carry out at 40 DEG C ~ 60 DEG C reduction reaction with by hexavalent chrome reduction for trivalent chromium, thus obtain the first solution, the reaction times can be 10min ~ 30min.If reduction reaction temperature is lower than 40 DEG C, reduction reaction rate is slow; If reduction reaction temperature is higher than 60 DEG C, then solution sulfite etc. decompose the part sulfurous gas that produces can along with steam disperse out, operating environment is worsened, while also can cause the waste of material.Further, if the reaction times be less than 10min, then reduction reaction carry out not thorough; If the reaction times is more than 30min, then cause the waste of the energy.
Then, in the first solution, add alkali lye obtain mixing solutions, alkali lye can be containing hydroxide radical or the water-soluble rear solution in alkalescence in chemical formula, alkali lye can comprise production water of condensation according to an exemplary embodiment of the present invention, producing water of condensation is the water that the steam produced in process of production is formed after condensation, such as, can be the production water of condensation produced in wastewater treatment operation.Owing to producing containing a large amount of ammonium ions in water of condensation, therefore produce water of condensation in alkalescence, particularly, the pH value of producing water of condensation can be 8 ~ 11.But the present invention is not limited thereto, alkali lye can also be such as ammoniacal liquor.When alkali lye is for producing water of condensation, the ratio being 0.5 ~ 3:1 by volume by the first solution and production water of condensation mixes, and obtain mixing solutions, the pH value of mixing solutions is 6 ~ 8.Then, mixing solutions is heated, Heating temperature is 60 DEG C ~ 90 DEG C, stir while heating, trivalent chromium in mixing solutions can be combined with hydroxide radical and form chromium hydroxide precipitation, when filtering after complete reaction, obtain chromium slag (i.e. chromium hydroxide precipitation) and the second solution.If Heating temperature is lower than 60 DEG C, be then unfavorable for forming chromium slag; If Heating temperature is higher than 90 DEG C, then can cause the waste of the energy.
According to exemplary embodiment of the present invention, in step (b), pressurized air can be utilized to stir while heating, churning time is 10min ~ 40min.Pressurized air is utilized to carry out stirring and not only can improve stirring velocity, the residual sulfite that simultaneously air can be utilized to drive out to be brought into by step (a) in mixing solutions or Sodium Pyrosulfite decompose the sulfur dioxide gas obtained, and the Heating temperature of 60 DEG C ~ 90 DEG C is also conducive to driveing sulfurous gas.
Then, in the second solution, add roasting grog, roasting grog is heated under oxidizing atmosphere by vanadium slag, make it oxidation after and sodium salt react the many vanadic acid sodiums being dissolvable in water water generated.Roasting grog is joined in the second solution, thus the solubility in roasting grog can be dissolved in the second solution by many vanadic acid sodiums.According to exemplary embodiment of the present invention, the mass ratio of the second solution and roasting grog can be 1 ~ 2:1, second solution and roasting grog are stirred 5min ~ 20min at 80 DEG C ~ 90 DEG C, alr mode can be 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, carry out solid-liquid separation to containing vanadium leachate and tailings, preferably, the solid-liquid separating method of vacuum filtration can be adopted.
Carry out except phosphorus reaction to containing adding dephosphorization agent in vanadium leachate and react 10min ~ 15min at 70 DEG C ~ 85 DEG C, and then add after gac stirs and purify containing vanadium leachate, then filter and obtain containing vanadium qualifying liquid.Why need to carry out impurity and purification to containing vanadium leachate, because be dissolved in the process of the second solution at many vanadic acid sodiums, some impurity also will enter into solution along with many vanadic acid sodiums together, to the quality of follow-up precipitation operation and product be affected, therefore carry out impurity and purification to containing vanadium leachate.Dephosphorization agent can comprise any dephosphorization agent can removed containing the phosphorus in vanadium leachate, preferably, dephosphorization agent can comprise calcium chloride or magnesium chloride, when dephosphorization agent be calcium chloride or magnesium chloride time, calcium chloride or magnesium chloride and the mol ratio containing the phosphorus in vanadium leachate are 2 ~ 4:1.When calcium chloride or magnesium chloride and containing the mol ratio of the phosphorus in vanadium leachate higher than 2 ~ 4:1 time, then can generate calcium vanadate or vanadic acid magnesium precipitate, cause the loss of vanadium.Be 1 ~ 3g/L to the amount containing the gac added in vanadium leachate.
Neutralization reaction is carried out to regulate the acid or alkali environment of applicable ammonium sulfate and the reaction of many vanadic acid sodiums to containing adding sulfuric acid in vanadium qualifying liquid, solution is heated simultaneously, when pH value be 4 ~ 6, temperature be 40 ~ 50 DEG C time, add ammonium sulfate, the quality of ammonium sulfate is 1.0 ~ 2.5:1 with the mass ratio containing the vanadium in vanadium qualifying liquid.After adding ammonium sulfate, add sulfuric acid again and pH value is adjusted to 2 ~ 2.5, and solution is heated to 85 ~ 95 DEG C, under the condition that solution is acid, additional ammonium sulfate and the ammonium sulfate entered 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 to be back in step (a) and carries out recycle according to an exemplary embodiment of the present invention.Preferably, when the concentration of the sodium ion in the first vanadium wastewater is less than 50g/L and the concentration of 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 being passed into wastewater treatment operation and processing.
Example 1
In 10L vanadium wastewater, add 110g Sodium Pyrosulfite, after being then heated to 50 DEG C, stirring reaction 10min obtains the first solution; In the first solution, add production water of condensation (pH value is 10) obtain mixing solutions, first solution and production water of condensation are by volume for 1:1 mixes, the pH value of mixing solutions is 7.0, after mixing solutions being heated to 85 DEG C, open pressurized air to stir mixing solutions, after stirring 15min, filter and obtain the second solution and chromium slag; 20kg roasting grog is added (wherein in the second solution, in roasting grog, the content of TV is 5.50%, the content of SV (solvable vanadium) is 4.26%), second solution and roasting grog are stirred 8min at 85 DEG C, then vacuum filtration is utilized to carry out solid-liquid separation, obtain containing vanadium leachate and tailings, wherein, the leaching yield (the solvable vanadium in roasting grog enters into the ratio of leach liquor) of vanadium is 95.8%; Add 27g calcium chloride to containing in vanadium leachate, at 80 DEG C, react 10min, add gac 36g, filter after stirring and obtain containing vanadium qualifying liquid; Add sulfuric acid to containing in vanadium qualifying liquid and it is heated, when pH value be 4 ~ 6, temperature be 40 ~ 50 DEG C time, add ammonium sulfate, the quality of ammonium sulfate is 1.8:1 with the mass ratio containing the vanadium in vanadium qualifying liquid, add that pH value is adjusted to 2.5 by sulfuric acid, heated solution to 85 ~ 95 DEG C again, crystallization goes out ammonium poly-vanadate.
Wherein, vanadium wastewater, containing vanadium leachate, containing the pH value of vanadium qualifying liquid and main component as shown in table 1, the composition of ammonium poly-vanadate is as shown in table 2.
Example 2
In 10L vanadium wastewater, add containing massfraction the sulfurous acid of the 1180mL being the sulfurous gas of 6%, after being then heated to 60 DEG C, stirring reaction 20min obtains the first solution; In the first solution, add production water of condensation (pH value is 9.5) obtain mixing solutions, first solution and production water of condensation are by volume for 0.5:1 mixes, the pH value of mixing solutions is 7.5, after mixing solutions being heated to 85 DEG C, open pressurized air to stir mixing solutions, after stirring 15min, filter and obtain the second solution and chromium slag; 20kg roasting grog is added (wherein in the second solution, in roasting grog, the content of TV is 5.63%, the content of SV (solvable vanadium) is 4.31%), second solution and roasting grog are stirred 8min at 85 DEG C, then vacuum filtration is utilized to carry out solid-liquid separation, obtain containing vanadium leachate and tailings, wherein, the leaching yield (the solvable vanadium in roasting grog enters into the ratio of leach liquor) of vanadium is 96.4%; Add 16g magnesium chloride to containing in vanadium leachate, at 80 DEG C, react 15min, add gac 28g, filter after stirring and obtain containing vanadium qualifying liquid; Add sulfuric acid to containing in vanadium qualifying liquid and it is heated, when pH value be 4 ~ 6, temperature be 40 ~ 50 DEG C time, add ammonium sulfate, the quality of ammonium sulfate is 2.2:1 with the mass ratio containing the vanadium in vanadium qualifying liquid, add that pH value is adjusted to 2.0 by sulfuric acid, heated solution to 85 ~ 95 DEG C again, crystallization goes out ammonium poly-vanadate.
Wherein, vanadium wastewater, containing vanadium leachate, containing the pH value of vanadium qualifying liquid and main component as shown in table 1, the composition of ammonium poly-vanadate is as shown in table 2.
Example 3
In 10L vanadium wastewater, add 138g Sodium Pyrosulfite, after being then heated to 45 DEG C, stirring reaction 15min obtains the first solution; In the first solution, add production water of condensation (pH value is 10.5) obtain mixing solutions, first solution and production water of condensation are by volume for 2:1 mixes, the pH value of mixing solutions is 6.6, after mixing solutions being heated to 80 DEG C, open pressurized air to stir mixing solutions, after stirring 30min, filter and obtain the second solution and chromium slag; 12kg roasting grog is added (wherein in the second solution, in roasting grog, the content of TV is 5.73%, the content of SV (solvable vanadium) is 4.41%), second solution and roasting grog are stirred 8min at 85 DEG C, then vacuum filtration is utilized to carry out solid-liquid separation, obtain containing vanadium leachate and tailings, wherein, the leaching yield (the solvable vanadium in roasting grog enters into the ratio of leach liquor) of vanadium is 94.5%; Add 25.5g magnesium chloride to containing in vanadium leachate, at 80 DEG C, react 10min, add gac 18g, filter after stirring and obtain containing vanadium qualifying liquid; Add sulfuric acid to containing in vanadium qualifying liquid and it is heated, when pH value be 4 ~ 6, temperature be 40 ~ 50 DEG C time, add ammonium sulfate, the quality of ammonium sulfate is 1.8:1 with the mass ratio containing the vanadium in vanadium qualifying liquid, add that pH value is adjusted to 2.2 by sulfuric acid, heated solution to 85 ~ 95 DEG C again, crystallization goes out ammonium poly-vanadate.
Wherein, vanadium wastewater, containing vanadium leachate, containing the pH value of vanadium qualifying liquid and main component as shown in table 1, the composition of ammonium poly-vanadate is as shown in table 2.
Example 4
In 10L vanadium wastewater, add containing massfraction the sulfurous acid of the 720mL being the sulfurous gas of 6%, after being then heated to 45 DEG C, stirring reaction 15min obtains the first solution; In the first solution, add production water of condensation (pH value is 11) obtain mixing solutions, first solution and production water of condensation are by volume for 3:1 mixes, the pH value of mixing solutions is 6.4, after mixing solutions being heated to 85 DEG C, open pressurized air to stir mixing solutions, after stirring 15min, filter and obtain the second solution and chromium slag; 12kg roasting grog is added (wherein in the second solution, in roasting grog, the content of TV is 5.29%, the content of SV (solvable vanadium) is 4.17%), second solution and roasting grog are stirred 8min at 85 DEG C, then vacuum filtration is utilized to carry out solid-liquid separation, obtain containing vanadium leachate and tailings, wherein, the leaching yield (the solvable vanadium in roasting grog enters into the ratio of leach liquor) of vanadium is 95.1%; Add 43g magnesium chloride to containing in vanadium leachate, at 80 DEG C, react 15min, add gac 10g, filter after stirring and obtain containing vanadium qualifying liquid; Add sulfuric acid to containing in vanadium qualifying liquid and it is heated, when pH value be 4 ~ 6, temperature be 40 ~ 50 DEG C time, add ammonium sulfate, the quality of ammonium sulfate is 2:1 with the mass ratio containing the vanadium in vanadium qualifying liquid, add that pH value is adjusted to 2.5 by sulfuric acid, heated solution to 85 ~ 95 DEG C again, crystallization goes out ammonium poly-vanadate.
Wherein, vanadium wastewater, containing vanadium leachate, containing the pH value of vanadium qualifying liquid and main component as shown in table 1, the composition of ammonium poly-vanadate is as shown in table 2.
Table 1 shows pH value and the main component of vanadium wastewater in example 1-4, leach liquor and qualifying liquid, 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 the leaching operation of roasting grog by vanadium wastewater, the chromium content be starkly lower than containing the chromium content in vanadium qualifying liquid in vanadium wastewater obtained.This is because before leaching, carried out reduction and precipitation process to the chromium in vanadium wastewater, so be the sexavalent chrome in roasting grog containing vanadium leachate and the chromium contained in vanadium qualifying liquid, not there is enrichment because using vanadium wastewater.
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 obtained is all higher than 48.5%, S content all lower than 0.25% (in ammonium poly-vanadate product be higher than 48.5% to the content requirement of TV, be 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, after vanadium wastewater is carried out pre-treatment, be applied to the leaching operation of roasting grog, vanadium wastewater can be made to be maximally utilised, reduce treatment capacity and the processing costs of vanadium wastewater.
Although describe some embodiments of the present invention with reference to the accompanying drawings, it should be appreciated by those skilled in the art that when not departing from by the principle of the present invention of claim and its scope of equivalents thereof and spirit, can modify to these embodiments.
Claims (9)
1. a method for vanadium wastewater recycle, is characterized in that, said method comprising the steps of:
A () adds reductive agent and carries out reduction reaction in described vanadium wastewater, make the hexavalent chrome reduction in vanadium wastewater be trivalent chromium, obtain the first solution;
B () adds alkali lye and obtains mixing solutions in the first solution, heat mixing solutions, and Heating temperature is 60 DEG C ~ 90 DEG C, stirring, when filtering after complete reaction, obtaining chromium slag and the second solution while heating;
C () adds roasting grog in the second solution, carry out solid-liquid separation and obtain containing vanadium leachate and tailings after stirring;
D () adds dephosphorization agent, gac to containing in vanadium leachate, carry out impurity and purification to containing vanadium leachate, obtains containing vanadium qualifying liquid after filtration;
E () adds ammonium sulfate, sulfuric acid to containing in vanadium qualifying liquid, carry out precipitation operation, obtain ammonium poly-vanadate and the first vanadium wastewater,
Wherein, alkali lye described in step (b) comprises production water of condensation, and the ratio being 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.
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, add reductive agent in step (a) after, at 40 DEG C ~ 60 DEG C, carry out reduction reaction, the reaction times is 10min ~ 30min.
4. method according to claim 1, is characterized in that, utilizes pressurized air to stir in step (b), and churning time is 10min ~ 40min.
5. 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 5min ~ 20min at 80 DEG C ~ 90 DEG C, carries out solid-liquid separation and obtains containing vanadium leachate and tailings.
6. method according to claim 1, it is characterized in that, impurity and purification in step (d) comprise carries out dephosphorization to containing adding dephosphorization agent and react 10min ~ 15min at 70 DEG C ~ 85 DEG C in vanadium leachate, add again after gac stirs and purify, wherein, dephosphorization agent comprises calcium chloride or magnesium chloride, and calcium chloride or magnesium chloride and the mol ratio containing the phosphorus in vanadium leachate are 2 ~ 4:1, are 1 ~ 3g/L to the amount containing the gac added in vanadium leachate.
7. method according to claim 1, it is characterized in that, in step (e), containing add in vanadium qualifying liquid sulfuric acid carry out in and, solution is heated simultaneously, when pH value be 4 ~ 6, temperature be 40 DEG C ~ 50 DEG C time, add ammonium sulfate, then add sulfuric acid pH value is adjusted to 2 ~ 2.5, and solution is heated to 85 DEG C ~ 95 DEG C, crystallization goes out ammonium poly-vanadate, and wherein, the quality of ammonium sulfate is 1.0 ~ 2.5:1 with the mass ratio containing the vanadium in vanadium qualifying liquid.
8. method according to claim 1, is characterized in that, described method also comprises makes the first vanadium wastewater in step (e) be back in step (a).
9. method according to claim 8, it is characterized in that, when the concentration of the sodium ion in the first vanadium wastewater in step (e) is less than 50g/L and the concentration of potassium ion is less than 0.6g/L, the first vanadium wastewater is back in step (a).
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| 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 |
| CN114349028B (en) * | 2021-11-29 | 2023-06-23 | 攀钢集团研究院有限公司 | Method for recycling 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 |
| 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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| 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 |
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| 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 |
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