CN101358282A - Method for vanadium-containing resin circulatory desorption from vanadate precipitating waste water - Google Patents
Method for vanadium-containing resin circulatory desorption from vanadate precipitating waste water Download PDFInfo
- Publication number
- CN101358282A CN101358282A CNA2008102124431A CN200810212443A CN101358282A CN 101358282 A CN101358282 A CN 101358282A CN A2008102124431 A CNA2008102124431 A CN A2008102124431A CN 200810212443 A CN200810212443 A CN 200810212443A CN 101358282 A CN101358282 A CN 101358282A
- Authority
- CN
- China
- Prior art keywords
- vanadium
- liquid
- desorption
- stripping liquid
- agent
- 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.)
- Granted
Links
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 method for circularly desorbing vanadiferous resin by using vanadium precipitating waste waster. The method comprises the following steps: step (1), vanadium precipitation agent containing Ca is adopted for the vanadium precipitation operation to desorption solution which is produced by the desorption of vanadiferous resin, and the solid-liquid separation is carried out after the reaction is basically completed to obtain calcium vanadate and vanadium precipitation waste water; step (2), decalcifying agent is adopted to decalcify the vanadium precipitating waste waster which is obtained in the step (1), and the solid-liquid separation is carried out after the reaction is basically completed to obtain calcium carbonate and supernatant clean liquor; step (3), the pH value of the supernatant clean liquor which is obtained in the step (2) is adjusted, and the supernatant clean liquor is returned to the desorption process to circularly desorb the vanadiferous resin. The method can circularly use all the vanadium precipitating waste waster to well solve the problem of the pollution of the vanadium precipitating waste waster and greatly reduce the dosage of the desorption agent.
Description
Technical field
The present invention relates to a kind of method that vanadium wastewater is handled.Specifically, the present invention relates to a kind of method, to solve the pollution problem of vanadium wastewater with vanadium-containing resin circulatory desorption from vanadate precipitating waste water.
Background technology
Vanadium is a kind of important strategic material, is mainly used in Iron And Steel Industry, fields such as national defence sophisticated technology, chemical industry and light and textile industries.Vanadium resource is many with low-grade and other mineral paragenesis.At present, the main raw material that is used for producing vanadium is a vanadium titano-magnetite.In addition, also have low-grade vanadium raw materials, for example contain vanadium mineral intergrowth, bone coal, vanadium-containing wasting catalyst and petroleum slag etc.
The research of China's development and use low grade vanadium raw material early.Form at present typical and be applied in the process for extracting vanadium of industrial low grade vanadium raw material, almost all adopt ammonium salt precipitation mode to carry out the precipitation operation, so the ubiquity environmental issue.The pollution problem of the vanadium wastewater that precipitation operation back produces is exactly one of them, and major cause is to have introduced a large amount of ammonia nitrogens in the precipitation operating process.
At present industrial the processing mode that adopts ammonium salt precipitation mode to carry out the vanadium wastewater that precipitation operation back produces is mainly contained following two kinds:
The first, directly to discharge or discharge with lime neutralization (being directed to acid waste water for depositing vanadium solution) back, quality does not reach emission standard.This processing mode is generally suitable for the bigger slightly vanadium extraction factory of scale.
The second, in vanadium wastewater, behind additional proper amount of sodium chloride and the sodium hydroxide, make vanadium wastewater return desorption step with circulating desorption.Yet the hand labor intensity that this processing mode needs is big, severe operational environment.And in the circulating desorption process, be easy to generate ammonium meta-vanadate precipitation obstruction resin, thus influence the circulating desorption operation, also can influence quality product.In addition, owing to need to add a large amount of sodium salts, so after the sodium salt concentration in the solution acquires a certain degree, must carry out emission treatment.In addition, the enforcement of this processing mode also needs bigger place, thereby the vanadium extraction factory that can only be suitable for usually on a small scale uses.
In addition, for fear of in the precipitation operating process, introducing a large amount of ammonia nitrogens, also developed and adopted the mode of precipitation vanadic acid calcium to carry out the precipitation operation.Yet, can contain a large amount of calcium ions in the vanadium wastewater after the precipitation vanadic acid calcium, carry out circulating desorption if directly this vanadium wastewater is returned desorption step, easily produce the vanadic acid calcium deposit and stop up resin, thereby influence the use of resin and influence the circulating desorption operation.
Summary of the invention
At the pollution problem of above-mentioned vanadium wastewater,, the invention provides a kind of method with vanadium-containing resin circulatory desorption from vanadate precipitating waste water in order to overcome shortcoming of the prior art.This method can all recycle vanadium wastewater, thereby solves the pollution problem of vanadium wastewater, and can reduce the consumption of strippant greatly.In addition, this method has also avoided adopting the pollution problem of the vanadium wastewater that contains ammonia nitrogen in a large number that traditional ammonium salt precipitation mode produces; Also avoided in the circulating desorption process, producing the problem that a large amount of ammonium meta-vanadates precipitations or vanadic acid calcium deposit stop up the circulating desorption operational difficulty that resin causes because of the vanadium wastewater that contains ammonia nitrogen or calcareous vanadium wastewater.
In order to realize the foregoing invention purpose, the method with vanadium-containing resin circulatory desorption from vanadate precipitating waste water according to the present invention can may further comprise the steps:
(1) adopts the precipitation agent that contains Ca to carry out the precipitation operation, after the reaction substantially fully, carry out solid-liquid separation, thereby obtain vanadic acid calcium and vanadium wastewater containing the stripping liquid that produces after the desorb of vanadium resin;
(2) adopt decalcifying agent that the vanadium wastewater that obtains in the step (1) is carried out the decalcification operation, after the reaction substantially fully, carry out solid-liquid separation, thereby obtain lime carbonate and supernatant liquid;
(3) the pH value of the supernatant liquid that obtains in the regulating step (2) makes supernatant liquid return desorption step then, thus vanadium-containing resin circulatory desorption.
Step (1) can also comprise that one or more pH values with stripping liquid that adopt in sodium hydroxide, potassium hydroxide or the calcium hydroxide are adjusted to about 8.0～12.0 operation; In addition, step (1) can also comprise that the temperature with stripping liquid is elevated to about 60 ℃ of operations to stripping liquid ebullient temperature.In step (1), be that about 1.0～3.0 ratio is added and contained the precipitation agent of Ca in the mol ratio of the v element that contains in calcium constituent that contains in the precipitation agent that contains Ca and the stripping liquid, and the precipitation agent that contains Ca can be CaCl
2, Ca (NO
3)
2In one or both.
In step (2), decalcifying agent can be in yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus or the carbonic acid gas one or more, is preferably carbonic acid gas or sodium bicarbonate.
In step (3), comprise that one or both pH values with supernatant liquid that adopt in sodium hydroxide or the potassium hydroxide are adjusted to about 9.0～13.0 operation.
By description and explanation hereinafter, it is more clear that above-mentioned purpose of the present invention and advantage will become.
Description of drawings
Fig. 1 is a schematic flow sheet of using the method for vanadium-containing resin circulatory desorption from vanadate precipitating waste water according to of the present invention.
Embodiment
With reference to Fig. 1, the method with vanadium-containing resin circulatory desorption from vanadate precipitating waste water according to the present invention comprises the steps:
(1) adopts the precipitation agent that contains Ca to carry out the precipitation operation, after the reaction substantially fully, carry out solid-liquid separation, thereby obtain vanadic acid calcium and vanadium wastewater containing the stripping liquid that produces after the desorb of vanadium resin;
(2) adopt decalcifying agent that the vanadium wastewater that obtains in the step (1) is carried out the decalcification operation, after the reaction substantially fully, carry out solid-liquid separation, thereby obtain lime carbonate and supernatant liquid;
(3) the pH value of the supernatant liquid that obtains in the regulating step (2) makes supernatant liquid return desorption step then, thus vanadium-containing resin circulatory desorption.
Below in conjunction with principle of the present invention above-mentioned steps is carried out specific description and description:
In step (1):
For fear of the pollution problem that the vanadium wastewater that contains a large amount of ammonia nitrogens causes, the present invention adopts the precipitation agent that contains Ca to carry out the precipitation operation to containing the stripping liquid that produces after the desorb of vanadium resin,, carries out the precipitation operation in the mode of precipitation vanadic acid calcium that is.Be that the ratio of about 1.0～3.0 (being preferably about 1.1～1.5) is added the precipitation agent that contains Ca wherein in the mol ratio of the v element that contains in calcium constituent that contains in the precipitation agent that contains Ca and the stripping liquid.The precipitation agent that contains Ca can be CaCl
2, Ca (NO
3)
2In one or both.Preferably select CaCl
2For containing Ca precipitation agent.
After the precipitation agent that contains Ca and stripping liquid fully act on, that is, when reaction basic fully after, can carry out solid-liquid separation by method such as filtering, centrifugal, thereby obtain vanadic acid calcium solid and vanadium wastewater.
Here, for the reaction that makes the precipitation operation more is tending towards fully, can under stirring condition, adopt one or more the pH values in sodium hydroxide, potassium hydroxide or the calcium hydroxide to be adjusted to about 8.0～12.0 with stripping liquid, preferably, be adjusted to about 9.0～10.5.Wherein preferably adopt calcium hydroxide to regulate the pH value of stripping liquid.In addition, can also by various type of heating with the temperature of stripping liquid be elevated to about 60 ℃ to stripping liquid ebullient temperature, preferably, be elevated to about 90 ℃ to stripping liquid ebullient temperature.In general, stripping liquid ebullient temperature is 100 ℃.Yet in different areas, stripping liquid ebullient temperature can be different.For example, in Panzhihua Region, stripping liquid ebullient temperature is at about 96 ℃.
In step (2):
Because still can contain calcium ion in the vanadium wastewater this moment,, need that also vanadium wastewater is carried out decalcification and handle so block resin for fear of in follow-up circulating desorption process, producing the vanadic acid calcium deposit.Consider the effect and the cost problem of decalcification, can select for use in yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus or the carbonic acid gas one or more for decalcifying agent, preferably adopting carbonic acid gas or sodium bicarbonate is decalcifying agent.
After decalcifying agent and vanadium wastewater fully act on, that is, when reaction basic fully after, can carry out solid-liquid separation by method such as filtering, centrifugal, thereby obtain lime carbonate solid and supernatant liquid.
Here, for the reaction that makes the decalcification operation more is tending towards fully, when comprising carbonic acid gas in the decalcifying agent that adopts, after the reaction substantially fully of decalcification operation, the pH value of supernatant liquid should be not less than 8.5.When comprising in yellow soda ash, sodium bicarbonate, salt of wormwood or the saleratus one or more in the decalcifying agent that adopts, press CO contained in the decalcifying agent
3 2-Or HCO
3 -With Ca contained in the vanadium wastewater
2+Mol ratio be that about 1.0～1.1 ratio is added decalcifying agent.
In step (3):
Adopt one or both the pH values in sodium hydroxide or the potassium hydroxide to be adjusted to about 9.0～13.0 (preferably, being adjusted to about 11.0～13.0), again supernatant liquid is returned stripping liquid, thereby carry out circulating desorption supernatant liquid.
Here, the ion for fear of introducing too much kind preferably adopts sodium hydroxide to regulate the pH value of supernatant liquid.
In the method according to the invention, the reaction equation that relates generally to is as follows:
In the precipitation operation steps:
2VO
3 -+Ca(OH)
2+Ca
2++H
2O＝Ca
2V
2O
7·2H
2O↓
In the decalcification operation steps:
Ca
2++ HCO
3 -+ OH
-=CaCO
3↓+H
2O or Ca
2++ CO
2+ H
2O
-=CaCO
3↓+2H
+
In general, the vanadium concentration that contains in the vanadium resin stripping liquid is about 30g/l, is after precipitation is operated, in the vanadic acid calcium of precipitation gained through step (1), the total content of vanadium is about 30%, and the Na content (Na ionic species) that vanadic acid calcium is mingled with surface adsorption is about 0.5%～1.0%.Can get according to this, for every liter of stripping liquid, the Na content that the vanadic acid calcium deposit of gained is taken away is about 0.5～1.0g.In step (2), generally contain Ca in the vanadium wastewater
2+1.0～1.5g/l is if adopt CO
2Carry out the decalcification operation, then can not bring the Na ion into; If adopt sodium bicarbonate to carry out the decalcification operation, then the sodium that has about 0.58～0.86g of every liter of solution enters.In step (3), during the pH of the supernatant liquid after regulating decalcification with sodium hydroxide, every liter of solution has the sodium that is about 0.23g again and enters.Like this, when handling the 1L stripping liquid, the total content of bringing the Na in the solution into is about 0.23～1.09g, and is basic suitable with the Na content of taking away from solution.
Be the exemplary embodiment of using the method for vanadium-containing resin circulatory desorption from vanadate precipitating waste water according to of the present invention below.
Exemplary embodiment 1
Getting vanadium concentration is the stripping liquid 1400ml of 33.1g/l, adds the precipitation agent CaCl that contains Ca
2Solution 250ml wherein, presses CaCl
2In the mol ratio of the v element that contains in the calcium constituent that contains and the stripping liquid be that 1.0 ratio is added CaCl
2Under stirring condition, add calcium hydroxide and be adjusted to 8.0, and solution is heated to 60 ℃ with pH value with stripping liquid.After reaction substantially fully, utilize centrifugal method to carry out solid-liquid separation, thereby obtain vanadic acid calcium solid and vanadium wastewater.Wherein, obtain vanadic acid calcium solid 153.7g, in this vanadic acid calcium solid, the total content of vanadium is 29.83%, and Na content is 0.8%; In the vanadium wastewater that obtains, the total content of vanadium is 0.34g/l, Ca
2+Concentration be 1.22g/l.In this vanadium wastewater, feed carbonic acid gas, to carry out the decalcification reaction.When the pH of solution value reaches 8.5, stop to feed carbonic acid gas.Then, utilize centrifugal method to carry out solid-liquid separation, thereby obtain lime carbonate solid and supernatant liquid.Utilize NaOH that the pH value of supernatant liquid is adjusted to 11.0, make supernatant liquid return desorption step then, thus vanadium-containing resin circulatory desorption.In the stripping liquid that obtains after vanadium-containing resin circulatory desorption, vanadium concentration is 30.7g/l.
Exemplary embodiment 2
Getting vanadium concentration is the stripping liquid 2000ml of 31.5g/l, adds the precipitation agent CaCl that contains Ca
2Solution 250ml wherein, presses CaCl
2In the mol ratio of the v element that contains in the calcium constituent that contains and the stripping liquid be that 1.1 ratio is added CaCl
2Under stirring condition, add calcium hydroxide and be adjusted to 9.0, and solution is heated to boiling with pH value with stripping liquid.After reaction substantially fully, utilize centrifugal method to carry out solid-liquid separation, thereby obtain vanadic acid calcium solid and vanadium wastewater.Wherein, obtain vanadic acid calcium solid 205.4g, in this vanadic acid calcium solid, the total content of vanadium is 30.43%, and Na content is 0.76%; In the vanadium wastewater that obtains, the total content of vanadium is 0.27g/l, Ca
2+Concentration be 1.42g/l.Under stirring condition, in this vanadium wastewater, add yellow soda ash, to carry out the decalcification reaction.Wherein with CO contained in the yellow soda ash
3 2-With Ca contained in the vanadium wastewater
2+Mol ratio be that 1.0 ratio adds yellow soda ash.After reaction substantially fully, utilize centrifugal method to carry out solid-liquid separation, thereby obtain lime carbonate solid and supernatant liquid.Utilize NaOH that the pH value of supernatant liquid is adjusted to 9.0, make supernatant liquid return desorption step then, thus vanadium-containing resin circulatory desorption.In the stripping liquid that obtains after vanadium-containing resin circulatory desorption, vanadium concentration is 30.20g/l.
Exemplary embodiment 3
Getting vanadium concentration is the stripping liquid 1500ml of 28.4g/l, adds the precipitation agent CaCl that contains Ca
2Solution 250ml wherein, presses CaCl
2In the mol ratio of the v element that contains in the calcium constituent that contains and the stripping liquid be that 1.2 ratio is added CaCl
2Under stirring condition, add calcium hydroxide and be adjusted to 9.46, and solution is heated to 90 ℃ with pH value with stripping liquid.After reaction substantially fully, utilize centrifugal method to carry out solid-liquid separation, thereby obtain vanadic acid calcium solid and vanadium wastewater.Wherein, obtain vanadic acid calcium solid 141.2g, in this vanadic acid calcium solid, the total content of vanadium is 29.88%, and Na content is 0.64%; In the vanadium wastewater that obtains, the total content of vanadium is 0.30g/l, Ca
2+Concentration be 1.34g/l.Under stirring condition, in this vanadium wastewater, add sodium bicarbonate, to carry out the decalcification reaction.Wherein with HCO contained in the sodium bicarbonate
3 2-With Ca contained in the vanadium wastewater
2+Mol ratio be that 1.05 ratio adds sodium bicarbonate.After reaction substantially fully, utilize centrifugal method to carry out solid-liquid separation, thereby obtain lime carbonate solid and supernatant liquid.Utilize NaOH that the pH value of supernatant liquid is adjusted to 13.0, make supernatant liquid return desorption step then, thus vanadium-containing resin circulatory desorption.In the stripping liquid that obtains after vanadium-containing resin circulatory desorption, vanadium concentration is 29.52g/l.
Exemplary embodiment 4
Getting vanadium concentration is the stripping liquid 2000ml of 33.1g/l, adds the precipitation agent CaCl that contains Ca
2Solution 300ml wherein, presses CaCl
2In the mol ratio of the v element that contains in the calcium constituent that contains and the stripping liquid be that 2.0 ratio is added CaCl
2Under stirring condition, add sodium hydroxide and be adjusted to 10.5, and solution is heated to 80 ℃ with pH value with stripping liquid.After reaction substantially fully, utilize centrifugal method to carry out solid-liquid separation, thereby obtain vanadic acid calcium solid and vanadium wastewater.Wherein, obtain vanadic acid calcium solid 213.5g, in this vanadic acid calcium solid, the total content of vanadium is 30.72%, and Na content is 0.74%; In the vanadium wastewater that obtains, the total content of vanadium is 0.37g/l, Ca
2+Concentration be 1.31g/l.Under the adjusting of stirring, in this vanadium wastewater, add salt of wormwood, to carry out the decalcification reaction.Wherein with CO contained in the salt of wormwood
3 2-With Ca contained in the vanadium wastewater
2+Mol ratio be that 1.1 ratio adds salt of wormwood.After reaction substantially fully, utilize centrifugal method to carry out solid-liquid separation, thereby obtain lime carbonate solid and supernatant liquid.Utilize NaOH that the pH value of supernatant liquid is adjusted to 12.5, make supernatant liquid return desorption step then, thus vanadium-containing resin circulatory desorption.In the stripping liquid that obtains after vanadium-containing resin circulatory desorption, vanadium concentration is 28.86g/l.
Exemplary embodiment 5
Getting vanadium concentration is the stripping liquid 1500ml of 28.4g/l, adds the precipitation agent Ca (NO that contains Ca
3)
2Solution 250ml wherein, presses Ca (NO
3)
2In the mol ratio of the v element that contains in the calcium constituent that contains and the stripping liquid be that 1.5 ratio is added Ca (NO
3)
2Under stirring condition, add potassium hydroxide and be adjusted to 12.0, and solution is heated to 70 ℃ with pH value with stripping liquid.After reaction substantially fully, utilize centrifugal method to carry out solid-liquid separation, thereby obtain vanadic acid calcium solid and vanadium wastewater.Wherein, obtain vanadic acid calcium solid 143.9g, in this vanadic acid calcium solid, the total content of vanadium is 29.36%, and Na content is 0.62%; In the vanadium wastewater that obtains, the total content of vanadium is 0.34g/l, Ca
2+Concentration be 1.28g/l.Under stirring condition, in this vanadium wastewater, add saleratus, to carry out the decalcification reaction.Wherein with HCO contained in the saleratus
3 2-With Ca contained in the vanadium wastewater
2+Mol ratio be that 1.1 ratio adds saleratus.After reaction substantially fully, utilize centrifugal method to carry out solid-liquid separation, thereby obtain lime carbonate solid and supernatant liquid.Utilize KOH that the pH value of supernatant liquid is adjusted to 12.7, make supernatant liquid return desorption step then, thus vanadium-containing resin circulatory desorption.In the stripping liquid that obtains after vanadium-containing resin circulatory desorption, vanadium concentration is 30.64g/l.
Exemplary embodiment 6
Getting vanadium concentration is the stripping liquid 1500ml of 28.4g/l, adds the precipitation agent CaCl that contains Ca
2Solution 250ml wherein, presses CaCl
2In the mol ratio of the v element that contains in the calcium constituent that contains and the stripping liquid be that 1.4 ratio is added CaCl
2Under stirring condition, add calcium hydroxide and be adjusted to 10.2, and solution is heated to boiling with pH value with stripping liquid.After reaction substantially fully, utilize centrifugal method to carry out solid-liquid separation, thereby obtain vanadic acid calcium solid and vanadium wastewater.Wherein, obtain vanadic acid calcium solid 142.7g, in this vanadic acid calcium solid, the total content of vanadium is 29.67%, and Na content is 0.83%; In the vanadium wastewater that obtains, the total content of vanadium is 0.32g/l, Ca
2+Concentration be 1.16g/l.Under stirring condition, in this vanadium wastewater, add sodium bicarbonate, to carry out the decalcification reaction.Wherein with HCO contained in the sodium bicarbonate
3 2-With Ca contained in the vanadium wastewater
2+Mol ratio be that 1.1 ratio adds sodium bicarbonate.After reaction substantially fully, utilize centrifugal method to carry out solid-liquid separation, thereby obtain lime carbonate solid and supernatant liquid.Utilize NaOH that the pH value of supernatant liquid is adjusted to 11.5, make supernatant liquid return desorption step then, thus vanadium-containing resin circulatory desorption.In the stripping liquid that obtains after vanadium-containing resin circulatory desorption, vanadium concentration is 29.57g/l.
Exemplary embodiment 7
Getting vanadium concentration is the stripping liquid 1400ml of 33.1g/l, adds the precipitation agent CaCl that contains Ca
2Solution 350ml wherein, presses CaCl
2In the mol ratio of the v element that contains in the calcium constituent that contains and the stripping liquid be that 3.0 ratio is added CaCl
2Under stirring condition, add calcium hydroxide and be adjusted to 9.8, and solution is heated to boiling with pH value with stripping liquid.After reaction substantially fully, utilize centrifugal method to carry out solid-liquid separation, thereby obtain vanadic acid calcium solid and vanadium wastewater.Wherein, obtain vanadic acid calcium solid 160.7g, in this vanadic acid calcium solid, the total content of vanadium is 28.83%, and Na content is 0.64%; In the vanadium wastewater that obtains, the total content of vanadium is 0.32g/l, Ca
2+Concentration be 1.37g/l.In this vanadium wastewater, feed carbonic acid gas, to carry out the decalcification reaction.When the pH of solution value reaches 8.7, stop to feed carbonic acid gas.Then, utilize centrifugal method to carry out solid-liquid separation, thereby obtain lime carbonate solid and supernatant liquid.Utilize NaOH that the pH value of supernatant liquid is adjusted to 11.0, make supernatant liquid return desorption step then, thus vanadium-containing resin circulatory desorption.In the stripping liquid that obtains after vanadium-containing resin circulatory desorption, vanadium concentration is 31.24g/l.
By the method with vanadium-containing resin circulatory desorption from vanadate precipitating waste water according to the present invention, can make vanadium wastewater obtain recycle, thereby solve the pollution problem of vanadium wastewater, and reduce the consumption of strippant greatly, for the scale that enlarges low grade vanadium raw material process for extracting vanadium provides technical guarantee.In addition, it is short, simple to operate and be easy to characteristics such as industrialization that this method also has flow process.
Although exemplary embodiments more of the present invention are described, the present invention should not be understood that to be limited to those illustrative embodiments.Within the spirit and scope of the present invention, those of ordinary skills can make variations and modifications.
Claims (17)
1, a kind of method with vanadium-containing resin circulatory desorption from vanadate precipitating waste water is characterized in that said method comprising the steps of:
Step 1 adopts the precipitation agent that contains Ca to carry out the precipitation operation to containing the stripping liquid that produces after the desorb of vanadium resin, after the reaction substantially fully, carries out solid-liquid separation, thereby obtains vanadic acid calcium and vanadium wastewater;
Step 2 adopts decalcifying agent that the vanadium wastewater that obtains in the step 1 is carried out the decalcification operation, after the reaction substantially fully, carries out solid-liquid separation, thereby obtains lime carbonate and supernatant liquid;
Step 3, the pH value of the supernatant liquid that obtains in the regulating step two makes supernatant liquid return desorption step then, thus vanadium-containing resin circulatory desorption.
2, the method for claim 1 is that 1.0～3.0 ratio is added the precipitation agent that contains Ca in the mol ratio of the v element that contains in calcium constituent that contains in the precipitation agent that contains Ca and the stripping liquid wherein.
3, method as claimed in claim 2 is that 1.1～1.5 ratio is added the precipitation agent that contains Ca in the mol ratio of calcium constituent in the precipitation agent that contains Ca and the v element in the stripping liquid wherein.
4, the method for claim 1, the precipitation agent that wherein contains Ca is CaCl
2, Ca (NO
3)
2In one or both.
5, method as claimed in claim 4, the precipitation agent that wherein contains Ca is CaCl
2
6, the method for claim 1, wherein step 1 comprises that also one or more pH values with stripping liquid that adopt in sodium hydroxide, potassium hydroxide or the calcium hydroxide are adjusted to 8.0～12.0.
7, method as claimed in claim 6, wherein step 1 comprises that also employing calcium hydroxide is adjusted to 8.0～12.0 with the pH value of stripping liquid.
8, as any described method in claim 6 or 7, wherein the pH value with stripping liquid is adjusted to 9.0～10.5.
9, the method for claim 1, wherein step 1 comprises that also the temperature with stripping liquid is elevated to 60 ℃ to stripping liquid ebullient temperature.
10, method as claimed in claim 9, wherein step 1 comprises that also the temperature with stripping liquid is elevated to 90 ℃ to stripping liquid ebullient temperature.
11, the method for claim 1, wherein decalcifying agent is one or more in yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus or the carbonic acid gas.
12, method as claimed in claim 11, wherein decalcifying agent is carbonic acid gas or sodium bicarbonate.
13, as any described method in claim 11 or 12, wherein when decalcifying agent comprised carbonic acid gas, after the reaction substantially fully that the decalcification of step 2 is operated, the pH value of supernatant liquid was not less than 8.5.
14,, wherein when decalcifying agent comprises in yellow soda ash, sodium bicarbonate, salt of wormwood or the saleratus one or more, press CO contained in the decalcifying agent as any described method in claim 11 or 12
3 2-Or HCO
3 -With Ca contained in the vanadium wastewater
2+Mol ratio be that 1.0～1.1 ratio is added decalcifying agent.
15, the method for claim 1, wherein step 3 comprises that one or both pH values with supernatant liquid that adopt in sodium hydroxide or the potassium hydroxide are adjusted to 9.0～13.0.
16, method as claimed in claim 15, wherein step 3 comprises that one or both pH values with supernatant liquid that adopt in sodium hydroxide or the potassium hydroxide are adjusted to 11.0～13.0.
17, as claim 15 or 16 described methods, wherein step 3 comprises the pH value that adopts sodium hydroxide to regulate supernatant liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102124431A CN101358282B (en) | 2008-08-26 | 2008-08-26 | Method for vanadium-containing resin circulatory desorption from vanadate precipitating waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102124431A CN101358282B (en) | 2008-08-26 | 2008-08-26 | Method for vanadium-containing resin circulatory desorption from vanadate precipitating waste water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101358282A true CN101358282A (en) | 2009-02-04 |
| CN101358282B CN101358282B (en) | 2010-08-11 |
Family
ID=40330880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102124431A Expired - Fee Related CN101358282B (en) | 2008-08-26 | 2008-08-26 | Method for vanadium-containing resin circulatory desorption from vanadate precipitating waste water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101358282B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948147A (en) * | 2010-09-25 | 2011-01-19 | 攀钢集团钢铁钒钛股份有限公司 | Processing method of vanadium-precipitation wastewater in vanadium oxide production |
| CN101660046B (en) * | 2009-09-30 | 2011-03-16 | 攀钢集团研究院有限公司 | Reductive desorption method of vanadium-containing resin |
| CN102424913A (en) * | 2011-12-13 | 2012-04-25 | 攀钢集团研究院有限公司 | Method for separating vanadium and chromium from mixing solution containing vanadium (V) and chromium (VI) |
| CN102603098A (en) * | 2012-03-26 | 2012-07-25 | 北京科技大学 | Circular processing method of stainless steel acid washing waste liquid |
| CN102838233A (en) * | 2012-09-11 | 2012-12-26 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recycling acidic vanadium deposit wastewater |
| CN102994751A (en) * | 2011-09-13 | 2013-03-27 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for reducing concentration of calcium ions in calcium-containing solution |
| CN104556522A (en) * | 2015-01-06 | 2015-04-29 | 河北钢铁股份有限公司承德分公司 | Method for treating waste water containing vanadium and chromium |
| CN104628087A (en) * | 2015-01-06 | 2015-05-20 | 河北钢铁股份有限公司承德分公司 | Method for treating vanadium-chromium wastewater by using ion-exchange fibers |
| 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 |
-
2008
- 2008-08-26 CN CN2008102124431A patent/CN101358282B/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101660046B (en) * | 2009-09-30 | 2011-03-16 | 攀钢集团研究院有限公司 | Reductive desorption method of vanadium-containing resin |
| CN101948147A (en) * | 2010-09-25 | 2011-01-19 | 攀钢集团钢铁钒钛股份有限公司 | Processing method of vanadium-precipitation wastewater in vanadium oxide production |
| CN102994751B (en) * | 2011-09-13 | 2014-10-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for reducing concentration of calcium ions in calcium-containing solution |
| CN102994751A (en) * | 2011-09-13 | 2013-03-27 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for reducing concentration of calcium ions in calcium-containing solution |
| CN102424913A (en) * | 2011-12-13 | 2012-04-25 | 攀钢集团研究院有限公司 | Method for separating vanadium and chromium from mixing solution containing vanadium (V) and chromium (VI) |
| CN102603098A (en) * | 2012-03-26 | 2012-07-25 | 北京科技大学 | Circular processing method of stainless steel acid washing waste liquid |
| CN102603098B (en) * | 2012-03-26 | 2015-04-01 | 北京科技大学 | Circular processing method of stainless steel acid washing waste liquid |
| CN102838233B (en) * | 2012-09-11 | 2014-05-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recycling acidic vanadium deposit wastewater |
| CN102838233A (en) * | 2012-09-11 | 2012-12-26 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recycling acidic vanadium deposit wastewater |
| CN104556522A (en) * | 2015-01-06 | 2015-04-29 | 河北钢铁股份有限公司承德分公司 | Method for treating waste water containing vanadium and chromium |
| CN104628087A (en) * | 2015-01-06 | 2015-05-20 | 河北钢铁股份有限公司承德分公司 | Method for treating vanadium-chromium wastewater by using ion-exchange fibers |
| CN104556522B (en) * | 2015-01-06 | 2016-02-24 | 河北钢铁股份有限公司承德分公司 | A kind of process is containing the method for vanadium, chrome waste water |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101358282B (en) | 2010-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101358282B (en) | Method for vanadium-containing resin circulatory desorption from vanadate precipitating waste water | |
| CN101538652B (en) | Method for separating and recovering vanadium and chrome from vanadium and chrome-containing waste | |
| CN105060545A (en) | System and method for softening treatment of desulfurization wastewater of coal-fired power plant | |
| CN101586185B (en) | Method for separating and recycling arsenic and iron from biological oxidation solution of sulfide ore | |
| CN101838064A (en) | Method for recycling manganese ion in electrolytic manganese production tail end wastewater | |
| CN102491402A (en) | Method for producing refined copper oxide by utilizing acidic waste etching solution | |
| CN101649397B (en) | Method for extracting vanadium from sodium salt roasting clinker | |
| CN110129561A (en) | A method of using fluorine in modified bentonite adsorbent removal lepidolite ore neutrality leachate | |
| CN103601228B (en) | Method for preparation of chemical raw materials by use of fly ash as raw material | |
| CN107828965B (en) | Method for separating and recovering cobalt and manganese in cobalt-manganese waste | |
| CN108479689A (en) | A kind of adsorbent of removal arsenic in waste water acid ion | |
| CN109133459A (en) | A kind of desulfurization wastewater recycling processing method | |
| CN103818969A (en) | Iron oxide red and preparation method thereof | |
| CN101665258A (en) | Process for recovering magnesium salts from Grignard reaction wastewater | |
| CN104587950A (en) | Heavy metal ion adsorbent and application thereof | |
| CN104163486A (en) | Method for treating glyphosate waste water by using calcium hypochlorite waste water | |
| CN103539242A (en) | Method used for reducing calcium content of rare earth industrial wastewater | |
| CN102745841B (en) | Novel brown algae chemical waste calcium water recycling process | |
| CN102351221B (en) | Method for preparing magnesium hydroxide from acid-dissolved magnesium ion-containing raw materials | |
| CN103787535A (en) | Treatment method of sludge water of underground water plant | |
| CN109280776A (en) | A kind of method that sub-molten salt method recycles chromium in electroplating sludge | |
| CN109368850A (en) | A kind of desulfurization wastewater recycling treatment system and application method | |
| CN108754140A (en) | A method of it is produced containing zinc complexes using containing zinc ore crude | |
| CN104402145B (en) | The waste water Han ferrous salt is utilized to prepare the production method of hydrated ferric oxide. | |
| CN106966445A (en) | A kind of method for removing arsenic in nickel sulfate solution containing arsenic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: PANZHIHUA IRON + STEEL INSTITUTE OF PANZHIHUA IRON Free format text: FORMER OWNER: PANZHIHUA IRON + STEEL INSTITUTE OF PANZHIHUA IRON + STEEL GROUP CO., LTD. |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20100415 Address after: 611731, Tianlong Road, Chengdu hi tech Zone (West Zone, Sichuan) 1 Applicant after: Pangang Group Institute Co., Ltd. Co-applicant after: Pangang Group Panzhihua Iron & Steel Research Institute Co., Ltd. Co-applicant after: Panzhihua New Steel & Vanadium Co., Ltd. Address before: 611731, Tianlong Road, Chengdu hi tech Zone (West Zone, Sichuan) 1 Applicant before: Pangang Group Institute Co., Ltd. Co-applicant before: Pangang Group Panzhihua Iron & Steel Research Institute Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100811 Termination date: 20160826 |