CN102070265A - Zero emission process of vanadium extraction wastewater - Google Patents
Zero emission process of vanadium extraction wastewater Download PDFInfo
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- CN102070265A CN102070265A CN 201010570484 CN201010570484A CN102070265A CN 102070265 A CN102070265 A CN 102070265A CN 201010570484 CN201010570484 CN 201010570484 CN 201010570484 A CN201010570484 A CN 201010570484A CN 102070265 A CN102070265 A CN 102070265A
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Abstract
The invention relates to a zero emission process of vanadium extraction wastewater. By adopting the zero emission process, the residual vanadium and chromium in vanadium extraction wastewater can be effectively recycled, the salts of the wastewater can also be recycled, the energy consumption is low, the technological operation is simple, the vanadium extraction tail washings can be completed returned and recycled, the zero emission of wastewater can be realized and the treatment problem of the vanadium extraction wastewater can be completely solved. The process is characterized in that D301 resin is used as adsorbing medium to adsorb vanadium ions and chromium ions.
Description
Technical field
The present invention relates to ion exchange resin is the separation method of sorbent treatment liquid, particularly a kind of vanadium extracting waste water technique of zero discharge specifically, is with the vanadium chromium ion in the ion exchange resin adsorption of vanadium waste water, then adopt crystallization process removal sodium salt wherein, realize the vanadium extracting waste water zero release.
Background technology
Leaching of Vanadium from Vanadium slag is the main method of producing Vanadium Pentoxide in FLAKES.With atomizing vanadium slag or converter vanadium slag is raw material, and when adopting the technology of sodium roast, water logging, acid vanadic salts precipitation, one ton of Vanadium Pentoxide in FLAKES of every production will be discharged about 60m
3Vanadium extracting waste water.Contained Cr in the vanadium extracting waste water
6+And V
5+On the one hand human body there is the intoxicating effect, can suppresses the growth of aquatic organism and farm crop; Can Yu vanadium and chromium are valuable important elements on the other hand.
Common vanadium extracting waste water treatment process has: ferrous sulfate one lime method, and this method equipment is simple, treatment capacity is big, vanadium removal is effective (V＜0.1mg/l), but the treating processes quantity of slag is big, collects the mummification difficulty, and can't reclaim vanadium, chromium etc.; Iron filings one lime method, this method energy treatment of wastes with processes of wastes against one another, processing cost is low, but the water purification ability is relatively poor, only is fit to handle low concentration wastewater, does not also possess the recovery function; The sulfurous gas method, this method can reclaim vanadium chromium, and realizes the zero release of waste water, but complex process is arranged, shortcoming such as the equipment that takies is many, energy consumption is big.
The vanadium extraction trade effluent is very harmful source of pollution, is again the secondary resource that certain value is arranged.For this reason, the present invention is directed to the shortcoming of existing vanadium extracting waste water treatment process, take effective technical measures, develop a kind of novel process that can effect a radical cure the vanadium extracting waste water pollution.
Summary of the invention
The present invention is directed to the shortcoming of existing vanadium extracting waste water treatment process, take effective technical measures, develop a kind of novel process that can effect a radical cure the vanadium extracting waste water pollution, promptly a kind of vanadium extracting waste water technique of zero discharge.
Novel process adopts the D301 resin absorption, can effectively reclaim the residual vanadium of vanadium extracting waste water, chromium, can also recycle salt wherein after the filtrate crystallization, energy consumption is low, technological operation is simple, can reach the vanadium extraction tail washings and all return and recycle, realize wastewater zero discharge, thoroughly solve the problem that vanadium extracting waste water is handled.
The D301 resin claims polystyrene macroporous type weak base anion-exchange resin again, functional group-N (CH3) 2, and outward appearance is generally the opaque spherical particle of oyster white.The D301 resin is the anionite-exchange resin that mainly has tertiary amine groups [N (CH3) 2] on vinylbenzene-divinylbenzene interpolymer at macroporous structure.Its alkalescence a little less than, can in the nearly neutral medium of acidity, exchange mineral acid and silicate effectively, and can the larger-size impurity of adsorbed molecules and in non-aqueous solution, use.This resin has regeneration efficiency height, exchange capacity is big, contamination resistance is strong, physical strength is good advantage.The D301 resin claims that also functional group is N, the polystyrene macroporous type weak base anion-exchange resin of N-dimethyl amido.
Technical solution of the present invention is as follows:
A kind of vanadium extracting waste water technique of zero discharge is characterized in that, adopts the D301 resin as adsorption medium absorption vanadium ion and chromium ion.
A kind of vanadium extracting waste water technique of zero discharge is characterized in that, may further comprise the steps:
1. vanadium extracting waste water is neutralized with neutralizing agent, obtain the vanadium extracting waste water neutralizer;
2. adopt the D301 resin vanadium chromium ion in the vanadium extracting waste water neutralizer to be adsorbed, obtain adsorbing back D301 resin and absorption back tail washings as adsorption medium;
3. carry out desorb to adsorbing back D301 resin, obtain resolving back D301 resin, and the vanadium chromium that parses is reclaimed; Separate out crystal solution to adsorbing the back tail washings by freezing and crystallizing acquisition saltcake;
4. saltcake is separated out crystal solution and filter, first mother liquor after obtaining saltcake and filtering saltcake, and first mother liquor is returned the leaching operation of process for extracting vanadium;
5. saltcake is carried out heat fused and filter, second mother liquor after obtaining Sodium sulfate anhydrous.min(99) and filtering Sodium sulfate anhydrous.min(99), and second mother liquor returned after the absorption of step in 3. in the tail washings.
Describedly be included under the naturally frozen condition crystallization by freezing and crystallizing and separate out saltcake, be i.e. Na adsorbing the back tail washings
2SO
410H
2O.
Described parsing back D301 resin utilizes regenerator to regenerate, with again as adsorption medium.
The D301 resin is as before the adsorption medium, comprises that the pre-treatment of D301 resin is to remove the soluble impurity that is adsorbed on the resin and/or D301 ion exchange resin conversion so that resin transfers the OH type to.
Described neutralizing agent adopts Na
2CO
3
The pre-treatment of D301 resin comprises that deionized water soaks, and the NaOH liquid caustic soda is washed and the pickling of HCI liquid.
The D301 ion exchange resin conversion comprises that the D301 resin carries out the oscillatory process in the certain hour in agent transition of NaOH liquid.
Utilizing regenerator to regenerate and being included in carries out in the certain hour and the oscillatory process in the certain temperature range in the NaOH liquid regenerator.
Described under the naturally frozen condition crystallization separate out saltcake, its naturally frozen temperature is 10 ℃ ± 1 ℃.
Advantage of the present invention is as follows:
The present invention is the tail washings incision after the vanadium extraction, following advantage is arranged: the rate of recovery that has 1. improved vanadium chromium; 2. realize freezing and crystallizing under natural temperature, energy consumption is low; 3. not having the waste gas peculiar smell produces; 4. implement easily, easy to operate.
Technique effect of the present invention is as follows:
Adopt the D301 resin absorption can reclaim vanadium chromium residual in the vanadium extracting waste water effectively, absorption back tail washings contains vanadium and is no more than 2mg/L, vanadium recovery height (〉=99.5%) contains chromium and is no more than 1mg/L, and chromium recovery ratio height (〉=99.9%) absorption back tail washings can return leach liquor behind freezing and crystallizing.D301 resin absorption vanadium capacity height (112.4 gram vanadium/rise wet resin) can return with easy desorb of sodium hydroxide solution and stripping liquid concentration height and to make sorbent material.
Description of drawings
Fig. 1 is that vanadium extracting waste water is recycled process flow sheet.
Embodiment
The invention discloses a kind of vanadium extracting waste water technique of zero discharge, promptly vanadium extracting waste water add in the yellow soda ash and after, adopt the D301 resin to adsorb, reclaim the vanadium chromium ion in the waste water, Na is separated out in Yu Shui crystallization under the naturally frozen condition
2SO
410H
2O filters rear filtrate and can return the leaching operation, realizes the vanadium extracting waste water zero release.The present invention is applied to the absorption of vanadium chromium ion in the vanadium extracting waste water with the D301 weakly-basic anion, makes the processing of vanadium extracting waste water become very simple, easy to operate with respect in the past technology; The present invention utilizes the weather in the north in addition, adopt the sodium sulfate in the naturally frozen crystallization recovery vanadium extracting waste water, the filter rear solution returns the technology with respect in the past, this invention energy consumption is low, can realize wastewater zero discharge, environmental pollution is very little, is the waste water comprehensive utilization process of a green cleaning, is suitable for the suitability for industrialized production of certain scale.
This is a kind of novel process of vanadium extracting waste water zero release, mode be vanadium extracting waste water add in the yellow soda ash and after, adopt the D301 resin to adsorb, reclaim the vanadium chromium ion in the waste water, Na is separated out in Yu Shui crystallization under the naturally frozen condition
2SO
410H
2O filters rear filtrate and can return the leaching operation, saltcake (Na
2SO
410H
2O) after heating and melting, obtain Sodium sulfate anhydrous.min(99) (Na
2SO
4), Yu Shui returns the freezing and crystallizing operation, realizes the vanadium extracting waste water zero release.The vanadium extracting waste water neutralizing agent adopts Na
2CO
3The vanadium extracting waste water sorbent material is the D301 resin, is the macroporous type weak base anion-exchange resin, and functional group is N, the polystyrene of N-dimethyl amido.The D301 resin need carry out pre-treatment and transition before absorption.Behind the pre-treatment employing deionized water rinsing 3 times, soaked 16 hours with 4 times of amount deionized waters again, 4 times of NaOH that measure 1mol/L of back adding anhydrate, when temperature is 298K, alkali lye is removed in vibration, is washed to that to add phenolphthalein be colourless, and the HCI that adds 1mol/L again vibrates under similarity condition and removes acid solution, with the deionized water rinsing resin until adding methyl orange endpoint flavescence look, till twice of the re-treatment.Agent transition is the NaOH solution of 1mol/L, vibrate 2 hours, makes resin transfer the OH type to, is washed till with deionized water that to add phenolphthalein be colourless afterwards standby again.The surplus water in absorption back adopts the naturally frozen crystallization, separates out saltcake (Na
2SO
410H
2O), the naturally frozen temperature is 10 ℃ (± 1 ℃).Mother liquor behind the filtration saltcake returns the leaching operation.The NaOH solution that 1mol/L is adopted in D301 resin regeneration agent under the temperature of 298K, vibrate 1 hour, and is promptly renewable complete, is washed till with deionized water that to add phenolphthalein be colourless standby again.
Technical conceive of the present invention is as follows:
Ion exchange resin is the insoluble macromolecular compound of a kind of organism synthetic, and a lot of active groups are arranged on the structure of resin, has stronger reactive behavior.Usually, ion exchange resin is made sphere, film like or fibrous.Utilize the ion exchange of resin, exchange the Ionized solute in the waste water, be used in more and reclaim and handle in the waste water of heavy metal.
Because ion exchange resin is also inequality for the ability of various ionic adsorption in the water, be easy to be adsorbed and other ions are difficult to adsorb for the some of them ion, the regenerated time, the ion that has is easy to be replaced by the ion of resin absorption, and being difficult to of having replaced.This performance that ion exchange resin had is called the selection performance.
The D301 resin is that functional group is N, the polystyrene macroporous type weak base anion-exchange resin of N-dimethyl amido.Have advantages such as regeneration efficiency height, alkaline consumption, the water consumption is low, exchange capacity is big, its performance index see Table 1
The performance index of table 1 large pore anion resin D301
| Index name | Index |
| Water content/% | 50～60 |
| Complete exchange capacity/(m mol/g) (doing) | ≥4.8 |
| Wet true density (20 ℃)/(g/ml) | 1.03～1.06 |
| Wet volume density/(g/ml) | 0.62～0.72 |
| Size range/mm | 0.355～1.25 |
| Granularity/% | ≥95 |
| The pH scope | 0～9 |
| Allowable temperature/℃ | ≤100 |
| Swelling ratio (OH -→Cl -) | ≤35 |
The present invention utilizes the performance of resin D301, selective adsorption vanadium chromium ion, the Na in the waste water
+, SO
4 2-Crystallization is separated out in low temperature crystallization test subsequently, not only realizes the recycling of vanadium chromium ion, and has removed Na in the vanadium extracting waste water
+, SO
4 2-, the vanadium extracting waste water after the crystallization can return the leaching operation, realizes recycle.
The enforcement of technical scheme of the present invention may further comprise the steps:
1. the pre-treatment of D301 resin
Commercially available ion exchange resin often contains solvent, does not participate in material and a spot of low-grade polymer of polyreaction, also may be adsorbed with metal ions such as iron, aluminium, copper.Therefore, should make resin swelling fully before using, and contact, to remove the soluble impurity that is adsorbed on the resin with acid, alkali or other solution.
Concrete treatment process: resin is first with behind the deionized water rinsing 3 times, soaked 16 hours with 4 times of amount deionized waters again, aqueous phase discarded, resin is washed till clarification with a large amount of deionized waters, 4 times of NaOH that measure 1mol/L of back adding anhydrate, in temperature is 298K, fixed rotating speed vibration 4 hours, remove alkali lye, be washed to that to add phenolphthalein be colourless, the HCI that adds 1mol/L again vibrated 4 hours under similarity condition, removed acid solution, with the deionized water rinsing resin until adding methyl orange endpoint flavescence look, till twice of the re-treatment.
2. transition of D301 resin
The NaOH that pretreated negative resin added 4 times of amount 1mol/L vibrates 2 hours under similarity condition, made resin transfer the OH type to, were washed till with deionized water that to add phenolphthalein be colourless afterwards standby again.
3. D301 Choice of Resin absorption vanadium chromium ion
Get the vanadium extracting waste water in vanadium chemical plant, Chengde, add yellow soda ash and regulate pH value, place the beaker of 5000ml, the D301 resin is immersed in the beaker, adsorption time is decided to be 40 minutes.
4. with the regeneration of anionite-exchange resin
To adsorb the regenerator of 4 times of amounts of resin adding of also desorb, regenerator adopts the NaOH solution of 1mol/L, under the temperature of 298K, vibrates 1 hour, and is promptly renewable complete.Be washed till with deionized water again that to add phenolphthalein be colourless standby.
5. adsorb the rear solution freezing and crystallizing
With the vanadium extracting waste water after the absorption, be placed in the 5000ml beaker, beaker is placed on again in the plastic tank that tap water is housed, and keeps tap water temperature≤8 ℃, and feed liquid is stirred at a slow speed, when feed temperature drops to 10 ℃, stop to stir, take out slurries filtration, filter cake is a sal glauberi, send the operation system of dissolving anhydrous sodium sulphate (Sodium sulfate anhydrous.min(99)), filtrate is returned the leaching operation.
Below describe by embodiment:
A kind of vanadium extracting waste water technique of zero discharge is characterized in that, adopts the D301 resin as adsorption medium absorption vanadium ion and chromium ion.
A kind of vanadium extracting waste water technique of zero discharge is characterized in that, may further comprise the steps: 1. vanadium extracting waste water is neutralized with neutralizing agent, obtain the vanadium extracting waste water neutralizer; 2. adopt the D301 resin vanadium chromium ion in the vanadium extracting waste water neutralizer to be adsorbed, obtain adsorbing back D301 resin and absorption back tail washings as adsorption medium; 3. carry out desorb to adsorbing back D301 resin, obtain resolving back D301 resin, and the vanadium chromium that parses is reclaimed; Separate out crystal solution to adsorbing the back tail washings by freezing and crystallizing acquisition saltcake; 4. saltcake is separated out crystal solution and filter, first mother liquor after obtaining saltcake and filtering saltcake, and first mother liquor is returned the leaching operation of process for extracting vanadium; 5. saltcake is carried out heat fused and filter, second mother liquor after obtaining Sodium sulfate anhydrous.min(99) and filtering Sodium sulfate anhydrous.min(99), and second mother liquor returned after the absorption of step in 3. in the tail washings.
Describedly be included under the naturally frozen condition crystallization by freezing and crystallizing and separate out saltcake, be i.e. Na adsorbing the back tail washings
2SO
410H
2O.Described parsing back D301 resin utilizes regenerator to regenerate, with again as adsorption medium.The D301 resin is as before the adsorption medium, comprises that the pre-treatment of D301 resin is to remove the soluble impurity that is adsorbed on the resin and/or D301 ion exchange resin conversion so that resin transfers the OH type to.Described neutralizing agent adopts Na
2CO
3The pre-treatment of D301 resin comprises that deionized water soaks, and the NaOH liquid caustic soda is washed and the pickling of HCI liquid.The D301 ion exchange resin conversion comprises that the D301 resin carries out the oscillatory process in the certain hour in agent transition of NaOH liquid.Utilizing regenerator to regenerate and being included in carries out in the certain hour and the oscillatory process in the certain temperature range in the NaOH liquid regenerator.Described under the naturally frozen condition crystallization separate out saltcake, its naturally frozen temperature is 10 ℃ ± 1 ℃.Fig. 1 has carried out brief description to above technology.
Embodiment one
Get the vanadium extraction tail washings 1L in one vanadium chemical plant, Chengde, its main chemical compositions sees Table 2; The capacity of putting into is the volumetric flask of 5L, and according to operating procedure of the present invention, vanadium extracting waste water for example shown in Figure 1 is recycled technical process, carries out the processing of vanadium extraction tail washings.
Table 2 vanadium extraction tail washings main chemical compositions (g/L)
| V 5+(mg/l | Cr 6+(mg/l | Na 2SO 4(mg/l) | Suspended substance (mg/l | PH |
| 200 | 300 | 80000 | 600 | 2.5 |
The primary standard of the national GB8978-1996 of table 3 " integrated wastewater discharge standard "
| V5+(mg/l) | Cr 6+(mg/l) | Suspended substance (mg/l) | PH |
| / | 0.5 | 70 | 7.3 |
As can be seen from the above table, it is acid that vanadium extracting waste water is, first kind pollutent V in the waste water
5+, Cr
6+Content is higher, be higher than the highest permission emission concentration of first kind pollutent in " integrated wastewater discharge standard " far away, and sulfate concentration is bigger in the waste water, and salts contg is higher.Through after the D301 resin absorption, vanadium wastewater is through the naturally frozen crystallization, and its composition is as shown in table 4 below:
Main chemical compositions after table 4 vanadium extraction tail washings is handled
| V 5+(mg/l) | Cr 6+(mg/l) | Na 2SO 4(mg/l) | Suspended substance (mg/l) | PH |
| 0.06 | 0.01 | 0.02 | 0 | 7.3 |
Vanadium wastewater can all be returned the workshop and recycle after neutralization-absorption-process for freezing and crystallizing is handled, and can realize wastewater zero discharge, thoroughly solves the problem that waste water exceeds standard and discharges.
Embodiment two
Get the vanadium extraction tail washings 1L in one vanadium chemical plant, Chengde, its main chemical compositions sees Table 5; The capacity of putting into is the volumetric flask of 5L, according to operating procedure of the present invention, carries out the processing of vanadium extraction tail washings, and the composition after the processing sees Table 6
Table 5 vanadium extraction tail washings main chemical compositions (g/L)
| V 5+(mg/l | Cr 6+(mg/l | Na 2SO 4(mg/l) | Suspended substance (mg/l | PH |
| 60 | 100 | 62000 | 400 | 3.1 |
Main chemical compositions after table 6 vanadium extraction tail washings is handled
| V 5+(mg/l) | Cr 6+(mg/l) | Na 2SO 4(mg/l) | Suspended substance (mg/l) | PH |
| 0.018 | 0.001 | 0.001 | 0 | 7.5 |
Have measuring result as can be known, suspended substance is all removed, and the rate of recovery of vanadium is 99.7%, the rate of recovery of chromium is 99.9%, has realized the efficient recovery of vanadium chromium substantially, after the crystallization in the tail washings sodium salt content reduce greatly, filtrate can be returned the leaching operation, realizes the vanadium extracting waste water zero release.
Indicate at this, more than narration helps those skilled in the art to understand the invention, but and the protection domain of unrestricted the invention.Any do not break away from the invention flesh and blood to being equal to replacement, modify improving and/or deleting numerous conforming to the principle of simplicity and the enforcement carried out of above narration, all fall into the protection domain of the invention.
Claims (10)
1. a vanadium extracting waste water technique of zero discharge is characterized in that, adopts the D301 resin as adsorption medium absorption vanadium ion and chromium ion.
2. a vanadium extracting waste water technique of zero discharge is characterized in that, may further comprise the steps:
1. vanadium extracting waste water is neutralized with neutralizing agent, obtain the vanadium extracting waste water neutralizer;
2. adopt the D301 resin vanadium chromium ion in the vanadium extracting waste water neutralizer to be adsorbed, obtain adsorbing back D301 resin and absorption back tail washings as adsorption medium;
3. carry out desorb to adsorbing back D301 resin, obtain resolving back D301 resin, and the vanadium chromium that parses is reclaimed; Separate out crystal solution to adsorbing the back tail washings by freezing and crystallizing acquisition saltcake;
4. saltcake is separated out crystal solution and filter, first mother liquor after obtaining saltcake and filtering saltcake, and first mother liquor is returned the leaching operation of process for extracting vanadium;
5. saltcake is carried out heat fused and filter, second mother liquor after obtaining Sodium sulfate anhydrous.min(99) and filtering Sodium sulfate anhydrous.min(99), and second mother liquor returned after the absorption of step in 3. in the tail washings.
3. vanadium extracting waste water technique of zero discharge according to claim 2 is characterized in that, describedly is included under the naturally frozen condition crystallization by freezing and crystallizing and separates out saltcake adsorbing the back tail washings, be i.e. Na
2SO
410H
2O.
4. vanadium extracting waste water technique of zero discharge according to claim 2 is characterized in that, described parsing back D301 resin utilizes regenerator to regenerate, with again as adsorption medium.
5. vanadium extracting waste water technique of zero discharge according to claim 2 is characterized in that, the D301 resin is as before the adsorption medium, comprises that the pre-treatment of D301 resin is to remove the soluble impurity that is adsorbed on the resin and/or D301 ion exchange resin conversion so that resin transfers the OH type to.
6. vanadium extracting waste water technique of zero discharge according to claim 2 is characterized in that, described neutralizing agent adopts Na
2CO
3
7. vanadium extracting waste water technique of zero discharge according to claim 5 is characterized in that, the pre-treatment of D301 resin comprises that deionized water soaks, and the NaOH liquid caustic soda is washed and the pickling of HCI liquid.
8. vanadium extracting waste water technique of zero discharge according to claim 5 is characterized in that, the D301 ion exchange resin conversion comprises that the D301 resin carries out the oscillatory process in the certain hour in agent transition of NaOH liquid.
9. vanadium extracting waste water technique of zero discharge according to claim 4 is characterized in that, utilizes regenerator to regenerate and is included in and carry out in the certain hour in the NaOH liquid regenerator and the oscillatory process in the certain temperature range.
10. vanadium extracting waste water technique of zero discharge according to claim 3 is characterized in that, described under the naturally frozen condition crystallization separate out saltcake, its naturally frozen temperature is 10 ℃ ± 1 ℃.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583822A (en) * | 2012-02-09 | 2012-07-18 | 湖南大学 | Method for removing heavy metal ion in waste water generated by vanadium extraction |
| CN103145187A (en) * | 2013-03-22 | 2013-06-12 | 中南大学 | Production technology of harmless high-purity vanadium pentoxide |
| CN104261607A (en) * | 2014-09-26 | 2015-01-07 | 浙江华友钴业股份有限公司 | Processing method of complex raffinate |
| 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 |
| CN109650406A (en) * | 2018-12-29 | 2019-04-19 | 江苏南大环保科技有限公司 | A kind of processing method of the high-salt wastewater containing chrome alum and the processing method of precipitation waste residue |
| CN109665548A (en) * | 2018-12-29 | 2019-04-23 | 江苏南大环保科技有限公司 | A kind of processing method of vanadium wastewater and the processing method of precipitation waste residue |
| CN110981059A (en) * | 2019-12-09 | 2020-04-10 | 常州中源工程技术有限公司 | System and process for treating waste water containing sodium sulfate salt and sodium sulfite salt dinaphthol |
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| CN101525189A (en) * | 2009-04-02 | 2009-09-09 | 葫芦岛辉宏有色金属有限公司 | Method for treating wastewater containing ammonia, vanadium, chrome and sodium sulfate |
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| CN101525189A (en) * | 2009-04-02 | 2009-09-09 | 葫芦岛辉宏有色金属有限公司 | Method for treating wastewater containing ammonia, vanadium, chrome and sodium sulfate |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583822A (en) * | 2012-02-09 | 2012-07-18 | 湖南大学 | Method for removing heavy metal ion in waste water generated by vanadium extraction |
| CN103145187A (en) * | 2013-03-22 | 2013-06-12 | 中南大学 | Production technology of harmless high-purity vanadium pentoxide |
| CN104261607A (en) * | 2014-09-26 | 2015-01-07 | 浙江华友钴业股份有限公司 | Processing method of complex raffinate |
| 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 |
| 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 |
| CN109650406A (en) * | 2018-12-29 | 2019-04-19 | 江苏南大环保科技有限公司 | A kind of processing method of the high-salt wastewater containing chrome alum and the processing method of precipitation waste residue |
| CN109665548A (en) * | 2018-12-29 | 2019-04-23 | 江苏南大环保科技有限公司 | A kind of processing method of vanadium wastewater and the processing method of precipitation waste residue |
| CN110981059A (en) * | 2019-12-09 | 2020-04-10 | 常州中源工程技术有限公司 | System and process for treating waste water containing sodium sulfate salt and sodium sulfite salt dinaphthol |
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Application publication date: 20110525 |