CN115679125B - Method for adjusting pH of vanadium-containing pickle liquor - Google Patents
Method for adjusting pH of vanadium-containing pickle liquor Download PDFInfo
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- CN115679125B CN115679125B CN202211221505.1A CN202211221505A CN115679125B CN 115679125 B CN115679125 B CN 115679125B CN 202211221505 A CN202211221505 A CN 202211221505A CN 115679125 B CN115679125 B CN 115679125B
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 156
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 235000021110 pickles Nutrition 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims abstract description 85
- 239000002253 acid Substances 0.000 claims abstract description 247
- 230000001105 regulatory effect Effects 0.000 claims abstract description 210
- 238000011084 recovery Methods 0.000 claims abstract description 117
- 239000007788 liquid Substances 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000004064 recycling Methods 0.000 claims abstract description 31
- 230000003750 conditioning effect Effects 0.000 claims description 79
- 239000012528 membrane Substances 0.000 claims description 64
- 238000005341 cation exchange Methods 0.000 claims description 41
- 239000003011 anion exchange membrane Substances 0.000 claims description 32
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 14
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 14
- 235000011152 sodium sulphate Nutrition 0.000 claims description 14
- 238000002386 leaching Methods 0.000 claims description 12
- 238000005554 pickling Methods 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 abstract description 17
- 239000002893 slag Substances 0.000 abstract description 12
- 238000005265 energy consumption Methods 0.000 abstract description 11
- 238000001223 reverse osmosis Methods 0.000 abstract description 10
- 239000002351 wastewater Substances 0.000 abstract description 10
- 239000003513 alkali Substances 0.000 abstract description 8
- 238000000746 purification Methods 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000002699 waste material Substances 0.000 description 10
- 238000000909 electrodialysis Methods 0.000 description 8
- 239000003014 ion exchange membrane Substances 0.000 description 6
- 230000003472 neutralizing effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- -1 hydrogen ions Chemical class 0.000 description 5
- 238000010979 pH adjustment Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910001456 vanadium ion Inorganic materials 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
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
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a method for adjusting the pH value of a vanadium-containing pickle liquor. The technical proposal is as follows: the pH of the vanadium-containing pickle liquor is regulated by adopting two identical regulating devices, wherein the first regulating device is in a constant-pressure mode, and the second regulating device is in a constant-current mode; the n-level adjusting chamber of the first adjusting device is communicated with the 1-level adjusting chamber of the second adjusting device, and the n-level acid recycling chamber of the second adjusting device is communicated with the 1-level acid recycling chamber of the first adjusting device; injecting the vanadium-containing pickle liquor into a 1-stage regulating chamber of a first regulating device, carrying out n-stage countercurrent treatment, obtaining recovered acid liquor in an n-stage acid recovery chamber, and obtaining pre-regulating liquor in the n-stage regulating chamber; injecting the pre-regulating liquid into a 1-stage regulating chamber of a second regulating device, carrying out n-stage countercurrent treatment, and then obtaining low acid liquid in an n-stage acid recovery chamber, and obtaining treated liquid with pH value of 1.5-2.5 in the n-stage regulating chamber. The invention has the characteristics of no waste water and slag, no vanadium loss, no water reverse osmosis, low energy consumption and good pH value regulating effect, and can effectively replace the alkali neutralization process.
Description
Technical Field
The invention belongs to the technical field of adjusting vanadium-containing pickle liquor. In particular to a method for adjusting the pH value of a vanadium-containing pickle liquor.
Background
Vanadium in the vanadium shale is generally low in grade, vanadium is mainly endowed in a mica aluminosilicate mineral lattice, and the structure is stable. The direct acid leaching method has the characteristics of high leaching rate and small pollution, and is the main flow leaching technology for extracting vanadium from the shale. The pH value of the vanadium-containing pickle liquor needs to be controlled to be about 2.0 in the subsequent purification and enrichment, however, the pH value of the obtained vanadium-containing pickle liquor is generally below 0, the direct purification and enrichment are difficult, and the pH adjustment is needed.
The current method for adjusting the pH of the acid leaching solution containing vanadium comprises an alkali neutralization method and an acid recovery method. The alkali neutralization method is simple and quick by adding lime or ammonia water to neutralize redundant acid. However, the alkali neutralization method consumes a large amount of medicament, a large amount of neutralization slag which is difficult to treat is generated in the neutralization process, and vanadium is lost due to entrainment and adsorption; the hardness of the pickle liquor is increased, so that scaling of an extraction pipeline is caused, normal operation of equipment is affected, and in addition, the treatment cost of the generated ammonia nitrogen wastewater is increased. The acid recovery method mainly utilizes an ion exchange membrane to separate and recover acid in the acid leaching solution containing vanadium, uses the ion exchange membrane to separate pure water from the acid leaching solution, uses concentration difference or an electric field as driving force, and utilizes the characteristic of large radius of vanadium ions to realize separation of vanadium and acid, so that the acid concentration of the acid leaching solution containing vanadium is reduced, and the pH value is increased.
Qi Dong et al (Qi Dong, wang Yi. Exploration of iron removal process of vanadium-containing leachate [ J ]. Nonferrous mining and metallurgy, 2015, 31 (3): 37-39) in exploration of iron removal process of vanadium-containing leachate, lime was used to adjust pH of the pickling solution. The result shows that as the lime dosage increases, the pH value gradually increases, the amount of the neutralized waste residue also gradually increases, and the vanadium loss rate also increases due to the entrainment adsorption effect of the waste residue; when the pH was controlled at 2.0, the vanadium loss was about 6%. In order to reduce the vanadium loss rate, the neutralization slag is washed later, and finally the vanadium loss rate is reduced to about 1 percent. The neutralization slag produced by the alkali neutralization method is difficult to treat, and can cause vanadium loss and complex process.
Li Wang (Li Wang) separation and purification process of novel anion exchange membrane high-acid multi-impurity element vanadium-containing solution and mechanism research (D) Wuhan: university of Wuhan technology, 2013:79-109) recovery of sulfuric acid in pickle liquor by using anion exchange membrane, and keeping flow rate of feed liquid at 0.21x10 -3 m 3 /(h·m 2 ) When the water flow rate ratio is 1.1-1.3, the recovery rate of sulfuric acid reaches 84%, and the pH value of the treated pickle liquor is raised from-1.08 to 0.8. The process has low cost, but the reverse osmosis of water is insufficient in reducing the concentration of vanadium ions and the pH adjusting capability, and cannot meet the requirements of purification and enrichment.
Wang Kui (Wang Kui. Study (D) of separating and recovering shale vanadium-extracting waste acid by coupling diffusion dialysis-bipolar membrane electrodialysis. Wuhan: university of technology, 2018:17-43), treating the vanadium-containing pickle liquor by forming a membrane stack by using a diffusion dialysis type anion exchange membrane, and circularly treating for 6 hours, wherein the pH of the vanadium-containing pickle liquor is increased from 0.04 to 1.0; then bipolar membrane electrodialysis is adopted to carry out secondary treatment on the pickle liquor, and the pH value of the pickle liquor is about 1.0The pH value is improved to 1.8 to 2.5, the requirement of purifying and enriching is met, but the energy consumption is as high as 0.5kWh/mol H + . The process can meet the requirements of purification and enrichment, but has long treatment flow and high energy consumption.
In the technology of the patent of 'a device and a method for recovering acid from waste liquid containing low-concentration acid and high-concentration metal ions by hydrogen ion selective electrodialysis' (CN 107746098A), the waste liquid with the concentration of hydrogen ions of 0-1.0 mol/L and the concentration of metal ions of 0.5-2.0 mol/L is treated by a hydrogen ion selective electrodialysis device, the concentration of hydrogen ions in the treated waste liquid is reduced to 0.01-0.05 mol/L, and the rejection rate of metal ions is more than 96%. Although the acid recovery capability of the technology is strong, the hydrogen ion concentration of the treatable waste liquid is lower than the metal ion concentration, and the hydrogen ion concentration in the vanadium-containing pickle liquor is higher than the vanadate ion concentration, so that the technology is not suitable for the pH adjustment of the vanadium-containing pickle liquor.
In summary, the existing alkali neutralization method generates a large amount of neutralization slag or ammonia nitrogen wastewater, and is difficult to treat, so that environmental pollution and vanadium loss are caused; the existing acid recovery method has the problems of serious reverse osmosis of water, high energy consumption and long treatment flow, and has limited pH adjusting capability.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and aims to provide a method for adjusting the pH of the vanadium-containing pickle liquor, which has the characteristics of no waste water and waste residue, no vanadium loss, no reverse osmosis, low energy consumption, short treatment flow and good pH adjustment effect.
In order to achieve the above purpose, the steps of the technical scheme adopted by the invention are as follows:
step 1, adjusting the device of the acid leaching liquid pH containing vanadium
The device for adjusting the pH of the vanadium-containing pickle liquor comprises: cathode, anode, membrane stack and DC power supply.
The cathode is connected with the negative electrode of the direct current power supply, the anode is connected with the positive electrode of the direct current power supply, and the cathode and the anode are correspondingly arranged on the right side and the left side of the membrane stack.
The membrane stack is composed of a 1 st cation exchange membrane, a 1 st anion exchange membrane, a 2 nd cation exchange membrane, a 2 nd anion exchange membrane, a 3 rd cation exchange membrane, a … …, an n cation exchange membrane, an n anion exchange membrane and an n+1 th cation exchange membrane in sequence from an anode to a cathode.
And n is a positive integer of 10-1000.
From the anode to cathode direction: the gap between the anode and the 1 st cation exchange membrane forms an anode electrode chamber, the gap between the 1 st cation exchange membrane and the 1 st anion exchange membrane forms a 1-stage regulating chamber, the gap between the 1 st anion exchange membrane and the 2 nd cation exchange membrane forms an n-stage recovery acid chamber, the gap between the 2 nd cation exchange membrane and the 2 nd anion exchange membrane forms a 2-stage regulating chamber, the gap between the 2 nd anion exchange membrane and the 3 rd cation exchange membrane forms an n-1-stage recovery acid chamber, … …, and so on, the gap between the n-1 st cation exchange membrane and the n-1 st anion exchange membrane forms an n-1-stage regulating chamber, the gap between the n-1 st anion exchange membrane and the n-th cation exchange membrane forms an n-stage recovery acid chamber, the gap between the n-th anion exchange membrane and the n+1 th cation exchange membrane forms a 1-stage recovery acid chamber, and the gap between the n+1 th cation exchange membrane and the cathode electrode forms a cathode electrode chamber.
The 1-level adjusting chamber, the 2-level adjusting chamber, the 3-level adjusting chamber, the … …, the n-1-level adjusting chamber and the n-level adjusting chamber are sequentially communicated; the 1-level acid recycling chamber, the 2-level acid recycling chamber, the 3-level acid recycling chamber, the … …, the n-1-level acid recycling chamber and the n-level acid recycling chamber are sequentially communicated.
And forming a serial loop of the anode electrode chamber, the 1-stage regulating chamber, the n-stage acid recovering chamber, the 2-stage regulating chamber, the n-1-stage acid recovering chamber, … …, the n-1-stage regulating chamber, the 2-stage acid recovering chamber, the n-stage regulating chamber, the 1-stage acid recovering chamber, the cathode electrode chamber and the direct current power supply in a working state, thereby obtaining the device for regulating the pH value of the vanadium-containing pickle liquor.
Step 2, method for regulating pH of vanadium-containing pickle liquor
Step 2.1, the process of adjusting the pH of the vanadium-containing pickle liquor is divided into two stages, wherein the 'devices for adjusting the pH of the vanadium-containing pickle liquor' adopted in the two stages are the same, and the device for adjusting the pH of the vanadium-containing pickle liquor used in the first stage is called a first adjusting device; the device used in the second stage for adjusting the pH of the vanadium-containing pickle liquor is called a second adjusting device.
The n-level adjusting chamber of the first adjusting device is communicated with the 1-level adjusting chamber of the second adjusting device, and the n-level acid recycling chamber of the second adjusting device is communicated with the 1-level acid recycling chamber of the first adjusting device.
Step 2.2, first stage of adjusting the pH of the vanadium-containing pickle liquor
Sodium sulfate solution is respectively injected into an anode electrode chamber and a cathode electrode chamber of the first regulating device, vanadium-containing pickle liquor is injected from a 1-stage regulating chamber inlet of the first regulating device, and water or low acid liquor is injected from a 1-stage recovery acid chamber inlet of the first regulating device.
And switching on a direct current power supply of the first regulating device, wherein the direct current power supply is set into a constant voltage mode.
The vanadium-containing pickle liquor injected from the inlet of the 1-stage regulating chamber of the first regulating device flows through the 2-stage regulating chamber, the 3-stage regulating chamber, the … …, the n-1-stage regulating chamber and the n-stage regulating chamber in sequence, and then flows out from the outlet of the n-stage regulating chamber to obtain the pre-regulating liquid.
The water injected from the inlet of the 1-grade acid recycling chamber of the first regulating device flows through the 2-grade acid recycling chamber, the 3-grade acid recycling chamber, the … …, the n-1 grade acid recycling chamber and the n-grade acid recycling chamber in sequence, and then flows out from the outlet of the n-grade acid recycling chamber to obtain the acid recycling solution.
The pH value of the pre-regulating liquid is 0.5-1.2.
Step 2.3, the second stage of adjusting the pH of the vanadium-containing pickle liquor
Sodium sulfate solution is respectively injected into an anode electrode chamber and a cathode electrode chamber of the second regulating device, the preconditioning liquid of the first regulating device flows in from a 1-stage regulating chamber inlet of the second regulating device, and water flows in from a 1-stage acid recovery chamber inlet of the second regulating device.
And switching on a direct current power supply of the second regulating device, wherein the direct current power supply is set into a constant current mode.
The pre-conditioning liquid injected from the inlet of the 1-stage conditioning chamber of the second conditioning device flows through the 2-stage conditioning chamber, the 3-stage conditioning chamber, the … …, the n-1-stage conditioning chamber and the n-stage conditioning chamber in sequence, and then flows out from the outlet of the n-stage conditioning chamber to obtain treated liquid.
The water injected from the inlet of the 1-stage acid recovery chamber flows through the 2-stage acid recovery chamber, the 3-stage acid recovery chamber, … …, the n-1-stage acid recovery chamber and the n-stage acid recovery chamber in sequence, and then flows out from the outlet of the n-stage acid recovery chamber to obtain low acid liquor; the low acid liquid returns to the 1-grade acid recovery chamber of the first regulating device.
The pH value of the treated liquid is 1.5-2.5.
The vanadium-containing pickle liquor comprises: the concentration of V is 1-20 g/L, and the concentration of Fe is less than or equal to 0.1g/L; the initial pH value of the vanadium-containing pickle liquor is-1.0-0.7.
The initial current density of the constant voltage mode is 120-300A/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The initial current density of the constant current mode is 120-300A/m 2 。
By adopting the method, compared with the prior art, the invention has the following positive effects:
1. after the vanadium-containing pickle liquor is treated, the pH value can be adjusted to meet the requirement of subsequent purification and enrichment, no neutralizing agent is needed to be added in the treatment process, and no neutralizing slag and neutralizing wastewater are generated, so that zero emission of wastewater and waste slag is realized at the source, the source emission reduction can be realized, and the environment is friendly.
2. The recovery liquid of the invention can be recycled, and no vanadium is lost. Firstly, after the acid leaching solution containing vanadium is treated by the method, the retention rate of the vanadium is measured to be more than 95%, so that the subsequent purification and enrichment are not influenced; second, although about 5% of the vanadium in the pickling solution will pass through the ion exchange membrane and enter the recovered acid solution, the recovered acid solution is recycled for the pickling process, and the low acid solution is returned to the n-stage recovered acid chamber of the first regulating device, so that no vanadium is lost; third, no neutralization slag is generated in the treatment process, and vanadium loss caused by the entrainment adsorption of the sediment is avoided.
3. In the existing process of recovering acid by using a diffusion dialysis method, because of concentration difference and flow velocity difference at two ends of an ion exchange membrane, water at a low acid side can permeate into a high acid side to generate a water reverse osmosis phenomenon, so that the concentration of vanadium ions in the pickle liquor is reduced, and the subsequent purification and enrichment are not facilitated. In the process of acid recovery by the electrodialysis method, anions, hydrogen ions and partial cations with smaller hydrated ion radius flow from the regulating chamber to the acid recovery chamber under the drive of electric field force, water molecules combined with the anions are also brought into the acid recovery chamber from the regulating chamber, water loss occurs, the concentration of the vanadium-containing pickle liquor in the regulating chamber is increased, the subsequent purification and enrichment are facilitated, and the reverse osmosis of water is avoided.
4. The prior bipolar membrane electrodialysis method is used for adjusting the pH value of the vanadium-containing pickle liquor, and OH is generated by electrolyzing water - Neutralization of the acid in the pickle liquor is realized, and the energy consumption is up to 0.5kWh/mol H + . The energy consumption of the method is 0.22 to 0.30kWh/mol H + Compared with the bipolar membrane electrodialysis method, the energy is saved by 40-56%, and the energy consumption can be obviously reduced.
5. When the constant voltage mode is adopted for operation, the current at two sides of the membrane stack is reduced along with the increase of the resistance of the membrane stack, so that the limit current density is not easy to reach in the operation, but the mass transfer rate in the process is slower, and compared with the constant current mode, the operation time is longer; while the constant-current mode can maintain the stable ion rate in the solution for mass transfer, the limiting current density is easy to reach in the operation process, and the surface of the membrane is subject to water dissociation. Therefore, the invention adopts the constant pressure mode to carry out the first stage treatment so as to recycle most of acid. However, when the pH value of the vanadium-containing pickle liquor is regulated to be more than 0.9, the mass transfer rate is greatly reduced due to the fact that the current at the two ends of the membrane stack is reduced along with the increase of the resistance of the membrane stack, and the continuation of the mass transfer is difficult. Therefore, the constant flow mode is adopted to carry out the second stage treatment, so that the pH value of the pre-adjustment liquid is maximally adjusted to 2.5, purification and enrichment can be directly carried out, and the pH adjustment capability is good. The invention adopts a combination mode of constant voltage and constant current, so that the treatment process is more efficient and stable. The measurement is as follows: the pH value of the vanadium-containing pickle liquor is adjusted to 2.5 at most; the concentration of the recovered acid reaches 1.5 to 2.5mol/L; the recovery rate of the acid reaches 85-95 percent.
Therefore, the invention has the characteristics of no waste water and slag, no vanadium loss, no water reverse osmosis, low energy consumption and good pH value regulating effect, and can effectively replace an alkali neutralization process.
Drawings
FIG. 1 is a schematic diagram of a device for adjusting the pH of a vanadium-containing pickle liquor according to the invention;
FIG. 2 is a schematic diagram of a method for adjusting the pH of a vanadium-containing pickle liquor using the apparatus shown in FIG. 1.
Detailed Description
The invention is further described in connection with the drawings and the detailed description which follow, without limiting the scope of the invention.
A method for regulating pH of vanadium-containing pickle liquor. The method in the specific embodiment comprises the following steps:
step 1, adjusting the device of the acid leaching liquid pH containing vanadium
As shown in fig. 1, the device for adjusting the pH of the vanadium-containing pickle liquor comprises: cathode, anode, membrane stack and DC power supply.
As shown in fig. 1, the cathode is connected to the negative electrode of the dc power supply, the anode is connected to the positive electrode of the dc power supply, and the cathode and the anode are disposed on the right and left sides of the membrane stack, respectively.
As shown in fig. 1, the membrane stack is composed of a 1 st cation exchange membrane, a 1 st anion exchange membrane, a 2 nd cation exchange membrane, a 2 nd anion exchange membrane, a 3 rd cation exchange membrane, a … … th cation exchange membrane, an nth anion exchange membrane and an n+1th cation exchange membrane in sequence from an anode to a cathode.
And n is a positive integer of 10-1000.
As shown in fig. 1, from the anode to the cathode: the gap between the anode and the 1 st cation exchange membrane forms an anode electrode chamber, the gap between the 1 st cation exchange membrane and the 1 st anion exchange membrane forms a 1-stage regulating chamber, the gap between the 1 st anion exchange membrane and the 2 nd cation exchange membrane forms an n-stage recovery acid chamber, the gap between the 2 nd cation exchange membrane and the 2 nd anion exchange membrane forms a 2-stage regulating chamber, the gap between the 2 nd anion exchange membrane and the 3 rd cation exchange membrane forms an n-1-stage recovery acid chamber, … …, and so on, the gap between the n-1 st cation exchange membrane and the n-1 st anion exchange membrane forms an n-1-stage regulating chamber, the gap between the n-1 st anion exchange membrane and the n-th cation exchange membrane forms an n-stage recovery acid chamber, the gap between the n-th anion exchange membrane and the n+1 th cation exchange membrane forms a 1-stage recovery acid chamber, and the gap between the n+1 th cation exchange membrane and the cathode electrode forms a cathode electrode chamber.
As shown in fig. 1, the 1-level regulating chamber, the 2-level regulating chamber, the 3-level regulating chamber, the … …, the n-1-level regulating chamber and the n-level regulating chamber are sequentially communicated; the 1-level acid recycling chamber, the 2-level acid recycling chamber, the 3-level acid recycling chamber, the … …, the n-1-level acid recycling chamber and the n-level acid recycling chamber are sequentially communicated.
As shown in FIG. 1, the anode electrode chamber, the 1-stage regulating chamber, the n-stage acid recovering chamber, the 2-stage regulating chamber, the n-1-stage acid recovering chamber, … …, the n-1-stage regulating chamber, the 2-stage acid recovering chamber, the n-stage regulating chamber, the 1-stage acid recovering chamber, the cathode electrode chamber and the direct current power supply form a series loop in a working state, so that the device for regulating the pH of the vanadium-containing pickle liquor is obtained.
Step 2, method for regulating pH of vanadium-containing pickle liquor
The process of adjusting the pH of the vanadium-containing pickle liquor is divided into two stages, wherein the 'devices for adjusting the pH of the vanadium-containing pickle liquor' adopted in the two stages are the same, the device for adjusting the pH of the vanadium-containing pickle liquor used in the first stage is called a first adjusting device, and the device for adjusting the pH of the vanadium-containing pickle liquor used in the second stage is called a second adjusting device.
As shown in fig. 2, the n-stage adjusting chamber of the first adjusting device is communicated with the 1-stage adjusting chamber of the second adjusting device, and the n-stage acid recovering chamber of the second adjusting device is communicated with the 1-stage acid recovering chamber of the first adjusting device.
Step 2.2, first stage of adjusting the pH of the vanadium-containing pickle liquor
As shown in fig. 2, sodium sulfate solution is respectively injected into the anode electrode chamber and the cathode electrode chamber of the first regulating device, vanadium-containing pickle liquor is injected from the inlet of the 1-stage regulating chamber of the first regulating device, and water or low acid liquor is injected from the inlet of the 1-stage recovery acid chamber of the first regulating device.
And switching on a direct current power supply of the first regulating device, wherein the direct current power supply is set into a constant voltage mode.
As shown in fig. 2, the vanadium-containing pickle liquor injected from the inlet of the 1-stage regulating chamber of the first regulating device flows through the 2-stage regulating chamber, the 3-stage regulating chamber, … …, the n-1-stage regulating chamber and the n-stage regulating chamber in sequence, and then flows out from the outlet of the n-stage regulating chamber to obtain the pre-regulating liquid.
As shown in fig. 2, the water injected from the inlet of the 1-stage recovery acid chamber of the first adjusting device flows through the 2-stage recovery acid chamber, the 3-stage recovery acid chamber, … …, the n-1-stage recovery acid chamber and the n-stage recovery acid chamber in sequence, and then flows out from the outlet of the n-stage recovery acid chamber, thereby obtaining the recovery acid solution.
The pH value of the pre-regulating liquid is 0.5-1.2.
Step 2.3, the second stage of adjusting the pH of the vanadium-containing pickle liquor
As shown in fig. 2, sodium sulfate solution is injected into the anode electrode chamber and the cathode electrode chamber of the second regulating device, respectively, the preconditioning liquid of the first regulating device flows in from the inlet of the 1-stage regulating chamber of the second regulating device, and water flows in from the inlet of the 1-stage recovery acid chamber of the second regulating device.
And switching on a direct current power supply of the second regulating device, wherein the direct current power supply is set into a constant current mode.
As shown in fig. 2, the preconditioning liquid injected from the inlet of the 1-stage conditioning chamber of the second conditioning apparatus flows through the 2-stage conditioning chamber, the 3-stage conditioning chamber, … …, the n-1-stage conditioning chamber, and the n-stage conditioning chamber in this order, and then flows out from the outlet of the n-stage conditioning chamber, to obtain a treated liquid.
As shown in fig. 2, water injected from the inlet of the 1-stage acid recovery chamber flows through the 2-stage acid recovery chamber, the 3-stage acid recovery chamber, the … …, the n-1-stage acid recovery chamber and the n-stage acid recovery chamber in sequence, and then flows out from the outlet of the n-stage acid recovery chamber to obtain low acid liquor; the low acid liquid returns to the 1-grade acid recovery chamber of the first regulating device.
The pH value of the treated liquid is 1.5-2.5.
The vanadium-containing pickle liquor comprises: the concentration of V is 1-20 g/L, and the concentration of Fe is less than or equal to 0.1g/L; the initial pH value of the vanadium-containing pickle liquor is-1.0-0.7.
The initial current density of the constant voltage mode is 120-300A/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The initial current density of the constant current mode is 120-300A/m 2 。
Example 1
A method for regulating pH of vanadium-containing pickle liquor. The method in this embodiment comprises the following steps:
and 1, adjusting the pH value of the vanadium-containing pickle liquor. The apparatus of this example was the same as the specific embodiment except that the number of stages n of the conditioning chamber and the acid recovery chamber was 10.
Step 2, method for regulating pH of vanadium-containing pickle liquor
Step 2.1, the process of adjusting the pH of the vanadium-containing pickle liquor is divided into two stages, and the 'devices for adjusting the pH of the vanadium-containing pickle liquor' adopted in the two stages are the same. The device for adjusting the pH value of the vanadium-containing pickle liquor used in the first stage is called a first adjusting device; the device used in the second stage for adjusting the pH of the vanadium-containing pickle liquor is called a second adjusting device.
As shown in fig. 2, the 10-stage conditioning chamber of the first conditioning device is communicated with the 1-stage conditioning chamber of the second conditioning device, and the 10-stage recovery acid chamber of the second conditioning device is communicated with the 1-stage recovery acid chamber of the first conditioning device.
Step 2.2, first stage of adjusting the pH of the vanadium-containing pickle liquor
As shown in fig. 2, sodium sulfate solution is respectively injected into the anode electrode chamber and the cathode electrode chamber of the first regulating device, vanadium-containing pickle liquor is injected from the inlet of the 1-stage regulating chamber of the first regulating device, and water or low acid liquor is injected from the inlet of the 1-stage recovery acid chamber of the first regulating device.
And switching on a direct current power supply of the first regulating device, wherein the direct current power supply is set into a constant voltage mode.
As shown in fig. 2, the vanadium-containing pickle liquor injected from the inlet of the 1-stage regulating chamber of the first regulating device flows through the 2-stage regulating chamber, the 3-stage regulating chamber, … …, the 9-stage regulating chamber and the 10-stage regulating chamber in sequence, and then flows out from the outlet of the 10-stage regulating chamber to obtain the pre-regulating liquid.
As shown in fig. 2, the water injected from the inlet of the 1-stage recovered acid chamber of the first adjusting device flows through the 2-stage recovered acid chamber, the 3-stage recovered acid chamber, … …, the 9-stage recovered acid chamber and the 10-stage recovered acid chamber in this order, and then flows out from the outlet of the 10-stage recovered acid chamber, thereby obtaining the recovered acid liquid.
The pH of the preconditioning fluid was 0.9.
Step 2.3, the second stage of adjusting the pH of the vanadium-containing pickle liquor
As shown in fig. 2, sodium sulfate solution is injected into the anode electrode chamber and the cathode electrode chamber of the second regulating device, respectively, the preconditioning liquid of the first regulating device flows in from the inlet of the 1-stage regulating chamber of the second regulating device, and water flows in from the inlet of the 1-stage recovery acid chamber of the second regulating device.
And switching on a direct current power supply of the second regulating device, wherein the direct current power supply is set into a constant current mode.
As shown in fig. 2, the preconditioning liquid injected from the inlet of the 1-stage conditioning chamber of the second conditioning apparatus flows through the 2-stage conditioning chamber, the 3-stage conditioning chamber, … …, the 9-stage conditioning chamber, and the 10-stage conditioning chamber in this order, and then flows out from the outlet of the 10-stage conditioning chamber, to obtain a treated liquid.
As shown in fig. 2, water injected from the inlet of the 1-stage acid recovery chamber flows through the 2-stage acid recovery chamber, the 3-stage acid recovery chamber, the … … -stage acid recovery chamber, the 9-stage acid recovery chamber and the 10-stage acid recovery chamber in sequence, and then flows out from the outlet of the 10-stage acid recovery chamber to obtain low acid liquid; the low acid liquid returns to the 1-grade acid recovery chamber of the first regulating device.
The pH of the treated solution was 1.5.
The vanadium-containing pickle liquor comprises: the concentration of V is 1g/L, and the concentration of Fe is 0.03g/L; the initial pH value of the vanadium-containing pickle liquor is 0.7.
The initial current density of the constant voltage mode is 120A/m 2 The initial current density of the constant current mode is 120A/m 2 。
Example 2
A method for regulating pH of vanadium-containing pickle liquor. The method in this embodiment comprises the following steps:
and 1, adjusting the pH value of the vanadium-containing pickle liquor. The apparatus of this example was the same as that of embodiment 4 except that the number of stages n of the conditioning chamber and the acid recovery chamber was 100.
Step 2, method for regulating pH of vanadium-containing pickle liquor
Step 2.1, the process of adjusting the pH of the vanadium-containing pickle liquor is divided into two stages, and the 'devices for adjusting the pH of the vanadium-containing pickle liquor' adopted in the two stages are the same. The device for adjusting the pH value of the vanadium-containing pickle liquor used in the first stage is called a first adjusting device; the device used in the second stage for adjusting the pH of the vanadium-containing pickle liquor is called a second adjusting device.
As shown in fig. 2, the 100-stage conditioning chamber of the first conditioning device is communicated with the 1-stage conditioning chamber of the second conditioning device, and the 100-stage recovery acid chamber of the second conditioning device is communicated with the 1-stage recovery acid chamber of the first conditioning device.
Step 2.2, first stage of adjusting the pH of the vanadium-containing pickle liquor
As shown in fig. 2, sodium sulfate solution is respectively injected into the anode electrode chamber and the cathode electrode chamber of the first regulating device, vanadium-containing pickle liquor is injected from the inlet of the 1-stage regulating chamber of the first regulating device, and water or low acid liquor is injected from the inlet of the 1-stage recovery acid chamber of the first regulating device.
And switching on a direct current power supply of the first regulating device, wherein the direct current power supply is set into a constant voltage mode.
As shown in fig. 2, the vanadium-containing pickle liquor injected from the inlet of the 1-stage regulating chamber of the first regulating device flows through the 2-stage regulating chamber, the 3-stage regulating chamber, … …, the 99-stage regulating chamber and the 100-stage regulating chamber in sequence, and then flows out from the outlet of the 100-stage regulating chamber to obtain the pre-regulating liquid.
As shown in fig. 2, the water injected from the inlet of the 1-stage recovered acid chamber of the first adjusting device flows through the 2-stage recovered acid chamber, the 3-stage recovered acid chamber, … …, the 99-stage recovered acid chamber and the 100-stage recovered acid chamber in order, and then flows out from the outlet of the 100-stage recovered acid chamber to obtain the recovered acid liquid.
The pH of the preconditioning fluid was 0.5.
Step 2.3, the second stage of adjusting the pH of the vanadium-containing pickle liquor
As shown in fig. 2, sodium sulfate solution is injected into the anode electrode chamber and the cathode electrode chamber of the second regulating device, respectively, the preconditioning liquid of the first regulating device flows in from the inlet of the 1-stage regulating chamber of the second regulating device, and water flows in from the inlet of the 1-stage recovery acid chamber of the second regulating device.
And switching on a direct current power supply of the second regulating device, wherein the direct current power supply is set into a constant current mode.
As shown in fig. 2, the preconditioning liquid injected from the inlet of the 1-stage conditioning chamber of the second conditioning apparatus flows through the 2-stage conditioning chamber, the 3-stage conditioning chamber, … …, the 99-stage conditioning chamber, and the 100-stage conditioning chamber in this order, and then flows out from the outlet of the 100-stage conditioning chamber, to obtain a treated liquid.
As shown in fig. 2, water injected from the inlet of the 1-stage acid recovery chamber flows through the 2-stage acid recovery chamber, the 3-stage acid recovery chamber, the … …, the 99-stage acid recovery chamber and the 100-stage acid recovery chamber in sequence, and then flows out from the outlet of the n-stage acid recovery chamber to obtain low acid liquid; the low acid liquid returns to the 1-grade acid recovery chamber of the first regulating device.
The pH of the treated solution was 1.8.
The vanadium-containing pickle liquor comprises: the concentration of V is 13g/L, and the concentration of Fe is 0.06g/L; the initial pH value of the vanadium-containing pickle liquor is-0.5.
The initial current density of the constant voltage mode is 200A/m 2 The initial current density of the constant current mode is 150A/m 2 。
Example 3
A method for regulating pH of vanadium-containing pickle liquor. The method in this embodiment comprises the following steps:
and 1, adjusting the pH value of the vanadium-containing pickle liquor. The apparatus of this example was the same as the specific embodiment except that the number of stages n of the conditioning chamber and the acid recovery chamber was 500.
Step 2, method for regulating pH of vanadium-containing pickle liquor
Step 2.1, the process of adjusting the pH of the vanadium-containing pickle liquor is divided into two stages, and the 'devices for adjusting the pH of the vanadium-containing pickle liquor' adopted in the two stages are the same. The device for adjusting the pH value of the vanadium-containing pickle liquor used in the first stage is called a first adjusting device; the device used in the second stage for adjusting the pH of the vanadium-containing pickle liquor is called a second adjusting device.
As shown in fig. 2, the 500-stage conditioning chamber of the first conditioning device is communicated with the 1-stage conditioning chamber of the second conditioning device, and the 500-stage recovery acid chamber of the second conditioning device is communicated with the 1-stage recovery acid chamber of the first conditioning device.
Step 2.2, first stage of adjusting the pH of the vanadium-containing pickle liquor
As shown in fig. 2, sodium sulfate solution is respectively injected into the anode electrode chamber and the cathode electrode chamber of the first regulating device, vanadium-containing pickle liquor is injected from the inlet of the 1-stage regulating chamber of the first regulating device, and water or low acid liquor is injected from the inlet of the 1-stage recovery acid chamber of the first regulating device.
And switching on a direct current power supply of the first regulating device, wherein the direct current power supply is set into a constant voltage mode.
As shown in fig. 2, the vanadium-containing pickle liquor injected from the inlet of the 1-stage regulating chamber of the first regulating device flows through the 2-stage regulating chamber, the 3-stage regulating chamber, the … …, 499-stage regulating chamber and the 500-stage regulating chamber in sequence, and then flows out from the outlet of the 500-stage regulating chamber to obtain the pre-regulating liquid.
As shown in fig. 2, the water injected from the inlet of the 1-stage recovered acid chamber of the first adjusting device flows through the 2-stage recovered acid chamber, the 3-stage recovered acid chamber, the … …, 499-stage recovered acid chamber, and the 500-stage recovered acid chamber in this order, and then flows out from the outlet of the 500-stage recovered acid chamber, thereby obtaining the recovered acid liquid.
The pH of the preconditioning fluid was 1.2.
Step 2.3, the second stage of adjusting the pH of the vanadium-containing pickle liquor
As shown in fig. 2, sodium sulfate solution is injected into the anode electrode chamber and the cathode electrode chamber of the second regulating device, respectively, the preconditioning liquid of the first regulating device flows in from the inlet of the 1-stage regulating chamber of the second regulating device, and water flows in from the inlet of the 1-stage recovery acid chamber of the second regulating device.
And switching on a direct current power supply of the second regulating device, wherein the direct current power supply is set into a constant current mode.
As shown in fig. 2, the preconditioning liquid injected from the inlet of the 1 st stage conditioning chamber of the second conditioning apparatus flows through the 2 nd stage conditioning chamber, the 3 rd stage conditioning chamber, … …, 499 th stage conditioning chamber, and the 500 th stage conditioning chamber in this order, and then flows out from the outlet of the 500 th stage conditioning chamber, to obtain the treated liquid.
As shown in fig. 2, water injected from the inlet of the 1-stage acid recovery chamber flows through the 2-stage acid recovery chamber, the 3-stage acid recovery chamber, the … … -499-stage acid recovery chamber and the 500-stage acid recovery chamber in sequence, and then flows out from the outlet of the 500-stage acid recovery chamber to obtain low acid liquid; the low acid liquid returns to the 1-grade acid recovery chamber of the first regulating device.
The pH of the treated solution was 2.0.
The vanadium-containing pickle liquor comprises: the concentration of V is 6g/L, and the concentration of Fe is 0.04g/L; the initial pH value of the vanadium-containing pickle liquor is 0. The initial current density of the constant voltage mode is 280A/m 2 The initial current density of the constant current mode is 200A/m 2 。
Example 4
A method for regulating pH of vanadium-containing pickle liquor. The method in this embodiment comprises the following steps:
and 1, adjusting the pH value of the vanadium-containing pickle liquor. The apparatus of this example was the same as the specific embodiment except that the number of stages n of the conditioning chamber and the acid recovery chamber was 1000.
Step 2, method for regulating pH of vanadium-containing pickle liquor
Step 2.1, the process of adjusting the pH of the vanadium-containing pickle liquor is divided into two stages, and the 'devices for adjusting the pH of the vanadium-containing pickle liquor' adopted in the two stages are the same. The device for adjusting the pH value of the vanadium-containing pickle liquor used in the first stage is called a first adjusting device; the device used in the second stage for adjusting the pH of the vanadium-containing pickle liquor is called a second adjusting device.
As shown in fig. 2, the 1000-stage conditioning chamber of the first conditioning device is communicated with the 1-stage conditioning chamber of the second conditioning device, and the 1000-stage recovery acid chamber of the second conditioning device is communicated with the 1-stage recovery acid chamber of the first conditioning device.
Step 2.2, first stage of adjusting the pH of the vanadium-containing pickle liquor
As shown in fig. 2, sodium sulfate solution is respectively injected into the anode electrode chamber and the cathode electrode chamber of the first regulating device, vanadium-containing pickle liquor is injected from the inlet of the 1-stage regulating chamber of the first regulating device, and water or low acid liquor is injected from the inlet of the 1-stage recovery acid chamber of the first regulating device.
And switching on a direct current power supply of the first regulating device, wherein the direct current power supply is set into a constant voltage mode.
As shown in fig. 2, the vanadium-containing pickle liquor injected from the inlet of the 1-stage regulating chamber of the first regulating device flows through the 2-stage regulating chamber, the 3-stage regulating chamber, … …, the 999-stage regulating chamber and the 1000-stage regulating chamber in sequence, and then flows out from the outlet of the 1000-stage regulating chamber to obtain the pre-regulating liquid.
As shown in fig. 2, the water injected from the inlet of the 1-stage acid recovery chamber of the first adjusting device flows through the 2-stage acid recovery chamber, the 3-stage acid recovery chamber, … …, the 999-stage acid recovery chamber and the 1000-stage acid recovery chamber in sequence, and then flows out from the outlet of the 1000-stage acid recovery chamber to obtain the acid recovery liquid.
The pH of the preconditioning fluid was 1.0.
Step 2.3, the second stage of adjusting the pH of the vanadium-containing pickle liquor
As shown in fig. 2, sodium sulfate solution is injected into the anode electrode chamber and the cathode electrode chamber of the second regulating device, respectively, the preconditioning liquid of the first regulating device flows in from the inlet of the 1-stage regulating chamber of the second regulating device, and water flows in from the inlet of the 1-stage recovery acid chamber of the second regulating device.
And switching on a direct current power supply of the second regulating device, wherein the direct current power supply is set into a constant current mode.
As shown in fig. 2, the preconditioning liquid injected from the inlet of the 1-stage conditioning chamber of the second conditioning apparatus flows through the 2-stage conditioning chamber, the 3-stage conditioning chamber, … …, 999-stage conditioning chamber, and 1000-stage conditioning chamber in this order, and then flows out from the outlet of the 1000-stage conditioning chamber, to obtain a treated liquid.
As shown in fig. 2, water injected from the inlet of the 1-stage acid recovery chamber flows through the 2-stage acid recovery chamber, the 3-stage acid recovery chamber, the … … -999-stage acid recovery chamber and the 1000-stage acid recovery chamber in sequence, and then flows out from the outlet of the 1000-stage acid recovery chamber to obtain low acid liquid; the low acid liquid returns to the 1-grade acid recovery chamber of the first regulating device.
The pH of the treated solution was 2.5.
The vanadium-containing pickle liquor comprises: the concentration of V is 20g/L, and the concentration of Fe is 0.05g/L; the initial pH value of the vanadium-containing pickle liquor is-1.0.
The initial current density of the constant voltage mode is 300A/m 2 The initial current density of the constant current mode is 300A/m 2 。
Compared with the prior art, the specific embodiment has the following positive effects:
1. after the vanadium-containing acid leaching solution is treated, the pH value can be adjusted to meet the requirement of subsequent purification and enrichment, no neutralizing agent is needed to be added in the treatment process, and no neutralizing slag and neutralizing wastewater are generated, so that zero emission of wastewater and waste slag is realized at the source, source emission reduction can be realized, and the method is environment-friendly.
2. The recycling liquid of the specific embodiment can be recycled, and vanadium loss is avoided. Firstly, after the vanadium-containing pickle liquor is treated by the method in the specific embodiment, the retention rate of vanadium is measured to be more than 95%, and the subsequent purification and enrichment are not affected; second, although about 5% of the vanadium in the pickling solution will pass through the ion exchange membrane and enter the recovered acid solution, the recovered acid solution is recycled for the pickling process, and the low acid solution is returned to the n-stage recovered acid chamber of the first regulating device, so that no vanadium is lost; third, no neutralization slag is generated in the treatment process of the specific embodiment, and vanadium loss caused by the entrainment adsorption of the sediment is avoided.
3. In the existing process of recovering acid by using a diffusion dialysis method, because of concentration difference and flow velocity difference at two ends of an ion exchange membrane, water at a low acid side can permeate into a high acid side to generate a water reverse osmosis phenomenon, so that the concentration of vanadium ions in the pickle liquor is reduced, and the subsequent purification and enrichment are not facilitated. In the process of recovering acid by the electrodialysis method according to the specific embodiment, anions, hydrogen ions and cations with smaller partial hydrated ion radius flow from the regulating chamber to the acid recovering chamber under the drive of electric field force, and water molecules combined with the anions are also brought into the acid recovering chamber from the regulating chamber, so that water loss phenomenon occurs, the concentration of the vanadium-containing pickle liquor in the regulating chamber is increased, the subsequent purification and enrichment are facilitated, and the reverse osmosis of water is avoided.
4. The prior bipolar membrane electrodialysis method is used for adjusting the pH value of the vanadium-containing pickle liquor, and OH is generated by electrolyzing water - Neutralization of the acid in the pickle liquor is realized, and the energy consumption is up to 0.5kWh/mol H + . The energy consumption of the method in the specific embodiment is 0.22 to 0.30kWh/mol H + Compared with the bipolar membrane electrodialysis method, the energy is saved by 40-56%, and the energy consumption can be obviously reduced.
5. When the constant voltage mode is adopted for operation, the current at two sides of the membrane stack is reduced along with the increase of the resistance of the membrane stack, so that the limit current density is not easy to reach in the operation, but the mass transfer rate in the process is slower, and compared with the constant current mode, the operation time is longer; while the constant-current mode can maintain the stable ion rate in the solution for mass transfer, the limiting current density is easy to reach in the operation process, and the surface of the membrane is subject to water dissociation. Therefore, the present embodiment first employs a constant pressure mode for the first stage treatment to recover a substantial portion of the acid. However, when the pH value of the vanadium-containing pickle liquor is regulated to be more than 0.9, the mass transfer rate is greatly reduced due to the fact that the current at the two ends of the membrane stack is reduced along with the increase of the resistance of the membrane stack, and the continuation of the mass transfer is difficult. Therefore, the constant flow mode is adopted to carry out the second stage treatment, so that the pH value of the pre-adjustment liquid is maximally adjusted to 2.5, purification and enrichment can be directly carried out, and the pH adjustment capability is good. The specific embodiment adopts a combination mode of constant voltage and constant current, so that the treatment process is more efficient and stable. The measurement is as follows: the pH value of the vanadium-containing pickle liquor is adjusted to 2.5 at most; the concentration of the recovered acid reaches 1.5 to 2.5mol/L; the recovery rate of the acid reaches 85-95 percent.
Therefore, the specific embodiment has the characteristics of no waste water and waste residue, no vanadium loss, no water reverse osmosis, low energy consumption and good pH value regulating effect, and can effectively replace an alkali neutralization process.
Claims (3)
1. A method for adjusting the pH of a vanadium-containing pickle liquor, which is characterized by comprising the following steps:
step 1, adjusting the device of the acid leaching liquid pH containing vanadium
The device for adjusting the pH of the vanadium-containing pickle liquor comprises: a cathode, an anode, a membrane stack and a direct current power supply;
the cathode is connected with the negative electrode of the direct current power supply, the anode is connected with the positive electrode of the direct current power supply, and the cathode and the anode are correspondingly arranged on the right side and the left side of the membrane stack;
the membrane stack sequentially comprises a 1 st cation exchange membrane, a 1 st anion exchange membrane, a 2 nd cation exchange membrane, a 2 nd anion exchange membrane, a 3 rd cation exchange membrane, a … …, an nth cation exchange membrane, an nth anion exchange membrane and an n+1th cation exchange membrane from anode to cathode;
n is a positive integer of 10-1000;
from the anode to cathode direction: the gap between the anode and the 1 st cation exchange membrane forms an anode electrode chamber, the gap between the 1 st cation exchange membrane and the 1 st anion exchange membrane forms a 1-stage regulating chamber, the gap between the 1 st anion exchange membrane and the 2 nd cation exchange membrane forms an n-stage recovered acid chamber, the gap between the 2 nd cation exchange membrane and the 2 nd anion exchange membrane forms a 2-stage recovered acid chamber, the gap between the 2 nd anion exchange membrane and the 3 rd cation exchange membrane forms an n-1 stage recovered acid chamber, … …, and so on, the gap between the n-1 st cation exchange membrane and the n-1 st anion exchange membrane forms an n-1 stage recovered acid chamber, the gap between the n-1 st anion exchange membrane and the n-th cation exchange membrane forms an n-stage recovered acid chamber, the gap between the n-th anion exchange membrane and the n+1 th cation exchange membrane forms a cathode electrode chamber;
the 1-level adjusting chamber, the 2-level adjusting chamber, the 3-level adjusting chamber, the … …, the n-1-level adjusting chamber and the n-level adjusting chamber are sequentially communicated; the 1-level acid recovery chamber, the 2-level acid recovery chamber, the 3-level acid recovery chamber, the … …, the n-1-level acid recovery chamber and the n-level acid recovery chamber are sequentially communicated;
forming a serial loop of the anode electrode chamber, the 1-stage regulating chamber, the n-stage acid recovering chamber, the 2-stage regulating chamber, the n-1-stage acid recovering chamber, … …, the n-1-stage regulating chamber, the 2-stage acid recovering chamber, the n-stage regulating chamber, the 1-stage acid recovering chamber, the cathode electrode chamber and the direct current power supply in a working state to obtain a device for regulating the pH value of the vanadium-containing pickle liquor;
step 2, method for regulating pH of vanadium-containing pickle liquor
Step 2.1, the process of adjusting the pH of the vanadium-containing pickle liquor is divided into two stages, wherein the 'devices for adjusting the pH of the vanadium-containing pickle liquor' adopted in the two stages are the same, and the device for adjusting the pH of the vanadium-containing pickle liquor used in the first stage is called a first adjusting device; the device for adjusting the pH value of the vanadium-containing pickle liquor used in the second stage is called a second adjusting device;
the n-level adjusting chamber of the first adjusting device is communicated with the 1-level adjusting chamber of the second adjusting device, and the n-level acid recycling chamber of the second adjusting device is communicated with the 1-level acid recycling chamber of the first adjusting device;
step 2.2, first stage of adjusting the pH of the vanadium-containing pickle liquor
Sodium sulfate solution is respectively injected into an anode electrode chamber and a cathode electrode chamber of the first regulating device, vanadium-containing pickle liquor is injected from a 1-stage regulating chamber inlet of the first regulating device, and water or low acid liquor is injected from a 1-stage recovery acid chamber inlet of the first regulating device;
switching on a direct current power supply of the first regulating device, wherein the direct current power supply is set to be in a constant voltage mode;
the vanadium-containing pickle liquor injected from the inlet of the 1-stage regulating chamber of the first regulating device flows through the 2-stage regulating chamber, the 3-stage regulating chamber, the … …, the n-1-stage regulating chamber and the n-stage regulating chamber in sequence, and then flows out from the outlet of the n-stage regulating chamber to obtain pre-regulating liquor;
the water injected from the inlet of the 1-grade acid recycling chamber of the first regulating device flows through the 2-grade acid recycling chamber, the 3-grade acid recycling chamber, the … …, the n-1 grade acid recycling chamber and the n-grade acid recycling chamber in sequence, and then flows out from the outlet of the n-grade acid recycling chamber to obtain acid recycling liquid;
the pH value of the pre-regulating liquid is 0.5-1.2;
step 2.3, the second stage of adjusting the pH of the vanadium-containing pickle liquor
Injecting sodium sulfate solution into an anode electrode chamber and a cathode electrode chamber of the second regulating device respectively, wherein the preconditioning liquid of the first regulating device flows in from a 1-stage regulating chamber inlet of the second regulating device, and water flows in from a 1-stage acid recovery chamber inlet of the second regulating device;
switching on a direct current power supply of the second regulating device, wherein the direct current power supply is set to be in a constant current mode;
the pre-conditioning liquid injected from the inlet of the 1-stage conditioning chamber of the second conditioning device flows through the 2-stage conditioning chamber, the 3-stage conditioning chamber, the … …, the n-1-stage conditioning chamber and the n-stage conditioning chamber in sequence, and then flows out from the outlet of the n-stage conditioning chamber to obtain treated liquid;
the water injected from the inlet of the 1-stage acid recovery chamber flows through the 2-stage acid recovery chamber, the 3-stage acid recovery chamber, … …, the n-1-stage acid recovery chamber and the n-stage acid recovery chamber in sequence, and then flows out from the outlet of the n-stage acid recovery chamber to obtain low acid liquor; the low acid liquid returns to a 1-grade acid recovery chamber of the first regulating device;
the pH value of the treated liquid is 1.5-2.5.
2. The method for adjusting the pH of a vanadium-containing pickling solution according to claim 1, characterized in that the vanadium-containing pickling solution: the concentration of V is 1-20 g/L, and the concentration of Fe is less than or equal to 0.1g/L; the initial pH value of the vanadium-containing pickle liquor is-1.0-0.7.
3. The method for regulating the pH of a vanadium-containing pickle liquor according to claim 1, wherein the initial current density in the constant voltage mode is 120-300A/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The initial current density of the constant current mode is 120-300A/m 2 。
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| CN104694748A (en) * | 2015-02-04 | 2015-06-10 | 河北钢铁股份有限公司承德分公司 | Method for removing sodium or potassium by electrodialysis in vanadium-containing solution |
| CN104805466A (en) * | 2015-04-09 | 2015-07-29 | 嘉兴学院 | Method for preparing 2-nitro-4-methylsulfonylbenzoic acid through indirect electro-oxidation |
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| CN110510713A (en) * | 2019-08-26 | 2019-11-29 | 北京廷润膜技术开发股份有限公司 | A kind of electrodialysis plant and the method using electrodialysis plant separating acid and salt |
| CN113023844A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院过程工程研究所 | Method for treating salt-containing fermentation waste liquid by combining diffusion dialysis with electrodialysis |
| CN217264980U (en) * | 2021-12-27 | 2022-08-23 | 杭州水处理技术研究开发中心有限公司 | Deacidification device of pickling spent acid |
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