Device and method for synchronously performing electrolytic purification treatment and electrolytic hydrogen production on mine water
By using a four-stage anodic electrolytic flocculation tank and a multi-stage electrolysis reaction, the problems of electrode passivation and corrosion in mine water treatment have been solved, achieving deep purification of mine water and simultaneous electrolytic hydrogen production, thus improving the purification effect and resource utilization efficiency.
Patent Information
- Application Number
- CN202512016053.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-30
- Publication Date
- 2026-03-20
AI Technical Summary
Traditional electrocoagulation technology suffers from problems such as electrode passivation, high corrosion rate, short lifespan, and high operation and maintenance costs when treating mine water. Furthermore, the purified water quality cannot meet the requirements for electrolytic hydrogen production, resulting in high energy consumption, low energy conversion efficiency, and limited utilization of mine water resources.
A four-stage anodic electrolytic flocculation tank is adopted to gradually remove pollutants from mine water through multi-stage continuous electrolysis and electrocoagulation reaction. By combining soluble metal composite anodes and stable metal substrates, and optimizing electrode materials and diaphragm design, the contact area between electrolyte and electrode is increased, thereby achieving deep purification of mine water and simultaneous electrolytic hydrogen production.
It significantly improves the purification effect of mine water, reduces the content of suspended solids and heavy metal ions, extends electrode life, reduces equipment failures, increases hydrogen production and energy conversion efficiency, and achieves efficient and comprehensive utilization of resources.
Smart Images
Figure CN121700463A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of mine water purification and hydrogen production technology, specifically relating to an apparatus and method for purifying mine water by electrolysis and simultaneously producing hydrogen by electrolysis. Background Technology
[0002] Mine water is a by-product of coal mining, characterized by high turbidity (suspended solids concentration often exceeding 5000 mg / L) and high hardness (Ca). 2+ Mg 2+ It is characterized by a total content > 300 mg / L and the presence of complex pollutants such as oil and heavy metals.
[0003] Traditional electrocoagulation technology faces numerous challenges in treating mine water. When using soluble anodes such as iron and aluminum, the electrode surface is easily passivated by particulate matter, resulting in large fluctuations in the metal dissolution rate (fluctuation rate > 30%). In mine water with high Cl- concentrations (> 1000 ppm), pure aluminum / iron electrodes exhibit high corrosion rates and a lifespan of < 200 hours, leading to frequent electrode replacements and high maintenance costs. Furthermore, water treated with traditional electrocoagulation technology still contains high concentrations of ions (such as Cl-). - SO 2- The residual colloids cannot meet the stringent requirements of low conductivity (<0.1μS / cm) and low impurity content for electrolytic hydrogen production. Direct electrolysis of this treated mine water will cause electrode scaling (hydrogen evolution active area decay rate >60% / 100h) and membrane fouling (operating pressure difference increases by 2-3 times).
[0004] Currently, the utilization of mine water resources is limited, mostly confined to industrial reuse (reuse rate less than 30%) or simple treatment followed by discharge, failing to achieve high-value-added transformation. Although existing technologies can reduce turbidity through sedimentation and filtration, they are difficult to remove hardness ions and trace pollutants simultaneously, resulting in high treatment costs (cost per ton of water > 5 yuan), and the purified mine water still cannot be directly used for electrolytic hydrogen production.
[0005] The global hydrogen electrolysis industry is highly dependent on high-purity water (9L of water is needed to produce 1kg of hydrogen). my country's annual mine water discharge exceeds 8 billion tons. Converting mine water into a hydrogen production source could significantly reduce water consumption costs. However, currently, mine water treatment and hydrogen electrolysis are mostly implemented in a series of independent systems. The electrocoagulation stage requires 1.5-2.5V to drive the dissolution of the soluble anode (such as aluminum or iron), and the subsequent hydrogen electrolysis requires an additional 2.0-2.4V. The overall energy consumption is >5.0kWh / m³, and the energy conversion efficiency of both stages is less than 40%. Summary of the Invention
[0006] The technical problem to be solved by this invention is to address the shortcomings of the prior art by providing an apparatus and method for electrolytic purification of mine water and simultaneous electrolytic hydrogen production. This invention employs a four-stage anodic electrolytic flocculation tank, using multi-stage continuous electrolysis and electrocoagulation reactions to progressively and thoroughly remove pollutants from mine water. Compared to traditional single-stage treatment methods, the purification effect is significantly improved, more effectively reducing the content of suspended solids, heavy metal ions, and other impurities in mine water, resulting in better water quality after treatment.
[0007] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is: a device for purifying and simultaneously producing hydrogen from mine water by electrolysis, characterized in that it includes four stages of anode electrolysis flocculation tanks arranged in series horizontally, each stage of anode electrolysis flocculation tank having two plate-shaped anodes symmetrically installed, and cathode electrolysis water production hydrogen production reaction tanks symmetrically arranged on both sides of each stage of anode electrolysis flocculation tank; a diaphragm is provided between each stage of anode electrolysis flocculation tank and its corresponding cathode electrolysis water production hydrogen production reaction tank; a disc-shaped microchannel is provided in the cathode electrolysis water production hydrogen production reaction tank, and a plate-shaped cathode is installed between the disc-shaped microchannel and the diaphragm; a water outlet is provided between adjacent stages of anode electrolysis flocculation tanks, and an electrolyte inlet and a gas-liquid outlet are provided on the cathode electrolysis water production hydrogen production reaction tank.
[0008] The above-mentioned apparatus for purifying and simultaneously producing hydrogen from mine water by electrolysis is characterized in that the four-stage anode electrolysis flocculation tank includes a stage I anode electrolysis flocculation tank, a stage II anode electrolysis flocculation tank, a stage III anode electrolysis flocculation tank, and a stage IV anode electrolysis flocculation tank; the stage I anode electrolysis flocculation tank is provided with a mine water inlet, and the stage IV anode electrolysis flocculation tank is provided with a clean water outlet.
[0009] The aforementioned apparatus for purifying and simultaneously electrolyzing mine water to produce hydrogen is characterized by further comprising a clean water storage tank, an electrolyte preparation tank, a gas-liquid separator, and a power supply; the clean water outlet is connected to the clean water storage tank via a pipeline; the electrolyte inlet is connected to the electrolyte preparation tank via a pipeline; the gas-liquid outlet is connected to the gas-liquid separator via a pipeline; the positive terminal of the power supply is electrically connected to the plate anode, and the negative terminal of the power supply is electrically connected to the plate cathode; the clean water storage tank is connected to the electrolyte preparation tank via a pipeline; and the liquid outlet of the gas-liquid separator is connected to the electrolyte preparation tank via a pipeline.
[0010] The above-mentioned apparatus for purifying and simultaneously producing hydrogen from mine water by electrolysis is characterized in that the diaphragm includes an ion membrane located in the middle layer, stainless steel support mesh disposed on both sides of the ion membrane, and nylon filter cloth disposed between the ion membrane and the stainless steel support mesh.
[0011] The aforementioned apparatus for purifying and simultaneously producing hydrogen from mine water by electrolysis is characterized in that: the plate anode in the first-stage anode electrolysis flocculation tank is made of pure aluminum or pure iron; the plate anode in the second-stage anode electrolysis flocculation tank is a soluble metal composite material based on a stable metal; the plate anode in the third-stage anode electrolysis flocculation tank is a soluble metal composite material based on a stable metal, or stainless steel, wherein the soluble metal is aluminum or iron, and the stable metal is titanium, nickel, or stainless steel; and the plate anode in the fourth-stage anode electrolysis flocculation tank is made of titanium or nickel.
[0012] Furthermore, the present invention provides a method for electrolytic purification of mine water and simultaneous electrolytic hydrogen production using the above-mentioned apparatus, characterized by comprising: introducing mine water into a primary anode electrolytic flocculation tank through a mine water inlet, and introducing the electrolyte in the electrolyte preparation tank into each cathode electrolytic water production reaction tank through an electrolyte inlet; turning on the power supply, the mine water is electrolyzed in the primary anode electrolytic flocculation tank, and the supernatant after removing contaminants flows into a secondary anode electrolytic flocculation tank through a water outlet, and after further electrolysis in the secondary anode electrolytic flocculation tank, the supernatant after removing residual contaminants flows into a secondary anode electrolytic flocculation tank through a water outlet. In the Stage III anode electrolysis flocculation tank, the supernatant, after further deep treatment by electrolysis, flows into the Stage IV anode electrolysis flocculation tank through the water outlet. After further purification by electrolysis in the Stage IV anode electrolysis flocculation tank, the supernatant flows into the clear water storage tank through the clear water outlet. During electrolysis, the mixture of hydrogen and electrolyte produced by the reaction in each cathode water electrolysis hydrogen production reaction tank enters the gas-liquid separator through the gas-liquid outlet. Gas-liquid separation is carried out using gravity sedimentation and circulating water cooling technology. The separated hydrogen is discharged and collected from the top, and the separated liquid is returned to the electrolyte preparation tank.
[0013] The above method is characterized in that the electrolyte is a potassium hydroxide solution with a mass concentration of 20% to 30%, the temperature of the electrolyte is 20℃ to 30℃, the electrolysis voltage is 5V to 60V, the current density is 5mA / cm2 to 25mA / cm2, and the flow rate of the electrolyte in the disc-shaped microchannel is controlled to be 0.1m / s to 0.3m / s during the electrolysis process.
[0014] The above method is characterized in that the electrolysis time in the stage I anodic electrolytic flocculation tank is 10 min to 30 min, the electrolysis time in the stage II anodic electrolytic flocculation tank is 10 min to 15 min, the electrolysis time in the stage III anodic electrolytic flocculation tank is 6 min to 12 min, and the electrolysis time in the stage IV anodic electrolytic flocculation tank is 5 min to 10 min.
[0015] The above method is characterized in that the device is stabilized before the mine water is purified by electrolysis and hydrogen is produced by electrolysis.
[0016] The above method is characterized in that the stabilization treatment method includes: firstly, introducing mine water into the first-stage anodic electrolytic flocculation tank and the second-stage anodic electrolytic flocculation tank, and adding clean water into the third-stage anodic electrolytic flocculation tank and the fourth-stage anodic electrolytic flocculation tank; then introducing the electrolyte in the electrolyte preparation tank into each cathode electrolytic water production hydrogen reaction tank, connecting the power supply and starting the machine, and continuously stabilizing the water flow circulation for 2h to 6h.
[0017] Compared with the prior art, the present invention has the following advantages:
[0018] 1. This invention purifies mine water using a four-stage anodic electrolytic flocculation tank arranged in horizontal series. The purification is achieved primarily through three mechanisms. First, electrocoagulation. Under the influence of an electric field, the anode (such as a soluble anode like iron or aluminum) loses electrons to form metal cations, such as Fe. 2+ Al 3+ They react with OH in the solution - First, it combines to form highly active flocculant groups, such as Fe(OH)₂ and Al(OH)₃, which can remove suspended solids from water; second, it involves electrochemical action. The OH groups produced during electrolysis... - These ions can combine with heavy metal ions (such as copper, nickel, zinc, iron, and manganese) in mine water to form insoluble hydroxide precipitates. For example, Cu... 2+ +2OH - =Cu(OH)₂↓. For some highly toxic high-valence heavy metal ions (such as Cr), 6+ The reducing agents such as ferrous iron produced by electrocoagulation can reduce it to lower valence ions, which then react with OH-. - The reaction produces a precipitate, which is then separated and removed. For example, Cr2O7. 2- +6e - +14H + =2Cr 3+ +7H2O, then Cr 3+ +3OH - =Cr(OH)3↓. The hardness of mine water is mainly determined by Ca. 2+ Mg 2+ Plasma-induced. The hydroxide flocculant generated during electrocoagulation can react with Ca through ion exchange, adsorption, and other processes. 2+ Mg 2 + A reaction occurs, removing the pollutants from the water and thus reducing the hardness of the mine water. The anodic process involves electrolytic oxidation, which can be divided into direct oxidation and indirect oxidation. Direct oxidation occurs when pollutants directly lose electrons at the anode; indirect oxidation utilizes anions with lower electrode potentials in the solution (such as OH-). - Cl -At the anode, electrons are lost, generating new strong oxidizing agents (such as ·OH, Cl2, etc.). These active substances can oxidize and decompose some organic pollutants in mine water, such as oxidizing organic matter into CO2 and H2O. Third, electrolytic flotation. For oil pollutants such as emulsified oil in mine water, the electrocoagulation equipment uses a strong electric field to cause charged emulsified oil particles to migrate directionally, neutralizing the charge on the electrode plate surface and achieving destabilized polymerization. Simultaneously, the flocculant groups generated by electrolysis can destroy the double-layer structure of the oil droplets, achieving demulsification. Afterwards, the microbubbles generated by synergistic electrolysis remove the demulsified oil droplets by flotation.
[0019] 2. This invention utilizes a four-stage anode electrolytic flocculation tank arranged horizontally in series. The first-stage anode electrolytic flocculation tank preferably uses pure aluminum or iron as the anode, generating electrocoagulation through metal dissolution. Aluminum and iron electrodes are inexpensive and consumed quickly, rapidly removing suspended solids, heavy metal ions, and other pollutants from the water. The second-stage anode electrolytic flocculation tank preferably uses soluble metal composite stable metals such as Fe / Al-Ti, Fe / Al-Ni, and Fe / Al-SS as the anode. Under the influence of an electric field, the soluble metal dissolves to generate metal ions, which are used in the electrocoagulation reaction to remove suspended solids, heavy metal ions, and other pollutants from the mine water. The stable metal substrate prevents... Soluble metals are rapidly corroded, preventing the electrode surface from being passivated by particulate matter in the mine water. Simultaneously, this ensures the stability of the corresponding cathodic hydrogen evolution reaction. The third-stage anodic electrolytic flocculation tank preferably uses stainless steel as the anode, as this electrode has good stability and is inexpensive. It removes pollutants from the water through electrochemical oxidation and electrolytic oxygen bubble flotation, while ensuring the high stability of the corresponding cathodic hydrogen evolution reaction. The fourth-stage electrolytic tank preferably uses titanium or nickel as the anode, which has good tolerance, stability, and electrochemical reactivity. It can further treat residual water pollutants and ensure the high activity and stability of the cathodic hydrogen evolution reaction. Using a four-stage anodic electrolytic flocculation tank, through multi-stage continuous electrolysis and electroflocculation reactions, pollutants in the mine water are gradually and thoroughly removed. Compared to traditional single-stage treatment methods, the purification effect is significantly improved, more effectively reducing the content of suspended solids, heavy metal ions, and other impurities in the mine water, resulting in better treated water quality.
[0020] 3. The electrode materials used in this invention are all industrially available materials, resulting in lower electrode costs. In particular, the anode in the Stage II anode electrolytic flocculation tank preferably employs a unique design combining a soluble metal and a stable metal substrate. This ensures a stable and continuous supply of metal ions required for the electrocoagulation reaction, while the stable metal substrate effectively prevents excessively rapid anode corrosion and electrode passivation, significantly extending electrode lifespan and reducing equipment maintenance frequency and costs.
[0021] 4. The present invention preferably features a five-layer diaphragm design. The middle ion membrane is responsible for electron transport, the two nylon filter cloths on both sides block particulate matter from damaging the ion membrane, and the outermost stainless steel support mesh provides structural support. The three layers work together to ensure the stability of the electrolysis process and the long-term reliable operation of the equipment, and reduce equipment failures caused by diaphragm damage.
[0022] 5. The cathode electrolysis water hydrogen production reaction cell of the present invention is provided with a disk-shaped microchannel, which greatly increases the contact area between the electrolyte and the electrode, optimizes the mass transfer and electric field distribution conditions of the electrolysis reaction, thereby improving the hydrogen production efficiency and yield. Compared with traditional hydrogen production devices, more hydrogen can be produced with the same energy consumption.
[0023] 6. This invention innovatively combines the electrolytic flocculation treatment of mine water with the electrolytic hydrogen production process, producing hydrogen while purifying mine water, realizing the efficient and comprehensive utilization of resources, improving the overall economic benefits of the process, and providing a new and effective approach for mine water resource treatment and clean energy production.
[0024] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description
[0025] Figure 1 This is a schematic diagram of the structure of the device of the present invention.
[0026] Figure 2 This is a schematic diagram showing the flow direction of mine water in the four-stage anode electrolytic flocculation tank of the present invention.
[0027] Explanation of reference numerals in the attached figures:
[0028] 1—Level I anode electrolytic flocculation tank; 2—Level II anode electrolytic flocculation tank; 3—Level III anode electrolytic flocculation tank; 4—Level IV anode electrolytic flocculation tank; 5—Mine water inlet; 6—Clear water outlet; 7—Plate anode; 8—Cathode electrolysis water to hydrogen production reaction tank; 9—Diaphragm; 91—Ion exchange membrane; 92—Nylon filter cloth; 93—Stainless steel support mesh; 10—Disc microchannel; 11—Plate cathode; 13—Electrolyte inlet; 14—Gas-liquid outlet; 15—Clear water storage tank; 16—Electrolyte preparation tank; 17—Gas-liquid separator; 18—Power supply. Detailed Implementation
[0029] Example 1
[0030] like Figure 1As shown, the apparatus for purifying and simultaneously producing hydrogen from mine water by electrolysis in this embodiment includes four horizontally connected anode electrolysis flocculation tanks. Each anode electrolysis flocculation tank contains two symmetrically installed plate-shaped anodes 7. Each anode electrolysis flocculation tank has symmetrically arranged cathode electrolysis water-to-hydrogen reaction tanks 8 on both sides. A diaphragm 9 is provided between each anode electrolysis flocculation tank and its corresponding cathode electrolysis water-to-hydrogen reaction tank 8. The cathode electrolysis water-to-hydrogen reaction tank 8 contains a disc-shaped microchannel 10, which increases the contact area between the electrolyte and the electrode, optimizing the electrolysis reaction conditions. A plate-shaped cathode 11 is installed between the disc-shaped microchannel 10 and the diaphragm 9. The cathode material is nickel or nickel-molybdenum composite material. A water outlet is provided between adjacent anode electrolysis flocculation tanks to allow the supernatant after electrolysis to flow sequentially into the next electrolysis tank. The cathode electrolysis water-to-hydrogen reaction tank 8 is provided with an electrolyte inlet 13 and a gas-liquid outlet 14.
[0031] In this embodiment, pollutants in mine water are gradually removed through multi-stage continuous electrolysis and electrocoagulation reaction. Compared with the traditional single-stage treatment method, the purification effect is significantly improved, and the content of impurities such as suspended solids and heavy metal ions in mine water can be reduced more effectively, resulting in better water quality after treatment.
[0032] In this embodiment, the four-stage anodic electrolytic flocculation tank includes a stage I anodic electrolytic flocculation tank 1, a stage II anodic electrolytic flocculation tank 2, a stage III anodic electrolytic flocculation tank 3, and a stage IV anodic electrolytic flocculation tank 4; the stage I anodic electrolytic flocculation tank 1 is provided with a mine water inlet 5, and the stage IV anodic electrolytic flocculation tank 4 is provided with a clean water outlet 6.
[0033] In this embodiment, the system also includes a clean water storage tank 15, an electrolyte preparation tank 16, a gas-liquid separator 17, and a power supply 18. The clean water outlet 6 is connected to the clean water storage tank 15 via a pipeline. The electrolyte inlet 13 is connected to the electrolyte preparation tank 16 via a pipeline. The gas-liquid outlet 14 is connected to the gas-liquid separator 17 via a pipeline. The positive terminal of the power supply 18 is electrically connected to the plate anode 7, and the negative terminal of the power supply 18 is electrically connected to the plate cathode 11. The clean water storage tank 15 is connected to the electrolyte preparation tank 16 via a pipeline. The liquid outlet of the gas-liquid separator 17 is connected to the electrolyte preparation tank 16 via a pipeline.
[0034] In this embodiment, the diaphragm 9 includes an ion membrane 91 located in the middle layer, which is mainly used for electron transport; stainless steel support mesh 93 disposed on both sides of the ion membrane 91, which plays a role in structural support; and nylon filter cloth 92 disposed between the ion membrane 91 and the stainless steel support mesh 93, which can effectively block particulate matter from scouring the ion membrane.
[0035] In this embodiment, the plate anode in the first-stage anodic electrolytic flocculation tank 1 is made of pure aluminum or pure iron; the plate anode in the second-stage anodic electrolytic flocculation tank 2 is a soluble metal composite material based on a stable metal, such as Fe / Al-Ti, Fe / Al-Ni, or Fe / Al-SS; the plate anode in the third-stage anodic electrolytic flocculation tank 3 is made of stainless steel, or a soluble metal composite material based on a stable metal, such as Fe / Al-Ti, Fe / Al-Ni, or Fe / Al-SS, wherein the soluble metal is aluminum or iron, and the stable metal is titanium, nickel, or stainless steel; the plate anode in the fourth-stage anodic electrolytic flocculation tank 4 is made of titanium or nickel.
[0036] Example 2
[0037] This embodiment uses the apparatus described in Example 1 to perform electrolytic purification of mine water and simultaneous electrolytic hydrogen production. The specific method includes:
[0038] Step 1, Stabilization Treatment: First, introduce mine water into the Level I anode electrolysis flocculation tank 1 and Level II anode electrolysis flocculation tank 2, and add clean water into the Level III anode electrolysis flocculation tank 3 and Level IV anode electrolysis flocculation tank 4; then introduce the electrolyte in the electrolyte preparation tank 16 into each cathode electrolysis water production hydrogen reaction tank 8, turn on the power, and allow the water circulation to remain stable for 4 hours before proceeding to the next step.
[0039] Step 2: Mine water is introduced into the first-stage anode electrolytic flocculation tank 1 through the mine water inlet 5, and the electrolyte in the electrolyte preparation tank 16 is introduced into each cathode electrolytic water-to-hydrogen reaction tank 8 through the electrolyte inlet 13; the power supply 18 is turned on, and the mine water is electrolyzed in the first-stage anode electrolytic flocculation tank 1. The supernatant after removing pollutants flows into the second-stage anode electrolytic flocculation tank 2 through the water outlet. After electrolysis in the second-stage anode electrolytic flocculation tank 2, the supernatant after further removing residual pollutants flows into the third-stage anode electrolytic flocculation tank 3 through the water outlet. After electrolysis in the third-stage anode electrolytic flocculation tank 3, the supernatant after further deep treatment flows into the fourth-stage anode electrolytic flocculation tank 4 through the water outlet. After electrolysis in the fourth-stage anode electrolytic flocculation tank 4, the deeply purified supernatant flows into the clean water storage tank 15 through the clean water outlet 6; the flow direction of the mine water in the fourth-stage anode electrolytic flocculation tank is as follows. Figure 2 As shown; during the electrolysis process, the mixture of hydrogen gas and electrolyte after the reaction in each cathode water electrolysis hydrogen production reaction cell 8 enters the gas-liquid separator 17 through the gas-liquid outlet 14. Gas-liquid separation is carried out by gravity sedimentation and circulating water cooling technology. The separated hydrogen gas is discharged from the top and collected, and the separated liquid is returned to the electrolyte preparation cell 16.
[0040] The parameter settings are as follows:
[0041] 1) Anode materials: Grade I: Pure aluminum plate; Grade II: Fe / Al-Ti composite plate (70% titanium substrate); Grade III: 316L stainless steel; Grade IV: Pure titanium plate;
[0042] 2) Cathode: Nickel-molybdenum alloy plate (molybdenum content 5%);
[0043] 3) Power-on parameters: Voltage: 25V; Current density: 15mA / cm2; Cycle time: 4 hours;
[0044] 4) Treatment time for each level: Level I: 25 minutes (initial SS = 500 mg / L); Level II: 12 minutes; Level III: 10 minutes; Level IV: 8 minutes;
[0045] 5) Electrolyte preparation: KOH concentration: 25%; temperature: 25℃; flow rate: 0.1m / s.
[0046] Example 3
[0047] The mine water was purified by electrolysis and simultaneously electrolyzed to produce hydrogen according to the method in Example 2, with the following parameter settings:
[0048] 1) Anode materials: Grade I: Pure iron plate; Grade II: Fe / Al-Ni composite plate (60% nickel substrate); Grade III: Fe / Al-Ni (same as Grade II); Grade IV: Pure nickel plate;
[0049] 2) Cathode: Nickel plate (99.9% purity);
[0050] 3) Power-on parameters: Voltage: 40V; Current density: 20mA / cm2; Cycle time: 5 hours;
[0051] 4) Processing time for each stage: Stage I: 30 minutes (initial Cu2) + =50mg / L); Level II: 15 minutes; Level III: 12 minutes; Level IV: 10 minutes;
[0052] 5) Electrolyte preparation: KOH concentration: 28%; temperature: 28℃; flow rate: 0.25m / s.
[0053] Example 4
[0054] The mine water was purified by electrolysis and simultaneously electrolyzed to produce hydrogen according to the method in Example 2, with the following parameter settings:
[0055] 1) Anode materials: Grade I: Pure aluminum plate; Grade II: Fe / Al-SS composite plate (50% stainless steel substrate); Grade III: 304 stainless steel; Grade IV: Pure titanium plate;
[0056] 2) Cathode: Nickel-molybdenum alloy plate (8% molybdenum content);
[0057] 3) Power-on parameters: Voltage: 5V; Current density: 5mA / cm2; Cycle time: 2 hours;
[0058] 4) Treatment time for each level: Level I: 10 minutes (initial SS = 150 mg / L); Level II: 10 minutes; Level III: 6 minutes; Level IV: 5 minutes;
[0059] 5) Electrolyte preparation: KOH concentration: 20%; temperature: 20℃; flow rate: 0.15m / s.
[0060] Example 5
[0061] The mine water was purified by electrolysis and simultaneously electrolyzed to produce hydrogen according to the method in Example 2, with the following parameter settings:
[0062] 1) Anode materials: Grade I: Pure iron plate; Grade II: Fe / Al-Ti composite plate (titanium substrate accounts for 40%); Grade III: Fe / Al-Ti (same as Grade II); Grade IV: Pure nickel plate;
[0063] 2) Cathode: Nickel-molybdenum alloy plate (molybdenum content 10%);
[0064] 3) Power-on parameters: Voltage: 60V; Current density: 25mA / cm2; Cycle time: 6 hours;
[0065] 4) Treatment times for each stage: Stage I: 30 minutes (initial Cl- = 1200 mg / L); Stage II: 15 minutes; Stage III: 12 minutes; Stage IV: 10 minutes;
[0066] 5) Electrolyte preparation: KOH concentration: 30%; temperature: 30℃; flow rate: 0.3m / s.
[0067] Example 6
[0068] The mine water was purified by electrolysis and simultaneously electrolyzed to produce hydrogen according to the method in Example 2, with the following parameter settings:
[0069] 1) Anode materials: Grade I: Pure aluminum plate; Grade II: Fe / Al-Ni composite plate (nickel substrate content 35%); Grade III: 316L stainless steel; Grade IV: Pure titanium plate;
[0070] 2) Cathode: Nickel plate (99.5% purity);
[0071] 3) Power-on parameters: Voltage: 35V; Current density: 18mA / cm2; Cycle time: 5 hours;
[0072] 4) Treatment time for each stage: Stage I: 25 minutes (initial SS = 350 mg / L, Mn2) +=15mg / L); Level II: 12 minutes; Level III: 10 minutes; Level IV: 8 minutes;
[0073] 5) Electrolyte preparation: KOH concentration: 26%; temperature: 26℃; flow rate: 0.2m / s.
[0074] Table 1. Processing results of each embodiment
[0075]
[0076] As can be seen from Table 1, the device and method of the present invention can effectively purify mine water and produce hydrogen gas at the same time as purifying mine water, realizing efficient and comprehensive utilization of resources, improving the economic benefits of the overall process, and providing a new and effective way for mine water resource treatment and clean energy production.
[0077] The above description is merely a preferred embodiment of the present invention and does not constitute any limitation on the present invention. Any simple modifications, alterations, or equivalent structural changes made to the above embodiments based on the technical essence of the invention shall still fall within the protection scope of the present invention.
Claims
1. An apparatus for purifying mine water by electrolysis and simultaneously producing hydrogen by electrolysis, characterized in that, The system includes four-stage anode electrolysis flocculation tanks arranged in series horizontally. Each stage of the anode electrolysis flocculation tank has two plate-shaped anodes (7) symmetrically installed. Each stage of the anode electrolysis flocculation tank has a cathode electrolysis water production hydrogen production reactor (8) symmetrically arranged on both sides. A diaphragm (9) is provided between each stage of the anode electrolysis flocculation tank and the corresponding cathode electrolysis water production hydrogen production reactor (8). The cathode electrolysis water production hydrogen production reactor (8) has a disc-shaped microchannel (10) installed inside. A plate-shaped cathode (11) is installed between the disc-shaped microchannel (10) and the diaphragm (9). A water outlet is opened between two adjacent stages of the anode electrolysis flocculation tank. The cathode electrolysis water production hydrogen production reactor (8) has an electrolyte inlet (13) and a gas-liquid outlet (14).
2. The apparatus for electrolytic purification of mine water and simultaneous electrolytic hydrogen production according to claim 1, characterized in that, The four-stage anode electrolytic flocculation tank includes a stage I anode electrolytic flocculation tank (1), a stage II anode electrolytic flocculation tank (2), a stage III anode electrolytic flocculation tank (3), and a stage IV anode electrolytic flocculation tank (4); the stage I anode electrolytic flocculation tank (1) is equipped with a mine water inlet (5), and the stage IV anode electrolytic flocculation tank (4) is equipped with a clean water outlet (6).
3. The apparatus for electrolytic purification of mine water and simultaneous electrolytic hydrogen production according to claim 2, characterized in that, It also includes a clean water storage tank (15), an electrolyte preparation tank (16), a gas-liquid separator (17), and a power supply (18); the clean water outlet (6) is connected to the clean water storage tank (15) through a pipeline; the electrolyte inlet (13) is connected to the electrolyte preparation tank (16) through a pipeline; the gas-liquid outlet (14) is connected to the gas-liquid separator (17) through a pipeline; the positive terminal of the power supply (18) is electrically connected to the plate anode (7), and the negative terminal of the power supply (18) is electrically connected to the plate cathode (11); the clean water storage tank (15) is connected to the electrolyte preparation tank (16) through a pipeline; the liquid outlet of the gas-liquid separator (17) is connected to the electrolyte preparation tank (16) through a pipeline.
4. The apparatus for electrolytic purification of mine water and simultaneous electrolytic hydrogen production according to claim 1, characterized in that, The diaphragm (9) includes an ion exchange membrane (91) located in the middle layer, a stainless steel support mesh (93) disposed on both sides of the ion exchange membrane (91), and a nylon filter cloth (92) disposed between the ion exchange membrane (91) and the stainless steel support mesh (93).
5. The apparatus for electrolytic purification of mine water and simultaneous electrolytic hydrogen production according to claim 2, characterized in that, The plate anode in the Class I anode electrolytic flocculation tank (1) is made of pure aluminum or pure iron; the plate anode in the Class II anode electrolytic flocculation tank (2) is a soluble metal composite material based on a stable metal; the plate anode in the Class III anode electrolytic flocculation tank (3) is a soluble metal composite material based on a stable metal, or stainless steel, wherein the soluble metal is aluminum or iron, and the stable metal is titanium, nickel or stainless steel; the plate anode in the Class IV anode electrolytic flocculation tank (4) is made of titanium or nickel.
6. A method for electrolytic purification of mine water and simultaneous electrolytic hydrogen production using the apparatus described in claim 3, characterized in that, include: Mine water is introduced into the first-stage anode electrolytic flocculation tank (1) through the mine water inlet (5), and the electrolyte in the electrolyte preparation tank (16) is introduced into each cathode electrolytic water production reactor (8) through the electrolyte inlet (13). The power supply (18) is turned on, and the mine water is electrolyzed in the first-stage anode electrolytic flocculation tank (1). The supernatant after removing pollutants flows into the second-stage anode electrolytic flocculation tank (2) through the water outlet. After electrolysis in the second-stage anode electrolytic flocculation tank (2), the supernatant after further removing residual pollutants flows into the third-stage anode electrolytic flocculation tank (3) through the water outlet. The supernatant after further deep treatment by electrolysis in pool (3) flows into the IV-level anode electrolysis flocculation pool (4) through the water outlet. After electrolysis in the IV-level anode electrolysis flocculation pool (4), the supernatant after deep purification flows into the clear water storage tank (15) through the clear water outlet (6). During the electrolysis process, the mixture of hydrogen and electrolyte after the reaction in each cathode electrolysis water hydrogen production reaction pool (8) enters the gas-liquid separator (17) through the gas-liquid outlet (14). Gas-liquid separation is carried out by gravity sedimentation and circulating water cooling technology. The separated hydrogen is discharged from the top and collected, and the separated liquid is returned to the electrolyte preparation pool (16).
7. The method according to claim 6, characterized in that, The electrolyte is a potassium hydroxide solution with a mass concentration of 20%–30%, and the temperature of the electrolyte is 20℃–30℃; the electrolysis voltage is 5V–60V, and the current density is 5mA / cm². 2 ~25mA / cm 2 During electrolysis, the flow rate of the electrolyte in the disc-shaped microchannel is controlled to be 0.1 m / s to 0.3 m / s.
8. The method according to claim 6, characterized in that, The electrolysis time in the Stage I anodic electrolytic flocculation tank is 10 min to 30 min, the electrolysis time in the Stage II anodic electrolytic flocculation tank is 10 min to 15 min, the electrolysis time in the Stage III anodic electrolytic flocculation tank is 6 min to 12 min, and the electrolysis time in the Stage IV anodic electrolytic flocculation tank is 5 min to 10 min.
9. The method according to claim 6, characterized in that, Before carrying out mine water electrolysis purification and simultaneous electrolysis hydrogen production, the equipment must first undergo stabilization treatment.
10. The method according to claim 9, characterized in that, The stabilization treatment method includes: first, introducing mine water into the Class I anode electrolytic flocculation tank (1) and the Class II anode electrolytic flocculation tank (2), and adding clean water into the Class III anode electrolytic flocculation tank (3) and the Class IV anode electrolytic flocculation tank (4); then introducing the electrolyte in the electrolyte preparation tank (16) into each cathode electrolytic water hydrogen production reaction tank (8), turning on the power supply, and continuously stabilizing the water flow for 2 to 6 hours.