Device for producing hydrogen by electrolyzing heavy alcohol wastewater through membrane-free method

Abstract

The utility model relates to the technical field of industrial wastewater treatment and hydrogen production by electrolyzing water, and discloses a device for producing hydrogen by electrolyzing heavy alcohol wastewater by a membrane-free method, which comprises an electrolytic bath end plate and an arranged electrolytic bath, the anode plates are arranged on the two sides of an inner cavity of the electrolytic cell, the cathode plates are installed in the center of the inner cavity of the electrolytic cell, and the partition plate assemblies are installed on the two sides of the center of the inner cavity of the electrolytic cell; the liquid outlet is formed in the surface of the partition plate assembly, the partition plate assembly divides the electrolytic tank into an anode reaction cavity and a cathode reaction cavity, and a salt bridge is connected between the anode reaction cavity and the cathode reaction cavity in a communicating mode. According to the device for producing hydrogen by electrolyzing the heavy alcohol wastewater through the membrane-free method, the electrolytic bath is separated into the chambers through the partition plate assembly, the anode reaction cavity and the cathode reaction cavity are connected through the salt bridge, and it is guaranteed that hydrogen is prepared while the heavy alcohol wastewater is electrolyzed under the condition that no cathode and anode substance exchange exists; the cost is reduced; and the heavy alcohol wastewater is prevented from leaking.

Description

Technical Field

[0001] The utility model relates to the technical field of industrial wastewater treatment and water electrolysis hydrogen production, in particular to a device for producing hydrogen by electrolyzing heavy alcohol wastewater without a membrane. Background Art

[0002] At present, the most common hydrogen production method in China is the chemical reforming technology of petrochemical fuels based on coal and natural gas. Coal hydrogen production is mainly divided into two methods: coal coking and coal gasification. Coal gasification technology to produce hydrogen is one of the most important methods for producing hydrogen in my country. Coal gasification hydrogen production is to chemically react coal with a gasifying agent under certain temperature, pressure and other conditions to gasify it into a gaseous product with hydrogen and CO as the main components, and then obtain a certain purity of product hydrogen through CO conversion and separation, purification and other treatments. This technology is mature, efficient and low-cost; natural gas hydrogen production technology mainly includes: steam reforming, partial oxidation, catalytic cracking, methane autothermal catalytic reforming, etc., among which steam reforming hydrogen production is more mature and widely used in other countries. However, fossil energy reforming hydrogen production technology consumes fossil fuels with limited reserves and cannot get rid of dependence on traditional energy, and will also cause environmental pollution. At the same time, biological fermentation hydrogen production technology is also developing. Biological fermentation hydrogen production is divided into three types: photofermentation (photoreaction) hydrogen production, dark fermentation hydrogen production and light-dark coupling hydrogen production. Among these three methods, light-dark coupling hydrogen production has the best theoretical effect, but it is limited by the coordination between bacterial species; photofermentation hydrogen production can best reduce energy consumption, but the process is not mature; dark fermentation hydrogen production is relatively mature, but its practical application is also affected. In summary, the water electrolysis hydrogen production process has a better application prospect. On the one hand, it is not affected by the scene environment and can be freely installed in various occasions; on the other hand, its hydrogen production effect and environmental friendliness are excellent, so water electrolysis hydrogen production has become the preferred hydrogen production solution today.

[0003] Common water electrolysis hydrogen production usually uses a diaphragm, that is, an ion exchange membrane to divide the electrolysis chamber into a cathode chamber and an anode chamber, which is used to separate the oxygen produced in the anode chamber and the hydrogen produced in the cathode chamber. For example, patent application No. 202210173439.9 discloses a filter press water electrolysis hydrogen production device and method, the invention includes an electrolytic cell; a plurality of diaphragms are arranged in parallel in the electrolytic cell; and the electrolytic cell is divided into a plurality of independent electrolysis chambers by the diaphragm; an anode electrode and a cathode electrode are respectively arranged in the two electrolysis chambers at both ends of the electrolytic cell; a partition assembly is arranged between any two diaphragms; the side of the partition assembly away from the anode electrode is arranged as an inert electrode, and the side close to the anode electrode is arranged as an alkaline water electrolysis electrode; an anode electrolysis area is formed between the diaphragm and the inert electrode, and between the diaphragm and the anode electrode; a cathode electrolysis area is formed between the diaphragm and the alkaline water electrolysis electrode, and between the diaphragm and the cathode electrode, thereby realizing the spatial separation and temporal synchronization of hydrogen and oxygen production by two-step water electrolysis, and can increase the capacity of the redox buffer medium, and improve the efficiency of water electrolysis hydrogen production. However, ion exchange membranes are expensive and costly, making them unsuitable for large-scale industrial production. They will increase the ohmic impedance during the electrolysis process, resulting in unnecessary energy consumption and heat generation. At the same time, as the membrane is used for a long time, the safety of electrolyte penetration caused by aging of the membrane is also an issue that needs attention. Therefore, a membraneless method for electrolyzing heavy alcohol wastewater to produce hydrogen is proposed. Utility Model Content

[0004] 1. Technical issues to be resolved

[0005] In view of the shortcomings of the prior art, the utility model provides a membraneless method for electrolyzing heavy alcohol wastewater to produce hydrogen, so as to solve the technical problems that the above-mentioned ion exchange membrane is expensive, costly, not suitable for large-scale industrial production, and will increase the ohmic impedance in the electrolysis process, causing unnecessary energy consumption and heat generation.

[0006] (II) Technical solution

[0007] In order to achieve the above-mentioned purpose, the utility model provides the following technical solution: a device for producing hydrogen by electrolyzing heavy alcohol wastewater without membrane, comprising:

[0008] An electrolytic cell end plate and an electrolytic cell are provided, wherein the front end of the upper outer side of the electrolytic cell end plate is provided with a liquid inlet and a gas outlet, and the front end of the lower outer side of the electrolytic cell end plate is provided with a liquid discharge port;

[0009] Anode plates are arranged on both sides of the inner cavity of the electrolytic cell, and cathode plates are installed at the center of the inner cavity of the electrolytic cell, and partition assemblies are installed on both sides of the inner cavity center of the electrolytic cell;

[0010] The liquid outlet is arranged at a corresponding position on the surface of the partition assembly, and the partition assembly is hollow in design and filled with electrolyte. The partition assembly divides the electrolytic cell into alternating anode reaction chambers and cathode reaction chambers, and the anode reaction chambers and the cathode reaction chambers are connected by a salt bridge, and the solution built in the salt bridge is an alkaline electrolyte. Add alkaline electrolyte to the cathode reaction chamber, add a certain proportion of the prepared mixture of heavy alcohol wastewater and alkaline solution to the anode reaction chamber, check the airtightness of the device, and prepare to collect hydrogen through the gas outlet of the cathode reaction chamber, power on the device, monitor the device voltage, and judge the reaction. The reaction in the cathode reaction chamber is 2H2O+2e-→H2+2OH-, and the reaction in the anode reaction chamber is HOCH2-CH2OH+10OH-→2CO2+8H2O+10e-. When the reaction is completed, discharge the anode and cathode liquids through the drain port, and recycle the anode liquid, which is the degraded ethylene glycol waste liquid. Replenish the liquid to the device, repeat the above operation, uniformly recycle the degraded ethylene glycol waste liquid and process it as a value-added product. At the same time, the above operation should be kept At the same time, since the electrolysis potential of ethylene glycol is lower than the anode oxygen evolution potential, it is easier to occur. While low energy consumption, it can not only degrade ethylene glycol waste liquid, but also not affect cathode hydrogen evolution and recover hydrogen. It can also inhibit anode oxygen evolution and eliminate the hidden dangers of hydrogen and oxygen mixing. The degradation of ethylene glycol can be judged not only by theoretical potential, but also by observing the color of the waste liquid. If the color of the anode liquid is white and transparent, it means that ethylene glycol has been almost completely degraded, and the liquid replenishment and liquid recovery of the device are very convenient. At the same time, since the degradation of ethylene glycol at the anode is slightly slower, the back-to-back electrolysis device can produce hydrogen with high efficiency without increasing the load of the device, and increase hydrogen recovery while synchronously reacting at the anode.

[0011] Preferably, a connection seat is installed at the center of the outer side of the electrolytic cell end plate, and a connection column is added at the center of the outer side of the connection seat. The connection column is installed on the electrolytic cell end plate through the connection seat.

[0012] Preferably, the outer ends of the connecting columns are all equipped with rotating seats, and the outer central rotating ends of the rotating seats are all hinged with adjustment blocks. The rotating seats are connected to the connecting columns, and the adjustment blocks can be rotated and adjusted on the rotating seats along with the rotating ends.

[0013] Preferably, a support base is hingedly connected to the bottom of the adjustment block, and the support base is designed as a cone. The support base can be adjusted on the adjustment block, and the cone design is small at the top and large at the bottom, which can increase the contact area, ensure the stability of the electrolytic cell end plate and its connection structure during operation, and the support base can be adjusted and connected and fixed at different positions.

[0014] (III) Beneficial effects

[0015] Compared with the prior art, the utility model provides a membrane-free electrolysis device for producing hydrogen from heavy alcohol wastewater, which has the following beneficial effects:

[0016] The membraneless method for electrolyzing heavy alcohol wastewater to produce hydrogen device uses a partition assembly to separate the electrolytic cell into compartments, and connects the anode reaction chamber and the cathode reaction chamber through a salt bridge, thereby ensuring that hydrogen is produced while electrolyzing heavy alcohol wastewater without the exchange of cathode and anode substances. This method not only replaces the traditional ion exchange membrane, but also upgrades the membraneless device that used expensive bipolar plate materials in the past, reduces costs, prevents leakage of heavy alcohol wastewater, and solves the safety problem of mutual penetration of electrolyte and gas. At the same time, the use of the partition assembly and the salt bridge replaces the traditional ion exchange membrane, which reduces the cost of the electrolytic cell. While reducing the overall energy consumption and heat generation, the tasks of degrading wastewater and coupling hydrogen production are completed. The partition assembly installed in the middle of the electrolytic cell realizes the separation of the anode and cathode electrolytic chambers, effectively avoiding the material exchange between the positive and negative electrodes, and at the same time can realize the classified treatment of the waste liquid after the electrolysis of the positive and negative electrodes. Compared with the double-tank electrolysis device, the process is simpler and more convenient. The hollow partition assembly has built-in alkaline electrolyte, which can replenish the positive and negative chambers at any time, and connect the anode and cathode electrolytic chambers to each other through a salt bridge, thereby realizing ion exchange and ensuring the smooth progress of the electrolysis reaction. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a schematic diagram of the internal structure of the utility model in overall cross-section;

[0018] Figure 2 It is a schematic structural diagram of the electrolytic cell end plate, anode electrode, cathode plate and separator assembly of the utility model.

[0019] In the figure: 1. electrolytic cell end plate; 2. anode plate; 3. cathode plate; 4. partition assembly; 5. liquid outlet; 6. liquid inlet; 7. gas outlet; 8. salt bridge; 9. drain port; 10. connecting seat; 11. connecting column; 12. rotating seat; 13. adjusting block; 14. supporting base; 101. anode reaction chamber; 102. cathode reaction chamber. DETAILED DESCRIPTION

[0020] The following will be combined with the drawings in the embodiments of the utility model to clearly and completely describe the technical solutions in the embodiments of the utility model. Obviously, the described embodiments are only part of the embodiments of the utility model, not all of the embodiments. Based on the embodiments in the utility model, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the utility model.

[0021] The utility model provides a technical solution, a membrane-free electrolysis device for producing hydrogen from heavy alcohol wastewater, comprising: Figure 1 , an electrolytic cell end plate 1, and an electrolytic cell, wherein a liquid inlet 6 and a gas outlet 7 are respectively provided at the front end of the upper outer side of the electrolytic cell end plate 1, and a liquid discharge port 9 is provided at the front end of the lower outer side of the electrolytic cell end plate 1;

[0022] See also Figure 2 , anode plates 2 are arranged on both sides of the inner cavity of the electrolytic cell, and cathode plates 3 are installed at the center of the inner cavity of the electrolytic cell, and partition plate assemblies 4 are installed on both sides of the inner cavity center of the electrolytic cell;

[0023] The liquid outlet 5 is arranged at a corresponding position on the surface of the partition assembly 4, and the partition assembly 4 is hollow in design and filled with electrolyte. The partition assembly 4 divides the electrolytic cell into alternating anode reaction chambers 101 and cathode reaction chambers 102, and the anode reaction chambers 101 and the cathode reaction chambers 102 are connected by a salt bridge 8, and the solution inside the salt bridge 8 is an alkaline electrolyte. Add alkaline electrolyte to cathode reaction chamber 102, add a prepared mixture of heavy alcohol wastewater and alkaline solution in a certain proportion to anode reaction chamber 101, check the air tightness of the device, and prepare to collect hydrogen through the gas outlet 7 of cathode reaction chamber 102, power on the device, monitor the device voltage, and judge the reaction progress, wherein the reaction of cathode reaction chamber 102 is 2H2O+2e-→H2+2OH-, and the reaction of anode reaction chamber 101 is HOCH2-CH2OH+10OH-→2CO2+8H2O+10e-. When the reaction is completed, discharge the anode and cathode liquids through the drain port 9, and recycle the anode liquid, which is degraded ethylene glycol waste liquid, and replenish the device, repeat the above operation, recycle the degraded ethylene glycol waste liquid and process it as a value-added product. At the same time, the above operations should ensure that the device is carried out at room temperature and that each outlet switch is correct. At the same time, since the electrolysis potential of ethylene glycol is lower than the anode oxygen evolution potential, it is more likely to occur. While reducing energy consumption, it can not only degrade the ethylene glycol waste liquid, but also not affect the cathode hydrogen evolution and recover the hydrogen. It can also inhibit the anode oxygen evolution and eliminate the hidden dangers of hydrogen and oxygen mixing. The degradation of ethylene glycol can be judged not only by the theoretical potential, but also by observing the color of the waste liquid. If the color of the anode liquid is white and transparent, it means that the ethylene glycol has been almost completely degraded, and the liquid replenishment and liquid recovery of the device are very convenient. At the same time, since the degradation of ethylene glycol at the anode is slightly slower, the back-to-back electrolysis device can produce hydrogen with high efficiency without increasing the load of the device, and increase the recovery of hydrogen while synchronously reacting at the anode.

[0024] See also Figure 1, a connecting seat 10 is installed at the outer center position of the electrolytic cell end plate 1, and a connecting column 11 is added to the outer center of the connecting seat 10. The connecting column 11 is installed on the electrolytic cell end plate 1 through the connecting seat 10. A rotating seat 12 is installed at the outer end of the connecting column 11, and an adjustment block 13 is hinged at the outer center rotating end of the rotating seat 12. The rotating seat 12 is connected to the connecting column 11, and the adjustment block 13 can be rotated and adjusted along with the rotating end on the rotating seat 12. A support base 14 is hinged just below the bottom of the adjustment block 13, and the support base 14 is of a conical design as a whole. The support base 14 can be adjusted on the adjustment block 13, and at the same time, it is a conical design with a small top and a large bottom, which can increase the contact area, ensure the stability of the electrolytic cell end plate 1 and its connection structure during operation, and the support base 14 can be adjusted to be connected and fixed at different positions.

[0025] This scheme: add alkaline electrolyte to cathode reaction chamber 102, add a prepared mixture of heavy alcohol wastewater and alkaline solution in a certain proportion to anode reaction chamber 101, check the air tightness of the device, and prepare to collect hydrogen through the gas outlet 7 of cathode reaction chamber 102, power on the device, monitor the device voltage, and judge the reaction progress, wherein the reaction of cathode reaction chamber 102 is 2H2O+2e-→H2+2OH-, and the reaction of anode reaction chamber 101 is HOCH2-CH2OH+10OH-→2CO2+8H2O+10e-. When the reaction is completed, the anode and cathode liquids are discharged through the drain port 9, and the anode liquid is recovered and processed, which is the degraded ethylene glycol waste liquid, and the device is replenished with liquid, and the above operation is repeated to uniformly recover the degraded ethylene glycol waste liquid and process it as a value-added product. At the same time, the above operations should ensure that the device is carried out at room temperature and that each outlet switch is correct. At the same time, since the electrolysis potential of ethylene glycol is lower than the anode oxygen evolution potential, it is more likely to occur. While low energy consumption, it can not only degrade ethylene glycol waste liquid, but also not affect cathode hydrogen evolution, recover hydrogen, inhibit anode oxygen evolution, and eliminate the hidden dangers of hydrogen and oxygen mixing accidents. The degradation of ethylene glycol can be judged not only by theoretical potential, but also by observing the color of the waste liquid. If the color of the anode outlet is white and transparent, it means that ethylene glycol has been almost completely degraded, and the liquid replenishment and liquid recovery of the device are very convenient. At the same time, since the degradation of ethylene glycol at the anode is slightly slower, the back-to-back electrolysis device can produce hydrogen with high efficiency without increasing the load of the device, and increase hydrogen recovery while synchronously reacting at the anode. The connecting column 11 is installed on the electrolytic cell end plate 1 through the connecting seat 10, and the rotating seat 12 is connected to the connecting column 11. At the same time, the adjusting block 13 can be rotated and adjusted along with the rotating end on the rotating seat 12, and the supporting base 14 can be adjusted on the adjusting block 13. At the same time, it is a conical design with a small top and a large bottom, which can increase the contact area and ensure the stability of the electrolytic cell end plate 1 and its connecting structure during operation. The supporting base 14 can be adjusted and connected and fixed at different positions.

[0026] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0027] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A membrane-free electrolysis device for producing hydrogen from heavy alcohol wastewater, characterized in that: include: An electrolytic cell end plate (1), and an electrolytic cell, wherein the front end of the upper outer portion of the electrolytic cell end plate (1) is provided with a liquid inlet (6) and a gas outlet (7), respectively, and the front end of the lower outer portion of the electrolytic cell end plate (1) is provided with a liquid discharge port (9); Anode plates (2) are arranged on both sides of the inner cavity of the electrolytic cell, and cathode plates (3) are installed at the center of the inner cavity of the electrolytic cell, and partition plate assemblies (4) are installed on both sides of the inner cavity center of the electrolytic cell; The liquid outlet (5) is arranged at a corresponding position on the surface of the partition assembly (4), and the partition assembly (4) is hollow and filled with electrolyte. The partition assembly (4) divides the electrolytic cell into anode reaction chambers (101) and cathode reaction chambers (102) that are alternately arranged, and a salt bridge (8) is connected between the anode reaction chambers (101) and the cathode reaction chambers (102), and the solution inside the salt bridge (8) is an alkaline electrolyte.

2. The device for producing hydrogen by electrolyzing heavy alcohol wastewater without membrane according to claim 1, characterized in that: A connection seat (10) is installed at the center of the outer side of the electrolytic cell end plate (1), and a connection column (11) is added at the center of the outer side of the connection seat (10).

3. The device for producing hydrogen by electrolyzing heavy alcohol wastewater without membrane according to claim 2, characterized in that: The outer ends of the connecting columns (11) are all equipped with rotating seats (12), and the outer central rotating ends of the rotating seats (12) are all hinged with adjusting blocks (13).

4. The device for producing hydrogen by electrolyzing heavy alcohol wastewater without membrane according to claim 3, characterized in that: A support base (14) is hingedly connected directly below the bottom of the adjustment block (13), and the support base (14) is of a conical design as a whole.

Images