Electrolytic hydrogen production device and method for reducing hydrogen content in oxygen

Abstract

The invention discloses an electrolytic hydrogen production device and method for reducing the hydrogen content in oxygen. The electrolytic hydrogen production device comprises an alkaline electrolytic bath, an enhanced removal pipeline accessory, an anode side gas-liquid separator, an anode side gas treatment device, a cathode side gas-liquid separator, a cathode side gas treatment device, an enhanced removal device, an alkali liquor tank and an alkali liquor circulating pump. The enhanced removal pipeline accessory is arranged on a pipeline between the alkaline electrolytic bath and the anode side gas-liquid separator, and the enhanced removal device is arranged in front of the alkaline liquor tank. According to the invention, the gas-liquid mixed solution on the anode side is primarily dehydrogenated by using the enhanced removal pipeline accessory, the circulating alkali solution is deeply dehydrogenated by using the enhanced removal device, and the hydrogen concentration in oxygen in the water electrolysis hydrogen production system is reduced by reducing the content of dissolved hydrogen in the circulating alkali solution, so that the safety of the system is improved.

Description

Technical Field

[0001] The invention relates to the technical field of hydrogen production by electrolysis of water, and in particular to an electrolysis hydrogen production device and method for reducing the hydrogen content in oxygen. Background Art

[0002] As a high-energy-density, clean, and renewable energy source, the development of hydrogen energy can reduce dependence on fossil fuels such as oil and natural gas, thereby reducing energy import costs and improving energy security. It is widely used in power generation, transportation, industrial production and other fields. These advantages make hydrogen energy an important part of the future energy system, helping to achieve sustainable development and the goal of "carbon neutrality". Hydrogen production by water electrolysis is to decompose water molecules into hydrogen and oxygen under direct current, and precipitate them at the cathode and anode respectively, and the resulting hydrogen has high purity. This technology is currently the most promising green hydrogen production method. In particular, the use of renewable energy to produce hydrogen by water electrolysis is the process with the lowest carbon emissions among the many hydrogen source solutions, which is most consistent with the global energy development trend of low-carbon emission reduction. Among them, alkaline water electrolysis hydrogen production technology is relatively mature, the lowest cost, more economical, and has been widely used. However, the performance of the alkaline water electrolysis hydrogen production system is limited by the hydrogen concentration in the oxygen in the system. The hydrogen concentration in oxygen increases as the operating load decreases. At low loads or unstable operating conditions, the hydrogen content in oxygen may exceed the safety value of 4% (the industrial requirement is usually 2%), posing a risk of explosion. Reducing the hydrogen concentration in oxygen in the water electrolysis system can not only minimize safety issues, but also improve electrolysis efficiency.

[0003] The theoretical products of hydrogen production by water electrolysis are pure hydrogen and pure oxygen, but hydrogen will inevitably diffuse across the membrane inside the electrolyzer, resulting in a certain amount of hydrogen mixed into the oxygen generated on the anode side of the alkaline electrolyzer, which may cause the problem of excessive hydrogen concentration in oxygen; and when the water electrolysis hydrogen production system is operated under low load or unstable conditions, the solubility of hydrogen in the electrolyte increases, resulting in an increase in the dissolved hydrogen content in the circulating alkali solution, and the gas-liquid separator cannot completely separate the dissolved oxygen and dissolved hydrogen in the circulating alkali solution. According to tests, when the alkaline electrolyzer is operated under low load (below 50%), the circulating alkali solution is only treated by the gas-liquid separator, and the dissolved hydrogen content in the circulating alkali solution can reach 2% to 4%. If the circulating alkali solution is directly returned to the alkaline electrolyzer to participate in the electrolysis reaction after gas-liquid separation, the hydrogen content in oxygen in the alkaline water electrolysis hydrogen production system will be further increased, and there is a risk of explosion. Summary of the invention

[0004] The object of the present invention is to provide an electrolytic hydrogen production device and method for reducing the hydrogen content in oxygen, so as to solve the problem that when the alkaline water electrolysis hydrogen production system is operated under low load or unstable conditions, the dissolved hydrogen content in the circulating alkaline solution and the hydrogen content in the oxygen on the anode side of the electrolytic cell increase.

[0005] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0006] The first aspect of the present invention is to provide an electrolytic hydrogen production device for reducing the hydrogen content in oxygen, comprising an alkaline electrolytic cell, an anode-side gas-liquid separator, an anode-side gas processing device, a cathode-side gas-liquid separator, a cathode-side gas processing device, an alkali liquid tank and an alkali liquid circulation pump;

[0007] The alkaline electrolytic cell has an anode chamber and a cathode chamber;

[0008] The anode chamber is connected to the anode side gas-liquid separator through a first pipeline, and an enhanced removal pipeline accessory is arranged on the first pipeline. The interior of the enhanced removal pipeline accessory is filled with hydrogen absorbing material for preliminary dehydrogenation of the gas-liquid mixture in the anode chamber;

[0009] The alkali liquid tank is provided with a circulating alkali liquid inlet, and a pipeline at the circulating alkali liquid inlet is provided with an enhanced removal device, the interior of the enhanced removal device is filled with catalytic resin or adsorption resin for deep dehydrogenation of the circulating alkali liquid.

[0010] Furthermore, the front and rear ends of the enhanced removal pipeline accessory are fixed on the first pipeline through a front partition and a rear partition respectively, and the front partition and the rear partition are full of sieve holes to ensure the normal circulation of the alkali solution inside the first pipeline; the hydrogen absorbing material is filled between the front partition and the rear partition.

[0011] Furthermore, the enhanced removal device has a vertical column cavity, the catalytic resin or adsorption resin is filled in the vertical column cavity, and grid plates are provided at the top and bottom of the vertical column cavity.

[0012] When the vertical column cavity is filled with catalytic resin, the catalytic resin catalyzes the dissolved oxygen and dissolved hydrogen in the circulating alkali solution to undergo an oxidation-reduction reaction to generate water (exothermic reaction), thereby removing the dissolved hydrogen in the circulating alkali solution; at the same time, a large amount of heat is generated during the reaction to raise the temperature of the circulating alkali solution, thereby reducing the solubility of hydrogen in the circulating alkali solution and further reducing the dissolved hydrogen content in the circulating alkali solution; when the vertical column cavity is filled with adsorption resin, the adsorption resin adsorbs the dissolved hydrogen in the circulating alkali solution, thereby effectively removing the dissolved hydrogen in the circulating alkali solution and thereby reducing the hydrogen content in the oxygen in the electrolysis system.

[0013] Furthermore, a first gas-liquid mixed phase outlet is provided at the top of the anode chamber, and a second gas-liquid mixed phase outlet is provided at the top of the cathode chamber;

[0014] The anode side gas-liquid separator is provided with a first gas phase outlet at the top, a first liquid phase outlet at the bottom, and a first gas-liquid mixed phase inlet at the middle of the side wall;

[0015] The cathode side gas-liquid separator is provided with a second gas phase outlet at the top, a second liquid phase outlet at the bottom, and a second gas-liquid mixed phase inlet at the middle of the side wall;

[0016] A mixed liquid inlet is provided at the top of the enhanced removal device, and a mixed liquid inlet line is provided at the mixed liquid inlet; a mixed liquid outlet is provided at the bottom of the enhanced removal device, and a mixed liquid outlet line is provided at the mixed liquid outlet;

[0017] The first pipeline connects the first gas-liquid mixed phase outlet and the first gas-liquid mixed phase inlet, and the first liquid phase outlet is connected to the mixed liquid inlet line through the second pipeline;

[0018] The second gas-liquid mixed phase outlet is connected to the second gas-liquid mixed phase inlet via a third pipeline, and the second liquid phase outlet is connected to the mixed liquid inlet line via a fourth pipeline;

[0019] The mixed solution outlet line is connected to the circulating alkali solution inlet, the alkali solution tank is connected to the bottom of the alkaline electrolytic cell through a fifth pipeline, and the alkali solution circulation pump is arranged on the fifth pipeline to pump the alkali solution in the alkali solution tank into the alkaline electrolytic cell;

[0020] The first gas phase outlet is connected to the anode side gas processing device through a sixth pipeline, and the second gas phase outlet is connected to the cathode side gas processing device through a seventh pipeline.

[0021] Furthermore, the first pipeline, the second pipeline, the third pipeline, the fourth pipeline, the fifth pipeline, the mixed liquid inlet line and the mixed liquid outlet line are all provided with stop valves.

[0022] Furthermore, the catalytic resin is a palladium catalyst, a platinum catalyst or an alumina catalyst; and the adsorption resin is a palladium-based resin or a polystyrene-based adsorption resin.

[0023] Furthermore, the mixed liquid inlet line, the mixed liquid outlet line, the first pipeline, the second pipeline and the sixth pipeline are all provided with pressure sensors or hydrogen sensors for detecting whether the operating load of the electrolysis system is normal and whether the hydrogen concentration in oxygen of the anode side gas-liquid separator is abnormal.

[0024] The second aspect of the present invention is to provide a method for producing hydrogen by electrolysis for reducing the hydrogen content in oxygen, using the above-mentioned device for producing hydrogen by electrolysis for reducing the hydrogen content in oxygen, comprising the following steps:

[0025] S1. Under the action of direct current, the water in the alkaline electrolytic cell is decomposed into a gas-liquid mixture containing a large number of fine bubbles;

[0026] S2. The gas-liquid mixture in the anode chamber is pumped into the enhanced removal pipeline attachment through the first pipeline by the alkali liquid circulation pump for preliminary removal of hydrogen and dissolved hydrogen, and then enters the anode side gas-liquid separator for gas-liquid separation; the gas-liquid mixture in the cathode chamber is pumped into the cathode side gas-liquid separator for gas-liquid separation by the alkali liquid circulation pump;

[0027] S3. The gas separated by the gas-liquid separator on the anode side enters the anode side gas treatment device for drying and pressurization treatment and then is collected, and the gas separated by the gas-liquid separator on the cathode side enters the cathode side gas treatment device for drying and pressurization treatment and then is collected; the circulating alkali liquid on the anode side and the circulating alkali liquid on the cathode side after gas-liquid separation are mixed and then enter the enhanced removal device for deep dehydrogenation;

[0028] S4. After completing deep dehydrogenation, the circulating alkali solution flows back to the alkali solution tank, and under the action of the alkali solution circulation pump, re-enters the alkaline electrolytic cell for electrolysis.

[0029] Furthermore, the volume of the gas-liquid mixed liquid in the anode side gas-liquid separator and the cathode side gas-liquid separator is controlled to be 1 / 2 to 3 / 4 of the volume of the gas-liquid separator.

[0030] Furthermore, the alkali solution pressure circulating through the enhanced removal pipeline accessories and the alkali solution pressure at the inlet of the enhanced removal device are 1.2-2.0 MPa, and the speed is 4-8 m / s; the outlet pressure of the alkali solution circulation pump is 1.2-2.0 MPa.

[0031] Compared with the prior art, the present invention has at least the following technical effects:

[0032] 1. The present invention arranges an enhanced removal pipeline accessory filled with hydrogen absorbing material at the front end of the first gas-liquid mixed phase inlet of the anode side gas-liquid separator, so that the gas-liquid mixed liquid on the anode side can complete preliminary dehydrogenation after passing through the enhanced removal pipeline accessory, thereby reducing the dissolved hydrogen in the circulating alkali solution and the hydrogen in the oxygen; by arranging an enhanced removal device before the circulating alkali solution re-enters the alkaline electrolytic cell for electrolysis, the circulating alkali solution is deeply dehydrogenated, thereby greatly reducing the hydrogen content in the oxygen in the electrolytic water hydrogen production system, and improving the safety of the electrolytic water hydrogen production system.

[0033] 2. The present invention can effectively reduce the concentration of hydrogen in oxygen in the electrolytic water system by strengthening the removal of pipeline accessories and strengthening the removal device, avoiding the hydrogen concentration from exceeding the safety limit, thereby reducing the risk of explosion. In addition, reducing the concentration of hydrogen in oxygen can improve the electrolysis efficiency, reduce corrosion and wear on the electrolysis equipment, thereby extending the service life of the equipment, reducing maintenance and replacement costs, and ensuring the smooth operation of the electrolysis process. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1This is a schematic diagram of the process flow of electrolytic hydrogen production for reducing the hydrogen content in oxygen according to the present invention.

[0035] Figure 2 It is a schematic diagram of the structure of the enhanced removal pipeline accessories of the present invention.

[0036] Figure 3 It is a schematic structural diagram of the enhanced removal device of the present invention.

[0037] In the figure: 10-alkaline electrolytic cell; 11-anode chamber; 111-first gas-liquid mixed phase outlet; 12-cathode chamber; 121-second gas-liquid mixed phase outlet;

[0038] 20-enhanced removal pipeline accessories; 21-front baffle; 22-rear baffle; 23-sieve hole; 24-hydrogen absorbing material

[0039] 30-anode side gas-liquid separator; 31-first gas-liquid mixed phase inlet; 32-first gas phase outlet; 33-first liquid phase outlet;

[0040] 40- anode side gas treatment device;

[0041] 50-cathode side gas-liquid separator; 51-second gas-liquid mixed phase inlet; 52-second gas phase outlet; 53-second liquid phase outlet;

[0042] 60- cathode side gas treatment device;

[0043] 70-enhanced removal device; 71-mixed liquid inlet; 711-mixed liquid inlet line; 72-mixed liquid outlet; 721-mixed liquid outlet line; 73-vertical column chamber; 74-catalytic resin particles / adsorption resin particles; 75-grid plate;

[0044] 81-first pipeline; 82-second pipeline; 83-third pipeline; 84-fourth pipeline; 85-fifth pipeline; 86-sixth pipeline; 87-seventh pipeline;

[0045] 90-alkali solution tank; 91-alkali solution circulation pump;

[0046] 100-stop valve;

[0047] 110-Pressure sensor / Hydrogen sensor DETAILED DESCRIPTION

[0048] The present invention is further described in detail below in conjunction with specific implementation methods and examples. It should be understood that the following examples are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-substantial improvements and adjustments made by professionals and technicians in this field based on the content of the present invention still belong to the scope of protection of the present invention.

[0049] In the existing alkaline water electrolysis hydrogen production device and method, only a gas-liquid separator is used to separate the gas-liquid mixture derived from the alkaline electrolyzer, and the dissolved hydrogen and dissolved oxygen in the circulating alkaline solution cannot be effectively separated, resulting in an increase in the concentration of hydrogen in oxygen in the alkaline water electrolysis hydrogen production system. In particular, when the electrolyzer load drops below a low load, the solubility of hydrogen in the alkaline solution further increases, resulting in a further increase in the dissolved hydrogen content in the circulating alkaline solution, and the gas-liquid separator cannot effectively separate the dissolved oxygen and dissolved hydrogen in the circulating alkaline solution. The circulating alkaline solution returns to the alkaline electrolyzer to participate in the electrolysis reaction, which will further increase the hydrogen content in oxygen in the alkaline water electrolysis system and there is a risk of explosion. In order to effectively solve the above technical problems, the present invention provides an alkaline water electrolysis hydrogen production device and method, which can effectively reduce the dissolved hydrogen content in the circulating alkaline solution and the hydrogen content in oxygen on the anode side of the electrolyzer, and improve the safety of the electrolysis system.

[0050] See also Figure 1 The electrolytic hydrogen production device for reducing the hydrogen content in oxygen of the present invention comprises an alkaline electrolytic cell 10, an enhanced removal pipeline accessory 20, an anode side gas-liquid separator 30, an anode side gas processing device 40, a cathode side gas-liquid separator 50, a cathode side gas processing device 60, an enhanced removal device 70, an alkali liquid tank 90 and an alkali liquid circulation pump 91;

[0051] The alkaline electrolytic cell 10 has an anode chamber 11 and a cathode chamber 12;

[0052] A first gas-liquid mixed phase outlet 111 is provided at the top of the anode chamber 11, and a second gas-liquid mixed phase outlet 121 is provided at the top of the cathode chamber 12;

[0053] The anode side gas-liquid separator 30 is provided with a first gas phase outlet 32 ​​at the top, a first liquid phase outlet 33 at the bottom, and a first gas-liquid mixed phase inlet 31 at the middle of the side wall;

[0054] The cathode side gas-liquid separator 50 has a second gas phase outlet 52 at the top, a second liquid phase outlet 53 at the bottom, and a second gas-liquid mixed phase inlet 51 at the middle of the side wall;

[0055] A mixed liquid inlet 71 is provided at the top of the enhanced removal device 70, and a mixed liquid inlet line 711 is provided at the mixed liquid inlet 71; a mixed liquid outlet 72 is provided at the bottom of the enhanced removal device 70, and a mixed liquid outlet line 721 is provided at the mixed liquid outlet;

[0056] The first gas-liquid mixed phase outlet 111 is connected to the first gas-liquid mixed phase inlet 31 through the first pipeline 81, the enhanced removal pipeline accessory 20 is arranged on the first pipeline 81, and the first liquid phase outlet 33 is connected to the mixed liquid inlet line 711 through the second pipeline 82;

[0057] The second gas-liquid mixed phase outlet 121 is connected to the second gas-liquid mixed phase inlet 51 through the third pipeline 83, and the second liquid phase outlet 53 is connected to the mixed liquid inlet line 711 through the fourth pipeline 84;

[0058] The alkali liquid tank 90 is provided with a circulating alkali liquid inlet, the mixed liquid outlet line 721 is connected to the circulating alkali liquid inlet on the alkali liquid tank 90, the alkali liquid tank 90 is connected to the bottom of the alkaline electrolytic cell 10 through the fifth pipeline 85, and the fifth pipeline 85 is provided with an alkali liquid circulation pump 91 for pumping the alkali liquid in the alkali liquid tank 90 into the alkaline electrolytic cell 10;

[0059] The first gas phase outlet 32 ​​is connected to the anode side gas processing device 40 through a sixth pipeline 86 , and the second gas phase outlet 52 is connected to the cathode side gas processing device 60 through a seventh pipeline 87 .

[0060] When the electrolytic hydrogen production device for reducing the hydrogen content in oxygen of the present invention is used, the alkaline electrolytic cell 10 is first connected to a direct current power supply, the positive electrode of the power supply is connected to the anode chamber 11 of the alkaline electrolytic cell 10, and the negative electrode of the power supply is connected to the cathode chamber 12 of the alkaline electrolytic cell 10; under the action of direct current, the water in the alkaline electrolytic cell 10 is decomposed into a gas-liquid mixed liquid containing a large number of fine bubbles; the gas-liquid mixed liquid in the anode chamber 11 is pumped into the anode side gas-liquid separator 30 through the first pipeline 81 by the alkaline liquid circulation pump 91 for gas-liquid separation, and the gas-liquid mixed liquid in the cathode chamber 12 is pumped into the cathode side gas-liquid separator 50 through the third pipeline 83 for gas-liquid separation; before entering the anode side gas-liquid separator 30, the gas-liquid mixed liquid in the anode chamber 11 flows through the enhanced removal pipeline attachment 20 for preliminary dehydrogenation, so that the dissolved hydrogen content in the alkaline solution and the hydrogen content in the oxygen are initially reduced, and then enters the anode side gas-liquid separator 30, and after gravity sedimentation, the oxygen is discharged from the first gas phase outlet 32 The gas-liquid mixture in the cathode chamber 12 is separated into gas and liquid in the cathode side gas-liquid separator 50, and hydrogen is discharged from the second gas phase outlet 52, enters the cathode side gas treatment device 60 through the seventh pipeline 87, is dried and pressurized, and then collected, the separated cathode side circulating alkali liquid is discharged through the second liquid phase outlet 53, and flows into the mixed liquid inlet line 711 through the fourth pipeline 84; the separated anode side circulating alkali liquid and cathode side circulating alkali liquid are mixed in the mixed liquid inlet line 711, and then enter the enhanced removal device for secondary dehydrogenation; after the secondary dehydrogenation is completed, the circulating alkali liquid flows to the alkali liquid tank 90 through the mixed liquid outlet line 721, and is pumped back into the alkaline electrolytic cell 10 for electrolysis under the action of the alkali liquid circulation pump 91.

[0061] See also Figure 2Preferably, the front and rear ends of the enhanced removal pipeline accessory 20 (the front and rear in the present invention refer to the front and rear along the fluid flow direction in the present invention) are fixed on the first pipeline 81 through a front baffle 21 and a rear baffle 22 respectively, and full sieve holes 23 are provided on the front baffle 21 and the rear baffle 22 to ensure the normal circulation of the alkali solution inside the first pipeline 81; the hydrogen absorbing material 24 is filled between the front baffle 21 and the rear baffle 22.

[0062] Preferably, the hydrogen absorbing material 24 of the present invention is an adsorption resin or porous activated carbon, which can effectively adsorb dissolved hydrogen and hydrogen gas.

[0063] See also Figure 3 Preferably, the enhanced removal device 70 of the present invention has a vertical column cavity 73, in which catalytic resin or adsorption resin is filled; grid plates 75 are provided at the top and bottom of the vertical column cavity 73 to prevent the catalytic resin or adsorption resin from being brought into other areas of the electrolysis system.

[0064] When the vertical column cavity 73 is filled with catalytic resin, the catalytic resin catalyzes the dissolved oxygen and dissolved hydrogen in the circulating alkali solution to undergo an oxidation-reduction reaction to generate water (exothermic reaction), thereby removing the dissolved hydrogen in the circulating alkali solution. At the same time, a large amount of heat is generated during the reaction to raise the temperature of the circulating alkali solution, thereby reducing the solubility of hydrogen in the circulating alkali solution and further reducing the content of dissolved hydrogen in the circulating alkali solution. When the vertical column cavity 73 is filled with adsorption resin, the adsorption resin adsorbs the dissolved hydrogen in the circulating alkali solution, thereby effectively removing the dissolved hydrogen in the circulating alkali solution and thereby reducing the content of hydrogen in oxygen in the electrolysis system.

[0065] Preferably, the catalytic resin and the adsorption resin are granular resins. The granular catalytic resin or the adsorption resin has a larger specific surface area and a higher utilization rate.

[0066] Continue to participate Figure 1 Preferably, in the present invention, a stop valve 100 is provided on the first pipeline 81 , the second pipeline 82 , the third pipeline 83 , the fourth pipeline 84 , the fifth pipeline 85 , the mixed liquid inlet line 711 and the mixed liquid outlet line 721 .

[0067] Preferably, the catalytic resin in the present invention is a palladium catalyst, a platinum catalyst or an alumina catalyst;

[0068] Preferably, the adsorption resin in the present invention is a palladium-based resin or a polystyrene-based adsorption resin.

[0069] Preferably, for the gas-liquid separator of the present invention with a diameter of 0.5 to 1 m and a height of 2 to 4 m, the diameter of the enhanced removal pipeline attachment 20 is 8 to 12 mm, the diameter of the enhanced removal device 70 is 0.3 to 0.8 m, and the height is 1.2 to 3.2 m;

[0070] Continue to participate Figure 1 Preferably, in the present invention, pressure sensors or hydrogen sensors 110 are provided on the mixed liquid inlet line 711, the mixed liquid outlet line 721, the first pipeline 81, the second pipeline 82 and the sixth pipeline 86 to detect whether the operating load of the electrolysis system is normal and whether the hydrogen concentration in oxygen of the anode side gas-liquid separator is abnormal.

[0071] The present invention also provides a method for producing hydrogen by electrolysis for reducing the hydrogen content in oxygen, using the above-mentioned device for producing hydrogen by electrolysis for reducing the hydrogen content in oxygen, comprising the following steps:

[0072] S1. Under the action of direct current, the water in the alkaline electrolytic cell 10 is decomposed into a gas-liquid mixture containing a large number of fine bubbles;

[0073] S2. The gas-liquid mixture of the anode chamber 11 is pumped into the enhanced removal pipeline attachment 20 through the first pipeline 81 by the alkali liquid circulation pump 91 for preliminary removal of hydrogen and dissolved hydrogen, and then enters the anode side gas-liquid separator 30 for gas-liquid separation; the gas-liquid mixture of the cathode chamber 12 is pumped into the cathode side gas-liquid separator 50 through the third pipeline 83 by the alkali liquid circulation pump 91 for gas-liquid separation;

[0074] S3. The gas separated by the anode-side gas-liquid separator 30 is discharged from the first gas phase outlet 32, enters the anode-side gas treatment device 40 through the sixth pipeline 86 for drying and pressurizing treatment and then collected, and the gas separated by the cathode-side gas-liquid separator 50 is discharged from the second gas phase outlet 52, enters the cathode-side gas treatment device 60 through the seventh pipeline 87 for drying and pressurizing treatment and then collected; the anode-side circulating alkali liquid and the cathode-side circulating alkali liquid after gas-liquid separation enter the mixed liquid inlet line 711 through the second pipeline 82 and the fourth pipeline 84 respectively, and then enter the enhanced removal device 70 for secondary removal of dissolved hydrogen;

[0075] S4. After completing the secondary removal, the circulating alkali solution flows back to the alkali solution tank 90 through the mixed solution outlet line 721, and under the action of the alkali solution circulation pump 91, re-enters the alkaline electrolytic cell 10 for electrolysis.

[0076] Furthermore, the volume of the gas-liquid mixture in the anode-side gas-liquid separator 30 and the cathode-side gas-liquid separator 50 is controlled to be 1 / 2 to 3 / 4 of the volume of the gas-liquid separator.

[0077] Furthermore, the alkali pressure at the alkali liquid mixed liquid inlet 71 of the enhanced removal pipeline accessory 20 is 1.2-2.0 MPa, and the speed is 4-8 m / s; the outlet pressure of the alkali liquid circulation pump is 1.2-2.0 MPa.

[0078] Example 1

[0079] The alkaline water electrolysis hydrogen production device of the present invention is used to prepare hydrogen, wherein the palladium catalyst resin particles are filled in the enhanced removal device; the anode side gas-liquid separator 30 and the cathode side gas-liquid separator 50 are vertical tanks with a diameter of 1m and a height of 3m; the diameter of the enhanced removal pipeline accessory 20 is 12mm; the diameter of the enhanced removal device 70 is 0.8m and the height is 2.4m; the volume of the gas-liquid mixed liquid in the anode side gas-liquid separator 30 and the cathode side gas-liquid separator 50 is controlled to be 3 / 4 of the volume of the gas-liquid separator:

[0080] S1. Under the action of direct current, the water in the alkaline electrolytic cell 10 is decomposed into a gas-liquid mixture containing a large number of fine bubbles;

[0081] S2. The gas-liquid mixture in the anode chamber 11 is pumped into the anode side gas-liquid separator 30 through the first pipeline 81 by the alkali liquid circulation pump 91 for gas-liquid separation, and the gas-liquid mixture in the cathode chamber 12 is pumped into the cathode side gas-liquid separator 50 through the third pipeline 83 for gas-liquid separation; before entering the anode side gas-liquid separator 30, the gas-liquid mixture in the anode chamber 11 flows through the enhanced removal pipeline attachment 20 for preliminary dehydrogenation, so that the dissolved hydrogen content in the alkali liquid and the hydrogen content in the oxygen are initially reduced, and then enters the anode side gas-liquid separator 30;

[0082] S3. The gas separated by the anode-side gas-liquid separator 30 is discharged from the first gas phase outlet 32, enters the anode-side gas treatment device 40 through the sixth pipeline 86 for drying and pressurizing treatment and then collected, and the gas separated by the cathode-side gas-liquid separator 50 is discharged from the second gas phase outlet 52, enters the cathode-side gas treatment device 60 through the seventh pipeline 87 for drying and pressurizing treatment and then collected; the anode-side circulating alkali liquid and the cathode-side circulating alkali liquid after gas-liquid separation enter the mixed liquid inlet line 711 through the second pipeline 82 and the fourth pipeline 84 respectively, and then mixed. Entering the enhanced removal device 70 for secondary removal of dissolved hydrogen: the circulating alkali solution pressure at the mixed solution inlet 71 is controlled to be 1.2 MPa, and the speed is 4 m / s. The dissolved oxygen and dissolved hydrogen in the alkali solution undergo an oxidation-reduction reaction under the action of the palladium catalyst: H2+O2→H2O (exothermic reaction), and the dissolved hydrogen and dissolved oxygen in the electrolyte are converted into water. At the same time, a large amount of heat is generated during the reaction to increase the temperature of the electrolyte, thereby reducing the solubility of hydrogen in the circulating alkali solution, thereby reducing the hydrogen content in the oxygen in the water electrolysis hydrogen production system, and achieving deep dehydrogenation;

[0083] S4. After completing the secondary removal, the circulating alkali solution flows back to the alkali solution tank through the mixed solution outlet line 72, and under the action of the alkali solution circulation pump 91, re-enters the alkaline electrolytic cell 10 for electrolysis.

[0084] The operating load parameter of the alkaline electrolytic cell is set to 15%, so that the alkaline electrolytic cell enters a low-load operating state; it is measured that the dissolved hydrogen content in the cathode side circulating alkali liquid separated by the cathode side gas-liquid separator 50 is 4% before entering the enhanced removal device 70; the dissolved hydrogen content in the circulating alkali liquid finally discharged from the enhanced removal device (i.e. the dissolved hydrogen content in the circulating alkali liquid at the inlet of the alkali liquid tank) is 0.95%.

[0085] Comparative Example 1

[0086] The difference between this comparative example and Example 1 is that the alkaline water electrolysis hydrogen production device does not use the enhanced removal pipeline accessories 20 and the enhanced removal device 70, but only uses traditional cathode side and anode side gas-liquid separators, and the circulating alkali solution directly enters the alkali solution tank 90.

[0087] According to the test, the dissolved hydrogen content of the circulating alkali solution at the inlet of the alkali solution tank is 2.1%.

[0088] From the comparison results, it can be seen that the electrolytic hydrogen production device for reducing the hydrogen content in oxygen of the present invention deeply removes the dissolved hydrogen in the circulating alkali solution through the enhanced removal pipeline accessories and the enhanced removal device, and the dissolved hydrogen content in the circulating alkali solution is reduced from 2.1% to 0.95%, which can effectively reduce the dissolved hydrogen content in the circulating alkali solution, thereby reducing the hydrogen content in oxygen in the electrolytic water hydrogen production system and improving the safety of alkaline water electrolysis hydrogen production.

[0089] It should be noted that the above-described embodiments should be understood as illustrative rather than limiting the scope of protection of the present invention. For those skilled in the art, non-essential improvements and adjustments made to the present invention without departing from the essence and scope of the present invention still fall within the scope of protection of the present invention.

Claims

1. An electrolytic hydrogen production device for reducing the hydrogen content in oxygen, comprising an alkaline electrolytic cell, an anode-side gas-liquid separator, an anode-side gas treatment device, a cathode-side gas-liquid separator, a cathode-side gas treatment device, an alkali liquid tank and an alkali liquid circulation pump; The alkaline electrolytic cell has an anode chamber and a cathode chamber; It is characterized in that The anode chamber is connected to the anode side gas-liquid separator through a first pipeline, and an enhanced removal pipeline accessory is arranged on the first pipeline. The interior of the enhanced removal pipeline accessory is filled with hydrogen absorbing material for preliminary dehydrogenation of the gas-liquid mixture in the anode chamber; The alkali liquid tank is provided with a circulating alkali liquid inlet, and a pipeline at the circulating alkali liquid inlet is provided with an enhanced removal device, the interior of the enhanced removal device is filled with catalytic resin or adsorption resin for deep dehydrogenation of the circulating alkali liquid.

2. The electrolytic hydrogen production device for reducing the hydrogen content in oxygen according to claim 1, characterized in that: The front and rear ends of the enhanced removal pipeline accessory are fixed on the first pipeline through a front baffle and a rear baffle respectively. Full sieve holes are provided on the front baffle and the rear baffle to ensure the normal circulation of the alkali solution inside the first pipeline; the hydrogen absorbing material is filled between the front baffle and the rear baffle.

3. The electrolytic hydrogen production device for reducing the hydrogen content in oxygen according to claim 1, characterized in that: The enhanced removal device has a vertical column cavity, the catalytic resin or adsorption resin is filled in the vertical column cavity, and grid plates are arranged on the top and bottom of the vertical column cavity.

4. The electrolytic hydrogen production device for reducing the hydrogen content in oxygen according to claim 1, characterized in that: The top of the anode chamber is provided with a first gas-liquid mixed phase outlet, and the top of the cathode chamber is provided with a second gas-liquid mixed phase outlet; The anode side gas-liquid separator is provided with a first gas phase outlet at the top, a first liquid phase outlet at the bottom, and a first gas-liquid mixed phase inlet at the middle of the side wall; The cathode side gas-liquid separator is provided with a second gas phase outlet at the top, a second liquid phase outlet at the bottom, and a second gas-liquid mixed phase inlet at the middle of the side wall; A mixed liquid inlet is provided at the top of the enhanced removal device, and a mixed liquid inlet line is provided at the mixed liquid inlet; a mixed liquid outlet is provided at the bottom of the enhanced removal device, and a mixed liquid outlet line is provided at the mixed liquid outlet; The first pipeline connects the first gas-liquid mixed phase outlet and the first gas-liquid mixed phase inlet, and the first liquid phase outlet is connected to the mixed liquid inlet line through the second pipeline; The second gas-liquid mixed phase outlet is connected to the second gas-liquid mixed phase inlet via a third pipeline, and the second liquid phase outlet is connected to the mixed liquid inlet line via a fourth pipeline; The mixed solution outlet line is connected to the circulating alkali solution inlet, the alkali solution tank is connected to the bottom of the alkaline electrolytic cell through a fifth pipeline, and the alkali solution circulation pump is arranged on the fifth pipeline to pump the alkali solution in the alkali solution tank into the alkaline electrolytic cell; The first gas phase outlet is connected to the anode side gas processing device through a sixth pipeline, and the second gas phase outlet is connected to the cathode side gas processing device through a seventh pipeline.

5. The electrolytic hydrogen production device for reducing the hydrogen content in oxygen according to claim 4, characterized in that: The first pipeline, the second pipeline, the third pipeline, the fourth pipeline, the fifth pipeline, the mixed liquid inlet line and the mixed liquid outlet line are all provided with stop valves.

6. The electrolytic hydrogen production device for reducing the hydrogen content in oxygen according to claim 1, characterized in that: The catalytic resin is a palladium catalyst, a platinum catalyst or an alumina catalyst; the adsorption resin is a palladium-based resin or a polystyrene-based adsorption resin.

7. The electrolytic hydrogen production device for reducing the hydrogen content in oxygen according to claim 4, characterized in that: The mixed liquid inlet line, the mixed liquid outlet line, the first pipeline, the second pipeline and the sixth pipeline are all provided with pressure sensors or hydrogen sensors.

8. A method for producing hydrogen by electrolysis for reducing the hydrogen content in oxygen, characterized in that: The electrolytic hydrogen production device for reducing the hydrogen content in oxygen according to any one of claims 1 to 7 comprises the following steps: S1. Under the action of direct current, the water in the alkaline electrolytic cell is decomposed into a gas-liquid mixture containing a large number of fine bubbles; S2. The gas-liquid mixture in the anode chamber is pumped into the enhanced removal pipeline attachment through the first pipeline by the alkali liquid circulation pump for preliminary removal of hydrogen and dissolved hydrogen, and then enters the anode side gas-liquid separator for gas-liquid separation; the gas-liquid mixture in the cathode chamber is pumped into the cathode side gas-liquid separator for gas-liquid separation by the alkali liquid circulation pump; S3. The gas separated by the gas-liquid separator on the anode side enters the anode side gas treatment device for drying and pressurization treatment and then is collected, and the gas separated by the gas-liquid separator on the cathode side enters the cathode side gas treatment device for drying and pressurization treatment and then is collected; the circulating alkali liquid on the anode side and the circulating alkali liquid on the cathode side after gas-liquid separation are mixed and then enter the enhanced removal device for deep dehydrogenation; S4. After completing deep dehydrogenation, the circulating alkali solution flows back to the alkali solution tank, and under the action of the alkali solution circulation pump, re-enters the alkaline electrolytic cell for electrolysis.

9. The method for producing hydrogen by electrolysis by reducing the hydrogen content in oxygen according to claim 8, characterized in that: The volume of the gas-liquid mixed liquid in the anode side gas-liquid separator and the cathode side gas-liquid separator is controlled to be 1 / 2 to 3 / 4 of the volume of the gas-liquid separator.

10. The method for producing hydrogen by electrolysis by reducing the hydrogen content in oxygen according to claim 8, characterized in that: The alkali solution pressure circulating in the enhanced removal pipeline accessories and the alkali solution pressure at the inlet of the enhanced removal device are 1.2-2.0 MPa, and the speed is 4-8 m / s; the outlet pressure of the alkali solution circulation pump is 1.2-2.0 MPa.

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