An electrolytic cell and electrolytic method for generating NO, and a NO preparation system and preparation method including the same

Abstract

The present invention provides an electrolytic cell and an electrolytic method for generating NO, and a NO preparation system and a preparation method thereof, wherein the electrolytic cell comprises an electrolytic tank, an electrolyte is injected into the electrolytic tank, a pair of plates are arranged in parallel in the longitudinal direction in the electrolytic tank, respectively recorded as an anode plate and a cathode plate, the anode plate and the cathode plate are respectively connected to the positive pole and the negative pole of an external power supply, and two rows of parallel fixing components are arranged on the bottom surface of the electrolytic tank, and the fixing components fix the anode plate and the cathode plate respectively. The present invention generates NO by electrolysis in the electrolytic cell, and can realize the instant generation of NO gas according to the use requirements, and the equipment occupies a smaller area, is more flexible in operation, has a higher degree of integration, is more convenient to carry, and is safer to use.

Description

Technical Field

[0001] The present invention belongs to the technical field of gas generation, and relates to an electrolytic cell and an electrolytic method for generating NO, and a NO preparation system and a preparation method thereof. Background Art

[0002] Nitric oxide (NO) is a new biologically active cell messenger and effector molecule discovered in recent years. It has a simple structure, short half-life, active chemical properties, is widely present in various tissues and organs in the body, and is involved in a variety of physiological and pathological processes.

[0003] NO plays a vital role in various systems of the body. For example, in the nervous system, vascular endothelial cells can often release NO. NO activates soluble guanylate cyclase (sGC) in vascular smooth muscle to synthesize cGMP, which reduces the concentration of free calcium ions and thus relaxes blood vessels. It regulates blood pressure and blood flow by regulating vascular tension. In the digestive system, NO, as an endogenous vasodilator, can regulate the blood flow of the gastric and small intestinal mucosa and maintain the integrity of mucosal blood vessels. Exogenous NO can reduce alcohol-induced hemorrhagic gastric mucosal damage. In the respiratory system, NO is the only non-adrenergic and non-cholinergic neurotransmitter with dilating nerve effects in the human airway system. In recent years, bronchial asthma has been considered to be an inflammatory disease. Inflammation causes an increase in oxygen free radicals, which consumes NO, restricts the relaxation of bronchial smooth muscles, causes airway spasms and asthma attacks. In the immune system, NO is an effective weapon for the immune system to fight against pathogens such as bacteria, viruses, and tumor cells. Studies have shown that when endotoxins or T cells in the body activate macrophages and polymorphonuclear leukocytes, they can produce a large amount of iNOS and O2 - At the same time, the respiratory burst of phagocytes produces a large amount of O2 - , NO reacts quickly with it to form ONOO - , which can kill a variety of pathogens and protect the body.

[0004] At present, the main processes for preparing NO include: (1) Synthesis method: nitrogen and oxygen mixed gas pass through an electric arc at 4000 degrees Celsius to directly synthesize nitric oxide; (2) Catalytic oxidation method: in the presence of palladium or platinum catalyst, ammonia burns in oxygen or air to produce gaseous nitric oxide, and after refining and compression, the nitric oxide product is obtained; (3) Thermal decomposition method: heating and decomposing nitrous acid or nitrite to obtain gas, which is refined and compressed to obtain nitric oxide product; (4) Acid hydrolysis method: sodium nitrite reacts with dilute sulfuric acid to produce crude nitric oxide, and then after alkali washing, separation, refining and compression, 99.5% pure nitric oxide can be obtained.

[0005] CN103255431B discloses a method for preparing N2O3 or a mixed gas of NO2 and NO by indirect electrolysis, the method comprising the following steps: (1) adding copper powder and concentrated nitric acid with a mass concentration of more than 30% into an electrolytic cell reactor, and fully reacting to generate NO2 gas and copper nitrate; (2) absorbing part of the NO2 gas generated in step (1) with a 5wt-15wt% nitric acid solution to generate NO gas; mixing the unabsorbed NO2 gas generated in step (1) with the NO gas generated by the reaction in a molar ratio of 1:1, and freezing and pressurizing to generate liquid N2O3; or pressurizing at room temperature to form a mixed gas with a volume ratio of NO2 to NO of 1:1; (3) leaving the reaction mother liquor containing Cu(NO3)2 and HNO3 obtained in the reaction of step (1) in the electrolytic cell reactor as an electrolyte, deprecipitating to obtain copper; then cutting off the power supply, adding fuming nitric acid to the reaction mother liquor until the nitric acid concentration is more than 30%, and carrying out the reaction described in step (1).

[0006] CN206731078U discloses a NO gas generator for producing laboratory-level NO, including a reactor body and a water bath cooling tube; the reactor body is a sealed glass container, and a sulfuric acid liquid inlet, a sodium nitrite liquid inlet and an interface for connecting a water bath cooling tube are provided above the container; the water bath cooling tube is provided with a gas output pipeline, and a cooling tube is provided on the outer wall of the gas output pipeline, and the cooling tube is provided with an inlet and an outlet for cooling water; sulfuric acid and sodium nitrate solution are introduced into the reactor to prepare NO gas, and NO gas is output through the gas output pipeline in the water bath cooling tube. By continuously adding the reaction solution and using a flexible buffer airbag, the continuous preparation of NO can be achieved, avoiding the disadvantages of NO being easily deteriorated and difficult to store during storage.

[0007] However, the current NO generator is large in size and cumbersome to operate, so there is an urgent need to design a new NO generator. Summary of the invention

[0008] In view of the shortcomings of the prior art, the purpose of the present invention is to provide an electrolytic cell and electrolytic method for generating NO, and a NO preparation system and preparation method thereof. The present invention generates NO by electrolysis in an electrolytic cell, and can realize the instant generation of NO gas according to the use requirements. The equipment occupies a smaller area, is more flexible in operation, has a higher degree of integration, is more convenient to carry, and is safer to use.

[0009] To achieve this object, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides an electrolytic cell for generating NO, the electrolytic cell comprising an electrolytic cell, an electrolyte being injected into the electrolytic cell, a pair of electrode plates being longitudinally arranged in parallel in the electrolytic cell, respectively referred to as an anode plate and a cathode plate, the anode plate and the cathode plate being respectively connected to a positive electrode and a negative electrode of an external power source, the bottom surface of the electrolytic cell being provided with two rows of parallel fixing components, the fixing components respectively fixing the anode plate and the cathode plate.

[0011] The present invention generates NO by electrolysis in an electrolytic cell, and can realize instant generation of NO gas according to use requirements. The equipment occupies a smaller area, is more flexible to operate, has a higher degree of integration, is more convenient to carry, and is safer to use.

[0012] As a preferred technical solution of the present invention, a water inlet and a water outlet are provided on the top of the electrolytic cell.

[0013] Preferably, the water inlet and the water outlet are located at the top of the electrolytic cell in the area between the anode plate and the cathode plate.

[0014] Preferably, the line connecting the water inlet and the water outlet is parallel to the electrode plate.

[0015] Preferably, the line connecting the water inlet and the water outlet is close to the cathode plate.

[0016] Preferably, the horizontal distance between the line connecting the water inlet and the water outlet and the cathode plate is 1 to 4 cm, for example, it can be 1.0 cm, 1.2 cm, 1.4 cm, 1.6 cm, 1.8 cm, 2.0 cm, 2.2 cm, 2.4 cm, 2.6 cm, 2.8 cm, 3.0, 3.2, 3.4, 3.6, 3.8 or 4.0 cm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0017] Preferably, the horizontal distance between the anode plate and the cathode plate is 5 to 8 cm, for example, 5.0 cm, 5.5 cm, 6.0 cm, 6.5 cm, 7.0 cm, 7.5 cm or 8.0 cm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0018] Preferably, a water inlet pipe is extended into the electrolytic cell through the water inlet, and a water outlet pipe is extended into the electrolytic cell through the water outlet.

[0019] Preferably, the outlet end of the water inlet pipe is located above the liquid level of the electrolyte, and the outlet end of the water outlet pipe is located below the liquid level of the electrolyte.

[0020] Preferably, two interface modules are provided on the side wall of the electrolytic cell close to one end of the electrode, and the anode plate and the positive electrode of the external power supply, as well as the cathode plate and the negative electrode of the external power supply are respectively connected through the interface modules.

[0021] Preferably, the interface module is a cylindrical metal block sealed and embedded in the side wall of the electrolytic cell.

[0022] As a preferred technical solution of the present invention, the anode plate and the cathode plate are composed of at least one electrode sheet.

[0023] Preferably, the anode plate and cathode plate are composed of at least two tightly fitted electrode sheets.

[0024] Preferably, the number of electrode sheets constituting the anode plate is the same as or different from the number of electrode sheets constituting the cathode plate.

[0025] Preferably, the electrode sheet is a mesh structure.

[0026] Preferably, the mesh number of the electrode sheet is 50 to 300 meshes, for example, it can be 50 mesh, 100 mesh, 150 mesh, 200 mesh, 250 mesh or 300 mesh, but it is not limited to the listed values. Other unlisted values ​​within the numerical range are also applicable. Further preferably, the mesh number of the electrode sheet is 100 mesh.

[0027] Preferably, the material of the electrode sheet is selected from gold, platinum, carbon or stainless steel.

[0028] Preferably, the material of the electrode sheet constituting the anode plate is the same as or different from the material of the electrode sheet constituting the cathode plate.

[0029] Preferably, the length of the electrode sheet is 10 to 15 cm, for example, it can be 10 cm, 11 cm, 12 cm, 13 cm, 14 cm or 15 cm, but it is not limited to the listed values. Other unlisted values ​​within the numerical range are also applicable. Further preferably, the length of the electrode sheet is 12.5 cm.

[0030] Preferably, the width of the electrode sheet is 4 to 7 cm, for example, it can be 4.0 cm, 4.5 cm, 5.0 cm, 5.5 cm, 6.0 cm, 6.5 cm or 7.0 cm, but it is not limited to the listed values. Other unlisted values ​​within the numerical range are also applicable. Further preferably, the width of the electrode sheet is 5 cm.

[0031] Preferably, the aspect ratio of the electrode sheet is (2-3):1, for example, it can be 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1 or 3:1, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0032] Preferably, the fixing assembly includes at least two fixing clamps, and the fixing assembly is fixed to the bottom of the electrolytic cell.

[0033] Preferably, the fixing assembly comprises three fixing clamps which are equidistant and collinearly arranged.

[0034] Preferably, the fixing clamp comprises two folded fixing plates, which clamp and fix the electrode plate after being folded together.

[0035] As a preferred technical solution of the present invention, the electrolyte includes a buffer solution, a nitrite and a copper-based catalyst.

[0036] Preferably, the concentration of the buffer is 0.01-3 mol / L, for example, 0.01 mol / L, 0.5 mol / L, 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L or 3 mol / L, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0037] Preferably, the buffer comprises 4-hydroxyethylpiperazineethanesulfonic acid buffer, 3-morpholinepropanesulfonic acid buffer, phosphate buffer or organic buffer.

[0038] Preferably, the concentration of nitrite is 0.01-5 mol / L, for example, it can be 0.01 mol / L, 0.5 mol / L, 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L, 3 mol / L, 3.5 mol / L, 4 mol / L, 4.5 mol / L or 5 mol / L, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0039] Preferably, the concentration of the copper-based catalyst is 1 to 7 mmol / L, for example, 1 mmol / L, 2 mmol / L, 3 mmol / L, 4 mmol / L, 5 mmol / L, 6 mmol / L or 7 mmol / L, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0040] Preferably, the copper-based catalyst is selected from one or a combination of at least two of tris(2-pyridylmethyl)amine copper(II), 1,4,7-triazacyclononane copper(II), 1,4,7-trimethyl-1,4,7-triazacyclononane copper(II), tris(2-aminoethyl)amine copper(II), tris(2-dimethylaminoethyl)amine copper(II) or bis(2-aminomethylpyridine)-propionic acid copper(II).

[0041] In a second aspect, the present invention provides an electrolytic method for generating NO, wherein NO gas is generated by electrolysis using the electrolytic cell described in the first aspect. The electrolytic method comprises: applying current to the anode plate and the cathode plate, and electrolyzing the electrolyte to generate NO gas under the action of the current.

[0042] As a preferred technical solution of the present invention, a current of 10 to 300 mA is applied to the anode plate and the cathode plate, for example, it can be 10 mA, 50 mA, 100 mA, 150 mA, 200 mA, 250 mA or 300 mA, but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0043] Preferably, a current of 200 to 300 mA is applied to the anode plate and the cathode plate, for example, it may be 200 mA, 210 mA, 220 mA, 230 mA, 240 mA, 250 mA, 260 mA, 270 mA, 280 mA, 290 mA or 300 mA, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0044] Preferably, the temperature of the electrolyte is controlled at 10-30°C, for example, it can be 10°C, 11°C, 12°C, 13°C, 14°C, 15°C, 16°C, 17°C, 18°C, 19°C, 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, 29°C or 30°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable. Further preferably, the temperature of the electrolyte is controlled at 20-25°C.

[0045] Preferably, the concentration of NO gas in the gas generated by electrolysis is 0 to 320 ppm, for example, 10 ppm, 50 ppm, 100 ppm, 150 ppm, 200 ppm, 250 ppm, 300 ppm or 320 ppm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0046] In a third aspect, the present invention provides a NO production system, the NO production system comprising an electrolytic cell and a gas-liquid separation device which are cyclically connected, the electrolytic cell being the electrolytic cell described in the first aspect.

[0047] As a preferred technical solution of the present invention, the gas-liquid separation device includes a cylindrical shell and a tubular membrane assembly horizontally arranged inside the shell along its axial direction, and an annular columnar gas containing chamber is formed between the inner circumference of the shell and the outer circumference of the membrane assembly; NO generated by the electrolytic cell enters the membrane assembly along with the electrolyte, the NO gas passes through the membrane assembly and enters the gas containing chamber, and the electrolyte flows back to the electrolytic cell.

[0048] Preferably, the shell is provided with an air inlet and an air outlet communicating with the gas containing chamber, the air inlet is externally connected to a carrier gas source, and the carrier gas source is used to transport carrier gas into the gas containing chamber to drive NO gas to be discharged from the air outlet.

[0049] Preferably, the liquid outlet of the membrane assembly is connected to the water inlet of the electrolytic cell via a water inlet pipe, and the liquid inlet of the membrane assembly is connected to the water outlet of the electrolytic cell via a water outlet pipe;

[0050] Preferably, a liquid pump is provided on the water outlet pipe, and the electrolyte from which NO gas has been filtered out flows back into the electrolytic cell through the liquid pump.

[0051] In a fourth aspect, the present invention provides a method for preparing NO using the preparation system described in the third aspect, the method comprising:

[0052] The NO generated by electrolysis in the electrolytic cell circulates into the gas-liquid separation device along with the electrolyte, and NO gas is obtained after gas-liquid separation.

[0053] As a preferred technical solution of the present invention, the method specifically comprises:

[0054] The NO gas generated by the electrolytic cell enters the gas-liquid separation device along with the electrolyte circulation, and the NO gas passes through the membrane component and enters the gas containing chamber for temporary storage. The carrier gas source introduces carrier gas into the gas containing chamber, and the NO gas is discharged from the gas-liquid separation device under the drive of the carrier gas. After the electrolyte is intercepted by the membrane component, it flows back to the electrolyte through the liquid pump for recycling.

[0055] Preferably, the carrier gas is air.

[0056] Preferably, the carrier gas is introduced into the gas containing chamber at a flow rate of 0.5 to 1.5 L / min, for example, it can be 0.5 L / min, 0.6 L / min, 0.7 L / min, 0.8 L / min, 0.9 L / min, 1.0 L / min, 1.1 L / min, 1.2 L / min, 1.3 L / min, 1.4 L / min or 1.5 L / min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0057] Preferably, the circulation volume of the electrolyte is 0.8 to 1.4 L / min, for example, it can be 0.8 L / min, 0.9 L / min, 1.0 L / min, 1.1 L / min, 1.2 L / min, 1.3 L / min or 1.4 L / min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0058] Preferably, NO and the carrier gas form a mixed gas and then discharge from the gas-liquid separation device. The flow rate of the mixed gas is 0.5 to 1.5 L / min, for example, it can be 0.5 L / min, 0.6 L / min, 0.7 L / min, 0.8 L / min, 0.9 L / min, 1.0 L / min, 1.1 L / min, 1.2 L / min, 1.3 L / min, 1.4 L / min or 1.5 L / min, but it is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0059] Preferably, the concentration of NO in the mixed gas formed by NO and the carrier gas is 0 to 320 ppm, for example, it can be 10 ppm, 50 ppm, 100 ppm, 150 ppm, 200 ppm, 250 ppm, 300 ppm or 320 ppm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0060] The system refers to an equipment system, a device system or a production device.

[0061] Compared with the prior art, the present invention has the following beneficial effects:

[0062] (1) The present invention generates NO by electrolysis in an electrolytic cell, and can realize the instant generation of NO gas according to the use requirements. The equipment occupies a smaller area, is more flexible in operation, has a higher degree of integration, is more convenient to carry, and is safer to use.

[0063] (2) The present invention separates NO gas from the electrolyte by providing a gas-liquid separation device, thereby achieving efficient separation of NO gas, generating NO with higher purity and low content of by-product NO2. BRIEF DESCRIPTION OF THE DRAWINGS

[0064] Figure 1 A schematic diagram of the structure of a NO production system provided in a specific embodiment of the present invention;

[0065] Figure 2 A side view of an electrolytic cell provided for one embodiment of the present invention;

[0066] Among them, 1-electrolytic cell; 11-electrolytic tank; 12-cathode plate; 13-anode plate; 14-fixed component; 15-water inlet; 16-water outlet; 17-power supply; 18-water outlet pipe; 19-water inlet pipe; 2-gas-liquid separation device; 21-shell; 22-membrane assembly; 23-gas containing chamber; 3-carrier gas source; 4-liquid pump.

[0067] Figure 3 A changing trend diagram of the influence of the water inlet and outlet positions on the NO concentration provided in Example 4;

[0068] Figure 4 The variation trend diagram of the effect of the number of electrode plate layers on NO concentration provided in Example 6

[0069] Figure 5 The trend diagram of the effect of current size on NO concentration provided in Example 7

[0070] Figure 6 A trend chart of the intra-batch difference of the same batch of electrolytes provided in Example 8;

[0071] Figure 7 A trend chart of the batch differences of different batches of electrolyte provided in Example 9;

[0072] Figure 8 This is a graph showing the changing trend of the effect of electrolyte placement time on NO concentration provided in Example 10. DETAILED DESCRIPTION

[0073] It should be understood that, in the description of the present invention, the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", etc., indicating the orientation or positional relationship are based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention. In addition, the terms "first", "second", etc. are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first", "second", etc. may explicitly or implicitly include one or more of the features. In the description of the present invention, unless otherwise specified, "multiple" means two or more.

[0074] It should be noted that in the description of the present invention, unless otherwise clearly specified and limited, the terms "disposed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two elements. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood by specific circumstances.

[0075] The technical solution of the present invention is further described below with reference to the accompanying drawings and through specific implementation methods.

[0076] In a specific embodiment, the present invention provides an electrolytic cell 1 for generating NO, wherein the electrolytic cell 1 is as follows: Figure 1 and Figure 2 As shown, it includes an electrolytic cell 11, into which electrolyte is injected, and a pair of electrode plates are longitudinally arranged in parallel in the electrolytic cell 11, which are respectively denoted as an anode plate 13 and a cathode plate 12, and the anode plate 13 and the cathode plate 12 are respectively connected to the positive electrode and the negative electrode of an external power supply 17, and two rows of parallel fixing components 14 are arranged on the bottom surface of the electrolytic cell 11, and the fixing components 14 respectively fix the anode plate 13 and the cathode plate 12.

[0077] The top of the electrolytic cell 11 is provided with a water inlet 15 and a water outlet 16, which are located at the top of the electrolytic cell in the area between the anode plate 13 and the cathode plate 12, and the line connecting the water inlet 15 and the water outlet 16 is close to the cathode plate 12 and parallel to the cathode plate 12. A water inlet pipe 19 is extended into the electrolytic cell 11 through the water inlet 15, and a water outlet pipe 18 is extended into the electrolytic cell through the water outlet 16, the outlet end of the water inlet pipe 19 is located above the liquid level of the electrolyte, and the outlet end of the water outlet pipe 18 is located below the liquid level of the electrolyte. Specifically, the horizontal distance between the line connecting the water inlet 15 and the water outlet 16 and the cathode plate 12 is 1 to 4 cm, and the horizontal distance between the anode plate 13 and the cathode plate 12 is 5 to 8 cm.

[0078] A first interface module and a second interface module are provided on the side wall of the electrolytic cell 11 near one end of the electrode. The first interface module is electrically connected to the anode plate 13 and the positive electrode of the external power supply 17, and the second module is electrically connected to the cathode plate 12 and the negative electrode of the external power supply 17. The first interface module and the second interface module are cylindrical metal blocks sealed and embedded in the side wall of the electrolytic cell 11.

[0079] The anode plate 13 and the cathode plate 12 are composed of at least one electrode sheet, and further, the anode plate 13 and the cathode plate 12 are composed of at least two tightly fitted electrode sheets. The number of electrode sheets constituting the anode plate 13 is the same as or different from the number of electrode sheets constituting the cathode plate 12. The electrode sheet is a mesh structure, the mesh number of the electrode sheet can be selected from 50 to 300 meshes, the material of the electrode sheet is selected from gold, platinum, carbon or stainless steel, and the material of the electrode sheet constituting the anode plate 13 is the same as or different from the material of the electrode sheet constituting the cathode plate 12. The length of the electrode sheet can be selected from 10 to 15 cm, the width of the electrode sheet can be selected from 4 to 7 cm, and the aspect ratio of the electrode sheet is (2 to 3): 1.

[0080] The fixing assembly 14 includes at least two fixing clamps, and the fixing assembly 14 is fixed to the bottom of the electrolytic cell 11. The fixing assembly 14 includes three fixing clamps that are equidistant and arranged in a collinear manner. The fixing clamps include two folded fixing plates, and the two fixing plates are folded to clamp and fix the electrode plates.

[0081] In another specific embodiment, the present invention provides a NO production system, wherein the NO production system is as follows: Figure 1 As shown, it includes an electrolytic cell 1 and a gas-liquid separation device 2 which are cyclically connected.

[0082] The gas-liquid separation device 2 includes a cylindrical shell 21 and a tubular membrane assembly 22 horizontally arranged inside the shell 21 along its axial direction. An annular cylindrical gas containing chamber 23 is formed between the inner circumference of the shell 21 and the outer circumference of the membrane assembly 22. The NO generated by the electrolytic cell 1 enters the membrane assembly 22 along with the electrolyte, and the NO gas passes through the membrane assembly 22 and enters the gas containing chamber 23, and the electrolyte flows back to the electrolytic cell 1. The shell 21 is provided with an air inlet and an air outlet connected to the gas containing chamber 23. The air inlet is externally connected to a carrier gas source 3, and the carrier gas source 3 is used to transport carrier gas into the gas containing chamber 23 to drive the NO gas to be discharged from the air outlet. A liquid pump 4 is arranged on the connecting pipeline between the liquid outlet of the membrane assembly 22 and the reflux port of the electrolytic cell 1, and the electrolyte from which the NO gas has been filtered flows back to the electrolytic cell 1 through the liquid pump 4.

[0083] In another specific embodiment, the present invention provides a method for preparing NO using the above-mentioned NO preparation system, the method comprising:

[0084] (1) applying a current of 10 to 300 mA to the anode plate 13 and the cathode plate 12, and an electrolyte at 10 to 30° C. is electrolyzed to generate NO gas under the action of the current; the electrolyte comprises 0.01 to 3 mol / L of a buffer solution, 0.01 to 5 mol / L of a nitrite, and 1 to 7 mmol / L of a copper-based catalyst; wherein the buffer solution comprises 4-hydroxyethylpiperazineethanesulfonic acid buffer solution, 3-morpholinepropanesulfonic acid buffer solution, phosphate buffer solution, or an organic buffer solution; and the copper-based catalyst is selected from one or a combination of at least two of tris(2-pyridylmethyl)amine copper(II), 1,4,7-triazacyclononane copper(II), 1,4,7-trimethyl-1,4,7-triazacyclononane copper(II), tris(2-aminoethyl)amine copper(II), tris(2-dimethylaminoethyl)amine copper(II), or bis(2-aminomethylpyridine)-propionic acid copper(II);

[0085] (2) NO gas generated by the electrolytic cell 1 enters the gas-liquid separation device 2 along with the electrolyte circulation, and the NO gas passes through the membrane assembly 22 and enters the gas containing chamber 23 for temporary storage;

[0086] (3) The carrier gas source 3 introduces air into the gas containing chamber 23 at a flow rate of 0.5 to 1.5 L / min, and the NO gas is discharged from the gas-liquid separation device 2 under the drive of the carrier gas. The mixed gas formed by NO and the carrier gas is discharged from the gas-liquid separation device 2 at a flow rate of 0.5 to 1.5 L / min, and the concentration of NO in the mixed gas is 0 to 320 ppm;

[0087] (4) After being intercepted by the membrane assembly 22, the electrolyte flows back to the electrolyte through the liquid pump 4 for recycling. The circulation rate of the electrolyte is 0.8 to 1.4 L / min.

[0088] Example 1

[0089] This embodiment provides a NO production system, wherein the NO production system is as follows: Figure 1 As shown, it includes an electrolytic cell 1 and a gas-liquid separation device 2 which are cyclically connected.

[0090] Among them, electrolytic cell 1 is as Figure 1 and Figure 2 As shown, it includes an electrolytic cell 11, into which electrolyte is injected, and a pair of electrode plates are longitudinally arranged in parallel in the electrolytic cell 11, which are respectively denoted as an anode plate 13 and a cathode plate 12, and the anode plate 13 and the cathode plate 12 are respectively connected to the positive electrode and the negative electrode of an external power supply 17, and two rows of parallel fixing components 14 are arranged on the bottom surface of the electrolytic cell 11, and the fixing components 14 respectively fix the anode plate 13 and the cathode plate 12.

[0091] The top of the electrolytic cell 11 is provided with a water inlet 15 and a water outlet 16, and the line connecting the water inlet 15 and the water outlet 16 is close to and parallel to the cathode plate 12. A water inlet pipe 19 is extended into the electrolytic cell 11 through the water inlet 15, and a water outlet pipe 18 is extended into the electrolytic cell through the water outlet 16. The outlet end of the water inlet pipe 19 is located above the liquid level of the electrolyte, and the outlet end of the water outlet pipe 18 is located below the liquid level of the electrolyte. The horizontal distance between the line connecting the water inlet 15 and the water outlet 16 and the cathode plate 12 is 1 cm, and the horizontal distance between the anode plate 13 and the cathode plate 12 is 5 cm.

[0092] A first interface module and a second interface module are provided on the side wall of the electrolytic cell 11 near one end of the electrode. The first interface module is electrically connected to the anode plate 13 and the positive electrode of the external power supply 17, and the second module is electrically connected to the cathode plate 12 and the negative electrode of the external power supply 17. The first interface module and the second interface module are cylindrical metal blocks sealed and embedded in the side wall of the electrolytic cell 11.

[0093] The anode plate 13 and the cathode plate 12 are composed of two closely fitting electrode plates. The electrode plates are 50 mesh mesh structures, and the electrode plate materials constituting the anode plate 13 and the electrode plate materials constituting the cathode plate 12 are both gold. The length of the electrode plate is 10 cm, and the width of the electrode plate is 4 cm.

[0094] The fixing assembly 14 includes three fixing clamps which are arranged equidistantly and collinearly. The fixing clamps include two fixing plates which are closed together, and the two fixing plates are closed together to clamp and fix the electrode plate.

[0095] The gas-liquid separation device 2 includes a cylindrical shell 21 and a tubular membrane assembly 22 horizontally arranged inside the shell 21 along its axial direction. An annular cylindrical gas containing chamber 23 is formed between the inner circumference of the shell 21 and the outer circumference of the membrane assembly 22. The NO generated by the electrolytic cell 1 enters the membrane assembly 22 along with the electrolyte, and the NO gas passes through the membrane assembly 22 and enters the gas containing chamber 23, and the electrolyte flows back to the electrolytic cell 1. The shell 21 is provided with an air inlet and an air outlet connected to the gas containing chamber 23. The air inlet is externally connected to a carrier gas source 3, and the carrier gas source 3 is used to transport carrier gas into the gas containing chamber 23 to drive the NO gas to be discharged from the air outlet. The liquid outlet of the membrane assembly 22 is connected to the water inlet 15 of the electrolytic cell 1 through the water inlet pipe 19, and the liquid inlet of the membrane assembly 22 is connected to the water outlet 16 of the electrolytic cell 1 through the water outlet pipe 18. A liquid pump 4 is provided on the water outlet pipe 18, and the electrolyte from which the NO gas has been filtered flows back to the electrolytic cell through the liquid pump.

[0096] This embodiment also provides a method for preparing NO using the above-mentioned NO preparation system, the method comprising:

[0097] (1) A current of 10 mA is applied to the anode plate 13 and the cathode plate 12, and an electrolyte at 10° C. is electrolyzed to generate NO gas under the action of the current; the electrolyte comprises 0.01 mol / L buffer, 0.01 mol / L nitrite and 1 mmol / L copper-based catalyst; wherein the buffer is 4-hydroxyethylpiperazineethanesulfonic acid buffer, and the copper-based catalyst is tris(2-pyridylmethyl)amine copper(II);

[0098] (2) NO gas generated by the electrolytic cell 1 enters the gas-liquid separation device 2 along with the electrolyte circulation, and the NO gas passes through the membrane assembly 22 and enters the gas containing chamber 23 for temporary storage;

[0099] (3) The carrier gas source 3 introduces air into the gas containing chamber 23 at a flow rate of 0.5 L / min, and the NO gas is discharged from the gas-liquid separation device 2 under the drive of the carrier gas. The mixed gas formed by NO and the carrier gas is discharged from the gas-liquid separation device 2 at a flow rate of 0.5 L / min, and the concentration of NO in the mixed gas is 12 ppm;

[0100] (4) After being intercepted by the membrane assembly 22, the electrolyte flows back to the electrolyte through the liquid pump 4 for recycling. The circulation rate of the electrolyte is 0.8 L / min.

[0101] Example 2

[0102] This embodiment provides a NO production system, wherein the NO production system is as follows: Figure 1 As shown, it includes an electrolytic cell 1 and a gas-liquid separation device 2 which are cyclically connected.

[0103] Among them, electrolytic cell 1 is as Figure 1 and Figure 2 As shown, it includes an electrolytic cell 11, into which electrolyte is injected, and a pair of electrode plates are longitudinally arranged in parallel in the electrolytic cell 11, which are respectively denoted as an anode plate 13 and a cathode plate 12, and the anode plate 13 and the cathode plate 12 are respectively connected to the positive electrode and the negative electrode of an external power supply 17, and two rows of parallel fixing components 14 are arranged on the bottom surface of the electrolytic cell 11, and the fixing components 14 respectively fix the anode plate 13 and the cathode plate 12.

[0104] The top of the electrolytic cell 11 is provided with a water inlet 15 and a water outlet 16, which are located at the top of the electrolytic cell in the area between the anode plate 13 and the cathode plate 12, and the line connecting the water inlet 15 and the water outlet 16 is close to the cathode plate 12 and parallel to the cathode plate 12. A water inlet pipe 19 is extended into the electrolytic cell 11 through the water inlet 15, and a water outlet pipe 18 is extended into the electrolytic cell through the water outlet 16, the outlet end of the water inlet pipe 19 is located above the liquid level of the electrolyte, and the outlet end of the water outlet pipe 18 is located below the liquid level of the electrolyte. The horizontal distance between the line connecting the water inlet 15 and the water outlet 16 and the cathode plate 12 is 2 cm, and the horizontal distance between the anode plate 13 and the cathode plate 12 is 6 cm.

[0105] A first interface module and a second interface module are provided on the side wall of the electrolytic cell 11 near one end of the electrode. The first interface module is electrically connected to the anode plate 13 and the positive electrode of the external power supply 17, and the second module is electrically connected to the cathode plate 12 and the negative electrode of the external power supply 17. The first interface module and the second interface module are cylindrical metal blocks sealed and embedded in the side wall of the electrolytic cell 11.

[0106] The anode plate 13 and the cathode plate 12 are composed of six closely fitting electrode plates. The electrode plates are 150 mesh mesh structures, and the electrode plates constituting the anode plate 13 and the electrode plates constituting the cathode plate 12 are both made of platinum. The length of the electrode plates is 12 cm, and the width of the electrode plates is 5 cm.

[0107] The fixing assembly 14 includes three fixing clamps which are arranged equidistantly and collinearly. The fixing clamps include two fixing plates which are closed together, and the two fixing plates are closed together to clamp and fix the electrode plate.

[0108] The gas-liquid separation device 2 includes a cylindrical shell 21 and a tubular membrane assembly 22 horizontally arranged inside the shell 21 along its axial direction. An annular cylindrical gas containing chamber 23 is formed between the inner circumference of the shell 21 and the outer circumference of the membrane assembly 22. The NO generated by the electrolytic cell 1 enters the membrane assembly 22 along with the electrolyte, and the NO gas passes through the membrane assembly 22 and enters the gas containing chamber 23, and the electrolyte flows back to the electrolytic cell 1. The shell 21 is provided with an air inlet and an air outlet connected to the gas containing chamber 23. The air inlet is externally connected to a carrier gas source 3, and the carrier gas source 3 is used to transport carrier gas into the gas containing chamber 23 to drive the NO gas to be discharged from the air outlet. The liquid outlet of the membrane assembly 22 is connected to the water inlet 15 of the electrolytic cell 1 through the water inlet pipe 19, and the liquid inlet of the membrane assembly 22 is connected to the water outlet 16 of the electrolytic cell 1 through the water outlet pipe 18. A liquid pump 4 is provided on the water outlet pipe 18, and the electrolyte from which the NO gas has been filtered flows back to the electrolytic cell through the liquid pump.

[0109] This embodiment also provides a method for preparing NO using the above-mentioned NO preparation system, the method comprising:

[0110] (1) A current of 200 mA is applied to the anode plate 13 and the cathode plate 12, and an electrolyte at 20° C. is electrolyzed to generate NO gas under the action of the current; the electrolyte comprises a 2 mol / L buffer solution, a 3 mol / L nitrite, and a 4 mmol / L copper-based catalyst; wherein the buffer solution is a 3-morpholinepropanesulfonic acid buffer solution; and the copper-based catalyst is 1,4,7-triazacyclononane copper (II);

[0111] (2) NO gas generated by the electrolytic cell 1 enters the gas-liquid separation device 2 along with the electrolyte circulation, and the NO gas passes through the membrane assembly 22 and enters the gas containing chamber 23 for temporary storage;

[0112] (3) The carrier gas source 3 introduces air into the gas containing chamber 23 at a flow rate of 1 L / min, and the NO gas is discharged from the gas-liquid separation device 2 under the drive of the carrier gas. The mixed gas formed by NO and the carrier gas is discharged from the gas-liquid separation device 2 at a flow rate of 1 L / min, and the concentration of NO in the mixed gas is 150 ppm;

[0113] (4) After being intercepted by the membrane assembly 22, the electrolyte flows back to the electrolyte through the liquid pump 4 for recycling. The circulation rate of the electrolyte is 1.1 L / min.

[0114] Example 3

[0115] This embodiment provides a NO production system, wherein the NO production system is as follows: Figure 1 As shown, it includes an electrolytic cell 1 and a gas-liquid separation device 2 which are cyclically connected.

[0116] Among them, electrolytic cell 1 is as Figure 1 and Figure 2 As shown, it includes an electrolytic cell 11, into which electrolyte is injected, and a pair of electrode plates are longitudinally arranged in parallel in the electrolytic cell 11, which are respectively denoted as an anode plate 13 and a cathode plate 12, and the anode plate 13 and the cathode plate 12 are respectively connected to the positive electrode and the negative electrode of an external power supply 17, and two rows of parallel fixing components 14 are arranged on the bottom surface of the electrolytic cell 11, and the fixing components 14 respectively fix the anode plate 13 and the cathode plate 12.

[0117] The top of the electrolytic cell 11 is provided with a water inlet 15 and a water outlet 16, which are located at the top of the electrolytic cell in the area between the anode plate 13 and the cathode plate 12, and the line connecting the water inlet 15 and the water outlet 16 is close to the cathode plate 12 and parallel to the cathode plate 12. A water inlet pipe 19 is extended into the electrolytic cell 11 through the water inlet 15, and a water outlet pipe 18 is extended into the electrolytic cell through the water outlet 16, the outlet end of the water inlet pipe 19 is located above the liquid level of the electrolyte, and the outlet end of the water outlet pipe 18 is located below the liquid level of the electrolyte. Specifically, the horizontal distance between the line connecting the water inlet 15 and the water outlet 16 and the cathode plate 12 is 4 cm, and the horizontal distance between the anode plate 13 and the cathode plate 12 is 8 cm.

[0118] A first interface module and a second interface module are provided on the side wall of the electrolytic cell 11 near one end of the electrode. The first interface module is electrically connected to the anode plate 13 and the positive electrode of the external power supply 17, and the second module is electrically connected to the cathode plate 12 and the negative electrode of the external power supply 17. The first interface module and the second interface module are cylindrical metal blocks sealed and embedded in the side wall of the electrolytic cell 11.

[0119] The anode plate 13 and the cathode plate 12 are composed of 12 closely fitting electrode sheets. The electrode sheets are 300 mesh mesh structures, and the electrode sheet materials constituting the anode plate 13 and the electrode sheet materials constituting the cathode plate 12 are both carbon materials. The length of the electrode sheet is 15 cm, and the width of the electrode sheet is 7 cm.

[0120] The fixing assembly 14 includes two fixing clamps, and the fixing assembly 14 is fixed to the bottom of the electrolytic cell 11. The fixing assembly 14 includes three fixing clamps that are equidistant and arranged in a collinear manner. The fixing clamps include two folded fixing plates, and the two fixing plates are folded together to clamp and fix the electrode plates.

[0121] The gas-liquid separation device 2 includes a cylindrical shell 21 and a tubular membrane assembly 22 horizontally arranged inside the shell 21 along its axial direction. An annular cylindrical gas containing chamber 23 is formed between the inner circumference of the shell 21 and the outer circumference of the membrane assembly 22. The NO generated by the electrolytic cell 1 enters the membrane assembly 22 along with the electrolyte, and the NO gas passes through the membrane assembly 22 and enters the gas containing chamber 23, and the electrolyte flows back to the electrolytic cell 1. The shell 21 is provided with an air inlet and an air outlet connected to the gas containing chamber 23. The air inlet is externally connected to a carrier gas source 3, and the carrier gas source 3 is used to transport carrier gas into the gas containing chamber 23 to drive the NO gas to be discharged from the air outlet. The liquid outlet of the membrane assembly 22 is connected to the water inlet 15 of the electrolytic cell 1 through the water inlet pipe 19, and the liquid inlet of the membrane assembly 22 is connected to the water outlet 16 of the electrolytic cell 1 through the water outlet pipe 18. A liquid pump 4 is provided on the water outlet pipe 18, and the electrolyte from which the NO gas has been filtered flows back to the electrolytic cell through the liquid pump.

[0122] This embodiment also provides a method for preparing NO using the above-mentioned NO preparation system, the method comprising:

[0123] (1) A current of 300 mA is applied to the anode plate 13 and the cathode plate 12, and an electrolyte at 30° C. is electrolyzed under the action of the current to produce NO gas; the electrolyte comprises 3 mol / L buffer, 5 mol / L nitrite and 7 mmol / L copper-based catalyst; wherein the buffer is phosphate buffer; and the copper-based catalyst is 1,4,7-trimethyl-1;

[0124] (2) NO gas generated by the electrolytic cell 1 enters the gas-liquid separation device 2 along with the electrolyte circulation, and the NO gas passes through the membrane assembly 22 and enters the gas containing chamber 23 for temporary storage;

[0125] (3) The carrier gas source 3 introduces air into the gas containing chamber 23 at a flow rate of 1.5 L / min, and the NO gas is discharged from the gas-liquid separation device 2 under the drive of the carrier gas. The mixed gas formed by NO and the carrier gas is discharged from the gas-liquid separation device 2 at a flow rate of 1.5 L / min, and the concentration of NO in the mixed gas is 120 ppm;

[0126] (4) After being intercepted by the membrane assembly 22, the electrolyte flows back to the electrolyte through the liquid pump 4 for recycling. The circulation rate of the electrolyte is 1.4 L / min.

[0127] Example 4

[0128] This embodiment provides a test experiment, the purpose of which is to explore the influence of the position of the water inlet and outlet 15 / 16 on the NO concentration. It should be noted that the position of the water inlet and outlet 15 / 16 referred to in this embodiment refers to the horizontal distance between the line connecting the water inlet 15 and the water outlet 16 and the cathode plate 12.

[0129] The experimental conditions for this test are as follows:

[0130] (1) Structural parameters: The horizontal distance between the anode plate 13 and the cathode plate 12 is 7 cm. The anode plate 13 and the cathode plate 12 are both composed of 16 layers of tightly fitted mesh-structured stainless steel electrode sheets, and the mesh number of the electrode sheet is 300 meshes. The length of the electrode sheet is 12.5 cm, and the width of the electrode sheet is 5 cm.

[0131] (2) Electrochemical parameters: A current of 200 mA was applied to the anode plate 13 and the cathode plate 12;

[0132] (3) Process parameters: The electrolyte temperature is room temperature, the carrier gas is introduced into the gas containing chamber 23 at a flow rate of 1 L / min, the circulation volume of the electrolyte is 0.8 L / min, the flow rate of the mixed gas is 1 L / min, and the mixed gas and air are mixed in a volume ratio of 1:4 to form a therapeutic gas.

[0133] The variable of this test is the distance between the water inlet and outlet 15 / 16 and the electrode. When the distance is 1 cm (i.e. the horizontal distance between the line connecting the water inlet 15 and the water outlet 16 and the cathode plate 12 is 1 cm), the NO concentration is continuously tested. The test results are as follows: Figure 3 When the distance is 3 cm (i.e., the horizontal distance between the line connecting the water inlet 15 and the water outlet 16 and the cathode plate 12 is 3 cm), the NO concentration in the treatment gas is continuously tested, and the test results are as follows: Figure 3 shown.

[0134] Depend on Figure 3 It can be seen that, from the horizontal comparison, no matter the distance is 1 cm or 3 cm, the NO concentration value is relatively stable over time, but from the vertical comparison, when the distance is 3 cm, the NO concentration is stable at 14.2ppm; when the distance is 1 cm, the NO concentration is stable at 16.6ppm; there is a difference of about 2.5ppm between the two, that is, the closer the distance between the water inlet and outlet 16 and the electrode, the higher the NO concentration generated. This is mainly because NO is generated on the electrode surface, and the water inlet and outlet 15 / 16 close to the electrode surface helps NO to disperse in the electrolyte.

[0135] Example 5

[0136] This embodiment provides a test experiment, the purpose of which is to explore the effect of electrolyte temperature on NO concentration. The experimental conditions of this test are as follows:

[0137] (1) Structural parameters: The horizontal distance between the line connecting the water inlet 15 and the water outlet 16 and the cathode plate 12 is 2 cm, and the horizontal distance between the anode plate 13 and the cathode plate 12 is 5 cm. The anode plate 13 and the cathode plate 12 are both composed of 4 layers of tightly fitted mesh-structured stainless steel electrode sheets, and the mesh number of the electrode sheet is 100 meshes. The length of the electrode sheet is 12.5 cm, and the width of the electrode sheet is 5 cm.

[0138] (2) Electrochemical parameters: A current of 200 mA was applied to the anode plate 13 and the cathode plate 12;

[0139] (3) Process parameters: The carrier gas is introduced into the gas containing chamber 23 at a flow rate of 1 L / min, the circulation volume of the electrolyte is 0.8 L / min, the flow rate of the mixed gas is 1 L / min, and the mixed gas and air are mixed in a volume ratio of 1:4 to form the therapeutic gas.

[0140] The variable of this test is the electrolyte temperature. The electrolyte is prepared at 13-25°C. The NO gas generated by electrolysis of the electrolyte at different temperatures is used to prepare the therapeutic gas. The NO concentration in the therapeutic gas is continuously tested. The test results are shown in the following table:

[0141]

[0142] It can be seen from the above figure that as the electrolyte temperature increases, the NO concentration in the treatment gas gradually increases.

[0143] Example 6

[0144] This embodiment provides a test experiment, the purpose of which is to explore the effect of the number of electrode plate layers on NO concentration. The experimental conditions of this test are as follows:

[0145] (1) Structural parameters: The horizontal distance between the line connecting the water inlet 15 and the water outlet 16 and the cathode plate 12 is 2 cm, and the horizontal distance between the anode plate 13 and the cathode plate 12 is 5 cm. The anode plate 13 and the cathode plate 12 are both composed of a multi-layer mesh structure stainless steel electrode sheet (in this embodiment, the NO concentration is tested by changing the number of layers), and the mesh number of the electrode sheet is 100 mesh. The length of the electrode sheet is 12.5 cm, and the width of the electrode sheet is 5 cm.

[0146] (2) Electrochemical parameters: A current of 200 mA was applied to the anode plate 13 and the cathode plate 12;

[0147] (3) Process parameters: The electrolyte temperature is room temperature, the carrier gas is introduced into the gas containing chamber 23 at a flow rate of 1 L / min, the circulation volume of the electrolyte is 0.8 L / min, the flow rate of the mixed gas is 1 L / min, and the mixed gas and air are mixed in a volume ratio of 1:7 to form a therapeutic gas.

[0148] The variable of this test is the number of electrode plate layers. When other experimental conditions remain unchanged, electrode plates with 2 layers, 4 layers and 8 layers are used as anode plates 13 and cathode plates 12 respectively (the number of layers of anode plates 13 and cathode plates 12 are ensured to be the same in each test), and the NO concentration in the treatment gas is continuously tested. The test results are as follows: Figure 4 shown.

[0149] Depend on Figure 4 It can be seen that under the action of 200mA current, the more electrode layers there are, the lower the measured NO concentration is. The reason is that due to the large number of electrode layers, the NO enriched on the electrode surface cannot diffuse out with the solution, resulting in a decrease in the measured concentration.

[0150] Example 7

[0151] This embodiment provides a test experiment, the purpose of which is to explore the effect of current size on NO concentration. The experimental conditions of this test are as follows:

[0152] (1) Structural parameters: The horizontal distance between the line connecting the water inlet 15 and the water outlet 16 and the cathode plate 12 is 2 cm, and the horizontal distance between the anode plate 13 and the cathode plate 12 is 5 cm. The anode plate 13 and the cathode plate 12 are both composed of 16 layers of tightly fitted mesh-structured stainless steel electrode sheets, and the mesh number of the electrode sheet is 300 meshes. The length of the electrode sheet is 15 cm, and the width of the electrode sheet is 6 cm.

[0153] (2) Electrochemical parameters: This example tests the relationship between current and NO concentration by changing the current magnitude;

[0154] (3) Process parameters: The electrolyte temperature is room temperature, the carrier gas is introduced into the gas containing chamber 23 at a flow rate of 1 L / min, the circulation volume of the electrolyte is 0.8 L / min, the flow rate of the mixed gas is 1 L / min, and the mixed gas and air are mixed in a volume ratio of 1 / 7 to form a therapeutic gas.

[0155] The variable of this test is the current size. When other experimental conditions remain unchanged, the current size is adjusted to test the NO concentration in the treatment gas. The test results are as follows: Figure 5 shown.

[0156] Depend on Figure 5 It can be seen that the NO concentration increases with the increase of the applied current, that is, the present invention can achieve the purpose of increasing the maximum output concentration of NO by changing the current size.

[0157] Example 8

[0158] This embodiment provides a test experiment, the purpose of which is to verify the intra-batch difference of the same batch of electrolytes, and the intra-batch difference represents the stability of the same batch of electrolytes.

[0159] The experimental conditions for this test are as follows:

[0160] (1) Structural parameters: The horizontal distance between the line connecting the water inlet 15 and the water outlet 16 and the cathode plate 12 is 2 cm, and the horizontal distance between the anode plate 13 and the cathode plate 12 is 7 cm. The anode plate 13 and the cathode plate 12 are both composed of 4 layers of tightly fitted mesh-structured stainless steel electrode sheets, and the mesh number of the electrode sheet is 100 meshes. The length of the electrode sheet is 12.5 cm, and the width of the electrode sheet is 5 cm.

[0161] (2) Electrochemical parameters: A current of 200 mA was applied to the anode plate 13 and the cathode plate 12;

[0162] (3) Process parameters: The electrolyte temperature is room temperature, the carrier gas is introduced into the gas containing chamber 23 at a flow rate of 1 L / min, the circulation volume of the electrolyte is 0.8 L / min, the flow rate of the mixed gas is 1 L / min, and the mixed gas and air are mixed in a volume ratio of 1:4 to form a therapeutic gas.

[0163] The test methods mainly include:

[0164] Three groups of electrolytes (respectively group 1, group 2 and group 3) were prepared at the same time under the same environment and at the same time period. When other experimental conditions remained unchanged, the NO produced by the three groups of electrolytes was used to prepare the therapeutic gas, and the NO concentration in the therapeutic gas was tested. If the difference in NO concentration produced by the three groups of electrolytes under the same experimental conditions was large, it means that the intra-batch difference of the electrolyte was large, the fluctuation was more violent, and the stability was not high; otherwise, it means that the intra-batch difference of the electrolyte was small and the stability was high. The test results are as follows: Figure 6 shown.

[0165] Depend on Figure 6 It can be seen that the NO concentrations produced by electrolysis using the three groups of electrolytes prepared from the same batch are basically the same.

[0166] Example 9

[0167] This embodiment provides a test experiment, the purpose of which is to verify the batch difference of different batches of electrolytes. The batch difference represents the repeatability of the preparation process of the electrolyte.

[0168] The experimental conditions for this test are as follows:

[0169] (1) Structural parameters: The horizontal distance between the line connecting the water inlet 15 and the water outlet 16 and the cathode plate 12 is 2 cm, and the horizontal distance between the anode plate 13 and the cathode plate 12 is 7 cm. The anode plate 13 and the cathode plate 12 are both composed of 4 layers of tightly fitted mesh-structured stainless steel electrode sheets, and the mesh number of the electrode sheet is 100 meshes. The length of the electrode sheet is 12.5 cm, and the width of the electrode sheet is 5 cm.

[0170] (2) Electrochemical parameters: A current of 200 mA was applied to the anode plate 13 and the cathode plate 12;

[0171] (3) Process parameters: The electrolyte temperature is room temperature, the carrier gas is introduced into the gas containing chamber 23 at a flow rate of 1 L / min, the circulation volume of the electrolyte is 0.8 L / min, the flow rate of the mixed gas is 1 L / min, and the mixed gas and air are mixed in a volume ratio of 1:4 to form a therapeutic gas.

[0172] The test methods mainly include:

[0173] Two batches of electrolyte were prepared at intervals of two days. The first time, three groups of electrolyte were prepared from the same batch, which were respectively recorded as 3-1, 3-2 and 3-3. After the preparation, the three groups of electrolyte were electrolyzed to test the NO concentration produced by electrolysis. The second time, two groups of electrolyte were prepared from the same batch, which were respectively recorded as 4-1 and 4-2. NO gas was produced by electrolysis and the therapeutic gas was prepared with the NO gas produced by electrolysis. The NO concentration in the therapeutic gas was tested. The test results are shown in Figure 7 .

[0174] Depend on Figure 7 It can be seen that the NO concentration of group 3-1 is 18.6ppm; the NO concentration of group 3-2 is 19.0ppm; the NO concentration of group 3-3 is 19.4ppm; the average NO concentration of group 3 is 19ppm; the NO concentration of group 4-1 is 18.7ppm; the NO concentration of group 4-2 is 19.8ppm, and the average NO concentration of group 4 is 19.25ppm. A longitudinal comparison of group 3 and group 4 shows that the batch difference between group 3 and group 4 is 0.25ppm, which is relatively small, indicating that the electrolyte provided by the present invention has high repeatability.

[0175] Example 10

[0176] This embodiment provides a test experiment, the purpose of which is to verify whether the electrolyte will be affected in the electrolysis effect of the electrolyte or even cause the electrolyte to fail after being placed for a long time.

[0177] The experimental conditions for this test are as follows:

[0178] (1) Structural parameters: The horizontal distance between the line connecting the water inlet 15 and the water outlet 16 and the cathode plate 12 is 2 cm, and the horizontal distance between the anode plate 13 and the cathode plate 12 is 7 cm. The anode plate 13 and the cathode plate 12 are both composed of 16 layers of tightly fitted mesh-structured stainless steel electrode sheets, and the mesh number of the electrode sheet is 300 meshes. The length of the electrode sheet is 12.5 cm, and the width of the electrode sheet is 5 cm.

[0179] (2) Electrochemical parameters: A current of 200 mA was applied to the anode plate 13 and the cathode plate 12;

[0180] (3) Process parameters: The electrolyte temperature is room temperature, the carrier gas is introduced into the gas containing chamber 23 at a flow rate of 1 L / min, the circulation volume of the electrolyte is 0.8 L / min, the flow rate of the mixed gas is 1 L / min, and the mixed gas and air are mixed in a volume ratio of 1:4 to form a therapeutic gas.

[0181] The test method mainly uses the same electrolyte to electrolyze and generate NO after being placed for 1 day, 2 days, 3 days and 11 days respectively, uses the generated NO to prepare therapeutic gas, and tests the NO concentration in the therapeutic gas.

[0182] The test results are as follows Figure 8 As shown by Figure 8 It can be seen that after being placed for a long time, the NO concentration generated by electrolysis remains basically unchanged, or even increases slightly. Specifically: the electrolyte was retested after being placed for 11 days. Under the action of 200mA current, the NO concentration at 5L / min was about 18.0ppm, which was higher than the NO concentration (16-17ppm) generated by the earliest (first day) electrolyte (about 1-2ppm), indicating that the long-term stability of the electrolyte provided by the present invention is generally good.

[0183] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. An electrolytic cell for generating NO, characterized in that The electrolytic cell comprises an electrolytic tank, an electrolyte is injected into the electrolytic tank, a pair of plates are longitudinally arranged in parallel in the electrolytic tank, respectively denoted as an anode plate and a cathode plate, the anode plate and the cathode plate are respectively connected to the positive electrode and the negative electrode of an external power supply, and two rows of parallel fixing components are arranged on the bottom surface of the electrolytic tank, the fixing components respectively fix the anode plate and the cathode plate; The electrolytic cell is provided with a water inlet and a water outlet on the top; the water inlet and the water outlet are located on the top of the electrolytic cell between the anode plate and the cathode plate; the line connecting the water inlet and the water outlet is parallel to the electrode plate; the line connecting the water inlet and the water outlet is close to the cathode plate; the horizontal distance between the line connecting the water inlet and the water outlet and the cathode plate is 1 to 3 cm; the horizontal distance between the anode plate and the cathode plate is 5 to 8 cm; A water inlet pipe is extended into the electrolytic cell through the water inlet, and a water outlet pipe is extended into the electrolytic cell through the water outlet; the outlet end of the water inlet pipe is located above the liquid level of the electrolyte, and the outlet end of the water outlet pipe is located below the liquid level of the electrolyte.

2. The electrolytic cell according to claim 1, characterized in that Two interface modules are arranged on the side wall of the electrolytic cell near one end of the electrode, and the anode plate and the positive electrode of the external power supply, as well as the cathode plate and the negative electrode of the external power supply are respectively connected through the interface modules.

3. The electrolytic cell according to claim 2, characterized in that The interface module is a cylindrical metal block sealed and embedded in the side wall of the electrolytic cell.

4. The electrolytic cell according to claim 1, characterized in that The anode plate and the cathode plate are composed of at least one electrode sheet.

5. The electrolytic cell according to claim 4, characterized in that The anode plate and cathode plate are composed of at least two tightly fitted electrode sheets.

6. The electrolytic cell according to claim 5, characterized in that The number of electrode sheets constituting the anode plate is the same as or different from the number of electrode sheets constituting the cathode plate.

7. The electrolytic cell according to claim 4, characterized in that The electrode sheet is a mesh structure.

8. The electrolytic cell according to claim 4, characterized in that The mesh number of the electrode sheet is 50-300 meshes.

9. The electrolytic cell according to claim 8, characterized in that The mesh number of the electrode sheet is 100 meshes.

10. The electrolytic cell according to claim 4, characterized in that The material of the electrode sheet is selected from gold, platinum, carbon or stainless steel.

11. The electrolytic cell according to claim 10, characterized in that The material of the electrode sheet constituting the anode plate is the same as or different from the material of the electrode sheet constituting the cathode plate.

12. The electrolytic cell according to claim 4, characterized in that The length of the electrode sheet is 10-15 cm.

13. The electrolytic cell according to claim 12, characterized in that The length of the electrode sheet is 12.5 cm.

14. The electrolytic cell according to claim 4, characterized in that The width of the electrode sheet is 4-7 cm.

15. The electrolytic cell according to claim 14, characterized in that The width of the electrode sheet is 5 cm.

16. The electrolytic cell according to claim 4, characterized in that The aspect ratio of the electrode sheet is (2-3):

1.

17. The electrolytic cell according to claim 1, characterized in that The fixing assembly comprises at least two fixing clamps, and the fixing assembly is fixed to the bottom of the electrolytic cell.

18. The electrolytic cell according to claim 17, characterized in that The fixing assembly comprises three fixing clamps which are arranged equidistantly and collinearly.

19. The electrolytic cell according to claim 18, characterized in that The fixing clamp comprises two folded fixing plates, which clamp and fix the pole plate after being folded together.

20. The electrolytic cell according to claim 1, characterized in that The electrolyte comprises a buffer solution, a nitrite and a copper-based catalyst.

21. The electrolytic cell according to claim 20, characterized in that The concentration of the buffer solution is 0.01-3 mol / L.

22. The electrolytic cell according to claim 20, characterized in that The buffer comprises 4-hydroxyethylpiperazineethanesulfonic acid buffer, 3-morpholinepropanesulfonic acid buffer or phosphate buffer.

23. The electrolytic cell according to claim 20, characterized in that The concentration of the nitrite is 0.01-5 mol / L.

24. The electrolytic cell according to claim 20, characterized in that The concentration of the copper-based catalyst is 1-7 mmol / L.

25. The electrolytic cell according to claim 20, characterized in that The copper-based catalyst is selected from one of tris(2-pyridylmethyl)amine copper(II), 1,4,7-triazacyclononane copper(II), 1,4,7-trimethyl-1,4,7-triazacyclononane copper(II), tris(2-aminoethyl)amine copper(II), tris(2-dimethylaminoethyl)amine copper(II) or bis(2-aminomethylpyridine)-propionic acid copper(II), or a combination of at least two thereof.

26. An electrolytic method for generating NO, characterized in that: The electrolytic cell according to any one of claims 1 to 25 is used to electrolyze and generate NO gas, wherein the electrolysis method comprises: applying current to the anode plate and the cathode plate, and the electrolyte is electrolyzed under the action of the current to generate NO gas.

27. The electrolysis method according to claim 26, characterized in that Apply a current of 10~300mA to the anode plate and the cathode plate.

28. The electrolysis method according to claim 27, characterized in that Apply a current of 200~300mA to the anode plate and the cathode plate.

29. The electrolysis method according to claim 26, characterized in that The temperature of the electrolyte is controlled at 10-30°C.

30. The electrolysis method according to claim 29, characterized in that The temperature of the electrolyte is controlled at 20-25°C.

31. A NO production system, characterized in that: The NO production system comprises a cyclically connected electrolytic cell and a gas-liquid separation device, and the electrolytic cell is the electrolytic cell according to any one of claims 1-25.

32. The NO production system according to claim 31, characterized in that: The gas-liquid separation device includes a cylindrical shell and a tubular membrane assembly horizontally arranged inside the shell along its axial direction, and an annular cylindrical gas containing cavity is formed between the inner circumference of the shell and the outer circumference of the membrane assembly; NO generated by the electrolytic cell enters the membrane assembly along with the electrolyte, and the NO gas passes through the membrane assembly into the gas containing cavity, and the electrolyte flows back to the electrolytic cell.

33. The NO production system according to claim 32, characterized in that: The shell is provided with an air inlet and an air outlet which are in communication with the gas containing chamber. The air inlet is externally connected to a carrier gas source, and the carrier gas source is used to transport carrier gas into the gas containing chamber to drive NO gas to be discharged from the air outlet.

34. The NO production system according to claim 32, characterized in that: The liquid outlet of the membrane assembly is connected to the water inlet of the electrolytic cell through a water inlet pipe, and the liquid inlet of the membrane assembly is connected to the water outlet of the electrolytic cell through a water outlet pipe.

35. The NO production system according to claim 34, characterized in that: The water outlet pipe is provided with a liquid pump, and the electrolyte from which NO gas has been filtered out flows back into the electrolytic cell through the liquid pump.

36. A method for preparing NO using the NO preparation system according to any one of claims 31 to 35, characterized in that: The method comprises: The NO generated by electrolysis in the electrolytic cell circulates into the gas-liquid separation device along with the electrolyte, and NO gas is obtained after gas-liquid separation.

37. The method according to claim 36, characterized in that The method specifically includes: The NO gas generated by the electrolytic cell enters the gas-liquid separation device along with the electrolyte circulation, and the NO gas passes through the membrane component and enters the gas containing chamber for temporary storage. The carrier gas source introduces carrier gas into the gas containing chamber, and the NO gas is discharged from the gas-liquid separation device under the drive of the carrier gas. After the electrolyte is intercepted by the membrane component, it flows back to the electrolyte through the liquid pump for recycling.

38. The method according to claim 37, characterized in that The carrier gas is air.

39. The method according to claim 37, characterized in that The carrier gas is introduced into the gas containing chamber at a flow rate of 0.5-1.5 L / min.

40. The method according to claim 37, characterized in that The circulation rate of the electrolyte is 0.8-1.4 L / min.

41. The method according to claim 37, characterized in that NO and the carrier gas form a mixed gas and then are discharged from the gas-liquid separation device. The flow rate of the mixed gas is 0.5-1.5 L / min.

42. The method according to claim 41, characterized in that The concentration of NO in the mixed gas formed by the NO and the carrier gas is 0-320 ppm.

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