CN114318381A

CN114318381A - NO generation system device and use method thereof

Info

Publication number: CN114318381A
Application number: CN202011502846.7A
Authority: CN
Inventors: 耿翔; 陈涛; 陈翠华; 郑盼盼; 毛雯
Original assignee: Nanjing Nuoling Biotechnology Co ltd
Current assignee: Nanjing Nuoling Biotechnology Co ltd
Priority date: 2020-12-18
Filing date: 2020-12-18
Publication date: 2022-04-12
Anticipated expiration: 2040-12-18
Also published as: CN114318381B

Abstract

The invention provides an NO generation system device and a using method thereof, wherein the system device comprises a generation unit, a purification unit and an output unit which are sequentially connected, wherein the generation unit comprises an electrolytic cell and a gas-liquid separator which are circularly connected; said output unit comprising NO₂A conversion filter element device; the nitric oxide generated by the electrolytic cell enters a purification unitNO in the output unit after conversion₂And (4) converting the filter element device and releasing, and removing the residual nitric oxide in the electrolytic cell by the gas-liquid separator after the electrolytic cell stops generating nitric oxide. By NO in the invention₂Conversion filter element device for converting NO₂Reduction to NO to effect NO₂Zero generation and efficient utilization of, and increase in NO concentration; in addition, through the gas-liquid separator who is connected with the electrolysis trough circulation, clear away the NO that remains in the electrolysis trough, avoid remaining NO to cause harm to electrolyte and electrode, guarantee that electrolyte and electrode can repetitious usage, produce stable nitric oxide concentration.

Description

NO generation system device and use method thereof

Technical Field

The invention belongs to the technical field of medical instruments, relates to an NO generating device, and particularly relates to an NO generating system device and a using method thereof.

Background

Nitric oxide is a gas that plays a role in transmitting important information and regulating cellular functions in the human body, and helps promote blood circulation in the body. It does not require any intermediary mechanism to rapidly diffuse across a biological membrane, transmitting the information produced by one cell to its surrounding cells. Nitric oxide has many biological functions, and is very involved in electron transfer reaction and redox process. The coordination of the nitric oxide molecule in turn makes it highly avidity for heme iron and non-heme iron to replace O₂And CO₂The position of (a). It has been reported that hemoglobin-NO can lose its nearby bases to become free pro-hemoglobin-NO, which means that the free base can freely participate in catalytic reactions, the free protein can freely change conformation, and the free heme can freely diffuse out of the protein, any one or combination of these three changes will play an important role in the activation of guanylate cyclase. The research on the biological action and mechanism of action of NO is underway, and its finding suggests the prospect of inorganic molecules in the medical field.

CN109568745A discloses a medical nitric oxide gas supply system and method, comprising a nitric oxide gas generation subsystem and a gas concentration monitoring subsystem, wherein the gas concentration monitoring subsystem is used for monitoring the concentration of nitric oxide and nitrogen dioxide actually inhaled by a user and controlling the concentration of nitric oxide gas output by the nitric oxide generation subsystem by feedback of a monitoring value.

CN107073239A discloses a system and method for synthesizing nitric oxide, comprising a pre-filter, an NO generating device comprising electrodes, and a filter located at the outlet of the NO generating device; the invention realizes the regulation and control of the concentration of the generated nitric oxide by controlling the spark characteristics of the electrode.

The existing nitric oxide generating devices all have the problems that the output of high-concentration nitric oxide is slow, the time is long and the like, so that the existing nitric oxide generating devices have the characteristics of simple structure and the like while ensuring that the nitric oxide generating devices can output high-concentration nitric oxide and short time, and become the problem which needs to be solved urgently at present.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide the NO generation system device and the using method thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides an NO generation system device, which comprises a generation unit, a purification unit and an output unit which are connected in sequence, wherein the generation unit comprises an electrolytic cell and a gas-liquid separator which are connected in a circulating manner; said output unit comprising NO₂A conversion filter element device; nitric oxide generated by the electrolytic cell enters the purification unit, and enters the NO output unit after being purified₂And (4) converting the filter element device and releasing, and removing the residual nitric oxide in the electrolytic cell by the gas-liquid separator after the electrolytic cell stops generating nitric oxide.

The invention purifies NO generated by an electrolytic cell, wherein the NO passes through the NO when being output₂Conversion filter element device for converting NO₂Reduction to NO, thereby realizing NO₂Zero generation and efficient utilization of, and also increase the concentration of NO; in addition, through the gas-liquid separator circularly connected with the electrolytic cell, NO remained in the electrolytic cell after the electrolysis is finished is removed, so that the harm of the remained NO to the electrolyte and the electrode is avoided, the electrolyte and the electrode can be used for multiple times, the stable nitric oxide concentration is generated, and the repeatability and the consistency of the electrolytic cell are realized.

As a preferred technical solution of the present invention, the system device further includes a nitrogen production unit, and the nitrogen production unit includes a filtering device and a nitrogen production device which are connected in sequence along a gas flow direction.

Preferably, the filtering device comprises a water vapor filter and a dust filter which are connected in sequence along the gas flow direction.

Preferably, the nitrogen making device comprises a nitrogen making membrane, and the gas enters the nitrogen making membrane and is separated to obtain nitrogen.

Preferably, the material of the nitrogen-making film comprises any one of poly (4-methyl-1-pentene), brominated polycarbonate, polypropylene, polyimide or polydimethylsiloxane or a combination of at least two of the poly (4-methyl-1-pentene) and the polydimethylsiloxane.

Preferably, the average pore diameter of the nitrogen-producing membrane is 0.005-0.02 μm, for example, the average pore diameter is 0.005 μm, 0.007 μm, 0.009 μm, 0.011 μm, 0.013 μm, 0.015 μm, 0.017 μm, 0.019 μm or 0.020 μm.

In a preferred embodiment of the present invention, the electrolytic cell includes a housing, the housing is filled with an electrolyte, and at least one pair of electrodes immersed in the electrolyte is disposed in the housing.

Preferably, the electrolytic cell is externally connected with an air inlet pipeline, and a nitrogen outlet of the nitrogen making device is connected to the electrolytic cell through the air inlet pipeline.

Preferably, a nitrogen flow regulating valve is arranged on the air inlet pipeline.

Preferably, the shell is externally connected with an air outlet pipeline, and the inlet end of the air outlet pipeline is positioned above the liquid level.

Preferably, the electrolytic cell comprises a circulating pipeline, the inlet end of the circulating pipeline is positioned above the liquid level in the shell, the outlet end of the circulating pipeline is connected to an air inlet pipeline, and gas in the electrolytic cell flows in a circulating mode through the circulating pipeline.

The invention ensures the circulation of nitrogen and nitric oxide generated by electrolysis in the electrolytic cell by arranging the circulating pipeline, thereby ensuring the concentration of the nitric oxide.

Preferably, a purging piece is arranged in the electrolytic cell and used for purging the electrode.

The invention uses the purging gas generated by the purging piece to blow away the nitric oxide gas generated on the surface of the electrode by arranging the purging piece, thereby avoiding the generated gas from being accumulated on the surface of the electrode and in the electrolyte.

Preferably, the purge is located below the electrode.

Preferably, the blowing member comprises an open box body, and the box body is filled with air stones.

The invention adopts the air bubble stone, increases the sweeping effect on the surface of the electrode and improves the electrolysis efficiency of the electrolytic cell.

Preferably, the opening direction of the box body faces to the corresponding electrode.

Preferably, the air inlet pipeline and the circulating pipeline are converged into one pipeline and then are respectively connected to the purging piece.

Preferably, a circulation pump is arranged on the circulation pipeline.

As a preferable technical scheme of the invention, the electrolytic cell is circularly connected with the gas-liquid separator through a first pipeline and a second pipeline, and the first pipeline extends into the shell below the liquid level; the second pipeline is connected above the liquid level in the shell.

Preferably, the first pipeline and the second pipeline are both connected to a switching valve at the same time, and the switching valve is used for switching the working state and the temporary stop state of the gas-liquid separator; the working state comprises: electrolyte flows through a switching valve through the first pipeline and enters the gas-liquid separator for gas-liquid separation, and the electrolyte flows back into the electrolytic cell through the second pipeline; the critical standstill state includes: and gas in the electrolytic cell flows through the switching valve through the second pipeline, enters the gas-liquid separator, purges residual electrolyte, and flows back into the electrolytic cell through the first pipeline.

The gas-liquid separator changes the running state including the working state and the temporary stopping state through the switching valve, and under the working state, the electrolyte in the electrolytic cell enters the gas-liquid separator, so that the residual nitric oxide in the electrolytic cell is removed, and the repeatability and consistency of the concentration of the nitric oxide generated in the next use are ensured; in the state of approaching to stop, through gaseous anti-blowing, blow remaining electrolyte in the vapour and liquid separator back to the electrolytic bath, avoid electrolyte to gather in the vapour and liquid separator, influence vapour and liquid separator's life.

Preferably, the gas-liquid separator is connected with an air pump, and the air pump injects carrier gas into the gas-liquid separator for bringing the separated gas out of the gas-liquid separator.

Preferably, the first line is provided with a filter, which is located between the electrolytic cell and the switching valve.

The invention is provided with the filter to prevent impurities in the electrolyte from entering the gas-liquid separator, damaging membrane components in the gas-liquid separator and influencing the separation effect of the gas-liquid separator.

Preferably, a solenoid valve is arranged on the first pipeline and is positioned between the filter and the switching valve.

According to the invention, the electromagnetic valve is arranged on the first pipeline, and the electromagnetic valve prevents the electrolyte in the electrolytic cell from being sucked back into the gas-liquid separator because the electrolytic cell has certain pressure during operation.

Preferably, a gas-liquid dual-purpose pump is arranged on the first pipeline, and the gas-liquid dual-purpose pump is positioned between the switching valve and the gas-liquid separator.

The gas-liquid dual-purpose pump provided by the invention can pump electrolyte and gas, and meets different functions of electrolyte delivery and gas delivery when the gas-liquid separator is in a working state and a temporary stop state.

Preferably, the area of the separation membrane in the gas-liquid separator is 1000-50000 cm²For example, an area of 1000cm²、5000cm²、10000cm²、15000cm²、20000cm²、25000cm²、30000cm²、35000cm²、40000cm²、45000cm²Or 50000cm²。

As a preferred technical scheme of the invention, the electrolyte comprises a buffer solution, a nitrogen source and a catalyst, wherein the catalyst comprises a metal-based complex; the central atom of the metal-based complex is a metal-based atom, and the ligand of the metal-based complex is a nitrogen-containing multi-site ligand.

According to the invention, the concentration of NO generated by electrolysis can be effectively improved by adding the metal-based complex catalyst into the electrolyte, and the generated gas does not contain nitrogen dioxide and other byproducts. The relevant reactions are as follows:

m (high valence) (L) + e^-→ M (Low price) (L)

Note: m is one or at least two of copper, iron, titanium, chromium, manganese, cobalt or nickel.

Preferably, the buffer solution comprises one or a combination of at least two of 4-hydroxyethyl piperazine ethanethiosulfonic acid buffer solution, 3-morpholine propanesulfonic acid buffer solution, tris, citrate buffer solution, phosphate buffer solution, boric acid-borax buffer solution or organic buffer solution.

Preferably, the buffer solution has a molar concentration of 0.01 to 3mol/L in the electrolyte, for example, a molar concentration of 0.01mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L or 3 mol/L.

Preferably, the nitrogen source comprises nitrite.

Preferably, the nitrite comprises an inorganic nitrite and/or an organic nitrite.

Preferably, the molar concentration of the nitrogen source in the electrolyte is 0.01-5 mol/L, for example, 0.01mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L or 5 mol/L.

Preferably, the metal-based atoms include one or a combination of at least two of copper, iron, titanium, chromium, manganese, cobalt, or nickel.

Preferably, the nitrogen-containing multi-site ligand comprises one or a combination of at least two of tris (2-pyridylmethyl) amine, 1, 4, 7-triazacyclononane, 1, 4, 7-trimethyl-1, 4, 7-triazacyclononane, tris (2-aminoethyl) amine, tris (2-dimethylaminoethyl) or bis (2-aminomethylpyridine) -propionic acid.

Preferably, the molar concentration of the catalyst in the electrolyte is 1-15 mmol/L, such as 1mmol/L, 2mmol/L, 3mmol/L, 4mmol/L, 5mmol/L, 6mmol/L, 7mmol/L, 8mmol/L, 9mmol/L, 10mmol/L, 11mmol/L, 12mmol/L, 13mmol/L, 14mmol/L or 15 mmol/L.

Preferably, the electrode plate is a single-component conductive material or a substrate coated with a conductive material.

Preferably, the conductive material comprises one or a combination of at least two of platinum, gold, carbon, glassy carbon, stainless steel, ruthenium iridium alloy or boron-doped diamond.

Preferably, the substrate is SiO₂One or a combination of at least two of conductive glass, tin-doped indium oxide, fluorine-doped indium oxide, a conductive plastic substrate, platinum, gold, carbon, glassy carbon, stainless steel, or ruthenium-iridium alloy.

As a preferable technical scheme of the invention, the purification unit comprises a purification membrane component and a clean filter which are connected in sequence along the gas flow direction.

Preferably, the purification membrane module comprises a desalination membrane and a Nafion membrane which are connected in sequence along the gas flow direction.

The invention further removes salt mist and water vapor by arranging the clean filter.

Preferably, the material of the salt fog removing film comprises any one or a combination of at least two of polytetrafluoroethylene, polyvinylidene fluoride, polyether sulfone, mixed cellulose ester, organic nylon 6 or organic nylon 66.

Preferably, the average pore diameter of the salt fog removing film is 0.1-2 μm, for example, the average pore diameter is 0.1 μm, 0.2 μm, 0.4 μm, 0.6 μm, 0.8 μm, 1.0 μm, 1.2 μm, 1.4 μm, 1.6 μm, 1.8 μm or 2.0 μm.

Preferably, said purification unit further comprises NO_xA gas outlet end of the gas-liquid separator is connected with NO_xA purification device.

Preferably, said NO_xThe purification device is filled with alumina loaded with potassium permanganate.

Preferably, the potassium permanganate-supporting alumina is spherical in shape.

Preferably, the output unit comprises a pressure tank and NO connected in sequence along the gas flow direction₂Conversion filter core device.

Preferably, the pressure tank is provided with an evacuation port and a pressure relief port.

Preferably, the NO is connected to a pressure relief opening of the pressure tank_xA purification device.

Preferably, the pressure tank is supplied with NO through a large-range pipeline and a small-range pipeline₂Conversion filter core device.

Preferably, a large-range flow controller is arranged on the large-range pipeline, and a small-range flow controller is arranged on the small-range pipeline.

Preferably, a pressure sensor is arranged in the pressure tank.

Preferably, the NO generation system device includes a concentration sensor disposed at an outlet of the converter, the concentration sensor is configured to detect a concentration of the released nitric oxide, the wide-range flow controller and the small-range flow controller are electrically connected to the concentration sensor, respectively, and both the wide-range flow controller and the small-range flow controller receive a signal sent by the concentration sensor and perform feedback control on an output flow of the nitric oxide.

As a preferred embodiment of the present invention, the NO is₂The conversion filter element device comprises a cylinder body; the interior of the cylinder body is divided into at least two baffling cavities,the baffling cavity axially penetrates through the cylinder body along the cylinder body, and NO is filled in the baffling cavity₂One end of each of two adjacent baffling cavities is communicated with each other, and gas enters the cylinder body and flows through the baffling cavities in sequence in a serpentine baffling mode.

The invention leads the smoke to be in snake-shaped flow deflection in the cylinder body by arranging the multilayer flow deflection cavity, thereby improving NO₂The contact time and the contact area of the gas and the filter element material reduce the occupied area of the equipment.

Preferably, said NO₂The conversion filter element material comprises a carrier and reducing vitamins coated on the surface of the carrier.

Preferably, the carrier comprises one or a combination of at least two of silica gel, molecular sieve, alumina, sponge, cotton or foaming resin.

Preferably, the reducing vitamin comprises one or a combination of at least two of vitamin C, vitamin E or vitamin a.

Preferably, the carrier is coated with 5-50 g of reducing vitamin per 100g of carrier, such as 5g, 10g, 15g, 20g, 25g, 30g, 35g, 40g, 45g or 50 g.

In a second aspect, the present invention provides a method of using the apparatus of the first aspect, the method comprising:

the electrolytic cell generates nitric oxide through electrolytic reaction, the generated nitric oxide enters the purification unit, and NO enters the output unit after purification₂And (4) converting the filter element device, releasing, and removing residual nitric oxide in the electrolytic cell through a gas-liquid separator after the electrolytic reaction is finished.

According to the invention, the residual nitric oxide in the electrolytic cell is separated and removed through the gas-liquid separator, so that the influence of the residual nitric oxide on the electrolyte and the electrode is effectively removed, and the stability and consistency of the concentration of nitric oxide generated by each electrolysis are ensured; furthermore, by means of NO₂Conversion filter element device for converting NO₂Reduction to NO to thereby effect NO₂The zero generation and the effective utilization of the NO can be realized, the concentration of NO can be increased, and the NO output range is enlarged.

As a preferred technical solution of the present invention, the using method specifically comprises:

the method comprises the following steps that (I) compressed gas sequentially enters a water vapor filter and a dust filter, water vapor and dust are removed respectively, then the compressed gas enters a nitrogen making device for separation, and nitrogen is obtained after the separation;

(II) nitrogen is let in electrolyte by the air inlet pipeline in, sweep gas on the electrode, take place the electrolytic reaction and produce nitric oxide, nitrogen and nitric oxide in the electrolytic cell pass through the circulating line and admit air together via sweeping the piece blowout, blow off the gas that produces on the electrode, after nitric oxide concentration satisfies the requirements, get into desalination fog membrane, Nafion membrane and clean filter in proper order, the nitric oxide after the purification gets into the overhead tank and stores, during the use, nitric oxide in the overhead tank is through NO₂Releasing the conversion filter element device after treatment;

(III) after the release of nitric oxide is stopped, the gas-liquid separator enters a working state, the electrolyte flows through the switching valve through the first pipeline and enters the gas-liquid separator for gas-liquid separation, the electrolyte flows back into the electrolytic cell through the second pipeline, and the carrier gas discharges the gas separated by the gas-liquid separator to NO_xThe purification device is used for refluxing the electrolyte into the electrolytic cell; and after the working state is finished, the switching valve is switched, the gas-liquid separator enters the temporary stop state, gas in the electrolytic cell flows through the switching valve through the second pipeline, enters the gas-liquid separator, purges residual electrolyte, and the electrolyte flows back into the electrolytic cell through the first pipeline.

In a preferred embodiment of the present invention, in step (i), the volume concentration of nitrogen is 99.0% or more, for example, the volume concentration of nitrogen is 99.00%, 99.10%, 99.20%, 99.30%, 99.40%, 99.50%, 99.60%, 99.70%, 99.80%, 99.90%, or 99.990%.

Preferably, the nitrogen gas has a flow rate of 50 to 600mL/min, for example, a flow rate of 50mL/min, 100mL/min, 150mL/min, 200mL/min, 250mL/min, 300mL/min, 350mL/min, 400mL/min, 450mL/min, 500mL/min, 550mL/min or 600 mL/min.

Preferably, in step (ii), the method of the electrolytic reaction comprises: and applying an excitation current or an excitation voltage higher than a set value to the electrode, and adjusting to the set current or the set voltage after a period of time, wherein NO is stably output in a short time.

According to the invention, the excitation current of large current is applied firstly, then the set current is applied, the concentration of NO generated by electrolysis is in direct proportion to the applied current or voltage, the larger excitation current or voltage is applied for a short time, the time for the concentration to reach a stable value is greatly shortened, and the application scene of the device is expanded. Meanwhile, the electrolysis method provided by the invention is matched with the electrolyte with special composition, so that high-concentration and rapid and stable output of NO is realized, NO by-products such as nitrogen dioxide are generated, specifically, the electrolyte prepared by adopting a special catalyst realizes high-concentration output of NO, NO by-products are generated, and the rapid and stable output of NO is realized by adopting the special electrolysis method.

In the electrolysis method provided by the present invention, the stage of applying the excitation current and the stage of applying the set current may both use unidirectional current or both use bidirectional current, but it is understood that one stage may use unidirectional current and the other stage uses bidirectional current.

Preferably, the excitation current or the excitation voltage is 2 to 8 times of the set value, for example, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times or 8 times.

Preferably, the excitation current or the excitation voltage acts for 0.5-3 min, for example, 0.5min, 1min, 1.5min, 2min, 2.5min or 3 min.

Preferably, the set current is 0 to 300mA, and does not include 0, and may be, for example, 10mA, 50mA, 100mA, 150mA, 200mA, 250mA or 300 mA.

Preferably, the set voltage is 1.4-3.0V, such as 1.4V, 1.5V, 1.6V, 1.7V, 1.8V, 1.9V, 2.0V, 2.1V, 2.2V, 2.3V, 2.4V, 2.5V, 2.6V, 2.7V, 2.8V, 2.9V or 3.0V.

Preferably, the NO is stably output within 2-10 min, for example, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10 min.

Preferably, in step (II), the flow rate of the gas in the circulation pipeline is 0.5-3L/min, such as 0.5L/min, 1L/min, 1.5L/min, 2L/min, 2.5L/min or 3L/min.

Preferably, in step (III), the working state is less than or equal to 20min, for example, 1min, 2min, 4min, 6min, 8min, 10min, 12min, 14min, 16min, 18min or 20 min.

Preferably, in step (iii), the carrier gas is air.

Preferably, in step (III), the time of the temporary stop state is 0.5-2 min, for example, 0.5min, 0.6min, 0.7min, 0.8min, 0.9min, 1.0min, 1.1min, 1.2min, 1.3min, 1.4min, 1.5min, 1.6min, 1.7min, 1.8min, 1.9min or 2.0 min.

The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.

Compared with the prior art, the invention has the beneficial effects that:

the invention purifies NO generated by an electrolytic cell, wherein NO passes through₂Conversion filter element device for converting NO₂Reduction to NO to thereby effect NO₂Zero generation and efficient utilization of, and also increase the concentration of NO; in addition, through the gas-liquid separator circularly connected with the electrolytic cell, NO remained in the electrolytic cell after the electrolysis is finished is removed, so that the harm of the remained NO to the electrolyte and the electrode is avoided, the electrolyte and the electrode can be used for multiple times, the stable nitric oxide concentration is generated, and the repeatability and the consistency of the electrolytic cell are realized.

Drawings

Fig. 1 is a schematic structural diagram of an apparatus of an NO generation system according to an embodiment of the present invention.

Wherein, 1-a water vapor filter; 2-a dust filter; 3-a nitrogen making device; 4-an air inlet pipeline; 5-an electrolytic cell; 6-an electrode; 7-purging; 8-a circulation line; 9-a circulating pump; 10-an air pump; 11-a gas-liquid separator; 12-gas-liquid dual-purpose pump; 13-a switching valve; 14-a filter; 15-first tubeA way; 16-a second conduit; 17-desalting fog film; 18-Nafion membrane; 19-cleaning the filter; 20-pressure tank; 21-wide range flow controller; 22-NO₂A conversion filter element device; 23-NO_xA purification device; 24-small range flow controller.

Detailed Description

It is to 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", "inner", "outer", etc., indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be taken as limiting the present invention. Furthermore, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.

It should be noted that, in the description of the present invention, unless otherwise explicitly specified or limited, the terms "disposed," "connected" and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.

It should be understood by those skilled in the art that the present invention necessarily includes necessary piping, conventional valves and general pump equipment for achieving the complete process, but the above contents do not belong to the main inventive points of the present invention, and those skilled in the art can select the layout of the additional equipment based on the process flow and the equipment structure, and the present invention is not particularly limited to this.

The technical solution of the present invention is further explained by the following embodiments.

In one embodiment, the present invention provides an NO generation system apparatus, as shown in fig. 1, comprising a generation unit, a purification unit and an output unit connected in sequence, the generation unit comprising an electrolytic cell 5 and a gas-liquid separator 11 connected in circulation; the output unit comprises NO₂A conversion cartridge assembly 22; nitric oxide generated by the electrolytic cell 5 enters the purification unit, and enters the output unit after purification₂The filter element device 22 is converted and released, and after the electrolytic cell 5 stops generating nitric oxide, the gas-liquid separator 11 removes the residual nitric oxide in the electrolytic cell 5.

The invention purifies NO generated by the electrolytic cell 5, wherein the NO is output and is passed through₂ Conversion cartridge assembly 22 converts NO₂Reduction to NO to thereby effect NO₂Zero generation and efficient utilization of, and also increase the concentration of NO; in addition, the gas-liquid separator 11 circularly connected with the electrolytic cell 5 is used for removing NO remained in the electrolytic cell 5 after the electrolysis is finished, so that the harm of the residual NO to the electrolyte and the electrode 6 is avoided, the electrolyte and the electrode 6 can be used for multiple times, the stable nitric oxide concentration is generated, and the repeatability and the consistency of the electrolytic cell 5 are realized.

The system device also comprises a nitrogen production unit, wherein the nitrogen production unit comprises a filtering device and a nitrogen production device 3 which are sequentially connected along the gas flow direction, and further, the filtering device comprises a water vapor filter 1 and a dust filter 2 which are sequentially connected along the gas flow direction; the nitrogen making device 3 comprises a nitrogen making film, gas enters the nitrogen making film and is separated to obtain nitrogen, furthermore, the material of the nitrogen making film comprises any one or the combination of at least two of poly (4-methyl-1-pentene), brominated polycarbonate, polypropylene, polyimide or polydimethylsiloxane, and the average pore diameter of the nitrogen making film is 0.005-0.02 μm, and is more preferably 0.01 μm.

Electrolytic cell 5 includes the casing, and the injection has electrolyte in the casing, is provided with at least a pair of electrode 6 of soaking electrolyte in the casing, and further, electrolytic cell 5 is external to have air inlet pipeline 4, and nitrogen gas outlet of nitrogen generator 3 passes through air inlet pipeline 4 and inserts electrolytic cell 5, is provided with nitrogen gas flow control valve on the air inlet pipeline 4. Furthermore, the shell is externally connected with an air outlet pipeline, and the inlet end of the air outlet pipeline is positioned above the liquid level.

Further, the electrolytic cell 5 comprises a circulating pipeline 8, the inlet end of the circulating pipeline 8 is positioned above the liquid level in the shell, the outlet end of the circulating pipeline 8 is connected to the air inlet pipeline 4, the gas in the electrolytic cell 5 circularly flows through the circulating pipeline 8, and the circulating pipeline 8 is provided with a circulating pump 9. The invention ensures the nitrogen and the nitric oxide generated by electrolysis to circulate in the electrolytic cell 5 by arranging the circulating pipeline 8, thereby ensuring the concentration of the nitric oxide.

Further, a purging element 7 is arranged in the electrolytic cell 5, and the purging element 7 is used for purging the electrode 6. According to the invention, the purging piece 7 is arranged, and the purging gas generated by the purging piece 7 is used for blowing away the nitric oxide gas generated on the surface of the electrode 6, so that the generated gas is prevented from being accumulated on the surface of the electrode 6 and in the electrolyte. Furthermore, the purging piece 7 is located below the electrode 6, the purging piece 7 comprises an open box body, the box body is filled with the air stones, the open direction of the box body faces the corresponding electrode 6, and the air inlet pipeline 4 and the circulating pipeline 8 are converged into one path and then respectively connected to the purging piece 7. According to the invention, the air bubble stone is adopted, so that the purging effect on the surface of the counter electrode 6 is increased, and the electrolysis efficiency of the electrolytic cell 5 is improved.

Further, the electrolytic cell 5 is circularly connected with the gas-liquid separator 11 through a first pipeline 15 and a second pipeline 16, and the first pipeline 15 extends into the shell below the liquid level; the second pipeline 16 is connected above the liquid level in the shell, furthermore, the first pipeline 15 and the second pipeline 16 are both connected into the switching valve 13 at the same time, and the switching valve 13 is used for switching the working state and the temporary stop state of the gas-liquid separator 11; the working state comprises the following steps: the electrolyte flows through the switching valve 13 through the first pipeline 15, enters the gas-liquid separator 11 for gas-liquid separation, and flows back into the electrolytic cell 5 through the second pipeline 16; the critical stop state comprises: the gas in the electrolytic cell 5 flows through the switching valve 13 via the second line 16, enters the gas-liquid separator 11, purges the remaining electrolyte, and the electrolyte flows back into the electrolytic cell 5 via the first line 15.

According to the invention, the operation state of the gas-liquid separator 11 is changed through the switching valve 13, wherein the operation state comprises a working state and a temporary stop state, and under the working state, the electrolyte in the electrolytic cell 5 enters the gas-liquid separator 11, so that the residual nitric oxide in the electrolytic cell 5 is removed, and the repeatability and consistency of the concentration of the nitric oxide generated in the next use are ensured; in the state of temporary stop, the residual electrolyte in the gas-liquid separator 11 is blown back into the electrolytic cell 5 through gas back blowing, so that the electrolyte is prevented from being accumulated in the gas-liquid separator 11, and the service life of the gas-liquid separator 11 is prevented from being influenced.

The gas-liquid separator 11 is connected with an air pump 10, and the air pump 10 injects carrier gas into the gas-liquid separator 11 for taking the separated gas out of the gas-liquid separator 11.

Further, the first line 15 is provided with a filter 14, the filter 14 being located between the electrolytic cell 5 and the switching valve 13. The filter 14 is provided in the invention to prevent impurities in the electrolyte from entering the gas-liquid separator 11, damaging membrane components in the gas-liquid separator 11 and affecting the separation effect of the gas-liquid separator 11.

Further, a solenoid valve is provided on the first line 15, and the solenoid valve is located between the filter 14 and the switching valve 13. In the invention, the electromagnetic valve is arranged on the first pipeline 15, and the electrolyte in the electrolytic cell 5 is prevented from being sucked back into the gas-liquid separator 11 by the electromagnetic valve because the electrolytic cell 5 has certain pressure during operation.

Further, a gas-liquid dual-purpose pump 12 is arranged on the first pipeline 15, the gas-liquid dual-purpose pump 12 is located between the switching valve 13 and the gas-liquid separator 11, and the area of a separation membrane in the gas-liquid separator 11 is 1000-50000 cm². The gas-liquid dual-purpose pump 12 provided by the invention can pump electrolyte and gas, and meets different functions of electrolyte delivery and gas delivery when the gas-liquid separator 11 is in a working state and a temporary stop state.

The electrolyte comprises a buffer solution, a nitrogen source and a catalyst, wherein the catalyst comprises a metal-based complex; the central atom of the metal-based complex is a metal-based atom, and the ligand of the metal-based complex is a nitrogen-containing multi-site ligand; the molar concentration of the buffer solution in the electrolyte is 0.01-3 mol/L, the molar concentration of the nitrogen source in the electrolyte is 0.01-5 mol/L, and the molar concentration of the catalyst in the electrolyte is 1-15 mmol/L.

m (high valence) (L) + e^-→ M (Low price) (L)

The buffer solution comprises one or the combination of at least two of 4-hydroxyethyl piperazine ethanesulfoacid buffer solution, 3-morpholine propanesulfonic acid buffer solution, tris (hydroxymethyl) aminomethane, citrate buffer solution, phosphate buffer solution, boric acid-borax buffer solution or organic buffer solution, the nitrogen source comprises nitrite, and the nitrite comprises inorganic nitrite and/or organic nitrite. The metal base atoms comprise one or the combination of at least two of copper, iron, titanium, chromium, manganese, cobalt or nickel; the nitrogen-containing multi-site ligand comprises one or a combination of at least two of tri (2-pyridylmethyl) amine, 1, 4, 7-triazacyclononane, 1, 4, 7-trimethyl-1, 4, 7-triazacyclononane, tri (2-aminoethyl) amine, tri (2-dimethylaminoethyl) or di (2-aminomethylpyridine) -propionic acid.

Further, the electrode 6 is a single-component conductive material or a base material coated with a conductive material, the conductive material comprises one or a combination of at least two of platinum, gold, carbon, glassy carbon, stainless steel, ruthenium iridium alloy or boron-doped diamond, and the base material is SiO₂One or a combination of at least two of conductive glass, tin-doped indium oxide, fluorine-doped indium oxide, a conductive plastic substrate, platinum, gold, carbon, glassy carbon, stainless steel, or ruthenium-iridium alloy.

The purification unit comprises a gas flowTo a purification membrane module and a clean filter 19 connected in sequence. The purification membrane component comprises a desalting fog membrane 17 and a Nafion membrane 18 which are sequentially connected along the gas flow direction, the material of the desalting fog membrane 17 comprises any one or the combination of at least two of polytetrafluoroethylene, polyvinylidene fluoride, polyether sulfone, mixed cellulose ester, organic nylon 6 or organic nylon 66, and the average pore diameter of the desalting fog membrane 17 is 0.1-2 mu m. The purification unit further comprises NO_xPurification device 23, gas outlet end of gas-liquid separator 11 is connected with NO_xPurification device 23, further, NO_xThe purification device 23 is filled with alumina loaded with spherical potassium permanganate.

The output unit comprises a pressure tank 20 and NO connected in series in the gas flow direction₂The conversion filter element device 22 is provided with an evacuation port and a pressure relief port on the pressure tank 20, and NO is connected to the pressure relief port of the pressure tank 20_xThe purification device 23, the pressure tank 20 enters NO through a large-range pipeline and a small-range pipeline₂The conversion filter element device 22 is provided with a large-range flow controller 21 on a large-range pipeline, a small-range flow controller 24 on a small-range pipeline, and a pressure sensor in the pressure tank 20.

Further, the NO generation system device comprises a concentration sensor arranged at the outlet of the converter, the concentration sensor is used for detecting the concentration of released nitric oxide, the wide-range flow controller 21 and the small-range flow controller 24 are respectively electrically connected with the concentration sensor, and the wide-range flow controller 21 and the small-range flow controller 24 both receive signals sent by the concentration sensor and control the output flow of nitric oxide in a feedback manner.

NO₂The conversion filter element device 22 comprises a cylinder body, the inside of the cylinder body is divided into at least two baffling cavities, the baffling cavities axially penetrate through the cylinder body, and NO is filled in the baffling cavities₂One end of each of two adjacent baffling cavities is communicated with each other, and gas enters the cylinder body and flows through the baffling cavities in sequence in a serpentine baffling mode. The invention leads the smoke to be in snake-shaped flow deflection in the cylinder body by arranging the multilayer flow deflection cavity, thereby improving NO₂The contact time and the contact area of the gas and the filter element material reduce the occupied area of the equipment.

NO₂The conversion filter element material comprises a carrier and reductive vitamins coated on the surface of the carrier, wherein the carrier comprises one or the combination of at least two of silica gel, molecular sieve, alumina, sponge, cotton or foaming resin; the reducing vitamin comprises one or more of vitamin C, vitamin E or vitamin A. Furthermore, every 100g of the carrier is coated with 5-50 g of reducing vitamins.

In another embodiment, the present invention provides a method for using the above device for generating NO, the method specifically comprises:

the compressed gas sequentially enters a water vapor filter 1 and a dust filter 2, water vapor and dust are respectively removed, then the compressed gas enters a nitrogen making device 3 for separation, and nitrogen with the volume concentration of more than or equal to 99.0% is obtained after the separation;

(II) introducing nitrogen into the electrolyte through the air inlet pipeline 4, wherein the flow of the nitrogen is 50-600 mL/min, purging gas on the electrode 6 to generate an electrolytic reaction to generate nitric oxide, spraying the nitrogen and the nitric oxide in the electrolytic cell 5 together with the air through the circulating pipeline 8 and the purging piece 7, wherein the flow of the gas in the circulating pipeline 8 is 0.5-3L/min, blowing away the gas generated on the electrode 6, and after the concentration of the nitric oxide meets the requirement, sequentially entering the desalting fog membrane 17, the Nafion membrane 18 and the cleaning filter 19, and storing the purified nitric oxide in the pressure tank 20, wherein when the nitrogen oxide in the pressure tank 20 is used, the nitric oxide passes through NO and then enters the pressure tank 20₂The conversion filter element device 22 is released after treatment;

(III) after the release of nitric oxide is stopped, the gas-liquid separator 11 enters a working state, the electrolyte flows through the switching valve 13 through the first pipeline 15 and enters the gas-liquid separator 11 for gas-liquid separation, the electrolyte flows back into the electrolytic cell 5 through the second pipeline 16, and the air carrier gas discharges the gas separated by the gas-liquid separator 11 to NO_xThe purification device 23 is used for refluxing the electrolyte into the electrolytic cell 5, and the working time is less than or equal to 20 min; after the working state is finished, the switching valve 13 is switched, the gas-liquid separator 11 enters the temporary stopping state, the gas in the electrolytic cell 5 flows through the switching valve 13 through the second pipeline 16, enters the gas-liquid separator 11, residual electrolyte is purged, the electrolyte flows back into the electrolytic cell 5 through the first pipeline 15, and the time of the temporary stopping stateIs 0.5-2 min.

According to the invention, the residual nitric oxide in the electrolytic cell 5 is separated and removed through the gas-liquid separator 11, so that the influence of the residual nitric oxide on the electrolyte and the electrode 6 is effectively removed, and the stability and consistency of the concentration of nitric oxide generated by each electrolysis are ensured; furthermore, by means of NO₂ Conversion cartridge assembly 22 converts NO₂Reduction to NO to thereby effect NO₂The zero generation and the effective utilization of the NO can be realized, the concentration of NO can be increased, and the NO output range is enlarged.

In the step (II), the method for electrolytic reaction comprises the following steps: and applying an excitation current or an excitation voltage which is 2-8 times of the set value to the electrode 6, and after the duration of 0.5-3 min, adjusting to the set current or the set voltage, wherein the set current is 0-300 mA, the set voltage is 1.4-3.0V, and NO is stably output within 2-10 min.

Example 1

The present embodiment provides an NO generation system device, which is based on an embodiment, wherein a material of the nitrogen generation membrane is poly (4-methyl-1-pentene), and an average pore diameter of the nitrogen generation membrane is 0.01 μm; the area of the separation membrane in the gas-liquid separator 11 was 25000cm²。

The buffer solution is 4-hydroxyethyl piperazine ethanethiosulfonic acid buffer solution, and the molar concentration of the buffer solution in the electrolyte is 0.01 mol/L. The nitrogen source is sodium nitrite, and the molar concentration in the electrolyte is 0.01 mol/L. The catalyst is a metal-based complex, the central atom of the metal-based complex is a copper-based atom, the ligand of the metal-based complex is tri (2-pyridylmethyl) amine, and the molar concentration of the catalyst in the electrolyte is 1 mmol/L. The electrodes 6 are all platinum.

The material of the desalting mist film 17 is polytetrafluoroethylene, and the average pore diameter of the desalting mist film 17 is 1 μm.

NO₂In the material of the conversion filter element, the carrier comprises alumina, the reducing vitamin comprises vitamin C, and every 100g of the carrier is coated with 25g of the reducing vitamin.

The embodiment also provides a use method of the NO generation system device, and the use method specifically includes:

compressed gas sequentially enters a water vapor filter 1 and a dust filter 2, water vapor and dust are respectively removed, then the compressed gas enters a nitrogen making device 3 for separation, and nitrogen with the volume concentration of 99.0% is obtained after the separation;

(II) nitrogen is introduced into the electrolyte through the air inlet pipeline 4, the flow of the nitrogen is 50mL/min, the gas on the purging electrode 6 is purged, the electrolytic reaction is carried out to generate nitric oxide, the nitrogen and the nitric oxide in the electrolytic cell 5 are sprayed out through the purging piece 7 together with the air inlet through the circulating pipeline 8, the flow of the gas in the circulating pipeline 8 is 0.5L/min, the gas generated on the electrode 6 is blown away, after the concentration of the nitric oxide meets the requirement, the nitric oxide sequentially enters the desalination film 17, the Nafion film 18 and the cleaning filter 19, the purified nitric oxide enters the pressure tank 20 for storage, and when the pressure tank is used, the nitric oxide in the pressure tank 20 is stored through the NO₂The conversion filter element device 22 is released after treatment;

(III) after the release of nitric oxide is stopped, the gas-liquid separator 11 enters a working state, the electrolyte flows through the switching valve 13 through the first pipeline 15 and enters the gas-liquid separator 11 for gas-liquid separation, the electrolyte flows back into the electrolytic cell 5 through the second pipeline 16, and the air carrier gas discharges the gas separated by the gas-liquid separator 11 to NO_xThe purification device 23 is used for refluxing the electrolyte into the electrolytic cell 5, and the working state time is 10 min; after the working state is finished, the switching valve 13 is switched, the gas-liquid separator 11 enters the temporary stop state, the gas in the electrolytic cell 5 flows through the switching valve 13 through the second pipeline 16 and enters the gas-liquid separator 11, the residual electrolyte is purged, and the electrolyte is purged through the first pipeThe loop 15 flows back into the electrolytic cell 5, and the time of the temporary stop state is 1 min.

In the step (II), the method for electrolytic reaction comprises the following steps: and applying an excitation current 2 times of the set value to the electrode 6, adjusting to the set current after the excitation current lasts for 0.5min, wherein the set current is 10mA, and NO is stably output within 10 min.

The concentration of released NO was 200 ppm.

Example 2

The present embodiment provides an NO generation system device, which is based on an embodiment, wherein a nitrogen generation membrane is made of brominated polycarbonate, and an average pore size of the nitrogen generation membrane is 0.02 μm; the area of the separation membrane in the gas-liquid separator 11 was 1000cm²。

The buffer solution is 3-morpholine propanesulfonic acid buffer solution, and the molar concentration of the buffer solution in the electrolyte is 1 mol/L. The nitrogen source is sodium nitrite, and the molar concentration of the sodium nitrite in the electrolyte is 1 mol/L. The catalyst is a metal-based complex, the central atom of the metal-based complex is an iron-based atom, the ligand of the metal-based complex is 1, 4, 7-triazacyclononane, and the molar concentration of the catalyst in the electrolyte is 3 mmol/L. The electrode 6 is made of gold.

The material of the desalting fog film 17 is polyvinylidene fluoride, and the average pore diameter of the desalting fog film 17 is 0.1 μm.

NO₂In the material of the conversion filter element, the carrier is cotton, the reducing vitamin is vitamin A, and 5g of the reducing vitamin is coated on every 100g of the carrier.

compressed gas sequentially enters a water vapor filter 1 and a dust filter 2, water vapor and dust are respectively removed, then the compressed gas enters a nitrogen making device 3 for separation, and nitrogen with the volume concentration of 99.6% is obtained after the separation;

(II) introducing nitrogen into the electrolyte through the air inlet pipeline 4, wherein the flow rate of the nitrogen is 100mL/min, purging the gas on the electrode 6 to generate an electrolytic reaction to generate nitric oxide, and the nitrogen and the nitric oxide in the electrolytic cell 5 pass through the circulating pipeline 8 and the air inlet IThe nitric oxide is sprayed out from the blowing piece 7, the flow rate of the gas in the circulating pipeline 8 is 1L/min, the gas generated on the blowing electrode 6 and the nitric oxide concentration meet the requirement, then the gas sequentially enters the desalting fog film 17, the Nafion film 18 and the cleaning filter 19, the purified nitric oxide enters the pressure tank 20 for storage, and when in use, the nitric oxide in the pressure tank 20 passes through NO to pass through the NO₂The conversion filter element device 22 is released after treatment;

(III) after the release of nitric oxide is stopped, the gas-liquid separator 11 enters a working state, the electrolyte flows through the switching valve 13 through the first pipeline 15 and enters the gas-liquid separator 11 for gas-liquid separation, the electrolyte flows back into the electrolytic cell 5 through the second pipeline 16, and the air carrier gas discharges the gas separated by the gas-liquid separator 11 to NO_xThe purification device 23 is used for refluxing the electrolyte into the electrolytic cell 5, and the working state lasts for 5 min; after the working state is finished, the switching valve 13 is switched, the gas-liquid separator 11 enters the temporary stopping state, gas in the electrolytic cell 5 flows through the switching valve 13 through the second pipeline 16 and enters the gas-liquid separator 11 to purge residual electrolyte, the electrolyte flows back into the electrolytic cell 5 through the first pipeline 15, and the time of the temporary stopping state is 0.5 min.

In the step (II), the method for electrolytic reaction comprises the following steps: and applying an excitation voltage which is 3 times of the set value to the electrode 6, adjusting to the set voltage after lasting for 1min, wherein the set voltage is 1.4V, and NO is stably output within 9 min.

The concentration of released NO was 1200 ppm.

Example 3

The present embodiment provides an NO generation system device, which is based on an embodiment, wherein the nitrogen making membrane is made of polypropylene, and an average pore size of the nitrogen making membrane is 0.012 μm; the area of a separation membrane in the gas-liquid separator 11 is 1000-50000 cm²。

The buffer solution is tris (hydroxymethyl) aminomethane, and the molar concentration of the buffer solution in the electrolyte solution is 1.5 mol/L. The nitrogen source is potassium nitrite, and the molar concentration of the potassium nitrite in the electrolyte is 2 mol/L. The catalyst is a metal-based complex, the central atom of the metal-based complex is a titanium-based atom, the ligand of the metal-based complex is 1, 4, 7-trimethyl-1, 4, 7-triazacyclononane, the molar concentration of the catalyst in the electrolyte is 4mmol/L, and the material of the electrode 6 is carbon.

The desalting fog membrane 17 is made of polyether sulfone; the average pore diameter of the desalination mist film 17 was 2 μm.

NO₂In the material of the conversion filter element, the carrier is foaming resin, the reducing vitamin is vitamin E, and 50g of the reducing vitamin is coated on each 100g of the carrier.

compressed gas sequentially enters a water vapor filter 1 and a dust filter 2, water vapor and dust are respectively removed, then the compressed gas enters a nitrogen making device 3 for separation, and nitrogen with the volume concentration of 99.7% is obtained after the separation;

(II) nitrogen is introduced into the electrolyte through the air inlet pipeline 4, the flow of the nitrogen is 200mL/min, the gas on the purging electrode 6 is purged, the electrolytic reaction is carried out to generate nitric oxide, the nitrogen and the nitric oxide in the electrolytic cell 5 are sprayed out through the purging piece 7 together with the air inlet through the circulating pipeline 8, the flow of the gas in the circulating pipeline 8 is 1.5L/min, the gas generated on the electrode 6 is blown away, after the concentration of the nitric oxide meets the requirement, the nitric oxide sequentially enters the desalination film 17, the Nafion film 18 and the cleaning filter 19, the purified nitric oxide enters the pressure tank 20 for storage, and when the pressure tank is used, the nitric oxide in the pressure tank 20 is stored through the NO₂The conversion filter element device 22 is released after treatment;

(III) after the release of nitric oxide is stopped, the gas-liquid separator 11 enters a working state, the electrolyte flows through the switching valve 13 through the first pipeline 15 and enters the gas-liquid separator 11 for gas-liquid separation, the electrolyte flows back into the electrolytic cell 5 through the second pipeline 16, and the air carrier gas discharges the gas separated by the gas-liquid separator 11 to NO_xThe purification device 23 is used for refluxing the electrolyte into the electrolytic cell 5, and the working state time is 12 min; after the working state is finished, the switching valve 13 is switched, the gas-liquid separator 11 enters the temporary stopping state, gas in the electrolytic cell 5 flows through the switching valve 13 through the second pipeline 16 and enters the gas-liquid separator 11 to purge residual electrolyte, the electrolyte flows back into the electrolytic cell 5 through the first pipeline 15, and the time of the temporary stopping state is 0.9 min.

In the step (II), the method for electrolytic reaction comprises the following steps: and applying an excitation current which is 5 times of the set value to the electrode 6, adjusting to the set current after lasting for 1.5min, wherein the set current is 100mA, and NO is stably output within 6 min.

The concentration of released NO was 3000 ppm.

Example 4

The present embodiment provides an NO generation system device, which is based on an embodiment, wherein the nitrogen generation membrane is made of polyimide, and an average pore size of the nitrogen generation membrane is 0.005 μm; the area of a separation membrane in the gas-liquid separator 11 is 1000-50000 cm²。

The buffer solution comprises a citrate buffer solution, and the molar concentration of the buffer solution in the electrolyte is 2 mol/L. The nitrogen source is sodium nitrite, and the molar concentration of the sodium nitrite in the electrolyte is 3 mol/L. The catalyst is a metal-based complex, the central atom of the metal-based complex is a chromium-based atom, the ligand of the metal-based complex is tri (2-aminoethyl) amine, and the molar concentration of the catalyst in the electrolyte is 5 mmol/L. The electrodes 6 are all made of SiO coated with glassy carbon coating₂。

The material of the desalting fog film 17 is organic nylon 6; the average pore diameter of the desalination mist film 17 was 0.1. mu.m.

NO₂In the material of the conversion filter element, a carrier is a molecular sieve, reducing vitamins comprise vitamin C, and 30g of reducing vitamins are coated on each 100g of carrier.

compressed gas sequentially enters a water vapor filter 1 and a dust filter 2, water vapor and dust are respectively removed, then the compressed gas enters a nitrogen making device 3 for separation, and nitrogen with the volume concentration of 99.990% is obtained after the separation;

(II) introducing nitrogen into the electrolyte through the air inlet pipeline 4, wherein the flow rate of the nitrogen is 300mL/min, purging gas on the electrode 6 to generate an electrolytic reaction to generate nitric oxide, spraying the nitrogen and the nitric oxide in the electrolytic cell 5 together with the air inlet through the circulating pipeline 8 through the purging piece 7, and spraying the gas in the circulating pipeline 8The flow of the body is 2L/min, the gas generated on the blowing electrode 6 is blown away, after the concentration of the nitric oxide meets the requirement, the nitric oxide sequentially enters the desalting fog film 17, the Nafion film 18 and the cleaning filter 19, the purified nitric oxide enters the pressure tank 20 for storage, and when the device is used, the nitric oxide in the pressure tank 20 passes through NO to be stored₂The conversion filter element device 22 is released after treatment;

(III) after the release of nitric oxide is stopped, the gas-liquid separator 11 enters a working state, the electrolyte flows through the switching valve 13 through the first pipeline 15 and enters the gas-liquid separator 11 for gas-liquid separation, the electrolyte flows back into the electrolytic cell 5 through the second pipeline 16, and the air carrier gas discharges the gas separated by the gas-liquid separator 11 to NO_xThe purification device 23 is used for refluxing the electrolyte into the electrolytic cell 5, and the working state time is 5 min; after the working state is finished, the switching valve 13 is switched, the gas-liquid separator 11 enters the temporary stopping state, gas in the electrolytic cell 5 flows through the switching valve 13 through the second pipeline 16 and enters the gas-liquid separator 11 to purge residual electrolyte, the electrolyte flows back into the electrolytic cell 5 through the first pipeline 15, and the time of the temporary stopping state is 1.5 min.

In the step (II), the method for electrolytic reaction comprises the following steps: and applying an excitation voltage 6 times of the set value to the electrode 6, adjusting to the set voltage after lasting for 2min, wherein the set voltage is 2V, and NO is stably output within 5 min.

The concentration of released NO was 4200 ppm.

Example 5

The embodiment provides an NO generation system device, which is based on an NO generation system device according to a specific embodiment, wherein a nitrogen making film is made of polydimethylsiloxane, and the average pore diameter of the nitrogen making film is 0.008 μm; the area of a separation membrane in the gas-liquid separator 11 is 1000-50000 cm²。

The buffer solution comprises phosphate buffer solution, and the molar concentration of the buffer solution in the electrolyte is 2.5 mol/L. The nitrogen source is sodium nitrite, and the molar concentration of the sodium nitrite in the electrolyte is 4 mol/L. The catalyst is a metal-based complex, the central atom of the metal-based complex is a manganese-based atom, the ligand of the metal-based complex is tris (2-dimethylaminoethyl), and the molar concentration of the catalyst in the electrolyte is 6 mmol/L. The electrodes 6 are all conductive glass coated with a stainless steel layer.

The material of the desalting fog film 17 is organic nylon 66; the average pore diameter of the desalination mist film 17 was 0.8. mu.m.

NO₂In the material of the conversion filter element, the carrier is sponge, the reducing vitamin comprises vitamin A, and 20g of the reducing vitamin is coated on each 100g of the carrier.

compressed gas sequentially enters a water vapor filter 1 and a dust filter 2, water vapor and dust are respectively removed, then the compressed gas enters a nitrogen making device 3 for separation, and nitrogen with the volume concentration of 99.8% is obtained after the separation;

(II) nitrogen is introduced into the electrolyte through the air inlet pipeline 4, the flow of the nitrogen is 400mL/min, the gas on the purging electrode 6 is purged, the electrolytic reaction is carried out to generate nitric oxide, the nitrogen and the nitric oxide in the electrolytic cell 5 are sprayed out through the purging piece 7 together with the air inlet through the circulating pipeline 8, the flow of the gas in the circulating pipeline 8 is 2.5L/min, the gas generated on the electrode 6 is blown away, after the concentration of the nitric oxide meets the requirement, the nitric oxide sequentially enters the desalination film 17, the Nafion film 18 and the cleaning filter 19, the purified nitric oxide enters the pressure tank 20 for storage, and when the pressure tank is used, the nitric oxide in the pressure tank 20 is stored through the NO₂The conversion filter element device 22 is released after treatment;

(III) after the release of nitric oxide is stopped, the gas-liquid separator 11 enters a working state, the electrolyte flows through the switching valve 13 through the first pipeline 15 and enters the gas-liquid separator 11 for gas-liquid separation, the electrolyte flows back into the electrolytic cell 5 through the second pipeline 16, and the air carrier gas discharges the gas separated by the gas-liquid separator 11 to NO_xThe purification device 23 is used for refluxing the electrolyte into the electrolytic cell 5, and the working state time is 20 min; after the working state is finished, the switching valve 13 is switched, the gas-liquid separator 11 enters the temporary stopping state, gas in the electrolytic cell 5 flows through the switching valve 13 through the second pipeline 16 and enters the gas-liquid separator 11 to purge residual electrolyte, the electrolyte flows back into the electrolytic cell 5 through the first pipeline 15, and the time of the temporary stopping state is 2 min.

In the step (II), the method for electrolytic reaction comprises the following steps: and applying an excitation current 7 times of the set value to the electrode 6, adjusting to the set current after lasting for 2.5min, wherein the set current is 200mA, and NO is stably output within 4.6 min.

The concentration of released NO was 6300 ppm.

Example 6

The present embodiment provides an NO generation system device, which is based on an embodiment, wherein a material of the nitrogen generation membrane includes brominated polycarbonate, and an average pore diameter of the nitrogen generation membrane is 0.015 μm; the area of a separation membrane in the gas-liquid separator 11 is 1000-50000 cm²。

The buffer solution is boric acid-borax buffer solution, and the molar concentration of the buffer solution in the electrolyte is 3 mol/L. The nitrogen source is potassium nitrite, and the molar concentration of the potassium nitrite in the electrolyte is 5 mol/L. The catalyst is a metal-based complex, the central atom of the metal-based complex is a cobalt-based atom, the ligand of the metal-based complex is bis (2-aminomethyl pyridine) -propionic acid, and the molar concentration of the catalyst in the electrolyte is 7 mmol/L. The electrodes 6 are all stainless steel coated with ruthenium iridium alloy coatings.

The material of the desalting fog film 17 is mixed cellulose ester; the average pore diameter of the desalination mist film 17 was 1.6. mu.m.

NO₂In the material of the conversion filter element, the carrier is silica gel, the reducing vitamin comprises vitamin E, and 15g of the reducing vitamin is coated on each 100g of the carrier.

compressed gas sequentially enters a water vapor filter 1 and a dust filter 2, water vapor and dust are respectively removed, then the compressed gas enters a nitrogen making device 3 for separation, and nitrogen with the volume concentration of 99.9% is obtained after the separation;

(II) introducing nitrogen into the electrolyte through the air inlet pipeline 4, wherein the flow rate of the nitrogen is 600mL/min, purging gas on the electrode 6 to generate an electrolytic reaction to generate nitric oxide, spraying the nitrogen and the nitric oxide in the electrolytic cell 5 together with the air inlet through the circulating pipeline 8 through the purging piece 7, and spraying the gas in the circulating pipeline 8 with the flow rate of 3LMin, blowing off gas generated on the electrode 6, enabling the nitric oxide to enter a desalting fog membrane 17, a Nafion membrane 18 and a cleaning filter 19 in sequence after the concentration of the nitric oxide meets the requirement, enabling the purified nitric oxide to enter a pressure tank 20 for storage, and enabling the nitric oxide in the pressure tank 20 to pass through NO for use₂The conversion filter element device 22 is released after treatment;

(III) after the release of nitric oxide is stopped, the gas-liquid separator 11 enters a working state, the electrolyte flows through the switching valve 13 through the first pipeline 15 and enters the gas-liquid separator 11 for gas-liquid separation, the electrolyte flows back into the electrolytic cell 5 through the second pipeline 16, and the air carrier gas discharges the gas separated by the gas-liquid separator 11 to NO_xThe purification device 23 is used for refluxing the electrolyte into the electrolytic cell 5, and the working state time is 18 min; after the working state is finished, the switching valve 13 is switched, the gas-liquid separator 11 enters the temporary stopping state, gas in the electrolytic cell 5 flows through the switching valve 13 through the second pipeline 16 and enters the gas-liquid separator 11 to purge residual electrolyte, the electrolyte flows back into the electrolytic cell 5 through the first pipeline 15, and the time of the temporary stopping state is 1.6 min.

In the step (II), the method for electrolytic reaction comprises the following steps: and applying an excitation voltage 8 times of the set value to the electrode 6, adjusting to the set voltage after lasting for 3min, wherein the set voltage is 3.0V, and NO is stably output within 5 min.

The concentration of released NO was 10400 ppm.

The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims

1. The NO generation system device is characterized by comprising a generation unit, a purification unit and an output unit which are sequentially connected, wherein the generation unit comprises an electrolytic cell and a gas-liquid separator which are circularly connected; said output unit comprising NO₂A conversion filter element device;

the electrolytic cell producesThe generated nitric oxide enters a purification unit, and enters NO in an output unit after being purified₂And (4) converting the filter element device and releasing, and removing the residual nitric oxide in the electrolytic cell by the gas-liquid separator after the electrolytic cell stops generating nitric oxide.

2. The system-plant according to claim 1, characterized in that the system-plant further comprises a nitrogen-producing unit, the nitrogen-producing unit comprises a filtering device and a nitrogen-producing device which are connected in series along a gas flow direction;

preferably, the filtering device comprises a water vapor filter and a dust filter which are connected in sequence along the gas flow direction;

preferably, the nitrogen making device comprises a nitrogen making membrane, and the gas enters the nitrogen making membrane and is separated to obtain nitrogen;

preferably, the material of the nitrogen making film comprises any one or a combination of at least two of poly (4-methyl-1-pentene), brominated polycarbonate, polypropylene, polyimide and polydimethylsiloxane;

preferably, the average pore diameter of the nitrogen making membrane is 0.005-0.02 μm.

3. The system set forth in claim 2 wherein said electrolytic cell comprises a housing, said housing being filled with an electrolyte, said housing having at least one pair of electrodes immersed in said electrolyte disposed therein;

preferably, the electrolytic cell is externally connected with an air inlet pipeline, and a nitrogen outlet of the nitrogen making device is connected to the electrolytic cell through the air inlet pipeline;

preferably, a nitrogen flow regulating valve is arranged on the air inlet pipeline;

preferably, the shell is externally connected with an air outlet pipeline, and the inlet end of the air outlet pipeline is positioned above the liquid level;

preferably, the electrolytic cell comprises a circulating pipeline, the inlet end of the circulating pipeline is positioned above the liquid level in the shell, the outlet end of the circulating pipeline is connected to an air inlet pipeline, and gas in the electrolytic cell flows in a circulating mode through the circulating pipeline;

preferably, a purging piece is arranged in the electrolytic cell and used for purging the electrode;

preferably, the purge is located below the electrode;

preferably, the blowing member comprises an open box body, and the box body is filled with air stones;

preferably, the opening direction of the box body faces to the corresponding electrode;

preferably, the air inlet pipeline and the circulating pipeline are converged into one pipeline and then are respectively connected to the purging parts;

preferably, a circulation pump is arranged on the circulation pipeline.

4. The system device according to any one of claims 1 to 3, wherein the electrolytic cell is circularly connected with the gas-liquid separator through a first pipeline and a second pipeline, and the first pipeline extends into the shell below the liquid level; the second pipeline is connected above the liquid level in the shell;

preferably, the first pipeline and the second pipeline are both connected to a switching valve at the same time, and the switching valve is used for switching the working state and the temporary stop state of the gas-liquid separator; the working state comprises: electrolyte flows through a switching valve through the first pipeline and enters the gas-liquid separator for gas-liquid separation, and the electrolyte flows back into the electrolytic cell through the second pipeline; the critical standstill state includes: gas in the electrolytic cell flows through the switching valve through the second pipeline, enters the gas-liquid separator, purges residual electrolyte, and the electrolyte flows back into the electrolytic cell through the first pipeline;

preferably, the gas-liquid separator is connected with an air pump, and the air pump injects carrier gas into the gas-liquid separator for bringing the separated gas out of the gas-liquid separator;

preferably, the first line is provided with a filter, the filter being located between the electrolytic cell and the switching valve;

preferably, an electromagnetic valve is arranged on the first pipeline and positioned between the filter and the switching valve;

preferably, a gas-liquid dual-purpose pump is arranged on the first pipeline and is positioned between the switching valve and the gas-liquid separator;

preferably, the area of the separation membrane in the gas-liquid separator is 1000-50000 cm²。

5. The system set forth in claim 3 or 4 wherein the electrolyte comprises a buffer, a nitrogen source, and a catalyst, wherein the catalyst comprises a metal-based complex; the central atom of the metal-based complex is a metal-based atom, and the ligand of the metal-based complex is a nitrogen-containing multi-site ligand;

preferably, the buffer solution comprises one or a combination of at least two of 4-hydroxyethyl piperazine ethanethiosulfonic acid buffer solution, 3-morpholine propanesulfonic acid buffer solution, tris (hydroxymethyl) aminomethane, citrate buffer solution, phosphate buffer solution, boric acid-borax buffer solution or organic buffer solution;

preferably, the molar concentration of the buffer solution in the electrolyte is 0.01-3 mol/L;

preferably, the nitrogen source comprises nitrite;

preferably, the nitrite comprises an inorganic nitrite and/or an organic nitrite;

preferably, the molar concentration of the nitrogen source in the electrolyte is 0.01-5 mol/L;

preferably, the metal-based atoms include one or a combination of at least two of copper, iron, titanium, chromium, manganese, cobalt, or nickel;

preferably, the nitrogen-containing multi-site ligand comprises one or a combination of at least two of tris (2-pyridylmethyl) amine, 1, 4, 7-triazacyclononane, 1, 4, 7-trimethyl-1, 4, 7-triazacyclononane, tris (2-aminoethyl) amine, tris (2-dimethylaminoethyl) or bis (2-aminomethylpyridine) -propionic acid;

preferably, the molar concentration of the catalyst in the electrolyte is 1-15 mmol/L;

preferably, the electrode plate is a single-component conductive material or a substrate coated with a conductive material;

preferably, the conductive material comprises one or a combination of at least two of platinum, gold, carbon, glassy carbon, stainless steel, ruthenium iridium alloy or boron-doped diamond;

6. The system-installation of any one of claims 1 to 5, wherein the purification unit comprises a purification membrane module and a clean filter connected in series in the gas flow direction;

preferably, the purification membrane module comprises a desalination membrane and a Nafion membrane which are sequentially connected along the gas flow direction;

preferably, the material of the salt and fog removing membrane comprises any one or a combination of at least two of polytetrafluoroethylene, polyvinylidene fluoride, polyether sulfone, mixed cellulose ester, organic nylon 6 or organic nylon 66;

preferably, the average pore diameter of the salt mist removing film is 0.1-2 μm;

preferably, said purification unit further comprises NO_xA gas outlet end of the gas-liquid separator is connected with NO_xA purification device;

preferably, said NO_xThe purification device is filled with alumina loaded with potassium permanganate;

preferably, the potassium permanganate-supporting alumina is spherical in shape;

preferably, the output unit comprises a pressure tank and NO connected in sequence along the gas flow direction₂A conversion filter element device;

preferably, the pressure tank is provided with an emptying port and a pressure relief port;

preferably, the NO is connected to a pressure relief opening of the pressure tank_xA purification device;

preferably, the pressure tank is supplied with NO through a large-range pipeline and a small-range pipeline₂A conversion filter element device;

preferably, a large-range flow controller is arranged on the large-range pipeline, and a small-range flow controller is arranged on the small-range pipeline;

preferably, a pressure sensor is arranged in the pressure tank;

7. The system apparatus as claimed in any one of claims 1 to 6, wherein said NO is₂The conversion filter element device comprises a cylinder body; the inner part of the cylinder body is divided into at least two baffling cavities, the baffling cavities axially penetrate through the cylinder body along the cylinder body, and NO is filled in the baffling cavities₂One end of each of two adjacent baffling cavities is communicated with each other, and gas enters the cylinder body and sequentially flows through the baffling cavities in a serpentine baffling manner;

preferably, said NO₂The conversion filter element material comprises a carrier and reductive vitamins coated on the surface of the carrier;

preferably, the carrier comprises one or a combination of at least two of silica gel, molecular sieve, alumina, sponge, cotton or foaming resin;

preferably, the reducing vitamin comprises one or a combination of at least two of vitamin C, vitamin E or vitamin A;

preferably, 5-50 g of reducing vitamin is coated on each 100g of carrier.

8. A method of using the apparatus of any of claims 1-7, the method comprising:

the electrolytic cell generates oxygen by electrolytic reactionThe generated nitric oxide enters a purifying unit and enters NO in an output unit after being purified₂And (4) converting the filter element device, releasing, and removing residual nitric oxide in the electrolytic cell through a gas-liquid separator after the electrolytic reaction is finished.

9. The use method according to claim 8, wherein the use method specifically comprises:

10. The use method as claimed in claim 9, wherein in the step (I), the volume concentration of the nitrogen is more than or equal to 99.0%;

preferably, the flow rate of the nitrogen is 50-600 mL/min;

preferably, in step (ii), the method of the electrolytic reaction comprises: applying an excitation current or an excitation voltage higher than a set value to the electrode, and after a period of time, adjusting to the set current or the set voltage, wherein NO is stably output in a short time;

preferably, the excitation current or the excitation voltage is 2-8 times of a set value;

preferably, the excitation current or the excitation voltage acts for 0.5-3 min;

preferably, the set current is 0-300 mA, and does not include 0;

preferably, the set voltage is 1.4-3.0V;

preferably, the NO is stably output within 2-10 min;

preferably, in the step (II), the flow rate of the gas in the circulating pipeline is 0.5-3L/min;

preferably, in the step (III), the time of the working state is less than or equal to 20 min;

preferably, in step (iii), the carrier gas is air;

preferably, in the step (III), the time of the temporary stop state is 0.5-2 min.