CN114318381B - NO generation system device and use method thereof - Google Patents

NO generation system device and use method thereof Download PDF

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Publication number
CN114318381B
CN114318381B CN202011502846.7A CN202011502846A CN114318381B CN 114318381 B CN114318381 B CN 114318381B CN 202011502846 A CN202011502846 A CN 202011502846A CN 114318381 B CN114318381 B CN 114318381B
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gas
pipeline
electrolytic cell
nitrogen
liquid separator
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CN114318381A (en
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耿翔
陈涛
陈翠华
郑盼盼
毛雯
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Nanjing Nuoling Biotechnology Co ltd
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Nanjing Nuoling Biotechnology Co ltd
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Priority to PCT/CN2021/139117 priority patent/WO2022127902A1/en
Priority to US18/043,900 priority patent/US20230313399A1/en
Priority to EP21844628.4A priority patent/EP4244406A1/en
Priority to KR1020237024202A priority patent/KR20230121851A/en
Priority to AU2021401099A priority patent/AU2021401099A1/en
Priority to CA3201125A priority patent/CA3201125A1/en
Priority to IL303679A priority patent/IL303679A/en
Priority to CN202180027930.4A priority patent/CN115398036B/en
Priority to CN202311033027.6A priority patent/CN117568825A/en
Priority to CN202311031041.2A priority patent/CN117070962A/en
Priority to JP2023537262A priority patent/JP2023554469A/en
Priority to CN202311032508.5A priority patent/CN117802515A/en
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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; the output unit comprises NO 2 A conversion filter element device; the nitric oxide generated by the electrolytic cell enters a purification unit, and enters NO in an output unit after purification 2 And (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 invention 2 Conversion filter element device for converting NO 2 Reduction to NO to effect NO 2 Zero generation and efficient utilization of, and increasing the concentration of NO; 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 generation device, and particularly relates to an NO generation system device and a using method thereof.
Background
Nitric oxide is a gas that plays a role in transmitting important messages and regulating cellular functions in the human body,can help promote blood circulation in vivo. It does not require any intermediary mechanism to rapidly diffuse across a biological membrane, transferring 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 O 2 And CO 2 The 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, including a nitric oxide gas generation subsystem and a gas concentration monitoring subsystem, where the gas concentration monitoring subsystem is used to monitor the concentration of nitric oxide and nitrogen dioxide actually inhaled by a user, and feedback-controls the concentration of nitric oxide gas output by the nitric oxide generation subsystem according to the monitored value, and the invention monitors and adjusts the concentration of nitric oxide actually inhaled by the user in real time.
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 characteristic 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 an NO generation system device and a 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; the output unit comprises NO 2 A conversion filter element device; the nitric oxide generated by the electrolytic cell enters a purification unit, and enters NO in an output unit after purification 2 And (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 electrolytic cell, wherein NO passes through NO during output 2 Conversion filter element device for converting NO 2 Reduction to NO to thereby effect NO 2 Zero 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 preferable technical solution of the present invention, the system device further comprises a nitrogen production unit, and the nitrogen production unit comprises 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 nitrogen-producing membrane has an average pore diameter of 0.005 to 0.02. Mu.m, for example, an average pore diameter of 0.005. Mu.m, 0.007. Mu.m, 0.009. Mu.m, 0.011. Mu.m, 0.013. Mu.m, 0.015. Mu.m, 0.017. Mu.m, 0.019. Mu.m, or 0.020. Mu.m.
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 purging 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 the switching valve through the first pipeline, enters the gas-liquid separator to be subjected to gas-liquid separation, and 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 cm 2 For example, an area of 1000cm 2 、5000cm 2 、10000cm 2 、15000cm 2 、20000cm 2 、25000cm 2 、30000cm 2 、35000cm 2 、40000cm 2 、45000cm 2 Or 50000cm 2 。
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)
Figure BDA0002844116500000051
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 3mol/L.
Preferably, the nitrogen source comprises a nitrite salt.
Preferably, the nitrite comprises an inorganic nitrite and/or an organic nitrite.
Preferably, the nitrogen source has a molar concentration of 0.01 to 5mol/L, for example, a molar concentration of 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 5mol/L in the electrolyte.
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 to 15mmol/L, for example, 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 15mmol/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 SiO 2 One 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 demisting membrane has an average pore size of 0.1 to 2 μm, for example an average pore size of 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 x A gas outlet end of the gas-liquid separator is connected with NO x A purification device.
Preferably, said NO x The 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 direction 2 Conversion 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 x A purification device.
Preferably, the pressure tank is supplied with NO through a large-range pipeline and a small-range pipeline 2 Conversion 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 is 2 The conversion filter element device comprises a cylinder body; the cylinder is internally divided into at least two baffling cavities, the baffling cavities axially penetrate through the cylinder along the cylinder, and NO is filled in the baffling cavities 2 One 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 snakelike deflection in the cylinder body by arranging the multilayer deflection cavities, thereby improving NO 2 The contact time and the contact area of the gas and the filter element material reduce the occupied area of the equipment.
Preferably, said NO 2 The 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 to 50g of reducing vitamin per 100g of carrier, which may be, for example, 5g, 10g, 15g, 20g, 25g, 30g, 35g, 40g, 45g or 50g.
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 purification 2 And (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 NO 2 Conversion filter element device for converting NO 2 Reduction to NO to thereby effect NO 2 The 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 NO 2 Releasing the conversion filter element device after treatment;
(III) after the release of nitric oxide is stopped, the gas-liquid separator enters the working chamberWhen the electrolyte is in the 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 x The 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 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 600mL/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 firstly applied, 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, for example, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, or 8 times the set value.
Preferably, the excitation current or the excitation voltage is applied for 0.5 to 3min, for example, 0.5min, 1min, 1.5min, 2min, 2.5min or 3min.
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 300mA.
Preferably, the set voltage is 1.4 to 3.0V, and may be, for example, 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, such as 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10min.
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 20min.
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 2.0min.
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 following beneficial effects:
the invention purifies NO generated by an electrolytic cell, wherein the NO passes through 2 Conversion filter element device for converting NO 2 Reduction to NO to thereby effect NO 2 Zero 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-a first conduit; 16-a second conduit; 17-desalting fog film; 18-Nafion membrane; 19-cleaning the filter; 20-pressure tank; 21-wide range flow controller; 22-NO 2 A conversion filter element device; 23-NO x A purification device; 24-small range flow controller.
Detailed Description
It is to be understood that in the description of the present invention, the terms "central," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in an orientation or positional relationship indicated in the drawings for convenience in describing the present invention and to simplify the description, but are not intended to indicate or imply that the device or element so referred to must have a particular orientation, be constructed in a particular orientation, and be operated in a particular manner and therefore are not to be construed as limiting the 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 described below by way of specific 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 NO 2 A conversion cartridge assembly 22; nitric oxide generated by the electrolytic cell 5 enters the purification unit, and enters the output unit after purification 2 The 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 present invention purifies NO generated from the electrolytic cell 5,wherein and passes NO at the time of output 2 Conversion cartridge assembly 22 converts NO 2 Reduction to NO to thereby effect NO 2 Zero 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 generator 3 includes a nitrogen generating membrane, and the gas is separated to obtain nitrogen gas after entering the nitrogen generating membrane, and further, the material of the nitrogen generating membrane includes any one or a combination of at least two of poly (4-methyl-1-pentene), brominated polycarbonate, polypropylene, polyimide, and polydimethylsiloxane, and the average pore diameter of the nitrogen generating membrane is 0.005 to 0.02 μm, and 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 arranged 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 influencing the separation effect of the gas-liquid separator 11.
Further, an electromagnetic valve is provided on the first line 15, and the electromagnetic 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 pump 12 for both gas and liquid is provided in the first pipe 15, the pump 12 for both gas and liquid is disposed between the switching valve 13 and the gas-liquid separator 11, and the area of the separation membrane in the gas-liquid separator 11 is 1000 to 50000cm 2 . 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.
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)
Figure BDA0002844116500000151
Note: m is one or at least two of copper, iron, titanium, chromium, manganese, cobalt or nickel.
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 a combination of at least two of copper, iron, titanium, chromium, manganese, cobalt or nickel; the nitrogen-containing multi-site ligand includes 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.
Further, the electrode 6 is a single-component conductive material or a substrate 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 substrate is SiO 2 One 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 purification membrane module and a clean filter 19 which are connected in sequence along the gas flow direction. 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 x A purification device 23, the gas outlet end of the gas-liquid separator 11 is connected with NO x Purification device 23, further, NO x The 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 direction 2 The conversion filter element device 22 is provided with an exhaust 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 x The purification device 23, the pressure tank 20 enters through a large-range pipeline and a small-range pipelineNO 2 The 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.
NO 2 The 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 are communicated with the cylinder body along the axial direction of the cylinder body, and NO is filled in the baffling cavities 2 One 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 NO 2 The contact time and the contact area of the gas and the filter element material reduce the occupied area of the equipment.
NO 2 The 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) nitrogen is introduced into the electrolyte through the air inlet pipeline 4, and the flow rate of the nitrogen is 50 to600mL/min, blowing the gas on the electrode 6 to generate an electrolytic reaction to generate nitric oxide, blowing out the nitrogen and the nitric oxide in the electrolytic cell 5 together with the inlet gas through the blowing piece 7 through the circulating pipeline 8, wherein the flow rate of the gas in the circulating pipeline 8 is 0.5-3L/min, blowing off the gas generated on the electrode 6, after the concentration of the nitric oxide meets the requirement, sequentially entering the desalting mist film 17, the Nafion film 18 and the cleaning filter 19, feeding the purified nitric oxide into the pressure tank 20 for storage, and when in use, feeding the nitric oxide in the pressure tank 20 through NO to generate the nitric oxide 2 The 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 x The purification device 23 is used for refluxing the electrolyte into the electrolytic cell 5, and the working time is less than or equal to 20min; after the working state is finished, the switching valve 13 is switched, the gas-liquid separator 11 enters the temporary stop 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, residual electrolyte is purged, the electrolyte flows back into the electrolytic cell 5 through the first pipeline 15, and the time of the temporary stop state is 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; in addition, by means of NO 2 Conversion cartridge assembly 22 converts NO 2 Reduction to NO to thereby effect NO 2 The zero generation and the effective utilization of the NO can be realized, the concentration of NO can be increased, and the NO output range can be improved.
In the step (II), the method for electrolytic reaction comprises the following steps: applying an excitation current or an excitation voltage which is 2-8 times of a set value to the electrode 6, after lasting for 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.
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.
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 25000cm 2 。
The buffer solution is 4-hydroxyethyl piperazine ethanethiosulfonic acid buffer solution, and the molar concentration of the buffer solution in the electrolyte is 0.01mol/L. The nitrogen source is sodium nitrite, and the molar concentration in the electrolyte is 0.01mol/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 1mmol/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.
NO 2 In 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 gasThe nitrogen is introduced into the electrolyte through the air inlet pipeline 4, the flow of the nitrogen is 50mL/min, the gas on the sweeping electrode 6 generates an electrolytic reaction to generate nitric oxide, the nitrogen and the nitric oxide in the electrolytic cell 5 are sprayed out through the sweeping part 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, the nitric oxide sequentially enters the desalination mist removing film 17, the Nafion film 18 and the cleaning filter 19 after the concentration of the nitric oxide meets the requirement, 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 stored in the pressure tank 20 2 The 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 x The purification device 23 is used for refluxing the electrolyte into the electrolytic cell 5, and the working state time is 10min; after the working state is finished, the switching valve 13 is switched, the gas-liquid separator 11 enters the temporary stop 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, residual electrolyte is purged, the electrolyte flows back into the electrolytic cell 5 through the first pipeline 15, and the time of the temporary stop state is 1min.
In the step (II), the method for electrolytic reaction comprises the following steps: an excitation current 2 times the set value was applied to the electrode 6, and after 0.5min, the current was adjusted to the set current, which was set to 10mA, and NO was stably output for 10min.
The concentration of released NO was 200ppm.
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 1000cm 2 。
The buffer solution is 3-morpholine propanesulfonic acid buffer solution, and the molar concentration of the buffer solution in the electrolyte is 1mol/L. The nitrogen source is sodium nitrite, and the molar concentration of the sodium nitrite in the electrolyte is 1mol/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 3mmol/L. The electrode 6 is made of gold.
The material of the desalting fog film 17 is polyvinylidene fluoride, and the average aperture of the desalting fog film 17 is 0.1 μm.
NO 2 In 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.
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 99.6% is obtained after the separation;
(II) nitrogen is introduced into the electrolyte through the air inlet pipeline 4, the flow of the nitrogen is 100mL/min, the gas on the electrode 6 is swept, 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 sweeping part 7 together with the air inlet through the circulating pipeline 8, the flow of the gas in the circulating pipeline 8 is 1L/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 fog removing membrane 17, the Nafion membrane 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 passes through the NO and is stored in the pressure tank 20 2 The 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 x The purification device 23 is used for refluxing the electrolyte into the electrolytic cell 5, and the working state time is 5min; after the working state is finished, the switching valve 13 is switched, the gas-liquid separator 11 enters the temporary stop state, and the gas in the electrolytic cell 5 flows through the second pipeline 16 and is switchedAnd the valve 13 enters the gas-liquid separator 11 to purge the residual electrolyte, the electrolyte flows back into the electrolytic cell 5 from the first pipeline 15, and the time of the temporary stop state is 0.5min.
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 the excitation voltage lasts for 1min, wherein the set voltage is 1.4V, and NO is stably output within 9min.
The concentration of released NO was 1200ppm.
Example 3
The present embodiment provides an NO generation system apparatus, which is based on the specific implementation manner, wherein the nitrogen making membrane is made of polypropylene, and the average pore size of the nitrogen making membrane is 0.012 μm; the area of the separation membrane in the gas-liquid separator 11 is 1000-50000 cm 2 。
The buffer solution is tris (hydroxymethyl) aminomethane, and the molar concentration of the buffer solution in the electrolyte solution is 1.5mol/L. The nitrogen source is potassium nitrite, and the molar concentration of the potassium nitrite in the electrolyte is 2mol/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.
NO 2 In 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.
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 99.7% is obtained after separation;
(II) introducing nitrogen into the electrolyte through an air inlet pipeline 4, wherein the flow rate of the nitrogen is 200mL/min, and purging gas on an electrode 6The 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 blowing piece 7 together with the inlet air through the circulating pipeline 8, the flow rate 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 desalting fog membrane 17, the Nafion membrane 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 stored 2 The 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 x The purification device 23 is used for refluxing the electrolyte into the electrolytic cell 5, and the working state time is 12min; after the working state is finished, the switching valve 13 is switched, the gas-liquid separator 11 enters the temporary stop 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, residual electrolyte is purged, the electrolyte flows back into the electrolytic cell 5 through the first pipeline 15, and the time of the temporary stop state is 0.9min.
In the step (II), the method for electrolytic reaction comprises the following steps: and applying an excitation current 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 6min.
The concentration of released NO was 3000ppm.
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 the separation membrane in the gas-liquid separator 11 is 1000-50000 cm 2 。
The buffer solution comprises a citrate buffer solution, and the molar concentration of the buffer solution in the electrolyte is 2mol/L. The nitrogen source is sodium nitrite, and the molar concentration of the sodium nitrite in the electrolyte is 3mol/L. The catalyst is metal-based complex, goldThe central atom of the metal-based complex is a chromium-based atom, the ligand of the metal-based complex is tris (2-aminoethyl) amine, and the molar concentration of the catalyst in the electrolyte is 5mmol/L. The electrodes 6 are all made of SiO coated with glassy carbon coating 2 。
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.
NO 2 In 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.
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 99.990% is obtained after the separation;
(II) nitrogen is introduced into the electrolyte through the air inlet pipeline 4, the flow of the nitrogen is 300mL/min, the gas on the electrode 6 is swept, 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 sweeping part 7 together with the air inlet through the circulating pipeline 8, the flow of the gas in the circulating pipeline 8 is 2L/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 fog removing membrane 17, the Nafion membrane 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 passes through the NO and is stored in the pressure tank 20 2 The 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 x The purification device 23 is used for refluxing the electrolyte into the electrolytic cell 5, and the working state time is 5min; 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, and residual gas is removedAnd (3) purging the electrolyte, wherein the electrolyte flows back into the electrolytic cell 5 from the first pipeline 15, and the time of the temporary stop state is 1.5min.
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 5min.
The concentration of released NO was 4200ppm.
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 the separation membrane in the gas-liquid separator 11 is 1000-50000 cm 2 。
The buffer solution comprises phosphate buffer solution, and the molar concentration of the buffer solution in the electrolyte is 2.5mol/L. The nitrogen source is sodium nitrite, and the molar concentration of the sodium nitrite in the electrolyte is 4mol/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 6mmol/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.
NO 2 In 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.
The embodiment also provides a use method of the NO generation system device, and the use method specifically comprises the following steps:
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 separation;
(II) introducing nitrogen into the electrolyte through an air inlet pipeline 4, wherein the flow rate of the nitrogen is 400mL/min, and purging the gas on an electrode 6 to generate an electrolytic reaction to generateNitric oxide, nitrogen and nitric oxide in the electrolytic cell 5 are sprayed out through the circulating pipeline 8 and the air inlet together through the blowing piece 7, the flow rate of gas in the circulating pipeline 8 is 2.5L/min, gas generated on the blowing electrode 6 is blown away, after the concentration of 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 sprayed out through the blowing piece 7 2 The 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 x The purification device 23 is used for refluxing the electrolyte into the electrolytic cell 5, and the working state time is 20min; 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 2min.
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 6300ppm.
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 the separation membrane in the gas-liquid separator 11 is 1000-50000 cm 2 。
The buffer solution is boric acid-borax buffer solution, and the molar concentration of the buffer solution in the electrolyte is 3mol/L. The nitrogen source is potassium nitrite, and the molar concentration of the potassium nitrite in the electrolyte is 5mol/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 7mmol/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.
NO 2 In the material of the conversion filter element, the carrier is silica gel, the reducing vitamins comprise vitamin E, and 15g of reducing vitamins are coated on each 100g of the carrier.
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 99.9% is obtained after the separation;
(II) nitrogen is introduced into the electrolyte through the air inlet pipeline 4, the flow of the nitrogen is 600mL/min, the gas on the electrode 6 is swept, 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 sweeping part 7 together with the air inlet through the circulating pipeline 8, the flow of the gas in the circulating pipeline 8 is 3L/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 fog removing membrane 17, the Nafion membrane 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 passes through the NO and is stored in the pressure tank 20 2 The 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 x The purification device 23 is used for refluxing the electrolyte into the electrolytic cell 5, and the working state time is 18min; 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, and the residual electrolyte is blownAnd (4) sweeping, wherein the electrolyte flows back into the electrolytic cell 5 from the first pipeline 15, and the time of the temporary stop state is 1.6min.
In the step (II), the method for electrolytic reaction comprises the following steps: an excitation voltage 8 times the set value was applied to the electrode 6, and after 3min, the voltage was adjusted to the set voltage, the set voltage was 3.0V, and NO was stably output within 5min.
The concentration of released NO was 10400ppm.
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 (68)

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; the output unit comprises NO 2 A conversion filter element device;
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, the electrolyte enters the gas-liquid separator through the first pipeline for gas-liquid separation, and the electrolyte flows back into the electrolytic cell through the second pipeline;
nitric oxide generated by the electrolytic cell enters the purification unit, and enters the NO output unit after being purified 2 And (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, and the nitrogen-producing unit comprises a filtering device and a nitrogen-producing device which are connected in series along the gas flow direction.
3. The system set forth in claim 2 wherein said filter means comprises a moisture filter and a dust filter connected in series in the gas flow direction.
4. The system apparatus of claim 2, wherein the nitrogen generator comprises a nitrogen generating membrane, and the gas is separated to obtain nitrogen after entering the nitrogen generating membrane.
5. The system device as claimed in claim 4, wherein the material of the nitrogen-making membrane comprises any one or a combination of at least two of poly (4-methyl-1-pentene), brominated polycarbonate, polypropylene, polyimide, and polydimethylsiloxane.
6. The system apparatus of claim 4, wherein the nitrogen-producing membrane has an average pore size of 0.005 to 0.02 μm.
7. 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 therein.
8. The system device of claim 7, wherein the electrolytic cell is externally connected with a gas inlet pipeline, and a nitrogen outlet of the nitrogen generator is connected to the electrolytic cell through the gas inlet pipeline.
9. The system device as claimed in claim 8, wherein a nitrogen flow regulating valve is disposed on the air inlet pipeline.
10. The system set forth in claim 7 wherein said housing is circumscribed by an outlet line, said outlet line having an inlet end above the liquid level.
11. The system device of claim 8, wherein the electrolytic cell comprises a circulation pipeline, an inlet end of the circulation pipeline is positioned above the liquid level in the shell, an outlet end of the circulation pipeline is connected to an air inlet pipeline, and gas in the electrolytic cell circularly flows through the circulation pipeline.
12. The system set forth in claim 11 wherein a purge is provided within the electrolytic cell for purging the electrodes.
13. The system-device of claim 12, wherein the purge is located below the electrode.
14. The system set forth in claim 12 wherein said purge member comprises an open box filled with air stones.
15. The system apparatus of claim 14, wherein the opening direction of the case is toward the corresponding electrode.
16. The system device as claimed in claim 12, wherein the air inlet pipeline and the circulating pipeline are connected into a purging piece respectively after being combined into a whole.
17. The system arrangement as claimed in claim 11, characterized in that a circulation pump is arranged on the circulation line.
18. The system device according to claim 1, wherein 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 the switching valve through the first pipeline, enters the gas-liquid separator to be subjected to gas-liquid separation, and 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.
19. The system device as claimed in claim 1, wherein the gas-liquid separator is connected with an air pump, and the air pump injects carrier gas into the gas-liquid separator for carrying the separated gas out of the gas-liquid separator.
20. The system arrangement of claim 18, wherein the first line is provided with a filter between the electrolytic cell and the switching valve.
21. The system set forth in claim 18 wherein a solenoid valve is disposed on the first line between the filter and the switching valve.
22. The system apparatus as claimed in claim 18, wherein a dual-purpose gas-liquid pump is provided in the first pipeline, and the dual-purpose gas-liquid pump is located between the switching valve and the gas-liquid separator.
23. The system device as set forth in claim 1, wherein the area of the separation membrane in the gas-liquid separator is 1000 to 50000cm 2 。
24. The system set forth in claim 1 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.
25. The system set forth in claim 24, wherein the buffer comprises one or a combination of at least two of 4-hydroxyethylpiperazine ethanesulfonic acid buffer, 3-morpholinopropanesulfonic acid buffer, tris, citrate buffer, phosphate buffer, or boric acid-borax buffer.
26. The system set forth in claim 24, wherein the buffer solution is present in the electrolyte at a molar concentration of 0.01 to 3mol/L.
27. The system of claim 24, wherein the nitrogen source comprises nitrite.
28. The system of claim 27, wherein said nitrite comprises inorganic nitrite and/or organic nitrite.
29. The system set forth in claim 24 wherein the nitrogen source is present in the electrolyte at a molar concentration of 0.01 to 5mol/L.
30. The system-assembly of claim 24, wherein said metal-based atoms comprise one or a combination of at least two of copper, iron, titanium, chromium, manganese, cobalt, or nickel.
31. The system-of-matter of claim 24, wherein said 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.
32. The system set forth in claim 24, wherein the molar concentration of said catalyst in said electrolyte is 1 to 15mmol/L.
33. The system of claim 7, wherein the electrodes are a single component of conductive material or a substrate coated with a conductive material.
34. The system set forth in claim 33 wherein the electrically conductive material comprises one or a combination of at least two of platinum, gold, carbon, stainless steel, ruthenium iridium alloy, or boron doped diamond.
35. The system-on-device of claim 33, wherein the substrate is SiO 2 One 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, stainless steel, or ruthenium-iridium alloy.
36. The system-assembly of claim 1, wherein the purification unit comprises a purification membrane module and a clean filter connected in series along the gas flow direction.
37. The system-device as claimed in claim 36, wherein the purification membrane module comprises a desalination membrane and a Nafion membrane connected in series along the gas flow direction.
38. The system device according to claim 37, wherein the material of the demisting membrane comprises one or a combination of at least two of polytetrafluoroethylene, polyvinylidene fluoride, polyethersulfone, mixed cellulose ester, organic nylon 6 or organic nylon 66.
39. The system-device of claim 37, wherein the average pore size of the demisting membrane is 0.1-2 μm.
40. The system of claim 1, wherein the purification unit further comprises NO x A gas outlet end of the gas-liquid separator is connected with NO x A purification device.
41. The system apparatus as claimed in claim 40, wherein said NO is x The purification device is filled with alumina loaded with potassium permanganate.
42. The system-device of claim 41, wherein the potassium permanganate-loaded alumina is spherical in shape.
43. The system apparatus as claimed in claim 40, wherein the output unit comprises a pressure tank and NO connected in series along the gas flow direction 2 Conversion filter core device.
44. The system device of claim 43, wherein the pressure tank is provided with a drain and a pressure relief port.
45. The system-on-device of claim 43, wherein a pressure relief port of the pressure tank is connected to the NO x A purification device.
46. The system set forth in claim 43 wherein the pressure tank is supplied NO via a large range line and a small range line 2 A conversion filter element device.
47. The system of claim 46 wherein a wide-range flow controller is disposed on the wide-range line and a narrow-range flow controller is disposed on the narrow-range line.
48. The system of claim 43 wherein a pressure sensor is disposed within said pressure tank.
49. The system of claim 47, wherein the NO generation system comprises a NO generator disposed in the NO generator 2 A concentration sensor at the outlet of the conversion cartridge device for detecting the releaseThe large-range flow controller and the small-range flow controller are respectively electrically connected with the concentration sensor, and both receive signals sent by the concentration sensor and feed back and control the output flow of nitric oxide.
50. The system of claim 1, wherein said NO is 2 The 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 cavities 2 One 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.
51. The system according to claim 50, wherein said NO 2 The conversion filter element material comprises a carrier and reducing vitamins coated on the surface of the carrier.
52. The system-device of claim 51, wherein the carrier comprises one or a combination of at least two of silica gel, molecular sieve, cotton, or foamed resin.
53. The system-device of claim 51, wherein the reductive vitamins comprise one or a combination of at least two of vitamin C, vitamin E or vitamin A.
54. The system-device of claim 51, wherein 5-50 g of reducing vitamins are coated per 100g of said carrier.
55. A method of using the apparatus of any of claims 1-54, said method comprising:
the electrolytic cell generates nitric oxide through electrolytic reaction, and the generated nitric oxideEnters a purification unit, and enters an output unit after purification 2 And (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.
56. The use method according to claim 55, wherein the use 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 NO 2 Releasing 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 x The 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.
57. The use of claim 56, wherein in step (I), the volume concentration of nitrogen is 99.0% or more.
58. The use according to claim 56, wherein the flow rate of nitrogen is 50-600 mL/min.
59. The use of claim 56, wherein in step (II), said electrolysis 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.
60. The use according to claim 59, wherein said excitation current or excitation voltage is 2-8 times the set value.
61. The use according to claim 59, wherein said excitation current or excitation voltage is applied for 0.5-3 min.
62. The use according to claim 59, wherein the set current is 0-300 mA, and does not include 0.
63. The use according to claim 59, wherein the set voltage is 1.4-3.0V.
64. The use according to claim 56, wherein said NO is stably output within 2-10 min.
65. The use according to claim 56, wherein in step (II), the gas flow rate in the circulation line is 0.5-3L/min.
66. The use according to claim 56, wherein in step (III), the time of the working state is less than or equal to 20min.
67. The use according to claim 56, wherein in step (III), the carrier gas is air.
68. The use according to claim 56, wherein in step (III), the time of the temporary stop state is 0.5-2 min.
CN202011502846.7A 2020-12-18 2020-12-18 NO generation system device and use method thereof Active CN114318381B (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
CN202011502846.7A CN114318381B (en) 2020-12-18 2020-12-18 NO generation system device and use method thereof
CN202311031041.2A CN117070962A (en) 2020-12-18 2021-12-17 Apparatus and method for generating nitric oxide
EP21844628.4A EP4244406A1 (en) 2020-12-18 2021-12-17 Apparatuses, systems, and methods for generating nitric oxide
KR1020237024202A KR20230121851A (en) 2020-12-18 2021-12-17 Devices, systems and methods for producing nitrogen monoxide
AU2021401099A AU2021401099A1 (en) 2020-12-18 2021-12-17 Apparatuses, systems, and methods for generating nitric oxide
CA3201125A CA3201125A1 (en) 2020-12-18 2021-12-17 Apparatuses, systems, and methods for generating nitric oxide
PCT/CN2021/139117 WO2022127902A1 (en) 2020-12-18 2021-12-17 Apparatuses, systems, and methods for generating nitric oxide
CN202180027930.4A CN115398036B (en) 2020-12-18 2021-12-17 Devices, systems, and methods for generating nitric oxide
CN202311033027.6A CN117568825A (en) 2020-12-18 2021-12-17 System and method for generating nitric oxide
US18/043,900 US20230313399A1 (en) 2020-12-18 2021-12-17 Apparatuses, systems, and methods for generating nitric oxide
JP2023537262A JP2023554469A (en) 2020-12-18 2021-12-17 Equipment, systems and methods for producing nitric oxide
CN202311032508.5A CN117802515A (en) 2020-12-18 2021-12-17 System for generating nitric oxide
IL303679A IL303679A (en) 2020-12-18 2021-12-17 Apparatuses, systems, and methods for generating nitric oxide

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