Carbon dioxide in-situ ionization oxygen generation device and oxygen preparation method

Abstract

The invention belongs to the technical field of oxygen preparation, and particularly relates to a carbon dioxide in-situ ionization oxygen production device and an oxygen preparation method.The carbon dioxide in-situ ionization oxygen production device comprises an air inlet tank and a plasma discharge cabin, the air inlet tank is connected with the plasma discharge cabin, and the plasma discharge cabin is connected with an oxygen permeable membrane reactor; a heating sleeve is arranged on the outer side of the oxygen permeable membrane reactor, the oxygen permeable membrane reactor is connected with a gas collecting bottle, and a vacuum pump is connected between the oxygen permeable membrane reactor and the gas collecting bottle; an electrode is arranged in the plasma discharge cabin, a plurality of hollow fiber oxygen-permeable membranes are arranged in the oxygen-permeable membrane reactor, the plurality of hollow fiber oxygen-permeable membranes are fixed on a bundling column, and a vacuum sealing head I and a vacuum sealing head II are respectively fixed at the left end and the right end of the oxygen-permeable membrane reactor. The device has the advantages of being simple in structure, easy to operate, high in efficiency, low in energy consumption, high in oxygen permeability, high in stability and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of oxygen preparation, and particularly relates to a carbon dioxide in-situ ionization oxygen generation device and an oxygen preparation method. Background Art

[0002] For a long time, sending astronauts to Mars has been an important goal of exploring outer space. The gas environment on Mars has a high content of CO2, and the rest are small amounts of N2, argon, and trace amounts of oxygen, water vapor, ozone, etc., making it difficult to meet human survival. Currently, the commonly used method for preparing oxygen is to use a solid oxide electrolytic cell with scandium oxide + zirconium oxide as the electrolyte to ionize CO2 into CO and O2, but O2 purification is not carried out; Chinese Patent CN114162787A discloses a CO2 oxygen generation device that uses plasma discharge technology to convert CO2 into O2 and CO through a low-temperature plasma reaction, then removes CO by adsorption, and separates O2 with a noble metal Ag-based oxygen permeable membrane. However, the oxygen permeation amount of the Ag-based separation membrane in this process is low, and it is easily eroded by plasma, unable to operate stably for a long time, restricting its application.

[0003] Mixed ionic-electronic perovskite (ABO3) oxygen permeable membranes have received extensive attention due to their 100% selectivity for oxygen. However, their poor stability and low oxygen permeation amount are the main bottleneck problems restricting their practical application. For example, the commonly used La 0.5 Sr 0.5 Co 0.3 Fe 0.7 O 3-δ perovskite oxygen permeable membrane has its oxygen permeation amount almost reduced by half after staying in a CO2 atmosphere for 5h, making it difficult to match the Mars oxygen generation environment. Analyzing the crystal structure of the perovskite-type oxygen permeable membrane material, it is unstable in a CO2 environment. The main reason is that the A-site cations react with CO2 to form carbonates covering its active sites. The high-entropy (i.e., configurational entropy greater than 1.5R) strategy will endow the oxygen permeable membrane with the characteristics of slow thermodynamic diffusion, lattice distortion, and the cocktail effect; slow diffusion is beneficial to the stability of the membrane, lattice distortion is beneficial to the formation of oxygen vacancies in the perovskite oxide oxygen permeable material to increase the oxygen permeation amount, the cocktail effect is beneficial to improving the CO2 tolerance of the cobalt-based perovskite oxygen permeable material, and at the same time, the toughening effect brought by high entropy also provides higher mechanical strength for the hollow fiber membrane.

[0004] Chinese Patent CN114904376A discloses an oxygen generation device for carbon dioxide conversion, which relates to the technical field of carbon dioxide conversion. The oxygen generation device for carbon dioxide conversion provided by the present invention includes an air extraction component, an air intake component, a tubular oxygen permeable membrane, a plasma generator, and a heating mechanism. The oxygen permeable membrane is installed inside the plasma generator, and a cavity for generating plasma is formed between the oxygen permeable membrane and the plasma generator. The cavity is communicated with the air intake component, the inside of the oxygen permeable membrane is communicated with the air extraction component, and the heating mechanism is located outside the plasma generator.

[0005] Combining the oxygen permeable membrane with the reaction electrode in this patent will cause damage to the performance of the oxygen permeable membrane, and the selection of the oxygen permeable membrane will be affected by the combination with the electrode, resulting in a decrease in the oxygen permeability and selectivity. Summary of the Invention

[0006] According to the deficiencies in the above prior art, the technical problem to be solved by the present invention is: to provide an in-situ carbon dioxide ionization oxygen generation device that can ionize CO2 into O2 and CO in a Martian environment with a high CO2 concentration. The oxygen preparation method provided by the present invention can realize the rapid separation of O2, with a high CO2 conversion rate, a fast O2 separation rate, and high purity.

[0007] The technical solution adopted by the present invention to solve its technical problems is: The in-situ carbon dioxide ionization oxygen generation device of the present invention includes an air intake tank and a plasma discharge chamber. The air intake tank is connected to the plasma discharge chamber. The plasma discharge chamber is connected to an oxygen permeable membrane reactor. A heating jacket is provided outside the oxygen permeable membrane reactor. The oxygen permeable membrane reactor is connected to a gas collecting bottle. A vacuum pump is connected between the oxygen permeable membrane reactor and the gas collecting bottle. An electrode is provided inside the plasma discharge chamber, and the electrode is connected to a plasma power supply. A number of hollow fiber oxygen permeable membranes are provided inside the oxygen permeable membrane reactor. The number of hollow fiber oxygen permeable membranes is fixed on a bundle column. Vacuum seals one and two are respectively fixed at the left and right ends of the oxygen permeable membrane reactor. Vacuum seal one is connected to the plasma discharge chamber, and vacuum seal two is connected to the vacuum pump. The bundle column is connected to vacuum seal two.

[0008] Among them: An air intake hole is provided at the top of the vacuum seal one, a tail gas hole is provided at the top of the vacuum seal two, an air outlet hole is provided at the side of the vacuum seal two, and a transmission pipe is provided inside the vacuum seal two. One end of the transmission pipe is connected to the bundle column, and the other end passes through the air outlet hole and is connected to the vacuum pump.

[0009] The tail gas hole is connected to a tail gas bottle.

[0010] A gas flow meter one is connected between the air intake tank and the plasma discharge chamber, and a gas flow meter two is connected between the plasma discharge chamber and the oxygen permeable membrane reactor.

[0011] The inner wall of the first vacuum sealing head, the inner wall of the second vacuum sealing head, and the outer wall of the oxygen permeable membrane reactor are made of quartz, and the hollow fiber oxygen permeable membrane is made of La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ material, with a particle size of 20 - 60 nm, where the particle size is the average particle diameter; its preparation process includes the following steps: a1. Add the metal salts after mixing lanthanum nitrate, calcium nitrate, strontium nitrate, bismuth nitrate, neodymium nitrate, cobalt nitrate, and iron nitrate into deionized water to form a uniformly mixed solution B; a2. Add an ethylene glycol dispersant and a citric acid complexing agent to the mixed solution B obtained in step a1, adjust it to neutral with ammonia water, and continue heating and stirring until a gel-like solution C is formed; a3. Heat and dry the gel-like solution C obtained in step a2 until a powder oxide D is formed; a4. After calcining the powder oxide D obtained in step a3, the La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ powder is obtained.

[0012] The described hollow fiber oxygen permeable membrane uses a zinc oxide composite material as a support, and through holes are provided on the support. The composite material composition is ZnO-La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ , a separation functional layer is provided on the outer surface of the support, and the material of the separation functional layer is La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ ; the mass ratio of the metal salts in step a1 to the ethylene glycol dispersant and the citric acid complexing agent in step a2 is 1:1 - 1.5:1; the calcination temperature of the powder oxide D in step a4 is 800 - 1000 °C, and the calcination time is 4.5 - 5 h. The preparation steps of the hollow fiber oxygen permeable membrane are as follows: b1. Mix La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ powder with ZnO to obtain mixed powder E; b2. Mix polyethersulfone and N-methylpyrrolidone and stir until completely dissolved to form a transparent solution F; b3. Add mixed powder E to solution F in batches and continue stirring to form a casting solution G; b4. Degas the casting solution G under vacuum, then introduce nitrogen. Use N-methylpyrrolidone and ethanol as the core liquid and internal coagulation bath, and water as the external coagulation bath. Under the drive of pressure, extrude the casting solution evenly through the spinneret into the external coagulation bath, soak and dry to obtain the support precursor H; b5. Mix La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ powder with 2-butanone, ethanol, triethanolamine, dibutyl phthalate, polyethylene glycol and polyvinyl butyral evenly to obtain the impregnation solution I; b6. Immerse the support precursor H in the impregnation solution I, then perform pulling. After drying, repeat the above pulling process to obtain the hollow fiber precursor J; b7. Sinter the hollow fiber precursor J to obtain the hollow fiber oxygen permeable membrane.

[0013] The outer diameter of the through holes of the said hollow fiber oxygen permeable membrane is 1.50 - 1.60 mm, and the thickness of the hollow fiber oxygen permeable membrane is 0.15 - 0.16 mm; In step b1, the mass ratio of La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ powder to ZnO is 7 - 8:2 - 3; In step b2, the mass ratio of polyethersulfone, N-methylpyrrolidone to the mixed powder E in step b1 is 1:4 - 5:8; In step b4, the vacuum degassing time is 1 - 2 h, and the nitrogen gas pressure is 0 - 0.2 MPa; In step b5, La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co0.3 Fe 0. 7O 3-δ The mass ratio of the powder to 2-butanone, ethanol, triethanolamine, dibutyl phthalate, polyethylene glycol and polyvinyl butyral is 1:0.8-1.2:1-1.5:0.5-0.8:0.6-0.9:0.5-1:1.2-1.5; the drying temperature in step b6 is 70-90 °C; the sintering temperature in step b7 is 1100-1200 °C, and the sintering time is 4.5-5.5 h.

[0014] The oxygen preparation method of the in-situ ionization of carbon dioxide oxygen generation device described above includes the following steps: S1. Pressurize and transport the CO2-containing gas in the intake tank into the plasma discharge chamber for ionization reaction to obtain an ionized gas containing oxygen. S2. Transport the ionized gas containing oxygen to the oxygen permeable membrane reactor. Under heating conditions, the ionized gas containing oxygen selectively permeates oxygen on the surface of the hollow fiber oxygen permeable membrane, and oxygen enters the inside of the hollow fiber oxygen permeable membrane, and the remaining gas accumulates outside the hollow fiber oxygen permeable membrane. S3. Collect the oxygen into the gas collecting bottle, and recycle the remaining gas to the tail gas bottle.

[0015] In step S1 described above, the pressure of the CO2-containing gas is 250-350 Pa, the ionization reaction temperature is 180-220 °C, the reaction time is 2-5 min, the reaction current is 0.2-0.25 A, and the flow rate of the CO2-containing gas is 50-200 sccm.

[0016] In step S2 described above, the heating temperature is 750-950 °C.

[0017] The present invention adopts the method of connecting the oxygen permeable membrane reactor to the plasma discharge chamber to realize the conversion of CO2 into O2 and the separation of O2. With the cooperation of the heating jacket and the vacuum pump, O2 is pumped out of the oxygen permeable membrane reactor, creating a negative pressure inside the oxygen permeable membrane reactor, which is conducive to the continuous passage of O2 in the ionized gas containing oxygen through the hollow fiber oxygen permeable membrane, separating more oxygen. A number of hollow fiber oxygen permeable membranes in the oxygen permeable membrane reactor are assembled and fixed through a beam column. Compared with the sheet membrane and single membrane, the effective oxygen permeable area of the oxygen permeable membrane is increased, and the ionized O2 can be selectively and continuously output in large quantities through the hollow fiber oxygen permeable membrane. By applying an external vacuum pump to break the chemical reaction equilibrium, the reaction continuously shifts forward to continuously generate O2, and the generated O2 is output in a timely and effective manner, improving the conversion rate of CO2. The present invention can be used in a CO2 atmosphere for more than 3000 h.

[0018] The plasma power supply, electrode, and plasma discharge chamber are collectively referred to as the plasma reaction device, and the plasma reaction device is connected between the intake tank and the oxygen permeable membrane reactor; multiple hollow fiber oxygen permeable membranes are assembled through a beam column and connected to a vacuum pump through a vacuum seal head two to discharge O2, and an external heating jacket provides energy.

[0019] During use, the intake tank sends the Martian atmosphere gas containing CO2 into the plasma discharge chamber after detection by a gas flowmeter one, and it is ionized into O2 on the electrode by starting the plasma power supply within the plasma reaction device; the resulting mixed gas containing O2 enters the oxygen permeable membrane reactor, and the hollow fiber oxygen permeable membrane selectively separates O2.

[0020] In the plasma discharge chamber of the present invention, CO2 is dissociated into O2 and CO through the action of glow discharge, and the mixed gas after dissociation selectively separates O2 through the hollow fiber membrane. Under the high-temperature environment of the hollow fiber membrane, O2 absorbs energy and dissociates into oxygen ions on the membrane surface to form adsorbed oxygen, which then combines with the oxygen vacancies in the perovskite structure to be transformed into lattice oxygen. Driven by the oxygen concentration difference on both sides of the membrane, lattice oxygen diffuses from the high-concentration end to the low-concentration end. At the same time, to maintain the electrical neutrality of the membrane, the movement direction of electrons is opposite to the diffusion direction of lattice oxygen. When lattice oxygen diffuses to the low-concentration end, it will obtain electrons on the membrane surface and transform into chemically adsorbed oxygen. Chemically adsorbed oxygen undergoes desorption to form oxygen molecules and leaves the membrane surface in a diffusive manner to achieve the selective separation of O2.

[0021] The beneficial effects of the present invention are as follows: The present invention in-situ ionizes CO2, and then uses a high-entropy perovskite La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0. 7O 3-δ material to directly separate the ionized CO and O2 without adsorption to achieve high-purity oxygen purification, so as to improve its oxygen permeation rate, CO2 tolerance, and long-term stability to meet the actual application in the Martian environment.

[0022] When the in-situ ionization of carbon dioxide oxygen generation device is working, first, the mixed gas of Mars atmosphere containing CO2 in the intake tank is sent into the plasma discharge chamber. At the electrodes of the plasma reaction device, CO2 is ionized into O2 and CO by the power supply drive, and then sent into the oxygen permeable membrane reactor. The heating jacket is started, and at a certain temperature, the hollow fiber oxygen permeable membrane can selectively separate the mixed gas containing O2. The vacuum pump extracts O2, increasing the oxygen partial pressure on both sides of the hollow fiber oxygen permeable membrane, thereby accelerating the entry and separation rate of O2. With the oxygen concentration gradient on both sides of the hollow fiber oxygen permeable membrane as the driving force, oxygen molecules enter the low-oxygen end in the form of diffusion from the high-oxygen end, obtaining O2 with a higher purity.

[0023] The present invention combines plasma ionization to produce O2 and the separation of O2 by an oxygen permeable membrane reactor, which has the advantages of simple equipment, easy operation, high efficiency, and low energy consumption. The in-situ ionization of carbon dioxide oxygen generation device combines a plasma reaction device and an oxygen permeable membrane reactor to realize the ionization of CO2 into O2 and CO, and can selectively separate O2, with simple operation.

[0024] The oxygen permeable membrane material adopts a multi-cation doping strategy, and is a high-entropy perovskite La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ material. In the present invention, by doping high-valent cations such as Ca 2+ 、Bi 3+ and Nd 3+ in the A-site, the oxygen vacancies and the surface reaction rate will be increased, thereby improving the oxygen ion conductivity and oxygen permeation flux; due to the weaker basicity of the doped cations and the enhancement of the A-O bond energy, it is more difficult to combine with CO2, so the stability of La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ is effectively improved; in the present invention, Ca 2+ 、Bi 3+ and Nd 3+The multi-cation doping and the ratio between each component endow the material with high-entropy characteristics; its configurational entropy at the A-site is 1.56R, featuring slow diffusion, severe lattice distortion, and the cocktail effect, etc. The lattice distortion is conducive to the formation of oxygen vacancies in the perovskite oxide oxygen permeation material, and the cocktail effect improves the CO2 tolerance of the Co-containing perovskite oxygen permeation material. Meanwhile, the toughening effect brought by high entropy also provides higher mechanical strength for the hollow fiber membrane; its tolerance factor is 0.859, meeting the regulation for the stability of the perovskite structure. Compared with other compositions, such as La 0.2 Ca 0.2 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ、 La 0.2 Ca 0.2 Sr 0.3 Bi 0.1 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ etc., La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ has a higher oxygen permeation rate and stability.

[0025] The oxygen permeation membrane is of a hollow fiber type and the oxygen separation process is in a negative pressure state, which can simultaneously maximize the reaction surface area, the oxygen permeation driving force, and minimize the resistance, and can stably operate in an acidic atmosphere for a long time while ensuring the oxygen permeation ability. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 is a schematic structural diagram of the present invention; Figure 2 is a schematic structural diagram of the oxygen permeation membrane reactor of the present invention; Figure 3 is a schematic structural diagram of the first vacuum seal head of the present invention; Figure 4 is a schematic structural diagram of the second vacuum seal head of the present invention; Figure 5 is a side view of the second vacuum seal head of the present invention; Figure 6 is a schematic structural diagram of the cluster column of the present invention; Figure 7 is a left view of the cluster column of the present invention; Figure 8It is the right view of the bundled column structure of the present invention; Figure 9 It is a schematic diagram of the hollow fiber oxygen permeable membrane structure in Embodiment 1 of the present invention; Figure 10 It is an SEM image of the hollow fiber oxygen permeable membrane in Embodiment 1 of the present invention at 500 μm; Figure 11 It is an SEM image of the hollow fiber oxygen permeable membrane in Embodiment 1 of the present invention at 50 μm; Figure 12 It is an SEM image of the hollow fiber oxygen permeable membrane in Embodiment 1 of the present invention at 100 μm; Figure 13 It is an SEM image of the hollow fiber oxygen permeable membrane in Embodiment 1 of the present invention at 20 μm; Figure 14 It is a graph of the detection data of the carbon dioxide content in the gas collecting bottles in Embodiments 1 - 5 of the present invention; Figure 15 It is a graph of the detection data of the carbon monoxide content in the gas collecting bottles in Embodiments 1 - 5 of the present invention; Figure 16 It is a graph of the detection data of the nitrogen content in the gas collecting bottles in Embodiments 1 - 5 of the present invention; Figure 17 It is a graph of the detection data of the oxygen content in the gas collecting bottles in Embodiments 1 - 5 of the present invention; Figure 18 It is a TEM image of the hollow fiber oxygen permeable membrane material prepared in Embodiment 1 of the present invention; Figure 19 It is a graph of the stability data of the hollow fiber oxygen permeable membrane prepared in Embodiment 1 of the present invention after purging with CO2 purge gas; In the figure: 1. Intake gas tank; 2. Plasma discharge chamber; 3. Oxygen permeable membrane reactor; 4. Heating jacket; 5. Gas collecting bottle; 6. Vacuum pump; 7. Tail gas bottle; 101. Gas flowmeter 1; 201. Plasma power supply; 202. Electrode; 203. Gas flowmeter 2; 301. Hollow fiber oxygen permeable membrane; 302. Bundled column; 303. Vacuum seal head 1; 304. Vacuum seal head 2; 3031. Intake hole; 3041. Tail gas hole; 3042. Exhaust hole; 3043. Transfer pipe. Detailed implementation mode

[0027] The following further describes the embodiments of the present invention with reference to the accompanying drawings.

[0028] Embodiment 1 As Figures 1-9As shown in the figure, the in-situ ionization oxygen generation device for carbon dioxide according to the present invention includes an intake tank 1 and a plasma discharge chamber 2. The intake tank 1 is connected to the plasma discharge chamber 2. The plasma discharge chamber 2 is connected to an oxygen permeable membrane reactor 3. A heating jacket 4 is provided outside the oxygen permeable membrane reactor 3. The oxygen permeable membrane reactor 3 is connected to a gas collecting bottle 5. A vacuum pump 6 is connected between the oxygen permeable membrane reactor 3 and the gas collecting bottle 5. An electrode 202 is provided inside the plasma discharge chamber 2. The electrode 202 is connected to a plasma power supply 201. A plurality of hollow fiber oxygen permeable membranes 301 are provided inside the oxygen permeable membrane reactor 3. The plurality of hollow fiber oxygen permeable membranes 301 are fixed on a beam column 302. Vacuum sealing heads 303 and 304 are respectively fixed at the left and right ends of the oxygen permeable membrane reactor 3. The vacuum sealing head 303 is connected to the plasma discharge chamber 2. The vacuum sealing head 304 is connected to the vacuum pump 6. The beam column 302 is connected to the vacuum sealing head 304.

[0029] An air inlet hole 3031 is provided at the top of the vacuum sealing head 303. An exhaust gas hole 3041 is provided at the top of the vacuum sealing head 304. An air outlet hole 3042 is provided at the side of the vacuum sealing head 304. A transmission pipe 3043 is provided inside the vacuum sealing head 304. One end of the transmission pipe 3043 is connected to the beam column 302, and the other end passes through the air outlet hole 3042 and is connected to the vacuum pump 6.

[0030] The exhaust gas hole 3041 is connected to an exhaust gas bottle 7.

[0031] A gas flowmeter 101 is connected between the intake tank 1 and the plasma discharge chamber 2. A gas flowmeter 203 is connected between the plasma discharge chamber 2 and the oxygen permeable membrane reactor 3.

[0032] The inner wall of the vacuum sealing head 303, the inner wall of the vacuum sealing head 304, and the outer wall of the oxygen permeable membrane reactor 3 are made of quartz. The hollow fiber oxygen permeable membrane 301 is made of La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ material, with a particle size of 20 nm. The preparation process includes the following steps: a1. Add a total of 100 g of metal salts after mixing lanthanum nitrate, calcium nitrate, strontium nitrate, bismuth nitrate, neodymium nitrate, cobalt nitrate, and iron nitrate to deionized water to form a uniformly mixed solution B; a2. Add 150 g of ethylene glycol dispersant and 100 g of citric acid complexing agent to the mixed solution B obtained in step a1. Then add ammonia water to adjust the pH value to neutral, and continue heating and stirring until a gel-like solution C is formed; a3. Heat and dry the solution C obtained in step a2 until a powdered oxide D is formed; a4. After calcining the oxide D obtained in step a3 at 800 °C for 5 h, La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ powder is obtained; The hollow fiber oxygen permeable membrane 301 uses a composite material composed of ZnO-La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ as the support. Through holes are provided on the support, and a separation functional layer is provided on the outer surface of the support. The material of the separation functional layer is La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ ; The preparation steps of the hollow fiber oxygen permeable membrane 301 are as follows: b1. Mix the La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ powder and ZnO in a mass ratio of 7:3 to obtain 80 g of mixed powder E; b2. Mix 10 g of polyethersulfone and 40 g of N-methylpyrrolidone and stir until completely dissolved into a light yellow transparent solution F; b3. Add the mixed powder E to the solution F in batches and continue stirring to form a casting solution G; b4. Debubble the casting solution G under vacuum for 1.5 h, then introduce nitrogen with a pressure of 0.1 MPa. Use N-methylpyrrolidone and ethanol as the core liquid and internal coagulation bath, and water as the external coagulation bath. Under the drive of pressure, extrude the casting solution evenly through the spinneret into the external coagulation bath, soak and dry to obtain the support precursor H; b5. According to the mass ratio of 1:0.8:1.5:0.5:0.8:0.7:1.5, La 0.3 Ca 0.1 Sr0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ The powder, 2-butanone, ethanol, triethanolamine, dibutyl phthalate, polyethylene glycol and polyvinyl butyral are added to a planetary ball mill and mixed evenly to obtain the impregnating solution I. b6. The support precursor H is impregnated in the impregnating solution I, then pulled up, dried at 80°C, and the above pulling process is repeated to obtain the hollow fiber precursor J. b7. The hollow fiber precursor J is sintered at 1200°C for 5 h to obtain the hollow fiber oxygen permeable membrane 301. The outer diameter of the through holes of the hollow fiber oxygen permeable membrane 301 is 1.50 mm, and the thickness of the hollow fiber oxygen permeable membrane 301 is 0.16 mm.

[0033] An oxygen preparation method using a carbon dioxide in-situ ionization oxygen generation device includes the following steps: S1. The pressure of the CO2-containing gas in the inlet gas tank 1 is adjusted to 300 Pa, and the delivery flow rate is stabilized at 150 sccm and delivered into the plasma discharge chamber 2 to simulate the Martian gas environment. The current of the electrode 202 is set to 0.22 A, and ionization is carried out in the 2 L plasma discharge chamber 2 at 200°C for 2 min to reach equilibrium, obtaining an ionized gas containing oxygen. S2. The ionized gas containing oxygen is delivered to the oxygen permeable membrane reactor 3, and then the heating jacket 4 is turned on. Under the heating condition of 750°C, the ionized gas containing oxygen undergoes selective oxygen permeation on the surface of the hollow fiber oxygen permeable membrane 301. Oxygen enters the inside of the hollow fiber oxygen permeable membrane 301, and the remaining gas accumulates outside the hollow fiber oxygen permeable membrane 301. The vacuum pump 6 is turned on to suck oxygen, and the oxygen is collected through the beam column 302 and separated from the air outlet 3042 through the transmission pipe 3043. S3. The oxygen sucked by the vacuum pump 6 continuously enters the gas collecting bottle 5, and the remaining gas in the oxygen permeable membrane reactor 3 is recovered to the tail gas bottle 7 through the tail gas hole 3041.

[0034] The hollow fiber oxygen permeable membrane 301 is detected by SEM and TEM, and the detection results are as Figures 10-13 、 Figure 18 shown.

[0035] Example 2 An oxygen preparation method using the carbon dioxide in-situ ionization oxygen generation device described in Example 1 includes the following steps: S1. Adjust the pressure of the CO₂-containing gas in the intake tank 1 to 350 Pa, and the delivery flow rate is stabilized at 200 sccm and delivered into the plasma discharge chamber 2 to simulate the Martian gas environment. Set the current of the electrode 202 to 0.25 A, and perform ionization in the 2 L plasma discharge chamber 2 at 220 °C for 3 minutes until equilibrium is reached to obtain the ionized gas containing oxygen. S2. The ionized gas enters the oxygen permeable membrane reactor 3 through the intake hole 3031. Subsequently, turn on the heating jacket 4 under the heating condition of 800 °C. The ionized gas containing oxygen performs selective permeation of oxygen on the surface of the hollow fiber oxygen permeable membrane 301. Oxygen enters the inside of the hollow fiber oxygen permeable membrane 301, and the remaining gas accumulates outside the hollow fiber oxygen permeable membrane 301. Turn on the vacuum pump 6 to suck oxygen, and the oxygen is collected through the beam column 302 and separated from the outlet hole 3042 through the transfer tube 3043. S3. The oxygen sucked by the vacuum pump 6 continuously enters the gas collecting bottle 5, and the remaining gas in the oxygen permeable membrane reactor 3 is recovered to the tail gas bottle 7 through the tail gas hole 3041.

[0036] Example 3 Adopt the oxygen preparation method of the carbon dioxide in-situ ionization oxygen generation device described in Example 1, including the following steps: S1. Adjust the pressure of the CO₂-containing gas in the intake tank 1 to 300 Pa, and the delivery flow rate is stabilized at 150 sccm and delivered into the plasma discharge chamber 2 to simulate the Martian gas environment. Set the current of the electrode 202 to 0.22 A, and perform ionization in the 2 L plasma discharge chamber 2 at 210 °C for 3 minutes until equilibrium is reached to obtain the ionized gas containing oxygen. S2. The ionized gas enters the oxygen permeable membrane reactor 3 through the intake hole 3031. Subsequently, turn on the heating jacket 4 under the heating condition of 850 °C. The ionized gas containing oxygen performs selective permeation of oxygen on the surface of the hollow fiber oxygen permeable membrane 301. Oxygen enters the inside of the hollow fiber oxygen permeable membrane 301, and the remaining gas accumulates outside the hollow fiber oxygen permeable membrane 301. Turn on the vacuum pump 6 to suck oxygen, and the oxygen is collected through the beam column 302 and separated from the outlet hole 3042 through the transfer tube 3043. S3. The oxygen sucked by the vacuum pump 6 continuously enters the gas collecting bottle 5, and the remaining gas in the oxygen permeable membrane reactor 3 is recovered to the tail gas bottle 7 through the tail gas hole 3041.

[0037] Example 4 Adopt the oxygen preparation method of the carbon dioxide in-situ ionization oxygen generation device described in Example 1, including the following steps: S1. Adjust the pressure of the CO₂-containing gas in the intake tank 1 to 250 Pa, and the delivery flow rate is stabilized at 50 sccm and delivered into the plasma discharge chamber 2 to simulate the Martian gas environment. Set the current of the electrode 202 to 0.2 A, and perform ionization in the 2 L plasma discharge chamber 2 at 180 °C for 5 minutes to reach equilibrium, obtaining an ionized gas containing oxygen. S2. The ionized gas enters the oxygen permeable membrane reactor 3 through the intake hole 3031. Subsequently, turn on the heating jacket 4 under the heating condition of 900 °C. The ionized gas containing oxygen undergoes selective permeation of oxygen on the surface of the hollow fiber oxygen permeable membrane 301. Oxygen enters the inside of the hollow fiber oxygen permeable membrane 301, and the remaining gas accumulates outside the hollow fiber oxygen permeable membrane 301. Turn on the vacuum pump 6 to suck oxygen, and the oxygen is collected through the beam column 302 and separated from the outlet hole 3042 through the transfer pipe 3043. S3. The oxygen sucked by the vacuum pump 6 continuously enters the gas collecting bottle 5, and the remaining gas in the oxygen permeable membrane reactor 3 is recovered to the tail gas bottle 7 from the tail gas hole 3041.

[0038] Example 5 An oxygen preparation method using the carbon dioxide in-situ ionization oxygen generation device described in Example 1, including the following steps: S1. Adjust the pressure of the CO₂-containing gas in the intake tank 1 to 300 Pa, and the delivery flow rate is stabilized at 150 sccm and delivered into the plasma discharge chamber 2 to simulate the Martian gas environment. Set the current of the electrode 202 to 0.25 A, and perform ionization in the 2 L plasma discharge chamber 2 at 200 °C for 2 minutes to reach equilibrium, obtaining an ionized gas containing oxygen. S2. The ionized gas enters the oxygen permeable membrane reactor 3 through the intake hole 3031. Subsequently, turn on the heating jacket 4 under the heating condition of 950 °C. The ionized gas containing oxygen undergoes selective permeation of oxygen on the surface of the hollow fiber oxygen permeable membrane 301. Oxygen enters the inside of the hollow fiber oxygen permeable membrane 301, and the remaining gas accumulates outside the hollow fiber oxygen permeable membrane 301. Turn on the vacuum pump 6 to suck oxygen, and the oxygen is collected through the beam column 302 and separated from the outlet hole 3042 through the transfer pipe 3043. S3. The oxygen sucked by the vacuum pump 6 continuously enters the gas collecting bottle 5, and the remaining gas in the oxygen permeable membrane reactor 3 is recovered to the tail gas bottle 7 from the tail gas hole 3041.

[0039] The gases in the gas collecting bottles 5 in Examples 1 - 5 were respectively subjected to concentration detection. Using nitrogen as the purge gas, the gas composition and concentration in the gas collecting bottles 5 were tested to obtain the content data of relevant gases, as shown in Table 1 and Figures 14-17 、 Figure 19 shown.

[0040]

[0041] Example 6 La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ The material preparation process includes the following steps: In step a2, 120 g of ethylene glycol dispersant and 100 g of citric acid complexing agent are added; in step a4, oxide D is calcined at 1000 °C for 4.5 h, and the remaining operations are the same as in Example 1; La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ The powder particle size is 60 nm; The preparation steps of the hollow fiber oxygen permeable membrane 301 are as follows: In step b1, La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ The powder and ZnO are mixed according to a mass ratio of 7.5:2.5 to obtain 80 g of mixed powder E; in step b2, 10 g of polyethersulfone and 40 g of N-methylpyrrolidone are mixed; in step b4, the casting solution G is degassed under vacuum for 1 h, and then nitrogen with a pressure of 0.2 MPa is introduced; in step b5, La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ The mass ratio of the powder and 2-butanone, ethanol, triethanolamine, dibutyl phthalate, polyethylene glycol and polyvinyl butyral is 1:1.2:1:0.6:0.9:1:1.2; in step b6, the drying temperature is 70 °C; in step b7, the sintering temperature is 1100 °C and the sintering time is 5.5 h; the remaining operations are the same as in Example 1, and a hollow fiber oxygen permeable membrane 301 with an outer diameter of the through-hole of 1.60 mm and a thickness of 0.16 mm is obtained.

[0042] Example 7 La 0.3 Ca 0.1 Sr 0.2 Bi0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ The material preparation process includes the following steps: In step a2, 100 g of ethylene glycol dispersant and 100 g of citric acid complexing agent are added; in step a4, oxide D is calcined at 900 °C for 5 h, and the remaining operations are the same as in Example 1; La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ The powder particle size is 40 nm; The preparation steps of the hollow fiber oxygen permeable membrane 301 are as follows: In step b1, La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ The powder and ZnO are mixed in a mass ratio of 8:2 to obtain 80 g of mixed powder E; in step b2, 10 g of polyethersulfone and 45 g of N-methylpyrrolidone are mixed; in step b4, the casting solution G is degassed under vacuum for 2 h, and then nitrogen with a pressure of 0 MPa is introduced; in step b5, La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ The mass ratio of the powder to 2-butanone, ethanol, triethanolamine, dibutyl phthalate, polyethylene glycol and polyvinyl butyral is 1:1:1.5:0.8:0.6:0.5:1.5; in step b6, the drying temperature is 90 °C; in step b7, the sintering temperature is 1100 °C and the sintering time is 4.5 h, and the remaining operations are the same as in Example 1; a hollow fiber oxygen permeable membrane 301 with an outer diameter of the through-hole of 1.55 mm and a thickness of 0.15 mm is obtained.

[0043] Example 8 La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ The material preparation process includes the following steps: In step a2, 110 g of ethylene glycol dispersant and 100 g of citric acid complexing agent are added; in step a4, oxide D is calcined at 900 °C for 5 h, and the remaining operations are the same as in Example 1; La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ The powder particle size is 30 nm; The preparation steps of the hollow fiber oxygen permeable membrane 301 are as follows: In step b1, La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ The powder and ZnO are mixed in a mass ratio of 7:3 to obtain 80 g of mixed powder E; in step b2, 10 g of polyethersulfone and 50 g of N-methylpyrrolidone are mixed; in step b4, the casting solution G is degassed under vacuum for 2 h, and then nitrogen with a pressure of 0 MPa is introduced; in step b5, La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ The mass ratio of the powder and 2-butanone, ethanol, triethanolamine, dibutyl phthalate, polyethylene glycol and polyvinyl butyral is 1:0.8:1.3:0.5:0.9:0.7:1.3; in step b6, the drying temperature is 75 °C; in step b7, the sintering temperature is 1150 °C and the sintering time is 5 h, and the remaining operations are the same as in Example 1; a hollow fiber oxygen permeable membrane 301 with an outer diameter of 1.6 mm and a thickness of 0.155 mm for the through hole is obtained.

[0044] Comparative Example 1 In step a1, bismuth nitrate is not added, and the remaining operations are the same as in Example 6 to obtain a permeable membrane.

[0045] Comparative Example 2 In step a1, neodymium nitrate is not added, and the remaining operations are the same as in Example 6 to obtain a permeable membrane.

[0046] Comparative Example 3 In step a1, neither neodymium nitrate nor bismuth nitrate is added, and the remaining operations are the same as in Example 6 to obtain a permeable membrane.

[0047] Comparative Example 4 In step a1, calcium nitrate is not added, and the remaining operations are the same as in Example 6 to obtain a permeation membrane.

[0048] The hollow fiber oxygen permeable membranes 301 prepared in Examples 6-8 and the permeation membranes prepared in Comparative Examples 1-4 were respectively subjected to the operation of preparing O2 from CO2 by the method of Example 3. Nitrogen was used as the purge gas, and the collected gas was detected. The data obtained are shown in Table 2;

[0049] As can be seen from the above, the hollow fiber oxygen permeable membrane 301 provided by the present invention can effectively separate oxygen, and the obtained oxygen content is relatively high. It can realize the preparation and separation of oxygen at different temperatures and different carbon dioxide concentrations, so as to realize the preparation, separation and purification of oxygen in the Martian environment. Moreover, the oxygen permeable membrane reactor 3 prepared by the present invention using stable materials can ensure the oxygen permeation ability while stably operating in an acidic atmosphere for a long time. Figure 19 It can be seen that the stable operation time is more than 3000 hours.

Claims

1. An in-situ ionization oxygen generation device for carbon dioxide, comprising an intake tank (1) and a plasma discharge chamber (2), characterized in that, The intake tank (1) is connected to the plasma discharge chamber (2), the plasma discharge chamber (2) is connected to an oxygen permeable membrane reactor (3), a heating jacket (4) is arranged outside the oxygen permeable membrane reactor (3), the oxygen permeable membrane reactor (3) is connected to a gas collecting bottle (5), and a vacuum pump (6) is connected between the oxygen permeable membrane reactor (3) and the gas collecting bottle (5); An electrode (202) is arranged inside the plasma discharge chamber (2), the electrode (202) is connected to a plasma power supply (201), a plurality of hollow fiber oxygen permeable membranes (301) are arranged inside the oxygen permeable membrane reactor (3), the plurality of hollow fiber oxygen permeable membranes (301) are fixed on a beam column (302), a vacuum seal head one (303) and a vacuum seal head two (304) are respectively fixed at the left and right ends of the oxygen permeable membrane reactor (3), the vacuum seal head one (303) is connected to the plasma discharge chamber (2), the vacuum seal head two (304) is connected to the vacuum pump (6), and the beam column (302) is connected to the vacuum seal head two (304).

2. The in-situ carbon dioxide ionization oxygen generation device according to claim 1, characterized in that, An air inlet hole (3031) is arranged at the top of the vacuum seal head one (303), a tail gas hole (3041) is arranged at the top of the vacuum seal head two (304), an air outlet hole (3042) is arranged at the side part of the vacuum seal head two (304), a transmission pipe (3043) is arranged inside the vacuum seal head two (304), one end of the transmission pipe (3043) is connected to the beam column (302), and the other end passes through the air outlet hole (3042) and is connected to the vacuum pump (6).

3. The in-situ carbon dioxide ionization oxygen generation device according to claim 2, characterized in that, The tail gas hole (3041) is connected to a tail gas bottle (7).

4. The in-situ carbon dioxide ionization oxygen generation device according to claim 1, characterized in that, A gas flowmeter one (101) is connected between the intake tank (1) and the plasma discharge chamber (2), and a gas flowmeter two (203) is connected between the plasma discharge chamber (2) and the oxygen permeable membrane reactor (3).

5. The in-situ carbon dioxide ionization oxygen generation device according to claim 1, characterized in that The inner wall of the first vacuum seal head (303), the inner wall of the second vacuum seal head (304), and the outer wall of the oxygen permeable membrane reactor (3) are made of quartz, and the hollow fiber oxygen permeable membrane (301) is made of La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ material, with a particle size of 20 - 60 nm; Its preparation process includes the following steps: a1. Add the metal salts after mixing lanthanum nitrate, calcium nitrate, strontium nitrate, bismuth nitrate, neodymium nitrate, cobalt nitrate and iron nitrate into deionized water to form a uniformly mixed solution B; a2. Add an ethylene glycol dispersant and a citric acid complexing agent to the mixed solution B obtained in step a1, adjust to neutral with ammonia water, and continue heating and stirring until a gel-like solution C is formed; a3. Heat and dry the gel-like solution C obtained in step a2 until a powder oxide D is formed; a4. After calcining the powder oxide D obtained in step a3, La is obtained. 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ powder.

6. The in-situ ionization oxygen generation device for carbon dioxide according to claim 5, wherein, The hollow fiber oxygen permeable membrane (301) uses a zinc oxide composite material as a support body, and through holes are provided on the support body. The composite material composition is ZnO-La 0.3 Ca 0. 1Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ , and a separation functional layer is provided on the outer surface of the support body. The material of the separation functional layer is La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ ; In step a1, the mass ratio of the metal salt to the ethylene glycol dispersant and the citric acid complexing agent in step a2 is 1:1 - 1.5:1; in step a4, the calcination temperature of the powder oxide D is 800 - 1000 °C, and the calcination time is 4.5 - 5 h. The preparation steps of the hollow fiber oxygen permeable membrane (301) are as follows: b1. Mix La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ powder with ZnO to obtain the mixed powder E; b2. Mix and stir polyethersulfone and N-methylpyrrolidone until completely dissolved into a transparent solution F; b3. Add the mixed powder E in batches to the solution F and continue stirring to form a casting solution G; b4. Degas the casting solution G under vacuum, then introduce nitrogen, use N-methylpyrrolidone and ethanol as the core liquid and the internal coagulation bath, use water as the external coagulation bath, and uniformly extrude the casting solution into the external coagulation bath through a spinneret under the drive of pressure, soak and dry in the air to obtain a support precursor H; b5. Mix La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ powder with 2-butanone, ethanol, triethanolamine, dibutyl phthalate, polyethylene glycol and polyvinyl butyral uniformly to obtain Impregnation Solution I; b6. Immerse the support precursor H in the impregnation solution I, then perform pulling, and repeat the above pulling process after drying to obtain a hollow fiber precursor J; b7. Sinter the hollow fiber precursor J to obtain the hollow fiber oxygen permeable membrane (301).

7. The in-situ ionization oxygen generation device for carbon dioxide according to claim 6, characterized in that, The outer diameter of the through holes of the hollow fiber oxygen permeable membrane (301) is 1.50 - 1.60 mm, and the thickness of the hollow fiber oxygen permeable membrane (301) is 0.15 - 0.16 mm; in step b1, the mass ratio of La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ powder and ZnO is 7 - 8:2 - 3; in step b2, the mass ratio of polyethersulfone, N-methylpyrrolidone to the mixed powder E in step b1 is 1:4 - 5:8; in step b4, the vacuum degassing time is 1 - 2 h, and the nitrogen gas pressure is 0 - 0.2 MPa; in step b5, the mass ratio of La 0.3 Ca 0.1 Sr 0.2 Bi 0.2 Nd 0.2 Co 0.3 Fe 0.7 O 3-δ powder and 2-butanone, ethanol, triethanolamine, dibutyl phthalate, polyethylene glycol and polyvinyl butyral is 1:0.8 - 1.2:1 - 1.5:0.5 - 0.8:0.6 - 0.9:0.5 - 1:1.2 - 1.5; in step b6, the drying temperature is 70 - 90 °C; in step b7, the sintering temperature is 1100 - 1200 °C, and the sintering time is 4.5 - 5.5 h.

8. A method for preparing oxygen using the carbon dioxide in-situ ionization oxygen generation device according to any one of claims 1-7, characterized in that, Including the following steps: S1. Pressurize and transport the CO₂-containing gas in the intake tank (1) into the plasma discharge chamber (2) for ionization reaction to obtain an ionized gas containing oxygen. S2. Transport the ionized gas containing oxygen to the oxygen permeable membrane reactor (3). Under heating conditions, the ionized gas containing oxygen undergoes selective permeation of oxygen on the surface of the hollow fiber oxygen permeable membrane (301). Oxygen enters the inside of the hollow fiber oxygen permeable membrane (301), and the remaining gas accumulates outside the hollow fiber oxygen permeable membrane (301). S3. Collect the oxygen into the gas collecting bottle (5) and recycle the remaining gas into the tail gas bottle (7).

9. The oxygen preparation method using the in-situ ionization of carbon dioxide oxygen generation device according to claim 8, characterized in that, In step S1, the pressure of the CO₂-containing gas is 250 - 350 Pa, the ionization reaction temperature is 180 - 220 °C, the reaction time is 2 - 5 min, the reaction current is 0.2 - 0.25 A, and the flow rate of the CO₂-containing gas is 50 - 200 sccm.

10. The oxygen preparation method using the in-situ ionization of carbon dioxide oxygen generation device according to claim 8, characterized in that, In step S2, the heating temperature is 750 - 950 °C.

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