CN113372970A - Low-concentration gas oxygen permeation purification system and method based on oxygen permeation membrane of solid oxide electrolytic cell - Google Patents

Low-concentration gas oxygen permeation purification system and method based on oxygen permeation membrane of solid oxide electrolytic cell Download PDF

Info

Publication number
CN113372970A
CN113372970A CN202110734332.2A CN202110734332A CN113372970A CN 113372970 A CN113372970 A CN 113372970A CN 202110734332 A CN202110734332 A CN 202110734332A CN 113372970 A CN113372970 A CN 113372970A
Authority
CN
China
Prior art keywords
ysz
oxygen
solid oxide
electrolytic cell
low
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110734332.2A
Other languages
Chinese (zh)
Other versions
CN113372970B (en
Inventor
田云峰
凌意瀚
王鑫鑫
周福宝
刘应科
欧雪梅
包航
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China University of Mining and Technology CUMT
Original Assignee
China University of Mining and Technology CUMT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China University of Mining and Technology CUMT filed Critical China University of Mining and Technology CUMT
Priority to CN202110734332.2A priority Critical patent/CN113372970B/en
Publication of CN113372970A publication Critical patent/CN113372970A/en
Application granted granted Critical
Publication of CN113372970B publication Critical patent/CN113372970B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention discloses a low-concentration gas oxygen permeation purification system and method based on an oxygen permeation membrane of a solid oxide electrolytic cell. The low-concentration gas in the coal bed is directly input into a fuel electrode of a solid oxide electrolytic cell, and oxygen ions in the low-concentration gas are transmitted to an air electrode through electrolyte by applying voltage, so that the dual purposes of methane purification and oxygen permeation in the low-concentration gas are realized. The invention solves the problems of low utilization rate of low-concentration gas, high utilization cost and serious direct-discharge pollution in the prior art.

Description

Low-concentration gas oxygen permeation purification system and method based on oxygen permeation membrane of solid oxide electrolytic cell
Technical Field
The invention relates to the technical field of low-concentration gas purification, in particular to a low-concentration gas oxygen permeation purification system and method based on an oxygen permeation membrane of a solid oxide electrolytic cell.
Background
The reduction of greenhouse gas emission and the relief of global warming are the focus of attention at home and abroad at present. The development and utilization of coal mine gas are effective measures for gas disaster control, so that the gas value can be utilized to the maximum extent, and the emission of greenhouse gas can be reduced. However, the coal mine gas has a low methane concentration (C) which is a low concentration of some gasCH4<30 percent of the gas, has large fluctuation and explosion danger, so the utilization difficulty is large, and the utilization rate of the low-concentration gas is generally low (<40%), a large amount of gas is directly discharged, resulting in serious energy waste and environmental pollution. In the coal mining process of China, a large amount of low-concentration gas is associated, and the low-concentration gas contains O2，N2，CO2And the low-concentration gas not only seriously threatens the safety of a coal mine, but also causes greenhouse gas emission and environmental pollution due to the large amount of low-concentration gas directly discharged. The effective component methane of the low-concentration gas is an important raw material for hydrogen production and power generation. The low-concentration gas is purified to be high-concentration gas with higher value, so that the influence of the low-concentration gas on the environment can be reduced, the dependence on energy sources such as coal, natural gas and the like can be reduced, and the waste is turned into wealth. The gas separation and concentration technologies commonly used at present comprise: low temperature liquefaction separation, pressure swing adsorption, and membrane separation. The low-temperature liquefaction separation method is to condense and compress a gas mixture to liquefy the gas mixture and to separate the gas mixture according to the boiling points of different gas components in the gas mixtureDifferent gases are separated, and CH with very high concentration can be obtained4A gas. However, this technique requires high-pressure compression of a low-concentration gas containing O2The compression technology has high explosion risk when being compressed, and the technology has huge energy consumption and high investment, so the compression technology is not popularized and applied in a large range. Similarly, the adsorption separation method is based on the fact that different adsorption speeds and adsorption capacities of different gas components are different for an adsorbent to perform gas separation, however, at present, a bottleneck exists in the technology of performing pressure swing adsorption purification on low-concentration gas in a coal mine according to the equilibrium selectivity principle, the main problem is that the required adsorption pressure is large, gas explosion may be caused by pressurizing oxygen-containing low-concentration gas, and the energy consumption cost is greatly increased in the compression link. The membrane separation method mainly utilizes different gas components with different permeabilities through the membrane, so that the component with high permeability is discharged out of the membrane, and the component with low permeability is remained in the membrane, thereby realizing gas separation. O is2And N2Has a permeability higher than CH4Thereby realizing the purpose of adding CH in the low-concentration gas4And (4) purifying. However, since the membrane material is mainly concentrated on the polymer membrane or the carbon membrane at present, the durability thereof does not meet the practical application requirement, and the cost of the membrane separation is too high for the gas separation with larger gas amount, the membrane separation technology needs to be studied intensively in the field of low-concentration gas concentration. In conclusion, the technical routes have the problems of long flow, high energy consumption, low system efficiency, high cost and the like.
Disclosure of Invention
One of the purposes of the invention is to provide a low-concentration gas oxygen permeation purification system based on an oxygen permeation membrane of a solid oxide electrolytic cell, which can efficiently permeate oxygen, purify methane and reduce energy consumption.
The invention also aims to provide a low-concentration gas oxygen permeation purification method using the purification system, which has simple route and low cost.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
on one hand, the invention provides a low-concentration gas oxygen permeation purification system based on an oxygen permeation membrane of a solid oxide electrolytic cell, which comprises the oxygen permeation membrane reactor of the solid oxide electrolytic cell, a vertical tubular furnace and an external power supply, wherein the oxygen permeation membrane reactor comprises a ceramic tube and the solid oxide electrolytic cell positioned in the ceramic tube, the solid oxide electrolytic cell comprises an air electrode, a fuel electrode, electrolyte and a blocking layer, the side of the fuel electrode is provided with a low-concentration gas inlet and outlet, the side of the air electrode is provided with an air inlet and outlet, and the side of the fuel electrode is also provided with a water vapor inlet; the oxygen-permeable membrane reactor is positioned in the vertical tubular furnace, two ends of the solid oxide electrolytic cell are connected with the external power supply, and the solid oxide electrolytic cell is electrolyzed under the external voltage and high temperature and used for high-efficiency oxygen-permeable concentration.
Preferably, the electrolyte is an oxygen ion conductor electrolyte of a zirconia series represented by yttria-stabilized zirconia (YSZ), the fuel electrode is a metallic nickel (Ni) -YSZ composite cermet, the air electrode is a composite of Lanthanum Strontium Manganese (LSM) or lanthanum strontium cobalt iron (LSCF) and a gadolinium oxide-stabilized ceria (GDC), and the barrier layer is gadolinium oxide-stabilized ceria (GDC).
More preferably, the electrolyte is YSZ, the fuel electrode is Ni-YSZ composite cermet, the air electrode is LSCF-GDC composite, and the barrier layer is GDC.
Preferably, the preparation method of the solid oxide electrolytic cell comprises the following steps:
(1) mixing yttria-stabilized zirconia, metal nickel powder and pore-forming agent starch according to the mass ratio of 6:4:3, adding alcohol, ball-milling, uniformly mixing, and drying; dry pressing the dried Ni-YSZ powder into Ni-YSZ biscuit sheets; then placing the Ni-YSZ biscuit sheet in an air atmosphere and sintering at 1000 ℃ for 3h to obtain a Ni-YSZ support body;
(2) mixing YSZ powder, KD1 and an organic adhesive, adding acetone, ball-milling and uniformly mixing to obtain electrolyte slurry; spin-coating on the surface of a Ni-YSZ support by a spin coater, and then placing Ni-YSZ/YSZ in an air atmosphere at 1450 ℃ for sintering for 10h to obtain a Ni-YSZ/YSZ half cell; the mass ratio of the YSZ powder to the organic binder is 1:2, and the addition amount of KD1 is 2% of the mass of the YSZ powder;
(3) mixing GDC powder, KD1 and organic adhesive, adding acetone, ball-milling and mixing uniformly to obtain barrier layer slurry; spin-coating the YSZ side of the half-cell prepared in step (2) by a spin coater; placing the Ni-YSZ/YSZ/GDC in an air atmosphere at 1300 ℃ and sintering for 5h to obtain a Ni-YSZ/YSZ/GDC half cell; the mass ratio of the GDC powder to the organic binder is 1:2, and the addition amount of KD1 is 2% of the mass of the GDC powder;
(4) mixing LSCF-GDC composite powder and an organic adhesive according to a mass ratio of 1: 1.5, mixing, ball-milling and uniformly mixing to obtain air electrode slurry, uniformly coating the prepared air electrode slurry on one side of the GDC of the Ni-YSZ/YSZ/GDC half cell prepared in the step (3) by adopting a screen printing mode, and sintering for 5 hours at 1000 ℃ in an air atmosphere to finally obtain the Ni-YSZ/YSZ/GDC/LSCF-GDC solid oxide electrolytic cell.
Preferably, the organic binder in step (2) and step (3) is 5% ethyl cellulose-terpineol, and the organic binder in step (4) is 10% ethyl cellulose-terpineol.
Further, the oxygen permeable membrane system of the solid oxide electrolytic cell also comprises a tail gas treatment device, and the tail gas treatment device is provided with a water outlet and an exhaust port.
On the other hand, the invention also provides a low-concentration gas oxygen permeation purification method using the purification system, which comprises the following steps:
and introducing low-concentration gas into the ceramic tube provided with the solid oxide electrolytic cell, preheating the solid oxide electrolytic cell to a required temperature through a vertical tube furnace, supplying power to the solid oxide electrolytic cell through an external power supply, so that oxygen in the low-concentration gas obtains electrons to generate oxygen ions, the oxygen ions are transmitted to an air electrode through a compact electrolyte under the drive of voltage to precipitate oxygen, and tail gas of the electrolyzed fuel electrode chamber does not contain oxygen and carbon dioxide impurity gases, so that the aim of deoxidation and purification is fulfilled.
Further, the method also comprises the following steps: the tail gas of the fuel electrode chamber is rich in methane and enters a tail gas collector through a gas outlet for retreatment.
Compared with the prior art, the invention has the following beneficial effects:
in the working process of the oxygen permeable membrane based on the solid oxide electrolytic cell, the fuel electrode side inlet gas of the oxygen permeable membrane reactor is low-concentration gas, the tail gas of the gas outlet is rich in methane and does not contain oxygen, the oxygen is completely removed, and the low-concentration gas is converted into high-concentration gas. Due to oxygen permeation reaction at the air side, tail gas of the air electrode is rich in oxygen, and the oxygen-rich air can be further utilized.
Drawings
FIG. 1 is a schematic diagram of the structure of a solid oxide electrolytic cell. In the figure: 1. an air electrode; 2. a barrier layer; 3. an electrolyte; 4. a fuel electrode.
FIG. 2 is a low concentration gas oxygen permeation purification system based on oxygen permeable membranes of solid oxide electrolytic cells according to the present invention. In the figure: 5. a ceramic tube; 6. a solid oxide electrolytic cell; 7. a vertical tube furnace; 8. and applying a power supply.
FIG. 3 is the working principle of the oxygen permeable membrane system of the solid oxide electrolytic cell.
FIG. 4 is an oxygen permeation current-voltage curve of low concentration gas at different temperatures for a solid oxide electrolytic cell.
FIG. 5 shows the short-term performance of oxygen purification of low-concentration gas at different voltages in a solid oxide electrolytic cell.
Detailed Description
The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which form a part hereof, and which together with the embodiments of the invention serve to explain the principles of the invention.
(1) Electrolytic cell for preparing solid oxide
Adding 6g of yttria-stabilized zirconia (YSZ), 4g of metal nickel powder (Ni) and 3g of pore-forming agent starch into alcohol, ball-milling for 10 hours on a ball mill together, and then drying in an oven at 80 ℃; pressing the dried Ni-YSZ powder into Ni-YSZ biscuit tablets by a powder tablet press; then heating the Ni-YSZ biscuit sheet to 1000 ℃ in a box-type high-temperature resistance furnace at the heating rate of 2 ℃/min, preserving heat for 3h, cooling to 300 ℃ at the cooling rate of 2 ℃/min, and naturally cooling to room temperature to obtain a Ni-YSZ support body with the diameter of about 12 mm;
taking 10g of YSZ powder, adding 0.2g of KD1 and 20g of 5% ethyl cellulose terpineol solution, adding a solvent acetone, and carrying out ball milling for 20 hours to obtain a key material electrolyte slurry of the oxygen permeable membrane of the solid oxide electrolytic cell; spin-coating on the surface of Ni-YSZ by a spin coater, heating Ni-YSZ/YSZ to 1450 ℃ at a heating rate of 2 ℃/min in a box-type high-temperature resistance furnace, preserving heat for 10h, cooling to 300 ℃ at a cooling rate of 2 ℃/min, and naturally cooling to room temperature to obtain the half-cell.
Taking 10g of GDC powder, adding 0.2g of KD1 and 20g of 5% ethyl cellulose terpineol solution, adding a solvent acetone, and ball-milling for 20 hours to obtain a barrier layer slurry; spin-coating on the surface of the half cell by a spin coater; heating Ni-YSZ/YSZ/GDC to 1450 ℃ at a heating rate of 2 ℃/min in a high-temperature resistance furnace, preserving heat for 10h, cooling to 300 ℃ at a cooling rate of 2 ℃/min, and naturally cooling to room temperature;
mixing 10g of LSCF-GDC composite powder with 15g of 10% ethyl cellulose terpineol solution, performing ball milling and uniform mixing to obtain air electrode slurry, uniformly coating the prepared air electrode slurry on one side of the GDC of the Ni-YSZ/YSZ/GDC half cell prepared in the step (3) by adopting a screen printing mode, and sintering for 5 hours at 1000 ℃ in an air atmosphere to finally obtain the Ni-YSZ/YSZ/GDC/LSCF-GDC solid oxide electrolytic cell, wherein as shown in figure 1, a fuel electrode 4, an electrolyte 3, a barrier layer 2 and an air electrode 1 are sequentially arranged from bottom to top.
(2) Low-concentration gas oxygen permeation purification system assembled based on oxygen permeation membrane of solid oxide electrolytic cell
As shown in fig. 2, the system comprises an oxygen permeable membrane reactor of a solid oxide electrolytic cell, a vertical tubular furnace 7 and an external power supply 8, wherein the oxygen permeable membrane reactor comprises a ceramic tube 5 and the solid oxide electrolytic cell 6 positioned in the ceramic tube 5, the solid oxide electrolytic cell 6 comprises an air electrode 1, a fuel electrode 4, a barrier layer 2 and an electrolyte 3, a low-concentration gas inlet and a low-concentration gas outlet are arranged on the side of the fuel electrode 4, an air inlet and an air outlet are arranged on the side of the air electrode 1, a water vapor inlet is also arranged on the side of the fuel electrode 1, the oxygen permeable membrane reactor is positioned in the vertical tubular furnace 7, and two ends of the solid oxide electrolytic cell 6 are connected with the external power supply 8. The temperature is raised to the desired temperature by heating through a vertical tube furnace 7. Generally, the oxygen permeable membrane system of the solid oxide electrolytic cell can carry out ion transmission efficiently at higher temperature.
The core device of the oxygen permeation purification system is a solid oxide electrolytic cell 6, and the solid oxide electrolytic cell 6 is sealed on a ceramic tube 5. As shown in FIG. 3, the ceramic electrolyte membrane in the oxygen permeable membrane section is sufficiently dense to divide the two electrode sides into a fuel electrode side and an air electrode side; the air electrode side is in air; the fuel electrode side is provided with a low-concentration gas inlet and outlet; the fuel pole side is sealed on the upper end of the ceramic tube 5 by ceramic glue, and is in a completely sealed state by a stainless steel part and a sealing ring. The gas outlet is connected with a tail gas treatment device, so that the purified low-concentration gas can be further utilized.
The electrolyte is used as a core device of the oxygen permeable membrane, can effectively isolate the flow of gas molecules on two sides, and can enable oxygen ions to directionally migrate from the fuel electrode side to the air electrode side under the action of an applied voltage to generate oxygen, namely the oxygen on the fuel electrode side is transported to the air electrode side, so that the effect of purifying low-concentration gas oxygen is achieved.
The test results are shown in fig. 4 and 5. FIG. 4 is a voltage-current density curve of oxygen permeable membranes of a solid oxide electrolytic cell at different temperatures using low-concentration gas as fuel. It can be seen that as the applied voltage increases, the current density also increases. Since the electrolyte is almost a pure oxygen ion conductor, the higher the current density, the better the oxygen permeation effect. In addition, as the temperature increases, the electrolytic current density also increases, indicating that the oxygen permeability is also better. FIG. 5 is a test of the short-term stability of oxygen permeable membrane systems of solid oxide electrolysis cells at different voltages, and it can be seen that as the voltage increases, the electrolysis current density also increases. And the current density is not attenuated, and the performance is kept stable.

Claims (8)

1. The low-concentration gas oxygen permeation purification system based on the oxygen permeation membrane of the solid oxide electrolytic cell is characterized by comprising the oxygen permeation membrane reactor of the solid oxide electrolytic cell, a vertical tubular furnace (7) and an external power supply (8), wherein the oxygen permeation membrane reactor comprises a ceramic tube (5) and the solid oxide electrolytic cell (6) positioned in the ceramic tube (5), the solid oxide electrolytic cell (6) comprises an air electrode (1), a fuel electrode (4), a barrier layer (2) and electrolyte (3), the side of the fuel electrode (4) is provided with a low-concentration gas inlet and outlet, the side of the air electrode (1) is provided with an air inlet and outlet, and the side of the fuel electrode (1) is also provided with a water vapor inlet; the oxygen permeable membrane reactor is positioned in the vertical tubular furnace (7), two ends of the solid oxide electrolytic cell (6) are connected with the external power supply (8), and the solid oxide electrolytic cell (6) is electrolyzed under the external voltage and high temperature for high-efficiency oxygen permeable concentration.
2. The system of claim 1, wherein the electrolyte is an oxygen ion conductor electrolyte of the zirconia series represented by yttria stabilized zirconia, the fuel is a metallic nickel-YSZ composite cermet, the air is a composite of lanthanum strontium manganese or lanthanum strontium cobalt iron and gadolinium oxide stabilized ceria series, and the barrier layer is gadolinium oxide stabilized ceria.
3. The system of claim 2, wherein the electrolyte is YSZ, the fuel electrode is Ni-YSZ composite cermet, the air electrode is LSCF-GDC composite, and the barrier layer is GDC.
4. The low-concentration gas oxygen-permeable purification system based on the oxygen-permeable membrane of the solid oxide electrolytic cell according to claim 3, characterized in that the preparation method of the solid oxide electrolytic cell (6) comprises the following steps:
(1) mixing yttria-stabilized zirconia, metal nickel powder and pore-forming agent starch according to the mass ratio of 6:4:3, adding alcohol, ball-milling, uniformly mixing, and drying; dry pressing the dried Ni-YSZ powder into Ni-YSZ biscuit sheets; then placing the Ni-YSZ biscuit sheet in an air atmosphere and sintering at 1000 ℃ for 3h to obtain a Ni-YSZ support body;
(2) mixing YSZ powder, KD1 and an organic adhesive, adding acetone, ball-milling and uniformly mixing to obtain electrolyte slurry; spin-coating on the surface of a Ni-YSZ support by a spin coater, and then placing Ni-YSZ/YSZ in an air atmosphere at 1450 ℃ for sintering for 10h to obtain a Ni-YSZ/YSZ half cell; the mass ratio of the YSZ powder to the organic binder is 1:2, and the addition amount of KD1 is 2% of the mass of the YSZ powder;
(3) mixing GDC powder, KD1 and organic adhesive, adding acetone, ball-milling and mixing uniformly to obtain barrier layer slurry; spin-coating the YSZ side of the half-cell prepared in step (2) by a spin coater; placing the Ni-YSZ/YSZ/GDC in an air atmosphere at 1300 ℃ and sintering for 5h to obtain a Ni-YSZ/YSZ/GDC half cell; the mass ratio of the GDC powder to the organic binder is 1:2, and the addition amount of KD1 is 2% of the mass of the GDC powder;
(4) mixing LSCF-GDC composite powder and an organic adhesive according to a mass ratio of 1: 1.5, mixing, ball-milling and uniformly mixing to obtain air electrode slurry, uniformly coating the prepared air electrode slurry on one side of the GDC of the Ni-YSZ/YSZ/GDC half cell prepared in the step (3) by adopting a screen printing mode, and sintering for 5 hours at 1000 ℃ in an air atmosphere to finally obtain the Ni-YSZ/YSZ/GDC/LSCF-GDC solid oxide electrolytic cell.
5. The low-concentration gas oxygen permeation purification system based on the oxygen permeable membrane of the solid oxide electrolytic cell is characterized in that the organic binder in the step (2) and the step (3) is 5% ethyl cellulose-terpineol, and the organic binder in the step (4) is 10% ethyl cellulose-terpineol.
6. The low-concentration gas oxygen permeation purification system based on the oxygen permeable membrane of the solid oxide electrolytic cell as claimed in claim 1, wherein the oxygen permeable membrane system of the solid oxide electrolytic cell further comprises a tail gas treatment device, and the tail gas treatment device is provided with a water outlet and an air outlet.
7. A low-concentration gas oxygen-permeable purification method using the purification system of any one of claims 1 to 6, characterized by comprising the steps of:
and (2) introducing low-concentration gas into the ceramic tube (5) provided with the solid oxide electrolytic cell (6), preheating the solid oxide electrolytic cell (6) to a required temperature through a vertical tube furnace (7), supplying power to the solid oxide electrolytic cell (6) through an external power supply (8), so that oxygen in the low-concentration gas obtains electrons to generate oxygen ions, transmitting the oxygen ions to an air electrode through a compact electrolyte under the drive of voltage to separate out oxygen, and ensuring that the tail gas of the fuel electrode chamber after electrolysis does not contain oxygen and carbon dioxide impurity gases, thereby achieving the purposes of deoxidation and purification.
8. The oxygen-permeable purification method for low-concentration gas as claimed in claim 7, further comprising the steps of: the tail gas of the fuel electrode chamber is rich in methane and enters a tail gas collector through a gas outlet for retreatment.
CN202110734332.2A 2021-06-30 2021-06-30 Low-concentration gas oxygen permeation purification system and method based on oxygen permeation membrane of solid oxide electrolytic cell Active CN113372970B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110734332.2A CN113372970B (en) 2021-06-30 2021-06-30 Low-concentration gas oxygen permeation purification system and method based on oxygen permeation membrane of solid oxide electrolytic cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110734332.2A CN113372970B (en) 2021-06-30 2021-06-30 Low-concentration gas oxygen permeation purification system and method based on oxygen permeation membrane of solid oxide electrolytic cell

Publications (2)

Publication Number Publication Date
CN113372970A true CN113372970A (en) 2021-09-10
CN113372970B CN113372970B (en) 2022-08-02

Family

ID=77580308

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110734332.2A Active CN113372970B (en) 2021-06-30 2021-06-30 Low-concentration gas oxygen permeation purification system and method based on oxygen permeation membrane of solid oxide electrolytic cell

Country Status (1)

Country Link
CN (1) CN113372970B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105220172A (en) * 2015-10-27 2016-01-06 中国科学技术大学 A kind of carbonic acid gas and water vapour gas mixture are converted into tubular structure of the gas being rich in methane and its preparation method and application
CN110551542A (en) * 2019-08-21 2019-12-10 中国矿业大学 Control system and method for preparing high-concentration methane gas by using low-concentration gas
CN111910201A (en) * 2020-08-17 2020-11-10 广东电网有限责任公司广州供电局 Hydrogen electrode of solid oxide electrolytic cell, preparation method of hydrogen electrode and solid oxide electrolytic cell

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105220172A (en) * 2015-10-27 2016-01-06 中国科学技术大学 A kind of carbonic acid gas and water vapour gas mixture are converted into tubular structure of the gas being rich in methane and its preparation method and application
CN110551542A (en) * 2019-08-21 2019-12-10 中国矿业大学 Control system and method for preparing high-concentration methane gas by using low-concentration gas
CN111910201A (en) * 2020-08-17 2020-11-10 广东电网有限责任公司广州供电局 Hydrogen electrode of solid oxide electrolytic cell, preparation method of hydrogen electrode and solid oxide electrolytic cell

Also Published As

Publication number Publication date
CN113372970B (en) 2022-08-02

Similar Documents

Publication Publication Date Title
Park et al. Hydrogen production from fossil and renewable sources using an oxygen transport membrane
Liu et al. A dual-phase bilayer oxygen permeable membrane with hierarchically porous structure fabricated by freeze-drying tape-casting method
Li et al. Effects of membrane thickness and structural type on the hydrogen separation performance of oxygen-permeable membrane reactors
CN112941547B (en) High-temperature electrolytic synthesis method of ammonia by taking low-concentration gas as fuel
Wu et al. Development of high performance intermediate temperature proton-conducting solid oxide electrolysis cells
Xie et al. CO2-tolerant Ni-La5. 5WO11. 25-δ dual-phase membranes with enhanced H2 permeability
CN111549355A (en) Low cost CO electrolysis in solid oxide electrolytic cell2System and method for preparing synthesis gas
CN111689777A (en) Symmetric ceramic hydrogen pump capable of realizing hydrogen purification in complex scene and preparation method thereof
Zhang et al. CO 2‐Tolerant Ceramic Membrane Driven by Electrical Current for Oxygen Production at Intermediate Temperatures
CN110273161A (en) A kind of electrolysis ammonia hydrogen generating system
CN113372970B (en) Low-concentration gas oxygen permeation purification system and method based on oxygen permeation membrane of solid oxide electrolytic cell
CN112349913A (en) High-performance reversible solid oxide battery electrode material composition and preparation method thereof
WO2017130092A1 (en) Electrolytic cell for generating hydrogen
CN114481175B (en) Repairable solid symmetrical electrolytic cell device based on strontium ferrite electrode catalytic layer
Liang et al. Stable Ce0. 8Gd0. 2O2-δ oxygen transport membrane reactor for hydrogen production
CN114191994A (en) Tubular high-temperature solid oxide oxygen permeable membrane and preparation method thereof
Liu et al. Nanofiber-structured Pr0. 4Sr0. 6Co0. 2Fe0. 7Nb0. 1O3-δ-Gd0. 2Ce0. 8O1. 9 symmetrical composite electrode for solid oxide fuel cells
Ivanov et al. Effect of hydrogen pressure on the electrochemical hydrogen pump performance
Hendriksen et al. Electrochemical Cells for Novel Routes to Ammonia
Shi et al. Electrochemical performance of Ba0. 5Sr0. 5Co0. 8Fe0. 2O3− δ in symmetric cells with Sm0. 2Ce0. 8O1. 9 electrolyte for nitric oxide reduction reaction
Cheng et al. Hydrogen separation via proton conducting ceramic membranes: A review
CN117443152A (en) Method for preparing double high-purity gas by electrically-driven separation of hydrogen and helium mixed gas
JP2001276555A (en) Oxygen separating membrane module and fuel battery using the module
EP4179585B1 (en) Method for operating an sofc for the combined production of electricity and nitric oxide
CN116196775A (en) Carbon dioxide and water co-permeation membrane and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant