CN-116785940-B - High-temperature-resistant ceramic separation membrane and preparation and application thereof

Abstract

The invention belongs to the technical field of separation membranes, and discloses a high-temperature-resistant ceramic separation membrane, and preparation and application thereof. The invention sequentially carries out acid etching, hydrophobic material soaking and irradiation crosslinking treatment on the tubular membrane or the hollow fiber membrane so as to obtain the high-temperature-resistant ceramic separation membrane. The high-temperature resistant ceramic membrane effectively realizes the separation of hydrogen and water vapor at high temperature, realizes the recycling of the water vapor, reduces the consumption of heat energy and water resources in the high-temperature electrolysis water vapor technology, and obviously reduces the production cost in the high-temperature electrolysis water vapor process.

Inventors

• LEI JINYONG
• LIAO ZIHAO
• ZHANG XING
• HE BINBIN
• XU QIN
• LU YANSHAN
• WANG JIANQIANG
• GAO NA
• HUANG XURUI
• XIAO GUOPING
• PAN JUN
• DU XIANLONG
• YANG YIPING
• MA CHENGGUO
• YU FENGYUAN

Assignees

• 广东电网有限责任公司广州供电局
• 中国科学院上海应用物理研究所

Dates

Publication Date

20260508

Application Date

20230602

Claims (4)

1. 1. The application of the high-temperature-resistant ceramic separation membrane in the hydrogen purification process in the high-temperature water electrolysis hydrogen production is characterized in that the preparation of the high-temperature-resistant ceramic separation membrane comprises the following steps: (1) Performing acid etching treatment on the tubular membrane or the hollow fiber membrane; the acid is one of sulfuric acid, nitric acid and hydrochloric acid, and the mass concentration of the acid is 50% -98%; the time of the acid etching treatment is 0.5-5 h; the preparation method of the tubular membrane and the hollow fiber membrane specifically comprises the following steps of mixing EDTA, citric acid and metal ions, adopting nitric acid and ammonia water to adjust the pH value to 5-8, stirring at 50-80 ℃ until gel is formed, burning at 150-400 ℃ to generate powder, extruding the powder to form, and then sintering at high temperature at 800-1500 ℃ to obtain the tubular membrane or the hollow fiber membrane; (2) Soaking the tubular membrane or the hollow fiber membrane obtained in the step (1) in a hydrophobic material solution, taking out the tubular membrane or the hollow fiber membrane, and drying to obtain a hydrophobic modified tubular membrane or a hollow fiber membrane; the hydrophobic material comprises at least one of polydimethylsiloxane, fluorosilicone resin, polytetrafluoroethylene and polyethylene, wherein the mass concentration of the hydrophobic material in the hydrophobic material solution is 50% -60%, and the soaking time is 1-5 minutes; (3) Performing irradiation crosslinking treatment on the hydrophobic modified tubular membrane or the hollow fiber membrane in the step (2) to obtain a high-temperature-resistant ceramic separation membrane; the irradiation crosslinking treatment is to irradiate the hydrophobically modified film by at least one of X rays and gamma rays for 10-30 min.
2. 2. The method of claim 1, wherein the metal ions in step (1) are provided by Ba (NO 3 ) 2 or Sr (one of NO 3 ) 2 , and Ce (NO 3 ) 3 and Ni (NO 3 ) 2 ), and Ba (NO 3 ) 2 or Sr (NO 3 ) 2 、Ce(NO 3 ) 3 and Ni (NO 3 ) 2 in a molar ratio of 1:1:0.1-1:1:0.5; and total metal ions: EDTA: citric acid in a molar ratio of 1:1:2-1:2:4).
3. 3. The use according to claim 1, characterized in that: the solvent of the hydrophobic material solution in the step (2) is at least one of acetone, tetrahydrofuran and n-hexane.
4. 4. The use according to claim 1, characterized in that it comprises in particular the following steps: A. adopting sealant to carry out adhesive combination on the high-temperature-resistant ceramic separation membrane to realize combination between the separation membranes; B. Assembling the combined ceramic membranes to obtain a high-temperature-resistant membrane separation assembly, and mounting the assembly on a membrane separation process, so that the high-temperature-resistant ceramic separation membrane is applied to a hydrogen purification process in high-temperature water electrolysis hydrogen production; and (C) the sealant in the step A is at least one of silicone adhesive and ceramic adhesive.

Description

High-temperature-resistant ceramic separation membrane and preparation and application thereof Technical Field The invention belongs to the technical field of separation membranes, and particularly relates to a high-temperature-resistant ceramic separation membrane, and preparation and application thereof. Background In high-temperature water electrolysis hydrogen production, product hydrogen and partial raw material steam which is not electrolyzed are discharged out of an electrolysis system together, so that the separation technology of the hydrogen and the steam is one of important steps in the hydrogen purification process. At present, after cooling is performed on high-temperature hydrogen and water vapor, water in the hydrogen is removed after the water vapor is condensed and absorbed by a steam-water separation and dryer, the process causes larger energy consumption, and the water vapor which is not electrolyzed is directly discharged through a bottom waste liquid drain after being separated by a steam-water separation tank, so that waste of water resources and heat energy is caused. The consumption of energy is increased, and the hydrogen production cost is higher. There is a need for a suitable high temperature separation material and technique to achieve separation of hydrogen and water vapor. At present, the separation technology of different gas components, different liquid components and gas components and liquid components can be related in the fields of chemical industry, medicine, biology and the like. The separation membrane has the advantages of low energy consumption, low emission, small occupied area and the like, and is increasingly used for separation processes among different components. The ceramic film is made up of alumina, zirconia, titania and silica as supporting body through surface coating and high-temp firing. Compared with the traditional polymer separation membrane material, the ceramic membrane has the advantages of good chemical stability, high temperature resistance, acid and alkali resistance, organic solvent resistance, narrow pore size distribution, high separation efficiency and the like, and is more suitable for separation technologies of different components under high temperature conditions. Disclosure of Invention In order to overcome the defects and shortcomings of the prior art, the primary purpose of the invention is to provide a preparation method of a high-temperature-resistant compact ceramic separation membrane. The invention also aims to provide the high-temperature-resistant ceramic separation membrane prepared by the method. The invention also aims to provide the application of the high-temperature-resistant ceramic separation membrane in a hydrogen purification process. The aim of the invention is achieved by the following scheme: The preparation method of the high-temperature-resistant ceramic separation membrane comprises the following steps: (1) Performing acid etching treatment on the tubular membrane or the hollow fiber membrane; (2) Soaking the tubular membrane or the hollow fiber membrane obtained in the step (1) in a hydrophobic material solution, taking out the tubular membrane or the hollow fiber membrane, and drying to obtain a hydrophobic modified tubular membrane or a hollow fiber membrane; (3) And (3) carrying out irradiation crosslinking treatment on the hydrophobic modified tubular membrane or the hollow fiber membrane in the step (2) to obtain the high-temperature-resistant ceramic separation membrane. The tubular membrane and the hollow fiber membrane in the step (1) are obtained by direct purchase or are prepared by the following steps: 1) Preparing a perovskite material by at least one of a coprecipitation method, a sol-gel method and a molten salt method; 2) The tubular membrane or the hollow fiber membrane is prepared by an extrusion molding process and a phase change conversion method respectively. The preparation method of the tubular membrane and the hollow fiber membrane comprises the following steps of mixing EDTA, citric acid and metal ions, adjusting pH to 5-8 by adopting nitric acid and ammonia water, stirring at 50-80 ℃ until gel is formed, burning at 150-400 ℃ to generate powder, extruding the powder to form, and sintering at high temperature at 800-1500 ℃ to obtain the tubular membrane or the hollow fiber membrane; The metal ions are provided by Ba (NO 3)2 or Sr (one of NO 3)2 and Ce (NO 3)3 and Ni (NO 3)2), and Ba (NO 3)2 or Sr (NO 3)2、Ce(NO3)3 and Ni (the mol ratio of NO 3)2 is 1:1:0.1-1:1:0.5; the mol ratio of total metal ions to EDTA to citric acid is 1:1:2-1:2:4). The acid in the step (1) is one of sulfuric acid, nitric acid and hydrochloric acid, and the mass concentration of the acid is 50% -98%. And (3) the time of the acid etching treatment in the step (1) is 0.5-5 h. The hydrophobic material in the step (2) comprises at least one of polydimethylsiloxane, fluorosilicone, polytetrafluoroethylene and polyethylene