CN-118164433-B - Hydrogen purification material and preparation and application thereof

Abstract

The invention belongs to the field of hydrogen purification, and particularly discloses a hydrogen purification material, and preparation and application thereof. The hydrogen purification material is a compound of copper silicate with a silica pore brome structure and an A-type molecular sieve, wherein the copper silicate with the silica pore brome structure contains 30-70% of copper silicate and the balance of the A-type molecular sieve. Copper silicate with a silica pore brome structure is prepared from copper ammonia solution and silica sol through coprecipitation, washing, drying and roasting, and then the copper silicate is compounded with an A-type molecular sieve and molded. The purification material can simultaneously remove trace CO, O 2 and sulfur in high-purity hydrogen at 60-120 ℃ so as to meet the requirements of the national hydrogen standard GB/T37244-2018 for fuel cell vehicles.

Inventors

• LEI JUN
• HU XUEWEI
• JIANG FAN
• TIAN SENLIN
• LIU HUAWEI
• ZHAO QUN
• WANG XIANHOU
• SONG HAORAN
• ZHANG QINGJIAN
• NING PING
• KONG YUHUA

Assignees

• 昆明理工大学
• 华烁科技股份有限公司

Dates

Publication Date

20260508

Application Date

20240322

Claims (9)

1. 1. The application of the hydrogen purification material in the simultaneous purification and removal of CO, O 2 and sulfur impurities in hydrogen-containing source gas is that the hydrogen purification material is a compound of copper silicate with a silica pore brome structure and an A-type molecular sieve, wherein the content of the copper silicate with the silica pore brome structure is 30-70%, and the balance is the A-type molecular sieve.
2. 2. The method of claim 1, wherein the hydrogen purification material is prepared by coprecipitating, washing, drying and roasting copper silicate with a silica pore brome structure from copper ammonia solution and silica sol, and then compounding with an A-type molecular sieve and molding.
3. 3. The method according to claim 2, wherein the molar ratio of CuO to SiO 2 in the copper silicate with the silica-pore-brome structure is 0.1-0.5:1, and the roasting temperature is 350-400 ℃.
4. 4. The method of claim 1, wherein the type A molecular sieve is a 3A, 4A or 5A molecular sieve.
5. 5. The application of the method of claim 1, wherein the purification and removal temperature is 60-120 ℃.
6. 6. The method of claim 1, wherein the hydrogen is purified by a fuel cell vehicle and CO, O 2 and sulfur impurities in the high-purity hydrogen are removed.
7. 7. The preparation method of the hydrogen purification material is characterized by comprising the following steps: (1) Preparing 0.05-1.0 mol/L copper ammonia solution and 0.1-1.0 mol/L silica sol, and adding the solution into a container with stirring in parallel flow for uniform stirring; (2) Steaming the solution by steam heating, repeatedly washing the steamed material with reverse osmosis purified water, drying the filtered material at 100-150 ℃, and roasting at 350-400 ℃ for 3-6 hours to obtain copper silicate with a silica pore brome structure; (3) Adding an A-type molecular sieve into the copper silicate with the silica pore brome structure in proportion for ball milling, and performing flaking and molding to obtain the hydrogen purification material with the silica pore brome structure.
8. 8. The method of claim 7, wherein the cuprammonium solution is a solution obtained by reacting a copper salt with an ammonia source substance, and the ammonia source substance is 1.5-2 times the theoretical amount.
9. 9. The method of claim 8, wherein the copper salt is one or more selected from the group consisting of copper nitrate, copper acetate and copper chloride, and the ammonia source is one or more selected from the group consisting of ammonia water, urea and ammonium bicarbonate.

Description

Hydrogen purification material and preparation and application thereof Technical Field The invention belongs to the field of hydrogen purification, and in particular relates to a hydrogen purification material, and preparation and application thereof, which are used for simultaneously removing trace CO, O 2, sulfur and other impurities in high-purity hydrogen. Background Hydrogen energy is one of the main energy sources of future society, and is currently listed in national development strategy all over the world. Hydrogen is used as the main fuel of Proton Exchange Membrane Fuel Cells (PEMFCs), and the quality of hydrogen greatly influences the performance of the fuel cells. When hydrogen is derived from fossil fuel reforming or industrial by-product hydrogen or electrolyzed water to produce hydrogen, it may contain impurities entrained from the feedstock as well as some by-products such as trace amounts of CO, O 2, sulfur, aldehydes, acids, ammonia, CO 2, halogens, etc. The presence of these impurities can have an impact on the stable operation of proton exchange membrane fuel cells, greatly reducing the efficiency and life of proton exchange membrane fuel cells, and therefore the impurity content in the hydrogen for fuel cells must be controlled. The national standard GB/T37244-2018 of hydrogen for fuel cell vehicles requires CO less than or equal to 0.2ppm, O2 less than or equal to 5ppm and sulfur less than or equal to 0.004ppm, the hydrogen for fuel cell vehicles is not applied on a large scale at present, small-scale PSA is mainly adopted to improve the purity of the hydrogen, and purified CO, O 2 and sulfur impurities are mainly purified respectively without a system solution. At present, the research on removing O 2 in hydrogen is most sufficient, a catalytic combustion catalyst of a noble metal system is generally adopted, the hydrogen-oxygen reaction generates water, the technology is mature, and the method has wide industrial application. Sulfur is a common poison of general industrial catalysts, sulfur removal research is very extensive and deep, and is generally classified into coarse desulfurization (1 ppm), fine desulfurization (0.1 ppm) and deep fine desulfurization (0.01 ppm) according to the tolerance of downstream catalysts to sulfur, and the index <0.004ppm in hydrogen for fuel cell vehicles is the most severe, and effective desulfurization materials are copper-zinc compounds. The removal of CO in hydrogen is mainly four, namely, cryogenic cooling, pressure Swing Adsorption (PSA), catalytic oxidation, methanation and complexation removal, wherein the cryogenic cooling is adopted on a large-scale device with the gas quantity of hundreds of thousands of Nm 3/h in consideration of economy, the economy is hardly achieved for the current smaller hydrogen energy industry, and the CO removal precision does not reach the national standard requirement of <0.2 ppm; pressure swing adsorption is a widely used purification and separation method at present, which can be used for small and medium-sized industrial devices, improves the purity of hydrogen by PSA on one hand, enables the hydrogen to meet the requirements of national standard >99.97%, simultaneously removes most of impurities including CO, has the defects that CO removal precision cannot meet the national standard requirements, is generally adopted to directionally purify materials by PSA strings to remove CO in two steps, CO in catalytic oxidation hydrogen removal is a research hot spot at present, the important point is to improve catalytic oxidation selectivity and low-temperature activity, the catalytic oxidation method mainly comprises the steps of purifying the content of CO in percent grade in hydrogen production by methanol cracking and hydrocarbon hydrogen to be less than 100ppm, has the advantages of obvious CO purification and removal of tens of ppm after PSA, high removal temperature, poor industrial application economy, and poor CO removal precision can not meet the national standard requirements of <0.2ppm, uses Cu + and CO in conjugated complex gas, wherein the catalytic oxidation method mainly comprises the steps of purifying CO in percent of methanol cracking hydrogen production and hydrocarbon hydrogen production to be less than 100ppm, has the advantages of purifying CO in bulk CO purification and removal by CO in a large scale under the condition of ordinary use of a complexation and development and separation method, has the advantages of ordinary separation and direct CO purification and separation in the development of a large scale of CO adsorption device, the national standard requirement of CO <0.2ppm can not be met. In another method for removing CO, a carrier is used to load a highly dispersed CuO material and react with CO to oxidize CO into CO 2, but the material is generally used for removing trace CO in inert materials such as hydrocarbons and the like, and cannot be used in a hydrogen-containing gas source,