Electrochemical hydrogen purification and compression membrane electrode capable of resisting carbon monoxide poisoning and preparation method of electrochemical hydrogen purification and compression membrane electrode

Abstract

The invention discloses a carbon monoxide poisoning resistant electrochemical hydrogen purification and compression membrane electrode and a preparation method thereof. The preparation method comprises the following steps: mixing a catalyst, a carrier, a binder and a solvent, and carrying out grinding, pulping and ultrasonic treatment to obtain catalyst ink; transferring the catalyst ink to two sides of a proton exchange membrane at room temperature, and performing vacuum high-temperature drying after the catalyst ink is naturally dried to obtain a catalyst layer; the two sides of the proton exchange membrane containing the catalyst layer are each covered with a gas diffusion layer, and then the gas diffusion layers and the membrane are subjected to hot pressing treatment; and respectively covering two sides of the gas diffusion layer with a layer of porous metal support plate to form the membrane electrode. The membrane electrode has good purification and compression effects on hydrogen mixed gas containing carbon monoxide, the hydrogen pressure can reach 50 MPa under the CO and H2 mixed gas inlet condition, and the hydrogen purity can reach 99.97%.

Description

Technical Field

[0001] The invention relates to the technical field of membrane separation, and in particular to an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning and a preparation method thereof. Background Art

[0002] With the rapid growth of the world's population, the world's energy shortage problem has become increasingly obvious. Hydrogen energy is regarded as the most promising secondary energy in the 21st century due to its abundant sources, high combustion calorific value, cleanness and sustainability. The hydrogen energy industry chain includes hydrogen preparation, storage, transportation and utilization. Hydrogen energy has a wide range of sources, but most raw hydrogen contains more impurities and the density of hydrogen is low under normal pressure, so hydrogen needs to be further purified and compressed before it can be used.

[0003] Electrochemical hydrogen purification and compression technology can purify and compress hydrogen in one step, and the equipment occupies a small area, has low energy consumption, and is noise-free, making it a hydrogen purification and compression method with great application prospects. The membrane electrode is the core component of the electrochemical hydrogen purification and compression technology. However, the current hydrogen preparation system often contains carbon monoxide impurity gas, which will cause the catalyst in the membrane electrode to be poisoned during electrochemical hydrogen purification and compression, making the membrane electrode ineffective. Therefore, the development of electrochemical hydrogen purification and compression membrane electrodes that are resistant to carbon monoxide poisoning is a technical problem that needs to be solved urgently in this field. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning and a preparation method thereof.

[0005] In a first aspect, the present invention provides a method for preparing an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning, which is achieved by adopting the following technical scheme.

[0006] A method for preparing an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning comprises the following steps:

[0007] S1. The catalyst, carrier, binder and solvent are mixed, and the catalyst ink is obtained by grinding, pulping and ultrasonication;

[0008] S2. At room temperature, the catalyst ink configured in step S1 is transferred to both sides of the proton exchange membrane, and after the catalyst ink is naturally dried, vacuum high-temperature drying is performed to obtain a catalyst layer;

[0009] S3. Covering both sides of the proton exchange membrane containing the catalyst layer obtained in step S2 with a gas diffusion layer, and then hot pressing the gas diffusion layer and the membrane;

[0010] S4. Covering both sides of the gas diffusion layer obtained in step S3 with a layer of porous metal support plate to form a membrane electrode.

[0011] Furthermore, in step S1, the catalyst is selected from platinum, palladium, rhodium and alloys of any two or more, with a concentration of 0.2wt%-2wt%.

[0012] Furthermore, in step S1, the carrier is selected from one or more of carbon black, porous carbon nanofibers, graphene, carbon nanotubes, and carbon aerogel, with a concentration of 0.1wt%-2wt%.

[0013] Furthermore, in step S1, the binder is selected from perfluorosulfonic acid resin and / or sulfonated hydrocarbon resin solution, and the total content of the resin is 0.2wt%-2wt%.

[0014] Furthermore, in step S1, the solvent is a mixed solvent of alcohol and water, and the alcohol is one or more of ethanol, isopropanol, and n-butanol. Specifically, the volume ratio of alcohol to water in the solvent is 1:0.5-3.

[0015] Furthermore, in step S1, the grinding time is 15-30 min.

[0016] Furthermore, in step S1, the ultrasonication time is 12-24 hours.

[0017] Furthermore, in step S2, the catalyst ink is transferred by a method selected from the group consisting of spraying, scraping, dipping, and transfer, and the catalyst layer thickness is 1-5 μm.

[0018] Furthermore, in step S2, the vacuum high temperature drying temperature is 80-100°C, and the drying time is 0.5-2h.

[0019] Furthermore, in step S3, the gas diffusion layer is made of carbon paper and / or carbon cloth.

[0020] Furthermore, in step S3, the hot pressing treatment temperature is 80-150° C. and the pressure is 5-20 MPa.

[0021] Furthermore, in step S4, the material of the porous metal support plate is selected from titanium, nickel, aluminum, and stainless steel, and the pore size is 20-400 meshes.

[0022] In a second aspect, the present invention provides an electrochemical hydrogen purification and compression membrane electrode that is resistant to carbon monoxide poisoning, which is achieved by adopting the following technical solution.

[0023] An electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning prepared by the above method.

[0024] This application has the following beneficial effects.

[0025] The membrane electrode prepared by the method of the present invention has a "sandwich" structure and has good purification and compression effects on hydrogen mixed gas containing carbon monoxide. Under the condition of mixed intake of CO and H2, the hydrogen pressure can reach 50MPa and the hydrogen purity can be as high as 99.97%. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is an exploded view of the electrochemical hydrogen purification and compression device used in the present invention.

[0027] Among them, 1. end plate; 2. sealing gasket; 3. membrane electrode; 4. insulating gasket; 5. middle end plate. DETAILED DESCRIPTION

[0028] The present patent application is further described below in conjunction with embodiments.

[0029] The structure of the electrochemical hydrogen purification and compression device used in the following embodiments of the present application is as follows: Figure 1 As shown, it includes two end plates 1, two intermediate end plates 5 are arranged between the two end plates 1, and the membrane electrode 3 of the present application is arranged between the end plate 1 and the intermediate end plate 5 and between two adjacent intermediate end plates 5. In addition, an insulating gasket 4 and a sealing gasket 2 are also arranged between the end plate 1 and the intermediate end plate 5 and between two adjacent intermediate end plates 5, and the above components are connected by bolts. Etching flow fields are formed on the end plates 1 and the intermediate end plates 5.

[0030] The proton exchange membrane of the present application is selected from the Nafion series membrane of DuPont of the United States.

[0031] Example 1

[0032] A method for preparing an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning comprises the following steps:

[0033] 0.2g of platinum catalyst was mixed with 0.1g of carbon black and ground for 5 minutes, 0.2g of perfluorosulfonic acid resin Nafion, 90g of ethanol and 9.5g of water were added, stirred for 2h to obtain a slurry, and the slurry was ultrasonicated for 2h to obtain a uniformly dispersed catalyst ink. The catalyst ink was electrostatically sprayed on the surfaces of both sides of the proton exchange membrane, and after natural drying, it was transferred to a vacuum oven at 80°C for drying for 0.5h to obtain a dried catalyst layer. A layer of carbon paper was covered on the surfaces of the catalyst layers on both sides, and hot-pressed at 80°C and 5MPa with a hot press, and then a layer of 20-mesh porous titanium support plate was covered on both sides of the carbon paper to obtain an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning.

[0034] The performance of the membrane electrode was tested using an electrochemical hydrogen purification and compression device. The intake gas composition was hydrogen, nitrogen, and carbon monoxide, with volume ratios of 80%, 19.9%, and 0.1%, respectively. The pressure was normal pressure. After purification and compression, the hydrogen purity reached 99.65% and the pressure was 5 MPa.

[0035] Example 2

[0036] A method for preparing an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning comprises the following steps:

[0037] 0.5g of palladium catalyst was mixed with 0.2g of porous carbon nanofibers and ground for 5 minutes, 0.5g of perfluorosulfonic acid resin Nafion, 90g of ethanol, and 9.5g of water were added, stirred for 2h to obtain a slurry, and the slurry was ultrasonicated for 2h to obtain a uniformly dispersed catalyst ink. The catalyst ink was electrostatically sprayed on the surfaces of both sides of the proton exchange membrane, and after natural drying, it was transferred to a vacuum oven at 80℃ and dried for 0.5h to obtain a dried catalyst layer. A layer of carbon paper was covered on the surfaces of the catalyst layers on both sides, and hot-pressed at 80℃ and 5MPa with a hot press, and then a layer of 50 mesh porous titanium-supported nickel plate was covered on both sides of the carbon paper to obtain an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning.

[0038] The performance of the membrane electrode was tested using an electrochemical hydrogen purification and compression device. The intake gas composition was hydrogen, nitrogen, and carbon monoxide, with volume ratios of 60%, 39.7%, and 0.3%, respectively. The pressure was normal pressure. After purification and compression, the hydrogen purity reached 99.82% and the pressure was 10MPa.

[0039] Example 3

[0040] A method for preparing an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning comprises the following steps:

[0041] 1g of rhodium catalyst was mixed with 0.5g of graphene and ground for 5 minutes, 1g of sulfonated hydrocarbon resin polyetheretherketone, 90g of ethanol, and 9.5g of water were added, stirred for 2h to obtain a slurry, and the slurry was ultrasonicated for 2h to obtain a uniformly dispersed catalyst ink. The catalyst ink was electrostatically sprayed on the surfaces of both sides of the proton exchange membrane, and after natural drying, it was transferred to a vacuum oven at 80°C for drying for 0.5h to obtain a dried catalyst layer. A layer of carbon paper was covered on the surfaces of the catalyst layers on both sides, and hot-pressed at 80°C and 5MPa with a hot press, and then a layer of 100 mesh porous aluminum support plate was covered on both sides of the carbon paper to obtain an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning.

[0042] The performance of the membrane electrode was tested using an electrochemical hydrogen purification and compression device. The intake gas composition was hydrogen, nitrogen, and carbon monoxide, with volume ratios of 40%, 59.5%, and 0.5%, respectively. The pressure was normal pressure. After purification and compression, the hydrogen purity reached 99.95% and the pressure was 20MPa.

[0043] Example 4

[0044] A method for preparing an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning comprises the following steps:

[0045] 2g of platinum-palladium alloy catalyst was mixed with 1g of carbon nanotubes and ground for 5 minutes, 2g of sulfonated hydrocarbon resin polyetheretherketone, 90g of ethanol, and 9.5g of water were added, stirred for 2h to obtain a slurry, and the slurry was ultrasonicated for 2h to obtain a uniformly dispersed catalyst ink. The catalyst ink was electrostatically sprayed on the surfaces of both sides of the proton exchange membrane, and after natural drying, it was transferred to a vacuum oven at 80°C and dried for 0.5h to obtain a dried catalyst layer. A layer of carbon paper was covered on the surfaces of the catalyst layers on both sides, and hot-pressed at 80°C and 5MPa with a hot press, and then a layer of 200 mesh porous stainless steel support plate was covered on both sides of the carbon paper to obtain an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning.

[0046] The performance of the membrane electrode was tested using an electrochemical hydrogen purification and compression device. The intake gas composition was hydrogen, nitrogen, and carbon monoxide, with volume ratios of 20%, 79.2%, and 0.8%, respectively. The pressure was normal pressure. After purification and compression, the hydrogen purity reached 99.97% and the pressure was 50MPa.

[0047] The embodiments of this specific implementation method are all preferred embodiments of the present invention, and are not intended to limit the protection scope of the present invention. Therefore, any equivalent changes made based on the structure, shape, and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning, characterized in that: The following steps are involved: S1. The catalyst, carrier, binder and solvent are mixed, and the catalyst ink is obtained by grinding, pulping and ultrasonication; S2. At room temperature, the catalyst ink configured in step S1 is transferred to both sides of the proton exchange membrane, and after the catalyst ink is naturally dried, vacuum high-temperature drying is performed to obtain a catalyst layer; S3. Covering both sides of the proton exchange membrane containing the catalyst layer obtained in step S2 with a gas diffusion layer, and then hot pressing the gas diffusion layer and the membrane; S4. Covering both sides of the gas diffusion layer obtained in step S3 with a layer of porous metal support plate to form a membrane electrode.

2. The method for preparing an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning according to claim 1, characterized in that: In step S1, the catalyst is selected from platinum, palladium, rhodium and alloys of any two or more, with a concentration of 0.2wt%-2wt%.

3. The method for preparing an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning according to claim 1, characterized in that: In step S1, the carrier is selected from one or more of carbon black, porous carbon nanofibers, graphene, carbon nanotubes, and carbon aerogel, with a concentration of 0.1wt%-2wt%.

4. The method for preparing an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning according to claim 1, characterized in that: In step S1, the binder is selected from perfluorosulfonic acid resin and / or sulfonated hydrocarbon resin solution, and the total content of the resin is 0.2wt%-2wt%.

5. The method for preparing an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning according to claim 1, characterized in that: In step S2, the catalyst ink is transferred by a method selected from the group consisting of spraying, scraping, dipping, and transfer, and the catalyst layer thickness is 1-5 μm.

6. The method for preparing an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning according to claim 1, characterized in that: In step S2, the vacuum high temperature drying temperature is 80-100°C, and the drying time is 0.5-2h.

7. The method for preparing an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning according to claim 1, characterized in that: In step S3, the gas diffusion layer is made of carbon paper and / or carbon cloth.

8. The method for preparing an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning according to claim 1, characterized in that: In step S3, the hot pressing treatment temperature is 80-150°C and the pressure is 5-20MPa.

9. The method for preparing an electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning according to claim 1, characterized in that: In step S4, the material of the porous metal support plate is selected from titanium, nickel, aluminum, and stainless steel, and the pore size is 20-400 mesh.

10. An electrochemical hydrogen purification and compression membrane electrode resistant to carbon monoxide poisoning prepared by the method according to any one of claims 1 to 9.

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