CN212103028U - PBI proton exchange membrane electrolysis module and seawater electrolysis hydrogen production device - Google Patents
PBI proton exchange membrane electrolysis module and seawater electrolysis hydrogen production device Download PDFInfo
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- CN212103028U CN212103028U CN201921973398.1U CN201921973398U CN212103028U CN 212103028 U CN212103028 U CN 212103028U CN 201921973398 U CN201921973398 U CN 201921973398U CN 212103028 U CN212103028 U CN 212103028U
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Abstract
The utility model relates to a PBI proton exchange membrane electrolysis module and sea water electrolysis hydrogen plant. The PBI proton exchange membrane electrolytic module comprises five layers from bottom to top, namely a PTFE waterproof membrane layer, a cathode catalysis membrane layer, a gas diffusion layer, a PBI proton exchange membrane layer, an anode catalysis membrane layer and a gas diffusion layer, wherein the PBI proton exchange membrane layer is a phosphoric acid doped PBI (polybenzimidazole) proton membrane with the tolerance temperature of 150-250 ℃. The seawater electrode device comprises a shell and a flat tube type hydrogen tube arranged in the shell, wherein an opening with a downward opening direction is formed in the side wall of the flat tube type hydrogen tube along the length direction; the PBI proton exchange membrane electrolysis module is arranged at the opening and is matched with the opening. Solves the problems of chlorine evolution, corrosion of seawater to electrodes and catalysts and poor long-term stability in the prior art when seawater is electrolyzed to produce hydrogen.
Description
Technical Field
The utility model relates to a water electrolysis hydrogen manufacturing field especially relates to a PBI proton exchange membrane electrolysis module and sea water electrolysis hydrogen manufacturing installation.
Background
The method for producing hydrogen by electrolyzing water by utilizing renewable energy is a clean scheme for solving the problem of hydrogen energy supply in the future, and is a scheme with great attraction for directly electrolyzing seawater by utilizing offshore wind energy and solar energy at sea.
However, the current commonly used water electrolysis hydrogen production technologies such as direct alkaline electrolysis and membrane electrolysis technologies based on Nafion proton exchange membranes are difficult to directly electrolyze, chlorine evolution and corrosion of seawater to electrodes and catalysts exist, and the long-term stability of an electrolysis device is difficult to meet the requirements.
Accordingly, the prior art is yet to be improved and developed.
SUMMERY OF THE UTILITY MODEL
In view of the above prior art not enough, the utility model aims to provide a PBI proton exchange membrane electrolysis module and sea water electrolysis hydrogen manufacturing installation, aim at solving current sea water electrolysis hydrogen manufacturing and have the problem that sea water is corroded to electrode, catalyst.
The utility model discloses a solve the technical scheme that above-mentioned technical problem adopted as follows:
in a first aspect, a PBI proton exchange membrane electrolysis module, comprising:
the membrane comprises a PBI proton exchange membrane layer, an anode catalyst layer arranged on the upper surface of the PBI proton exchange membrane layer, a cathode catalyst layer arranged on the lower surface of the PBI proton exchange membrane layer, a first gas diffusion layer arranged on the upper surface of the anode catalyst layer, a second gas diffusion layer arranged on the lower surface of the cathode catalyst layer and a polytetrafluoroethylene waterproof membrane layer arranged on the lower surface of the second gas diffusion layer.
Preferably, the PBI proton exchange membrane electrolysis module has a tolerance temperature of 150-250 ℃.
In a second aspect, a seawater electrolytic hydrogen production apparatus comprises:
the hydrogen pipe comprises a shell and a flat pipe type hydrogen pipe arranged in the shell, wherein an opening with a downward opening direction is formed in the side wall of the flat pipe type hydrogen pipe along the length direction; the PBI proton exchange membrane electrolysis module is arranged at the opening and is matched with the opening; the PBI proton exchange membrane electrolysis module is the PBI proton exchange membrane electrolysis module.
Preferably, the outer side wall of the flat tube type hydrogen pipe is provided with a water retaining rib for retaining water.
Preferably, the seawater electrolysis hydrogen production device is characterized in that a seawater inlet, an air extraction opening for extracting gas in the shell and a seawater outlet arranged at the lower part of the shell are further arranged at the upper part of the shell.
The seawater electrolysis hydrogen production device also comprises an end plate, and the end plate is detachably connected with the shell.
Preferably, in the seawater electrolysis hydrogen production device, the first gas diffusion layer of the PBI proton exchange membrane electrolysis module is close to the opening of the flat tube hydrogen tube.
Preferably, in the seawater electrolysis hydrogen production device, the flat-tube hydrogen tube material is made of stainless steel.
Preferably, in the seawater electrolysis hydrogen production device, the flat-tube hydrogen tube is of a blind tube structure, and the open end of the flat-tube hydrogen tube penetrates through the end plate and is exposed outside the end plate.
Preferably, in the seawater electrolysis hydrogen production device, a sealing ring is arranged at a contact part of the open end of the flat tube type hydrogen pipe and the end plate.
Has the advantages that: the utility model provides a PBI proton electrolysis membrane group in device has avoided the direct contact of sea water with the PBI membrane as the inoxidizing coating with the waterproof ventilated membrane of high temperature resistant PTFE (polytetrafluoroethylene), and has guaranteed the sufficient supply of sea water vapour in the module, slows down the inefficacy of PBI membrane catalyst.
Drawings
Fig. 1 is a schematic structural diagram of a PBI proton exchange membrane according to an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of a seawater electrolysis hydrogen production device based on a PBI proton exchange membrane provided by an embodiment of the present invention.
Fig. 3 is a schematic cross-sectional structure diagram of a seawater electrolysis hydrogen production device based on a PBI proton exchange membrane provided by an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer and clearer, the present invention will be described in further detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in fig. 1, the utility model discloses a PBI (polybenzimidazole) proton exchange membrane electrolysis module 30, it includes five layers, and the outmost gas diffusion layer (two-layer altogether inside and outside, inside be second gas diffusion layer 320, outside be first gas diffusion layer 360) based on carbon paper, can be 1mm as the thickness of example gas diffusion layer, and cathode catalysis layer 330 is on the seawater vapor chamber side of membrane group, and thickness can be 0.3 mm. The anode catalytic layer 350 may be 0.3mm thick on the inside of the hydrogen tubes of the membrane stack. The cathode and anode catalytic layers both supported commercial platinum carbon catalyst. The intermediate PBI membrane 340 is a phosphoric acid doped commercial PBI (polybenzimidazole) proton membrane 10, which may be 0.1mm thick.
In the prior art, hydrogen is prepared by electrolyzing seawater, the problems of chlorine evolution, corrosion of seawater to an electrode and a catalyst and the like exist, and the long-term stability of an electrolysis device can not meet the requirement.
In order to solve the problem of the corrosion of sea water counter electrode, the utility model provides a PBI proton exchange membrane electrolysis module for sea water electrolysis hydrogen manufacturing, this module mainly used electrolysis (sea) steam hydrogen manufacturing is about to wait to electrolyze the sea water and generates sea water steam through the heating, electrolyzes sea water steam and prepares hydrogen, and wherein PBI proton exchange membrane can use under high temperature. And meanwhile, the PBI proton exchange membrane electrolysis module is protected by adopting a PTFE (polytetrafluoroethylene) waterproof membrane, so that the seawater is prevented from directly contacting with the PBI proton exchange membrane and the cathode catalyst layer to corrode the PBI proton exchange membrane and the cathode catalyst layer. The water vapor is electrolyzed into oxygen and proton at the catalyst layer in the proton exchange membrane, and the proton reaches the anode catalyst layer at the outer side of the exchange membrane through the exchange membrane to generate electrons and generate hydrogen. The seawater evaporation-electrolysis hydrogen production is realized.
In this embodiment, the PBI proton exchange membrane can withstand a temperature of 150-. In the electrolysis process, the electrode dynamics process is accelerated along with the increase of the temperature, and the electrolysis efficiency is higher than that of the low-temperature Nafion proton exchange membrane.
As shown in fig. 2-3, based on the same concept of the present invention, the present invention further provides a seawater electrolysis hydrogen production apparatus, which comprises a housing 10 made of corrosion-resistant metal or corrosion-resistant engineering plastic with certain strength. Of course, a protective coating or the like may be applied to the housing in order to prevent corrosion by seawater. The shape of the housing 10 can be adaptively designed according to the actual use environment, and the specific shape of the housing is not limited herein. For example, the housing may be designed to have an oval cross-section, with one end closed and the other open. The flat tube type hydrogen pipe 20 is arranged inside the casing 10, the flat tube type hydrogen pipe 20 has a blind pipe structure, an opening 210 with a downward opening direction is arranged on the side wall of the flat tube type hydrogen pipe 20 along the length direction, and the width of the opening 210 is smaller than or equal to the width of the flat tube type hydrogen pipe. Still including setting up the PBI proton exchange membrane electrolysis module 30 that is used for carrying out the electrolysis to sea water steam in opening 210 department, PBI proton exchange membrane electrolysis module 30 includes from supreme down in proper order, high temperature resistant waterproof ventilative PTFE rete 310, overlaps the second gas diffusion layer 320 of establishing on high temperature resistant waterproof ventilative PTFE rete 310, sets up the cathode catalysis layer 330 on second gas diffusion layer 320, and the last platinum carbon catalyst that is loaded of cathode catalysis layer 330. PBI proton exchange membrane layer 340, anode catalyst layer 350, and first gas diffusion layer 360. The first gas diffusion layer 360 is close to the opening 210 of the flat tube type hydrogen tube, that is, the PBI proton exchange membrane electrolysis module 30 is installed in a manner that the first gas diffusion layer 360 faces the opening of the flat tube type hydrogen tube.
In this embodiment, a power supply device for electrolysis is further included. The power supply device is a conventional circuit device, and is not limited herein.
In the embodiment, the flat tube type hydrogen tube is made of stainless steel, can be used as a membrane electrode anode current collector and a hydrogen output pipeline, and is simple in air sealing and high in safety; in addition, the flat tube design increases the contact heat exchange area with the seawater sprayed from the upper part, increases the vaporization rate of the seawater, improves the concentration of the seawater vapor in the seawater evaporation cavity, and reduces the concentration loss of electrolysis.
In this embodiment, the upper portion of the housing 10 is further provided with a seawater inlet 110 for injecting seawater, a pumping port 120 for pumping gas in the housing, and a seawater outlet 130 disposed at the lower portion of the housing.
In the present embodiment, the flat tube type hydrogen pipe is disposed inside the housing, that is, the internal space of the housing is divided into an upper part and a lower part by the flat tube type hydrogen pipe. Seawater is injected into the shell 10 through the seawater inlet 110, and in order to better realize heat exchange and evaporation, the seawater entering from the seawater inlet is sprayed on the flat tube type hydrogen pipe in a spraying mode. The unevaporated seawater is at the bottom of the shell and can be discharged through the seawater outlet 130, so that the shell is prevented from being corroded by salt component crystallization and scaling in the seawater inside the cavity. Because the discharged seawater has higher salt concentration, the seawater can be used as a brine raw material for preparing chlorine and salt from seawater, and the circulation of the seawater is realized.
In this embodiment, before the electrolysis operation, i.e. before the seawater is electrolyzed, the air inside the casing 10 is pumped out through the air pumping port 120 to reduce the pressure inside the casing, and the evaporation temperature of the seawater is reduced by the way of reduced pressure evaporation to increase the evaporation amount. In addition, oxygen products in the water electrolysis process are removed at constant pressure during electrolysis operation, and the oxygen concentration of the seawater cavity is reduced, so that the concentration loss in the electrolysis process is reduced.
In one or more embodiments, the outer sidewall of the flat tube type hydrogen pipe 20 is provided with a water blocking rib 220 for blocking seawater from directly contacting the electrolysis module to prevent the seawater from washing off the catalyst particles. The water retaining ribs are obliquely arranged obliquely upwards along the side wall of the flat tube type hydrogen pipe, as shown in fig. 3, the water retaining ribs are arranged on both sides of the flat tube type hydrogen pipe, the water retaining ribs on the same side can be arranged at intervals or can be a whole, and the specific arrangement form can be set according to specific conditions. The material of the water retaining rib can be the same as that of the flat tube type hydrogen pipe or different from that of the flat tube type hydrogen pipe.
In one embodiment, the seawater electrolytic hydrogen production apparatus further comprises an end plate 40, and the end plate 40 can be detachably connected with the housing 10 through screws. The arrangement of the end plate can facilitate the maintenance of the seawater electrolysis hydrogen production device. The end plate 40 is provided with a through hole (not shown) for the flat tube type hydrogen tube hydrogen outlet 230 to pass through, i.e. the open end of the flat tube type hydrogen tube with a blind tube structure passes through the end plate and is exposed outside the end plate. A sealing ring 50 is arranged between the open end of the flat tube type hydrogen pipe and the through hole on the end plate.
The specific process of electrolyzing seawater by using the seawater electrolysis hydrogen production device shown in FIG. 2 is as follows:
when direct current generated by the offshore wind driven generator is input into the cathode and the anode of the electrolytic film after being simply modulated, as shown in figure 1, air in the shell is pumped out before electrolysis begins, (constant pressure and continuous exhaust are carried out during electrolysis), the pressure of an evaporation cavity is controlled to be 0.2MPa, the evaporation temperature is controlled to be about 120 ℃, and the peripheral heating heat load for maintaining the system to work is reduced. The high-temperature PBI proton electrode membrane group in the high-temperature resistant PTFE waterproof breathable membrane is provided with five layers, the outermost layer is a gas diffusion layer (two layers of inner and outer layers) based on carbon paper, the thickness of the high-temperature PBI proton electrode membrane group is 1mm, and the cathode catalyst layer is arranged on the seawater steam chamber side of the membrane group and is 0.3 mm. The anode catalyst layer was on the inside side of the hydrogen tube of the membrane group and was 0.3mm thick. The cathode and anode catalytic layers all supported commercial platinum carbon catalysts. The middle PBI membrane was a phosphoric acid doped commercial PBI (polybenzimidazole) proton membrane with a thickness of 0.1 mm. The membrane group electrolytic cell is designed to work at 1.3 to 1.5V, and the seawater steam is electrolyzed by the electrolytic current. Wherein, the electrolysis half reaction of the seawater vapor occurs at the cathode side:
2H2O→4H++O2+4e-
the protons produced pass through the PBI membrane module to the anode, the other half of the reaction taking place:
4H++4e-→2H2
the overall water electrolysis reaction of the membrane stack is as follows:
2H2O→2H2+O2
to sum up, the utility model provides a PBI proton exchange membrane electrolysis module and sea water electrolysis hydrogen plant, the PBI proton exchange membrane electrolysis module that provides, including PBI proton exchange rete, set up the positive pole catalysis layer of PBI proton exchange rete upper surface sets up the negative pole catalysis layer of PBI proton exchange rete lower surface sets up the first gas diffusion layer of positive pole catalysis layer upper surface sets up the second gas diffusion layer and the setting of negative pole catalysis layer lower surface are in the waterproof rete of PTFE of second gas diffusion layer lower surface. Wherein the PBI proton exchange membrane is a phosphoric acid doped PBI (polybenzimidazole) proton membrane with the tolerance temperature of 150-250 ℃. The seawater electrolysis hydrogen production device comprises: the side wall of the flat tube type hydrogen tube is provided with an opening with a downward opening direction along the length direction; the PBI proton exchange membrane electrolysis module is arranged at the opening and is matched with the opening. The seawater electrolysis hydrogen production device is prepared based on a high-temperature proton exchange membrane, can produce hydrogen by electrolyzing seawater steam, has low requirement on humidity, is simple in water management, and has accelerated dynamic process of electrodes due to the fact that the seawater electrolysis hydrogen production device is carried out at high temperature, and the electrolysis efficiency is higher than that of low-temperature Nafion proton exchange membrane electrolysis. Solves the problems of chlorine evolution, corrosion of seawater to electrodes and catalysts and poor long-term stability in the prior art when seawater is electrolyzed to produce hydrogen.
It is to be understood that the invention is not limited to the above-described embodiments, and that modifications and variations may be made by those skilled in the art in light of the above teachings, and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (10)
1. A PBI proton exchange membrane electrolysis module characterized by comprising:
the membrane comprises a PBI proton exchange membrane layer, an anode catalyst layer arranged on the upper surface of the PBI proton exchange membrane layer, a cathode catalyst layer arranged on the lower surface of the PBI proton exchange membrane layer, a first gas diffusion layer arranged on the upper surface of the anode catalyst layer, a second gas diffusion layer arranged on the lower surface of the cathode catalyst layer and a polytetrafluoroethylene waterproof membrane layer arranged on the lower surface of the second gas diffusion layer.
2. The PBI proton exchange membrane electrolysis module as recited in claim 1, wherein the PBI proton exchange membrane is resistant to a temperature of 150-250 ℃.
3. A seawater electrolysis hydrogen production device is characterized by comprising:
the hydrogen pipe comprises a shell and a flat pipe type hydrogen pipe arranged in the shell, wherein an opening with a downward opening direction is formed in the side wall of the flat pipe type hydrogen pipe along the length direction; the PBI proton exchange membrane electrolysis module is arranged at the opening and is matched with the opening; the PBI proton exchange membrane electrolysis module is the PBI proton exchange membrane electrolysis module of any one of claims 1-2.
4. The seawater electrolytic hydrogen production device according to claim 3, wherein a water-retaining rib for retaining water is provided on an outer side wall of the flat tube type hydrogen pipe.
5. The seawater electrolytic hydrogen production apparatus according to claim 3, wherein the upper part of the housing is further provided with a seawater inlet, a gas extraction port for extracting gas in the housing, and a seawater outlet arranged at the lower part of the housing.
6. The seawater electrolytic hydrogen production apparatus of claim 3, further comprising an end plate detachably connected to the housing.
7. The seawater electrolytic hydrogen production device according to claim 3, wherein the first gas diffusion layer of the PBI proton exchange membrane electrolysis module is close to the opening of the flat tube type hydrogen tube.
8. The seawater electrolytic hydrogen production device according to claim 3, wherein the flat tube type hydrogen tube material is made of stainless steel.
9. The apparatus for producing hydrogen by electrolyzing seawater as claimed in claim 6, wherein the flat tube type hydrogen tube is a blind tube structure, and the open end of the flat tube type hydrogen tube is exposed outside the end plate through the end plate.
10. The seawater electrolytic hydrogen production device according to claim 9, wherein a sealing ring is arranged at a contact part of the open end of the flat tube type hydrogen pipe and the end plate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110820007A (en) * | 2019-11-14 | 2020-02-21 | 深圳大学 | PBI proton exchange membrane electrolysis module and seawater electrolysis hydrogen production device |
| CN113969409A (en) * | 2021-12-01 | 2022-01-25 | 清华大学 | Hydrogen and oxygen production system |
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2019
- 2019-11-14 CN CN201921973398.1U patent/CN212103028U/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110820007A (en) * | 2019-11-14 | 2020-02-21 | 深圳大学 | PBI proton exchange membrane electrolysis module and seawater electrolysis hydrogen production device |
| CN113969409A (en) * | 2021-12-01 | 2022-01-25 | 清华大学 | Hydrogen and oxygen production system |
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