CN212467646U - Membrane separation assembly for hydrogen separation - Google Patents
Membrane separation assembly for hydrogen separation Download PDFInfo
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- CN212467646U CN212467646U CN202020730831.5U CN202020730831U CN212467646U CN 212467646 U CN212467646 U CN 212467646U CN 202020730831 U CN202020730831 U CN 202020730831U CN 212467646 U CN212467646 U CN 212467646U
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Abstract
The utility model belongs to the technical field of hydrogen energy, a membrane separation subassembly for hydrogen separation is related to, and the membrane separation subassembly mainly includes hydrogen separation chamber, baffle, palladium and the compound membrane pipe of alloy and hydrogen collection chamber, the hydrogen separation intracavity sets up the compound membrane pipe of palladium and alloy, and the through-hole that the open end of membrane pipe passed the baffle gets into hydrogen and collects the chamber and is connected with the baffle through welded mode. When the device is used together with equipment for producing hydrogen-rich gas, the electric heating element is used for heating the membrane separation assembly to reach the use temperature, and then the hydrogen-rich gas is connected to realize the processes of hydrogen separation, collection and the like. The membrane separation component has compact structure, and is particularly suitable for a fuel cell device for on-site hydrogen production.
Description
Technical Field
The utility model belongs to the technical field of hydrogen can, a membrane separation subassembly is related to, especially relates to a membrane separation subassembly for hydrogen separation.
Background
In recent years, hydrogen fuel cell vehicles have been receiving high attention from governments and well-known automobile manufacturers, and have been rapidly developed. One of the best fuels for fuel cells is hydrogen because its product is water and zero emissions can be truly achieved. To promote the commercialization of hydrogen-oxygen fuel cells (proton membrane fuel cells), it is necessary to solve the problems of hydrogen source and cost reduction. At present, the hydrogen is produced by reforming methanol steam and has remarkable advantages as a hydrogen source of a communication base station or a small-sized mobile power supply because the methanol has wide sources, is convenient to store and transport and has high hydrogen storage capacity which is up to 18.8 percent of the mass of the methanol. The core of the methanol hydrogen production is a catalyst which mainly comprises two systems of noble metal and non-noble metal. Among them, the copper-based catalysts in non-noble metal catalyst systems are the most studied, such as CuO/ZnO/Al2O3、Cu/ZnO、Cu/Ce/Zn/Al、Cu-Ni /monolith/TiO2The reaction temperature of methanol steam reforming hydrogen production based on copper-based catalyst is 200-300 ℃, the higher the temperature is, the higher the hydrogen production rate and the conversion efficiency are, and when the reaction temperature is raised to 300 ℃, the methanol can be completely converted.
Hydrogen energy is regarded as the most promising clean energy in the 21 st century, and plays an increasingly important role in the fields of chemical industry, food, semiconductor industry, communication base stations, low-temperature superconduction, military, aviation and the like. The utilization of hydrogen energy relates to the links of hydrogen preparation, separation, purification, storage and transportation and the like. The preparation method of the hydrogen mainly comprises coal hydrogen production, hydrocarbon hydrogen production, biological hydrogen production, water electrolysis hydrogen production and the like, but the purity of the prepared hydrogen is not high, and the hydrogen needs to be separated and purified in order to meet the industrial requirements on various high-purity hydrogen. Common hydrogen separation methods include low-temperature separation, pressure swing adsorption, membrane separation, and the like. The membrane separation method has the advantages of small volume, simple and convenient operation, low noise and the like, and is particularly suitable for occasions with medium and small scale and high requirements on the purity of hydrogen. The metal palladium and the alloy film thereof have unique selective permeability to hydrogen, and only hydrogen can be dissolved and diffusedThe palladium membrane permeates and intercepts other impurity gases, so that the hydrogen with the purity of 100 percent can be obtained theoretically, and the palladium membrane is the membrane material which is applied to hydrogen separation and purification at the earliest. Because the metal palladium or palladium alloy film reacts with H at low temperature2Hydride is formed during contact, the hydrogen embrittlement phenomenon is generated, the integrity and the compactness of the pure palladium or palladium alloy membrane are damaged, and crystal grains on the surface of the palladium membrane are rearranged and sintered during high-temperature use, so that pinholes and defects are generated on the palladium membrane, and even the palladium membrane is cracked. Therefore, in order to ensure the long-term stability of the palladium membrane, it is necessary to provide a suitable and stable palladium membrane use temperature, and the suitable working temperature of the palladium membrane is 350-.
Aiming at the characteristics of small volume and compact structure of a hydrogen source system of a communication base station or a small-sized mobile power supply, the development of a membrane separator which has compact structure, low energy consumption and high heat utilization efficiency is particularly important.
Disclosure of Invention
An object of the utility model is to provide a membrane separation subassembly that has hydrogen separation function, is applicable to the low temperature hydrogen rich gas source and carries out hydrogen separation purification, design benefit, compact structure.
The utility model discloses a concrete technical scheme does:
a membrane separation component for hydrogen separation mainly comprises a closed hollow chamber, a partition board is arranged in the hollow chamber, the partition board divides the interior of the hollow chamber into two closed cavities which are not communicated with each other, one is a hydrogen separation cavity, the other is a hydrogen collection cavity,
a palladium and/or palladium alloy composite membrane tube is arranged in the hydrogen separation cavity, one end of the palladium and/or palladium alloy composite membrane tube is closed, and the other end of the palladium and/or palladium alloy composite membrane tube is opened; the open end penetrates through the partition board and extends into the hydrogen collecting cavity, or the open end penetrates through the partition board and extends into the hydrogen collecting cavity through the guide pipe, so that the hydrogen collecting cavity is communicated with the interior of the palladium and/or palladium alloy composite membrane pipe through the open end;
a gas inlet and a gas outlet are arranged on the side wall surface of the hollow cavity where the hydrogen separation cavity is arranged; and a hydrogen outlet is arranged on the side wall surface of the hollow cavity where the hydrogen collecting cavity is positioned.
The partition plate is a stainless steel plate provided with one or more through holes;
the hydrogen separation cavity is internally provided with a palladium and/or palladium alloy composite membrane tube, one end of the palladium and/or palladium alloy composite membrane tube is closed, the other end of the palladium and/or palladium alloy composite membrane tube is opened, and the open end penetrates through the partition plate to extend into the hydrogen collection cavity 4 and is fixedly connected with the partition plate in a welding mode.
The hydrogen gas outlet pipe 5 is arranged on the side wall or the end cover of the hydrogen gas collecting cavity 4, the gas inlet pipe 6 is arranged on the side wall of the hydrogen gas separating cavity 1 close to the partition board 2, the gas outlet pipe 7 is arranged on the side wall or the end cover far away from the partition board 2, and the positions of the gas inlet pipe and the gas outlet pipe can be interchanged.
The palladium and/or palladium alloy composite membrane tube is a pure palladium membrane, or a palladium-silver alloy membrane, or a palladium-copper alloy membrane, or a palladium-gold alloy membrane, or a palladium-ruthenium alloy membrane loaded by porous stainless steel; the number of the palladium and/or palladium alloy composite membrane tubes is one or more, the diameter of the membrane tube is 2-20mm, and the effective length of the palladium and/or palladium alloy composite membrane is 10-1000 mm.
When the device is used together with equipment for producing hydrogen-rich gas, the electric heating element is used for heating the membrane separation assembly to reach the use temperature, and then the hydrogen-rich gas is connected to realize the processes of hydrogen separation, collection and the like. The membrane separation component has compact structure, and is particularly suitable for a fuel cell device for on-site hydrogen production.
The specific operation steps of the hydrogen separation and purification system applying the membrane separation component for hydrogen separation to the on-site hydrogen production fuel cell device are as follows:
a. starting a vacuum pump, and slowly increasing the output power of the electric heating device 202 through the temperature control device 201 under the vacuum-pumping condition, so that the temperature of the membrane separation assembly 203 gradually rises to a set temperature (such as 350-;
b. introducing hydrogen-rich mixed gas (such as mixed gas for hydrogen production by methanol reforming, mixed gas for hydrogen production by ethanol reforming, mixed gas for hydrogen production by ammonia decomposition, etc.) from the hydrogen production unit 204 into a hydrogen separation cavity of the membrane separation assembly;
c. under the push of pressure difference, hydrogen diffuses to the surface of the palladium membrane and is adsorbed and dissociated, then permeates through the palladium membrane by a dissolving and diffusing mechanism and is combined into hydrogen molecules, and the hydrogen molecules are desorbed from the surface of the palladium membrane and are diffused into bulk gas, so that the separation and purification of the hydrogen are realized;
d. high-purity hydrogen obtained by palladium membrane separation is collected in a palladium membrane tube and flows into a hydrogen collecting cavity under the pushing of pressure difference;
e. the high-purity hydrogen in the hydrogen collecting cavity sequentially enters the methanation reactor 205 and the plate heat exchanger 206 through pipelines, exchanges heat with the liquid raw material of the hydrogen production equipment in the plate heat exchanger, and then is conveyed to the hydrogen fuel cell device 207 through a pipeline;
f. the residual gas after the palladium membrane separation is discharged from the tail gas pipe and enters the plate heat exchanger 208, exchanges heat with part of the liquid raw material of the hydrogen production equipment in the plate heat exchanger 208, and then goes to the combustion chamber of the hydrogen production unit.
Compared with the prior art, the utility model has the advantages of: compact structure and reduced size. Has the advantages that: the utility model provides a membrane separation subassembly for hydrogen separation can realize at the direct butt joint with high temperature methanol steam reforming hydrogen manufacturing equipment, through the power module heating membrane separation subassembly of device internal coupling to service temperature, then connect rich hydrogen reformate gas, realize that palladium membrane preheats, processes such as hydrogen separation and heat transfer. The membrane separation component has compact structural design, reduces the volume of the device, and is particularly suitable for small-sized mobile power generation equipment such as a communication base station and the like.
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments. The scope of the present invention is not limited to the specific embodiments but is defined by the appended claims.
Drawings
FIG. 1 is a schematic view (square) of a membrane separation module for hydrogen separation
FIG. 2 is a schematic view of the structure of a membrane separation module for hydrogen separation (cylindrical)
FIG. 3 is a schematic diagram of a hydrogen separation and purification system of a fuel cell device with a membrane separation assembly for on-site hydrogen production
Detailed Description
Example 1
As shown in fig. 1, the structural schematic diagram of a membrane separation assembly (square) for hydrogen separation is shown, and the membrane separation assembly mainly comprises a hydrogen separation cavity 1, a partition plate 2, a palladium and/or palladium alloy composite membrane tube 3 and a hydrogen collection cavity 4;
the hydrogen separation cavity and the hydrogen collection cavity are divided into a left cavity and a right cavity through a partition plate, the left side is the hydrogen collection cavity, the right side is the hydrogen separation cavity, the hydrogen separation cavity is connected with the right side of the partition plate in a welding mode, and the hydrogen collection cavity is connected with the left side of the partition plate in a welding mode;
the clapboard 2 is a stainless steel plate provided with one or more through holes;
the hydrogen separation cavity is internally provided with a palladium and/or palladium alloy composite membrane tube, one end of the palladium and/or palladium alloy composite membrane tube is closed, the other end of the palladium and/or palladium alloy composite membrane tube is opened, and the open end penetrates through the partition plate to extend into the hydrogen collection cavity 4 and is fixedly connected with the partition plate in a welding mode.
The hydrogen gas outlet pipe 5 is arranged on the side wall or the end cover of the hydrogen gas collecting cavity 4, the gas inlet pipe 6 is arranged on the side wall of the hydrogen gas separating cavity 1 close to the partition board 2, the gas outlet pipe 7 is arranged on the side wall or the end cover far away from the partition board 2, and the positions of the gas inlet pipe and the gas outlet pipe can be interchanged.
As shown in fig. 3, a membrane separation assembly for hydrogen separation is applied to a hydrogen separation and purification system of an on-site hydrogen production fuel cell device, and the specific operation steps are as follows:
a. starting the vacuum pump 209, and slowly increasing the output power of the electric heating device 202 through the temperature control device 201 under the vacuum condition, so that the temperature of the membrane separation assembly 203 gradually rises to the set temperature (for example, 350-;
b. introducing hydrogen-rich mixed gas (such as mixed gas for hydrogen production by methanol reforming, mixed gas for hydrogen production by ethanol reforming, mixed gas for hydrogen production by ammonia decomposition, etc.) from the hydrogen production unit 204 into a hydrogen separation cavity of the membrane separation assembly through an air inlet pipe 6;
c. under the push of pressure difference, hydrogen diffuses to the surface of the palladium membrane and is adsorbed and dissociated, then permeates through the palladium membrane by a dissolving and diffusing mechanism and is combined into hydrogen molecules, and the hydrogen molecules are desorbed from the surface of the palladium membrane and are diffused into bulk gas, so that the separation and purification of the hydrogen are realized;
d. high-purity hydrogen obtained by palladium membrane separation is collected in a palladium membrane tube and flows into a hydrogen collecting cavity under the pushing of pressure difference;
e. the high-purity hydrogen in the hydrogen collecting cavity flows out from the hydrogen outlet pipe 5, sequentially enters the methanation reactor 205 and the plate heat exchanger 206 through pipelines, exchanges heat with the liquid raw material of the hydrogen production equipment in the plate heat exchanger, and is conveyed to the hydrogen fuel cell device 207 through a pipeline;
f. the residual gas after the palladium membrane separation is discharged from the tail gas pipe (gas outlet pipe 7) and enters the plate heat exchanger 208, exchanges heat with part of the liquid raw material of the hydrogen production equipment in the plate heat exchanger 208, and then goes to the combustion chamber of the hydrogen production unit.
The outer wall of the membrane separation assembly is wrapped by a heating sheet with the rated voltage of 24V and the rated power of 500W, 8 palladium/porous stainless steel composite membranes are arranged in a hydrogen separation cavity, the diameter is 6mm, the average thickness is 5 microns, the effective length is 250 mm, when the temperature rise is finished and the temperature is kept, the temperature thermocouple in the hydrogen separation cavity displays that the fluctuation of the ambient temperature is only plus or minus 1 ℃, the actual power consumption of the electric heating sheet is 200W and only 40% of the rated power, the hydrogen production unit 204 is methanol reforming hydrogen production equipment, the pressure of the delivered hydrogen-rich reformed gas is 1.0MPa, the concentration of the hydrogen in the reformed gas is 65.5%, the purity of the high-purity hydrogen after the palladium membrane separation is 99.999%, and hydrogen-containing tail gas after the palladium membrane separation enters a hydrogen production combustion chamber of the hydrogen production unit to be combusted so as to.
Example 2
The difference from the embodiment 1 in the embodiment 1 is that the outer wall of the square membrane separation assembly is wrapped by a heating sheet with a rated voltage of 24V and a rated power of 500W, 21 palladium-silver/porous stainless steel composite membranes with a diameter of 6mm and an average thickness of 8 microns are installed in a hydrogen separation cavity, the effective length is 350 mm, when the temperature rise is finished and the temperature preservation stage is started, a temperature thermocouple in the hydrogen separation cavity displays that the fluctuation of the ambient temperature is only plus or minus 1 ℃, the actual power consumption of the electric heating sheet is 300W and is only 60% of the rated power, the hydrogen production unit 204 is an ethanol reforming hydrogen production device, the pressure of the hydrogen-rich reformed gas is 1.2MPa, the concentration of the hydrogen in the reformed gas is 55.8%, the purity of the high-purity hydrogen after the palladium membrane separation is 99.999%, and the hydrogen-containing tail gas after the palladium membrane separation enters a combustion chamber of the hydrogen production unit to be combusted.
Example 3
The outer wall of the cylindrical membrane separator is wrapped by a heating sheet with the rated voltage of 48V and the rated power of 800W, 37 palladium-copper/porous stainless steel composite membranes are arranged in a hydrogen separation cavity, the diameter is 6mm, the average thickness is 10 microns, the effective length is 500 mm, when the temperature rise is finished and the temperature preservation stage is started, a temperature thermocouple in the hydrogen separation cavity displays that the environmental temperature fluctuation is only plus or minus 1 ℃, the actual power consumption of an electric heating sheet is 500W and is only 62.5 percent of the rated power, a hydrogen production unit 204 is ammonia decomposition hydrogen production equipment, the pressure of a delivered hydrogen-rich mixed gas is 0.8MPa, the concentration of hydrogen in the mixed gas is 75 percent, and the purity of high-purity hydrogen separated by a palladium membrane is
99.999 percent of hydrogen-containing tail gas separated by the palladium membrane enters a combustion chamber of the hydrogen production unit for combustion, and provides heat energy for the hydrogen production unit 204.
Example 4
The outer wall of the square membrane separator is wrapped by a heating sheet with the rated voltage of 48V and the rated power of 800W, 52 palladium-gold/porous stainless steel composite membranes are arranged in a hydrogen separation cavity, the diameter is 6mm, the average thickness is 10 microns, the effective length is 350 mm, when the temperature rise is finished and the temperature preservation stage is carried out, a temperature thermocouple in the hydrogen separation cavity displays that the fluctuation of the ambient temperature is only plus or minus 1.5 ℃, the actual power consumption of an electric heating sheet is 600W and only 75% of the rated power, the hydrogen production unit 204 is methanol steam reforming hydrogen production equipment, the pressure of the delivered hydrogen-rich mixed gas is 2.0MPa, the concentration of the hydrogen in the mixed gas is 56.5%, the purity of the high-purity hydrogen after the palladium membrane separation is 99.999%, and hydrogen-containing tail gas after the palladium membrane separation enters a combustion chamber of the hydrogen production unit to be combusted so.
Example 5
The outer wall of the cylindrical membrane separator is wound with a heating pipe with the rated voltage of 220V and the rated power of 2000W, 19 palladium-ruthenium/porous stainless steel composite membranes with the diameter of 12mm, the average thickness of 10 microns and the effective length of 950 mm are arranged in a hydrogen separation cavity, when the temperature rise is finished and the temperature preservation stage is carried out, a temperature thermocouple in the hydrogen separation cavity displays that the fluctuation of the ambient temperature is only plus or minus 2 ℃, the actual power consumption of the electric heating pipe is 600W and only 30% of the rated power, the hydrogen production unit 204 is methanol steam reforming hydrogen production equipment, the pressure of the delivered hydrogen-rich mixed gas is 2.0MPa, the concentration of the hydrogen in the mixed gas is 55.5%, the purity of the high-purity hydrogen after the separation of a palladium membrane is 99.999%, and hydrogen-containing tail gas after the separation of the palladium membrane enters a hydrogen production combustion chamber of.
Claims (4)
1. A membrane separation module for hydrogen separation, characterized by:
mainly comprises a closed hollow cavity, a clapboard (2) is arranged in the hollow cavity, the clapboard (2) divides the interior of the hollow cavity into two closed cavities which are not communicated with each other, one is a hydrogen separation cavity (1), the other is a hydrogen collection cavity (4),
a palladium and/or palladium alloy composite membrane tube (3) is arranged in the hydrogen separation cavity (1), one end of the palladium and/or palladium alloy composite membrane tube (3) is closed, and the other end is opened; the open end penetrates through the partition plate (2) and extends into the hydrogen collecting cavity (4), or the open end penetrates through the partition plate (2) through a guide pipe and extends into the hydrogen collecting cavity (4), so that the hydrogen collecting cavity (4) is communicated with the interior of the palladium and/or palladium alloy composite membrane tube (3) through the open end;
a gas inlet and a gas outlet are arranged on the side wall surface of the hollow cavity chamber where the hydrogen separation chamber (1) is positioned; a hydrogen outlet is arranged on the side wall surface of the hollow cavity chamber where the hydrogen collecting cavity (4) is positioned.
2. The membrane separation module of claim 1, wherein:
the hydrogen separation cavity and the hydrogen collection cavity are divided into a left cavity and a right cavity by a partition plate, the left side is the hydrogen collection cavity, the right side is the hydrogen separation cavity, and the inner wall surface of the hollow cavity is hermetically connected with the peripheral edge of the partition plate in a welding mode;
the partition plate (2) is a stainless steel plate provided with one or more through holes; each through hole is provided with 1 or more than 2 palladium and/or palladium alloy composite membrane tubes or conduits, and the inner wall surface of each through hole is hermetically connected with the outer wall surface of each palladium and/or palladium alloy composite membrane tube or conduit.
3. The membrane separation module of claim 1, wherein: and a hydrogen outlet pipe (5) is arranged at a hydrogen outlet on the side wall surface of the hollow cavity of the hydrogen collecting cavity.
4. The membrane separation module of claim 1, wherein: the gas inlet on the outside lateral wall that is close to the baffle of hydrogen separation chamber is equipped with intake pipe (6), and the gas outlet on the outside lateral wall of hydrogen separation chamber or the end cover of keeping away from the baffle is equipped with outlet duct (7) to the position of intake pipe and outlet duct can be interchanged.
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| CN202020730831.5U CN212467646U (en) | 2020-05-07 | 2020-05-07 | Membrane separation assembly for hydrogen separation |
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| CN202020730831.5U CN212467646U (en) | 2020-05-07 | 2020-05-07 | Membrane separation assembly for hydrogen separation |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115138186A (en) * | 2022-06-29 | 2022-10-04 | 中国石油大学(华东) | Hydrogen separation device with spiral structure membrane module |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115138186A (en) * | 2022-06-29 | 2022-10-04 | 中国石油大学(华东) | Hydrogen separation device with spiral structure membrane module |
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