CN112919411A - Membrane separator with heating and hydrogen separation functions - Google Patents
Membrane separator with heating and hydrogen separation functions Download PDFInfo
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- CN112919411A CN112919411A CN201911232275.7A CN201911232275A CN112919411A CN 112919411 A CN112919411 A CN 112919411A CN 201911232275 A CN201911232275 A CN 201911232275A CN 112919411 A CN112919411 A CN 112919411A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
- C01B3/505—Membranes containing palladium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/047—Decomposition of ammonia
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention belongs to the technical field of hydrogen energy, and relates to a membrane separator with heating and hydrogen separation functions. When the device is used together with low-temperature methanol steam reforming hydrogen production equipment, the device is heated to the use temperature by commercial power, and then connected with hydrogen-rich reformed gas, so that the processes of palladium membrane preheating, reformed gas heating, hydrogen separation and the like are realized. The special structural design of the membrane separator reduces the heat loss of the electric heating device, reduces the operation energy consumption of the hydrogen separation system, improves the heat utilization efficiency and has more compact structure.
Description
Technical Field
The invention belongs to the technical field of hydrogen energy, relates to a membrane separator, and particularly relates to a membrane separator with heating and hydrogen separation functions.
Background
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 membrane thereof have unique selective permeability to hydrogen, and only hydrogen can permeate the palladium membrane by a dissolution and diffusion mechanism and intercept other impurity gases, so that the hydrogen with the purity of 100 percent can be obtained theoretically, and the metal palladium and the alloy membrane thereof are the membrane materials which are 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-.
In recent years, hydrogen fuel cell vehicles have been receiving high attention from governments and well-known automobile manufacturers, and have been rapidly developed. The best fuel for fuel cells is hydrogen because the product is water and zero emissions are 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, methanol steam reforming hydrogen production is adopted as a hydrogen source of a distributed hydrogenation stationHas obvious advantages because of wide methanol source, convenient storage and transportation and high hydrogen storage capacity, which reaches 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.
However, even if the temperature of the reformed gas for hydrogen production by methanol steam reforming reaches 300 ℃, the temperature is still lower than the working temperature of a palladium membrane (350-.
Disclosure of Invention
The invention aims to provide a membrane separator which has the functions of heating and hydrogen separation and is suitable for hydrogen separation and purification of a low-temperature hydrogen-rich gas source, so that the heat utilization efficiency is improved, the energy consumption is reduced, and the operation stability of the membrane separator is ensured.
The invention adopts the specific technical scheme that:
a membrane separator with heating and hydrogen separation functions mainly comprises an explosion-proof cavity 1 and a container;
the container is a closed container with a closed left end and an open right end, a hydrogen collecting cavity bottom plate 17 is vertically arranged in the container, the cavity in the container is divided into two chambers which are not communicated with each other left and right by the hydrogen collecting cavity bottom plate, the hydrogen collecting cavity 6 is arranged on the left side, the hydrogen separating cavity 5 is arranged on the right side, a hydrogen outlet pipe 25 is arranged on the side wall of the hydrogen collecting cavity 6, a tail gas pipe 23 is arranged on the side wall of the hydrogen separating cavity 5 close to the open end of the container, an inner pipe 18 with an open left end and an open right end and serving as a heating cavity 4 is arranged in the hydrogen separating cavity, and the open end of the container is;
a second flange 3 is arranged on the outer side wall surface of the right opening end of the inner pipe extending out of the container, the right opening end of the inner pipe 18 is sealed by a first flange 2 fixedly connected with the second flange 3, an air inlet pipe 21 is arranged on the side wall surface of the inner pipe between the container and the second flange (3), a gap is left between the left opening end of the inner pipe and a hydrogen collecting cavity bottom plate 17 or a through hole is arranged on the side wall surface of the inner pipe close to the hydrogen collecting cavity bottom plate to be used as a gas circulation pore channel 19;
the explosion-proof cavity 1 is arranged on the right side of the first flange 2, is a closed cavity with a closed left end and an open right end, a sealing end cover is arranged at the right opening end of the cavity, more than 2 sleeves sequentially extend into the heating cavity 4 from the explosion-proof cavity 1 through the left wall surface of the explosion-proof cavity and the first flange, the left opening end of each sleeve is positioned in the heating cavity, and the right opening end of each sleeve is positioned in the explosion-proof cavity; at least one electric heating device 12 penetrates through a sleeve and extends into the heating cavity from the explosion-proof cavity, and at least one thermocouple penetrates through a sleeve and extends into the heating cavity from the explosion-proof cavity;
and a tubular palladium and/or palladium alloy composite membrane 20 is arranged in the hydrogen separation cavity and between the inner tube and the inner wall surface of the hydrogen separation cavity, one end of the tubular palladium and/or palladium alloy composite membrane is closed, the other end of the tubular palladium and/or palladium alloy composite membrane is open, and the open end of the tubular palladium and/or palladium alloy composite membrane penetrates through the hydrogen collection cavity bottom plate 17 and extends into the hydrogen collection cavity 6.
An electric heating device wiring terminal 7 and a thermocouple wiring terminal 8 are arranged in the explosion-proof cavity; the electric heating device 12 and the thermocouple are respectively connected with a terminal 7 of the electric heating device and a terminal 8 of the thermocouple in the explosion-proof cavity;
the side wall of the explosion-proof cavity 1 is provided with a heating wire connecting tube 14 for penetrating a wire to connect with a wiring end of an electric heating device, and a temperature control and measurement thermocouple wire connecting tube 15 for penetrating a wire to connect with a wiring end of an electric heating device.
The first flange 2 and the explosion-proof cavity 1 are fixedly welded through a group of sleeves 9; the second flange is fixedly connected with the heating cavity in a welding mode;
a graphite wound gasket 10 is arranged between the first flange and the second flange and is tightly connected through bolts 11.
An electric heating device and semicircular supporting tube plates 13 which are uniformly distributed and staggered up and down are arranged in the heating cavity; the heating cavity is connected with the explosion-proof cavity through a second flange, a first flange and a group of sleeves 9, one end of an electric heating device is fixedly welded with the explosion-proof cavity, the other end of the electric heating device penetrates into the heating cavity through the explosion-proof cavity through the sleeves, a heating wire penetrates into a wiring terminal connected with the electric heating device through a heating wiring pipe of the explosion-proof cavity, and a temperature control and measurement wire penetrates into the wiring terminal connected with a thermocouple through the thermocouple wiring pipe of the explosion-proof cavity.
The electric heating device and the thermocouple are externally provided with a plurality of uniformly distributed supporting tube plates 13 with the electric heating device and the thermocouple penetrating through the through hole, the supporting tube plates close to the flange are circular plates, the supporting tube plates of the electric heating tube, close to the front part and the middle part of the hydrogen collecting cavity 6, are respectively semicircular, the semicircular supporting tube plates which are sequentially and uniformly distributed are respectively arranged in an up-and-down staggered manner, and the supporting tube plate close to the rear part of the flange is a circular plate.
And a supporting tube plate with a through hole for the sleeve to pass through is arranged outside the sleeve between the first flange 2 and the explosion-proof cavity 1.
The hydrogen separation cavity 5 is positioned at the outer side of the heating cavity, is of a sleeve type structure, is in epitaxial connection with a hydrogen collection cavity bottom plate in a welding mode, is connected with the outer wall of the heating cavity in a welding mode, a gas circulation pore passage is arranged on the wall of the heating cavity close to the bottom plate, the hydrogen separation cavity and the heating cavity are communicated through the pore passage, and the number of the pore passages can be 1 or more; the hydrogen separation cavity is internally provided with a tubular palladium and palladium alloy composite membrane, one end of the tubular palladium and/or palladium alloy composite membrane is closed, the other end of the tubular palladium and/or palladium alloy composite membrane is opened, and the open end penetrates through the hydrogen collection cavity bottom plate to extend into the hydrogen collection cavity and is fixedly connected with the hydrogen collection cavity bottom plate in a welding mode.
The hydrogen collecting cavity and the heating cavity are fixedly welded through an ellipsoidal end cover 24 and a collecting cavity bottom plate 17, and a hydrogen outlet pipe 25 is arranged on the ellipsoidal end cover of the hydrogen collecting cavity.
The electric heating device is an electric heating pipe, and the number of the electric heating pipes is 1 or more.
The tubular palladium and alloy composite membrane is a porous stainless steel-loaded pure palladium membrane, or a porous stainless steel-loaded palladium-silver alloy membrane, or a porous stainless steel-loaded palladium-copper alloy membrane, or a porous stainless steel-loaded palladium-gold alloy membrane, or a porous stainless steel-loaded palladium-ruthenium alloy membrane; the number of the tubular palladium and alloy composite membranes is 1 or more.
The specific operation steps of the membrane separator with the heating and hydrogen separation functions applied to the hydrogen separation and purification system are as follows:
a. starting a vacuum pump, and slowly increasing the output power of the electric heating device through the temperature control equipment under the vacuum pumping condition so that the temperature of the heating cavity is gradually increased to a set temperature (such as 350-;
b. introducing low-temperature 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 and the like) from the hydrogen production unit 204 into the wound tube type heat exchanger 203, exchanging heat with high-purity hydrogen separated by a palladium membrane, then entering a heating cavity through an air inlet pipe, and enabling the hydrogen-rich mixed gas to sequentially pass through uniformly distributed semicircular supporting pipe plates which are arranged in an up-and-down staggered manner, so that the gas flows in an S shape, and the hydrogen-rich mixed gas is heated to the working temperature suitable for the palladium membrane;
c. the hydrogen-rich mixed gas enters the hydrogen separation cavity through a channel on the wall of the heating cavity;
d. 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;
e. 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;
f. the hydrogen is sent to hydrogen utilization equipment through a hydrogen outlet pipe;
g. the remaining gas after separation by the palladium membrane is discharged from the tail gas pipe and goes to the combustion chamber of the hydrogen production unit. Compared with the prior art, the invention has the innovation points that: 1. the electric heating pipe is arranged in the reactor, so that the heat efficiency can be obviously improved, the low-temperature hydrogen-rich gas source can be fully heated, and the volume of the reactor is reduced; 2. can realize direct connection with reformed gas of low-temperature methanol steam reforming hydrogen production, and reduces the volume of the device.
Has the advantages that: the membrane separator with the heating and hydrogen separation functions can be directly butted with low-temperature methanol steam reforming hydrogen production equipment, the membrane separator is heated to the use temperature through commercial power, and then hydrogen-rich reformed gas is connected, so that the processes of palladium membrane preheating, reformed gas heating, hydrogen separation and the like are realized. The special structural design of the membrane separator reduces the heat loss of the electric heating device, reduces the operation energy consumption of the hydrogen separation system, improves the heat utilization efficiency and has more compact structure.
The invention is described in detail below with reference to the figures and specific embodiments. The scope of the invention is not to be limited by the specific embodiments but by the claims.
Drawings
FIG. 1 is a schematic structural diagram of a membrane separator with heating and hydrogen separation functions
FIG. 2 is a schematic structural diagram of a hydrogen separation and purification system using a membrane separator
Detailed Description
Example 1
As shown in fig. 1, which is a schematic structural diagram of a membrane separator with heating and hydrogen separation functions, the membrane separator mainly comprises an explosion-proof chamber 1, a first flange 2, a second flange 3, a heating chamber 4, a hydrogen separation chamber 5 and a hydrogen collection chamber 6.
And a heating device terminal 7 and a thermocouple terminal 8 are arranged in the explosion-proof cavity.
The first flange and the explosion-proof cavity are fixedly welded through a group of sleeves 9; the second flange is fixedly connected with the heating cavity in a welding mode; a graphite wound gasket 10 is arranged between the first flange and the second flange and is tightly connected through bolts 11.
An electric heating device 12 and semicircular supporting tube plates 13 which are uniformly distributed and staggered up and down are arranged in the heating cavity; the heating cavity is connected with the explosion-proof cavity through a second flange, a first flange and a group of sleeves, one end of the electric heating device is fixedly welded with the explosion-proof cavity, the other end of the electric heating device penetrates into the heating cavity through the explosion-proof cavity through the sleeves, a heating wire penetrates into a wiring terminal connected with the electric heating device through a heating wiring pipe 14 of the explosion-proof cavity, and a temperature control and measurement wire penetrates into a thermocouple wiring terminal through a thermocouple wiring pipe 15 of the explosion-proof cavity.
The electric heating device is provided with a plurality of uniformly distributed supporting tube plates, the supporting tube plates close to the second flange are a whole circle, the supporting tube plates at the front part and the middle part of the electric heating tube are respectively semicircular, the semicircular supporting tube plates which are sequentially and uniformly distributed from front to back are respectively arranged in an up-and-down staggered manner, and the supporting tube plate at the rear part is a whole circle. An air inlet pipe 21 is arranged on the outer wall of the heating cavity and close to the second flange.
The hydrogen separation cavity 5 is located on the outer side of the heating cavity, is of a sleeve type structure, is in epitaxial connection with a hydrogen collection cavity bottom plate 17 in a welding mode, is connected with the outer wall 18 of the heating cavity in a welding mode, a gas circulation pore passage 19 is formed in the wall of the heating cavity close to the bottom plate, a tubular palladium and alloy composite membrane 20 is arranged in the hydrogen separation cavity, and the tubular palladium membrane penetrates through the bottom plate and is fixedly connected with the bottom plate in a welding mode.
An exhaust pipe 23 is provided on the outer wall 22 of the hydrogen separation chamber and adjacent to the inlet pipe.
The hydrogen collecting cavity 6 is fixedly welded with the heating cavity through an ellipsoidal end cover 24 and a bottom plate, and a hydrogen outlet pipe 25 is arranged on the ellipsoidal end cover of the hydrogen collecting cavity
As shown in fig. 2, which is a schematic structural diagram of a membrane separator with heating and hydrogen separation functions applied to a hydrogen separation and purification system, the specific operation steps of separating hydrogen by the membrane separator are as follows:
a. starting the vacuum pump 201, and slowly increasing the output power of the electric heating device through the temperature control device 202 under the vacuum condition, so that the temperature of the heating cavity gradually rises to the set temperature (for example, 350-;
b. introducing low-temperature 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 and the like) from the hydrogen production unit 204 into the wound tube type heat exchanger 203, exchanging heat with high-purity hydrogen separated by a palladium membrane, then entering a heating cavity through an air inlet pipe, and enabling the hydrogen-rich mixed gas to sequentially pass through uniformly distributed semicircular supporting pipe plates which are arranged in an up-and-down staggered manner, so that the gas flows in an S shape, and the hydrogen-rich mixed gas is heated to the working temperature suitable for the palladium membrane;
c. the hydrogen-rich mixed gas enters the hydrogen separation cavity through a channel on the wall of the heating cavity;
d. 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;
e. 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;
f. the hydrogen is sent to hydrogen utilization equipment through a hydrogen outlet pipe;
g. the remaining gas after separation by the palladium membrane is discharged from the tail gas pipe and goes to the combustion chamber of the hydrogen production unit.
2 heating pipes with rated voltage of 12V and rated power of 1000W are arranged in a heating cavity of the membrane separator, 6 palladium/porous stainless steel composite membranes with diameter of 6mm, average thickness of 5 microns and effective length of 350 mm are arranged in a hydrogen separation cavity, when the temperature rise is finished and the temperature is kept in a heat preservation stage, a temperature thermocouple in the heating cavity displays that the fluctuation of the ambient temperature is only plus or minus 1 ℃, the actual power consumption of the electric heating pipe is 300W and only 30% of the rated power, the hydrogen production unit 204 is a methanol reforming hydrogen production device, 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 separated by the palladium membrane is 99.999%, and the hydrogen-containing tail gas separated by the palladium membrane enters a combustion chamber of the hydrogen production unit to be combusted so as to provide.
Example 2
3 heating pipes with the rated voltage of 24V and the rated power of 1500W are arranged in a heating cavity of the membrane separator, 20 palladium-silver/porous stainless steel composite membranes with the diameter of 6mm, the average thickness of 8 microns and the effective length of 350 mm are arranged in a hydrogen separation cavity, when the temperature rise is finished and the temperature preservation stage is started, a temperature thermocouple in the heating cavity displays that the fluctuation of the ambient temperature is only plus or minus 1 ℃, the actual power consumption of the electric heating pipe is 500W and only 30% of the rated power, the hydrogen production unit 204 is an ethanol reforming hydrogen production device, the pressure of the conveyed 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 separation of the palladium membrane is 99.999%, and the hydrogen-containing tail gas after the separation of the palladium membrane enters a hydrogen production combustion chamber of the hydrogen.
Example 3
The membrane separator is characterized in that 6 heating pipes with the rated voltage of 220V and the rated power of 3000W are arranged in a heating cavity of the membrane separator, 6 palladium-ruthenium/porous stainless steel composite membranes with the diameter of 6mm, the average thickness of 10 microns and the effective length of 350 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 heating cavity displays that the fluctuation of the ambient temperature is only plus or minus 1 ℃, the actual power consumption of the electric heating pipe is 600W and only 20% of the rated power, a hydrogen production unit 204 is ammonia decomposition hydrogen production equipment, the pressure of the delivered hydrogen-rich mixed gas is 0.8MPa, the concentration of the hydrogen in the mixed gas is 75%, the purity of the high-purity hydrogen separated by a palladium membrane is 99.999%, and hydrogen-containing tail gas separated by the palladium membrane enters a combustion chamber of the hydrogen.
Claims (10)
1. A membrane separator with heating and hydrogen separation functions mainly comprises an explosion-proof cavity (1) and a container;
the container is a closed container with a closed left end and an open right end, a hydrogen collecting cavity bottom plate (17) is vertically arranged in the container, a cavity in the container is divided into two chambers which are not communicated with each other left and right by the hydrogen collecting cavity bottom plate, the hydrogen collecting cavity (6) is arranged on the left side, the hydrogen separating cavity (5) is arranged on the right side, a hydrogen outlet pipe (25) is arranged on the side wall of the hydrogen collecting cavity, a tail gas pipe (23) is arranged on the side wall of the hydrogen separating cavity, which is close to the open end of the container, an inner pipe (18) which is used as a heating cavity (4) and is provided with an open left end and an open right end is arranged in;
a second flange (3) is arranged on the outer side wall surface of the right opening end of the inner pipe extending out of the container, the right opening end of the inner pipe is sealed by a first flange (2) fixedly connected with the second flange, an air inlet pipe (21) is arranged on the side wall surface of the inner pipe between the container and the second flange, a gap is left between the left opening end of the inner pipe and a hydrogen collection cavity bottom plate (17) or a through hole is arranged on the side wall surface of the inner pipe close to the hydrogen collection cavity bottom plate to be used as a gas circulation pore channel (19);
the explosion-proof cavity (1) is arranged on the right side of the first flange (2) and is a closed cavity with a closed left end and an open right end, a sealing end cover is arranged at the right opening end of the cavity, more than 2 sleeves sequentially extend into the heating cavity (4) from the explosion-proof cavity through the left wall surface of the explosion-proof cavity and the first flange, the left opening end of each sleeve is positioned in the heating cavity, and the right opening end of each sleeve is positioned in the explosion-proof cavity; at least one electric heating device (12) penetrates through a sleeve and extends into the heating cavity from the explosion-proof cavity, and at least one thermocouple penetrates through a sleeve and extends into the heating cavity from the explosion-proof cavity;
a tubular palladium and/or palladium alloy composite membrane (20) is arranged in the hydrogen separation cavity (5) and between the inner tube (18) and the inner wall surface of the hydrogen separation cavity, one end of the tubular palladium and/or palladium alloy composite membrane is closed, the other end of the tubular palladium and/or palladium alloy composite membrane is open, and the open end of the tubular palladium and/or palladium alloy composite membrane penetrates through a hydrogen collection cavity bottom plate (17) and extends into the hydrogen collection cavity (6).
2. The membrane separator of claim 1, wherein: an electric heating device wiring terminal and a thermocouple wiring terminal are arranged in the explosion-proof cavity; the electric heating device (12) and the thermocouple are respectively connected with an electric heating device terminal (7) and a thermocouple terminal (8) arranged in the explosion-proof cavity;
the side wall of the explosion-proof cavity (1) is provided with a heating wire connecting pipe (14) for penetrating a wire to connect a wire terminal (7) of an electric heating device and a temperature control and measurement thermocouple wire connecting pipe (15) for penetrating a wire to connect a wire terminal (8) of the electric heating device.
3. The membrane separator of claim 1, wherein: the first flange and the explosion-proof cavity are fixedly welded through a group of sleeves (9); the second flange is fixedly connected with the heating cavity in a welding mode;
a graphite winding gasket (10) is arranged between the first flange and the second flange and is tightly connected through a bolt (11).
4. The membrane separator of claim 1, wherein: an electric heating device and semicircular supporting tube plates (13) which are uniformly distributed and staggered up and down are arranged in the heating cavity; the heating cavity is connected with the explosion-proof cavity through a second flange, a first flange and a group of sleeves (9), one end of the electric heating device is fixedly welded with the explosion-proof cavity, the other end of the electric heating device penetrates into the heating cavity through the explosion-proof cavity through the sleeves, the heating wire penetrates into a wiring terminal connected with the electric heating device through a heating wiring pipe of the explosion-proof cavity, and the temperature control and measurement wire penetrates into the wiring terminal connected with a thermocouple through a thermocouple wiring pipe of the explosion-proof cavity.
5. The membrane separator of claim 1, wherein:
the electric heating device and the thermocouple are externally provided with a plurality of uniformly distributed supporting tube plates (13) through which the electric heating device and the thermocouple pass through the through hole, the supporting tube plates close to the flange are circular plates, the supporting tube plates of the electric heating tube, which are close to the front part and the middle part of the hydrogen collecting cavity (6), are respectively semicircular, the semicircular supporting tube plates which are sequentially and uniformly distributed are respectively arranged in an up-and-down staggered manner, and the supporting tube plate close to the rear part of the flange is a circular plate.
6. The membrane separator of claim 1, wherein: and a supporting tube plate with a through hole for the sleeve to pass through is arranged outside the sleeve between the first flange (2) and the explosion-proof cavity (1).
7. The membrane separator of claim 1, wherein: the hydrogen separation cavity (5) is positioned at the outer side of the heating cavity, is of a sleeve type structure, is in epitaxial connection with a hydrogen collection cavity bottom plate (17) in a welding mode, is connected with the outer wall of the heating cavity in a welding mode, a gas circulation pore passage is arranged on the wall of the heating cavity close to the hydrogen collection cavity bottom plate, the hydrogen separation cavity and the heating cavity are communicated with each other through the pore passage, and the number of the pore passages can be 1 or more;
the hydrogen separation cavity is internally provided with a tubular palladium and palladium alloy composite membrane (20), one end of the tubular palladium and/or palladium alloy composite membrane is closed, the other end of the tubular palladium and/or palladium alloy composite membrane is opened, and the open end penetrates through the hydrogen collection cavity bottom plate to extend into the hydrogen collection cavity (6) and is fixedly connected with the hydrogen collection cavity bottom plate in a welding mode.
8. The membrane separator of claim 1, wherein: the hydrogen collecting cavity is fixedly welded with the heating cavity through an ellipsoidal end cover (24) and a hydrogen collecting cavity bottom plate, and a hydrogen outlet pipe (25) is arranged on the ellipsoidal end cover of the hydrogen collecting cavity.
9. The membrane separator of claim 1, wherein: the electric heating device is an electric heating pipe, and the number of the electric heating pipes is 1 or more.
10. The membrane separator of claim 1, wherein: the tubular palladium and alloy composite membrane (20) is a porous stainless steel-loaded pure palladium membrane, or a porous stainless steel-loaded palladium-silver alloy membrane, or a porous stainless steel-loaded palladium-copper alloy membrane, or a porous stainless steel-loaded palladium-gold alloy membrane, or a porous stainless steel-loaded palladium-ruthenium alloy membrane; the number of the tubular palladium and alloy composite membranes is 1 or more.
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