CN112919407B - Ammonia decomposition membrane reactor and application - Google Patents
Ammonia decomposition membrane reactor and application Download PDFInfo
- Publication number
- CN112919407B CN112919407B CN201911232150.4A CN201911232150A CN112919407B CN 112919407 B CN112919407 B CN 112919407B CN 201911232150 A CN201911232150 A CN 201911232150A CN 112919407 B CN112919407 B CN 112919407B
- Authority
- CN
- China
- Prior art keywords
- cavity
- hydrogen
- heating
- explosion
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
Abstract
The invention belongs to the technical field of inorganic membrane reactors and hydrogen energy, and relates to an ammonia decomposition membrane reactor which mainly comprises an explosion-proof cavity, a first flange, a second flange, a heating and catalyzing cavity, a hydrogen separation cavity and a hydrogen collecting cavity, wherein a heating device wiring terminal and a thermocouple wiring terminal are arranged in the explosion-proof cavity, an electric heating device, an ammonia decomposition catalyst and uniformly distributed semicircular supporting tube plates which are staggered from top to bottom are arranged in the heating and catalyzing cavity, and a palladium and palladium alloy composite membrane tube is arranged in the hydrogen separation cavity. When the membrane reactor works, ammonia enters a catalyst bed layer after being preheated by a heating cavity, the ammonia is decomposed to obtain hydrogen-rich mixed gas, and high-purity hydrogen with the purity of 99.999 percent is obtained by palladium membrane separation. The special structural design of the membrane reactor reduces the heat loss of an electric heating device, reduces the running energy consumption of an ammonia decomposition and hydrogen separation system, improves the heat utilization efficiency, and saves the energy consumption by removing hydrogen in time by the palladium membrane to promote the forward ammonia decomposition reaction.
Description
Technical Field
The invention belongs to the technical field of hydrogen energy, relates to a membrane reactor, and particularly relates to a membrane separator of an ammonia decomposition membrane reactor.
Background
Hydrogen energy is a clean and efficient secondary energy, is regarded as the most promising energy source in the 21 st century, and plays an increasingly important role in the fields of transportation, communication, military, aviation and the like. With the gradual industrialization of hydrogen fuel cell technology, the safe, efficient and COx-free utilization of hydrogen energy will be realized. The large-scale utilization of hydrogen energy relates to the links of hydrogen preparation, separation and purification, storage and transportation and the like, wherein a high-efficiency and safe hydrogen storage technology is a key technology influencing the popularization of the hydrogen energy, and is particularly used for providing low-price hydrogen sources for fuel cells and medium and small hydrogen stations. The ammonia gas has the advantages of high hydrogen storage density (17.6 wt%), easy liquefaction, mature production, storage and transportation technology and the like, and is an ideal hydrogen carrier. The ammonia decomposition hydrogen production process has the advantages of simplicity, good safety, low price, no COx impurity in the product and the like, and the theoretical hydrogen storage amount is obviously higher than that of hydrogen production systems such as electrolyzed water (11.1 wt%), methanol-steam reforming (12 wt%), gasoline-steam reforming (12.4 wt%), hydride hydrolysis (5.2 wt% -8.6 wt%) and the like. However, the ammonia decomposition product contains hydrogen up to 75%, and further separation and purification are required to obtain high-purity hydrogen suitable for a hydrogen fuel cell.
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 small and medium 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 to 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.
At present, the key problem of the ammonia decomposition hydrogen production technology is to prepare a low-temperature and high-efficiency ammonia decomposition catalyst. The ammonia decomposition catalysts reported in the patent and literature are mainly divided into two main groups, namely noble metal catalysts represented by ruthenium and platinum and non-noble metal catalysts represented by iron and nickel (A mini-review on ammonia decomposition catalysts for on-site generation of hydrogen for fuel cell applications, Applied Catalysis A: General 277(2004) 1-9). The non-noble metal catalyst generally has better catalytic activity at the temperature of more than 550 ℃, but has lower catalytic performance in a medium-low temperature region lower than 500 ℃. The ruthenium-based noble metal catalyst has higher low-temperature catalytic activity and stability, and the catalytic performance of the ruthenium-based noble metal catalyst is closely related to a carrier, an auxiliary agent and a preparation method.
The following patents relate to noble metal ammonia decomposition catalysts:
the catalyst for preparing zero Cox hydrogen by ammonia decomposition reaction and the preparation method thereof are reported in Chinese invention patent (application number 03143112.7). The active components of the catalyst are noble metal ruthenium Ru, noble metal rhodium (Rh) and molybdenum nitride (MoN), the carrier is carbon nano tube, and the auxiliary agent is alkali metal, alkaline earth metal and rare earth metal compound. The catalyst reported in this patent needs to be used at 470-550 ℃.
The invention patent (application number 03134691.X) in China reports a catalyst for preparing hydrogen by low temperature ammonia decomposition and a preparation method thereof. The active components of the catalyst are precious metal ruthenium Ru, precious metal rhodium (Rh), non-precious metal nickel (Ni) and molybdenum nitride (MoN), and the carrier is nanocrystalline metal oxide: aluminum oxide (Al)2O3) Magnesium oxide (MgO), zirconium oxide (ZrO)2) And zinc oxide (ZnO), and the auxiliary agent is alkali metal, alkaline earth metal and rare earth metal compound. The catalyst reported in this patent needs to be used at 480 ℃ to 550 ℃.
The invention patent (application number 200510031519.7) in China reports an efficient supported nano catalyst for preparing hydrogen zero COx hydrogen by ammonia decomposition and a preparation method thereof. The active components of the catalyst are noble metal ruthenium Ru and noble metal rhodium (Rh), and the carrier is solid superbase: Na/NaOH/gamma-Al 2O3，K/KOH/γ-Al2O3And Na/KOH/ZrO2The auxiliary agent is a rare earth metal compound. The catalyst reported in the patent has higher catalytic activity when used at the temperature of above 400 ℃.
A ruthenium-based catalyst for ammonia decomposition of hydrogen and its preparation method are reported in the Chinese invention patent (application No. 201611106718.4). The active component of the catalyst is noble metal ruthenium Ru, and the carrier is a carbon nano tube. The catalyst reported in the patent has excellent ammonia decomposition catalytic activity, the ammonia decomposition conversion rate of the stearylamine system catalyst is the highest, the conversion rate reaches 89.44% at 450 ℃, and the conversion rate is close to complete conversion at 500 ℃.
The Chinese invention patent (application No. 201611115105.7) reports a magnesium oxide supported ruthenium catalyst for hydrogen production by ammonia decomposition and preparation and application thereof. The catalyst comprises a noble metal ruthenium Ru as an active component, a carrier magnesium oxide and an auxiliary agent, wherein the auxiliary agent is one or more than two of alkali metal compounds such as potassium hydroxide, potassium nitrate, potassium carbonate, cesium nitrate, cesium carbonate and the like, and the content of the active component ruthenium is preferably 1-5 wt.%. The catalyst reported in this patent has excellent catalytic activity for ammonia decomposition, with the composition KOH-5 wt.% Ru/MgO having a conversion of 83.7% at 450 ℃ and 100% at 500 ℃.
The Chinese patent (application number 201811399363.1) reports a ruthenium-based catalyst for ammonia decomposition hydrogen production and a preparation method thereof. The active component of the catalyst is noble metal ruthenium Ru, the carrier is a composite carrier of metal oxide and active carbon, and the auxiliary agent is cesium and/or potassium. The catalyst reported in the patent has excellent ammonia decomposition catalytic activity, and the conversion rate reaches 96.8% at the maximum at 400 ℃ and 99.2% at the maximum at 450 ℃.
There are also many reports in the literature and patents on ammonia decomposition reactors, such as Reactor technology options for distributed hydrogen generation, A review, international journal of hydrogen generation 38(2013)14968 and High hydrogen generation by low temperature catalytic amplification in a functional Reactor, Catalysis Communications 9(2008)482, CN101172575A, CN101863455A, CN 101466632A.
The ammonia decomposition membrane reactor is generally reported to couple a membrane material for hydrogen separation with an ammonia decomposition catalyst, and the catalyst is either directly contacted with the membrane material or placed in a membrane material tube, and aims to realize timely removal of hydrogen generated by ammonia decomposition through the membrane material, so as to promote forward reaction, improve catalytic efficiency and reduce reaction temperature. However, there is no report on coupling the hydrogen separation membrane material, the ammonia decomposition catalyst and the heat to the same reactor.
Disclosure of Invention
The invention aims to provide an ammonia decomposition membrane reaction with heating and hydrogen separation functions, which is suitable for providing hydrogen sources for portable and distributed power generation systems or small and medium-sized hydrogenation stations.
The invention adopts a specific technical scheme that:
an ammonia decomposition membrane reactor 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 catalysis cavity bottom plate 19 is vertically arranged in the container, the catalysis cavity bottom plate divides a cavity in the container into two cavities which are not communicated with each other left and right, a hydrogen collection cavity 6 is arranged on the left side, a hydrogen separation cavity 5 is arranged on the right side, a hydrogen outlet pipe 26 is arranged on the side wall of the hydrogen collection cavity, a tail gas pipe 24 is arranged on the side wall of the hydrogen separation cavity 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 separation cavity, and the open end of the container is connected with the outer wall surface of the inner pipe in a closed manner;
A second flange 3 is arranged on the outer side wall surface of the right opening end of the inner tube extending out of the container, the right opening end of the inner tube is sealed by a first flange 2 fixedly connected with the second flange, an air inlet tube 22 is arranged on the side wall surface of the inner tube between the container and the second flange, the left opening end of the inner tube is hermetically connected with a bottom plate 19 of the catalytic cavity, and a through hole is arranged on the side wall surface of the inner tube close to the bottom plate of the catalytic cavity and is used as a gas circulation pore channel 20;
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 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 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 21 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 penetrates through the bottom plate 19 of the catalysis cavity and extends into the hydrogen collection cavity 6;
A supporting tube plate 16 with a ventilation through hole is vertically arranged in the heating cavity to divide the heating cavity into a left cavity and a right cavity, an ammonia decomposition catalyst 17 is filled between the supporting tube plate and a bottom plate 19 of the catalysis cavity to serve as a heating and catalysis cavity 4, and a stainless steel tube 27 used for communicating the heating and catalysis cavity with the outside is arranged on the bottom plate of the catalysis cavity on the left side of the heating and catalysis cavity.
An electric heating device terminal 7 and a thermocouple terminal 8 are arranged in the explosion-proof cavity 1; the electric heating device and the thermocouple are respectively connected with a wiring terminal of the electric heating device and a wiring terminal of the thermocouple in the explosion-proof cavity;
and a heating wiring tube 14 for penetrating a lead to connect a wiring terminal 7 of an electric heating device and a temperature control and measurement thermocouple wiring tube 15 for penetrating a lead to connect a wiring terminal 8 of a temperature control and measurement thermocouple are arranged on the side wall of the explosion-proof cavity 1.
The first flange 2 and the explosion-proof cavity 1 are fixedly welded through a group of sleeves 9; the second flange 3 is fixedly connected with the heating and catalyzing cavity 4 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, an ammonia decomposition catalyst 17, and a support tube plate 13 which is uniformly distributed, is provided with semicircular electric heating devices in an up-down staggered arrangement and a thermocouple penetrating through a through hole are arranged in the heating and catalyzing cavity 4; the heating and catalyzing 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 and catalyzing cavity from 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 a thermocouple wiring pipe of the explosion-proof cavity;
A plurality of supporting tube plates which are uniformly distributed and provided with electric heating devices and thermocouples penetrate through holes are arranged outside the electric heating devices and the thermocouples, the supporting tube plate close to the flange is circular, the supporting tube plates at the front part and the middle part of the electric heating tube close to 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, the supporting tube plate close to the rear part of the flange is circular, sieve holes with the diameter of 0.5-1.0mm are distributed, and an ammonia decomposition catalyst is filled between the rear supporting tube plate and the bottom plate of the heating and catalyzing cavity;
a supporting tube plate with a through hole for the sleeve to pass through is arranged outside the sleeve 9 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 and catalyzing cavity 4, is of a sleeve type structure, is in epitaxial connection with a bottom plate of the heating and catalyzing cavity in a welding mode, is connected with the outer wall of the heating and catalyzing cavity in a welding mode, a gas circulation pore channel is arranged on the wall of the heating and catalyzing cavity close to the bottom plate, the hydrogen separation cavity and the heating and catalyzing cavity are communicated with each other through the pore channel, and the number of the pore channels can be 1 or more; and a tubular palladium and alloy composite membrane thereof 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 manner.
The hydrogen collecting cavity is formed by fixedly welding the outer edges of an ellipsoidal end cover 25 and a bottom plate 19 of the catalytic cavity, a hydrogen outlet pipe 26 is arranged on the ellipsoidal end cover of the hydrogen collecting cavity, round holes with the same diameter are arranged at the centers of the bottom plate and the ellipsoidal end cover, and a stainless steel pipe 27 with the same diameter is welded at the corresponding round hole position and is used for filling the ammonia decomposition catalyst.
The electric heating device is a heating pipe, and the number of the heating pipes is 1 or more.
The ammonia decomposition catalyst is a metal ruthenium-based catalyst, the active component is ruthenium, the carrier can be one or more than two of magnesium oxide, active carbon, carbon nano tube and the like, wherein a promoter can be added or not added, and the promoter is alkali metal oxide and can be one or more than two of cesium and/or potassium.
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 the alloy composite membrane thereof is 1 or more.
The specific operation steps of the ammonia decomposition membrane reactor for hydrogen production and hydrogen purification of an on-site hydrogen production or hydrogenation station are as follows:
a. Starting a vacuum pump, and under the condition of vacuum pumping, gradually increasing the output power of the electric heating device through the temperature control equipment so as to gradually raise the temperature of the heating cavity to a set temperature (such as 350-;
b. ammonia gas exchanges heat with high-purity hydrogen separated by a palladium membrane through a heat exchanger, enters a heating and catalyzing cavity through an air inlet pipe, and then sequentially passes through uniformly distributed semicircular supporting tube plates which are arranged in an up-and-down staggered manner, so that the gas flows in an S shape, the ammonia gas is heated to the working temperature suitable for ammonia decomposition, enters a catalytic bed layer, and is completely decomposed into mixed gas of hydrogen and nitrogen under the action of a catalyst;
c. the hydrogen-rich mixed gas enters the hydrogen separation cavity through a pore channel on the wall of the heating and catalyzing 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 palladium membrane separation is discharged from the tail gas pipe and goes to the combustion chamber of the hydrogen production unit.
The design has the advantages that the electric heating pipe is arranged in the reactor, so that the heat efficiency can be obviously improved, the ammonia gas can be fully heated, and the volume of the reactor is reduced; the palladium membrane removes hydrogen in the ammonia decomposition product in time, promotes the forward proceeding of the ammonia decomposition reaction, breaks thermodynamic equilibrium, improves the ammonia conversion rate, reduces the reaction temperature and saves energy consumption.
Drawings
FIG. 1 is a schematic diagram of an ammonia decomposition membrane reactor
FIG. 2 is a schematic structural view of an ammonia decomposition membrane separator applied to a hydrogen separation and purification system
Detailed Description
Example 1
As shown in fig. 1, which is a schematic structural diagram of an ammonia decomposition membrane reactor, the membrane separator mainly comprises an explosion-proof cavity 1, a first flange 2, a second flange 3, a heating and catalyzing cavity 4, a hydrogen separation cavity 5 and a hydrogen collecting cavity 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 and catalyzing 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 and catalyzing 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 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 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, the supporting tube plate at the rear part is a whole circle and is provided with sieve pores with the diameter of 1mm, and an ammonia decomposition catalyst 17 is filled between the rear supporting tube plate 16 and the heating and catalyzing cavity bottom plate.
An air inlet pipe 22 is arranged at the position of the inner pipe outer wall 18 and close to the second flange.
The hydrogen separation cavity 5 is positioned at the outer side of the heating and catalyzing cavity, is in a sleeve type structure, is connected with the extension of a bottom plate 19 of the heating and catalyzing cavity in a welding mode, is connected with the outer wall of the heating and catalyzing cavity in a welding mode, a gas circulation pore channel 20 is arranged on the wall of the heating and catalyzing cavity close to the bottom plate, the hydrogen separation cavity is communicated with the heating and catalyzing cavity through holes, and the number of the pore channels can be 1 or more; the tubular palladium and alloy composite membrane 21 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.
A tail gas pipe 24 is arranged on the outer wall 23 of the hydrogen separation chamber and close to the inlet pipe.
The hydrogen collecting cavity 6 is formed by fixedly welding an ellipsoidal end cover 25 and the outer edge of a bottom plate, a hydrogen outlet pipe 26 is arranged on the ellipsoidal end cover of the hydrogen collecting cavity, round holes with the same diameter are arranged at the centers of the bottom plate and the ellipsoidal end cover, and stainless steel pipes 27 with the same diameter are welded at the corresponding round hole positions and are used for filling the ammonia decomposition catalyst.
FIG. 2 shows an ammonia decomposition membrane reactor with the following specific steps for hydrogen production and hydrogen purification in an on-site hydrogen production or hydrogenation station:
a. starting a vacuum pump 201, under the condition of vacuum pumping, gradually increasing the output power of the electric heating device through a temperature control device 202, so that the heating cavity is gradually heated to a set temperature (for example, 350-;
b. ammonia gas exchanges heat with high-purity hydrogen separated by a palladium membrane through a heat exchanger 203, enters a heating and catalyzing cavity through an air inlet pipe, and then sequentially passes through uniformly distributed semicircular supporting tube plates which are arranged in an up-and-down staggered manner, so that the gas flows in an S shape, the ammonia gas is heated to the working temperature suitable for ammonia decomposition, enters a catalytic bed layer, and is completely decomposed into a mixed gas of hydrogen and nitrogen under the action of a catalyst;
c. The hydrogen-rich gas mixture enters the hydrogen separation cavity through a pore channel on the wall of the heating and catalyzing 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 passed to the combustor 204 of the hydrogen-producing unit. 2 heating pipes with rated voltage of 12V and rated power of 1000W are arranged in a heating and catalyzing cavity of the membrane separator, 50g of KOH-5 wt.% Ru/MgO ammonia decomposition catalyst is filled between a rear supporting tube plate 16 and a bottom plate 19, 6 palladium/porous stainless steel composite membranes are arranged in a hydrogen separating cavity, the diameter is 6mm, the average thickness is 5 microns, the effective length is 350 mm, when the temperature rise is finished and the temperature preservation stage is started, a temperature thermocouple in the heating cavity displays that the ambient temperature is 450 ℃, the fluctuation is only plus or minus 1 ℃, and the actual power consumption of the electric heating pipes is 400W and is only 40% of the rated power. After ammonia gas is introduced, a temperature measurement thermocouple displays that the temperature of a catalytic bed layer is 435 ℃, mixed gas generated by ammonia decomposition is separated by a palladium membrane to obtain hydrogen with the purity of 99.999 percent, and hydrogen-containing tail gas separated by the palladium membrane enters a combustion chamber of a hydrogen production unit for combustion and then is exhausted; and (4) analyzing the hydrogen-containing tail gas subjected to palladium membrane separation by using gas chromatography, wherein ammonia is not detected, which indicates that ammonia gas is completely converted.
Example 2
3 heating pipes with rated voltage of 24V and rated power of 1500W are arranged in a heating cavity of the membrane separator, 80g of KOH-5 wt.% Ru/CNT ammonia decomposition catalyst is filled between a rear supporting tube plate 16 and a bottom plate 19, 20 palladium-silver/porous stainless steel composite membranes with diameter of 6mm, average thickness of 8 microns and effective length of 350 mm are arranged in a hydrogen separation cavity, when the temperature rise is finished and the hydrogen separation enters a heat preservation stage, a temperature thermocouple in the heating cavity displays that the ambient temperature is 430 ℃, the fluctuation is only plus or minus 1 ℃, and the actual power consumption of the electric heating pipes is 600W and is only 40% of the rated power. After ammonia gas is introduced, measuring the temperature of a thermocouple to display that the temperature of a catalytic bed layer is 420 ℃, separating mixed gas generated by ammonia decomposition by a palladium membrane to obtain hydrogen with the purity of 99.999 percent, and feeding hydrogen-containing tail gas separated by the palladium membrane into a combustion chamber of a hydrogen production unit for combustion and then emptying; and (4) analyzing the hydrogen-containing tail gas subjected to palladium membrane separation by using gas chromatography, wherein ammonia is not detected, which indicates that ammonia gas is completely converted.
Example 3
The method comprises the following steps that 6 heating pipes with rated voltage of 220V and rated power of 3000W are installed in a heating cavity of a membrane separator, 120g of Cs-5 wt.% Ru/active carbon ammonia decomposition catalyst is filled between a rear supporting pipe plate 16 and a bottom plate 19, 30 palladium-ruthenium/porous stainless steel composite membranes are installed 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 a heat preservation stage is started, a temperature thermocouple in the heating cavity displays that the fluctuation of the ambient temperature is 410 ℃ is only plus or minus 1 ℃, and the actual power consumption of the electric heating pipes is 600W and is only 20% of the rated power. After ammonia gas is introduced, measuring the temperature of a thermocouple to display that the temperature of a catalytic bed layer is 390 ℃, separating mixed gas generated by ammonia decomposition by a palladium membrane to obtain hydrogen with the purity of 99.99%, and introducing hydrogen-containing tail gas separated by the palladium membrane into a combustion chamber of a hydrogen production unit for combustion and then emptying; the hydrogen-containing tail gas after palladium membrane separation is analyzed by gas chromatography, and the conversion rate of ammonia gas is 99%.
Claims (10)
1. An ammonia decomposition membrane reactor 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 catalysis cavity bottom plate (19) 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 catalysis cavity bottom plate (19), the left side is a hydrogen collection cavity (6), the right side is a hydrogen separation cavity (5), a hydrogen outlet pipe (26) is arranged on the side wall of the hydrogen collection cavity (6), a tail gas pipe (24) is arranged on the side wall of the hydrogen separation cavity close to the open end of the container, an inner pipe (18) which is used as a heating cavity and is provided with an opening at the left end and the right end is arranged in the hydrogen separation cavity, and the open end of the container is hermetically connected with the outer wall surface of the inner pipe;
a second flange (3) is arranged on the outer side wall surface of the right opening end of the inner tube extending out of the container, the right opening end of the inner tube is sealed by a first flange (2) fixedly connected with the second flange, an air inlet pipe (22) is arranged on the side wall surface of the inner tube between the container and the second flange, the left opening end of the inner tube is hermetically connected with a catalytic cavity bottom plate (19), and a through hole is arranged on the side wall surface of the inner tube close to the catalytic cavity bottom plate and is used as a gas circulation pore channel (20);
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 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 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 (21) 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 (21) is closed, the other end of the tubular palladium and/or palladium alloy composite membrane is open, and the open end penetrates through the bottom plate (19) of the catalysis cavity and extends into the hydrogen collection cavity (6);
a supporting tube plate (16) with a ventilation through hole is vertically arranged in the heating cavity to divide the heating cavity into a left cavity and a right cavity, an ammonia decomposition catalyst (17) is filled between the supporting tube plate and a catalysis cavity bottom plate (19) to serve as a heating and catalysis cavity (4), and a stainless steel tube (27) used for communicating the heating and catalysis cavity (4) with the outside is arranged on the catalysis cavity bottom plate on the left side of the heating and catalysis cavity (4).
2. The ammonia decomposition membrane reactor of claim 1 wherein: the explosion-proof cavity is internally provided with an electric heating device wiring terminal and a thermocouple wiring terminal; the electric heating device and the thermocouple are respectively connected with a wiring terminal (7) of the electric heating device and a wiring terminal (8) of the thermocouple in the explosion-proof cavity;
the side wall of the explosion-proof cavity (1) is provided with a heating wiring tube (14) for penetrating a wiring end (7) of a lead connected with an electric heating device and a wiring end (8) of a temperature control and measurement thermocouple wiring tube (15) for penetrating a lead connected with a temperature control and measurement thermocouple.
3. The ammonia decomposition membrane reactor of claim 1 wherein: the first flange and the explosion-proof cavity are fixedly welded through a group of sleeves; the second flange is fixedly connected with the heating and catalyzing 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 ammonia decomposition membrane reactor of claim 1 wherein: an electric heating device (12), an ammonia decomposition catalyst (17), and a support tube plate which is uniformly distributed, is provided with a semicircular electric heating device in an up-down staggered arrangement and a thermocouple penetrating through a through hole are arranged in the heating and catalyzing cavity (4); a second flange, a first flange and a group of sleeves are arranged between the heating and catalyzing cavity and the explosion-proof cavity
(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 and catalyzing cavity from the explosion-proof cavity through the sleeve, the heating wire penetrates into the wiring end connected with the electric heating device through the heating wiring pipe of the explosion-proof cavity, and the temperature control and measurement wire penetrates into the wiring end connected with the thermocouple through the thermocouple wiring pipe of the explosion-proof cavity;
a plurality of supporting tube plates which are uniformly distributed and provided with electric heating devices and thermocouples penetrate through the through holes are arranged outside the electric heating devices and the thermocouples, the supporting tube plate close to the flange is circular, the supporting tube plates at the front part and the middle part of the electric heating tube close to 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, the supporting tube plate close to the rear part of the flange is circular, sieve holes with the diameter of 0.5-1.0mm are distributed, and ammonia decomposition catalysts are filled between the rear supporting tube plate and the bottom plate of the heating and catalyzing cavity;
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).
5. The ammonia decomposition membrane reactor of claim 1 wherein: the hydrogen separation cavity is positioned at the outer side of the heating and catalyzing cavity, is of a sleeve type structure, is connected with the extension of the bottom plate of the heating and catalyzing cavity in a welding mode, is connected with the outer wall of the heating and catalyzing cavity in a welding mode, a gas circulation pore channel is arranged on the wall of the heating and catalyzing cavity close to the bottom plate, the hydrogen separation cavity is communicated with the heating and catalyzing cavity through the pore channel, and the number of the pore channels can be 1 or more; and a tubular palladium and alloy composite membrane thereof 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 manner.
6. The ammonia decomposition membrane reactor of claim 1 wherein: the hydrogen collecting cavity is formed by fixedly welding an ellipsoidal end cover and the outer edge of a bottom plate, a hydrogen outlet pipe is arranged on the ellipsoidal end cover of the hydrogen collecting cavity, round holes with the same diameter are arranged at the centers of the bottom plate and the ellipsoidal end cover, and a stainless steel pipe with the same diameter is welded at the corresponding round hole position and is used for filling the ammonia decomposition catalyst.
7. The ammonia decomposition membrane reactor of claim 1 wherein: the electric heating device is a heating pipe, and the number of the heating pipes is 1 or more.
8. The ammonia decomposition membrane reactor of claim 1 wherein: the ammonia decomposition catalyst is a metal ruthenium-based catalyst, the active component is ruthenium, the carrier is one or more than two of magnesium oxide, active carbon and carbon nano tubes, wherein promoters can be added or not added, and the promoters are one or more than two of alkali metal oxide, cesium and potassium.
9. The ammonia decomposition membrane reactor of claim 1 wherein: 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.
10. Use of an ammonia decomposition membrane reactor according to any of claims 1-9 in the decomposition of ammonia to produce hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911232150.4A CN112919407B (en) | 2019-12-05 | 2019-12-05 | Ammonia decomposition membrane reactor and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911232150.4A CN112919407B (en) | 2019-12-05 | 2019-12-05 | Ammonia decomposition membrane reactor and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112919407A CN112919407A (en) | 2021-06-08 |
| CN112919407B true CN112919407B (en) | 2022-06-28 |
Family
ID=76161072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911232150.4A Active CN112919407B (en) | 2019-12-05 | 2019-12-05 | Ammonia decomposition membrane reactor and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112919407B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112919411B (en) * | 2019-12-05 | 2022-09-27 | 中国科学院大连化学物理研究所 | Membrane separator with heating and hydrogen separation functions |
| CN115010087B (en) * | 2022-08-08 | 2022-11-11 | 浙江百能科技有限公司 | HI decomposition hydrogen production membrane reactor and hydrogen production method and system thereof |
| CN115650159B (en) * | 2022-08-15 | 2024-01-26 | 南京工业大学 | Membrane coupling ammonia decomposition hydrogen production device and technology |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0015428A1 (en) * | 1979-02-15 | 1980-09-17 | Eugene Farrell Hill | Process and apparatus for separating hydrogen from fluids |
| CN101208264A (en) * | 2005-06-28 | 2008-06-25 | 赫多特普索化工设备公司 | Compact reforming reactor |
| CN103269765A (en) * | 2010-10-11 | 2013-08-28 | 伊达科技公司 | Systems and methods for maintaining hydrogen-selective membranes during periods of inactivity |
| CN203610022U (en) * | 2013-11-21 | 2014-05-28 | 中国科学院大连化学物理研究所 | Metal palladium or palladium alloy composite membrane hydrogen purifier |
| CN105698391A (en) * | 2016-01-27 | 2016-06-22 | 江苏亿能电气有限公司 | Thermal insulation energy-saving type anti-explosion electric heater |
| CN107585741A (en) * | 2017-09-30 | 2018-01-16 | 西北有色金属研究院 | A kind of ultra-pure hydrogen separator |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7989511B2 (en) * | 2008-05-21 | 2011-08-02 | Texaco Inc. | Process and apparatus for synthesis gas and hydrocarbon production |
-
2019
- 2019-12-05 CN CN201911232150.4A patent/CN112919407B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0015428A1 (en) * | 1979-02-15 | 1980-09-17 | Eugene Farrell Hill | Process and apparatus for separating hydrogen from fluids |
| CN101208264A (en) * | 2005-06-28 | 2008-06-25 | 赫多特普索化工设备公司 | Compact reforming reactor |
| CN103269765A (en) * | 2010-10-11 | 2013-08-28 | 伊达科技公司 | Systems and methods for maintaining hydrogen-selective membranes during periods of inactivity |
| CN203610022U (en) * | 2013-11-21 | 2014-05-28 | 中国科学院大连化学物理研究所 | Metal palladium or palladium alloy composite membrane hydrogen purifier |
| CN105698391A (en) * | 2016-01-27 | 2016-06-22 | 江苏亿能电气有限公司 | Thermal insulation energy-saving type anti-explosion electric heater |
| CN107585741A (en) * | 2017-09-30 | 2018-01-16 | 西北有色金属研究院 | A kind of ultra-pure hydrogen separator |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112919407A (en) | 2021-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112919407B (en) | Ammonia decomposition membrane reactor and application | |
| Nguyen et al. | Recent developments in the design of photoreactors for solar energy conversion from water splitting and CO2 reduction | |
| CN109399561B (en) | Online hydrogen production system and method | |
| CN100417588C (en) | Process of preparing high purity hydrogen with liquid hydrocarbon in a palladium film reactor | |
| CN108854928B (en) | Preparation method of double-effect compact ceramic membrane reactor for ammonia decomposition hydrogen production reaction and separation | |
| CN209418658U (en) | A kind of liquefied ammonia hydrogen-generating fuel cell device and automobile | |
| CN101172575A (en) | Integral minitype reactor for manufacturing hydrogen with ammonia decomposition | |
| CN102674247B (en) | A kind of method of decarburization and the dual forced methane steam reforming hydrogen manufacturing of dehydrogenation and device | |
| CN111676484A (en) | Method and system for reducing energy consumption, electrolyzing water, producing hydrogen and symbiotically producing value-added chemicals | |
| CN101148249A (en) | On-site hydrogen producing method and on-site hydrogen producing device | |
| CN101295795B (en) | Alkane cracking and fuel cell compound power generation system | |
| RU2638350C1 (en) | Integrated membrane-catalytic reactor and coproduction method of synthesis gas and ultrapure hydrogen | |
| CN218755051U (en) | System for directly synthesizing green ammonia by electrolyzing water to produce hydrogen by using renewable energy sources | |
| CN103159297B (en) | Hydrogen-production and on-line separation device for decomposing water by optical electrolytic cell | |
| CN114132896A (en) | Device and method for preparing hydrogen by oxidizing and reforming ethanol | |
| CN115432666A (en) | Self-heating ammonia decomposition hydrogen production device | |
| CN212467646U (en) | Membrane separation assembly for hydrogen separation | |
| KR102168018B1 (en) | Fuel cell system associated with a fuel reformer that additionally performs methanation | |
| CN111101146B (en) | H2/CO2Separation from CO2Hydrogenation self-coupling method | |
| CN113880046A (en) | Hydrogen production reactor device with gas replacement and high-efficiency methane cracking carrier | |
| CN112919411B (en) | Membrane separator with heating and hydrogen separation functions | |
| CN113457684A (en) | Non-supported methanol reforming hydrogen production catalyst and preparation method and application thereof | |
| Liang et al. | Promotion effects of different methods in CO x-free hydrogen production from ammonia decomposition | |
| CN216336599U (en) | Device for producing hydrogen by oxidizing and reforming ethanol | |
| CN217881590U (en) | Hydrogen fuel cell system combining methanol reforming and solid oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230830 Address after: D101A-132, 1st Floor, B-2 Building, Zhongguancun Dongsheng Science and Technology Park, No. 66 Xixiaokou Road, Haidian District, Beijing, 100192 Patentee after: Beijing Zhongke Meian Technology Co.,Ltd. Address before: 116023 No. 457-41 Zhongshan Road, Shahekou District, Dalian City, Liaoning Province Patentee before: DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES |
|
| TR01 | Transfer of patent right |