CN107324281B - Quick-start self-heating type methanol reforming hydrogen production micro-reactor - Google Patents
Quick-start self-heating type methanol reforming hydrogen production micro-reactor Download PDFInfo
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- CN107324281B CN107324281B CN201710567730.3A CN201710567730A CN107324281B CN 107324281 B CN107324281 B CN 107324281B CN 201710567730 A CN201710567730 A CN 201710567730A CN 107324281 B CN107324281 B CN 107324281B
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 738
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 125
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000001257 hydrogen Substances 0.000 title claims abstract description 124
- 238000002407 reforming Methods 0.000 title claims abstract description 111
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 96
- 238000010438 heat treatment Methods 0.000 title claims abstract description 12
- 238000002485 combustion reaction Methods 0.000 claims abstract description 194
- 239000000446 fuel Substances 0.000 claims abstract description 58
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 238000007084 catalytic combustion reaction Methods 0.000 claims abstract description 20
- 238000007789 sealing Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims description 56
- 239000010935 stainless steel Substances 0.000 claims description 49
- 229910001220 stainless steel Inorganic materials 0.000 claims description 49
- 239000000567 combustion gas Substances 0.000 claims description 27
- 229910000838 Al alloy Inorganic materials 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000007789 gas Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 2
- 239000008358 core component Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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
- C01B3/32—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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN A CARRIER GAS OR AIR
- F23C13/00—Apparatus in which combustion takes place in the presence of catalytic material
-
- 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
-
- 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
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
-
- 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
- C01B2203/16—Controlling the process
- C01B2203/169—Controlling the feed
-
- 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
- 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
- Y02E60/50—Fuel cells
Abstract
The invention discloses a rapid starting self-heating methanol reforming hydrogen production microreactor which is formed by sealing and assembling a cover plate assembly, a reforming hydrogen production plate, a first methanol combustion plate, a methanol combustion porous plate and a second methanol combustion plate in sequence from top to bottom. A methanol reforming cavity is arranged on the reforming hydrogen production plate, and a reforming catalyst is loaded and used for preparing hydrogen through methanol reforming; a methanol catalytic combustion cavity is arranged in the first methanol combustion plate, and a combustion catalyst is loaded and used for supplying heat for methanol combustion; the self-heating operation of the micro-reactor is realized by providing energy for the hydrogen production by methanol reforming through methanol combustion. The invention supplies the combustion fuel methanol and air separately, improves the air inflow of the combustion channel and the service efficiency of the catalyst, and reduces the starting time of the micro-reactor. The invention has the advantages of short starting time, compact structure, high energy density, high hydrogen production efficiency, low manufacturing cost and easy assembly of the whole structure, and can directly supply hydrogen to the hydrogen fuel cell for the occasion of hydrogen production by reforming the medium-flow and low-flow methanol.
Description
Technical Field
The invention relates to an autothermal methanol hydrogen production micro-reactor, in particular to a rapid starting autothermal methanol reforming hydrogen production micro-reactor.
Technical Field
The hydrogen fuel cell has the advantages of compact structure, high energy conversion efficiency, low pollution discharge and the like, and has wide application prospect in vehicles such as automobiles, ships and the like. However, the hydrogen gas required for the hydrogen fuel cell is a secondary energy source, and energy needs to be converted by other energy sources. An effective way is to supply hydrogen by adopting an on-site reforming hydrogen production mode, namely, adopting an autothermal methanol reforming hydrogen production micro-reactor to perform on-site reforming hydrogen production and supplying hydrogen for a hydrogen fuel cell. Because the liquid fuel similar to gasoline is adopted, the on-site reforming hydrogen production mode has no defect of a direct hydrogen supply mode of a high-pressure hydrogen storage tank, and a new idea is provided for the large-scale application of the hydrogen fuel cell automobile.
Aiming at the defects of large structural size, low volume energy efficiency and the like of the conventional self-heating type methanol reforming hydrogen production micro-reactor. Chinese patent application No. 180818079472.0 discloses a stacked autothermal reformer. The reformer integrates an endothermic reaction chip and an exothermic reaction chip and adopts half-positioning pin holes for positioning. The reformer has simple and compact structure, easy expansion of structural form and convenient installation. However, the reaction carrier of the reformer has high manufacturing cost, low efficiency and long starting time;
in order to reduce the manufacturing cost and improve the reaction efficiency, chinese patent application No. 180910100100.0 discloses an autothermal methanol reforming hydrogen production microchannel reformer with a micro-boss array structure. The reformer comprises a catalytic reforming hydrogen production channel and a combustion channel, and heat required by reforming hydrogen production is provided by the combustion channel, so that the autothermal operation of the reformer is realized. By adopting the micro-boss array structure as a reaction carrier, the energy efficiency of the reformer is further improved. However, this reactor also has a problem of long start-up time.
Although the energy efficiency of the autothermal methanol reforming hydrogen-producing microreactor is greatly improved by the efforts of researchers in various countries. The micro reactor for hydrogen production by autothermal methanol reforming needs a certain temperature (about 230 ℃). Therefore, to enable the microreactor to rapidly realize hydrogen production operation and meet the starting requirement of a hydrogen fuel cell automobile, the microreactor needs to be rapidly heated to the working temperature. At present, the heat supply of the self-heating type methanol reforming hydrogen production micro-reactor is mainly realized by the catalytic combustion of fuel methanol and air in a combustion channel. In terms of energy conservation, a large inlet flow of combustion fuel (methanol/air) is required in order to achieve a rapid temperature rise of the microreactor. While a large combustion fuel inlet flow will blow off the combustion catalyst on the one hand, causing the microreactor to become plugged; on the other hand, when the fuel is burned by the large-flow inlet and the catalyst are in contact, a great amount of heat released by severe catalytic combustion can cause the local temperature of the microreactor to be too high, influence the service life of the catalyst and even cause the burning catalyst to fail. For the above reasons, the existing autothermal methanol reforming hydrogen production micro-reactor generally has the problem of long start-up time, which restricts the large-scale application of the reactor. Therefore, it is necessary to invent an autothermal methanol reforming hydrogen production reactor which can be started up quickly, has a compact structure, high energy density, and low manufacturing cost, and can directly supply hydrogen to a hydrogen fuel cell.
Disclosure of Invention
The invention aims to provide a micro-reactor for quickly starting self-heating methanol reforming hydrogen production. The reactor supplies combustion fuel methanol and air separately. Since the combustion fuel methanol and air flow in two separate channels, the gas flow rate when the fuel contacts the catalyst is reduced, which increases the supply of methanol and air and increases the start-up rate of the microreactor. In addition, the air and the methanol are contacted in sections when the gas flows in the reaction channel, so that the problems of large quantity of inlet fuel, local high temperature caused by severe reaction and the like can be avoided, the temperature of the combustion channel of the micro-reactor can be homogenized, the combustion efficiency is improved, and the service life of the catalyst is prolonged. In addition, the reforming hydrogen production plate of the reactor is provided with a staggered non-uniformly distributed micro-boss array structure with high heat and mass transfer efficiency, so that the hydrogen production efficiency of the micro-reactor can be effectively improved. The invention has the advantages of short starting time, compact structure, high energy density, high hydrogen production efficiency, low manufacturing cost and easy assembly of the whole structure, and can be used as a hydrogen source in the occasion of supplying hydrogen with medium and small flow.
The technical scheme adopted by the invention is as follows:
the self-heating methanol reforming hydrogen production microreactor is formed by sealing and assembling a cover plate assembly, a reforming hydrogen production plate, a first methanol combustion plate, a methanol combustion porous plate and a second methanol combustion plate from top to bottom in sequence; the cover plate assembly is used for reforming the hydrogen production plate, the first methanol combustion plate, the methanol combustion porous plate and the second methanol combustion plate are respectively rectangular structures with equal sizes; wherein:
the cover plate assembly comprises a rectangular upper cover plate, and a reforming fuel inlet stainless steel pipe, a reforming fuel outlet stainless steel pipe, a methanol inlet stainless steel pipe, an air inlet stainless steel pipe and a combustion gas outlet stainless steel pipe are arranged on the rectangular upper cover plate;
the reforming hydrogen production plate is provided with a parallelogram groove serving as a methanol reforming cavity, a micro boss is arranged at a rectangular position in the middle of the parallelogram groove, a methanol reforming hydrogen production catalyst is loaded on the micro boss, and first triangular fluid distribution cavities are symmetrically arranged on the parallelogram groove by taking two sides of the micro boss positioned at the rectangular position as the center; the reforming hydrogen production plate is also provided with a first combustion raw material air inlet hole, a first combustion raw material methanol inlet hole and a combustion gas outlet hole; the reformed fuel outlet stainless steel pipe is correspondingly arranged with the parallelogram groove; the first combustion raw material air inlet hole is formed in a position corresponding to the stainless steel pipe with the air inlet; the first combustion raw material methanol inlet hole is correspondingly formed in the position of the methanol inlet stainless steel pipe; the combustion gas outlet hole is correspondingly formed in the position of the stainless steel tube at the combustion gas outlet; the reforming fuel inlet stainless steel pipe, the parallelogram groove and the reforming fuel outlet stainless steel pipe are communicated to form a reforming fuel flow channel;
the first methanol combustion plate is provided with a parallelogram through groove serving as a methanol catalytic combustion cavity, and the direction of the parallelogram through groove arranged on the first methanol combustion plate is exactly opposite to the direction of the parallelogram groove arranged on the reforming hydrogen production plate; the first methanol combustion plate is also provided with a second combustion raw material methanol inlet hole, and the second combustion raw material methanol inlet hole is correspondingly arranged with the first combustion raw material methanol inlet hole; the first combustion raw material air inlet hole and the combustion gas outlet hole are formed corresponding to the positions in the parallelogram through groove; the air inlet stainless steel tube, the first combustion raw material air inlet hole, the parallelogram through groove on the first methanol combustion plate, the combustion gas outlet hole and the combustion gas outlet stainless steel tube are communicated to form a combustion raw material air flow channel;
circular through holes distributed in an array are formed in the middle of the methanol combustion porous plate; the circular through holes are correspondingly formed in the positions of the parallelogram through grooves on the first methanol combustion plate; the upper surface of the round through hole is sintered with a thin layer of methanol catalytic combustion catalyst; the methanol combustion porous plate is also provided with a third combustion raw material methanol inlet hole, and the position of the third combustion raw material methanol inlet hole is correspondingly provided with that of the second combustion raw material methanol inlet hole;
a micro-channel is arranged in the middle of the second methanol combustion plate, and a second triangular fluid distribution cavity is arranged on the second methanol combustion plate at one side of the micro-channel; the micro-channel is communicated with the second triangular fluid distribution cavity; the micro-channel on the second methanol combustion plate is correspondingly arranged with the circular through hole on the methanol combustion porous plate; the methanol inlet stainless steel pipe, the first combustion raw material methanol inlet hole, the second combustion raw material methanol inlet hole, the third combustion raw material methanol inlet hole, the second triangular fluid distribution cavity on the second methanol combustion plate, the micro-channel on the second methanol combustion plate, the circular through holes on the methanol combustion porous plate, the parallelogram through grooves on the first methanol combustion plate, the combustion gas outlet hole and the combustion gas outlet stainless steel pipe are communicated to form a combustion raw material methanol flow channel.
The reforming hydrogen production plate is provided with cylindrical micro-bosses with consistent structures, the micro-bosses are distributed in staggered mode, and the number of the micro-bosses in odd columns is the same and the number of the micro-bosses in even columns is the same.
The micro-boss is loaded with a copper-based catalyst Cu/ZnO/Al 2 O 3 Or noble metal palladium-based catalyst Pd/Al 2 O 3 。
The upper surface of the round through hole is sintered with a platinum-based catalyst Pt/Al 2 O 3 A thin layer.
The width of the micro-channel on the second methanol combustion plate is larger than the aperture of the circular through hole on the methanol combustion porous plate.
The reforming hydrogen production plate is a common aluminum alloy reforming hydrogen production plate, the first methanol combustion plate is a common aluminum alloy first methanol combustion plate, the methanol combustion porous plate is a common aluminum alloy methanol combustion porous plate, and the second methanol combustion plate is a common aluminum alloy second methanol combustion plate.
The cover plate assembly is used for reforming the hydrogen production plate, the first methanol combustion plate, the methanol combustion porous plate and the second methanol combustion plate are assembled in a sealing mode.
The invention has the beneficial effects that:
1) The combustion fuel methanol and air are separately supplied by improving the micro-reactor structure. Since the combustion fuel methanol and air flow in two separate channels, the gas flow rate when the fuel contacts the catalyst is reduced, which increases the supply of methanol and air and increases the start-up rate of the microreactor.
2) Because the air and the methanol are contacted in sections when the gas flows in the reaction channel, the problems of large quantity of inlet fuel, local high temperature caused by severe reaction and the like can be avoided, the temperature of the combustion channel of the micro-reactor can be homogenized, the combustion efficiency is improved, and the service life of the catalyst is prolonged.
3) The reforming hydrogen production plate of the micro-reactor is provided with the staggered non-uniformly distributed micro-boss array structure with high heat and mass transfer efficiency, so that the hydrogen production efficiency of the micro-reactor can be effectively improved. Compared with the parallel and staggered micro-boss array structures, the staggered non-uniformly distributed micro-boss array structure can further improve the residence time of fuel in the micro-reactor and improve the heat and mass transfer performance of the micro-reactor, thereby improving the efficiency of the micro-reactor.
4) The core components (the reforming hydrogen production plate and the second methanol combustion plate) of the microreactor can be processed by adopting a semi-solid micro thixotropic forming process, and the micro-reactor has high manufacturing efficiency and low processing cost.
5) The micro-reactor has compact structure and can be used for the occasion of hydrogen production with medium and small power. And the scale is easy to expand, and the hydrogen yield can be expanded only by stacking a plurality of reactors and designing an inlet flow channel.
Drawings
FIG. 1 is a schematic view of the overall structure of the present invention;
FIG. 2 is an enlarged schematic view of the structure of the cover plate assembly of FIG. 1;
FIG. 3 is an enlarged schematic view of the structure of the reforming plate of FIG. 1;
FIG. 4 is an enlarged schematic view of the structure of the first methanol combustion plate of FIG. 1;
FIG. 5 is an enlarged schematic view of the structure of the methanol combustion perforated plate in FIG. 1;
FIG. 6 is an enlarged schematic view of the structure of the second methanol combustion plate of FIG. 1;
FIG. 7 is a cross-sectional view A-A of FIG. 6;
fig. 8 is a schematic diagram of the hydrogen production operation of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and examples.
The fast starting self-heating methanol reforming hydrogen production micro-reactor is formed by sealing and assembling a cover plate assembly 1, a reforming hydrogen production plate 2, a first methanol combustion plate 3, a methanol combustion porous plate 4 and a second methanol combustion plate 5 in sequence from top to bottom as shown in fig. 1-7; the cover plate assembly 1, the reforming hydrogen production plate 2, the first methanol combustion plate 3, the methanol combustion porous plate 4 and the second methanol combustion plate 5 are respectively rectangular structures with equal sizes; wherein:
the cover plate assembly 1 comprises a rectangular upper cover plate 6, wherein a reforming fuel inlet stainless steel pipe 7, a reforming fuel outlet stainless steel pipe 8, a methanol inlet stainless steel pipe 9, an air inlet stainless steel pipe 10 and a combustion gas outlet stainless steel pipe 11 are arranged on the rectangular upper cover plate 6; the inner and outer diameters of the non-repaired steel pipes are the same, and the non-repaired steel pipes are connected and sealed with the rectangular upper cover plate 6 by adopting an argon arc welding method.
The reforming hydrogen production plate 2 is provided with parallelogram grooves 17 serving as methanol reforming cavities, cylindrical micro-bosses 18 are arranged in rectangular positions in the middle of the parallelogram grooves 17, the micro-bosses 18 are distributed in staggered mode, the micro-bosses 18 in odd columns are identical in number, and the micro-bosses 18 in even columns are identical in number. The cylindrical micro-boss 18 is loaded with a catalyst for preparing hydrogen by reforming methanol, wherein the catalyst for preparing hydrogen by reforming methanol in the embodiment adopts a copper-based catalyst or a noble metal catalyst, and the parallelogram groove 17 is symmetrically provided with first triangular fluid distribution cavities 19 for homogenizing methanol reforming hydrogen fuel (methanol/water mixed solution) by taking two sides of the cylindrical micro-boss 18 positioned on a rectangular position as centers; the reforming hydrogen production plate 2 is also provided with a first combustion raw material air inlet hole 12, a first combustion raw material methanol inlet hole 13 and a combustion gas outlet hole 14; the reforming fuel inlet stainless steel pipe 7, the reforming fuel outlet stainless steel pipe 8 and the parallelogram groove 17 are correspondingly arranged in position; the first combustion raw material air inlet hole 12 is correspondingly formed in the position of the air inlet stainless steel pipe 10; the first combustion raw material methanol inlet hole 13 is correspondingly formed in the position of the methanol inlet stainless steel pipe 9; the combustion gas outlet hole 14 is arranged corresponding to the position of the stainless steel tube 11 at the combustion gas outlet; the reforming fuel inlet stainless steel pipe 7, the parallelogram groove 17 and the reforming fuel outlet stainless steel pipe 8 are communicated to form a reforming fuel flow passage; the methanol/water mixed solution of the methanol reforming fuel flows into the reforming fuel flow channel and contacts with the methanol reforming hydrogen production catalyst to generate methanol reforming hydrogen production reaction, so as to prepare hydrogen.
The first methanol combustion plate 3 is provided with a parallelogram through groove 20 serving as a methanol catalytic combustion cavity, and the direction of the parallelogram through groove 20 arranged on the first methanol combustion plate 3 is exactly opposite to the direction of the parallelogram groove 17 arranged on the reforming hydrogen production plate 2; the first methanol combustion plate 3 is also provided with a second combustion raw material methanol inlet hole 15, and the second combustion raw material methanol inlet hole 15 is correspondingly arranged with the first combustion raw material methanol inlet hole 13; the first combustion raw material air inlet hole 12 and the combustion gas outlet hole 14 are respectively arranged corresponding to the positions in the parallelogram through groove 20; the air inlet stainless steel pipe 10, the first combustion raw material air inlet hole 12, the parallelogram-shaped through groove 20 on the first methanol combustion plate 3, the combustion gas outlet hole 14 and the combustion gas outlet stainless steel pipe 11 are communicated to form a combustion raw material air flow passage.
The middle of the methanol combustion porous plate 4 is provided with circular through holes 21 distributed in an array manner, the circular through holes 21 are correspondingly arranged with the parallelogram through grooves 20 on the first methanol combustion plate 3, a thin layer of methanol catalytic combustion catalyst (such as a platinum-based catalyst) is sintered on the upper surface of the circular through holes 21, and the combustion catalyst is of a porous structure and cannot block the circular through holes 21; the methanol combustion porous plate 4 is also provided with a third combustion raw material methanol inlet hole 16, and the position of the third combustion raw material methanol inlet hole 16 is correspondingly provided with the position of the second combustion raw material methanol inlet hole 15.
A micro-channel 22 is arranged in the middle of the second methanol combustion plate 5, and a second triangular fluid distribution cavity 23 is arranged on the second methanol combustion plate 5 at one side of the micro-channel 22 and used for homogenizing the flow velocity of methanol in the micro-channel 22 and improving the utilization efficiency of the methanol; and the micro-channel 22 is communicated with the second triangular fluid distribution cavity 23; the micro-channel 22 on the second methanol combustion plate 5 is correspondingly arranged with the circular through hole 21 on the methanol combustion porous plate 4, and the width of the micro-channel 22 is larger than the aperture of the circular through hole 21 on the methanol combustion porous plate 4; the methanol inlet stainless steel pipe 9, the first combustion raw material methanol inlet hole 13, the second combustion raw material methanol inlet hole 15, the third combustion raw material methanol inlet hole 16, the second triangular fluid distribution cavity 23 on the second methanol combustion plate 5, the micro-channel 22 on the second methanol combustion plate 5, the circular through holes 21 on the methanol combustion porous plate 4, the parallelogram through groove 20 on the first methanol combustion plate 3, the combustion gas outlet hole 14 and the combustion gas outlet stainless steel pipe 11 are communicated to form a combustion raw material methanol flow channel.
The reforming hydrogen production plate 2 is a common aluminum alloy reforming hydrogen production plate, the first methanol combustion plate 3 is a common aluminum alloy first methanol combustion plate, the methanol combustion porous plate 4 is a common aluminum alloy methanol combustion porous plate, and the second methanol combustion plate 5 is a common aluminum alloy second methanol combustion plate.
The cover plate assembly 1, the reforming hydrogen production plate 2, the first methanol combustion plate 3, the methanol combustion porous plate 4 and the second methanol combustion plate 5 are assembled in a sealing way in a welding way; the compactness and the tightness of the reforming hydrogen production reactor are improved.
The reforming hydrogen production plate 2 and the second methanol combustion plate 5 have low machining efficiency due to the complex structure and the microstructure, so that the reforming hydrogen production plate can be manufactured by adopting a semi-solid micro thixotropic forming technology; the remaining sheets may be manufactured using conventional machining techniques.
In the self-heating type methanol reforming hydrogen production micro-reactor for quick start of the embodiment, a methanol reforming hydrogen production reaction is carried out in a methanol steam reforming hydrogen production reaction cavity formed by a cover plate assembly 1 and a reforming hydrogen production plate 2, so that hydrogen-rich reformed gas is prepared. The methanol catalytic combustion reaction is carried out in a methanol catalytic combustion cavity formed by the reforming hydrogen production plate 2, the first methanol combustion plate 3 and the methanol combustion porous plate 4, and heat is provided for the operation of the reactor. The methanol steam reforming hydrogen production performed in the methanol reforming hydrogen production reaction chamber includes three reactions, as follows:
CH 3 OH+H 2 O→3H 2 +CO 2 ，
CO 2 +H 2 →CO+H 2 O，
CH 3 OH→2H 2 +CO。
the fuel combustion process performed in the methanol catalytic combustion chamber includes a reaction as follows:
CH 3 OH+1.5O 2 →2H 2 O+CO 2 。
the reforming hydrogen production catalyst loaded on the micro-boss 18 array of the reforming hydrogen production plate 2 can be a copper-based catalyst Cu/ZnO/Al 2 O 3 Or noble metal palladium based catalyst Pd/Al 2 O 3 Is used for preparing hydrogen by reforming methanol and steam.
The methanol catalytic combustion chamber is internally loaded with a platinum-based catalyst Pt/Al 2 O 3 The catalyst is used for catalytic combustion of methanol.
The working principle of the invention is as follows:
fig. 8 is a schematic diagram of a hydrogen production process of the instant start-up autothermal methanol reforming hydrogen production microreactor according to this embodiment. Before the hydrogen production reaction starts, nitrogen as a protective gas is introduced into the microreactor to remove residual air in the channel. The flow of nitrogen is controlled by a mass flow meter. Then, air is introduced into the combustion raw material air flow path of the microreactor by an air pump, and methanol liquid is introduced into the combustion raw material methanol flow path by a flow pump. Air flows into the methanol catalytic combustion chamber through the air inlet stainless steel tube 10, the first combustion feed air inlet port 12. The combustion fuel methanol passes through the methanol inlet stainless steel pipe 9, the first combustion raw material methanol inlet hole 13 and the second combustion raw material methanol inlet hole 15The third combustion raw material methanol inlet holes 16 flow into the micro-channels 22 of the second methanol combustion plate 5, and then flow into the methanol catalytic combustion chamber through the array of circular through holes 21 of the methanol combustion porous plate 4 above the micro-channels 22. After contacting methanol and air, catalytic combustion reaction is carried out (the products after combustion are carbon dioxide, water and the like) so as to provide heat for the reactor. Heating the microreactor to 230 ℃ by utilizing heat generated by catalytic combustion; when the temperature of the reactor is raised to 230 ℃, H-containing materials are introduced into the microreactor 2 N with volume fraction of 5% 2 /H 2 And reducing the catalyst for preparing hydrogen by reforming methanol by the mixed gas. After the first reduction of the micro-reactor is completed, the micro-reactor can always carry out reforming hydrogen production reaction. In the absence of external air oxidation, no further reduction is necessary.
When the micro-reactor needs to operate for reforming hydrogen production, the flow of the methanol fuel inlet of the methanol catalytic combustion cavity is regulated, and the temperature of the reactor is quickly increased and regulated to the reaction temperature for reforming hydrogen production. Then, the reformed fuel (such as mixed solution of methanol and water) is pumped into a reformed fuel flow channel of the microreactor under the drive of a power source such as a pump, and the reformed fuel flow channel is subjected to a methanol reforming hydrogen production reaction process to prepare gases such as hydrogen, carbon dioxide, carbon monoxide and the like. In the hydrogen production process, the temperature of the microreactor is controlled by a thermocouple and a temperature controller, the flow of the reformed fuel is controlled by a flow pump or a liquid flowmeter, and the pressure in the hydrogen production process is monitored by a pressure transmitter.
The invention can be used as medium and small hydrogen production equipment and applied to a mobile hydrogen fuel cell hydrogen source.
This embodiment separately supplies the combustion fuel methanol and air by improving the micro-reactor structure. Since the combustion fuel methanol and air flow in two separate channels, the gas flow rate when the fuel contacts the catalyst is reduced, which increases the supply of methanol and air and increases the start-up rate of the microreactor. Secondly, because the air and the methanol are contacted in sections when the gas flows in the reaction channel in the embodiment, the problems of large quantity of inlet fuel, local high temperature caused by severe reaction and the like can be avoided, the temperature of the combustion channel of the micro-reactor can be homogenized, and the combustion efficiency and the service life of the catalyst are improved. The micro-reactor of the third embodiment is provided with a staggered non-uniformly distributed micro-boss array structure with high heat and mass transfer efficiency, so that the hydrogen production efficiency of the micro-reactor can be effectively improved. Compared with the parallel and staggered micro-boss array structures, the staggered non-uniformly distributed micro-boss array structure can further improve the residence time of fuel in the micro-reactor and improve the heat and mass transfer performance of the micro-reactor, thereby improving the efficiency of the micro-reactor. The core components (the catalytic combustion plate and the second methanol combustion plate) of the microreactor of the fourth embodiment can be processed by adopting a semi-solid micro-thixoforming process, so that the manufacturing efficiency is high and the processing cost is low. The fifth embodiment has compact structure and can be used in the occasions of medium and low power hydrogen production. And the scale is easy to expand, and the hydrogen yield can be expanded only by stacking a plurality of reactors and designing an inlet flow channel.
Claims (7)
1. A fast start self-heating methanol reforming hydrogen production micro-reactor is characterized in that: the device is formed by sealing and assembling a cover plate assembly (1), a reforming hydrogen production plate (2), a first methanol combustion plate (3), a methanol combustion porous plate (4) and a second methanol combustion plate (5) from top to bottom in sequence; the cover plate assembly (1), the reforming hydrogen production plate (2), the first methanol combustion plate (3), the methanol combustion porous plate (4) and the second methanol combustion plate (5) are respectively rectangular structures with equal sizes; wherein:
the cover plate assembly (1) comprises a rectangular upper cover plate (6), wherein a reforming fuel inlet stainless steel pipe (7), a reforming fuel outlet stainless steel pipe (8), a methanol inlet stainless steel pipe (9), an air inlet stainless steel pipe (10) and a combustion gas outlet stainless steel pipe (11) are arranged on the rectangular upper cover plate (6);
the reforming hydrogen production plate (2) is provided with a parallelogram groove (17) serving as a methanol reforming cavity, a micro-boss (18) is arranged at a rectangular position in the middle of the parallelogram groove (17), a methanol reforming hydrogen production catalyst is loaded on the micro-boss (18), and first triangular fluid distribution cavities (19) are symmetrically arranged on the parallelogram groove (17) by taking two sides of the micro-boss (18) positioned at the rectangular position as the center; the reforming hydrogen production plate (2) is also provided with a first combustion raw material air inlet hole (12), a first combustion raw material methanol inlet hole (13) and a combustion gas outlet hole (14); the reforming fuel inlet stainless steel pipe (7), and the reforming fuel outlet stainless steel pipe (8) and the parallelogram groove (17) are correspondingly arranged in position; the first combustion raw material air inlet hole (12) is correspondingly formed in the position of the air inlet stainless steel tube (10); the first combustion raw material methanol inlet hole (13) is correspondingly formed in the position of the methanol inlet stainless steel pipe (9); the combustion gas outlet hole (14) is correspondingly formed in the position of the stainless steel tube (11) of the combustion gas outlet; the reforming fuel inlet stainless steel pipe (7), the parallelogram groove (17) and the reforming fuel outlet stainless steel pipe (8) are communicated to form a reforming fuel flow channel;
the first methanol combustion plate (3) is provided with a parallelogram through groove (20) serving as a methanol catalytic combustion cavity, and the direction of the parallelogram through groove (20) arranged on the first methanol combustion plate (3) is exactly opposite to the direction of the parallelogram groove (17) arranged on the reforming hydrogen production plate (2); the first methanol combustion plate (3) is also provided with a second combustion raw material methanol inlet hole (15), and the second combustion raw material methanol inlet hole (15) is correspondingly arranged with the first combustion raw material methanol inlet hole (13); the first combustion raw material air inlet hole (12) and the combustion gas outlet hole (14) are formed corresponding to the positions in the parallelogram through groove (20); the air inlet stainless steel tube (10), the first combustion raw material air inlet hole (12), the parallelogram through groove (20) on the first methanol combustion plate (3), the combustion gas outlet hole (14) and the combustion gas outlet stainless steel tube (11) are communicated to form a combustion raw material air flow channel;
the middle of the methanol combustion porous plate (4) is provided with circular through holes (21) distributed in an array manner, and the circular through holes (21) are correspondingly arranged with the parallelogram through grooves (20) on the first methanol combustion plate (3); the upper surface of the round through hole (21) is sintered with a thin layer of methanol catalytic combustion catalyst; the methanol combustion porous plate (4) is also provided with a third combustion raw material methanol inlet hole (16), and the position of the third combustion raw material methanol inlet hole (16) is correspondingly provided with the position of the second combustion raw material methanol inlet hole (15);
a micro-channel (22) is arranged in the middle of the second methanol combustion plate (5), and a second triangular fluid distribution cavity (23) is arranged on the second methanol combustion plate (5) at one side of the micro-channel (22); and the micro-channel (22) is communicated with the second triangular fluid distribution cavity (23); the micro-channels (22) on the second methanol combustion plate (5) are correspondingly arranged at the positions of the round through holes (21) on the methanol combustion porous plate (4); the methanol combustion device is characterized in that the methanol inlet stainless steel tube (9), the first combustion raw material methanol inlet hole (13), the second combustion raw material methanol inlet hole (15), the third combustion raw material methanol inlet hole (16), the second triangular fluid distribution cavity (23) on the second methanol combustion plate (5), the micro-channel (22) on the second methanol combustion plate (5), the circular through hole (21) on the methanol combustion porous plate (4), the parallelogram through groove (20) on the first methanol combustion plate (3), the combustion gas outlet hole (14) and the combustion gas outlet stainless steel tube (11) are communicated to form a combustion raw material methanol flow channel.
2. A rapid start-up autothermal methanol reforming hydrogen-producing microreactor as defined in claim 1, wherein: cylindrical micro-bosses (18) with the same structure are arranged on the reforming hydrogen production plate (2), the micro-bosses (18) are distributed in staggered mode, the number of the micro-bosses (18) in odd columns in the micro-bosses (18) is the same, and the number of the micro-bosses (18) in even columns is the same.
3. A rapid start-up autothermal methanol reforming hydrogen-producing microreactor as defined in claim 1, wherein: the micro boss (18) is loaded with a copper-based catalyst Cu/ZnO/Al 2 O 3 Or noble metal palladium-based catalyst Pd/Al 2 O 3 。
4. A rapid start-up autothermal methanol reforming hydrogen-producing microreactor as defined in claim 1, wherein: the upper surface of the round through hole (21) is sintered with a platinum-based catalyst Pt/Al 2 O 3 A thin layer.
5. A rapid start-up autothermal methanol reforming hydrogen-producing microreactor as defined in claim 1, wherein: the width of the micro-channel (22) on the second methanol combustion plate (5) is larger than the aperture of the circular through hole (21) on the methanol combustion porous plate (4).
6. A rapid start-up autothermal methanol reforming hydrogen-producing microreactor as defined in claim 1, wherein: the reforming hydrogen production plate (2) is a common aluminum alloy reforming hydrogen production plate, the first methanol combustion plate (3) is a common aluminum alloy first methanol combustion plate, the methanol combustion porous plate (4) is a common aluminum alloy methanol combustion porous plate, and the second methanol combustion plate (5) is a common aluminum alloy second methanol combustion plate.
7. A rapid start-up autothermal methanol reforming hydrogen-producing microreactor as defined in claim 1, wherein: the cover plate assembly (1), the reforming hydrogen production plate (2), the first methanol combustion plate (3), the methanol combustion porous plate (4) and the second methanol combustion plate (5) are assembled in a sealing way.
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| CN110155946B (en) * | 2019-05-17 | 2021-03-23 | 浙江大学 | Hydrogen production micro-reformer with fractal structure catalyst carrier |
| CN110316700B (en) * | 2019-06-27 | 2022-05-10 | 大连民族大学 | Array type reforming reactor |
| CN110420644A (en) * | 2019-08-16 | 2019-11-08 | 广西氢朝能源科技有限公司 | A kind of production method of palladium membrane component and its application in hydrogen from methyl alcohol reactor |
| CN110589764A (en) * | 2019-09-23 | 2019-12-20 | 厦门大学 | Self-heating methanol reforming hydrogen production equipment |
| CN110803679B (en) * | 2019-12-09 | 2021-04-16 | 浙江大学 | Methanol reforming hydrogen production reactor with flow velocity distribution uniformity |
| CN112499585B (en) * | 2020-12-03 | 2022-05-03 | 厦门大学 | Self-heating methanol reforming hydrogen production micro-reactor with sealing and assembling and disassembling properties |
| CN113432125B (en) * | 2021-07-15 | 2023-03-28 | 山西新源煤化燃料有限公司 | White oil hydrogen-mixed combustion device |
| CN115504433B (en) * | 2022-09-30 | 2023-12-08 | 大连大学 | Combustion coupling electric heating device for integrated methanol reforming hydrogen production reactor |
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