CN116002615A - Reforming hydrogen production reactor - Google Patents
Reforming hydrogen production reactor Download PDFInfo
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- CN116002615A CN116002615A CN202211536919.3A CN202211536919A CN116002615A CN 116002615 A CN116002615 A CN 116002615A CN 202211536919 A CN202211536919 A CN 202211536919A CN 116002615 A CN116002615 A CN 116002615A
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- 238000002407 reforming Methods 0.000 title claims abstract description 141
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 84
- 239000001257 hydrogen Substances 0.000 title claims abstract description 84
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 238000002485 combustion reaction Methods 0.000 claims abstract description 101
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 239000000446 fuel Substances 0.000 claims abstract description 64
- 238000012546 transfer Methods 0.000 claims abstract description 52
- 239000002994 raw material Substances 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 51
- 239000007789 gas Substances 0.000 claims description 27
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 238000009423 ventilation Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 4
- 239000004519 grease Substances 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 118
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 239000003546 flue gas Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 238000006057 reforming reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 239000012466 permeate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 238000005755 formation reaction Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
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- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The invention relates to a reforming hydrogen production reactor, which comprises a reaction kettle, a reforming bed layer, a raw material pipeline, a heating structure and a heat conduction part, wherein the reaction kettle is provided with a heat conduction part; the reaction kettle is provided with a reaction cavity; the reforming bed layer is arranged in the reaction cavity and separates the reaction cavity into a combustion cavity and a preheating cavity which are communicated with each other, and a hydrogen outlet pipeline positioned outside the reaction cavity is communicated with the reforming bed layer; the raw material pipeline part is positioned in the preheating cavity, one end of the raw material pipeline part extends out of the reaction cavity, and the other end of the raw material pipeline part extends into the inner cavity of the reforming bed layer; the heating structure comprises a fuel pipeline and an igniter, wherein the fuel pipeline is arranged in the reaction kettle, a discharge hole of the fuel pipeline is communicated with the combustion cavity, and the igniter corresponds to the discharge hole of the fuel pipeline and is used for igniting fuel conveyed by the fuel pipeline to generate heat; the heat conduction part corresponds to the reforming bed layer and the combustion chamber and is used for conducting heat in the combustion chamber to the reforming bed layer. The scheme does not need to be additionally matched with heating equipment with higher cost, has higher heat transfer efficiency, does not need an external heat source to supply heat at the same time, and has a relatively simple structure and saves cost.
Description
Technical Field
The invention relates to the technical field of alcohol reforming hydrogen production equipment, in particular to a reforming hydrogen production reactor.
Background
In recent years, the development prospect of the hydrogen energy industry is expected due to the increase of the hydrogen energy support in countries and places. The hydrogen energy is a green and efficient secondary energy source, and has the characteristics of higher heat value, abundant reserves, reproducibility, cleanness, no pollution, various sources, wide application, multiple utilization forms and the like. The hydrogen energy can not only provide energy, but also meet the requirements of resources, environment and sustainable development. The fuel cell is the best mode for effectively utilizing hydrogen energy, can directly convert clean hydrogen energy into electric energy, and the reaction process only discharges water and heat, so that the fuel cell is an energy conversion technology which is more advanced, more efficient and more environment-friendly than a conventional internal combustion engine.
Under certain temperature and pressure, methanol and steam can undergo methanol cracking reaction and CO conversion reaction by a catalyst to generate H 2 And CO 2 . The methanol steam reforming technology is combined with the fuel cell technology, so that the dependence on a hydrogenation station can be eliminated, and the commercial operation cost is greatly reduced. Meanwhile, methanol is used as a power energy source, so that the problem of high external dependence of energy sources in China can be effectively solved. In terms of fuel sources, china is the country with the largest production of methanol, and the most main source is coal-to-methanol. The problem that the atmosphere is polluted by direct combustion of coal can be effectively solved by using the methanol prepared from coal; secondly, natural gas can be used for preparing methanol; third, the catalyst can be synthesized by recovering carbon dioxide, which is a greenhouse gas, together with hydrogen. In addition, hydrogen is in a gaseous state in a normal state, and can be converted into a liquid state to be stored and transported under special temperature and pressure, so that certain potential safety hazards exist. In contrast, methanol is liquid at normal air temperature and pressure, and is easier to transport and store. The methanol steam reforming reactor is the key direction of current research as the core equipment of the methanol reforming hydrogen production technology。
For example, patent CN 105293432A discloses a hydrogen production machine by reforming methanol and water and a hydrogen production method thereof, wherein low-frequency voltage or direct-current voltage is converted into high-frequency voltage after passing through a frequency converter, and is supplied to an electromagnetic coil of an electromagnetic heater, and a high-frequency magnetic field is generated after the electromagnetic coil is electrified, so that metal of the electromagnetic heater is heated by the induction of a magnetic field, and a temperature is provided for a reforming chamber, so that the reforming hydrogen production reaction of methanol and water is performed, and a high-temperature mixed gas mainly comprising carbon dioxide and hydrogen is prepared. However, since the apparatus requires an additional electromagnetic heater and corresponding auxiliary equipment to provide a heat source, the equipment cost is increased.
Disclosure of Invention
In view of the foregoing, it is desirable to provide a reforming hydrogen production reactor that solves the technical problems of the prior art.
The invention provides a reforming hydrogen production reactor, which comprises:
the reaction kettle is provided with a reaction cavity;
the reforming bed layer is arranged in the reaction cavity, separates the reaction cavity into a combustion cavity and a preheating cavity which are communicated with each other, is used for reforming raw materials conveyed to the inner cavity of the reforming bed layer and generating hydrogen, and is communicated with a hydrogen outlet pipeline positioned outside the reaction cavity;
the raw material pipeline is partially positioned in the preheating cavity, one end of the raw material pipeline extends out of the reaction cavity, and the other end of the raw material pipeline extends into the inner cavity of the reforming bed layer, so that raw materials are input into the reforming bed layer;
the heating structure comprises a fuel pipeline and an igniter, wherein the fuel pipeline and the igniter are arranged in the reaction kettle, a discharge hole of the fuel pipeline is communicated with the combustion cavity and is used for conveying fuel into the combustion cavity, and the igniter corresponds to the discharge hole of the fuel pipeline and is used for igniting the fuel conveyed by the fuel pipeline so as to generate heat; the method comprises the steps of,
and the heat conduction part is corresponding to the reforming bed layer and the combustion cavity and is used for conducting heat in the combustion cavity to the reforming bed layer.
Optionally, the reforming bed layer is in a cylinder body, and is arranged along an inner side wall of the reaction cavity at intervals in an inner-outer direction, so that the preheating cavity is formed between an outer side wall of the reforming bed layer and an inner side wall of the reaction cavity, and the combustion cavity is formed by surrounding the inner side wall of the reforming bed layer.
Optionally, one end of the reforming bed layer in the axial direction is spaced from the inner wall corresponding to the reaction chamber, so as to form a connecting channel, and the connecting channel is communicated with the preheating chamber and the combustion chamber.
Optionally, the hydrogen outlet pipe and the connecting channel are located at two opposite ends of the reforming bed layer in the axial direction.
Optionally, the reforming hydrogen production reactor comprises a main pipeline arranged outside the reaction kettle, wherein the main pipeline is communicated with the combustion cavity and is positioned at two ends of the reforming bed layer opposite to the connecting channel in the axial direction;
the discharging port of the fuel pipeline extends into the main pipeline, the main pipeline is further communicated with an air inlet pipeline positioned outside the reaction kettle, and a connecting port of the air inlet pipeline and the main pipeline corresponds to the discharging port of the fuel pipeline.
Optionally, the reforming hydrogen production reactor further comprises a palladium alloy pipe partially positioned in the reforming bed layer, and one end of the palladium alloy pipe extends out of the reaction cavity and is communicated with the hydrogen outlet pipeline.
Optionally, the heat conducting part is a plurality of heat transfer fins connected to the outer wall of the palladium alloy tube, the plurality of heat transfer fins are arranged at intervals along the extending direction of the palladium alloy tube, and one end of each heat transfer fin is connected with one side wall of the reforming bed layer, which is close to the combustion chamber.
Optionally, each heat transfer fin is provided with a jack through which a palladium alloy tube passes along the thickness direction of the heat transfer fin, and is provided with a preheating heat transfer end and a combustion heat transfer end, wherein the preheating heat transfer end is connected with a side wall of the reforming bed layer, which is close to the preheating cavity, and the combustion heat transfer end is connected with a side wall of the reforming bed layer, which is close to the combustion cavity; and/or the number of the groups of groups,
the palladium alloy pipes are arranged in a plurality of mode, and the palladium alloy pipes are circumferentially distributed at intervals; and/or the number of the groups of groups,
and the joint of each heat transfer fin and the palladium alloy pipe is coated with heat conduction silicone grease.
Optionally, the reforming hydrogen production reactor further comprises a tail gas pipeline arranged in the reaction kettle, one end of the tail gas pipeline is communicated with the inner cavity of the reforming bed layer, and the other end of the tail gas pipeline extends into the combustion cavity.
Optionally, a plurality of ventilation holes are formed at one end of the tail gas pipeline extending into the combustion cavity.
Compared with the prior art, in the reforming hydrogen production reactor provided by the invention, the reaction cavity is divided into the combustion cavity and the preheating cavity through the reforming bed layer, fuel (methanol fuel) is conveyed into the combustion cavity by utilizing the fuel pipeline, and after the igniter ignites the methanol fuel, the methanol fuel is combusted in the combustion cavity and releases a large amount of heat; the generated heat in the combustion chamber is diffused into a preheating chamber communicated with the combustion chamber along with the flue gas so as to heat a raw material pipeline in the preheating chamber, so that raw materials (methanol water solution) in the raw material pipeline are vaporized into methanol water vapor; the other part is transferred into the reforming bed layer through the heat conducting part so as to adjust the temperature in the reforming bed layer to a proper temperature, so that the methanol vapor in the reforming bed layer can undergo reforming reaction and generate hydrogen, and the generated hydrogen is discharged and collected through the hydrogen outlet pipeline.
Therefore, the scheme does not need to be additionally matched with heating equipment with higher cost, but transfers the heat generated by the combustion of the methanol fuel in the combustion cavity to the preheating cavity and the reforming bed layer so that the temperature of the preheating cavity and the reforming bed layer can be adjusted to a proper temperature; the combustion chamber is directly communicated with the preheating chamber, and the heat conducting part is arranged between the combustion chamber and the reforming bed layer, so that heat in the combustion chamber can be effectively transferred into the preheating chamber and the reforming bed layer, the heat transfer efficiency is higher, an external heat source is not needed for supplying heat, and the structure is relatively simple and compact, and the cost is saved.
The foregoing description is only an overview of the present invention, and is intended to provide a better understanding of the present invention, as it is embodied in the following description, with reference to the preferred embodiments of the present invention and its details set forth in the accompanying drawings. Specific embodiments of the present invention are given in detail by the following examples and the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiments of the invention and together with the description serve to explain the invention and do not constitute a limitation on the invention. In the drawings:
FIG. 1 is a schematic diagram of a reforming reactor for hydrogen production according to an embodiment of the present invention;
FIG. 2 is an enlarged schematic view of FIG. 1 at A;
FIG. 3 is an enlarged schematic view at B in the drawing;
FIG. 4 is a schematic cross-sectional view of the C-C plane of FIG. 2;
fig. 5 is a schematic view of the structure of the heat transfer fin of fig. 4.
Reference numerals illustrate:
the device comprises a 100-reforming hydrogen production reactor, a 1-reaction kettle, a1 a-reaction cavity, a 1-combustion cavity, a 1a 2-preheating cavity, a 1a 3-connecting channel, an 11-sealing head, a 12-seat, a 2-reforming bed layer, a 21-hydrogen outlet pipeline, a 22-raw material pipeline, a 221-main body section, a 222-material conveying section, a 3-heating structure, a 31-fuel pipeline, a 32-igniter, a 4-heat conducting part, a 41-heat transfer fin, a 41 a-jack, a 411-preheating heat transfer end, a 412-combustion heat transfer end, a 5-preheating exhaust pipeline, a 6-main body pipeline, a 61-air inlet pipeline, a 7-palladium alloy pipe, an 8-tail gas pipeline, an 8 a-ventilation hole and 9-bolts.
Detailed Description
Preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which form a part hereof, and together with the description serve to explain the principles of the invention, and are not intended to limit the scope of the invention.
Referring to fig. 1 to 4, the reforming hydrogen production reactor 100 includes a reaction kettle 1, a reforming bed layer 2, a raw material pipe 22, a heating structure 3 and a heat conducting part 4; the reaction kettle 1 is provided with a reaction cavity 1a; the reforming bed layer 2 is arranged in the reaction cavity 1a, separates the reaction cavity 1a into a combustion cavity 1a1 and a preheating cavity 1a2 which are communicated with each other, is used for reforming raw materials conveyed to the inner cavity of the reforming bed layer 2 to generate hydrogen, and is communicated with a hydrogen outlet pipeline 21 positioned outside the reaction cavity 1a; the raw material pipeline 22 is partially positioned in the preheating cavity 1a2, one end of the raw material pipeline extends out of the reaction cavity 1a, and the other end of the raw material pipeline extends into the inner cavity of the reforming bed 2, so as to input raw materials into the reforming bed 2; the heating structure 3 comprises a fuel pipeline 31 and an igniter 32 which are arranged in the reaction kettle 1, wherein a discharge hole of the fuel pipeline 31 is communicated with the combustion cavity 1a1 and is used for conveying fuel into the combustion cavity 1a1, and the igniter 32 corresponds to the discharge hole of the fuel pipeline 31 and is used for igniting the fuel conveyed by the fuel pipeline 31 to generate heat; the heat conducting portion 4 corresponds to the reforming bed 2 and the combustion chamber 1a1, and is used for conducting heat in the combustion chamber 1a1 to the reforming bed 2.
In the reforming hydrogen production reactor 100 provided by the invention, a reaction cavity 1a is divided into a combustion cavity 1a1 and a preheating cavity 1a2 through a reforming bed layer 2, fuel (methanol fuel) is conveyed into the combustion cavity 1a1 by a fuel pipeline 31, and after the methanol fuel is ignited by an igniter 32, the methanol fuel is combusted in the combustion cavity 1a1 and releases a large amount of heat; the generated heat part in the combustion chamber 1a1 diffuses into the preheating chamber 1a2 communicated with the combustion chamber along with the flue gas to heat the raw material pipeline 22 positioned in the preheating chamber 1a2, so that the raw material (methanol water solution) in the raw material pipeline 22 is vaporized into methanol water vapor; the other part is transferred to the reforming bed 2 via the heat conducting part 4 to adjust the temperature in the reforming bed 2 to a proper temperature so that the methanol vapor transferred into the reforming bed 2 can undergo a reforming reaction and generate hydrogen, and the generated hydrogen is discharged and collected via the hydrogen outlet pipe 21.
Therefore, the scheme does not need to be matched with a heating device with higher cost, but transfers the heat generated by the combustion of the methanol fuel in the combustion cavity 1a1 to the preheating cavity 1a2 and the reforming bed layer 2 so as to enable the temperature of the preheating cavity 1a2 and the reforming bed layer 2 to be adjusted to a proper temperature; the combustion chamber 1a1 is directly communicated with the preheating chamber 1a2, and the heat conducting part 4 is arranged between the combustion chamber 1a1 and the reforming bed 2, so that heat in the combustion chamber 1a1 can be effectively transferred into the preheating chamber 1a2 and the reforming bed 2, the heat transfer efficiency is high, and meanwhile, an external heat source is not required for supplying heat, the structure is relatively simple, and the cost is saved.
In this embodiment, the reforming bed layer 2 contains a methanol reforming catalyst, the methanol reforming catalyst is uniformly filled in the reforming bed layer 2, a complete metal honeycomb substrate is adopted, the catalyst is supported on the wall surface of the substrate in a coating manner, the preferred substrate is FeCrAl alloy, the coating is ce0.8zr0.2o2, and the preferred reaction temperature is 400-450 ℃. The integral metal honeycomb matrix catalyst layer utilizes the alloy matrix with high heat conductivity coefficient and the porous structure, and has the characteristics of reduced bed lamination, uniform material and temperature distribution, large reaction area and good thermal stability.
Furthermore, the raw material pipe 22 is provided in the form of a coil pipe to improve heat transfer efficiency. Preferably, the raw material pipe 22 is a seamless stainless steel tube spirally wound, and preferably, fins are welded on the outer surface of the coil by laser welding or high frequency welding. Specifically, the raw material pipeline 22 comprises a main body section 221 arranged in a coil pipe shape and a plurality of material conveying sections 222 communicated with the main body section 221, wherein the material conveying sections 222 are circumferentially distributed at intervals and are communicated with the reforming bed layer 2.
The discharge port of the fuel pipe 31 is provided with a solid cone wide-angle nozzle, preferably having a spray angle of 120 to 130 °. And the igniter 32 includes an ignition rod and a semiconductor electrode provided on the ignition rod, the semiconductor electrode forming a high-energy arc spark ignition, preferably at an ignition frequency of 6 to 12 times/s.
Further, the reforming bed layer 2 is arranged in a cylinder and is spaced from the inner side wall of the reaction chamber 1a along the inner and outer directions, so that a preheating chamber 1a2 is formed between the outer side wall of the reforming bed layer 2 and the inner side wall of the reaction chamber 1a, and the inner side wall of the reforming bed layer 2 is surrounded to form a combustion chamber 1a1. That is, in this embodiment, the combustion chamber 1a1 is located at the inner ring of the reforming bed layer 2, and the preheating chamber 1a2 is located between the outer ring of the reforming bed layer 2 and the inner side wall of the reaction chamber 1a, so that the overall structure of the reaction kettle 1 is more compact and reasonable. And the reforming bed layer 2 surrounds the combustion chamber 1a1, so that heat transfer can be better carried out between the reforming bed layer and the combustion chamber, and the heat transfer efficiency is improved. In the scheme, the preheating cavity 1a2 is communicated with a preheating exhaust pipeline 5 arranged in the reaction kettle 1, and combustion flue gas is timely discharged.
Further, in the present embodiment, one end of the reforming bed 2 in the axial direction is disposed at an interval from the inner wall corresponding to the reaction chamber 1a to form a connection passage 1a3, and the connection passage 1a3 communicates the preheating chamber 1a2 with the combustion chamber 1a1. In this way, the reforming bed layer 2 is arranged at an end in the axial direction at intervals with the inner wall corresponding to the reaction cavity 1a, so that the preheating cavity 1a2 and the combustion cavity 1a1 are communicated, and a pipeline is not required to be additionally arranged, so that the cost is saved. Specifically, the hydrogen outlet pipe 21 and the connecting passage 1a3 are located at axially opposite ends of the reforming bed 2. In this scheme, be relative setting with play hydrogen pipeline 21 and connecting channel 1a3 to avoid reforming bed 2 to take place to interfere with the connecting channel of play hydrogen pipeline 21, make holistic space arrangement compacter reasonable.
Further, the reforming hydrogen production reactor 100 comprises a main body pipeline 6 arranged outside the reaction kettle 1, wherein the main body pipeline 6 is communicated with the combustion cavity 1a1 and is positioned at two ends of the reforming bed layer 2 opposite to the connecting channel 1a3 in the axial direction; wherein, the discharge gate of fuel pipe 31 stretches into main pipe 6, and main pipe 6 still communicates and is located the outer air intake pipe 61 of reation kettle 1, and air intake pipe 61 corresponds the discharge gate of fuel pipe 31 with the connector of main pipe 6. In the present embodiment, the main pipe 6 is communicated with the combustion chamber 1a1, so that the volume of the combustion chamber 1a1 is increased, and the combustion space is enlarged; while the intake duct 61 communicates with the main body duct 6 so as to be able to timely input the combustion improver (air). In this embodiment, the igniter 32 is provided on the side wall of the main pipe 6.
Further, the reforming hydrogen production reactor 100 further comprises a palladium alloy tube 7 partially positioned in the reforming bed layer 2, and one end of the palladium alloy tube 7 extends out of the reaction chamber 1a and is communicated with a hydrogen pipeline 21. In this scheme, by means of the characteristic of the palladium alloy tube 7 for purifying hydrogen, the hydrogen-rich gas generated by the reforming reaction in the reforming bed 2 permeates the palladium alloy tube 7 to obtain ultra-pure hydrogen, and the ultra-pure hydrogen flows to the hydrogen outlet pipeline 21 through the palladium alloy tube 7 for collection.
The upper section of the palladium alloy tube 7 is closed, the lower end is open, the ultra-pure hydrogen is obtained by utilizing the adsorption dissociation-composite desorption reaction of hydrogen on the surface of the palladium alloy, the palladium alloy tube 7 is preferably PdAG, pdCu or PdArg Ni alloy, the diameter is preferably 2-4 mm, and the wall thickness is 50-100 mu m.
Further, referring to fig. 4 and 5, the heat conducting portion 4 is a plurality of heat transfer fins 41 connected to the outer wall of the palladium alloy tube 7, the plurality of heat transfer fins 41 are arranged at intervals along the extending direction of the palladium alloy tube 7, and one end of each heat transfer fin 41 is connected to one side wall of the reforming bed 2 close to the combustion chamber 1a1. In this way, on the one hand, the heat in the combustion chamber 1a1 can be uniformly diffused in the reforming bed 2, and on the other hand, the heat transfer fins 41 can directly transfer the heat in the combustion chamber 1a1 to the palladium alloy tube 7, so that the palladium alloy tube 7 can be at a proper temperature, and further the hydrogen is purified. In this embodiment, the palladium alloy tube 7 extends along the axial direction of the reforming bed 2, and the plurality of heat transfer fins 41 are arranged at intervals along the extending direction of the palladium alloy tube 7, so as to further ensure the heat transfer effect of the reforming bed 2 and the palladium alloy tube 7, and further improve the hydrogen quality of the product.
Further, each heat transfer fin 41 is provided with a jack 41a through which the palladium alloy tube 7 passes along the thickness direction, and is provided with a preheating heat transfer end 411 and a combustion heat transfer end 412, wherein the preheating heat transfer end 411 is connected with one side wall of the reforming bed 2 close to the preheating cavity 1a2, and the combustion heat transfer end is connected with one side wall of the reforming bed 2 close to the combustion cavity 1a 1; and/or the palladium alloy pipes 7 are provided with a plurality of palladium alloy pipes 7 which are circumferentially distributed at intervals; and/or the connection part of each heat transfer fin 41 and the palladium alloy pipe 7 is coated with heat conduction silicone grease. In the present embodiment, each heat transfer fin 41 is disposed in a ring shape, and has a preheating heat transfer end 411 on the outside and a combustion heat transfer end 412 on the inside, so as to fully utilize the heat in the combustion chamber 1a1 and the preheating chamber 1a2, and to realize heat transfer while making the overall structure more compact. Meanwhile, the joint of each heat transfer fin 41 and the palladium alloy tube 7 is coated with heat conduction silicone grease to improve the overall heat transfer coefficient. In addition, a plurality of palladium alloy tubes 7 are provided to improve the hydrogen collection efficiency, and correspondingly, a plurality of insertion holes 41a of each heat transfer fin 41 are provided.
Further, in an embodiment, the reforming hydrogen production reactor 100 further includes an exhaust pipe 8 disposed in the reaction kettle 1, where one end of the exhaust pipe 8 is communicated with the inner cavity of the reforming bed layer 2, and the other end extends into the combustion cavity 1a1. Thus, part of hydrogen in the hydrogen-rich gas which cannot permeate through the palladium alloy pipe 7 is conveyed to the combustion chamber 1a1 together with other impurity gases through the tail gas pipeline 8 so as to generate combustion reaction, generate high-temperature flue gas, provide heat for methanol reforming reaction, methanol aqueous solution vaporization and palladium alloy pipe 7 purification, and improve the overall heat efficiency.
Further, the end of the tail gas pipe 8 extending into the combustion chamber 1a1 is provided with a plurality of ventilation holes 8a, so that part of the hydrogen gas and other impurity gases which cannot permeate through the palladium alloy pipe 7 can uniformly flow into the combustion chamber 1a1 through the ventilation holes 8a, and can be fully combusted. Specifically, the tail gas pipelines 8 are provided with a plurality of tail gas pipelines 8 which are circumferentially arranged at intervals, and the part of each tail gas pipe in the combustion chamber 1a1 is uniformly distributed with ventilation holes 8a so as to ensure that the hydrogen-containing tail gas can be uniformly combusted in the combustion chamber 1a1.
In this embodiment, one end of the tail gas pipe 8 is connected to the reforming bed 2, and the other end extends into the main pipe 6. In addition, in this scheme, reation kettle 1 includes head 11 and pedestal 12, encloses jointly between head 11 and the pedestal 12 and establishes formation reaction chamber 1a, and can dismantle through bolt 9 between head 11 and the pedestal 12 and be connected. Correspondingly, the structure of the reforming bed 2 may be similarly arranged. Therefore, when faults such as the activity of the catalyst is reduced, the palladium alloy pipe 7 leaks and the like and the shutdown maintenance or the replacement of parts is needed, the sealing head of the reaction kettle 1 and the sealing head of the reforming bed layer 2 can be sequentially removed to maintain or replace the whole catalyst and the palladium alloy pipe 7, so that the whole cycle life of the reactor is prolonged.
Based on the above structure, the specific workflow of the reforming hydrogen production reactor 100 provided by the present invention is as follows:
when the reforming hydrogen production reactor 100 works, methanol fuel is conveyed into the combustion chamber 1a1 through the fuel pipeline 31, atomized through a nozzle at a discharge hole of the fuel pipeline 31 and enters the combustion chamber 1a1, meanwhile, air is conveyed into the combustion chamber 1a1 through the air inlet pipeline 61, and the igniter 32 is electrified to ignite the mixed methanol and air.
The heat of the generated high-temperature flue gas is transferred to the reforming bed layer 2 and the palladium alloy tube 7 by the combustion chamber 1a1 and the heat transfer fins 41, and the tail gas is preheated; the high-temperature flue gas further enters the preheating chamber 1a2 via the connection channel 1a3 to heat the raw material pipe 22 located in the preheating chamber 1a 2. At this time, the aqueous methanol solution is fed from the inlet of the raw material pipe 22, and the aqueous methanol solution in the raw material pipe 22 is completely vaporized into aqueous methanol vapor by the high-temperature flue gas. And meanwhile, the high-temperature flue gas in the preheating cavity 1a2 is further heated to the reforming bed layer 2, and after the heat of the high-temperature flue gas is fully utilized, the high-temperature flue gas is discharged from the preheating exhaust pipeline 5.
The methanol vapor enters the reforming bed layer 2 through the raw material pipe 22, the methanol vapor reforming reaction occurs in the bed layer which has reached the optimal reaction temperature, and the product gas permeates the ultra-pure hydrogen obtained by the palladium alloy pipe 7 and flows to the hydrogen outlet pipe 21 to be collected by the palladium alloy pipe 7 for being used by the fuel cell power generation system.
And part of hydrogen which does not permeate the palladium alloy pipe 7 in the product gas enters the combustion chamber 1a1 through the tail gas pipeline 8 together with other impurity gases, and the ventilation holes 8a which are uniformly distributed at the upper part of the tail gas pipeline 8 are uniformly sprayed into the combustion chamber 1a1 for combustion reaction, so that high-temperature flue gas is generated, heat is provided for methanol reforming reaction, methanol aqueous solution vaporization and palladium alloy pipe 7 purification, and the overall heat efficiency of the reactor is improved.
In one embodiment, the methanol fuel enters the combustion chamber 1a1 from the fuel pipe 31, and the upper part of the fuel pipe 31 is a solid cone wide-angle nozzle with a spray angle of 120 degrees; air enters the combustion chamber 1a1 through the air inlet pipe 61, the igniter 32 ignites, the ignition frequency is 6 times/s, and methanol fuel is combusted in the combustion chamber 1a1. When the temperature of the reforming bed layer 2 is raised to 380 ℃, a methanol water solution is introduced into the raw material pipeline 22, the molar ratio of methanol to water is 1:1.1, the methanol water solution is vaporized into methanol water vapor in the raw material pipeline 22, and the methanol water vapor enters the reforming bed layer 2 to carry out reforming reaction. The matrix of the catalyst in the reforming bed layer 2 is honeycomb FeCrAl alloy, ce0.8Zr0.2O2 is used as a coating, and the reaction temperature is 400 ℃. The palladium alloy tube 7 is made of PdAG alloy, has the diameter of 2mm and the wall thickness of 50 mu m, has 16 palladium alloy tubes, and has the temperature of 7 ℃ of 400 ℃. After the reforming hydrogen production reactor 100 stably operates, the hydrogen pressure of the product is measured to be more than or equal to 0.25Mpa, the purity is measured to be more than or equal to 99.99999%, and the use requirement of a fuel cell power generation system is met.
In another embodiment, methanol fuel enters the combustion chamber 1a1 from the fuel pipe 31, and the upper part of the fuel pipe 31 is a solid cone wide-angle nozzle with a spray angle of 130 degrees; air enters the combustion chamber 1a1 through the air inlet pipe 61, the igniter 32 ignites, the ignition frequency is 12 times/s, and methanol fuel is combusted in the combustion chamber 1a1. When the temperature of the reforming bed layer 2 is increased to 400 ℃, a methanol water solution is introduced into the raw material pipeline 22, the molar ratio of the methanol to the water is 1:1.2, the methanol water solution is vaporized into methanol water vapor in the raw material pipeline 22, and the methanol water vapor enters the reforming bed layer 2 to carry out reforming reaction. The matrix of the catalyst in the reforming bed layer 2 is honeycomb FeCrAl alloy, ce0.8Zr0.2O2 is used as a coating, and the reaction temperature is 450 ℃. The palladium alloy tube 7 is made of PdAG alloy, has the diameter of 2mm and the wall thickness of 50 mu m, has the number of 16 and has the temperature of 450 ℃. After the reforming hydrogen production reactor 100 stably operates, the hydrogen pressure of the product is measured to be more than or equal to 0.3Mpa, the purity is measured to be more than or equal to 99.99999%, and the use requirement of a fuel cell power generation system is met.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. A reforming hydrogen production reactor, comprising:
the reaction kettle is provided with a reaction cavity;
the reforming bed layer is arranged in the reaction cavity, separates the reaction cavity into a combustion cavity and a preheating cavity which are communicated with each other, is used for reforming raw materials conveyed to the inner cavity of the reforming bed layer and generating hydrogen, and is communicated with a hydrogen outlet pipeline positioned outside the reaction cavity;
the raw material pipeline is partially positioned in the preheating cavity, one end of the raw material pipeline extends out of the reaction cavity, and the other end of the raw material pipeline extends into the inner cavity of the reforming bed layer, so that raw materials are input into the reforming bed layer;
the heating structure comprises a fuel pipeline and an igniter, wherein the fuel pipeline and the igniter are arranged in the reaction kettle, a discharge hole of the fuel pipeline is communicated with the combustion cavity and is used for conveying fuel into the combustion cavity, and the igniter corresponds to the discharge hole of the fuel pipeline and is used for igniting the fuel conveyed by the fuel pipeline so as to generate heat; the method comprises the steps of,
and the heat conduction part is corresponding to the reforming bed layer and the combustion cavity and is used for conducting heat in the combustion cavity to the reforming bed layer.
2. A reforming hydrogen production reactor as defined in claim 1, wherein the reforming bed is arranged in a cylindrical shape and is spaced apart from the inner wall of the reaction chamber in an inward-outward direction to form the preheating chamber between the outer wall of the reforming bed and the inner wall of the reaction chamber, and the inner wall of the reforming bed encloses the combustion chamber.
3. A reforming hydrogen production reactor as defined in claim 2, wherein one end of the reforming bed layer in the axial direction is disposed at a distance from the inner wall corresponding to the reaction chamber to form a connection passage, and the connection passage communicates the preheating chamber with the combustion chamber.
4. A reforming hydrogen-production reactor as defined in claim 3, wherein the hydrogen-producing conduit and the connecting channel are located at axially opposite ends of the reforming bed.
5. A reforming and hydrogen-producing reactor as defined in claim 3, comprising a main body pipe provided outside the reaction vessel, the main body pipe being communicated with the combustion chamber and being located at axially opposite ends of the reforming bed from the connecting passage;
the discharging port of the fuel pipeline extends into the main pipeline, the main pipeline is further communicated with an air inlet pipeline positioned outside the reaction kettle, and a connecting port of the air inlet pipeline and the main pipeline corresponds to the discharging port of the fuel pipeline.
6. A reforming hydrogen production reactor as defined in any one of claims 1 to 5, further comprising a palladium alloy tube partially within the reforming bed, one end of the palladium alloy tube extending out of the reaction chamber and communicating with the hydrogen outlet conduit.
7. A reforming hydrogen production reactor as defined in claim 6, wherein the heat conducting portion is a plurality of heat transfer fins connected to an outer wall of the palladium alloy tube, the plurality of heat transfer fins are arranged at intervals along an extending direction of the palladium alloy tube, and one end of each heat transfer fin is connected to a side wall of the reforming bed layer close to the combustion chamber.
8. A reforming hydrogen production reactor as defined in claim 7, wherein each heat transfer fin is provided with a jack through which a palladium alloy tube passes in a thickness direction thereof, and has a preheating heat transfer end and a combustion heat transfer end, the preheating heat transfer end being connected to a side wall of the reforming bed adjacent to the preheating chamber, and the combustion heat transfer end being connected to a side wall of the reforming bed adjacent to the combustion chamber; and/or the number of the groups of groups,
the palladium alloy pipes are arranged in a plurality of mode, and the palladium alloy pipes are circumferentially distributed at intervals; and/or the number of the groups of groups,
and the joint of each heat transfer fin and the palladium alloy pipe is coated with heat conduction silicone grease.
9. A reforming and hydrogen-producing reactor as defined in claim 6, further comprising a tail gas pipe provided to the reaction vessel, one end of the tail gas pipe being connected to the inner cavity of the reforming bed layer, and the other end of the tail gas pipe extending into the combustion chamber.
10. A reforming hydrogen production reactor as defined in claim 9, wherein a plurality of ventilation holes are provided at an end of the tail gas pipe extending into the combustion chamber.
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| CN1629065A (en) * | 2003-12-16 | 2005-06-22 | 中国科学院大连化学物理研究所 | Microchannel plate-fin type water vapour reforming reactor for hydrogen production |
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- 2022-12-02 CN CN202211536919.3A patent/CN116002615A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1629065A (en) * | 2003-12-16 | 2005-06-22 | 中国科学院大连化学物理研究所 | Microchannel plate-fin type water vapour reforming reactor for hydrogen production |
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| CN113019280A (en) * | 2021-03-18 | 2021-06-25 | 大连大学 | Hydrogen production spiral plate membrane reactor for liquid fuel atomization feeding |
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