CN109761193B - Methanol reforming hydrogen production reactor - Google Patents
Methanol reforming hydrogen production reactor Download PDFInfo
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- CN109761193B CN109761193B CN201910212857.2A CN201910212857A CN109761193B CN 109761193 B CN109761193 B CN 109761193B CN 201910212857 A CN201910212857 A CN 201910212857A CN 109761193 B CN109761193 B CN 109761193B
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000001257 hydrogen Substances 0.000 title claims abstract description 74
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 74
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000002407 reforming Methods 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000012530 fluid Substances 0.000 claims abstract description 127
- 239000007789 gas Substances 0.000 claims abstract description 58
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 238000003860 storage Methods 0.000 claims abstract description 20
- 238000000746 purification Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000001833 catalytic reforming Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 230000008016 vaporization Effects 0.000 claims abstract description 4
- 238000001704 evaporation Methods 0.000 claims description 20
- 238000007789 sealing Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 230000008020 evaporation Effects 0.000 claims description 17
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910003460 diamond Inorganic materials 0.000 claims description 5
- 239000010432 diamond Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 238000010926 purge Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 5
- 238000006057 reforming reaction Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000002918 waste heat Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 210000001503 joint Anatomy 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Hydrogen, Water And Hydrids (AREA)
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Abstract
The invention discloses a methanol reforming hydrogen production reactor, which comprises an evaporator, a reformer and a purification storage, wherein the evaporator is used for heating and vaporizing a methanol-water mixed solution raw material, and the formed methanol-water mixed gas enters the reformer to carry out catalytic reforming reaction; the purge storage is used for hydrogen purging and hydrogen storage of the hydrogen-rich product obtained from the reformer. The reformer is internally provided with a plurality of layers of serially connected cold fluid channels and a plurality of layers of parallel connected hot fluid channels, reforming catalysts are arranged in each layer of cold fluid channels, the methanol-water mixed gas enters the cold fluid channels of the reformer, the hot tail gas uniformly enters each layer of hot fluid channels of the reformer, the cold fluid channels and the hot fluid channels are all of a layered cavity structure, and the cold fluid channels and the hot fluid channels are alternately arranged in the inner layers of the reformer. The reformer and the evaporator recover the heat of the hot tail gas in a layer-by-layer heat exchange mode, so that the utilization rate of the heat of the hot tail gas is greatly improved.
Description
Technical Field
The invention relates to a hydrogen production reactor, in particular to a methanol reforming hydrogen production reactor.
Background
Researches show that the energy discharged by the motor vehicle in the form of waste heat accounts for 55% -80% of the total energy of the fuel, so that the waste heat recovery and utilization of tail gas are very important for improving the fuel utilization rate and saving energy. In the face of urgent energy crisis, hydrogen fuel cell automobiles have very broad prospects. The existing fuel cell automobile generally adopts a high-pressure hydrogen storage mode to carry hydrogen on the automobile, so that not only is the filling difficult, but also the hidden danger of leakage and explosion in accidents exists when a large amount of hydrogen is carried. The method for preparing hydrogen on site well solves the problems. Method for obtaining hydrogen by comprehensive comparison and reforming methanolHydrogen production has the unique advantage. The hydrogen producing process with methanol reforming includes the steps of preparing methanol at 250-300 deg.c, 1-5MPa and water-alcohol ratio of 1-5 in the presence of Cu/Al catalyst 2 O 3 The following multi-component complex reactions occur, mainly comprising:
steam reforming reaction:
methanol decomposition reaction:
and (3) carrying out water vapor reverse transformation reaction:
the way in which methanol is reformed to produce hydrogen generally has several advantages: from the reactant point of view: firstly, the source way of the methanol is wide, and the methanol can be obtained from the traditional fossil energy source by processing and can also be obtained from biomass such as animals, plants and the like. Second, the hydrogen production efficiency of methanol reforming hydrogen production is higher and fewer impurities are present than other hydrogen production methods. From the perspective of the hydrogen production process: the methanol reforming hydrogen production process is mature, the operation is simple, and the reaction is safe. From a device perspective: the reaction temperature of the methanol reforming hydrogen production is low, and the required pressure is not high, so that the requirement on a reaction device is not high, and the method is safer to use on automobiles.
H produced by reforming reactor 2 And a small amount of CO 2 And separating by a palladium membrane to obtain high-purity hydrogen. During the entire reforming reaction, both methanol and water as reactants must remain in the gaseous state. In addition, the methanol steam reforming hydrogen production is a strong endothermic reaction, and the exterior must provide continuous heat supply. The energy discharged by the automobile tail gas in the form of waste heat accounts for 55% -80% of the total energy, meanwhile, the flow is sufficient, the temperature is up to 500 ℃ -700 ℃, and the waste heat of the automobile tail gas is utilized to supply heat for the reaction to completely meet the reaction condition; meanwhile, clean hydrogen is generated by reaction, and the clean hydrogen can be directly fed into an internal combustion engine for combustion, so that the combustion efficiency is improved, and the pollutant emission is reduced. At present, most of methanol reforming hydrogen production reactorsThe external heat supply mode is adopted, so that the device is complex in structure and wastes a large amount of energy.
Disclosure of Invention
Aiming at the technical problems existing in the prior art, the invention aims to provide a reactor for preparing hydrogen by reforming methanol.
The reactor is characterized by comprising an evaporator, a reformer and a purification storage device which are arranged from bottom to top, wherein the evaporator, the reformer and the purification storage device are connected in series through vertical guide rods to form an integral structure; the top of the reformer is provided with a hot fluid inlet and a cold fluid outlet, and the bottom of the reformer is provided with a hot fluid outlet and a cold fluid inlet; a plurality of layers of serially connected cold fluid channels and a plurality of layers of parallelly connected hot fluid channels are arranged in the reformer, reforming catalysts are arranged in each layer of cold fluid channels, an inlet of the first layer of cold fluid channels is communicated with the cold fluid inlet, and an outlet of the last layer of cold fluid channels is communicated with the cold fluid outlet; the inlet of each layer of hot fluid channel is communicated with the hot fluid inlet, hot tail gas enters each layer of hot fluid channel of the reformer from the hot fluid inlet, and the outlet of each layer of hot fluid channel is communicated with the hot fluid outlet; the cold fluid channel and the hot fluid channel are both in a layered cavity structure, and are alternately arranged in the inner layer of the reformer; the evaporator is used for heating and vaporizing the raw material of the methanol-water mixed solution, and the formed methanol-water mixed gas enters a cold fluid channel of the reformer from a cold fluid inlet to perform catalytic reforming reaction to generate a hydrogen-rich product; the purification reservoir is used for purifying and storing hydrogen from the hydrogen-rich product obtained from the reformer.
The methanol reforming hydrogen production reactor is characterized in that the reformer is formed by sequentially overlapping a first plate, a second plate and a rubber gasket which is arranged between the first plate and the second plate and seals, and a sealed lamellar cavity is formed by encircling the first plate, the rubber gasket and the second plate; the laminar cavity formed among the front surface of the first plate, the rubber gasket and the back surface of the second plate is the cold fluid channel, and the laminar cavity formed among the back surface of the first plate, the rubber gasket and the front surface of the second plate is the hot fluid channel; the reformer further comprises a reforming sub-runner for enabling the cold fluid channels of each layer to be communicated in sequence, a first reforming main runner for enabling the inlets of the hot fluid channels of each layer to be communicated, and a second reforming main runner for enabling the outlets of the hot fluid channels of each layer to be communicated.
The methanol reforming hydrogen production reactor is characterized in that a pair of first cold punched holes are symmetrically arranged on one diagonal of a first plate, a first hot punched hole and a first hot punched hole are respectively arranged on the other diagonal of the first plate, a pair of second cold punched holes are symmetrically arranged on the corresponding diagonal of a second plate, and a second hot punched hole are respectively arranged on the corresponding other diagonal of the second plate; when the first plate and the second plate are sequentially overlapped, the first cold punched hole and the second cold punched hole are aligned and are enclosed by the rubber gasket to form a reforming sub-runner for circulating the methanol-water mixture, the first hot punched hole and the second hot punched hole are aligned and are enclosed by the rubber gasket to form a first reforming main runner for flowing in hot tail gas, and the first hot punched hole and the second hot punched hole are aligned and are enclosed by the rubber gasket to form a second reforming main runner for flowing out hot tail gas.
The reactor for preparing hydrogen by reforming methanol is characterized by further comprising a catalyst supporting plate, wherein the reforming catalyst is CuO-ZnO-Al 2 O 3 The reforming catalyst is of a cylindrical block structure and is uniformly fixed on the catalyst supporting plate in a row; the front surface of the first plate is provided with a plate groove matched with the shape of the catalyst supporting plate, and the catalyst supporting plate is matched and placed in the plate groove.
The methanol reforming hydrogen production reactor is characterized in that two sides of a first plate are provided with first rhombic grooves, a pair of first cold punched holes of the first plate are symmetrically arranged in a pair of angles of a longer diagonal line of the first rhombic groove, the plate groove is positioned in the center of the first rhombic groove, and two sides of a second plate are provided with second rhombic grooves matched with the first rhombic grooves; when the first plate and the second plate are sequentially overlapped, the layered cavity formed among the front surface of the first plate, the rubber gasket and the back surface of the second plate and the layered cavity formed among the back surface of the first plate, the rubber gasket and the front surface of the second plate are of diamond structures.
The methanol reforming hydrogen production reactor is characterized in that an evaporator tail gas inlet and an evaporator methanol vapor outlet are arranged at the top of the evaporator, and an evaporator tail gas outlet and an evaporator methanol aqueous solution inlet are arranged at the bottom of the evaporator; the air inlet pipe on the tail gas inlet of the evaporator is divided into two paths, one path is connected with a hot fluid outlet pipeline at the bottom of the reformer, the other path is connected with a hot tail gas inlet pipeline, and a first electromagnetic flowmeter is arranged on the air inlet pipe on the tail gas inlet of the evaporator; and the methanol vapor outlet of the evaporator is connected with a cold fluid inlet pipeline at the bottom of the reformer through a second electromagnetic flowmeter.
The reactor for producing hydrogen by reforming methanol is characterized in that a hot steam flow channel and a raw material liquid flow channel which are alternately arranged layer by layer are arranged in the evaporator, and the hot steam flow channel and the raw material liquid flow channel are both in a layered cavity structure; the inlet of each layer of hot steam flow cavity is communicated with the tail gas inlet of the evaporator, and the outlet of each layer of hot steam flow cavity is communicated with the tail gas outlet of the evaporator; the inlet of each layer of raw material liquid flowing cavity is communicated with the methanol water solution inlet of the evaporator, and the outlet of each layer of raw material liquid flowing cavity is communicated with the methanol water vapor outlet of the evaporator.
The reactor is characterized in that the evaporator is formed by sequentially overlapping an evaporation plate, a sealing backing plate and a rubber gasket which is arranged between the evaporation plate and the sealing backing plate and seals, and a sealed lamellar cavity is formed by enclosing the evaporation plate, the rubber gasket and the sealing backing plate; the laminar cavity formed among the front surface of the evaporation sheet, the rubber gasket and the back surface of the sealing backing plate is the raw material liquid flowing cavity, and the front surface of the evaporation sheet is provided with a corrugated bump so as to increase the turbulence intensity of the flow of the methanol aqueous solution from the raw material liquid flowing cavity; and a layered cavity formed among the back surface of the evaporation plate, the rubber gasket and the front surface of the sealing backing plate is the hot steam flow channel.
The reactor for producing hydrogen by reforming methanol is characterized in that a hydrogen outlet and a hydrogen-rich product inlet are respectively arranged at the top and the bottom of a purification storage device, and the hydrogen-rich product inlet is connected with a cold fluid outlet pipeline at the top of the reformer.
Compared with the prior art, the invention has the following beneficial effects:
1. the device of the invention is mainly divided into three parts, namely an evaporator, a reformer and a purification storage, which are mutually independent and closely connected. And the three parts all adopt plate structures, and different functions of the device are determined by different plates inside, so that the whole structure of the device is compact and reasonable, and the device is convenient to assemble, disassemble and maintain. The evaporator and the reformer of the invention greatly reduce the thickness of the air film during heat exchange and improve the heat exchange area by means of layer-by-layer heat exchange of the cold and hot fluid, thereby remarkably improving the utilization rate of heat of hot tail gas and having high heat exchange efficiency.
2. The device adopts methanol and water as raw materials for hydrogen production by reforming, and the methanol has the advantages of high energy density, easy production, storage and transportation, etc.
3. The reformer and the evaporator of the device can recycle the heat of the automobile hot tail gas, thereby greatly saving energy. The arrangement mode of the catalyst in the reformer of the device is beneficial to the reforming reaction, and the modularized arrangement mode of the catalyst (the catalyst is arranged in a cylindrical block shape and is uniformly and fixedly arranged on the catalyst supporting plate in a row) is beneficial to the maintenance and the updating.
Drawings
FIG. 1 is a schematic diagram of the overall structure of a methanol reforming hydrogen production reactor according to the present invention;
FIG. 2 is a schematic elevational view of a first plate;
FIG. 3 is a schematic view of the back structure of the first plate;
FIG. 4 is a schematic view of the structure of a reforming catalyst disposed on a catalyst support plate;
FIG. 5 is a schematic view of the front structure of the second plate;
FIG. 6 is a schematic view of the front structure of the evaporation sheet;
FIG. 7 is a schematic diagram of the flow path of a cold and hot fluid within a reformer;
in the figure: 1-evaporator, 11-evaporator tail gas inlet, 12-evaporator methanol vapor outlet, 13-evaporator tail gas outlet, 14-evaporator methanol aqueous solution inlet, 15-evaporation sheet, 15 a-corrugated bump, 16-sealing pad, 2-reformer, 21-hot fluid inlet, 22-hot fluid outlet, 23-cold fluid inlet, 24-cold fluid outlet, 25-first sheet, 25 a-first cold punched hole, 25 b-first hot punched hole, 25 c-first hot punched hole, 25 d-sheet groove, 25 e-first diamond groove, 26-second sheet, 26 a-second cold punched hole, 26 b-second hot punched hole, 26 c-second hot punched hole, 26 e-second diamond groove, 3-purification reservoir, 31-hydrogen outlet, 32-hydrogen-rich product inlet, 4-catalyst support plate, 5-hot tail gas inlet, 6-first electromagnetic flowmeter, 7-second electromagnetic flowmeter, 8-compacting plate.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Examples: comparing FIGS. 1 to 7
The invention relates to a methanol reforming hydrogen production reactor, which comprises an evaporator 1, a reformer 2 and a purification storage 3 which are arranged from bottom to top, wherein guide rods positioned at two sides of the structure of the invention connect the evaporator 1, the reformer 2 and the purification storage 3 in series to form a whole. The evaporator 1 is used for heating and vaporizing the raw material of the methanol-water mixed solution, and the formed methanol-water mixed gas enters the reformer 2 to carry out catalytic reforming reaction to generate a hydrogen-rich product; the purification storage 3 is used for purifying and storing hydrogen from the hydrogen-rich product obtained by the reformer 2 (the purification storage 3 adopts a device for purifying hydrogen and storing hydrogen which is conventional in the prior art, the interior of the purification storage 3 is of a plate structure and is divided into 4 areas, the lowermost area is a palladium membrane separation area, only hydrogen can pass through the purification storage 3 to play a role in purifying hydrogen, and the interior of the remaining 3 areas is provided with a porous hydrogen storage material for storing and releasing hydrogen).
The reformer 2 is provided at the top with a hot fluid inlet 21 and a cold fluid outlet 24, and the reformer 2 is provided at the bottom with a hot fluid outlet 22 and a cold fluid inlet 23.
The top of the evaporator 1 is provided with an evaporator tail gas inlet 11 and an evaporator methanol water vapor outlet 12, and the bottom of the evaporator 1 is provided with an evaporator tail gas outlet 13 and an evaporator methanol water solution inlet 14; the air inlet pipe on the evaporator tail gas inlet 11 is divided into two paths, one path is connected with a hot fluid outlet 22 at the bottom of the reformer 2 through a pipeline, the other path is connected with a hot tail gas inlet 5 through a pipeline, and a first electromagnetic flowmeter 6 is arranged on the air inlet pipe on the evaporator tail gas inlet 11; the evaporator methanol vapor outlet 12 is connected with a cold fluid inlet 23 at the bottom of the reformer 2 through a second electromagnetic flowmeter 7.
The top and bottom of the purge reservoir 3 are provided with a hydrogen outlet 31 and a hydrogen rich product inlet 32, respectively, which hydrogen rich product inlet 32 is in piping connection with the cold fluid outlet 24 at the top of the reformer 2.
The reformer 2 and the evaporator 1 are both plate-type structures, and the reformer 2 and the evaporator 1 are respectively heated by taking automobile hot tail gas as a heat source.
The reformer 2 is internally provided with a plurality of layers of cold fluid channels connected in series and a plurality of layers of hot fluid channels connected in parallel, a reforming catalyst is arranged in each layer of cold fluid channel, an inlet of the first layer of cold fluid channel is communicated with the cold fluid inlet 23, and an outlet of the last layer of cold fluid channel is communicated with the cold fluid outlet 24, so that a methanol water mixed gas flows into the cold fluid channels of the reformer 2 through the cold fluid inlet 23, catalytic reforming reaction is carried out under the action of the reforming catalyst, and a hydrogen-rich product generated by the reaction finally flows out from the cold fluid outlet 24 and then enters the purification storage 3 for hydrogen purification and hydrogen storage. The inlets of each layer of hot fluid channels are communicated with the hot fluid inlet 21, and the outlets of each layer of hot fluid channels are communicated with the hot fluid outlet 22, namely, automobile hot tail gas is introduced from the hot fluid inlet 21 as a heat source and uniformly enters each layer of hot fluid channels of the reformer 2 to heat the reformer 2. The cold fluid channel and the hot fluid channel are of a layered cavity structure, and the cold fluid channel and the hot fluid channel are alternately arranged in the inner layer of the reformer 2, so that the methanol-water mixed gas and the automobile hot tail gas exchange heat layer by layer in the reformer 2, the energy utilization rate of the automobile hot tail gas is greatly improved, the automobile hot tail gas is uniformly divided into a plurality of branches and enters the parallel hot fluid channels of the reformer 2, the heating temperature in each hot fluid channel is uniform, the temperature of the hot tail gas is prevented from being gradually reduced after passing through a longer heat exchange path, and the problem of nonuniform reforming reaction temperature is caused (if the hot fluid channels are connected in series layer by layer, the temperature of the hot tail gas is gradually reduced in the flowing process from the first layer of the hot fluid channel to the last layer of the hot fluid channel). The methanol-water mixed gas sequentially passes through a plurality of layers of cold fluid channels connected in series of the reformer 2, so that sufficient residence time of reforming reaction raw materials in the reformer 2 is ensured, and the reforming reaction is more sufficient. By the structure of the present invention, methanol water flows in a nearly plug flow manner in the cold fluid channels of several layers in series of the reformer 2. In contrast, in fig. 7, the route c→b is the flow route of the methanol-water mixture in the cold fluid channel in the reformer 2, and the route a→d is the flow route of the hot exhaust gas of the automobile in the hot fluid channel in the reformer 2.
The reformer 2 is internally provided with a structure of cold fluid channels and hot fluid channels alternately layer by layer, and the reformer 2 may adopt a structure formed by: the reformer 2 is formed by sequentially overlapping a first plate 25, a second plate 26 and rubber gaskets arranged between the first plate 25 and the second plate 26 for sealing, wherein a sealed lamellar cavity is formed by encircling the first plate 25, the rubber gaskets and the second plate 26, and the rubber gaskets form the side wall of the lamellar cavity, so that the thickness of the lamellar cavity is the thickness of the rubber gaskets (adhesive glue can be arranged on two sides of the rubber gaskets, and the first plate 25 and the rubber gaskets and the second plate 26 and the rubber gaskets are all adhered and sealed through the adhesive glue). The lamellar cavity formed among the front surface of the first plate 25, the rubber gasket and the back surface of the second plate 26 is the cold fluid channel, and the lamellar cavity formed among the back surface of the first plate 25, the rubber gasket and the front surface of the second plate 26 is the hot fluid channel; the reformer 2 further comprises a reforming sub-runner for enabling the cold fluid channels of each layer to be communicated in sequence, a first reforming main runner for enabling the inlets of the hot fluid channels of each layer to be communicated, and a second reforming main runner for enabling the outlets of the hot fluid channels of each layer to be communicated.
The reformer 2 may be provided with a reforming sub-channel, a first reforming main channel, and a second reforming main channel: several pipes are penetrated on the integral structure formed by sequentially overlapping the first plate 25, the rubber gasket and the second plate 26, and holes are properly formed on the penetrated pipes, so that a plurality of layers of cold fluid channels in the reformer 2 are sequentially connected in series and the hot fluid channels are sequentially connected in parallel. For example: a pipe vertically passes through the whole structure of the reformer 2, and the upper end opening of the pipe is abutted with the hot fluid inlet 21, the lower end opening of the pipe is plugged, and the part of the pipe in each layer of hot fluid cavity is properly perforated, so that the pipe forms the first reforming main flow channel.
The reformer 2 may be provided with a reforming sub-channel, a first reforming main channel, and a second reforming main channel: the four corners of the first plate 25 and the second plate 26 are respectively provided with a punched hole, a pair of first cold punched holes 25a are symmetrically arranged on one diagonal corner of the first plate 25, a first hot punched hole 25b and a first hot punched hole 25c are respectively arranged on the other diagonal corner of the first plate 25, a pair of second cold punched holes 26a are symmetrically arranged on the corresponding diagonal corner of the second plate 26, and a second hot punched hole 26b and a second hot punched hole 26c are respectively arranged on the corresponding other diagonal corner of the second plate 26; when the first sheet 25 and the second sheet 26 are sequentially stacked, the first cold punched hole 25a and the second cold punched hole 26a are aligned and surrounded by a rubber gasket to form a reforming sub-channel for circulating the methanol-water mixture (the reforming sub-channel is specifically formed in such a manner that the first cold punched hole 25a and the second cold punched hole 26a are surrounded by a rubber gasket to form a tubular channel, the side wall of the tubular channel is the rubber gasket, and the openings at the two ends of the tubular channel are the first cold punched hole 25a and the second cold punched hole 26a, respectively, the side of the tubular channel is not perforated in the hot fluid channel portion, the side of the tubular channel is properly perforated in the cold fluid channel portion, and the upper end opening of the tubular channel is plugged when the side opening of the tubular channel is communicated with the inlet of the cold fluid channel, and the lower end opening of the tubular channel is plugged when the side opening of the tubular channel is communicated with the outlet of the cold fluid channel, thereby the methanol-water mixture flows upward in a zigzag disc in the reformer 2, as compared with fig. 1 and 7. The first hot punching hole 25b and the second hot punching hole 26b are aligned and surrounded by a rubber gasket to form a first reforming main flow path for flowing in hot exhaust gas, and the first hot punching hole 25c and the second hot punching hole 26c are aligned and surrounded by a rubber gasket to form a second reforming main flow path for flowing out hot exhaust gas.
The structure of the present invention further includes a catalyst supporting plate 4, and the reforming catalyst is CuO-ZnO-Al, as shown in FIG. 4 2 O 3 The compound is characterized in that the reforming catalyst is of a cylindrical block structure and is uniformly fixed on the catalyst supporting plate 4 in rows; the front surface of the first plate 25 is provided with a plate groove 25d matched with the shape of the catalyst supporting plate 4, and the catalyst supporting plate 4 is matched and placed in the plate groove 25 d. The arrangement mode of the reforming catalyst also forms a reactant flow channel, and when the methanol-water vapor mixture flows through, the catalyst is fully contacted with the cylindrical bulk catalyst, and the catalyst flows according to a set rule to complete the catalytic reforming reaction.
In order to enhance the circulation effect of the methanol vapor mixture in the cold fluid channel of the reformer 2, the following modifications are adopted: the two sides of the first plate 25 are respectively provided with a first rhombic groove 25e, a pair of first cold punched holes 25a of the first plate 25 are symmetrically arranged in a pair of opposite angles of a longer diagonal line of the first rhombic groove 25e, the plate groove 25d is positioned in the center of the first rhombic groove 25e, and two sides of the second plate 26 are respectively provided with a second rhombic groove 26e matched with the first rhombic groove 25 e; when the first plate 25 and the second plate 26 are sequentially stacked, the layered cavity formed between the front surface of the first plate 25, the rubber gasket and the back surface of the second plate 26, and the layered cavity formed between the back surface of the first plate 25, the rubber gasket and the front surface of the second plate 26 are diamond structures. Thus, when the methanol vapor mixture flows in the cold fluid channel, the methanol vapor mixture flows along the longer diagonal direction of the first rhombic groove 25e, and the reactant raw material is not easy to form dead angles in the cold fluid channel, so that a directional flow path is formed.
The evaporator 1 is internally provided with a hot steam flowing cavity and a raw material liquid flowing cavity which are alternately arranged layer by layer, and the hot steam flowing cavity and the raw material liquid flowing cavity are both in a layered cavity structure; the inlet of each layer of hot steam flow cavity is communicated with the evaporator tail gas inlet 11, and the outlet of each layer of hot steam flow cavity is communicated with the evaporator tail gas outlet 13; the inlet of each layer of raw material liquid flow channel is communicated with the methanol aqueous solution inlet 14 of the evaporator, and the outlet of each layer of raw material liquid flow channel is communicated with the methanol aqueous vapor outlet 12 of the evaporator.
The evaporator 1 may have the following specific structure: the evaporator 1 is formed by sequentially overlapping an evaporation sheet 15, a sealing backing plate 16 and rubber gaskets arranged between the evaporation sheet 15 and the sealing backing plate 16 for sealing, wherein a sealed lamellar cavity is formed by enclosing the evaporation sheet 15, the rubber gaskets and the sealing backing plate 16; the laminar cavity formed between the front surface of the evaporation sheet 15, the rubber gasket and the back surface of the sealing pad 16 is the raw material liquid flow channel, and the front surface of the evaporation sheet 15 is provided with a corrugated bump 15a to increase the turbulence intensity of the methanol aqueous solution flowing from the raw material liquid flow channel, and the methanol aqueous solution is easy to change into a gaseous state under the stronger turbulence intensity; the laminar cavity formed between the back of the evaporating plate 15, the rubber gasket and the front of the sealing pad 16 is the hot steam flow channel. The inlet of each layer of hot steam flow channel is communicated with the evaporator tail gas inlet 11 in the following manner: the evaporator 1 is provided with a pipeline in a penetrating mode, the pipeline vertically penetrates through the whole structure of the evaporator 1, an upper end opening of the pipeline is in butt joint with an evaporator tail gas inlet 11, a lower end opening of the pipeline is plugged, and side openings are formed in the parts, located in each layer of hot steam flowing cavity, of the pipeline, so that hot steam uniformly enters each layer of hot steam flowing cavity through the pipeline.
According to the invention, the evaporator 1 and the reformer 2 can be compressed and fixed through the compression plates 8, the two compression plates 8 are respectively arranged at the upper end and the lower end of the evaporator 1 or the reformer 2, screw holes are arranged on the compression plates 8, and the compression plates 8 at the upper end and the lower end of the evaporator 1 or the reformer 2 are compressed and fixed through bolts, so that the evaporator 1 or the reformer 2 has better overall stability.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present invention to the specific forms set forth in the examples.
Claims (7)
1. The methanol reforming hydrogen production reactor is characterized by comprising an evaporator (1), a reformer (2) and a purification storage (3) which are arranged from bottom to top, wherein the evaporator (1), the reformer (2) and the purification storage (3) are connected in series through vertical guide rods to form an integral structure; the top of the reformer (2) is provided with a hot fluid inlet (21) and a cold fluid outlet (24), and the bottom of the reformer (2) is provided with a hot fluid outlet (22) and a cold fluid inlet (23);
a plurality of layers of serially connected cold fluid channels and a plurality of layers of parallel connected hot fluid channels are arranged in the reformer (2), reforming catalysts are arranged in each layer of cold fluid channels, an inlet of the first layer of cold fluid channels is communicated with a cold fluid inlet (23), and an outlet of the last layer of cold fluid channels is communicated with a cold fluid outlet (24); the inlet of each layer of hot fluid channel is communicated with the hot fluid inlet (21), hot tail gas enters each layer of hot fluid channel of the reformer (2) from the hot fluid inlet (21), and the outlet of each layer of hot fluid channel is communicated with the hot fluid outlet (22); the cold fluid channel and the hot fluid channel are both in a layered cavity structure, and are alternately arranged in the inner layer of the reformer (2);
the evaporator (1) is used for heating and vaporizing the raw material of the methanol-water mixed solution, and the formed methanol-water mixed gas enters a cold fluid channel of the reformer (2) from a cold fluid inlet (23) to perform catalytic reforming reaction to generate a hydrogen-rich product; the purification storage (3) is used for purifying and storing hydrogen from the hydrogen-rich product obtained by the reformer (2);
the top of the evaporator (1) is provided with an evaporator tail gas inlet (11) and an evaporator methanol water vapor outlet (12), and the bottom of the evaporator (1) is provided with an evaporator tail gas outlet (13) and an evaporator methanol water solution inlet (14); an air inlet pipe on the tail gas inlet (11) of the evaporator is divided into two paths, one path is connected with a hot fluid outlet (22) at the bottom of the reformer (2) through a pipeline, the other path is connected with a hot tail gas inlet (5) through a pipeline, and a first electromagnetic flowmeter (6) is arranged on the air inlet pipe on the tail gas inlet (11) of the evaporator; the evaporator methanol vapor outlet (12) is connected with a cold fluid inlet (23) at the bottom of the reformer (2) through a second electromagnetic flowmeter (7) in a pipeline manner;
the top and the bottom of the purification reservoir (3) are respectively provided with a hydrogen outlet (31) and a hydrogen-rich product inlet (32), and the hydrogen-rich product inlet (32) is connected with a cold fluid outlet (24) at the top of the reformer (2) in a pipeline way.
2. A reactor for reforming methanol to produce hydrogen as defined in claim 1, wherein the reformer (2) is formed by sequentially overlapping a first plate (25), a second plate (26) and a rubber gasket arranged between the first plate (25) and the second plate (26) for sealing, wherein a sealed lamellar cavity is formed by enclosing the first plate (25), the rubber gasket and the second plate (26); the laminar cavity formed among the front surface of the first plate (25), the rubber gasket and the back surface of the second plate (26) is the cold fluid channel, and the laminar cavity formed among the back surface of the first plate (25), the rubber gasket and the front surface of the second plate (26) is the hot fluid channel; the reformer (2) further comprises a reforming sub-runner for enabling the cold fluid channels of each layer to be communicated in sequence, a first reforming main runner for enabling the inlets of the hot fluid channels of each layer to be communicated and a second reforming main runner for enabling the outlets of the hot fluid channels of each layer to be communicated.
3. A reactor for reforming methanol to produce hydrogen as defined in claim 2, characterized in that a pair of first cold punched holes (25 a) are symmetrically provided at a pair of opposite corners of the first sheet (25) and a first hot punched hole (25 b) and a first hot punched hole (25 c) are provided at the other pair of opposite corners, respectively, and a pair of second cold punched holes (26 a) are symmetrically provided at a corresponding pair of opposite corners of the second sheet (26) and a second hot punched hole (26 b) and a second hot punched hole (26 c) are provided at the other corresponding pair of opposite corners, respectively; when the first plate (25) and the second plate (26) are sequentially overlapped, the first cold punched hole (25 a) and the second cold punched hole (26 a) are aligned and are enclosed by a rubber gasket to form a reforming sub-runner for circulating methanol-water mixture, the first hot punched hole (25 b) and the second hot punched hole (26 b) are aligned and are enclosed by the rubber gasket to form a first reforming main runner for flowing in hot tail gas, and the first hot punched hole (25 c) and the second hot punched hole (26 c) are aligned and are enclosed by the rubber gasket to form a second reforming main runner for flowing out hot tail gas.
4. A reactor for the reforming of methanol to produce hydrogen as defined in claim 2 further comprising a catalyst support plate (4), the reforming catalyst being CuO-ZnO-Al 2 O 3 The reforming catalyst is of a cylindrical block structure and is uniformly fixed on the catalyst supporting plate (4) in rows; the front surface of the first plate (25) is provided with a plate groove (25 d) matched with the shape of the catalyst supporting plate (4), and the catalyst supporting plate (4) is placed in the plate groove (25 d) in a matched mode.
5. A reactor for reforming methanol to produce hydrogen as defined in claim 4, wherein a first rhombic groove (25 e) is provided on both sides of the first sheet (25), a pair of first cold punched holes (25 a) of the first sheet (25) are symmetrically provided in a pair of corners of a longer diagonal line of the first rhombic groove (25 e), the sheet groove (25 d) is located at the center of the first rhombic groove (25 e), and a second rhombic groove (26 e) adapted to the first rhombic groove (25 e) is provided on both sides of the second sheet (26); when the first plate (25) and the second plate (26) are sequentially overlapped, a layered cavity formed among the front surface of the first plate (25), the rubber gasket and the back surface of the second plate (26) and a layered cavity formed among the back surface of the first plate (25), the rubber gasket and the front surface of the second plate (26) are of a diamond structure.
6. A reactor for producing hydrogen by reforming methanol according to claim 1, characterized in that the evaporator (1) is internally provided with a layer-by-layer alternating hot steam flow channel and a raw material liquid flow channel, and the hot steam flow channel and the raw material liquid flow channel are both in a layered cavity structure; the inlet of each layer of hot steam flow cavity is communicated with the evaporator tail gas inlet (11), and the outlet of each layer of hot steam flow cavity is communicated with the evaporator tail gas outlet (13); the inlet of each layer of raw material liquid flowing cavity is communicated with the methanol water solution inlet (14) of the evaporator, and the outlet of each layer of raw material liquid flowing cavity is communicated with the methanol water vapor outlet (12) of the evaporator.
7. The reactor for producing hydrogen by reforming methanol according to claim 6, wherein the evaporator (1) is formed by sequentially overlapping an evaporation sheet (15), a sealing pad (16) and a rubber gasket arranged between the evaporation sheet (15) and the sealing pad (16), and a sealed lamellar cavity is formed by enclosing the evaporation sheet (15), the rubber gasket and the sealing pad (16); the laminar cavity formed among the front surface of the evaporation sheet (15), the rubber gasket and the back surface of the sealing backing plate (16) is the raw material liquid flowing cavity, and the front surface of the evaporation sheet (15) is provided with a corrugated lug (15 a) so as to increase the turbulence intensity of the flow of the methanol aqueous solution from the raw material liquid flowing cavity; the laminar cavity formed among the back surface of the evaporating plate (15), the rubber gasket and the front surface of the sealing backing plate (16) is the hot steam flow channel.
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