CN110902651B - Self-heating annular methanol reforming hydrogen production reactor - Google Patents
Self-heating annular methanol reforming hydrogen production reactor Download PDFInfo
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- CN110902651B CN110902651B CN201911234640.8A CN201911234640A CN110902651B CN 110902651 B CN110902651 B CN 110902651B CN 201911234640 A CN201911234640 A CN 201911234640A CN 110902651 B CN110902651 B CN 110902651B
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
- C01B2203/1023—Catalysts in the form of a monolith or honeycomb
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
Abstract
The invention discloses an autothermal annular methanol reforming hydrogen production reactor. The reactor is respectively provided with an evaporation cavity, a combustion cavity and a reforming reaction cavity from inside to outside; the innermost evaporation cavity comprises an evaporation cavity pipe; the middle layer combustion cavity consists of an evaporation cavity pipe, a combustion cavity top cover and a combustion cavity bottom cover, is an annular space and is embedded with honeycomb-shaped silicon carbide; the outer layer reforming reaction cavity consists of a combustion cavity pipe, a reforming cavity barrel and a reforming cavity bottom cover, is an annular space and is embedded with honeycomb-shaped silicon carbide; reactants enter each cavity body simultaneously to react, so that heat absorption and release balance is achieved, and continuous hydrogen production is realized. The invention achieves good sealing property according to the smallest circular circumference with the same area, and can adjust the size of each ring to achieve higher power density before manufacturing according to actual reaction requirements; meanwhile, the high-efficiency heat-conducting material has good heat-conducting property, small density and light weight, can homogenize the flow velocity distribution of reactants, improves the conversion rate of the reactants and improves the flow directionality.
Description
Technical Field
The invention belongs to a methanol reforming hydrogen production reactor, and particularly relates to an autothermal annular methanol reforming hydrogen production reactor.
Technical Field
With the gradual depletion of fossil energy over the 21 st century, people are continuously looking for and developing clean and renewable energy. Among the current new energy sources, hydrogen energy has the advantages of high combustion heat value, low pollution, renewability and the like, and is an ideal alternative energy source of fossil fuels.
Hydrogen fuel cells are one of the primary ways in which hydrogen energy can be utilized. The device is a high-efficiency power generation device, is not limited by Carnot cycle, and has the advantages of high energy conversion efficiency and clean reaction products.
The current development of hydrogen energy economy has the main bottleneck of difficult hydrogen storage. The existing mobile hydrogen storage technology has small energy density and high manufacturing cost, and has a certain gap from commercial application. Therefore, the hydrogen storage problem seriously hinders the application of the hydrogen fuel cell in the fields of automobiles, unmanned planes and the like. The technology for producing hydrogen by reforming methanol water vapor on site is expected to break through the bottleneck, and an effective solution is provided for the technology.
The Chinese invention patent (application number: 201821291857.3) discloses a quick-start self-heating methanol reforming hydrogen production microreactor, which comprises a second methanol combustion plate, a methanol reforming hydrogen production plate, a reforming fuel outlet pipe and a reforming hydrogen production catalyst boss, wherein a methanol preheating layer is added in a methanol combustion chamber, so that methanol is combusted and gasified by using the heat of the methanol, and the combustion is more sufficient.
Chinese invention patent (application No. 201610483078.2) discloses a reactor for generating a reformed gas containing hydrogen from a raw material containing a carbon compound and water, the reactor comprising: a reforming section for reforming the raw material to generate a reformed gas containing hydrogen; a combustion section for supplying heat to the reforming section by combusting the raw material; a carbon monoxide removal reaction section for removing carbon monoxide in the reformed gas containing hydrogen; heating the raw material conveying pipe; and a reforming material phase change tube which is located in the combustion part and heats the material, wherein a first shell, a second shell and a heating material delivery pipe are arranged in sequence at intervals in a concentric structure from the outside, and the reforming part and the combustion part are independently formed by the space at intervals of the first shell and the second shell and the space at intervals of the second shell and the heating material delivery pipe respectively.
However, the structure of the self-heating methanol steam reforming reactor disclosed at present does not consider the effective sealing problem and the structural redundancy, and simultaneously, the substrate of the reactor is thicker, the heat capacity of the reactor is large, and the dynamic response speed and the mass power density of the system are reduced. Therefore, it is necessary to further optimize the structural design of the autothermal methanol steam reforming reactor, improve the compactness of the reactor structure, realize the lightweight design of the reactor, and improve the hydrogen production performance and power density of the reactor.
Disclosure of Invention
The invention provides an autothermal type annular methanol reforming hydrogen production reactor, which aims to solve the problems of different reaction rates and difficult sealing of methanol aqueous solution vaporization reaction, methanol catalytic combustion reaction and methanol steam reforming reaction in the autothermal type methanol steam reforming reactor in the background art, and achieves the purposes of optimizing the reactor structure, improving the compactness and power density of the reactor and improving the sealing performance of the reactor.
The technical scheme adopted by the invention is as follows:
the invention comprises an evaporation cavity, a combustion cavity and a reforming reaction cavity from inside to outside in sequence, wherein the reforming reaction cavity is an annular space mainly defined by a reforming cavity barrel, a combustion cavity pipe and a reforming cavity bottom cover, the combustion cavity is an annular space mainly defined by the combustion cavity pipe, the evaporation cavity pipe, a combustion cavity top cover and the combustion cavity bottom cover, and the evaporation cavity is mainly composed of the evaporation cavity pipe.
The evaporation cavity pipe, the combustion cavity pipe and the reforming cavity barrel are coaxially arranged from inside to outside in sequence.
The bottom of the reforming cavity barrel is provided with a reforming cavity bottom cover through a fastening bolt, and the lower end surface of the reforming cavity bottom cover is provided with four reforming product outlet pipes communicated with the reforming reaction cavity at equal intervals along the circumferential direction; the top end of the combustion cavity pipe is welded with a combustion cavity top cover, the upper end surface of the combustion cavity top cover is provided with four combustion product outlet pipes communicated with the combustion cavity at equal intervals along the circumferential direction, the combustion product outlet pipes penetrate through the upper end cover of the reforming cavity barrel from bottom to top, the combustion product outlet pipe between the upper end cover of the reforming cavity barrel and the combustion cavity top cover is provided with a fixing boss, and a gap for gas circulation is reserved between the upper end cover of the reforming cavity barrel and the combustion cavity top cover through the fixing boss; the bottom of the combustion cavity pipe is welded with a combustion cavity bottom cover, four combustion reactant inlet pipes communicated with the combustion cavity are arranged on the lower end face of the combustion cavity bottom cover at equal intervals along the circumferential direction, and the combustion reactant inlet pipes penetrate out of the reforming cavity bottom cover from top to bottom through combustion reactant inlet pipe through holes of the reforming cavity bottom cover.
The lower end face of the reforming cavity bottom cover is provided with an annular embedded groove positioned between the through hole and the reformate outlet pipe, the fuel gas buffer cavity cover is embedded in the lower end face of the reforming cavity bottom cover through the annular embedded groove, and a fuel gas buffer cavity fluororubber sealing ring is embedded between the fuel gas buffer cavity cover and the annular embedded groove; the gas buffering cavity cover is provided with a gas buffering cavity annular groove communicated with the four combustion reactant inlet pipes, the bottom of the gas buffering cavity annular groove is provided with a gas buffering cavity inlet pipe communicated with the outside, the inner groove wall of the gas buffering cavity annular groove is enclosed to form a pressing boss, and the outer groove wall of the gas buffering cavity annular groove is the edge of the gas buffering cavity cover.
The middle of the combustion cavity pipe is provided with an evaporation cavity pipe which vertically penetrates through the top cover of the combustion cavity and the bottom cover of the combustion cavity, and the bottom of the evaporation cavity pipe sequentially extends out of the reactor through a through hole arranged in the middle of the bottom cover of the reforming cavity and the gas buffer cavity cover.
A combustion product outlet pipe of the combustion cavity pipe extending out of the upper end cover of the reforming cavity barrel is fixed through a combustion cavity fixing nut, and a fluororubber gasket for preventing gas in the reforming cavity from leaking is sleeved between the combustion cavity fixing nut and the upper end cover of the reforming cavity barrel;
the upper surface of the combustion chamber bottom cover is provided with a combustion chamber fluororubber sealing ring embedded into the annular groove at a position close to the edge, and the combustion chamber fluororubber sealing ring embedded into the annular groove is embedded with a combustion chamber fluororubber sealing ring for isolating the reforming reaction chamber and the combustion chamber.
A reforming cavity fluororubber sealing layer for isolating the combustion cavity from the reforming cavity is arranged between the combustion cavity bottom cover and the reforming cavity bottom cover; the connection part of the reforming cavity bottom cover and the reforming cavity barrel is provided with two annular grooves which are opposite up and down, the two annular grooves which are opposite up and down enclose an annular groove together, and a reforming cavity fluorine rubber sealing ring is embedded in the annular groove.
The evaporation cavity pipe extending out of the reactor is sleeved with a central compression nut, and a compression boss of the gas buffer cavity cover compresses the fluororubber sealing element between the cavities under the action of the central compression nut; each cavity comprises an evaporation cavity, a combustion cavity and a reforming reaction cavity, and the fluororubber sealing element comprises a fluororubber sealing ring of the combustion cavity, a fluororubber sealing layer of the reforming cavity, a fluororubber sealing ring of the reforming cavity and a fluororubber sealing ring of the gas buffer cavity.
Honeycomb-shaped silicon carbide is filled and embedded in the reforming reaction cavity and the combustion cavity, a methanol water vapor reforming catalyst is coated on the honeycomb-shaped silicon carbide in the reforming reaction cavity, a methanol catalytic combustion catalyst is coated on the honeycomb-shaped silicon carbide in the combustion cavity, the honeycomb-shaped silicon carbide in the reforming reaction cavity and the honeycomb-shaped silicon carbide in the combustion cavity are located at the same height position, and gaps for gas circulation are reserved at the upper end and the lower end of the honeycomb-shaped silicon carbide in the reforming reaction cavity and the upper end and the lower end of the.
The reactor comprises two gas paths of methanol catalytic combustion and methanol water vapor reforming;
methanol catalytic combustion gas circuit: methanol and air enter a gas buffering cavity annular groove from a gas buffering cavity inlet pipe of a gas buffering cavity cover, the methanol and the air entering the gas buffering cavity annular groove are divided into four paths to respectively enter a combustion cavity from four combustion reactant inlet pipes, the methanol and the air generate catalytic combustion reaction under the action of a methanol catalytic combustion catalyst when flowing through honeycomb-shaped silicon carbide in the combustion cavity, and gas generated by the catalytic combustion reaction is discharged through a combustion reactant outlet
Methanol water vapor reforming gas circuit: and pumping methanol water solution from the bottom of the evaporation cavity pipe by an air pump, wherein a methanol water vapor mixture generated after the methanol water solution is vaporized in the evaporation cavity pipe enters the reforming reaction cavity through a gap reserved by the fixed boss, and the methanol water vapor mixture generates reforming reaction under the action of a methanol water vapor reforming catalyst when flowing through the honeycomb-shaped silicon carbide in the reforming reaction cavity, so that hydrogen-enriched reformed gas required by the fuel cell is discharged from a reformed product outlet pipe.
The heat released by the catalytic combustion reaction supplies heat for the endothermic reaction in the whole reactor and maintains the working temperature required by the reforming reaction; the endothermic reaction includes a gasification reaction of the aqueous methanol solution in the evaporation chamber and a reforming reaction in the reforming chamber.
The reactor only works in a methanol catalytic combustion gas circuit at the initial starting stage, when the catalytic combustion reaction in the combustion chamber releases heat to enable the temperature in the reforming chamber to reach the reforming reaction temperature, the reactor enters a stable working stage, and the methanol water vapor reforming gas circuit and the methanol catalytic combustion gas circuit start to work simultaneously.
The evaporation cavity, the combustion cavity and the reforming reaction cavity which are sequentially arranged from inside to outside are closely arranged in a ring-buckled manner, so that the heat generated by the catalytic combustion reaction of the combustion cavity is fully utilized; the evaporation cavity is communicated with the reforming reaction cavity through a gap reserved on the fixed boss, and the methanol catalytic combustion reaction gas circuit and the methanol catalytic reforming gas circuit are staggered.
The thickness of the tube wall of the evaporation cavity tube is 1-2 mm, the thickness of the tube wall of the combustion cavity tube is 2-2.5 mm, and the thickness of the reforming cavity barrel is more than 3 mm; the inner diameter of the evaporation cavity pipe is larger than 8mm, the difference between the inner diameter of the combustion cavity pipe and the outer diameter of the evaporation cavity pipe is larger than 30mm, the difference between the inner diameter of the reforming cavity barrel and the outer diameter of the combustion cavity pipe is larger than 50mm, and the size can be adjusted according to an actual simulation result.
The height of a fixed boss arranged on the top cover of the combustion chamber is more than 5mm, and the height difference of four fixed bosses is within 0.1 mm; the height of the compression boss of the gas buffer cavity cover is larger than 8mm and is 1-2 mm higher than the edge of the gas buffer cavity cover.
The sealing component is made of fluororubber; the preparation material of the reforming cavity barrel at the outermost layer of the reactor is stainless steel, and the preparation material of the evaporation cavity pipe and the combustion cavity pipe is aluminum alloy; the honeycomb silicon carbide may be replaced with honeycomb cordierite.
The invention has the beneficial effects that:
1) the invention improves the power density of the structural design of the self-heating methanol water vapor reforming reactor, adopts the annular design, and can adjust the size of each annular cavity by analog simulation before manufacture aiming at the characteristic that each cavity has different reaction rates, thereby achieving higher output power in the same volume.
2) According to the invention, the circular circumference is the smallest under the same area, and the annular design is adopted for the reactor, so that the gas tightness of the reactor is favorably improved, and the efficiency reduction or the environmental pollution caused by gas mutual leaping or gas leakage among the cavities in the reaction process is prevented.
3) The combustion cavity is completely wrapped by the evaporation cavity and the reforming cavity, so that heat generated by methanol catalytic combustion reaction can be fully utilized, and the energy conversion efficiency is improved. Meanwhile, the evaporating pipe is in a slender design and is wrapped by the combustion cavity, so that the vaporization of the methanol water solution can be accelerated, and the hydrogen production rate of the reactor is improved.
4) The reactor has good heat transfer and mass transfer performance. In the reactor, the metal and the silicon carbide both have good heat conducting performance, and the metal and the silicon carbide are closely attached, so that the heat transfer condition in the reactor is improved. The elongated pores in the silicon carbide porous honeycomb carrier can play a role in enhancing the directionality of the flow of reactants, reducing the turbulence in the traditional metal foam, and simultaneously increasing the contact area of the gas and the catalyst. The good heat and mass transfer performance can obviously improve the utilization rate of the catalyst and the hydrogen production performance of the reactor.
5) The reactor adopts a lightweight design, and is beneficial to improving the dynamic response speed of the reactor. The inner and outer surfaces of each cavity tube are fully utilized to form an annular chamber, so that the reactor is more compact, and meanwhile, a large amount of light-weight excellent heat conduction materials are adopted. Through the lightweight design, the whole quality and the heat capacity of the reactor are reduced, and the starting time and the response time of the reactor can be shortened.
Drawings
FIG. 1 is a schematic cross-sectional view of the present invention.
FIG. 2 is a left and right isometric view of the combustion chamber cap of the present invention.
Figure 3 is a top view of a reformer chamber barrel of the present invention.
Fig. 4 is a sectional view a-a of fig. 3.
FIG. 5 is a left and right isometric view of a combustion chamber bottom cover of the present invention.
FIG. 6 is a top view of a reforming chamber bottom cover of the present invention.
Fig. 7 is a sectional view a-a of fig. 6.
FIG. 8 is an isometric view of the upper and lower halves of the gas buffer chamber cover of the present invention.
FIG. 9 is a flow diagram of the reactants of the present invention.
In the figure: 1. a combustion chamber top cover, 2, a combustion chamber fixing nut, 3, a fluororubber gasket, 4, honeycomb silicon carbide coated with a methanol water vapor reforming catalyst, 5, an evaporation chamber pipe, 6, honeycomb silicon carbide coated with a methanol catalytic combustion catalyst, 7, a combustion chamber pipe, 8, a reforming chamber barrel, 9, a combustion chamber fluororubber sealing ring, 10, a combustion chamber bottom cover, 11, a reforming chamber fluororubber sealing layer, 12, a reforming chamber fluororubber sealing ring, 13, a gas buffer chamber fluororubber sealing ring, 14, a reforming chamber bottom cover, 15, a gas buffer chamber cover, 16, a central gland nut, 17, a fastening nut, 18, a fastening bolt, 19, a combustion reactant outlet pipe, 20, a methanol water vapor mixture outlet, 21, a fixing boss, 22, a combustion reactant outlet pipe through hole, 23, a reforming chamber fluororubber sealing ring embedded groove, 24, a bolt hole, 25, a combustion chamber fluororubber sealing ring embedded in an annular groove, 26. combustion reactant inlet pipes, 27, combustion reactant inlet pipes, through holes, 28, annular insert grooves, 29, reformate outlet pipes, 30, compression bosses, 31, gas buffer chamber inlet pipes.
Detailed Description
The invention is further described below with reference to the figures and examples.
As shown in fig. 1, the reactor is respectively provided with an evaporation cavity, a combustion cavity, a reforming reaction cavity and a fuel gas buffer cavity from inside to outside; the innermost layer evaporation cavity comprises the inner surface of an evaporation cavity pipe 5, the lower end of the evaporation cavity pipe 5 is a catalytic reforming reactant inlet, and the methanol water solution is vaporized into a mixed gas of methanol and water vapor in the pipe to prepare for the next catalytic reforming reaction of the methanol water vapor. The middle layer combustion cavity body is composed of the outer surface of the evaporation cavity pipe 5, the inner surface of the combustion cavity pipe 7, the lower surface of the combustion cavity top cover 1 and the upper surface of the combustion cavity bottom cover 10, and is an annular space, the honeycomb-shaped silicon carbide 6 coated with the methanol catalytic combustion catalyst is embedded in the combustion cavity, the evaporation cavity pipe 5 and the combustion cavity pipe 7 are coaxial and are welded with the combustion cavity top cover 1, and the combustion cavity bottom cover 10 is embedded with the combustion cavity fluororubber sealing ring 9 for isolating the reforming reaction cavity from the combustion cavity. The outer layer reforming reaction cavity consists of a combustion cavity pipe 7, a reforming cavity barrel 8 and a reforming cavity bottom cover 14 and is an annular space, a reforming cavity fluororubber sealing layer 11 is padded between the combustion cavity bottom cover 10 and the reforming cavity bottom cover 14 and is used for isolating the combustion cavity from a fuel gas buffer cavity, and honeycomb-shaped silicon carbide 4 coated with a methanol water vapor reforming catalyst is embedded in the reforming reaction cavity. The bottom fuel gas buffer cavity consists of a reforming cavity bottom cover 14 and a fuel gas buffer cavity cover 15; the upper surface of the combustion chamber top cover 1 is provided with a catalytic combustion reactant outlet pipe 19 which passes through the reforming chamber barrel 8, so as to achieve the purpose of discharging catalytic combustion reaction gas. The gas buffer cavity is communicated with the combustion cavity, and the evaporation cavity is communicated with the reforming cavity.
As shown in fig. 2, the upper surface of the combustion chamber top cover 1 has a combustion reactant outlet pipe 19 for discharging catalytic combustion reaction gas. The combustion reactant outlet tube 19 is fitted with 4 through holes 22 in the upper surface of the reformer chamber barrel 8. The outlet pipe is provided with external threads for additionally arranging a fixing nut 2 and a fluororubber gasket 3 to prevent gas leakage in the reforming cavity. The upper surface of the combustion chamber top cover 1 is provided with a fixing boss 21 at the root of the combustion reactant outlet pipe 19, so that the upper surface of the combustion chamber top cover 1 is separated from the inner surface of the combustion chamber barrel 8 to generate a gap, thereby connecting the methanol-water mixture outlet 20 at the upper end of the evaporation chamber pipe 5 with the reforming chamber.
As shown in fig. 3 and 4, the reforming chamber barrel 8 is provided with 4 combustion reactant outlet pipes on the upper surface thereof through holes 22 for extending the methanol catalytic combustion reactant outlet pipe 19; the lower surface is provided with a reforming cavity fluororubber sealing ring embedded groove 23 which is matched with the reforming cavity fluororubber sealing ring 12. The reforming cavity barrel 8 and the reforming cavity bottom cover 14 are provided with 8 bolt holes 24 for fixing the fastening bolts 18 and the fastening nuts 17, and the central compression nuts 16 on the middle evaporation cavity pipe 5 are matched to play a role in compression and sealing.
As shown in fig. 5, the combustion chamber bottom cover 10 is provided with a combustion chamber fluororubber sealing ring embedded annular groove 25 on the upper surface for embedding the combustion chamber fluororubber sealing ring 9. The lower surface is provided with four combustion reactant inlet tubes 26 which extend from the reforming chamber bottom cover 14 through the holes 27.
As shown in fig. 6 and 7, an annular groove is formed on the upper surface of the reforming cavity bottom cover 14 and is matched with the reforming cavity fluororubber sealing ring 12; the lower surface is provided with an annular groove 28 which is matched with the fluororubber sealing ring 13 of the gas buffer cavity; four outlet pipes 29 for collecting methanol steam reformed gas which is a product of catalytic reforming reaction are arranged on the lower surface of the reforming cavity bottom cover 14 at equal intervals.
As shown in fig. 8, a compression boss 30 is provided at the center of the interior of the gas buffer cavity cover 15, and is used for compressing the fluororubber sealing components between the cavities under the action of the central compression nut 16; the lower surface of the gas buffer cavity cover 15 is provided with a gas inlet pipe 31, and the gas buffer cavity is communicated with a combustion reactant inlet pipe 26 on the lower surface of the combustion cavity bottom cover 10; the gas inlet pipe 31 is communicated with the combustion reactant inlet pipe 26, and the combustion reactant entering the gas inlet pipe 31 is uniformly distributed in the flow velocity of the reaction gas in the combustion chamber by passing through the four combustion reactant inlet pipes 26.
The specific embodiment is as follows:
as shown in fig. 9, there are two gas circuits in the reactor: catalytic combustion of methanol and reforming of methanol water vapor.
The 1 st way gas circuit is methyl alcohol catalytic combustion, and methyl alcohol gets into the gas cushion chamber with the air from gas cushion chamber inlet tube 31 of gas cushion chamber lid 15, and the back evenly gets into the combustion chamber through burning reactant inlet tube 26, and the catalytic combustion reaction takes place under the effect of methyl alcohol catalytic combustion catalyst when the burning chamber flows through honeycomb carborundum, and the heat of release is the endothermic reaction heat supply in the reactor to the required operating temperature of maintenance reactor.
The 2 nd path gas circuit is used for reforming methanol water vapor, methanol aqueous solution enters from the bottom of the evaporation cavity tube 5, and the vaporization and preheating of reactants are completed under the surrounding of the combustion cavity; then enters the methanol water vapor reforming cavity through a gap given by the combustion cavity fixing lug boss 21, and the reactant generates reforming reaction under the action of a methanol water vapor reforming catalyst when flowing through the honeycomb-shaped silicon carbide to generate hydrogen-rich reformed gas required by the fuel cell.
The main reactions involved are:
(1) catalytic combustion of methanol: CH (CH)3OH+1.5O2→CO2+2H2O
(2) Methanol water vapor reaction: CH (CH)3OH+H2O→CO2+3H2
In the structural design of the reactor, an annular design is adopted, and aiming at the characteristic that the reaction rate of each cavity is different, the size of each annular cavity can be adjusted through analog simulation before manufacturing, so that higher output power in the same volume is achieved. Meanwhile, according to the minimum circumference of the circle with the same area, the annular design is beneficial to improving the air tightness of the reactor, and the efficiency reduction or the environmental pollution caused by gas mutual leaping or gas leakage among the cavities in the reaction process is prevented. The reactor is largely made of a light-weight, excellent heat-conducting material. Through the lightweight design, the whole quality and the heat capacity of the reactor are reduced, and the starting time and the response time of the reactor can be shortened.
In the starting stage of the reactor, only the methanol catalytic combustion gas circuit works. Methanol is pumped into the gas buffer inlet pipe 31 of the gas buffer cover 15 by using a peristaltic pump, and air is pumped into the gas buffer inlet pipe 31 by using a main air pump. After methanol and air enter the combustion cavity, catalytic combustion reaction occurs to release heat, so that the temperature of the reactor is raised. When the temperature of the reforming cavity barrel 8 reaches the set temperature, the start-up phase is finished and the stable working phase is entered.
The foregoing detailed description is intended to illustrate and not limit the invention, and all changes and modifications that come within the spirit of the invention and the scope of the appended claims, including the description and equivalents thereof, are intended to be embraced therein.
Claims (8)
1. An annular methanol reforming hydrogen production reactor of self-heating type which characterized in that: the reforming reaction cavity mainly comprises an annular space surrounded by a reforming cavity barrel (8), a combustion cavity pipe (7) and a reforming cavity bottom cover (14), the combustion cavity mainly comprises an annular space surrounded by the combustion cavity pipe (7), an evaporation cavity pipe (5), a combustion cavity top cover (1) and a combustion cavity bottom cover (10), and the evaporation cavity mainly comprises the evaporation cavity pipe (5);
the evaporation cavity pipe (5), the combustion cavity pipe (7) and the reforming cavity barrel (8) are coaxially arranged from inside to outside in sequence;
the bottom of the reforming cavity barrel (8) is provided with a reforming cavity bottom cover (14) through a fastening bolt (18), and the lower end surface of the reforming cavity bottom cover (14) is provided with four reforming product outlet pipes (29) communicated with the reforming reaction cavity at equal intervals along the circumferential direction; the top end of the combustion cavity pipe (7) is welded with a combustion cavity top cover (1), the upper end surface of the combustion cavity top cover (1) is provided with four combustion product outlet pipes (19) communicated with the combustion cavity at equal intervals along the circumferential direction, the combustion product outlet pipes (19) penetrate through the upper end cover of the reforming cavity barrel (8) from bottom to top, the combustion product outlet pipes (19) between the upper end cover of the reforming cavity barrel (8) and the combustion cavity top cover (1) are provided with fixed bosses (21), and gaps for gas circulation are reserved between the upper end cover of the reforming cavity barrel (8) and the combustion cavity top cover (1) through the fixed bosses (21); a combustion cavity bottom cover (10) is welded at the bottom of the combustion cavity pipe (7), four combustion reactant inlet pipes (26) communicated with the combustion cavity are arranged on the lower end face of the combustion cavity bottom cover (10) at equal intervals along the circumferential direction, and the combustion reactant inlet pipes (26) penetrate through the reforming cavity bottom cover (14) from top to bottom through combustion reactant inlet pipe through holes (27) of the reforming cavity bottom cover (14);
an annular embedded groove (28) positioned between a combustion reactant inlet pipe through hole (27) and a reformate outlet pipe (29) is formed in the lower end face of the reforming cavity bottom cover (14), the gas buffer cavity cover (15) is embedded in the lower end face of the reforming cavity bottom cover (14) through the annular embedded groove (28), and a gas buffer cavity fluororubber sealing ring (13) is embedded between the gas buffer cavity cover (15) and the annular embedded groove (28); the gas buffer cavity cover (15) is provided with a gas buffer cavity annular groove communicated with the four combustion reactant inlet pipes (26), the bottom of the gas buffer cavity annular groove is provided with a gas buffer cavity inlet pipe communicated with the outside, the inner groove wall of the gas buffer cavity annular groove is enclosed to form a pressing boss (30), and the outer groove wall of the gas buffer cavity annular groove is the edge of the gas buffer cavity cover (15);
an evaporation cavity pipe (5) which vertically penetrates through the combustion cavity top cover (1) and the combustion cavity bottom cover (10) is arranged in the middle of the combustion cavity pipe (7), and the bottom of the evaporation cavity pipe (5) sequentially extends out of the reactor through a through hole arranged in the middle of the reforming cavity bottom cover (14) and the fuel gas buffer cavity cover (15).
2. The autothermal annular methanol reforming hydrogen production reactor of claim 1, wherein: a combustion product outlet pipe (19) of the combustion cavity pipe (7) extending out of the upper end cover of the reforming cavity barrel (8) is fixed through a combustion cavity fixing nut (2), and a fluororubber gasket (3) for preventing gas leakage in the reforming cavity is sleeved between the combustion cavity fixing nut (2) and the upper end cover of the reforming cavity barrel (8);
a burning cavity fluorine rubber sealing ring embedded annular groove (25) is arranged on the upper surface of the burning cavity bottom cover (10) close to the edge, and a burning cavity fluorine rubber sealing ring (9) used for isolating the reforming reaction cavity and the burning cavity is embedded in the burning cavity fluorine rubber sealing ring embedded annular groove (25);
a reforming cavity fluororubber sealing layer (11) for isolating the combustion cavity from the reforming cavity is padded between the combustion cavity bottom cover (10) and the reforming cavity bottom cover (14); the connection part of the reforming cavity bottom cover (14) and the reforming cavity barrel (8) is provided with two annular grooves which are opposite up and down, the two annular grooves which are opposite up and down enclose an annular groove together, and a reforming cavity fluororubber sealing ring (12) is embedded in the annular groove;
the evaporation cavity pipe (5) extending out of the reactor is sleeved with a central compression nut (16), and a compression boss (30) of the gas buffer cavity cover (15) compresses the fluororubber sealing element between the cavities under the action of the central compression nut (16).
3. The autothermal annular methanol reforming hydrogen production reactor of claim 1, wherein: honeycomb-shaped silicon carbide is filled and embedded in the reforming reaction cavity and the combustion cavity, a methanol water vapor reforming catalyst is coated on the honeycomb-shaped silicon carbide in the reforming reaction cavity, a methanol catalytic combustion catalyst is coated on the honeycomb-shaped silicon carbide in the combustion cavity, the honeycomb-shaped silicon carbide in the reforming reaction cavity and the honeycomb-shaped silicon carbide in the combustion cavity are located at the same height position, and gaps for gas circulation are reserved at the upper end and the lower end of the honeycomb-shaped silicon carbide in the reforming reaction cavity and the upper end and the lower end of the.
4. The autothermal annular methanol reforming hydrogen production reactor of claim 3, wherein: the reactor comprises two gas paths of methanol catalytic combustion and methanol water vapor reforming;
methanol catalytic combustion gas circuit: methanol and air enter a gas buffer cavity annular groove from a gas buffer cavity inlet pipe (31) of a gas buffer cavity cover (15), the methanol and the air entering the gas buffer cavity annular groove are divided into four paths and respectively enter a combustion cavity from four combustion reactant inlet pipes (26), the methanol and the air generate catalytic combustion reaction under the action of a methanol catalytic combustion catalyst when flowing through honeycomb-shaped silicon carbide in the combustion cavity, and gas generated by the catalytic combustion reaction is discharged through a combustion reactant outlet (19);
methanol water vapor reforming gas circuit: methanol water solution is pumped from the bottom of the evaporation cavity pipe (5) by an air pump, methanol water vapor mixture generated after the methanol water solution is vaporized in the evaporation cavity pipe (5) enters the reforming reaction cavity through a gap reserved by the fixed boss (21), and the methanol water vapor mixture generates reforming reaction under the action of a methanol water vapor reforming catalyst when flowing through the honeycomb-shaped silicon carbide in the reforming reaction cavity, so that hydrogen-enriched reformed gas required by the fuel cell is led out from a reformed product outlet pipe (29).
5. The autothermal annular methanol reforming hydrogen production reactor of claim 4, wherein the heat released by the catalytic combustion reaction supplies heat for the endothermic reaction throughout the reactor and maintains the operating temperature required for the reforming reaction; the endothermic reaction includes a gasification reaction of the methanol aqueous solution in the evaporation cavity tube (5) and a reforming reaction in the reforming cavity.
6. The self-heating annular methanol reforming hydrogen production reactor according to claim 4, wherein the reactor only works in the methanol catalytic combustion gas circuit during the initial start-up stage, and when the catalytic combustion reaction in the combustion chamber releases heat to make the temperature in the reforming chamber reach the reforming reaction temperature, the reactor enters the stable working stage, and the methanol water vapor reforming gas circuit and the methanol catalytic combustion gas circuit start to work simultaneously.
7. The autothermal annular methanol reforming hydrogen production reactor of claim 1, wherein: the tube wall thickness of the evaporation cavity tube (5) is 1-2 mm, the tube wall thickness of the combustion cavity tube (7) is 2-2.5 mm, and the thickness of the reforming cavity barrel (8) is more than 3 mm; the inner diameter of the evaporation cavity pipe (5) is larger than 8mm, the difference between the inner diameter of the combustion cavity pipe (7) and the outer diameter of the evaporation cavity pipe (5) is larger than 30mm, and the difference between the inner diameter of the reforming cavity barrel (8) and the outer diameter of the combustion cavity pipe (7) is larger than 50 mm.
8. The autothermal annular methanol reforming hydrogen production reactor of claim 1, wherein: the height of a fixed boss (21) arranged on the top cover (1) of the combustion cavity is more than 5 mm; the height of the pressing boss (30) of the gas buffer cavity cover (15) is larger than 8mm and is 1-2 mm higher than the edge of the gas buffer cavity cover (15).
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| CN112573482B (en) * | 2020-12-10 | 2022-07-08 | 洛阳沃达节能科技有限公司 | Hydrogen production pipe of hydrogen production device and hydrogen production device |
| CN112892460B (en) * | 2020-12-25 | 2022-02-01 | 宁波申江科技股份有限公司 | Self-heating methanol reforming hydrogen production reactor |
| CN114436210B (en) * | 2022-03-07 | 2023-08-11 | 广东工业大学 | High-efficient integrated distributed methanol reforming hydrogen production purification system |
| CN115650165B (en) * | 2022-11-15 | 2024-04-12 | 中国科学院大连化学物理研究所 | Fuel evaporation chamber structure matched with fuel cell hydrogen production reformer for use |
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