CN108002347B - Methanol-steam reforming hydrogen production reactor with ultrasonic assistance - Google Patents
Methanol-steam reforming hydrogen production reactor with ultrasonic assistance Download PDFInfo
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- CN108002347B CN108002347B CN201610969269.XA CN201610969269A CN108002347B CN 108002347 B CN108002347 B CN 108002347B CN 201610969269 A CN201610969269 A CN 201610969269A CN 108002347 B CN108002347 B CN 108002347B
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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
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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
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Abstract
The invention relates to the field of hydrogen production by methanol steam reforming, and discloses an ultrasonic-assisted hydrogen production reactor by methanol steam reforming, which comprises: the reactor comprises a reactor body, wherein an inner cavity enclosed by the reactor body is a reaction cavity, and the reactor body is provided with an ultrasonic probe and an ultrasonic amplitude transformer connected with the ultrasonic probe; the two ends of the reactor body are provided with a material inlet for introducing a methanol water solution and a material outlet for introducing hydrogen; according to the material flow direction, the reaction cavity comprises an evaporation area containing an evaporation plate and a reforming area containing a metal carrier reaction plate in sequence. When the ultrasonic-assisted methanol-steam reforming hydrogen production reactor provided by the invention is used for producing hydrogen from a methanol water solution, the ultrasonic-assisted methanol-steam reforming hydrogen production reactor has the advantages of high reforming hydrogen production efficiency and high methanol conversion rate.
Description
Technical Field
The invention relates to the field of hydrogen production by methanol steam reforming, in particular to an ultrasonic-assisted hydrogen production reactor by methanol steam reforming.
Background
The microchannel reactor has the advantages of simple structure, no amplification effect, easy control of operating conditions, safety, reliability and the like, and therefore, the microchannel reactor has received great attention from a plurality of researchers including those in chemical engineering and related fields in recent years.
In the microchannel reactor, the thickness of a flowing boundary layer is very small, so that the heat conduction and diffusion mass transfer resistance of fluid is very small, the heat and mass transfer rate is increased rapidly, meanwhile, the microchannel greatly improves the contact specific surface area of the fluid and the unit volume of the channel, and the volume of the whole reactor is more than one order of magnitude smaller than that of a conventional reactor. Because the expansion of flame in the microchannel reactor is restrained, the reactor can be operated in an explosion range without adding any special safety measures, and is particularly suitable for reaction processes such as catalytic reforming, hydrogenation reaction, fuel mixing, energy conservation, chemical analysis, extraction analysis and the like.
In recent years, low-carbon alcohol fuels such as methanol are used as reactants, and hydrogen is prepared by catalytic reforming reaction conversion, so that the method has the advantages of mild process conditions and low energy consumption, is considered to be most suitable for mobile hydrogen production, and becomes the most promising technical method for solving the problem of online hydrogen source of fuel cells.
Currently, in hydrogen production microchannel reactors, the catalytic reaction rate and catalytic conversion rate mainly depend on the catalytic reaction carrier. The reaction carrier structure adopts two structural forms of a micro-channel metal sheet and a porous metal sheet.
Internationally, the microchannel on the surface of the metal sheet is usually processed and formed by adopting technologies such as MEMS, laser processing, electric spark processing, micro milling, chemical etching and the like, the size of the microchannel can be controlled to be in a submicron to sub-millimeter order, and then the carrier with the geometric characteristics of the microchannel is formed by superposition, so that the microchannel has the advantages of good flow channel consistency and stable performance, but the problems of low production rate, high manufacturing cost and the like become the biggest obstacles for large-scale popularization and use of the microchannel metal sheet carrier. The porous metal sheet is prepared into a porous metal material serving as a reaction carrier by adopting the technologies of foaming, powder sintering, metal deposition and the like, and becomes an ideal material of a novel catalytic reaction carrier due to the characteristics of a three-dimensional network structure, full-communicated pore diameter and high porosity. However, the problems of low methanol conversion rate, low hydrogen yield and the like exist at present.
Disclosure of Invention
One of the purposes of the invention is to overcome the defects of low reforming hydrogen production efficiency and low methanol conversion rate of methanol steam reforming hydrogen production in the prior art, and provide an ultrasonic-assisted methanol steam reforming hydrogen production reactor capable of improving reforming hydrogen production efficiency.
The second purpose of the invention is to apply the ultrasonic technology to the ultrasonic-assisted methanol-steam reforming hydrogen production reactor.
In order to achieve the above object, the present invention provides an ultrasound-assisted methanol steam reforming hydrogen production reactor, comprising: the reactor comprises a reactor body, wherein an inner cavity enclosed by the reactor body is a reaction cavity, and the reactor body is provided with an ultrasonic probe and an ultrasonic amplitude transformer connected with the ultrasonic probe; the two ends of the reactor body are provided with a material inlet for introducing a methanol water solution and a material outlet for introducing hydrogen; according to the material flow direction, the reaction cavity comprises an evaporation area containing an evaporation plate and a reforming area containing a metal carrier reaction plate in sequence.
When the ultrasonic-assisted methanol-steam reforming hydrogen production reactor provided by the invention is used for producing hydrogen from a methanol water solution, the ultrasonic-assisted methanol-steam reforming hydrogen production reactor has the advantages of high reforming hydrogen production efficiency and high methanol conversion rate.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
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 specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic perspective view of an ultrasonic assisted methanol steam reforming hydrogen production reactor of the present invention;
FIG. 2 is a left side view of an ultrasonic assisted methanol steam reforming hydrogen production reactor of the present invention;
FIG. 3 is a cross-sectional view taken along A-A of FIG. 2;
fig. 4 is a schematic structural diagram of a first evaporating plate of the ultrasonic-assisted methanol-steam reforming hydrogen production reactor of the present invention.
Description of the reference numerals
1. Reactor body 11, ultrasonic probe 12, ultrasonic amplitude transformer
1010. Material inlet 1020, material outlet 13, heating plate
15. Thermocouple placing port 10, reaction chamber 1012 and first evaporation plate
1013. Second evaporation plate 1014, third evaporation plate 101, evaporation area
1021. Metal carrier reaction plate 102, reforming zone 16, gasket
1015. Through groove 1011, evaporation zone fixing gasket
1022. Reforming region fixing gasket
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides an ultrasonic-assisted methanol-steam reforming hydrogen production reactor, which comprises: the reactor comprises a reactor body, wherein an inner cavity enclosed by the reactor body is a reaction cavity, and the reactor body is provided with an ultrasonic probe and an ultrasonic amplitude transformer connected with the ultrasonic probe; the two ends of the reactor body are provided with a material inlet for introducing a methanol water solution and a material outlet for introducing hydrogen; according to the material flow direction, the reaction cavity comprises an evaporation area containing an evaporation plate and a reforming area containing a metal carrier reaction plate in sequence.
The ultrasonic probe and the ultrasonic amplitude transformer connected with the ultrasonic probe can provide ultrasonic vibration for the ultrasonic-assisted methanol-steam reforming hydrogen production reactor, so that the ultrasonic-assisted methanol-steam reforming hydrogen production reactor has the advantages of high reforming hydrogen production efficiency and high methanol conversion rate when hydrogen is prepared from methanol water solution.
The ultrasonic amplitude transformer can be connected with an ultrasonic generator to provide ultrasonic vibration for the ultrasonic-assisted methanol-steam reforming hydrogen production reactor.
Preferably, the ultrasonic-assisted methanol-steam reforming hydrogen production reactor is a microreactor. The volume of the reaction cavity of the reactor is (40-70 cm)3)。
Preferably, the reactor body of the ultrasonic-assisted methanol-steam reforming hydrogen production reactor is cylindrical, so that an inner cavity defined by the reactor body is a reaction cavity with a circular cross section.
Preferably, the connection mode of the ultrasonic probe and the ultrasonic amplitude transformer is a threaded connection or a welding connection. Particularly preferably, the ultrasonic probe and the ultrasonic horn are connected by welding.
Preferably, the ultrasonic horn vibrates at a frequency of 5 to 500 kHz.
Preferably, the ultrasonic probe is disposed at a middle portion of the reactor body.
Preferably, heating plates are provided in the reactor body around the reaction chamber. Preferably, the heating plate is a ring-shaped heating plate attached to the reactor body to provide heat energy to the entire reactor. The heating plate of the present invention may be embedded in the material of the reactor body, or may be disposed at the outermost layer of the reactor body. It should be noted that the outermost layer is only the outermost layer of the reactor body material, and in fact, other materials such as insulation may be provided or wrapped in addition to the heating plate.
Preferably, the heating plate is disposed at an outermost layer of the reactor body.
Preferably, the outer layer of the heating plate is provided with an insulating layer.
Preferably, the material of the heating plate is at least one selected from mica sheets, copper, ceramic, and cast aluminum.
Preferably, the heating plate is provided in at least one of a unitary type, a separated type and a crawler type.
Preferably, mica sheets are used as the material of the heating plate of the ultrasonic-assisted methanol-steam reforming hydrogen production reactor, and the heating temperature of the heating plate is above 150 ℃, preferably 200-320 ℃.
Further preferably, the heating plate is an annular heating plate, and the heating plate is in a two-semicircle separated type and is wrapped on two sides of the reactor body through bolt connection.
Preferably, the reactor body of the present invention is further provided with a thermocouple placement port for detecting the temperature of the reaction chamber.
The number of the evaporation plates in the evaporation zone is not particularly required in the invention, and more than 2 evaporation plates are preferably arranged. Particularly preferably, a first evaporation plate, a second evaporation plate and a third evaporation plate are arranged in parallel in the evaporation zone in sequence according to the material flow direction.
Preferably, gaskets are arranged among the first evaporation plate, the second evaporation plate and the third evaporation plate and used for spacing the first evaporation plate from the second evaporation plate and spacing the second evaporation plate from the third evaporation plate. Preferably, the gasket is an annular gasket, and the difference between the inner radius and the outer radius of the annular gasket is 0.5-1 mm.
Preferably, the first evaporation plate is provided with a through groove for passing the material.
Preferably, the through grooves are parallel or staggered strips.
According to a preferred embodiment, the strip-shaped through grooves of the first evaporation plate are arranged in parallel, and the width of each strip-shaped through groove is the same; more preferably, the width of the space between the strip-shaped through grooves is equal to the width of the strip-shaped through grooves.
Preferably, the width of the strip-shaped through groove is 0.3-1 mm.
Preferably, the second evaporation plate and the third evaporation plate are provided with through holes.
Preferably, the through holes are circular through holes distributed in an annular array.
According to a preferred embodiment, the through holes of the second evaporation plate are of uniform size, the through holes of the third evaporation plate are of uniform size, and the diameter of the through holes of the second evaporation plate is greater than the diameter of the through holes of the third evaporation plate. More preferably, the diameter of the circular through holes on the second evaporation plate and the third evaporation plate is 0.1-0.5 mm.
The phrase "the through holes on the second evaporation plate are uniform in size" means that the through holes on the second evaporation plate are all the same in size.
The phrase "the through holes of the third evaporation plate have the same size" means that the through holes of the third evaporation plate have the same size.
According to another preferred embodiment, the through holes of the second evaporation plate have different sizes, the through holes of the third evaporation plate have different sizes, and the minimum diameter of the through holes of the second evaporation plate is greater than or equal to the maximum diameter of the through holes of the third evaporation plate. More preferably, the diameter of the circular through holes on the second evaporation plate and the third evaporation plate is 0.1-0.5 mm.
The phrase "the through holes of the second evaporation plate have different sizes" means that the sizes of the through holes of the second evaporation plate are not completely the same, and at least one through hole has a size different from the sizes of the other through holes of the second evaporation plate.
The phrase "the through holes of the third evaporation plate have different sizes" means that the sizes of the through holes of the third evaporation plate are not completely the same, and at least one through hole has a size different from the sizes of the other through holes of the third evaporation plate.
Preferably, the circular through holes on the second evaporation plate and the third evaporation plate are distributed in an annular array.
Preferably, in the present invention, the thickness of each of the evaporation plates may be the same or different, and each is independently 1 to 3 mm.
The present invention does not require any particular number of metal carrier reaction plates in the reforming zone, and preferably 2 or more metal carrier reaction plates are provided. Preferably, a first metal carrier reaction plate, a second metal carrier reaction plate and a third metal carrier reaction plate are arranged in parallel in the reforming zone in sequence according to the material flow direction.
Preferably, the first and second metal carrier reaction plates and the second and third metal carrier reaction plates are in contact connection. The inventor of the invention finds that the hydrogen production efficiency and the methanol conversion rate can be obviously improved by matching the characteristics of the ultrasonic-assisted methanol steam reforming hydrogen production reactor, namely the first metal carrier reaction plate, the second metal carrier reaction plate and the contact connection between the second metal carrier reaction plate and the third metal carrier reaction plate.
Preferably, each of the metal carrier reaction plates has a porosity of 60 to 90%. The porosity of the plurality of metal support reaction plates of the present invention may be the same or different. Preferably, when the plurality of metal support reaction plates have different porosities, the porosity of each metal support reaction plate increases in order in the direction of flow.
Preferably, the metal carrier reaction plate is at least one of a copper fiber sintered plate, a copper foam plate and a nickel foam plate.
Preferably, the metal carrier reaction plate contains a catalyst for catalyzing the reaction of methanol and water to produce hydrogen. The catalyst of the present invention is not particularly limited in kind, and may be a catalyst conventionally used in the art for catalyzing the reaction of methanol and water to produce hydrogen. The catalyst may be, for example, a catalyst disclosed in "research on catalyst for producing hydrogen by reforming methanol steam", such as Zhangieyi, and in particular, the catalyst may be a copper-based catalyst (containing Cu (NO) therein)3)2、Zn(NO3)2、Al(NO3)3And Ar (NO)3)4)。
The thickness of each of the metal carrier reaction plates may be the same or different, and each is independently 2 to 6 mm.
The reaction chamber of the present invention is not subject to strict boundary distinction between the evaporation zone and the reforming zone, and preferably the region of the material after entering the reaction chamber and before contacting the metal support reaction plate is the evaporation zone and the region from the beginning of the material contacting the metal support reaction plate to the material outlet is the reforming zone.
In a preferred embodiment of the invention, the evaporation zone corresponds to the internal diameter of the reforming zone.
The structure of the ultrasonic-assisted methanol-steam reforming hydrogen production reactor of the present invention is described below with reference to fig. 1:
the ultrasonic-assisted methanol-steam reforming hydrogen production reactor comprises: the reactor comprises a reactor body 1, wherein an inner cavity defined by the reactor body 1 is a reaction cavity, and an ultrasonic probe 11 and an ultrasonic amplitude transformer 12 connected with the ultrasonic probe are arranged on the reactor body 1; both ends of the reactor body 1 are provided with a material inlet 1010 for introducing a methanol aqueous solution and a material outlet 1020 for leading out hydrogen; according to the material flow direction, the reaction cavity comprises an evaporation area containing an evaporation plate and a reforming area containing a metal carrier reaction plate in sequence. A heating plate 13 surrounding the reaction chamber is arranged in the reactor body 1, and a thermocouple placing port 15 for detecting the temperature of the reaction chamber is arranged on the reactor body 1.
FIG. 3 is a view taken along line A of FIG. 21-A2The structure of the ultrasonic-assisted methanol-steam reforming hydrogen production reactor of the present invention is further illustrated below with reference to fig. 3, along the sectional view of the line:
the ultrasonic-assisted methanol-steam reforming hydrogen production reactor comprises: the reactor comprises a reactor body 1, wherein an inner cavity defined by the reactor body 1 is a reaction cavity 10, and an ultrasonic probe 11 and an ultrasonic amplitude transformer 12 connected with the ultrasonic probe are arranged on the reactor body 1; both ends of the reactor body 1 are provided with a material inlet 1010 for introducing a methanol aqueous solution and a material outlet 1020 for leading out hydrogen; the reaction chamber 10 comprises, in order of the direction of flow, an evaporation zone 101 comprising a first evaporation plate 1012, a second evaporation plate 1013 and a third evaporation plate 1014, and a reforming zone 102 comprising a metal support reaction plate 1021. The outermost layer of the reactor body 1 is provided with a heating plate surrounding the reaction chamber 10; and the outer layer of the heating plate is provided with a heat-insulating layer. A gasket 16 for spacing the first, second and third evaporation plates 1012, 1013 and 1014 is disposed between the first, second and third evaporation plates 1012, 1013 and 1014. The second evaporation plate 1013 and the third evaporation plate 1014 are provided with through holes. The metal carrier reaction plate 1021 comprises a first metal carrier reaction plate, a second metal carrier reaction plate and a third metal carrier reaction plate which are sequentially arranged in parallel, and the first metal carrier reaction plate and the second metal carrier reaction plate are in contact connection with each other and the second metal carrier reaction plate and the third metal carrier reaction plate are in contact connection with each other. Preferably, an evaporation zone fixing gasket 1011 is disposed on the inner wall of the evaporation zone 101, and a reforming zone fixing gasket 1022 is disposed on the inner wall of the reforming zone 102.
As shown in fig. 4, the first evaporation plate 1012 is provided with a through groove 1015 for passing the material.
The ultrasonic-assisted methanol-steam reforming hydrogen production reactor also has the following specific advantages:
1. the ultrasonic-assisted methanol-steam reforming hydrogen production reactor is internally provided with an ultrasonic amplitude transformer and an ultrasonic probe which are connected with an ultrasonic generator to provide ultrasonic vibration for the whole reaction system, and by utilizing the ultrasonic catalysis effect, the service life of the catalyst is prolonged, the activity of the catalyst is improved, the heat and mass transfer effect is improved, and the reforming hydrogen production efficiency is improved;
2. the annular heating plate and the heat preservation layer are arranged around the reactor main body of the ultrasonic-assisted methanol-steam reforming hydrogen production reactor, so that the heating effect is more uniform, and the heat preservation effect is better;
3. the ultrasonic-assisted methanol-steam reforming hydrogen production reactor is characterized in that a first evaporation plate, a second evaporation plate and a third evaporation plate are sequentially arranged in an evaporation area of the ultrasonic-assisted methanol-steam reforming hydrogen production reactor, the three evaporation plates are separated from one another through annular gaskets, strip-shaped through grooves are formed in the first evaporation plate, the effect of increasing evaporation can be achieved, circular through holes are uniformly distributed in the second evaporation plate and the third evaporation plate in an annular array mode, and fluid and temperature at an inlet of a reforming cavity can be distributed more uniformly;
4. the porosity of the metal carrier reaction plate of the ultrasonic-assisted methanol steam reforming hydrogen production reactor is 60-90%, and the porosity is different, so that the existence of a cold spot phenomenon in the reaction can be effectively avoided, and the hydrogen production efficiency and the methanol conversion rate are improved;
5. the metal carrier reaction plate of the ultrasonic-assisted methanol steam reforming hydrogen production reactor is a copper fiber sintered plate, a foam copper plate or a foam nickel plate, and has the advantages of large specific surface area, low processing cost, high hydrogen production efficiency and the like.
The condition parameters in the specific method related to the hydrogen production from the methanol aqueous solution by using the ultrasonic-assisted methanol-steam reforming hydrogen production reactor do not have special requirements, and the condition can be the conventional hydrogen production condition from the methanol aqueous solution in the field, for example, the temperature of the methanol aqueous solution introduced from the material inlet is preferably 20-100 ℃. Preferably, the volume of the reaction cavity is 40-70cm3According to the ultrasonic-assisted methanol-steam reforming hydrogen production reactor disclosed by the invention, in a methanol-water solution introduced from the material inlet, the volume ratio of methanol to water is (1-5): 1; according to the invention, the temperatures of the evaporation zone and the reforming zone of the ultrasonic-assisted methanol-steam reforming hydrogen production reactor are preferably 220-280 ℃, and the pressure is preferably 0.3-0.5 MPa. Preferably, the flow rate of the methanol water solution introduced from the material inlet is 6-14 mL/min.
The present invention will be described in detail below by way of examples.
Example 1
Hydrogen is produced from methanol aqueous solution using the ultrasound-assisted methanol-steam reforming hydrogen production reactor described in fig. 1-4. Specifically, the method comprises the following steps:
the volume of the reaction cavity of the ultrasonic-assisted methanol-steam reforming hydrogen production reactor is 55.26cm3The cross-sectional area of the reaction chamber is 12.56cm2. Metal carrier reaction plates 1021 (specifically, those containing copper-based catalyst (Cu (NO) therein) with porosity of 70%, 80%, 90% are stacked from left to right in the reforming section 1023)2、Zn(NO3)2、Al(NO3)3And Ar (NO)3)4In a molar ratio of 11: 6: 4: 1) copper fiber sintered plate of (1); the strip-shaped through grooves in the first evaporation plate are arranged in parallel, and the width of the intervals among the strip-shaped through grooves is equal to that of the strip-shaped through grooves and is 0.3 mm; circular through holes distributed in an annular array are formed in the second evaporation plate and the third evaporation plate, the circular through holes of the second evaporation plate are different in size, the minimum diameter is 0.3mm, the maximum diameter is 0.5mm, and the average diameter is 0.4 mm; and the size of the circular through hole of the third evaporating plate is inconsistent, and the diameter minimum is 0.1mm, the diameter maximum is 0.3mm, the average diameter is 0.2mm, the thickness of each evaporating plate is 0.3mm, and the thickness of each metal carrier reaction plate is 0.3mm, be provided with between first evaporating plate, second evaporating plate and the third evaporating plate and be used for the interval first evaporating plate with second evaporating plate and interval the second evaporating plate with the cyclic annular packing ring of third evaporating plate, the inside and outside radius difference of cyclic annular packing ring is 0.5 mm. And opening an ultrasonic generator, connecting the ultrasonic generator with the ultrasonic probe 11 and the reactor body through an ultrasonic amplitude transformer 12, and providing ultrasonic vibration for the whole reaction system, wherein the ultrasonic frequency is 50 kHz. The annular heating plate located at the outermost layer of the reactor body was set to a temperature of 250 c, and the average temperature of the evaporation zone and the average temperature of the reforming zone in the reaction chamber were 250 c. Methanol water solution with the flow rate of 10mL/min and the temperature of 30 ℃ enters the evaporation area 101 through the material inlet 1010 and is vaporized into gas through the first evaporation plate 1012; the vaporized hydroalcoholic gas then passes through the second evaporation plate 1013 and the third evaporation plate 1014 in sequence, and then is uniformly distributed before contacting the metal support reaction plates of the reforming region 102. Then the water alcohol vapor enters the reforming area 102, when passing through the first metal carrier reaction plate, the methanol and the water generate reforming reaction, the unreacted gas completely reacts on the subsequent metal carrier reaction plate, and simultaneously, each metal carrier reaction plate can make the fluid and the temperature distribution more uniform, thereby avoiding the existence of cold spot phenomenon. Then, hydrogen generated by the reaction flows out from a material outlet 1020, and the whole methanol steam reforming hydrogen production reaction is completed.
According to detection, the hydrogen production efficiency in the embodiment is 92%, and the methanol conversion rate is 94%.
Example 2
The reactor for hydrogen production by ultrasonic-assisted methanol steam reforming in this example is similar to that in example 1, except that in this example, metal carrier reaction plates with porosities of 80%, 80% (the catalyst in the metal carrier reaction plates is identical to that in example 1, and is also a copper fiber sintered plate) are stacked from left to right in the reforming region 102. The rest is the same as in example 1.
The hydrogen production efficiency in this example was found to be 94% and the methanol conversion rate was found to be 96%.
Example 3
The ultrasound-assisted methanol-steam reforming hydrogen production reactor in this embodiment is similar to that in embodiment 1, except that, in this embodiment, the outermost layer of the reactor body is not provided with an annular heating plate, but is replaced by four identical long cylindrical heating rods with the temperature of 250 ℃ and arranged at equal intervals, that is, the four heating rods are arranged on the periphery of the reactor body, the diameter of each heating rod is 6mm, and the length of each heating rod is 20 mm.
The rest is the same as in example 1.
Through detection, the hydrogen production efficiency in the embodiment is 90%, and the methanol conversion rate is 90%.
Comparative example 1
This comparative example was carried out using a methanol steam reforming hydrogen production reactor similar to that of example 1, except that the methanol steam reforming hydrogen production reactor of this comparative example was not provided with an ultrasonic probe and an ultrasonic horn, that is, the comparative example was carried out without ultrasonic vibration.
The rest is the same as in example 1.
According to detection, the hydrogen production efficiency in the comparative example is 82%, and the methanol conversion rate is 83%.
From the results of the foregoing examples and comparative examples, it can be seen that the ultrasound-assisted methanol steam reforming hydrogen production reactor of the present invention can achieve significantly higher hydrogen production efficiency and methanol conversion at lower temperatures, with the same process parameters.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (36)
1. An ultrasonic-assisted methanol steam reforming hydrogen production reactor, characterized in that the reactor comprises: the reactor comprises a reactor body (1), wherein an inner cavity defined by the reactor body is a reaction cavity (10), and the reactor body is provided with an ultrasonic probe (11) and an ultrasonic amplitude transformer (12) connected with the ultrasonic probe; both ends of the reactor body (1) are provided with a material inlet (1010) for introducing a methanol water solution and a material outlet (1020) for leading out hydrogen; according to the material flow direction, the reaction cavity sequentially comprises an evaporation area (101) containing an evaporation plate and a reforming area (102) containing a metal carrier reaction plate (1021), and according to the material flow direction, a first metal carrier reaction plate, a second metal carrier reaction plate and a third metal carrier reaction plate are sequentially arranged in parallel in the reforming area (102); the first metal carrier reaction plate and the second metal carrier reaction plate and the third metal carrier reaction plate are in contact connection.
2. A reactor according to claim 1, characterized in that the connection of the ultrasonic probe (11) and the ultrasonic horn (12) is a threaded connection or a welded connection.
3. Reactor according to claim 1, characterized in that said ultrasonic probe (11) is arranged in the middle of said reactor body (1).
4. A reactor according to any of claims 1-3, characterized in that heating plates (13) are arranged in the reactor body (1) around the reaction chamber (10).
5. A reactor according to claim 4, characterized in that the heating plate (13) is arranged at the outermost layer of the reactor body (1).
6. A reactor according to claim 4, characterized in that the outer layer of the heating plate is provided with an insulating layer.
7. The reactor according to claim 4, wherein the material of the heating plate (13) is at least one selected from mica sheets, copper, ceramic, and cast aluminum.
8. A reactor according to claim 7, characterized in that the heating plate (13) is provided in at least one of a one-piece, a split and a caterpillar type.
9. Reactor according to any of claims 1-3 and 5-8, characterized in that a first evaporating plate (1012), a second evaporating plate (1013) and a third evaporating plate (1014) are arranged in parallel in the evaporating zone (101) in sequence according to the flow direction.
10. A reactor according to claim 9, wherein gaskets (16) are provided between the first (1012), second (1013) and third (1014) evaporation plates for spacing the first (1012) and second (1013) and third (1014) evaporation plates.
11. Reactor according to claim 4, characterized in that a first evaporating plate (1012), a second evaporating plate (1013) and a third evaporating plate (1014) are arranged in parallel in the evaporating zone (101) in sequence according to the flow direction.
12. A reactor according to claim 11, wherein gaskets (16) are provided between the first (1012), second (1013) and third (1014) evaporation plates for spacing the first (1012) and second (1013) and third (1014) evaporation plates.
13. A reactor according to claim 9, characterized in that the first evaporating plate (1012) is provided with through channels (1015) for the passage of the material.
14. Reactor according to claim 13, characterized in that said through slots (1015) are in the form of parallel or mutually staggered strips.
15. A reactor according to any of claims 10-12, characterized in that the first evaporating plate (1012) is provided with through-channels (1015) for the passage of material.
16. Reactor according to claim 15, characterized in that said through slots (1015) are in the form of parallel or mutually staggered strips.
17. A reactor according to any of claims 10-14, 16, characterized in that the second evaporation plate (1013) and the third evaporation plate (1014) are provided with through holes.
18. The reactor of claim 17 wherein said through holes are circular through holes distributed in an annular array.
19. A reactor according to claim 9, characterized in that said second evaporation plate (1013) and said third evaporation plate (1014) are provided with through holes.
20. The reactor of claim 19 wherein said through holes are circular through holes distributed in an annular array.
21. A reactor according to claim 15, characterized in that said second evaporation plate (1013) and said third evaporation plate (1014) are provided with through holes.
22. The reactor of claim 21 wherein said through holes are circular through holes distributed in an annular array.
23. The reactor according to any of claims 18 to 22, wherein the through holes of the second evaporation plate (1013) are of uniform size, the through holes of the third evaporation plate (1014) are of uniform size, and the diameter of the through holes of the second evaporation plate is larger than the diameter of the through holes of the third evaporation plate; or
The sizes of the through holes on the second evaporation plate are different, the sizes of the through holes on the third evaporation plate are different, and the minimum diameter of the through holes on the second evaporation plate is larger than or equal to the maximum diameter of the through holes on the third evaporation plate.
24. The reactor according to claim 17, wherein the through holes of the second evaporation plate (1013) are of uniform size, the through holes of the third evaporation plate (1014) are of uniform size, and the diameter of the through holes of the second evaporation plate is greater than the diameter of the through holes of the third evaporation plate; or
The sizes of the through holes on the second evaporation plate are different, the sizes of the through holes on the third evaporation plate are different, and the minimum diameter of the through holes on the second evaporation plate is larger than or equal to the maximum diameter of the through holes on the third evaporation plate.
25. A reactor as claimed in any one of claims 1 to 3, 5 to 8, 10 to 14, 16, 18 to 22 and 24 wherein the metal support reaction plate has a porosity of 60 to 90%.
26. The reactor of claim 25 wherein said metal support reaction plate is at least one of a copper fiber sintered plate, a copper foam plate, and a nickel foam plate.
27. The reactor of claim 4, wherein the porosity of the metal support reaction plate is 60-90%.
28. The reactor of claim 27 wherein said metal support reaction plate is at least one of a copper fiber sintered plate, a copper foam plate, and a nickel foam plate.
29. The reactor of claim 9, wherein the porosity of the metal support reaction plate is 60-90%.
30. The reactor of claim 29 wherein said metal support reaction plate is at least one of a copper fiber sintered plate, a copper foam plate, and a nickel foam plate.
31. The reactor of claim 15, wherein the porosity of the metal support reaction plate is 60-90%.
32. The reactor of claim 31 wherein said metal support reaction plate is at least one of a copper fiber sintered plate, a copper foam plate, and a nickel foam plate.
33. The reactor of claim 17, wherein the porosity of the metal support reaction plate is 60-90%.
34. The reactor of claim 33 wherein said metal support reaction plate is at least one of a copper fiber sintered plate, a copper foam plate, and a nickel foam plate.
35. The reactor of claim 23, wherein the porosity of the metal support reaction plate is 60-90%.
36. The reactor of claim 35 wherein said metal support reaction plate is at least one of a copper fiber sintered plate, a copper foam plate, and a nickel foam plate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1899954A (en) * | 2006-07-27 | 2007-01-24 | 西安交通大学 | Method for preparing hydrogen from methanol |
| CN102358617A (en) * | 2011-06-29 | 2012-02-22 | 西安交通大学 | Methanol hydrogen production apparatus, and method for preparing hydrogen by using the same |
| CN104118848A (en) * | 2014-07-25 | 2014-10-29 | 厦门大学 | Reaction device for reforming and producing hydrogen from methanol vapor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1899954A (en) * | 2006-07-27 | 2007-01-24 | 西安交通大学 | Method for preparing hydrogen from methanol |
| CN102358617A (en) * | 2011-06-29 | 2012-02-22 | 西安交通大学 | Methanol hydrogen production apparatus, and method for preparing hydrogen by using the same |
| CN104118848A (en) * | 2014-07-25 | 2014-10-29 | 厦门大学 | Reaction device for reforming and producing hydrogen from methanol vapor |
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