CN110155945B - Self-heating methanol reforming hydrogen production reactor integrating CO selective methanation - Google Patents
Self-heating methanol reforming hydrogen production reactor integrating CO selective methanation Download PDFInfo
- Publication number
- CN110155945B CN110155945B CN201910323448.XA CN201910323448A CN110155945B CN 110155945 B CN110155945 B CN 110155945B CN 201910323448 A CN201910323448 A CN 201910323448A CN 110155945 B CN110155945 B CN 110155945B
- Authority
- CN
- China
- Prior art keywords
- methanol
- plate
- catalytic combustion
- heat exchange
- selective methanation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
- C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
- C01B3/586—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being a methanation reaction
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0415—Purification by absorption in liquids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0435—Catalytic purification
- C01B2203/0445—Selective methanation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/048—Composition of the impurity the impurity being an organic compound
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0495—Composition of the impurity the impurity being water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0866—Methods of heating the process for making hydrogen or synthesis gas by combination of different heating methods
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses an integrated CO selective methanation self-heating methanol reforming hydrogen production reactor. The device comprises an upper cover plate, an upper heat exchange plate, a heat exchange plate interlayer, an evaporation plate, a first methanol catalytic combustion plate, a first methanol water vapor reforming plate, a second methanol catalytic combustion plate, a second methanol water vapor reforming plate, a CO selective methanation reaction plate, a lower heat exchange plate and a lower cover plate from top to bottom. CO selective methanation reaction is integrated in the reactor and is directly completed by utilizing hydrogen in reformed gas; after the reformed gas prepared by reforming the methanol water vapor reaction is subjected to CO selective methanation treatment, the CO content is reduced; during the CO removing process of the reactor, other reactants are not introduced, and the hydrogen content in the final product gas is over 70 percent. The gradient distribution of the temperature in the reactor is realized through the stacking sequence and the connecting gas circuit of each reaction plate, so that two different catalysts are both in the optimal working temperature; the reactor has designed heat transfer board in upper and lower both ends and preheats the recovery, improves energy utilization.
Description
Technical Field
The invention relates to a methanol reforming hydrogen production reactor, in particular to an autothermal methanol reforming hydrogen production reactor integrated with CO selective methanation.
Technical Field
Energy is the basis on which human society depends on survival and continuous development. Since the 21 st century, China is facing severe energy crisis and environmental crisis, and therefore the development of clean energy is imperative. Among them, hydrogen energy has a high combustion heat value and the combustion product is water, which is called the most ideal clean energy.
Hydrogen fuel cells are one of the primary ways in which hydrogen energy can be utilized. Because the fuel cell is not limited by Carnot cycle, the direct generating efficiency reaches more than 45%, and the generating efficiency of the cogeneration system can reach 90%. The hydrogen energy also has the characteristics of environmental friendliness, long service life and the like. The novel energy automobile has wide market space in the fields of new energy automobiles, trams, unmanned planes, distributed power supplies and the like.
However, the current commercialization of hydrogen energy economy is limited by the current state of the art for mobile hydrogen storage. The existing mobile hydrogen storage technology has certain gap from commercial application in the aspects of mass energy density, volume energy density, cost and the like. The hydrogen storage problem in mobile applications has severely hampered the use of Proton Exchange Membrane Fuel Cells (PEMFCs) in mobile applications. The methanol steam on-site reforming hydrogen production technology provides an effective solution for the hydrogen supply problem of mobile hydrogen energy application.
The Chinese invention patent (application number 200710159028. X) discloses a miniaturized methanol autothermal reforming hydrogen production integrated device and a hydrogen production method, wherein methanol autothermal reforming and CO selective oxidation are used for preparing hydrogen-rich gas with low CO content, the CO content in product gas can be reduced to be below 30 ppm without a traditional CO water vapor conversion unit, and the hydrogen content in the product gas is more than 53%.
Chinese patent application No. 201310340475.0 discloses a system and method for producing hydrogen from methanol and water, wherein the system comprises a reforming chamber of a methanol and steam reformer, a methanol cracking reaction and a carbon monoxide shift reaction are carried out in the reforming chamber at the temperature of 350-409 ℃ and under the pressure of 1-5M Pa by using a catalyst to generate hydrogen and carbon dioxide, and H is separated by a palladium membrane separator in a separation chamber2And CO2Separating to obtain high-purity hydrogen.
In the two technical schemes, an oxidant is required to be introduced in the CO selective oxidation scheme, so that the complexity of a hydrogen production system is increased; air is used as a common oxidant, and the nitrogen gas dilutes the content of hydrogen in the product gas. In the palladium membrane separation technology, a pressure difference needs to be provided on two sides of the palladium membrane, so that the complexity of the system is increased, and the requirement on the air tightness of the system is high. The existing methanol reforming hydrogen production device still has room for improvement in terms of CO removal and system integration.
Disclosure of Invention
In order to overcome the defects of the prior hydrogen production device, the invention aims to provideAn integrated CO selective methanation self-heating methanol reforming hydrogen production reactor. After the preparation of the hydrogen-rich reformate gas by autothermal reforming of methanol, the hydrogen in the hydrogen-rich product gas is used to convert CO to CH in a selective methanation reaction4And additional reactants are not required to be introduced, so that the integration of the system is facilitated and the energy efficiency is improved.
The technical scheme adopted by the invention is as follows:
the reactor comprises an upper cover plate, an upper heat exchange plate, a heat exchange plate interlayer, an evaporation plate, a first methanol catalytic combustion plate, a first methanol water vapor reforming plate, a second methanol catalytic combustion plate, a second methanol water vapor reforming plate, a CO selective methanation reaction plate, a lower heat exchange plate and a lower cover plate from top to bottom in sequence; the same position of each layer is provided with a bolt mounting hole, a reactant gas path through hole and a graphite gasket sealing groove; the first methanol steam reforming plate and the second methanol steam reforming plate are identical in structure, the middle part of the upper surface is provided with a methanol steam reforming reaction cavity, and catalyst particles for hydrogen production by methanol steam reforming are filled in the cavities respectively; the first methanol catalytic combustion chamber and the second methanol catalytic combustion chamber are identical in structure, the middle part of the upper surface is provided with a methanol catalytic combustion chamber, and the methanol catalytic combustion catalyst particles are respectively filled in the methanol catalytic combustion chambers;
the middle part of the upper surface of the CO selective methanation reaction plate is provided with a CO selective methanation reaction cavity, and CO selective methanation catalyst particles are filled in the cavity.
And micro-channel heat exchange arrays are arranged in the methanol catalytic combustion cavities of the first methanol catalytic combustion plate and the second methanol catalytic combustion plate, and a methanol catalytic combustion catalyst is filled between the micro-channel heat exchange arrays.
The width of the micro-channel heat exchange array is 1-5 mm, and the interval is 3-5 mm.
And a snake-shaped runner evaporation cavity is arranged in the evaporation plate.
The width of snakelike runner evaporation chamber is 5 ~ 10 mm, and the degree of depth is 3 ~ 10 mm.
In the upper heat exchange plate and the lower heat exchange plate, two sides are triangular flow guide areas, and the middle part is a micro-channel heat exchange fin.
The side surfaces of the first and second methanol catalytic combustion plates, the first and second methanol water vapor reforming plates and the CO selective methanation reaction plate are respectively provided with a temperature measuring hole with the diameter of 1 mm and the depth of 10 mm.
A methanol catalytic combustion reactant inlet, a methanol water vapor reforming reactant inlet and a methanol water vapor reforming reactant outlet are formed in one side of the upper surface of the upper cover plate; one side of the lower surface of the lower cover plate, which is the same as one side of the upper surface of the upper cover plate, is provided with a methanol catalytic combustion reactant outlet and a CO selective methanation reaction inlet, and the other side of the lower surface of the lower cover plate is provided with a CO selective methanation reaction outlet.
The invention has the beneficial effects that:
1) the reactor is integrated with CO selective methanation reaction, thereby realizing the removal of CO from the hydrogen-rich reformed gas and omitting the conventional inverse steam transformation process. The CO selective methanation process can be completed by directly utilizing the hydrogen in the reformed gas without introducing additional reactants, and the complexity of system integration is not increased.
2) After the reformed gas prepared by methanol water vapor reaction reforming is subjected to CO selective methanation treatment, the CO content is reduced to below 10 ppm, and the hydrogen supply requirement of a commercial PEMFC can be met.
3) In the CO removing process of the reactor, other reactants are not introduced, and the hydrogen content in the final product gas is higher than 70%.
4) The gradient distribution of the temperature in the reactor can be realized by reasonably arranging the stacking sequence and the connecting gas circuit of each reaction plate, so that two different catalysts are both in the optimal working temperature.
5) The reactor has been designed heat transfer board at upper and lower both ends and has been preheated the recovery, improves the energy utilization of reactor.
Drawings
Fig. 1 is a schematic three-dimensional explosion of the present invention.
Figure 2 is a top and bottom isometric view of the upper deck of the present invention.
Figure 3 is an isometric view of the upper and lower halves of the lower deck of the present invention.
Fig. 4 is a top view of two methanol water vapor reforming plates of the present invention.
FIG. 5 is a top view of a CO selective methanation reaction plate of the present invention.
FIG. 6 is a top view of two methanol catalytic combustion plates according to the present invention.
Fig. 7 is a top view of an evaporation plate of the present invention.
Fig. 8 is an isometric view of an upper and lower double corner of a heat exchange panel of the present invention.
In the figure: 1. the device comprises an upper cover plate, 2, an upper heat exchange plate, 3, a heat exchange plate interlayer, 4, an evaporation plate, 5, a methanol catalytic combustion plate, 6, a methanol steam reforming plate, 7, a CO selective methanation reaction plate, 8, a lower heat exchange plate, 9, a lower cover plate, 10, bolt mounting holes, 11, a methanol catalytic combustion reactant inlet, 12, a methanol steam reforming reactant inlet, 13, a methanol steam reforming reactant outlet, 14, a methanol catalytic combustion reactant outlet, 15, a CO selective methanation reaction inlet, 16, a CO selective methanation reaction outlet, 17, a reactant gas path through hole, 18, a graphite gasket sealing groove, 19, a methanol steam reforming reaction cavity, 20, a methanol catalytic combustion cavity, 21, a CO selective methanation reaction cavity, 22, a microchannel heat exchange array, 23, a serpentine channel evaporation cavity, 24, a triangular flow guide area, 25 and a microchannel heat exchange fin.
Detailed Description
The invention is further described below with reference to the figures and examples.
As shown in fig. 1, the reactor of the present invention comprises, from top to bottom, an upper cover plate 1, an upper heat exchange plate 2, a heat exchange plate interlayer 3, an evaporation plate 4, a first methanol catalytic combustion plate 5, a first methanol water vapor reforming plate 6, a second methanol catalytic combustion plate 5, a second methanol water vapor reforming plate 6, a CO selective methanation reaction plate 7, a lower heat exchange plate 8, and a lower cover plate 9;
the same position of each layer is provided with a bolt mounting hole 10, a reactant gas path through hole 17 and a graphite gasket sealing groove 18.
As shown in fig. 4, the first methanol water vapor reforming plate 6 and the second methanol water vapor reforming plate 6 have the same structure, and the middle parts of the upper surfaces of the first methanol water vapor reforming plate and the second methanol water vapor reforming plate are respectively provided with a methanol water vapor reforming reaction cavity 19 filled with methanol water vapor reforming hydrogen production catalyst particles.
As shown in fig. 6, the first methanol catalytic combustion chamber and the second methanol catalytic combustion chamber have the same structure, and the middle part of the upper surface is provided with a methanol catalytic combustion chamber 20, which is filled with methanol catalytic combustion catalyst particles.
As shown in fig. 5, a CO selective methanation reaction chamber 21 is provided in the middle of the upper surface of the CO selective methanation reaction plate 7, and CO selective methanation catalyst particles are filled in the chamber.
As shown in fig. 6, the methanol catalytic combustion chambers 20 of the first and second methanol catalytic combustion plates 5 are provided with micro-channel heat exchange arrays 22, and a methanol catalytic combustion catalyst is filled between the micro-channel heat exchange arrays 22.
The width of the micro-channel heat exchange array 22 is 1-5 mm, and the interval is 3-5 mm.
As shown in fig. 7, a serpentine channel evaporation cavity 23 is provided in the evaporation plate 4.
The width of snakelike runner evaporation chamber 23 is 5 ~ 10 mm, and the degree of depth is 3 ~ 10 mm.
As shown in fig. 8, in the upper heat exchange plate 2 and the lower heat exchange plate 8, triangular flow guide areas 24 are arranged at two sides, and a microchannel heat exchange fin 25 is arranged at the middle.
In order to realize temperature measurement and control of the reactor, the side surfaces of the first and second methanol catalytic combustion plates 5, the first and second methanol water vapor reforming plates 6 and the CO selective methanation reaction plate 7 are respectively provided with a temperature measuring hole (not marked in the figure) with the diameter of 1 mm and the depth of 10 mm.
As shown in fig. 2 and 3, one side of the upper surface of the upper cover plate 1 is provided with a methanol catalytic combustion reactant inlet 11, a methanol water vapor reforming reactant inlet 12 and a methanol water vapor reforming reactant outlet 13; a methanol catalytic combustion reactant outlet 14 and a CO selective methanation reaction inlet 15 are arranged on one side of the lower surface of the lower cover plate 9, which is the same as the upper surface of the upper cover plate 1, and a CO selective methanation reaction outlet 16 is arranged on the other side of the lower surface of the lower cover plate 9.
The working principle of the invention is as follows:
the self-heating methanol reforming hydrogen production reactor integrating CO selective methanation has 3 gas circuits in total: catalytic combustion of methanol, reforming of methanol water vapor and selective methanation of CO.
The gas circuit of the 1 st path is used for methanol catalytic combustion, methanol and air enter the methanol catalytic combustion plate 5 from a methanol catalytic combustion reactant inlet 11 of the upper cover plate 1 through the upper heat exchange plate 2, the heat exchange plate interlayer 3 and the evaporation plate 4, heat released in the catalytic combustion reaction supplies heat for endothermic reaction in the reactor, and the working temperature required by the reactor is maintained.
The 2 nd gas path is used for reforming methanol water vapor, methanol water solution enters the heat exchange plate 2 from a methanol water vapor reforming reactant inlet 12 of the upper cover plate 1 and enters the evaporation plate 4 through the partition plate 3 to complete the vaporization and preheating of reactants; then enters a methanol water vapor reforming plate 6 through a methanol catalytic combustion plate 5, and generates a methanol water vapor reforming reaction in the methanol water vapor reforming plate to generate hydrogen-rich reformed gas required by the fuel cell; in the process of reforming methanol water vapor, 0.5-2% of CO impurity gas is generated due to the existence of side reaction; the resulting hydrogen-rich reformate gas is passed into a scrubber to remove unreacted, small amounts of methanol and water.
The gas circuit in the path 3 selects methanation for CO, the hydrogen-rich reformed gas after water washing enters the lower heat exchange plate 8 from the methanol water vapor reforming reactant inlet 12 of the lower cover plate 9, enters the CO selective methanation reaction plate 7 through the catalytic combustion reaction plate 5, the CO content of the product gas is reduced to be below 10 ppm by using the hydrogen in the reformed gas through selective methanation reaction, and the hydrogen content of the product gas is kept to be more than 70%. The main reactions involved are:
(1) catalytic combustion of methanol:
(2) methanol water vapor reaction:
(3) selecting CO for methanation reaction:
on the stacking arrangement of the reactor, an upper cover plate 1, an upper heat exchange plate 2, a heat exchange plate clapboard 3, an evaporation plate 4, a methanol catalytic combustion plate 5, a methanol water vapor reforming plate 6, a CO selective methanation reaction plate 7, a lower heat exchange plate 8 and a lower cover plate 9 are arranged from top to bottom in sequence. By adopting the series design, the heat released by the methanol catalytic combustion plate is gradually reduced along with the consumption of catalytic combustion reactants, so that the gradient distribution of the temperature in the reactor can be realized, and the temperature of the methanol steam reforming cavity 19 and the temperature of the CO selective methanation reaction cavity 21 are both in the optimal working temperature range of the catalyst.
On the structural design of the reactor, a catalyst sectional arrangement mode is adopted in the methanol catalytic combustion plate 5, so that the methanol catalytic combustion reaction is gradually carried out, and the uniformity of temperature distribution in a reaction cavity is improved; the micro-channel heat exchange array 22 is arranged in the methanol catalytic combustion plate 5, so that the heat transfer capacity of the reaction cavity is enhanced. A snakelike flow channel design is adopted in the CO selective methanation reaction plate 7, so that the phenomenon of insufficient reaction caused by uneven flow velocity distribution is avoided. In order to improve the overall energy efficiency of the reactor, an upper heat exchange plate 2 and a lower heat exchange plate 8 are designed at the upper end and the lower end of the reactor and used for recovering waste heat in product gas. The cold end of the upper heat exchange plate 2 is methanol water solution, and the hot end is high-temperature hydrogen-rich reformed gas; the cold end of the lower heat exchange plate 8 is hydrogen-rich reformed gas after water washing, and the hot end is high-temperature methanol catalytic combustion tail gas.
In the starting stage of the reactor, only the methanol catalytic combustion gas circuit works. Methanol is pumped into the methanol catalytic combustion plate 5 by a peristaltic pump, and air is pumped into the methanol catalytic combustion plate 5 by a main air pump. The methanol catalytic combustion 5 releases heat to heat the reactor. And when the temperature of the methanol water vapor reforming plate 6 reaches the set temperature, ending the starting stage and entering a stable working stage.
In a stable working stage, in a methanol water vapor reforming gas circuit, a methanol water solution firstly enters an upper heat exchange plate 2 through an inlet of an upper cover plate 1 and exchanges heat with high-temperature hydrogen-rich reformed gas generated by reaction; then enters an evaporation plate 3 of the reactor, is preheated and vaporized in an evaporation cavity and leads to a methanol water vapor reforming plate 6; in the methanol water vapor reforming cavity 19, under the action of a catalyst, methanol reacts with water to generate hydrogen-rich reformed gas, and in the process, 0.5-2% of CO is generated by side reaction; the hydrogen-rich reformed gas is led to the upper heat exchange plate 2, exchanges heat with the methanol water solution, leaves the reactor and enters a gas washing bottle; washing the hydrogen-rich reformed gas with water to remove unreacted methanol and part of water vapor, and then entering a selective methanation gas circuit; the hydrogen-rich reformed gas after water washing enters the lower part for replacementThe hot plate 8 exchanges heat with methanol catalytic combustion tail gas, and then the hot plate is led to a CO selective methanation reaction plate 7; CO is selectively methanated in the reaction cavity 21, and CO reacts with hydrogen in the reformed gas under the action of the catalyst to be converted into CH4The removal of CO is realized; the hydrogen-rich reformate gas that completes the removal of CO exits the reactor to provide a source of hydrogen for the fuel cell.
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 (7)
1. An integrated CO selects the autothermal form methanol reforming hydrogen making reactor of methanation, characterized by that: the reactor is sequentially provided with an upper cover plate (1), an upper heat exchange plate (2), a heat exchange plate interlayer (3), an evaporation plate (4), a first methanol catalytic combustion plate, a first methanol water vapor reforming plate, a second methanol catalytic combustion plate, a second methanol water vapor reforming plate, a CO selective methanation reaction plate (7), a lower heat exchange plate (8) and a lower cover plate (9) from top to bottom;
the same position of each layer is provided with a bolt mounting hole (10), a reactant gas path through hole (17) and a graphite gasket sealing groove (18); the first methanol steam reforming plate and the second methanol steam reforming plate have the same structure, the middle part of the upper surface is provided with a methanol steam reforming reaction cavity (19), and the cavities are respectively filled with methanol steam reforming hydrogen production catalyst particles; the first methanol catalytic combustion chamber and the second methanol catalytic combustion chamber are identical in structure, the middle parts of the upper surfaces of the first methanol catalytic combustion chamber and the second methanol catalytic combustion chamber are respectively provided with a methanol catalytic combustion chamber (20), and the methanol catalytic combustion catalyst particles are respectively filled in the methanol catalytic combustion chambers; a CO selective methanation reaction cavity (21) is arranged in the middle of the upper surface of the CO selective methanation reaction plate (7), and CO selective methanation catalyst particles are filled in the cavity;
one side of the upper surface of the upper cover plate (1) is provided with a methanol catalytic combustion reactant inlet (11), a methanol water vapor reforming reactant inlet (12) and a methanol water vapor reforming reactant outlet (13); one side of the lower surface of the lower cover plate (9) which is the same as one side of the upper surface of the upper cover plate (1) is provided with a methanol catalytic combustion reactant outlet (14) and a CO selective methanation reaction inlet (15), and the other side of the lower surface of the lower cover plate (9) is provided with a CO selective methanation reaction outlet (16).
2. The autothermal methanol reforming hydrogen production reactor integrated with CO selective methanation of claim 1, wherein: and micro-channel heat exchange arrays (22) are arranged in the methanol catalytic combustion cavities (20) of the first methanol catalytic combustion plate and the second methanol catalytic combustion plate, and a methanol catalytic combustion catalyst is filled between the micro-channel heat exchange arrays (22).
3. The autothermal methanol reforming hydrogen production reactor integrated with CO selective methanation of claim 2, wherein: the width of the micro-channel heat exchange array (22) is 1-5 mm, and the interval is 3-5 mm.
4. The autothermal methanol reforming hydrogen production reactor integrated with CO selective methanation of claim 1, wherein: and a snake-shaped runner evaporation cavity (23) is arranged in the evaporation plate (4).
5. The autothermal methanol reforming hydrogen production reactor integrated with CO selective methanation of claim 4, wherein: the width of snakelike runner evaporation chamber (23) is 5 ~ 10 mm, and the degree of depth is 3 ~ 10 mm.
6. The autothermal methanol reforming hydrogen production reactor integrated with CO selective methanation of claim 1, wherein: in the upper heat exchange plate (2) and the lower heat exchange plate (8), triangular flow guide areas (24) are arranged on two sides, and micro-channel heat exchange fins (25) are arranged in the middle.
7. The autothermal methanol reforming hydrogen production reactor integrated with CO selective methanation of claim 1, wherein: the side surfaces of the first and second methanol catalytic combustion plates, the first and second methanol water vapor reforming plates and the CO selective methanation reaction plate (7) are respectively provided with a temperature measuring hole with the diameter of 1 mm and the depth of 10 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910323448.XA CN110155945B (en) | 2019-04-22 | 2019-04-22 | Self-heating methanol reforming hydrogen production reactor integrating CO selective methanation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910323448.XA CN110155945B (en) | 2019-04-22 | 2019-04-22 | Self-heating methanol reforming hydrogen production reactor integrating CO selective methanation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110155945A CN110155945A (en) | 2019-08-23 |
| CN110155945B true CN110155945B (en) | 2020-12-25 |
Family
ID=67639735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910323448.XA Active CN110155945B (en) | 2019-04-22 | 2019-04-22 | Self-heating methanol reforming hydrogen production reactor integrating CO selective methanation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110155945B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112960645B (en) * | 2019-12-14 | 2022-08-05 | 中国科学院大连化学物理研究所 | Water-steam shift reactor for autothermal reforming hydrogen production reaction and method for improving CO conversion rate of water-steam shift reaction |
| CN111545149B (en) * | 2020-04-27 | 2021-07-13 | 西安交通大学 | High-concentration system for photocatalytic water decomposition reaction and using method thereof |
| CN113735059B (en) * | 2021-08-23 | 2023-09-22 | 中南大学 | Alcohol reforming micro-reactor and hydrogen production method |
| CN113707920B (en) * | 2021-08-27 | 2022-10-11 | 中南大学 | Alcohol reforming fuel cell system |
| CN114933280B (en) * | 2022-05-20 | 2023-05-23 | 大连大学 | Methanol hydrogen production device capable of automatically removing CO and application method thereof |
| CN114976164B (en) * | 2022-06-21 | 2023-03-24 | 哈尔滨工业大学（深圳） | Highly integrated thermal self-sustaining methanol reforming fuel cell device |
| CN115504434B (en) * | 2022-11-09 | 2023-08-01 | 常州创氢能源科技有限公司 | Self-heating reforming hydrogen production reactor |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19918997C2 (en) * | 1999-04-27 | 2001-06-07 | Xcellsis Gmbh | Process for operating a plant for steam reforming of hydrocarbons, in particular methanol, and corresponding plant |
| US8053387B2 (en) * | 2002-11-07 | 2011-11-08 | Tufts University | Catalyst having metal in reduced quantity and reduced cluster size |
| CN101148249B (en) * | 2006-09-22 | 2010-09-29 | 比亚迪股份有限公司 | On-site hydrogen producing method and on-site hydrogen producing device |
| CN101462694B (en) * | 2007-12-19 | 2011-04-20 | 中国科学院大连化学物理研究所 | Miniaturized methanol self-heating reforming hydrogen making integrated apparatus and hydrogen production method |
| CN102627259A (en) * | 2012-03-27 | 2012-08-08 | 成都赛普瑞兴科技有限公司 | Method for preparing hydrogen by methanol-water reforming |
| CN203540511U (en) * | 2013-08-19 | 2014-04-16 | 浙江大学 | Laminated microchannel reactor with evenly distributed channel flow velocity |
| CN104671204B (en) * | 2015-02-15 | 2016-08-24 | 浙江大学 | Cascading double-sided how snakelike microchannel reforming hydrogen-preparation reactor |
| CN204454569U (en) * | 2015-02-15 | 2015-07-08 | 浙江大学 | A kind of cascading double-sided how snakelike microchannel reforming hydrogen-preparation reactor |
| CN205933214U (en) * | 2016-08-25 | 2017-02-08 | 晋城市阿邦迪能源有限公司 | Methanation reaction purifies CO's methanol reforming reactor |
| CN106629598B (en) * | 2016-11-11 | 2018-08-07 | 浙江大学 | The self-heating type reforming hydrogen-preparation reactor of filled high-temperature phase-change material |
| CN107986232A (en) * | 2017-11-28 | 2018-05-04 | 四川亚联高科技股份有限公司 | The method of methanol preparing high purity hydrogen |
-
2019
- 2019-04-22 CN CN201910323448.XA patent/CN110155945B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110155945A (en) | 2019-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110155945B (en) | Self-heating methanol reforming hydrogen production reactor integrating CO selective methanation | |
| US5380600A (en) | Fuel cell system | |
| US20070184310A1 (en) | Molten Carbonate Fuel Cell Provided with Indirect Internal Steam Reformer | |
| CN102910584B (en) | Self-heating laminated micro-channel reforming hydrogen production reactor | |
| US8034496B2 (en) | Fuel cell | |
| CN113830733B (en) | Foam copper integrated reformer with variable catalyst distribution | |
| CN110801785B (en) | Hydrogen production reactor with honeycomb SiC ceramic as catalyst carrier | |
| CN101580227B (en) | Self-heating type alcohol reforming hydrogen production micro channel reactor with micro-lug boss array structure | |
| CN112892460B (en) | Self-heating methanol reforming hydrogen production reactor | |
| CN110143575B (en) | Corrugated substrate-porous metal self-heating methanol reforming hydrogen production reactor | |
| JP5021691B2 (en) | Reformer integrated solid oxide fuel cell | |
| CN114361505B (en) | Three-runner solid oxide fuel cell unit structure and cell stack | |
| JP3831688B2 (en) | Reformer system | |
| TWI465393B (en) | Hydrogen generator and the application of the same | |
| KR101243767B1 (en) | Hydrogen production system for pemfc | |
| CN112820914A (en) | Fuel cell system directly utilizing methanol reformed gas and working method thereof | |
| US20100143755A1 (en) | Multi-Channel Fuel Reformer with Augmented Heat Transfer | |
| JPS58119167A (en) | Fuel cell device | |
| CN115138300A (en) | Catalytic reforming device | |
| KR100475587B1 (en) | A Plate type fuel processor for fuel cell | |
| CN203033764U (en) | Self-heating laminated micro-channel reforming hydrogen production reactor | |
| Kawamura et al. | Multi-layered microreactor system with methanol reformer for small PEMFC | |
| JP2001263968A (en) | Plate fin type heat exchanger | |
| CN101771160B (en) | Thermal-coupling natural gas reformer | |
| KR20150135560A (en) | Plate Type Reformer for Fuel Cell System |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |