CN116262603A - Methanol reforming device and method - Google Patents

Methanol reforming device and method Download PDF

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Publication number
CN116262603A
CN116262603A CN202111538463.XA CN202111538463A CN116262603A CN 116262603 A CN116262603 A CN 116262603A CN 202111538463 A CN202111538463 A CN 202111538463A CN 116262603 A CN116262603 A CN 116262603A
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reforming
tail gas
combustion
catalyst
methanol
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CN202111538463.XA
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王素力
吴私
孙公权
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Priority to CN202111538463.XA priority Critical patent/CN116262603A/en
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    • 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
    • C01B3/02—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
    • 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
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

The application relates to a methanol reforming device and a method. The device comprises a heat supply unit and a reforming unit; the preheating unit comprises a fuel inlet, a combustion chamber, a heat transfer channel penetrating the reforming unit and a combustion tail gas outlet; the reforming unit includes a methanol steam inlet and a reformed tail gas outlet. The high-temperature proton exchange membrane fuel cell (HT-PEMFC) has a highly compact structure, can be manufactured in an extrusion mode, is low in manufacturing cost and high in thermal efficiency, solves the problems of quick start, low-temperature operation and the like, is particularly suitable for the field of hydrogen production reaction by reforming methanol steam in a high-temperature proton exchange membrane fuel cell (HT-PEMFC), and effectively improves the efficiency of a fuel processor and a fuel cell system.

Description

Methanol reforming device and method
Technical Field
The application relates to a methanol reforming device and a method, which are particularly suitable for the field of hydrogen production reaction by reforming methanol steam in a high-temperature proton exchange membrane fuel cell (HT-PEMFC) and are used for providing needed reaction gas for a fuel cell unit.
Background
A fuel cell is a device that directly converts chemical energy stored in a compound fuel into electric energy through a chemical reaction. The fuel processor is a hydrogen supply device of the fuel cell and mainly comprises an endothermic reforming chamber, a combustion chamber for providing a heat source, related accessories and the like, and if the arrangement is unreasonable, the conditions of large compactness, long starting time, low fuel heat utilization efficiency, poor hydrogen production efficiency, short service life and the like can occur, so that the power generation efficiency and the service life of the whole battery pack are greatly influenced; meanwhile, due to multiple functions, complex structure and higher manufacturing cost.
Disclosure of Invention
The application provides a fuel processor, has highly compact structure, can make through extrusion mode, low in manufacturing cost, and thermal efficiency is high, solves the quick start, low temperature operation scheduling problem simultaneously, is particularly useful for the methyl alcohol vapor reforming hydrogen manufacturing reaction field in high temperature proton exchange membrane fuel cell (HT-PEMFC), effectively promotes fuel processor and fuel cell system efficiency.
The purpose of this application is to propose a fuel processor, has highly compact structure, can make through extrusion mode, low in manufacturing cost, and thermal efficiency is high, solves the problem such as quick start, low temperature operation simultaneously, is particularly useful for the methyl alcohol vapor reforming hydrogen manufacturing reaction field in high temperature proton exchange membrane fuel cell (HT-PEMFC), effectively promotes fuel processor and fuel cell system efficiency.
According to an aspect of the present application, there is provided a methanol reforming apparatus including a heat supply unit and a reforming unit;
the heat supply unit comprises a fuel inlet, a combustion chamber, a heat transfer channel penetrating the reforming unit and a combustion tail gas outlet;
the reforming unit comprises a methanol steam inlet and a reformed tail gas outlet.
In the preheating unit, the combustion chamber comprises an igniter and a catalytic burner.
The catalytic burner is filled with a catalytic combustion catalyst;
the catalytic combustion catalyst is selected from platinum alumina; the mass content of the platinum element in the catalyst is 0.4-0.6%.
The specific heat exchange surface area of the device is 3x10 3 ～4x10 3 m 2 /m 3
Baffles are disposed in the heat transfer channels extending through the reforming unit.
The reforming unit is filled with a reforming catalyst;
the reforming catalyst is selected from CuO/ZnO/Al 2 O 3 A catalyst;
CuO and Al in the catalyst 2 O 3 The mass ratio of ZnO to Al is 5-6 2 O 3 Quality ofThe ratio is 1.5-2;
the working temperature of a reforming cavity of the device is 220-300 ℃;
the device is heated from 25 ℃ to 300 ℃ for 10-15 min.
According to another aspect of the present application, there is provided a methanol reforming method, employing the above-described methanol reforming apparatus;
at least comprises the following steps:
the fuel enters the combustion chamber through the fuel inlet, the igniter ignites and burns, and the igniter is closed after the reforming unit reaches the working temperature; the combustion tail gas is discharged from a combustion tail gas outlet through a heat transfer channel penetrating through the reforming unit, enters the combustion chamber from a fuel inlet, and is subjected to catalytic combustion through a catalytic combustor;
the methanol steam enters from a methanol steam inlet, contacts with a reforming catalyst in a reforming unit, reforms, and the reformed tail gas is discharged from a reformed tail gas outlet.
The mass flow rate of the fuel entering the fuel inlet is 0.0001-0.0004 kg/s;
the mass flow rate of the methanol steam entering the methanol steam inlet is 0.000145-0.00058 kg/s.
The volume fraction of hydrogen in the reformed tail gas is 65% -75%; the volume fraction of carbon monoxide is less than 1%.
The beneficial effects of this application are:
the reforming cavity adopts an aluminum extrusion structure, the center and the periphery of the reforming cavity are provided with combustion tail gas chambers, the reforming cavity is wrapped, the heat conversion area is increased, the heat exchange capacity is enhanced, and the reforming cavity is filled with reforming catalyst for reforming hydrogen production reaction; the front end of the reforming cavity is a combustion cavity, the fuel is instantaneously ignited by an igniter in the starting stage, the rear end is filled with a combustion catalyst, and a heat source is provided by catalytic combustion.
The reforming cavity is wrapped by the combustion tail gas cavity, so that the heat transfer distance of the reforming cavity is shortened, more and more uniform heat is transferred to the heat-absorbing reforming cavity through the peripheral zigzag fins, and the reforming reaction can be efficiently carried out and can be rapidly heated in the simultaneous starting stage; in the starting stage of the combustion chamber, fuel is instantaneously ignited through an igniter, so that the starting time is greatly shortened, and meanwhile, the ignition device is little influenced by environmental factors, can instantaneously start combustion even in a low-temperature environment, and heats products; a section of combustion catalyst is arranged at the rear end of the combustion chamber, tail gas hydrogen of a pile anode in the operation stage of the fuel cell system is utilized for catalytic combustion to provide heat for reforming, and fuels such as methanol which is not completely combusted in the starting stage are combusted and utilized, so that the stability of the combustion chamber is also ensured.
Drawings
Fig. 1 is an overall schematic diagram 1 of the methanol reforming unit of example 1.
Fig. 2 is an overall schematic diagram 2 of the methanol reforming unit of example 1.
Fig. 3 is a schematic cross-sectional view of the methanol reforming unit of example 1.
Fig. 4 is a cross-sectional view of a reforming chamber of the methanol reformer of example 1.
Fig. 5 is a schematic view of a reforming chamber baffle of the methanol reformer of example 1.
Fig. 6A, 6B, and 6C are schematic diagrams of the combustion chamber of the methanol reforming unit of example 1.
Fig. 7 is an overall sectional view of the methanol reformer of example 1.
In the figure: A. combustion air inlet, anode tail gas inlet, start fuel inlet, combustion tail gas outlet, reformed methanol steam inlet
1. Reforming chamber, combustion chamber, baffle plate, igniter, tail gas combustion chamber, cover plate and combustion catalyst.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Example 1
The present application is described in detail below with reference to the attached drawings and detailed description.
As shown in fig. 1 and 2, the device comprises a reforming chamber 1, a combustion chamber 2, a baffle plate 3, an igniter 4, a combustion tail row chamber 5 and a cover plate 6; in the system starting stage, the reforming reaction liquid enters an igniter through a starting fuel inlet C, is vaporized and ignited by the igniter 4, is mixed with air to be used as a burner fuel, and enters a combustion chamber 2 to burn and release heat through open flame; in the system operation stage, cathode and anode tail gas of the galvanic pile is mixed to be used as a burner fuel, the fuel enters the combustion chamber 2 through the anode tail gas inlet B to catalyze combustion to release heat, and the combustion tail gas is discharged from the outlet D; the reforming reaction liquid enters the reforming chamber 1 through the inlet F, fully reacts to generate hydrogen-rich reaction gas through an S-shaped flow channel formed by an internal baffle plate, is discharged from the reforming outlet E, enters the electric pile to participate in the reaction, and the redundant hydrogen-rich tail gas enters the combustion chamber 2 through the anode tail gas inlet B to catalyze and burn to provide heat for reforming.
The reforming cavity 1 adopts an aluminum extrusion type structure, a combustion tail gas cavity 5 is arranged at the center and the periphery, the reforming cavity is wrapped, the heat conversion area is increased, the heat exchange capacity is enhanced, and the reforming cavity 1 is filled with a reforming catalyst and is used for reforming hydrogen production reaction; the front end of the reforming cavity is a combustion cavity 2, the fuel is instantaneously ignited by an igniter 4 in the starting stage, the rear end is filled with a combustion catalyst, and a heat source is provided by catalytic combustion.
The reforming cavity 1 is wrapped by the combustion tail gas cavity 5, so that the heat transfer distance of the reforming cavity is shortened, and heat is more uniformly transferred to the heat-absorbing reforming cavity 1 through the peripheral zigzag fins, thereby being beneficial to the efficient simultaneous start-up stage of the reforming reaction and being capable of rapidly heating; in the starting stage of the combustion chamber 2, the fuel is instantaneously ignited by the igniter 4 to heat the product; a section of combustion catalyst 7 is arranged at the rear end of the combustion chamber 2, tail gas hydrogen of a pile anode in the operation stage of the fuel cell system is utilized for catalytic combustion to provide heat for reforming, and fuels such as methanol which is not completely combusted in the starting stage are combusted and utilized, so that the stability of the combustion chamber is ensured.
The methanol reforming device in this embodiment is used to reform methanol and steam to produce hydrogen, 60% volume content of methanol aqueous solution is used as reforming reaction liquid, the mass flow is 0.000145kg/s, the igniter is used to burn 0.0001kg/s methanol aqueous solution with mass flow through open fire until the temperature of the combustion chamber is about 400 ℃ in the system starting stage, after the system is normally operated, the igniter is closed, the anode tail gas of the galvanic pile returns to the combustion chamber to perform catalytic combustion, and the catalyst is platinum alumina and platinumThe content is 0.5%, the reforming reaction liquid is vaporized by external evaporation and enters a reforming cavity at about 160 ℃, the temperature of the reforming cavity is between 220 and 300 ℃, and CuO/ZnO/Al is filled in the reforming cavity 2 O 3 The catalyst has the hydrogen content of about 75 percent (volume) in the reformed tail gas, the hydrogen standard condition flow is about 10L/min, and the carbon monoxide content is lower than 1 percent (volume), and can be used for meeting the hydrogen with the condition of 500W of the operating power generation of the fuel cell stack; the heat of the combustion chamber and the tail heat of the combustion chamber in the starting stage is directly and rapidly transferred to the reforming cavity, and the temperature is increased from the normal temperature of 25 ℃ to 300 ℃ for 10-15 min.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.

Claims (10)

1. A methanol reforming device, which is characterized by comprising a heat supply unit and a reforming unit;
the heat supply unit comprises a fuel inlet, a combustion chamber, a heat transfer channel and a combustion tail gas outlet which are sequentially connected;
the reforming unit comprises a methanol steam inlet, a reforming cavity and a reformed tail gas outlet which are sequentially connected.
2. The apparatus of claim 1, wherein in the preheating unit, the combustion chamber comprises an igniter and a catalytic burner.
3. The apparatus of claim 2, wherein the catalytic burner is packed with a catalytic combustion catalyst;
the catalytic combustion catalyst is selected from platinum alumina; the mass content of the platinum element in the catalyst is 0.4-0.6%.
4. The device according to claim 1Characterized in that the specific heat exchange surface area of the device is 3x10 3 ～4x10 3 m 2 /m 3 。
5. The apparatus of claim 1, wherein baffles are disposed in the heat transfer channels extending through the reforming unit.
6. The apparatus of claim 1, wherein the reforming unit is filled with a reforming catalyst;
the reforming catalyst is selected from CuO/ZnO/Al 2 O 3 A catalyst;
CuO and Al in the catalyst 2 O 3 The mass ratio of ZnO to Al is 5-6 2 O 3 The mass ratio is 1.5-2.
7. The apparatus of claim 1, wherein the reforming chamber of the apparatus operates at a temperature of 220-300 ℃;
the device is heated from 25 ℃ to 300 ℃ for 10-15 min.
8. A methanol reforming method, characterized in that the methanol reforming apparatus according to any one of claims 1 to 7 is used;
at least comprises the following steps:
the fuel enters the combustion chamber through the fuel inlet, the igniter ignites and burns, and the igniter is closed after the reforming unit reaches the working temperature; the combustion tail gas is discharged from a combustion tail gas outlet through a heat transfer channel penetrating through the reforming unit, enters the combustion chamber from a fuel inlet, and is subjected to catalytic combustion through a catalytic combustor;
the methanol steam enters from a methanol steam inlet, contacts with a reforming catalyst in a reforming unit for reforming, and reformed tail gas is discharged from a reformed tail gas outlet.
9. The method of claim 8, wherein the mass flow of fuel into the fuel inlet is from 0.0001 to 0.0004kg/s; the mass flow rate of the methanol steam entering the methanol steam inlet is 0.000145-0.00058 kg/s.
10. The method of claim 8, wherein the volume fraction of hydrogen in the reformed tail gas is 65% to 75%; the volume fraction of carbon monoxide is less than 1%.
CN202111538463.XA 2021-12-15 2021-12-15 Methanol reforming device and method Pending CN116262603A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111538463.XA CN116262603A (en) 2021-12-15 2021-12-15 Methanol reforming device and method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111538463.XA CN116262603A (en) 2021-12-15 2021-12-15 Methanol reforming device and method

Publications (1)

Publication Number Publication Date
CN116262603A true CN116262603A (en) 2023-06-16

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Application Number Title Priority Date Filing Date
CN202111538463.XA Pending CN116262603A (en) 2021-12-15 2021-12-15 Methanol reforming device and method

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Country Link
CN (1) CN116262603A (en)

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