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CN113830732A - Reformer combining partial oxidation reforming with steam reforming - Google Patents

Reformer combining partial oxidation reforming with steam reforming Download PDF

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Publication number
CN113830732A
CN113830732A CN202111281322.4A CN202111281322A CN113830732A CN 113830732 A CN113830732 A CN 113830732A CN 202111281322 A CN202111281322 A CN 202111281322A CN 113830732 A CN113830732 A CN 113830732A
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steam
chamber
steam reforming
reforming
reaction chamber
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CN202111281322.4A
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Chinese (zh)
Inventor
成功
杨卫华
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Suzhou Junfeng New Energy Technology Co ltd
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Suzhou Junfeng New Energy Technology Co ltd
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Priority to CN202111281322.4A priority Critical patent/CN113830732A/en
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/025Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/085Methods of heating the process for making hydrogen or synthesis gas by electric heating
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005Arrangement or shape of catalyst
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • C01B2203/1047Group VIII metal catalysts
    • C01B2203/1064Platinum group metal catalysts
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • C01B2203/1047Group VIII metal catalysts
    • C01B2203/1064Platinum group metal catalysts
    • C01B2203/107Platinum catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

A reformer combining partial oxidation reforming with steam reforming is disclosed. The technical scheme of the invention is as follows: comprises a burner module and a steam reformer module; the burner module comprises a fuel gasification chamber for a burner, an autothermal reforming reaction chamber and a combustion chamber; the steam reformer module includes a water gasification chamber for steam reforming, a fuel gasification chamber for steam reforming, and a steam reforming reaction chamber, the water gasification chamber for steam reforming transmits steam to the steam reforming reaction chamber, and the steam reforming reaction chamber outputs steam reformed gas. The scheme provided by the invention obtains hydrogen through a partial oxidation reforming method to be used for catalyst combustion, provides heat for steam reforming reaction, realizes that the reformer can finish quick start by using the same fuel, and the concentration of the hydrogen in the reformed gas is maintained at a higher level without nitrogen-containing compound impurities.

Description

Reformer combining partial oxidation reforming with steam reforming
Technical Field
The invention relates to the technical field of reforming hydrogen production reaction equipment, in particular to a reformer for light hydrocarbon, alcohol, diesel oil and other fuels.
Background
With the development of fuel cell and hydrogen gas internal combustion engine technology, hydrogen energy is used as an alternative energy source and becomes a consensus of scientific research and product developers. Due to the problems of high pressure, explosion and the like in the hydrogen storage and transportation process, the scheme of directly storing hydrogen as an energy source has high use cost and great potential safety hazard. Therefore, the production of hydrogen by catalytic reforming using a hydrogen-rich liquid fuel is favored by researchers.
There are various fuel reforming technologies, and among them, the steam reforming method is widely used. The steam reforming method is to react gaseous fuel with steam at high temperature through the action of catalyst to produce hydrogen, and the hydrogen source is not only from fuel, but also replaces hydrogen in water, so that the hydrogen concentration in the product is high, and the main products are hydrogen, carbon dioxide and carbon monoxide. However, the reforming reaction is a high-temperature endothermic reaction, and external heat supply such as catalytic combustion is required, and particularly, a long heating process is required during starting; the catalytic combustion has a very good catalytic effect on hydrogen, methanol and other small molecules, particularly on hydrogen, the catalytic combustion can be started at a lower temperature, but for fuels with more carbon atoms in the molecules, the catalytic combustion effect is poor, the combustion is often insufficient, and most of light hydrocarbons and diesel oil cannot be directly used as a system heat source by catalytic combustion.
The partial oxidation reforming method generates hydrogen and CO through the direct reaction of fuel and oxygen, is a strong exothermic reaction compared with a steam reforming reaction, has the characteristics of short cold start time and fast dynamic response, and has a compact reactor structure because external heat supply is not needed. However, in practical application, oxygen is obtained by introducing air, and a large amount of nitrogen exists in the air, so that a large amount of nitrogen is contained in the components of the reformed gas, the hydrogen concentration is reduced, and the nitrogen easily reacts with hydrogen under the action of a catalyst at high temperature to produce byproducts such as ammonia. Meanwhile, partial oxidation reforming needs to burn part of hydrogen to provide heat for reforming, and the hydrogen yield is low, so that the method is not much in practical application.
Disclosure of Invention
In view of the defects of the prior art, the main object of the present invention is to provide a reformer which uses fuel to obtain hydrogen through a partial oxidation reforming method for catalyst combustion, provides heat for steam reforming reaction, and realizes that the reformer can use the same fuel to complete quick start, and the hydrogen concentration in the reformed gas maintains a high level, and the partial oxidation reforming and the steam reforming which do not contain nitrogen-containing compound impurities are combined.
In order to achieve the purpose, the invention provides the following technical scheme: a reformer combining partial oxidation reforming with steam reforming comprising a burner module and a steam reformer module; the burner module comprises a fuel gasification chamber for a burner, an autothermal reforming reaction chamber and a combustion chamber, wherein the fuel gasification chamber for the burner conveys fuel gas to the autothermal reforming reaction chamber, the autothermal reforming reaction chamber conveys partial oxidation reformed gas containing hydrogen to the combustion chamber, and the combustion chamber conveys high-temperature tail gas to the steam reformer module; the steam reformer module comprises a water gasification chamber for steam reforming, a fuel gasification chamber for steam reforming and a steam reforming reaction chamber, wherein the water gasification chamber for steam reforming conveys steam to the steam reforming reaction chamber, the fuel gasification chamber for steam reforming conveys fuel gas to the steam reforming reaction chamber, the steam reforming reaction chamber outputs steam reforming gas, and high-temperature tail gas forms low-temperature combustion tail gas after heat exchange through the steam reformer module.
Preferably, the combustion chamber and the autothermal reforming reaction chamber are both provided with a catalyst which is integrated in a granular or honeycomb form or coated on the surfaces of the combustion chamber and the autothermal reforming reaction chamber.
Compared with the prior art, the invention has the advantages that the scheme combines the partial oxidation reforming method with the steam reforming method, designs the reformer, obtains hydrogen through the partial oxidation reforming method for the combustion of the catalyst, provides heat for the steam reforming reaction, realizes that the reformer can finish quick start by using the same fuel, maintains higher hydrogen concentration in the reformed gas and does not contain nitrogen compound impurities. Compared with the prior art, the heat supply of steam reforming by using the same fuel is realized especially for the multi-carbon hydrocarbon and the diesel oil. The preheating time of the existing steam reforming reactor is 1-2 hours, and the time can be shortened to 0.5-1 hour by adopting the technology.
Drawings
FIG. 1 is a schematic representation of a reformer incorporating partial oxidation reforming in combination with steam reforming in accordance with the present invention.
In the figure: 1. a burner module; 2. a steam reformer module; 3. a fuel for the burner; 4. a fuel vaporizing chamber for the burner; 5. a fuel gas for the burner; 6. air for autothermal reforming; 7. an autothermal reforming reaction chamber; 8. partially oxidizing the reformed gas; 9. air for the combustion chamber; 10. a combustion chamber; 11. high temperature tail gas; 12. water for steam reforming; 13. a fuel for steam reforming; 14. a water gasification chamber for steam reforming; 15. a fuel vaporizing chamber for steam reforming; 16. steam for steam reforming; 17. a fuel gas for steam reforming; 18. a steam reforming reaction chamber; 19. steam reformed gas; 20. and (4) low-temperature combustion of tail gas.
Detailed Description
The invention will be further explained with reference to the drawings.
As shown in fig. 1, a reformer combining partial oxidation reforming with steam reforming includes a burner module 1 and a steam reformer module 2; the burner module 1 comprises a fuel gasification chamber 4 for burner, an autothermal reforming reaction chamber 7 and a combustion chamber 10, wherein the fuel gasification chamber 4 for burner supplies fuel gas to the autothermal reforming reaction chamber 7, the autothermal reforming reaction chamber 7 supplies partial oxidation reformed gas containing hydrogen to the combustion chamber 10, and the combustion chamber 10 supplies high-temperature tail gas 11 to the steam reformer module 2; the steam reformer module 2 includes a water gasification chamber 14 for steam reforming, a fuel gasification chamber 15 for steam reforming, and a steam reforming reaction chamber 18, the water gasification chamber 14 for steam reforming transmits steam to the steam reforming reaction chamber 18, the fuel gasification chamber 15 for steam reforming transmits fuel gas to the steam reforming reaction chamber 18, the steam reforming reaction chamber 18 outputs steam reformed gas, and the high temperature exhaust gas 11 forms low temperature combustion exhaust gas 20 after heat exchange by the steam reformer module 2.
Preferably, the combustion chamber 10 and the autothermal reforming reaction chamber 7 are each provided with a catalyst in the form of particles or a honeycomb or coated on the surfaces of the combustion chamber 10 and the autothermal reforming reaction chamber 7.
The reformer is designed by combining a partial oxidation reforming method and a steam reforming method, hydrogen obtained by the fuel through the partial oxidation reforming method is used for catalyst combustion, heat is provided for steam reforming reaction, the reformer can be started quickly by using the same fuel, the hydrogen concentration in reformed gas is maintained at a high level, and no nitrogen-containing compound impurity is generated. Compared with the prior art, the heat supply of steam reforming by using the same fuel is realized especially for the multi-carbon hydrocarbon and the diesel oil. The preheating time of the existing steam reforming reactor is 1-2 hours, and the time can be shortened to 0.5-1 hour by adopting the technology.
The reformer combining partial oxidation reforming and steam reforming of the present invention can be roughly divided into two parts, a burner module 1 and a steam reformer module 2, and the burner module 1 includes a feed line for a fuel 3 for a burner and a fuel gasification chamber 4 for a burner, a partial oxidation reforming reaction chamber and a combustion chamber 10. After the whole combustion chamber 10 is preheated to a certain temperature, fuel is gasified to generate fuel gas 5 for a combustor, the fuel gas enters the partial oxidation reforming reaction chamber and reacts with air 6 for autothermal reforming under the action of a catalyst to obtain partial oxidation reforming gas 8 containing hydrogen, the partial oxidation reforming gas 8 enters the combustion chamber 10 and is completely combusted with air 9 for the combustion chamber under the action of the catalyst to give high-temperature tail gas 11.
The steam reforming reactor includes a steam reforming fuel vaporization chamber 15 for vaporizing the steam reforming water 12 and the steam reforming fuel 13, and a pipe line, and a steam reforming reaction chamber 18 containing a catalyst. The steam reforming reaction chamber 18 is preheated by the high-temperature exhaust gas 11, the water and the fuel entering the steam reforming reaction chamber 18 are gasified, and the steam 16 and the fuel gas 17 for steam reforming after the gasification are supplied to the steam reforming reaction chamber 18, thereby obtaining a steam reformed gas 19 having a high hydrogen concentration and a small impurity content. The heat of the steam reforming reaction is obtained by heat exchange with the high temperature off-gas 11 of the combustor.
The gasification chamber of the fuel in the burner can be directly gasified at high temperature or gasified at high temperature after being sprayed, can be integrally formed with the burner to carry out bulk heat transfer, and can also adopt combustion tail gas to supply heat independently of the burner; in order to reduce the volume and improve the heat efficiency, the integral molding is suggested. The system needs to be preheated when being started, and the preheating mode can adopt modes such as electric heating or fuel combustion direct heating. The partial oxidation reforming reaction chamber contains a catalyst, and the catalyst may be in the form of particles, a honeycomb monolith, a coating on the surface of the autothermal reforming reaction chamber 7, or the like.
The combustion chamber 10 contains a catalyst which can be in the form of particles, honeycomb integration, coating on the surface of the autothermal reforming reaction chamber 7 and the like, wherein the catalyst is Pt, Pd and other noble metals and composite catalyst.
The gasification chamber of water and fuel in the steam reforming reactor can be directly gasified at high temperature or gasified at high temperature after being sprayed, can be integrally formed with a combustor to carry out bulk heat transfer, and can also adopt combustion tail gas for heat supply independently of the combustor; in order to reasonably utilize the heat of the tail gas, the tail gas is recommended to be heated by burning the tail gas independently of a burner.
The steam reforming reaction chamber 18 contains a catalyst, which may be in the form of a pellet, a honeycomb monolith, or a coating on the surface of the autothermal reforming reaction chamber 7, and different fuels may be classified into a noble metal-based, copper-based, nickel-based, or rare earth-based catalyst, depending on the catalyst used.
Taking a 10kW diesel reformer as an example, a burner is made of steel, a gasification flow channel of fuel is integrated on one side of the wall surface of the burner, a partial oxidation reforming reaction chamber is integrated on the other side of the wall surface of the burner, a granular Pt-based catalyst is filled in the partial oxidation reforming reaction chamber and used for an autothermal reforming reaction, and the combustion effect is monitored by a thermocouple in tail gas. The middle of the burner is a cylindrical cordierite ceramic honeycomb carrier catalyst with the diameter of 100 and the length of 100, the burner is preheated by an electric heating pipe, when the preheating temperature is reached, diesel oil enters the self-heating reaction chamber through the gasification runner and is partially oxidized and reformed with introduced air, and then generated reformed gas enters the combustion chamber 10 and is catalytically combusted with the air to provide high-temperature gas for preheating the steam reformer. The initial preheating power is 2.5kW, and the preheating mode can be completed within 45 minutes.
The steam reformer comprises a steam reforming reaction chamber 18 and a water and fuel gasification chamber, wherein the steam reforming chamber is a tube type gas-gas heat exchanger and is made of steel, a granular Pt-based catalyst is filled in the steam reforming chamber, and the running condition of the reactor is monitored by thermocouples on the reactor and the gasification chamber. Because the diesel oil gasification temperature is higher, the next stage is a diesel oil gasification chamber which is made of aluminum alloy, and the tail gas flowing through the steam reforming reaction chamber 18 is used for diesel oil gasification; and finally, the water vapor gasification chamber is made of aluminum alloy, and the temperature of tail gas flowing through the diesel oil gasification chamber is utilized, so that the reasonable utilization of heat is realized. When the steam reforming reaction chamber 18 reaches the reaction temperature, the reaction temperature is controlled by the amount of fuel for combustion, and the reformed gas with high hydrogen concentration and low impurity content can be obtained by introducing water and fuel into the steam reformer in a proper proportion.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.

Claims (2)

1. A reformer for combining partial oxidation reforming with steam reforming, characterized by: comprises a burner module and a steam reformer module; the burner module comprises a fuel gasification chamber for a burner, an autothermal reforming reaction chamber and a combustion chamber, wherein the fuel gasification chamber for the burner conveys fuel gas to the autothermal reforming reaction chamber, the autothermal reforming reaction chamber conveys partial oxidation reformed gas containing hydrogen to the combustion chamber, and the combustion chamber conveys high-temperature tail gas to the steam reformer module; the steam reformer module comprises a water gasification chamber for steam reforming, a fuel gasification chamber for steam reforming and a steam reforming reaction chamber, wherein the water gasification chamber for steam reforming conveys steam to the steam reforming reaction chamber, the fuel gasification chamber for steam reforming conveys fuel gas to the steam reforming reaction chamber, the steam reforming reaction chamber outputs steam reforming gas, and high-temperature tail gas forms low-temperature combustion tail gas after heat exchange through the steam reformer module.
2. A reformer in combination with steam reforming according to claim 1, characterized in that: the combustion chamber and the autothermal reforming reaction chamber are both provided with catalysts which are integrated in a granular or honeycomb mode or coated on the surfaces of the combustion chamber and the autothermal reforming reaction chamber.
CN202111281322.4A 2021-11-01 2021-11-01 Reformer combining partial oxidation reforming with steam reforming Pending CN113830732A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030022950A1 (en) * 2001-07-28 2003-01-30 Ballard Power Systems Ag Device for producing hydrogen-containing gas for a fuel cell system
CN102910584A (en) * 2012-10-24 2013-02-06 华南理工大学 Self-heating laminated micro-channel reforming hydrogen production reactor
US20140045085A1 (en) * 2011-04-28 2014-02-13 Honda Motor Co., Ltd. Fuel cell module
CN215974955U (en) * 2021-11-01 2022-03-08 苏州钧峰新能源科技有限公司 Reformer combining partial oxidation reforming with steam reforming

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030022950A1 (en) * 2001-07-28 2003-01-30 Ballard Power Systems Ag Device for producing hydrogen-containing gas for a fuel cell system
US20140045085A1 (en) * 2011-04-28 2014-02-13 Honda Motor Co., Ltd. Fuel cell module
CN102910584A (en) * 2012-10-24 2013-02-06 华南理工大学 Self-heating laminated micro-channel reforming hydrogen production reactor
CN215974955U (en) * 2021-11-01 2022-03-08 苏州钧峰新能源科技有限公司 Reformer combining partial oxidation reforming with steam reforming

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