Cold start method suitable for liquid fuel reforming hydrogen production gasification reactor
By using reduced metal catalysts to react with air to release heat in the gasification reactor, and combining the gasification and catalytic combustion reactions of low-boiling-point liquids, a low-energy, rapid cold start-up of the liquid fuel reforming hydrogen production gasification reactor is achieved, solving the problems of high energy consumption and long startup cycle of traditional electric heating methods, and achieving uniform and stable heat release and material protection.
Patent Information
- Application Number
- CN202510826118.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-19
- Publication Date
- 2025-10-03
AI Technical Summary
The existing liquid fuel reforming hydrogen production gasification reactor has the problems of high heating energy consumption, long startup cycle, concentrated thermal stress of the reactor internal material and single heat transfer path under the traditional electric heating scheme.
The reduced metal catalyst is used to react with air to release heat, and the temperature is gradually increased through the gasification of low-boiling-point liquid and catalytic combustion reaction, thereby achieving a cold start of the gasification reactor. The heat released by the chemical reaction is used to gasify the liquid fuel, avoiding electric heating.
It achieves low-energy rapid cold start, solves the problems of high energy consumption and long start-up cycle of traditional electric heating methods, and realizes uniform and stable heat release through chemical reaction, reducing the problems of material thermal stress concentration and single heat transfer path in low-temperature environments.
Smart Images
Figure CN120733659A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of thermochemistry, and in particular relates to a cold start method for a gasification reactor suitable for hydrogen production from liquid fuel reforming. Background Art
[0002] With the expansion of hydrogen energy application scenarios, liquid fuel (such as methanol, ethanol and diesel, etc.) reforming hydrogen production technology has attracted much attention in the field of mobile and distributed energy supply due to its easy storage and transportation of raw materials and high energy density. This technology converts liquid hydrocarbon fuels into hydrogen-rich gas through catalytic reforming reactions, and the gasification reactor is one of its key components. However, existing gasification reactors face significant technical bottlenecks: traditional electric heating solutions have large heat capacity of the reactor body, resulting in high heating energy consumption and long startup cycles. In addition, problems such as concentrated thermal stress of the reactor internal materials and a single heat transfer path in low-temperature environments further restrict the ability to start quickly. Summary of the Invention
[0003] In order to overcome the above problems existing in the prior art, the present invention provides a cold start method for a liquid fuel reforming hydrogen production gasification reactor, which is used to solve the above problems existing in the prior art.
[0004] A cold start method for a liquid fuel reforming hydrogen production gasification reactor, the method comprising: S1. at ambient temperature, a reduced metal catalyst in the gasification reactor reacts with air entering the gasification reactor to release heat;
[0005] S2. When the exothermic temperature in the gasification reactor rises to the vaporization temperature of the low-boiling-point liquid, the low-boiling-point liquid enters the gasification reactor and vaporizes;
[0006] S3. The vaporized low-boiling-point liquid undergoes a catalytic combustion reaction with the air entering the gasification reactor and releases heat;
[0007] S4. When the heat release causes the temperature of the gasification reactor to rise to the gasification temperature of the reformed hydrogen-producing liquid fuel, the reformed hydrogen-producing liquid fuel enters the gasification reactor for liquid gasification, and the gasified liquid fuel is used for the reforming hydrogen-producing reaction.
[0008] According to the above aspects and any possible implementations, further provided is an implementation, wherein the reforming hydrogen-producing liquid fuel comprises one of methanol, ethanol, gasoline, bio-oil, glycerin, diesel, acetone, benzene, toluene, dimethylformamide, and dimethyl sulfoxide, and their aqueous solutions, or a combination thereof. According to the above aspects and any possible implementations, further provided is an implementation, wherein the ambient temperature is between -50°C and room temperature.
[0009] According to the above aspects and any possible implementation, there is further provided an implementation, wherein the low boiling point liquid is one or more combinations of methanol, ethanol, isopropanol, acetone, dimethyl ether, diesel, gasoline and aviation fuel.
[0010] According to the above aspects and any possible implementation, a further implementation is provided, in which the low boiling point liquid
[0011] When methanol is used, the vaporization temperature in S1 is about 70°C.
[0012] The above aspects and any possible implementations further provide an implementation in which the hydrogen production liquid fuel is reformed
[0013] In the case of methanol aqueous solution, the vaporization temperature in S4 is about 110°C.
[0014] According to the above aspects and any possible implementation, an implementation is further provided, wherein the reduced metal catalyst is a copper-based catalyst.
[0015] According to the above aspects and any possible implementation, an implementation is further provided, wherein a plurality of gasification pipelines are provided inside the gasification reactor, and each gasification pipeline is connected to an external storage tank via a pump.
[0016] According to the above aspects and any possible implementation, there is further provided an implementation, wherein the gasification reactor is connected to the external atmosphere via a valve provided on an external pipeline.
[0017] According to the above aspects and any possible implementation, an implementation is further provided, wherein the exothermic chemical reaction between the air and the reduced metal catalyst in the gasification reactor is:
[0018] M+xO2→MO y +Exothermic
[0019] Wherein, M is the reduced metal; <x<2,y=2x。
[0020] Beneficial effects of the present invention
[0021] The cold start method of a gasification reactor for reforming hydrogen production from liquid fuels of the present invention comprises: at ambient temperature, a reduced metal catalyst in the gasification reactor reacts with air entering the gasification reactor to release heat; when the heat release causes the temperature in the gasification reactor to rise to the vaporization temperature of the low-boiling-point liquid, the low-boiling-point liquid enters the gasification reactor and is gasified; the gasified low-boiling-point liquid undergoes a catalytic combustion reaction with the air entering the gasification reactor and releases heat; when the heat release causes the gasification reactor temperature to rise to the vaporization temperature of the reformed hydrogen production liquid fuel, the reformed hydrogen production liquid fuel enters the gasification reactor for liquid gasification, and the gasified liquid fuel is used for the reforming hydrogen production reaction. The method basically does not consume electrical energy and has low energy consumption; liquid fuel is gasified by chemical reaction heat release, which has the advantages of large heat release and fast gasification time; the gasification process uses air and methanol, which is low in cost. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 This is a schematic diagram of the cold start of the gasification reactor of the present invention. DETAILED DESCRIPTION
[0023] To better understand the technical solutions of the present invention, the present invention includes but is not limited to the specific embodiments described below. Similar technologies and methods should be considered within the scope of protection of the present invention. To further clarify the technical problems, technical solutions, and advantages to be solved by the present invention, the following detailed description is provided in conjunction with the accompanying drawings and specific embodiments.
[0024] It should be understood that the embodiments described herein are only a portion of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0025] The terms used in the embodiments of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The singular forms "a", "an", "the" and "the" used in the embodiments of the present invention and the appended claims are also intended to include plural forms unless the context clearly indicates otherwise.
[0026] The present invention provides a cold start method for a liquid fuel reforming hydrogen production gasification reactor, the method comprising: S1. at ambient temperature, a reduced metal catalyst in the gasification reactor reacts with air entering the gasification reactor to release heat;
[0027] S2. When the exothermic temperature in the gasification reactor rises to the vaporization temperature of the low-boiling-point liquid, the low-boiling-point liquid enters the gasification reactor and vaporizes;
[0028] S3. The vaporized low-boiling-point liquid undergoes a catalytic combustion reaction with the air entering the gasification reactor and releases heat;
[0029] S4. When the heat release causes the temperature of the gasification reactor to rise to the gasification temperature of the reformed hydrogen-producing liquid fuel, the reformed hydrogen-producing liquid fuel enters the gasification reactor for liquid gasification, and the gasified liquid fuel is used for the reforming hydrogen-producing reaction.
[0030] Furthermore, the reforming hydrogen-producing liquid fuel includes one of methanol, ethanol, gasoline, bio-oil, glycerol, diesel, acetone, benzene, toluene, dimethylformamide and dimethyl sulfoxide, and their aqueous solutions, or a combination of multiple ones.
[0031] Furthermore, the ambient temperature is between -50°C and room temperature.
[0032] Furthermore, the low-boiling-point liquid is one or more combinations of methanol, ethanol, isopropanol, acetone, dimethyl ether, diesel, gasoline and aviation fuel.
[0033] Furthermore, when the low-boiling-point liquid is methanol, the vaporization temperature in S1 is about 70°C.
[0034] Furthermore, when the reformed hydrogen-producing liquid fuel is a methanol-water solution, the gasification temperature in S4 is 110°C.
[0035] Furthermore, the reduced metal catalyst is a copper-based catalyst, preferably a copper-zinc-aluminum catalyst.
[0036] Furthermore, a plurality of gasification pipelines are provided inside the gasification reactor, and each gasification pipeline is connected to an external storage tank via a pump.
[0037] Furthermore, the gasification reactor is connected to the external atmosphere through a valve provided on an external pipeline.
[0038] Furthermore, the exothermic chemical reaction between the air and the reduced metal catalyst in the gasification reactor is:
[0039] M+xO2→MO y +Exothermic
[0040] Wherein, M is the reduced metal; <x<2,y=2x。
[0041] The present invention is described by taking low-boiling-point liquid methanol as an example:
[0042] like Figure 1As shown, gasification reactor 5 is equipped with several gas pipelines, each connected to a storage tank via a pump. Storage tank 2 stores a low-boiling-point liquid, such as methanol, and is connected to gasification reactor 5 via pump 4. Storage tank 1 stores reformed hydrogen-producing liquid fuel and is connected to gasification reactor 5 via pump 3. Gasification reactor 5 is connected to the outside atmosphere via a valve installed on an external pipeline. When air is introduced into gasification reactor 5, the valve opens to discharge the combustion exhaust gas after the reaction. The valve is fed back by a pressure sensor. When air or other gas is introduced, pressure is generated, and the valve opens based on the feedback from the pressure sensor.
[0043] The gasification reactor 5 is a shell-and-tube structure, the shell layer is filled with reduced metal catalysts, and the tube layer is a gasification pipeline for low-boiling-point liquid and reformed hydrogen-producing liquid fuel. The shell-and-tube structure can enhance heat exchange by adding fins.
[0044] Storage tank 1 stores reformed hydrogen production liquid fuel, which is one of methanol, ethanol, gasoline, bio-oil, glycerol, diesel, acetone, benzene, toluene, dimethylformamide and dimethyl sulfoxide and their aqueous solutions, or a combination of multiples; storage tank 2 stores low-boiling point liquid, which is one or more combinations of methanol, ethanol, isopropanol, acetone, dimethyl ether, diesel, gasoline and aviation fuel.
[0045] Step 1: At ambient temperature, i.e., between -50°C and room temperature, the temperature of the gasification reactor 5 when not in operation is consistent with the ambient temperature. Generally, the ambient temperature is maintained at room temperature, but in winter and in some extremely cold regions, the ambient temperature can drop below room temperature, even reaching -50°C. At this ambient temperature, air is introduced into the gasification reactor 5. The air reacts with the reduced metal catalyst within the gasification reactor 5, releasing heat. This heat heats the gasification reactor 5, raising its temperature. The reduced metal catalyst within the gasification reactor 5 reacts with air at ambient temperature to form an oxidized metal catalyst. This reaction releases a large amount of heat. Without the use of electric heating, heating the gasification reactor 5 raises its temperature, thus resolving the technical issues of the reactor's large heat capacity, resulting in high energy consumption and a long startup cycle due to electric heating. When the temperature within the gasification reactor 5 rises to the methanol vaporization temperature, the methanol solution within the storage tank 2 enters the gasification reactor 5 via pump 4 and vaporizes, facilitating the mixing of the vaporized methanol and air and the catalytic combustion reaction in subsequent steps. Methanol vaporizes at approximately 70°C, which is 65°C at standard atmospheric pressure. When methanol passes through the pump, the pressure rises above standard atmospheric pressure, correspondingly increasing the vaporization temperature. Therefore, the methanol vaporization temperature is around 70°C. This first step, the first step of a cold start, heats the gasification reactor 5 from room temperature to the methanol vaporization temperature, providing gaseous fuel for the catalytic combustion of methanol and air in the second step of the cold start. The gasification reactor 5 is a shell-and-tube structure, with the shell filled with a reduced metal catalyst. The reaction between air and catalyst occurs within the shell, and the tubes serve as the vaporization conduit for the low-boiling-point liquid and reformed hydrogen-producing liquid fuel. This shell-and-tube structure can be enhanced by adding fins.
[0046] Step 2: The vaporized methanol is mixed with air and enters the gasification reactor 5, where a catalytic combustion reaction occurs, releasing heat. When the temperature of the gasification reactor 5 rises to the vaporization temperature of the reformed hydrogen-producing liquid fuel (for example, methanol-water solution, its vaporization temperature is approximately 110°C), the reformed hydrogen-producing liquid fuel in the storage tank 1 enters the gasification reactor 5 via pump 3 for liquid vaporization. The vaporized liquid fuel is then used in the reforming hydrogen-producing reaction, thereby achieving a cold start of the gasification reactor 5 and vaporization of the reformed hydrogen-producing liquid fuel.
[0047] This method raises the temperature of the gasification reactor 5 through a chemical looping combustion reaction between air and a reduced metal catalyst, achieving the first cold start. Catalytic combustion of vaporized methanol and air within the gasification reactor 5 further raises the temperature of the gasification reactor 5, achieving a complete cold start and vaporizing the reformed hydrogen-producing liquid fuel. This method, through chemical looping combustion and catalytic combustion, achieves rapid, large-scale, uniform, and stable heat release, resolving issues such as high energy consumption associated with traditional electric heating methods, high heating energy consumption due to localized heating, long startup cycles, concentrated thermal stresses in reactor materials, and a single heat transfer path at low temperatures.
[0048] The reduced metal catalyst in the above process is a copper-based catalyst, preferably a copper-zinc-aluminum catalyst. The heat release chemical reaction between air and the reduced metal catalyst in the gasification reactor 5 is as follows:
[0049] M+xO2→MO y + exothermic (M refers to reduced metal), where 0 <x<2,y=2x。
[0050] Taking copper-zinc-aluminum catalyst as an example, the chemical reactions involved are as follows:
[0051] Cu + 0.5O2 → CuO
[0052] In the above process, the chemical reactions involved in the catalytic combustion reaction of methanol and air in the reactor 5 and the release of heat are:
[0053]
[0054] CH3OH+xMO y →xM+2H2O+CO2+exothermic, where 0 <x<10,y=3 / x;
[0055] CH3OH→2H2+CO+endothermic
[0056] H2+xMO y →xM+H2O+exothermic, where 0 <x<10,y=1 / x;
[0057] CO+xMO y →xM+CO2+exothermic, where 0 <x<10,y=1 / x。
[0058] This chemical reaction illustrates the process involved in the catalytic combustion of methanol. Heat is released through the chemical reaction to increase the temperature of the gasification reactor 5, thereby achieving cold start-up and gasification of the reformed hydrogen-producing liquid fuel. This solves the problems of high energy consumption in traditional electric heating, high energy consumption for heating caused by local heating, long startup cycle, concentrated thermal stress in the reactor internal material under low-temperature conditions, and a single heat transfer path.
[0059] The above chemical reactions are general examples, where M refers to different metal catalysts such as copper, zinc, aluminum, nickel, iron, and magnesium. The following examples are specific cases, taking copper-zinc-aluminum catalysts as an example, mainly involving chemical reactions involving copper. The following chemical reactions occur in step 2. The catalytic combustion chemical reactions involved are as follows:
[0060]
[0061] CH3OH+3CuO→3Cu+2H2O+CO2+exothermic
[0062] CH3OH→2H2+CO+endothermic
[0063] H2+CuO→Cu+2H2O+exothermic
[0064] CO+CuO→Cu+CO2+releases heat.
[0065] The above chemical reaction, under the action of the copper-zinc-aluminum catalyst, generates a catalytic combustion reaction between methanol and air. The heat released by the reaction causes the gasification reactor 5 to heat up, thereby achieving a cold start.
[0066] In summary, the method of the present invention reacts air with a reduced metal catalyst in a gasification reactor to release heat to gasify methanol, and then the air and the gasified methanol undergo a catalytic combustion reaction in the gasification reactor to release heat for gasification reforming to produce liquid fuel for hydrogen production.
[0067] The foregoing description shows and describes several preferred embodiments of the present invention. However, as previously stated, it should be understood that the present invention is not limited to the form disclosed herein and should not be construed as excluding other embodiments. Rather, the present invention can be used in various other combinations, modifications, and environments and can be modified within the scope of the application concept described herein by the teachings above or by techniques or knowledge in the relevant field. Modifications and variations made by those skilled in the art that do not depart from the spirit and scope of the present invention are intended to be protected by the appended claims.
Claims
1. A cold start method for a liquid fuel reforming hydrogen production gasification reactor, characterized in that: The method comprises: S1. at ambient temperature, the reduced metal catalyst in the gasification reactor reacts with air entering the gasification reactor to release heat; S2. When the exothermic temperature in the gasification reactor rises to the vaporization temperature of the low-boiling-point liquid, the low-boiling-point liquid enters the gasification reactor and vaporizes; S3. The vaporized low-boiling-point liquid undergoes a catalytic combustion reaction with the air entering the gasification reactor and releases heat; S4. When the heat release causes the temperature of the gasification reactor to rise to the gasification temperature of the reformed hydrogen-producing liquid fuel, the reformed hydrogen-producing liquid fuel enters the gasification reactor for liquid gasification, and the gasified liquid fuel is used for the reforming hydrogen-producing reaction.
2. The method according to claim 1, characterized in that The reforming hydrogen-producing liquid fuel comprises one of methanol, ethanol, gasoline, bio-oil, glycerol, diesel, acetone, benzene, toluene, dimethylformamide and dimethyl sulfoxide, and their aqueous solutions or a combination thereof.
3. The method according to claim 1 or 2, characterized in that The ambient temperature is from -50°C to room temperature.
4. The method according to claim 1, wherein The low-boiling-point liquid is one or more combinations of methanol, ethanol, isopropanol, acetone, dimethyl ether, diesel, gasoline and aviation fuel.
5. The method according to claim 4, characterized in that When the low-boiling-point liquid is methanol, the vaporization temperature in S1 is about 70°C.
6. The method according to claim 2, characterized in that When the reformed hydrogen-producing liquid fuel is a methanol-water solution, the vaporization temperature in S4 is about 110°C.
7. The method according to claim 1, characterized in that The reduced metal catalyst is a copper-based catalyst.
8. The method according to claim 2, characterized in that A plurality of gasification pipelines are arranged inside the gasification reactor, and each gasification pipeline is connected to an external storage tank via a pump.
9. The method according to claim 2, characterized in that The gasification reactor is connected to the external atmosphere through a valve arranged on an external pipeline.
10. The method according to claim 1, characterized in that The exothermic chemical reaction between the air and the reduced metal catalyst in the gasification reactor is: M+xO2→MO y +Exothermic Wherein, M is the reduced metal; <x<2,y=2x。