Coupling adsorption enhanced plasma induced methanol low-temperature reforming hydrogen production method

Abstract

The invention discloses a coupling adsorption enhanced plasma induced methanol low-temperature reforming hydrogen production method, which inhibits CO formation through adsorption enhancement, and induces methanol low-temperature activation through plasma discharge. The method comprises the following steps: putting a reduced catalytic adsorbent sample into a plasma reactor, introducing nitrogen, completely emptying gas in the device, and detecting leakage. Then, a switch of the heating belt is turned on to preheat the device to 120 DEG C, the prepared methanol aqueous solution is introduced into a heating belt area through a constant flow pump to be vaporized, then the vaporized methanol aqueous solution is introduced into a plasma reactor to be subjected to a discharge experiment, and an outlet is connected with gas chromatography (GC) to detect gas components in a product. According to the method, high-energy electrons generated by dielectric barrier discharge in a low-temperature state are utilized to collide to induce activation of methanol; when the temperature is 160 DEG C, the concentration of H2 can reach 95% or above, and the methanol conversion rate can reach 80%.

Description

Technical Field

[0001] The invention relates to a method for producing hydrogen by low-temperature reforming of methanol by plasma-induced coupled adsorption enhancement, and belongs to the technical field of combustion chemical industry and materials. Background Art

[0002] As global warming, air pollution, energy shortages and other issues become increasingly prominent, the large-scale development and utilization of clean, low-carbon emerging energy is imminent. Hydrogen energy has the advantages of wide sources, renewable, high energy density, and pollution-free products, and is known as the "ultimate energy" of the 21st century. The terminal uses of hydrogen energy are very wide, and its applications involve many fields such as electricity, transportation, aerospace, and chemical industry. Among them, fuel cells are one of the important new technologies for efficient and clean use of hydrogen energy. Hydrogen fuel cell vehicles that directly convert hydrogen into electricity as power through fuel cells can achieve truly low pollution or even zero emissions, providing a feasible technical path for the electrification of transportation.

[0003] Traditional hydrogen production processes mainly include coal-to-hydrogen, natural gas-to-hydrogen and water electrolysis. Among them, coal-to-hydrogen is usually only used for large-scale hydrogen production due to its high investment; natural gas is an important clean energy source, so its application is strictly restricted; and water electrolysis hydrogen production is currently only suitable for small-scale applications due to its high power consumption. Methanol is an ideal liquid hydrogen storage carrier and in-situ hydrogen supply carrier, with outstanding advantages such as high hydrogen storage capacity, wide sources, convenient transportation and low price. Under different process conditions, methanol can be converted into hydrogen through a variety of pathways, among which steam reforming is one of the most promising conversion methods for hydrogen production. However, the reforming process is often accompanied by methanol cracking and reverse water-gas shift side reactions, resulting in problems such as high product CO selectivity, low methanol conversion rate, and low energy utilization efficiency.

[0004] Although the introduction of adsorption enhancement technology can promote the forward movement of the CO water-gas shift reaction to remove CO2 in situ, the CO2 desorption temperature is high, which can easily cause the catalytic adsorbent to deactivate. Based on the above research, a new method of coupled adsorption-enhanced plasma-induced methanol low-temperature reforming hydrogen production is proposed. On the basis of effectively inhibiting the formation of CO by adsorption enhancement, plasma discharge is used to induce methanol to activate the reaction at low temperature. It is hoped that high-yield, high-quality, and high-energy-efficiency methanol steam reforming hydrogen production can be achieved, and the research results of methanol real-time hydrogen supply technology can be promoted to application. Summary of the invention

[0005] In view of the problems of high CO selectivity, low methanol conversion rate, low energy utilization efficiency, etc. in the existing methanol steam reforming technology, the present invention proposes a coupled adsorption enhanced plasma induced methanol low-temperature reforming hydrogen production method, which aims to improve the hydrogen purity, reduce the carbon monoxide concentration, and realize the efficient conversion of methanol to hydrogen.

[0006] A method for producing hydrogen by coupled adsorption-enhanced plasma-induced methanol low-temperature reforming comprises the following steps:

[0007] Step 1): Mix the methanol reforming reaction catalyst with the CO2 adsorbent to obtain a catalytic adsorbent sample, weigh the reduced catalytic adsorbent sample and put it into a plasma reactor, introduce nitrogen, exhaust all the gas in the device and check the air tightness;

[0008] Step 2): prepare a methanol aqueous solution and pass it into a preheating device for vaporization at a flow rate of 0.004-0.01 ml / min through a constant flow pump;

[0009] Step 3): The generated methanol vapor is passed into a plasma reactor for a discharge experiment. The reactor outlet is connected to a gas chromatograph to detect H2, CO2, CO, N2, CH4 and unreacted methanol CH3OH products. When the reaction is stopped, the constant current pump is first turned off to stop feeding, the transformer input voltage is adjusted to 0, the plasma generator power switch is turned off, and finally the nitrogen pressure reducing valve is adjusted to 0;

[0010] Step 4): The catalytic adsorbent after the reaction is purged with nitrogen at 250-450° C. to perform desorption regeneration, and the regenerated catalytic adsorbent is recycled according to steps 1) to 3).

[0011] The present invention is the first to couple adsorption enhancement with plasma for methanol reforming to produce hydrogen. On the basis of utilizing adsorption enhancement to effectively inhibit the formation of CO, plasma discharge is used to induce methanol to achieve reaction activation at low temperature, thereby achieving efficient hydrogen production from methanol at low temperature.

[0012] In the present invention, the reaction device comprises a gas cylinder, a valve, a mass flow meter, a constant flow pump, a heating belt, a plasma reactor and a gas chromatograph, and the plasma reactor is composed of a plasma generator, a transformer, an oscilloscope and a power supply.

[0013] In step 1) of the present invention, copper-based, palladium-based, platinum-based and rhodium-based materials are used as catalysts for methanol steam reforming reaction to provide active sites for the reaction, reduce the reaction activation energy, and increase the reaction rate. Low-temperature potassium-based, sodium-based and medium-temperature magnesium-based materials are used as CO2 adsorption materials to promote the reaction to move in the forward direction and increase the hydrogen concentration. The high-energy electron collision in a low temperature state generated by non-thermal dielectric barrier discharge is used to induce methanol activation, thereby achieving high-conversion low-temperature reforming of methanol to produce hydrogen.

[0014] In the present invention, in step 1), the reaction space velocity range is 1000~4000h -1 .

[0015] In the present invention, in step 1), the plasma reactor is composed of a plasma generator, a transformer, an oscilloscope and a power supply.

[0016] In the present invention, in step 2), the water-to-alcohol ratio is 0.8-1.5:1.

[0017] In the present invention, in step 3), the plasma discharge power is 30-70W, and the discharge temperature is 120-200°C.

[0018] In the present invention, in step 4), the desorption regeneration temperature of the catalytic adsorbent is 250-450°C.

[0019] In the present invention, the thermal catalytic methanol steam reforming experiment under the action of a single catalyst is carried out in a fixed bed reactor as a control group, the experimental steps are the same as above, and the reaction temperature of the fixed bed reactor is 160-220°C.

[0020] The beneficial effects of the present invention are:

[0021] 1) This invention reports for the first time that the adsorption enhancement is coupled with plasma to achieve the preparation of low-temperature high-purity hydrogen. Within 1.5 minutes before the reaction, the H2 concentration can reach 100%, that is, the CO2 generated at the beginning of the reaction is completely adsorbed by the adsorbent. As time goes on, the CO2 adsorption reaches saturation, and the H2 concentration stabilizes at about 75%. In addition, the equilibrium of methanol cracking and reverse water gas shift reaction under the adsorption enhancement condition is restricted, effectively inhibiting the formation of CO. Compared with a single catalyst and a single plasma discharge reaction, the adsorption enhanced coupled plasma significantly improves the methanol conversion rate and hydrogen concentration at low temperature.

[0022] 2) Active substances such as high-energy electrons, ions and free radicals generated during plasma discharge can collide and react with methanol molecules, thereby effectively promoting the decomposition and conversion of methanol. These active substances can interact with the active sites on the catalyst surface to form more active centers, significantly increasing the rate of methanol reforming reaction. Plasma discharge can also ensure a high methanol conversion rate at low temperatures <160°C, so it can effectively inhibit the deactivation of the catalytic adsorbent and reduce the desorption and regeneration temperature of the catalytic adsorbent.

[0023] 3) Compared with conventional methanol steam reforming, the adsorption-enhanced coupled plasma reaction is carried out at lower temperature and pressure, which reduces the requirements for reaction equipment and reduces energy consumption. The reaction can obtain higher quality hydrogen, thereby improving the energy density and power generation efficiency when used in conjunction with proton exchange membrane fuel cells, providing a new idea for achieving high-yield, high-quality, and high-energy-efficiency methanol steam reforming hydrogen production.

[0024] Based on the above analysis, we can see that the coupled adsorption enhanced plasma induced methanol low-temperature reforming hydrogen production method has a low methanol conversion temperature, high product hydrogen purity, a simple and easy method, and convenient operation. The produced hydrogen can be directly used in proton exchange membrane fuel cells, with high energy efficiency and a wide range of applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 The experimental device diagram for hydrogen production from methanol-water vapor low-temperature reforming for adsorption-enhanced coupled plasma activation;

[0026] Figure 2 This is a diagram of the experimental device for producing hydrogen by low-temperature reforming of methanol and water vapor enhanced by single adsorption;

[0027] Figure 3 The graph of methanol conversion rate and product concentration over time in Example 1;

[0028] Figure 4 The graph of methanol conversion rate and product concentration over time in Example 2;

[0029] Figure 5 The graph of methanol conversion rate and product concentration over time in Example 3;

[0030] Figure 6 The graph of methanol conversion rate and product concentration variation over time in Example 4;

[0031] Figure 7 The graph of methanol conversion rate and product concentration over time in Example 5;

[0032] Figure 8 The graph of methanol conversion rate and product concentration variation over time of Comparative Example 1;

[0033] Fig. 9 The graph of methanol conversion rate and product concentration variation over time of Comparative Example 2;

[0034] Fig.10 It is the Lissajous diagram of Example 1 when the discharge power is 60W;

[0035] Fig.11 It is the Lissajous diagram of Example 2 when the discharge power is 45W;

[0036] Fig.12 This is the Lissajous diagram of Example 3 when the discharge power is 75 W;

[0037] Fig.13 This is a graph showing the temperature inside the plasma reactor changing with discharge power. DETAILED DESCRIPTION

[0038] The present invention will be further described below with reference to the embodiments, comparative examples and accompanying drawings.

[0039] Embodiment 1:

[0040] Tested by experiment

[0041] 1) Weigh 0.3 g of a mixture of a copper-based catalyst and a magnesium-based adsorbent and place it in a plasma reactor;

[0042] 2) Mix water and methanol at a molar ratio of 1.2:1 to prepare 100 ml of methanol-water solution;

[0043] 3) Nitrogen was introduced into the reaction device at 40 ml / min and the air tightness of the device was checked. The reaction space velocity was 2500 h -1 .

[0044] 4) After the airflow is stable, turn on the plasma generator power switch, use a transformer to adjust the discharge power to 60W, adjust the discharge frequency to about 9.5kHz to make the device discharge steadily, and use an infrared thermometer to record the temperature in the reactor at this time. Then, pass the mixed liquid with a water-to-alcohol ratio of 1.2 through a constant flow pump, pass it into a preheater (120°C) for vaporization, and then pass it into the plasma reactor;

[0045] 5) The reactor outlet is connected to a gas chromatograph (GC) to detect H2, CO2, CO, N2, CH4 and unreacted methanol CH3OH and other products. When stopping the reaction, first turn off the constant flow pump to stop feeding, adjust the transformer input voltage to 0, turn off the plasma generator power switch, and finally adjust the nitrogen pressure reducing valve to 0.

[0046] Figure 3 The graph of methanol conversion rate and product concentration changing with time shows that at 1.5 minutes of reaction, the hydrogen concentration is as high as 99.98%. It tends to be stable at about 15 minutes of reaction, with the hydrogen concentration being 72%. The methanol conversion rate is 72%, and no CO and methane are generated during the reaction. Fig.10 It is the Lissajous diagram corresponding to the discharge power of 60W.

[0047] Embodiment 2:

[0048] Compared with Example 1, the only difference is that the plasma discharge power is 45W.

[0049] 1) Weigh 0.3 g of a mixture of a copper-based catalyst and a magnesium-based adsorbent and place it in a plasma reactor;

[0050] 2) Mix water and methanol at a molar ratio of 1.2:1 to prepare 100 ml of methanol-water solution;

[0051] 3) Nitrogen was introduced into the reaction device at 40 ml / min and the air tightness of the device was checked. The reaction space velocity was 2500 h -1 .

[0052] 4) After the airflow is stable, turn on the plasma generator power switch, use a transformer to adjust the discharge power to 45W, adjust the discharge frequency to about 9.5kHz to make the device discharge steadily, and use an infrared thermometer to record the temperature in the reactor at this time. Then, pass the mixed liquid with a water-to-alcohol ratio of 1.2 through a constant flow pump and pass it into the preheater (120°C) at a specific flow rate for vaporization, and then pass it into the plasma reactor;

[0053] 5) The reactor outlet is connected to a gas chromatograph (GC) to detect H2, CO2, CO, N2, CH4 and unreacted methanol CH3OH and other products. When stopping the reaction, first turn off the constant flow pump to stop feeding, adjust the transformer input voltage to 0, turn off the plasma generator power switch, and finally adjust the nitrogen pressure reducing valve to 0.

[0054] Figure 4 The graph of methanol conversion rate and product concentration over time in Example 2 shows that at 1.5 minutes of reaction, the hydrogen concentration is as high as 99.95%, and it tends to be stable after about 15 minutes of reaction. At this time, CO2 adsorption reaches saturation, the hydrogen concentration is 72%, and the methanol conversion rate is 59%. No CO and methane are generated during the reaction. Fig.11 It is the Lissajous diagram corresponding to the discharge power of 45 W. Compared with Example 1, the methanol conversion rate is reduced and the area of ​​the Lissajous diagram is reduced.

[0055] Embodiment 3:

[0056] Compared with Example 1, the only difference is that the plasma discharge power is 75W.

[0057] 1) Weigh 0.3 g of a mixture of a copper-based catalyst and a magnesium-based adsorbent and place it in a plasma reactor;

[0058] 2) Mix water and methanol at a molar ratio of 1.2:1 to prepare 100 ml of methanol-water solution;

[0059] 3) Nitrogen was introduced into the reaction device at 40 ml / min and the air tightness of the device was checked. The reaction space velocity was 2500 h -1 .

[0060] 4) After the airflow is stable, turn on the plasma generator power switch, use a transformer to adjust the discharge power to 75W, adjust the discharge frequency to about 9.5kHz to make the device discharge steadily, and use an infrared thermometer to record the temperature in the reactor at this time. Then, pass the mixed liquid with a water-to-alcohol ratio of 1.2 through a constant flow pump and pass it into the preheater (120°C) at a specific flow rate for vaporization, and then pass it into the plasma reactor;

[0061] 5) The reactor outlet is connected to a gas chromatograph (GC) to detect H2, CO2, CO, N2, CH4 and unreacted methanol CH3OH and other products. When stopping the reaction, first turn off the constant flow pump to stop feeding, adjust the transformer input voltage to 0, turn off the plasma generator power switch, and finally adjust the nitrogen pressure reducing valve to 0.

[0062] Figure 5 The graph of methanol conversion rate and product concentration over time in Example 3 shows that at 1.5 minutes of reaction, the hydrogen concentration is as high as 99.99%, and it becomes stable after about 15 minutes of reaction. At this time, CO2 adsorption reaches saturation, the hydrogen concentration is 73%, the methanol conversion rate is 81%, and no CO and methane are generated during the reaction. Fig.12 It is the Lissajous diagram corresponding to the discharge power of 75 W. Compared with Example 1, the methanol conversion rate is increased and the area of ​​the Lissajous diagram is increased.

[0063] Fig.13 Graph showing the temperature in the plasma reactor as a function of discharge power in Example 1, Example 2 and Example 3. As can be seen from the graph, the reaction temperature increases as the discharge power increases.

[0064] Embodiment 4:

[0065] Compared with Example 1, the only difference is that the molar ratio of water to methanol is 1:1.

[0066] 1) Weigh 0.3 g of a mixture of a copper-based catalyst and a magnesium-based adsorbent and place it in a plasma reactor;

[0067] 2) Mix water and methanol in a molar ratio of 1:1 to prepare 100 ml of methanol-water solution;

[0068] 3) Nitrogen was introduced into the reaction device at 40 ml / min and the air tightness of the device was checked. The reaction space velocity was 2500 h -1 .

[0069] 4) After the airflow is stable, turn on the plasma generator power switch, use a transformer to adjust the discharge power to 45W, adjust the discharge frequency to about 9.5kHz to make the device discharge steadily, and use an infrared thermometer to record the temperature in the reactor at this time. Then, pass the mixed liquid with a water-to-alcohol ratio of 1:1 through a constant flow pump and pass it into the preheater (120°C) at a specific flow rate for vaporization, and then pass it into the plasma reactor;

[0070] 5) The reactor outlet is connected to a gas chromatograph (GC) to detect H2, CO2, CO, N2, CH4 and unreacted methanol CH3OH and other products. When stopping the reaction, first turn off the constant flow pump to stop feeding, adjust the transformer input voltage to 0, turn off the plasma generator power switch, and finally adjust the nitrogen pressure reducing valve to 0.

[0071] Figure 6 The graph of methanol conversion rate and product concentration over time in Example 4 shows that the hydrogen concentration is as high as 99.98% at 1.5 minutes of reaction, and becomes stable at about 72% after 15 minutes of reaction, and the methanol conversion rate is 62%. Compared with Example 1, the methanol conversion rate is lower.

[0072] Embodiment 5:

[0073] Compared with Example 1, the only difference is that the nitrogen flow rate is changed and the reaction space velocity is 3500h -1 .

[0074] 1) Weigh 0.3 g of a mixture of a copper-based catalyst and a magnesium-based adsorbent and place it in a plasma reactor;

[0075] 2) Mix water and methanol at a molar ratio of 1.2:1 to prepare 100 ml of methanol-water solution;

[0076] 3) Nitrogen was introduced into the reaction device at 50 ml / min and the air tightness of the device was checked. The reaction space velocity was 3500 h -1 .

[0077] 4) After the airflow is stable, turn on the plasma generator power switch, use a transformer to adjust the discharge power to 45W, adjust the discharge frequency to about 9.5kHz to make the device discharge steadily, and use an infrared thermometer to record the temperature in the reactor at this time. Then, pass the mixed liquid with a water-to-alcohol ratio of 1:1 through a constant flow pump and pass it into the preheater (120°C) at a specific flow rate for vaporization, and then pass it into the plasma reactor;

[0078] 5) The reactor outlet is connected to a gas chromatograph (GC) to detect H2, CO2, CO, N2, CH4 and unreacted methanol CH3OH and other products. When stopping the reaction, first turn off the constant flow pump to stop feeding, adjust the transformer input voltage to 0, turn off the plasma generator power switch, and finally adjust the nitrogen pressure reducing valve to 0.

[0079] Figure 7 The graph of methanol conversion rate and product concentration over time in Example 5 shows that the hydrogen concentration is as high as 99.96% at 1.5 minutes of reaction, and becomes stable at about 71% after 15 minutes of reaction. The methanol conversion rate is 51%. Compared with Example 1, the methanol conversion rate is lower.

[0080] Comparative Example 1:

[0081] Compared with Example 1, the only difference is that no catalytic adsorbent is added into the reactor and only plasma discharge occurs.

[0082] 1) Mix water and methanol in a molar ratio of 1.2:1 to prepare 100 ml of methanol-water solution;

[0083] 2) Nitrogen was introduced into the reaction device at 40 ml / min and the air tightness of the device was checked. The reaction space velocity was 2500 h -1 ;

[0084] 3) After the airflow is stable, turn on the plasma generator power switch, use a transformer to adjust the discharge power to 45W, adjust the discharge frequency to about 9.5kHz to make the device discharge steadily, and use an infrared thermometer to record the temperature in the reactor at this time. Then, pass the mixed liquid with a water-to-alcohol ratio of 1.2 through a constant flow pump and pass it into the preheater (120°C) at a specific flow rate for vaporization, and then pass it into the plasma reactor;

[0085] 4) The reactor outlet is connected to a gas chromatograph (GC) to detect H2, CO2, CO, N2, CH4 and unreacted methanol CH3OH and other products. When stopping the reaction, first turn off the constant flow pump to stop feeding, adjust the transformer input voltage to 0, turn off the plasma generator power switch, and finally adjust the nitrogen pressure reducing valve to 0.

[0086] Figure 8 The graph of methanol conversion rate and product concentration over time in comparative example 1 shows that the hydrogen concentration is about 60%, CH4 and CO are generated in the product, and the methanol conversion rate is about 40%. Compared with example 1, the hydrogen concentration and methanol conversion rate are both reduced.

[0087] Comparative Example 2:

[0088] Compared with Example 1, the only difference is that there is only a single adsorption enhancement effect and the reaction is carried out in a fixed bed reactor.

[0089] 1) Weigh 0.3 g of a mixture of a copper-based catalyst and a magnesium-based adsorbent and place it in a quartz tube (Φ=8 mm), and support it in a constant temperature zone of a vertical furnace using quartz wool and a liner;

[0090] 2) Nitrogen was introduced into the reaction device at 40 ml / min and the air tightness of the device was checked. The reaction space velocity was 2500 h -1 .

[0091] 3) Mix water and methanol at a molar ratio of 1.2:1 to prepare 100 ml of methanol-water solution;

[0092] 4) The mixed liquid is passed through a constant flow pump at a specific flow rate into a heating zone (120° C.) for vaporization, and then passed into a fixed bed reactor at a reaction temperature of 180° C.

[0093] 5) The reactor outlet is connected to a gas chromatograph (GC) to detect H2, CO2, CO, N2, CH4 and unreacted methanol CH3OH and other products. When stopping the reaction, first turn off the constant flow pump to stop feeding, turn off the furnace, and finally adjust the nitrogen pressure reducing valve to 0.

[0094] Fig. 9 The graph of methanol conversion rate and product concentration over time for comparative example 2 shows that at 1.5 minutes of reaction, the hydrogen concentration is as high as 98.12%, and it becomes stable at about 15 minutes of reaction, with the hydrogen concentration being 70%. The methanol conversion rate is 71%, and no CO and methane are generated during the reaction.

[0095] Table 1 summarizes the results of methanol conversion and product concentration under the experimental conditions of the embodiments and comparative examples. It can be seen from the table that under the experimental conditions of plasma + adsorption enhancement and single adsorption enhancement, no CO and CH4 are generated in the product, indicating that adsorption enhancement has an inhibitory effect on the reaction byproduct CO. The hydrogen concentration and methanol conversion rate under the plasma + adsorption enhancement reaction conditions are significantly higher than those under single plasma and single adsorption enhancement, indicating that the plasma-induced methanol low-temperature reforming hydrogen production method coupled with adsorption enhancement can achieve a higher methanol conversion rate at low temperature, providing a new idea for achieving high-yield, high-quality, and high-energy-efficiency methanol steam reforming hydrogen production.

[0096] Table 1

[0097]

[0098] The above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, a person of ordinary skill in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents, and these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for producing hydrogen by plasma-induced methanol low-temperature reforming enhanced by coupled adsorption, comprising: Step 1): Mix the methanol reforming reaction catalyst with the CO2 adsorbent to obtain a catalytic adsorbent sample, weigh the reduced catalytic adsorbent sample and put it into a plasma reactor, introduce nitrogen, exhaust all the gas in the device and check the air tightness; Step 2): prepare a methanol aqueous solution and pass it into a preheating device for vaporization at a flow rate of 0.004-0.01 ml / min through a constant flow pump; Step 3): The generated methanol vapor is passed into a plasma reactor for a discharge experiment. The reactor outlet is connected to a gas chromatograph to detect H2, CO2, CO, N2, CH4 and unreacted methanol CH3OH products. When the reaction is stopped, the constant current pump is first turned off to stop feeding, the transformer input voltage is adjusted to 0, the plasma generator power switch is turned off, and finally the nitrogen pressure reducing valve is adjusted to 0; Step 4): The catalytic adsorbent after the reaction is purged with nitrogen at 250-450° C. to perform desorption regeneration, and the regenerated catalytic adsorbent is recycled according to steps 1) to 3).

2. A method for producing hydrogen by coupled adsorption-enhanced plasma-induced methanol low-temperature reforming according to claim 1, wherein: In step 1), copper-based, palladium-based, platinum-based and rhodium-based materials are used as methanol steam reforming reaction catalysts, and low-temperature potassium-based, sodium-based and medium-temperature magnesium-based materials are used as CO2 adsorbents.

3. The method for producing hydrogen by coupled adsorption-enhanced plasma-induced methanol low-temperature reforming according to claim 1, wherein: In step 1), the reaction space velocity range is 1000~4000h -1 .

4. The method for producing hydrogen by coupled adsorption-enhanced plasma-induced methanol low-temperature reforming according to claim 1, wherein: In step 2), the molar ratio of water to methanol is 0.8 to 1.5:

1.

5. The method for producing hydrogen by coupled adsorption enhanced plasma induced methanol low temperature reforming according to claim 1, wherein: In step 3), the discharge type of the plasma is non-thermal dielectric barrier discharge.

6. The method for producing hydrogen by coupled adsorption-enhanced plasma-induced methanol low-temperature reforming according to claim 1, wherein: In step 3), the plasma discharge power is 30-70W, and the discharge temperature is 120-200°C.

7. The method for producing hydrogen by coupled adsorption-enhanced plasma-induced methanol low-temperature reforming according to claim 1, wherein: In step 4), the desorption regeneration temperature is 250-450°C.

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