A methanol reforming hydrogen production system and process

Abstract

The present invention discloses a methanol reforming hydrogen production system, comprising: a reforming reaction unit, comprising a raw material tank for mixing desalted water and methanol, and a reforming reactor connected to the outlet of the raw material tank; a temperature regulating unit is also arranged between the raw material tank and the reforming reactor; a hydrogen purification unit, comprising a palladium membrane purification device arranged downstream of the reforming reactor, for purifying the hydrogen-rich gas after the reforming reaction, the palladium membrane purification device having a purified hydrogen outlet and a residual gas outlet; a combustion unit, the combustion unit having a feed inlet and a tail gas outlet, the feed inlet being connected to the residual gas outlet of the palladium membrane purification device, and the tail gas outlet being connected to the temperature regulating unit; wherein the reaction temperature in the reforming reactor is controlled not to exceed the purification temperature range of the palladium membrane purification device. According to the above system, a methanol reforming hydrogen production process can also be provided. The hydrogen production system and process of the present invention not only have a compact structure and a simple process, but also have a high energy utilization rate and a high purity of the purified hydrogen.

Description

Technical Field

[0001] The invention belongs to the technical field of methanol reforming hydrogen production, and relates to a methanol reforming hydrogen production system and process. Background Art

[0002] Fuel cells are highly efficient, green and quiet power generation devices. Due to their high energy density, water as the main emission, few moving parts and flexible assembly, they are particularly suitable for automotive power, marine power, distributed power stations, aerospace, etc.

[0003] As a fuel for fuel cells, hydrogen has low storage density and poor safety due to its low density, flammability and explosiveness, which seriously affects the technical application and promotion of fuel cells. Methanol reforming hydrogen production mainly uses methanol and water to undergo a reforming reaction at a certain temperature to generate hydrogen-rich gas, which is purified to produce high-purity hydrogen. Its tail gas can be burned to provide heat for the reforming reaction. Since methanol reforming hydrogen production extracts hydrogen atoms from methanol and water, the hydrogen storage density is relatively high. At the same time, methanol and water are stored in liquid form, which improves portability and safety. Therefore, it is one of the main development directions of hydrogen storage technology.

[0004] In industry, methanol reforming to produce hydrogen mainly involves the reaction of methanol and water at 200-300°C, followed by purification through pressure swing adsorption. Due to the large footprint of the adsorption tower, this technology is limited in the application of fuel cells and cannot meet application requirements. Membrane separation technology mainly uses palladium alloy membrane technology to purify hydrogen-rich gas, greatly reducing the space size of the hydrogen purification device, and is therefore particularly suitable for fuel cell applications.

[0005] Chinese patent document CN102874754B discloses a system and method for preparing hydrogen using methanol water, wherein since the temperature of the reforming reactor is lower than the temperature of the separation chamber, a preheating temperature control mechanism is added between the reforming reactor and the separation chamber. This design not only increases the complexity of the system, but also improves the requirements for the thermal management of the system.

[0006] Chinese patent document CN105720285A discloses a closed fuel cell hydrogen source system, which uses CO selective oxidation to remove CO after the reforming reaction, reducing the concentration of CO to below 10 ppm, and then passing the hydrogen-rich gas into a steam-water separator to remove trace methanol and water vapor. The hydrogen-rich gas is then passed into the fuel cell. At this time, the hydrogen-rich gas is mainly hydrogen and CO2, of which CO2 accounts for about 25%, which greatly reduces the calorific value of the fuel, thereby reducing the energy density of the fuel cell.

[0007] Chinese patent document CN104276542B discloses a reformer for a methanol-water hydrogen production system, which provides a start-up device for the reforming reactor. The device specifically uses open flame combustion to gasify methanol and hydrogen to provide heat to the reforming reactor. However, both methanol and hydrogen are flammable and explosive chemicals, and there is a certain risk of explosion when encountering open flames. Summary of the invention

[0008] The purpose of the present invention is to provide a methanol reforming hydrogen production system and process to address the deficiencies in the above-mentioned prior art, which has a compact structure, simple process, high energy utilization rate and high purity of purified hydrogen.

[0009] One of the purposes of the present invention is to provide a methanol reforming hydrogen production system, the technical scheme adopted is as follows:

[0010] A methanol reforming hydrogen production system, comprising:

[0011] The reforming reaction unit comprises a raw material tank for mixing desalted water and methanol, and a reforming reactor connected to the outlet of the raw material tank; a temperature regulating unit is also arranged between the raw material tank and the reforming reactor;

[0012] A hydrogen purification unit, comprising a palladium membrane purification device disposed downstream of the reforming reactor, wherein the palladium membrane purification device has a purified hydrogen outlet and a residual gas outlet;

[0013] A combustion unit, wherein the combustion unit has a feed inlet and a tail gas outlet, wherein the feed inlet is connected to the residual gas outlet of the palladium membrane purification device, and the tail gas outlet is connected to the temperature adjustment unit;

[0014] Wherein, the reaction temperature in the reforming reactor is controlled not to exceed the purification temperature range of the palladium membrane purification device.

[0015] Preferably, the temperature control unit includes a preheater and a superheater which are sequentially arranged downstream of the raw material tank, and the outlet of the superheater is connected to the reforming reactor; the outlet of the reforming reactor is connected to the palladium membrane purification device to purify and separate the hydrogen.

[0016] Furthermore, the combustion unit includes a burner, the residual gas outlet of the palladium membrane purification device is connected to the burner for combustion, and the exhaust gas outlet of the burner is connected to the preheater for supplying the heat of the combustion exhaust gas to the preheater; the burner is also provided with an air inlet.

[0017] Furthermore, the burner is also connected to a methanol supplementary combustion pipeline for passing methanol into the burner for supplementary combustion; the methanol supplementary combustion pipeline includes a heat exchanger, and the heat exchanger is connected to the exhaust gas outlet of the preheater, so that the combustion exhaust gas in the preheater can provide heat for the methanol while being discharged after heat exchange.

[0018] Furthermore, the burner, reforming reactor and superheater have a circulating intermediate heat exchange medium.

[0019] Preferably, the purification temperature range in the palladium membrane purification device is 380-420°C, and the reaction temperature in the reforming reactor is controlled to be 400-410°C.

[0020] Preferably, the hydrogen purification unit further comprises a methanation device, and the methanation device is connected to the purified hydrogen outlet of the palladium membrane purification device.

[0021] The second object of the present invention is to provide a methanol reforming hydrogen production process, comprising the following steps:

[0022] Desalted water and methanol are mixed in the raw material tank, heated by the temperature control unit, and then undergo a methanol reforming hydrogen production reaction in the reforming reactor to produce hydrogen-rich gas; the hydrogen-rich gas then directly enters the palladium membrane purification device for purification, the purified hydrogen is discharged, and the purified residual gas is mixed with air in the combustion unit for oxidation reaction, and the tail gas after the reaction is passed into the temperature control unit for heat exchange;

[0023] Among them, the reaction temperature of the raw materials entering the reforming reactor is controlled not to exceed the purification temperature range in the palladium membrane purification device.

[0024] Preferably, the temperature control unit includes a preheater and a superheater. The desalted water and methanol first enter the preheater in the temperature control unit for preheating, then pass through the superheater for heating, and then enter the reforming reactor for reaction to produce hydrogen-rich gas.

[0025] Furthermore, the combustion unit includes a burner, in which the purified residual gas and air undergo a hydrogen catalytic oxidation reaction, and the combustion tail gas after the reaction enters a preheater for heat exchange to provide heat for the methanol water raw material.

[0026] Furthermore, the burner also supplements methanol through a methanol supplementary combustion pipeline to simultaneously carry out a methanol oxidation reaction; and the tail gas entering the preheater is discharged after heat exchange in a heat exchanger on the methanol supplementary combustion pipeline.

[0027] Furthermore, the burner, reforming reactor and superheater have a circulating intermediate heat exchange medium. The intermediate heat exchange medium is heated by the heat in the burner reaction, condensed by the reforming reactor and the superheater, and then flows back to the burner, circulating continuously.

[0028] Preferably, the purification temperature range in the palladium membrane purification device is 380-420°C, and the reaction temperature in the reforming reactor is controlled to be 400-410°C.

[0029] Preferably, the purified hydrogen enters a methanation unit to further remove CO, reducing CO to below 0.2 ppm.

[0030] The present invention can bring the following beneficial effects:

[0031] 1) The present invention adopts a high-temperature reforming reactor to produce hydrogen. By utilizing the energy in the system, the reaction temperature in the reforming reactor is increased, and the temperature of the reforming reaction is controlled within the palladium membrane purification temperature range, so that the reaction temperature and the purification temperature are basically consistent. There is no need to add a temperature control device between the reforming reactor and the palladium membrane purification device, thereby improving the compactness and thermal management level of the methanol reforming hydrogen production system.

[0032] 2) The present invention uses a methanation device to remove CO from the purified hydrogen in the palladium membrane purification device, reducing CO to below 0.2 ppm, which can meet the needs of fuel cells.

[0033] 3) The present invention oxidizes methanol and unpurified hydrogen in the burner, thereby improving the energy utilization rate of the system and also improving the safety design of the system; the heat released by the reaction is provided to the reforming reactor and the superheater through the intermediate heat exchange medium, and the exhaust gas after combustion is preheated by the preheater and the heat exchanger to preheat the methanol aqueous solution and the methanol solution, thereby not only improving the energy utilization rate of the system, but also directly avoiding the possibility of explosion caused by open flame combustion. At the same time, since the residual gas after purification by the palladium membrane has a relatively high content of CO2 and water vapor, accounting for about 80% of the residual gas volume fraction, after passing into the burner, the concentration of methanol and hydrogen is reduced, so that the methanol and hydrogen can be diluted to below their respective explosion limits, thereby improving the safety of the system. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 It is a schematic diagram of the layout of the methanol reforming hydrogen production system of the present invention.

[0035] The meanings of the symbols in the figure are as follows:

[0036] 1-reforming reaction unit, 10-raw material tank, 100-desalted water tank, 101-desalted water pump, 102-methanol storage tank, 103-methanol pump, 11-reforming reactor, 12-temperature adjustment unit, 120-preheater, 121-superheater;

[0037] 2-hydrogen purification unit, 20-palladium membrane purification device, 21-methanation device;

[0038] 3-combustion unit, 30-burner, 31-heat exchanger, 32-air compressor. DETAILED DESCRIPTION

[0039] In order to facilitate the understanding of the present application, in order to make the above-mentioned purposes, features and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application are described in detail below in conjunction with the accompanying drawings. In the following description, many specific details are set forth to facilitate a full understanding of the present application, and the preferred embodiments of the present application are given in the accompanying drawings. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present application more thoroughly understood. The present application can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present application, so the present application is not limited by the specific embodiments disclosed below.

[0040] In order to simplify the drawings, each figure only schematically shows the parts related to the present invention, which do not represent the actual structure of the product.

[0041] According to an embodiment provided by the present invention, see Figure 1 As shown, a methanol reforming hydrogen production system comprises: a reforming reaction unit 1, which comprises a raw material tank 10 for mixing desalted water and methanol, and a reforming reactor 11 connected to the outlet of the raw material tank 10; a temperature control unit 12 is also arranged between the raw material tank 10 and the reforming reactor 11; a hydrogen purification unit 2, comprising a palladium membrane purification device 20 arranged downstream of the reforming reactor 11, the palladium membrane purification device 20 having a purified hydrogen outlet and a residual gas outlet; a combustion unit 3, the combustion unit 3 having a feed inlet and a tail gas outlet, the feed inlet is connected to the residual gas outlet of the palladium membrane purification device 20, and the tail gas outlet is connected to the temperature control unit 12; wherein, the reaction temperature in the reforming reactor 11 is controlled not to exceed the purification temperature range in the palladium membrane purification device 20. According to this embodiment, after the desalted water and methanol are mixed in the raw material tank 10, the reaction temperature of the raw materials entering the reforming reactor 11 can be controlled by the temperature control unit 12 so that it does not exceed the purification temperature range of the palladium membrane purification device 20, so that the reaction product of the reforming reactor 11 does not need to be heated again and can be directly sent to the palladium membrane purification device 20 for purification and separation to obtain hydrogen; at the same time, the residual gas (containing a small amount of hydrogen) separated by the palladium membrane purification device 20 is sent to the combustion unit 3 for catalytic oxidation reaction, and the released heat is supplied to the temperature control unit 12 to heat the reforming reactor, that is, the heat of the temperature control unit 12 comes from the system itself. It not only improves the energy utilization rate of the system and meets the temperature requirements of the reforming reaction, but also is more environmentally friendly and safe. Make the system of this embodiment more compact and have a higher level of thermal management.

[0042] As a preferred embodiment, the temperature control unit 12 includes a preheater 120 and a superheater 121 which are sequentially arranged downstream of the raw material tank 10. The outlet of the superheater 121 is connected to the reforming reactor 11. The methanol water raw material is preheated by the preheater 120 and then further heated in the superheater 121 to make the temperature meet the requirements of the reforming reaction; the outlet of the reforming reactor 11 is connected to the palladium membrane purification device 20, so that the product after the reforming reaction enters the palladium membrane purification device to purify and separate the hydrogen to obtain high-purity hydrogen.

[0043] As another preferred embodiment, the combustion unit 3 includes a burner 30, and the residual gas outlet of the palladium membrane purification device 20 is connected to the burner 30 for combustion, and the tail gas outlet of the burner 30 is connected to the preheater 120, which is used to supply the heat of the combustion tail gas to the preheater 120 to heat the raw material; the burner 30 is also provided with an air inlet, through which air is introduced to recover heat from the residual gas (containing a small amount of hydrogen) separated by the palladium membrane purification device 20 through catalytic oxidation; specifically, the air inlet is connected through an air compressor 32 to realize the delivery of air to ensure the catalytic oxidation reaction.

[0044] More preferably, there is a circulating intermediate heat exchange medium in the burner 30, the reforming reactor 11 and the superheater 121. In actual applications, the intermediate heat exchange medium adopts natural circulation or forced circulation (that is, a circulating pump is added to the circulation loop) to exchange heat between the burner 30, the reforming reactor 11 and the superheater 121. When natural circulation is adopted, the latent heat of the intermediate heat exchange medium is mainly used for heat exchange. After the intermediate heat exchange medium in the burner 30 absorbs heat and is heated and evaporated, it is condensed into liquid after passing through the reforming reactor 11 and the superheater 121 in sequence. The liquid medium circulates back to the burner 30 under the action of gravity; when forced circulation is adopted, the sensible heat of the intermediate heat exchange medium is mainly used for heat exchange. The intermediate heat exchange medium is heated by the burner 30, the temperature rises, and then flows through the reforming reactor 11 and the superheater 121 for heat exchange, and then flows back to the burner 30 under the action of the circulation pump to complete the circulation. In addition to adding a circulation pump in the forced circulation, it is also necessary to control the pressure of the circulation loop to ensure that the fluid in the loop is liquid. In this way, the recovered heat is fully utilized through the intermediate heat exchange medium.

[0045] In order to match the operating temperature range of 380-420°C of the palladium membrane purification device 20, the reaction temperature in the reforming reactor is controlled between 400-410°C through an intermediate heat exchange medium, so that the temperature range of the reforming reaction and the palladium membrane purification are consistent. The product of the reforming reaction can directly enter the palladium membrane purification device 20 for separation and purification, saving the temperature control structure added between the reforming reactor 11 and the palladium membrane purification device 20 in the prior art, and improving the compactness and thermal management level of the system.

[0046] In the process of hydrogen-containing tail gas entering the burner 30 for heat recovery, if the capacity of hydrogen catalytic oxidation cannot meet the heat demand of the reforming reactor 11 and the superheater 121, a methanol supplementary combustion pipeline is also connected to the reforming reactor 11 and the burner 30, and methanol is supplemented to carry out methanol catalytic oxidation in the burner 30 to meet the heating demand. Among them, the methanol supplementary combustion pipeline includes a heat exchanger 31, and the heat exchanger is connected to the tail gas outlet of the preheater 120, so that the tail gas from the burner 30 is discharged after heat exchange in the preheater 120 and the heat exchanger 31, and at the same time, heat is provided for methanol, thereby further improving the utilization rate of system energy.

[0047] In addition, the inlet of the raw material tank 10 is connected to the desalted water pipeline and the methanol inlet pipeline respectively. In practical applications, the desalted water pipeline is provided with a desalted water tank 100 and a desalted water pump 101, the methanol inlet pipeline is provided with a methanol storage tank 102 and a methanol pump 103, the methanol supplementary combustion pipeline and the methanol replenishment pipeline can share the methanol storage tank 102 and the methanol pump 103, and the heat exchanger 31 is used to heat the supplemented methanol, making the system layout more concise.

[0048] In order to further improve the purity of the purified hydrogen, the hydrogen purification unit 2 also includes a methanation device 21, and the purified hydrogen outlet of the palladium membrane purification device 20 is connected to the methanation device 21. The palladium membrane purification device 20 purifies the hydrogen-rich gas after the reforming reaction. The concentration of hydrogen in the hydrogen-rich gas is generally above 60% (including unreacted water vapor). The purity of hydrogen is related to the palladium membrane purification area and the pressure of the hydrogen-rich gas. After purification by the palladium membrane, the purity of hydrogen can reach more than 99.9%. On the basis of the palladium membrane purification device 20, the methanation device 21 is combined to further purify the hydrogen purified by the palladium membrane, so that CO and hydrogen react to remove CO in the hydrogen, so that the CO concentration in the hydrogen is less than 0.2ppm. In addition, the methanation device 21 adopts the existing technology in this field and is directly purchased from the market, so its specific structure is not further described here.

[0049] According to another embodiment provided by the present invention, a methanol reforming hydrogen production process comprises the following steps:

[0050] Combination Figure 1 As shown in the main reaction process route and the tail gas emission process route, desalted water and methanol are mixed in the raw material tank 5, and after being heated by the temperature control unit 12, a methanol reforming hydrogen production reaction is carried out in the reforming reactor 11 to produce hydrogen-rich gas; then the hydrogen-rich gas directly enters the palladium membrane purification device 20 for purification, and the purified hydrogen is discharged, and the purified residual gas is mixed with air in the combustion unit 3 to undergo an oxidation reaction, and the tail gas after the reaction is passed into the temperature control unit for heat exchange; wherein, the reaction temperature of the raw materials entering the reforming reactor is controlled not to exceed the purification temperature range in the palladium membrane purification device.

[0051] As a preferred embodiment, wherein:

[0052] The temperature control unit 12 includes a preheater 120 and a superheater 121. The desalted water and methanol first enter the preheater 120 in the temperature control unit 12 for preheating, then pass through the superheater 121 for heating, and then enter the reforming reactor 11 for reaction to produce hydrogen-rich gas.

[0053] The combustion unit 3 includes a burner 30. The purified residual gas is mixed with air to undergo an oxidation reaction in the burner 30. On the one hand, the combustion exhaust gas after the reaction enters the preheater 30 for heat exchange, which is used to preheat the methanol water raw material. On the other hand, the burner 30, the reforming reactor 11, and the superheater 121 have a circulating intermediate heat exchange medium. The intermediate heat exchange medium uses a natural circulation or a forced circulation method to continuously transfer the heat in the reaction of the burner 11 to the reforming reactor and the superheater, and circulates continuously. For the specific circulation method, please refer to the detailed description of the natural circulation and forced circulation in the previous embodiment, which will not be repeated here. Therefore, part of the heat generated by the reaction in the burner 30 is supplied to the preheater 120 in the temperature control unit 12 through the exhaust gas after combustion, and part of it is supplied to the superheater 121 in the temperature control unit 12 and the reforming reactor 11 through the intermediate heat exchange medium to meet the reaction temperature requirements in the reforming reactor 11. Figure 1 The middle dotted line shows the direction of the intermediate heat exchange medium.

[0054] In order to match the operating temperature of the palladium membrane purification device 20 of 380-420°C, the reaction temperature in the reforming reactor 11 is controlled between 400-410°C through the intermediate heat exchange medium, so that the temperature range of the reforming reaction and the palladium membrane purification is consistent, and the product after the reforming reaction can directly enter the palladium membrane purification device 20 for separation and purification. Not only can the energy generated by the system be fully utilized, but the system layout is also more concise and compact, and the thermal management level is higher.

[0055] If the combustion heat supply of the hydrogen-containing tail gas purified by the palladium membrane is insufficient, the burner also supplements methanol through the methanol supplementary combustion pipeline to simultaneously carry out the methanol oxidation reaction to meet the heating demand. In addition, a heat exchanger 31 is also provided on the methanol supplementary combustion pipeline. The combustion tail gas entering the preheater 120 is discharged after heat exchange in the heat exchanger 31, and at the same time provides heat for the supplementary methanol, so as to make more full use of energy.

[0056] In addition, in order to further improve the purity of hydrogen, the hydrogen purified by the palladium membrane purification device 20 enters the methanation device 21 to further remove CO, reducing CO to below 0.2 ppm to meet the use requirements of the fuel cell.

[0057] It should be noted that the above embodiments can be freely combined as needed. The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered as the protection scope of the present invention.

Claims

1. A methanol reforming hydrogen production system, characterized in that: include: The reforming reaction unit comprises a raw material tank for mixing desalted water and methanol, and a reforming reactor connected to the outlet of the raw material tank; a temperature regulating unit is also arranged between the raw material tank and the reforming reactor; The temperature adjustment unit comprises a preheater and a superheater which are sequentially arranged downstream of the raw material tank, and the outlet of the superheater is connected to the reforming reactor; A hydrogen purification unit, comprising a palladium membrane purification device disposed downstream of a reforming reactor, the palladium membrane purification device having a purified hydrogen outlet and a residual gas outlet, the outlet of the reforming reactor being connected to the palladium membrane purification device to purify and separate the hydrogen; A combustion unit, wherein the combustion unit has a feed inlet and a tail gas outlet, wherein the feed inlet is connected to the residual gas outlet of the palladium membrane purification device, and the tail gas outlet is connected to the temperature adjustment unit; The combustion unit comprises a burner, the residual gas outlet of the palladium membrane purification device is connected to the burner for combustion, and the tail gas outlet of the burner is connected to the preheater for supplying the heat of the combustion tail gas to the preheater; the burner is also provided with an air inlet; The burner, reforming reactor and superheater have an intermediate heat exchange medium circulating; Wherein, the reaction temperature in the reforming reactor is controlled not to exceed the purification temperature range of the palladium membrane purification device; The burner is also connected to a methanol supplementary combustion pipeline for passing methanol into the burner for supplementary combustion; The methanol supplementary combustion pipeline includes a heat exchanger, and the heat exchanger is connected to the tail gas outlet of the preheater.

2. The methanol reforming hydrogen production system according to claim 1, characterized in that: The purification temperature range in the palladium membrane purification device is 380-420°C, and the reaction temperature in the reforming reactor is controlled at 400-410°C; and / or; The hydrogen purification unit further comprises a methanation device, and the methanation device is connected to the purified hydrogen outlet of the palladium membrane purification device.

3. A methanol reforming hydrogen production process, characterized in that: The steps include: Desalted water and methanol are mixed in the raw material tank, heated by the temperature control unit, and then undergo a methanol reforming hydrogen production reaction in the reforming reactor to produce hydrogen-rich gas; the hydrogen-rich gas then directly enters the palladium membrane purification device for purification, the purified hydrogen is discharged, and the purified residual gas is mixed with air in the combustion unit for oxidation reaction, and the tail gas after the reaction is passed into the temperature control unit for heat exchange; The temperature control unit includes a preheater and a superheater. The desalted water and methanol first enter the preheater in the temperature control unit for preheating, then pass through the superheater for temperature increase, and then enter the reforming reactor for reaction to produce hydrogen-rich gas. The combustion unit includes a burner, in which the purified residual gas and air undergo an oxidation reaction, and the combustion tail gas after the reaction enters a preheater for heat exchange; The burner, reforming reactor and superheater have a circulating intermediate heat exchange medium, which is heated by the heat in the burner reaction, condensed by the reforming reactor and superheater, and then refluxed to the burner, in a continuous cycle; Wherein, the reaction temperature of the raw materials entering the reforming reactor is controlled not to exceed the purification temperature range in the palladium membrane purification device; The burner also supplements methanol through a methanol supplementary combustion pipeline to simultaneously carry out a methanol oxidation reaction, and the tail gas entering the preheater is discharged after heat exchange in a heat exchanger on the methanol supplementary combustion pipeline.

4. The process for producing hydrogen by methanol reforming according to claim 3, characterized in that: The purification temperature range in the palladium membrane purification device is 380-420°C, and the reaction temperature in the reforming reactor is controlled at 400-410°C; and / or; The purified hydrogen enters the methanation unit to further remove CO, reducing CO to below 0.2ppm.

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