Hydrogen production reaction system, application and method for producing hydrogen from methane

Abstract

The invention relates to the field of hydrogen production reactors, and discloses a hydrogen production reaction system, application and a method for producing hydrogen from methane, the hydrogen production reaction system comprises an integrated reaction device, the integrated reaction device comprises a separation unit, a hydrogen production reaction unit and a heat supply unit which are nested from inside to outside, the heat supply unit is used for providing heat for the reaction of the hydrogen production reaction unit, and the separation unit is used for separating at least two streams of discharged materials from the reacted materials. According to the hydrogen production reaction system, heat supply, heat absorption and separation are integrated, in-situ separation of reaction products can be achieved, the hydrogen production reaction system has the advantages that energy consumption is low, the process is simple, industrialization and device miniaturization are easy to achieve, and furthermore, the productivity of the device can be increased through parallel connection of multiple pieces of integrated reaction equipment.

Description

Technical Field

[0001] The invention relates to the field of hydrogen production reactors, and in particular to a hydrogen production reaction system and application thereof, and a method for producing hydrogen from methane. Background Art

[0002] Hydrogen energy is a typical secondary energy source, serving as an intermediate link between primary energy and energy users. At present, the extensive use of primary energy such as gasoline, jet fuel and diesel in the transportation field has brought serious environmental and ecological problems. Green hydrogen energy, as the "ultimate energy" to replace petroleum products in the future, is an ideal choice for responding to climate change and building a decarbonized society. The development of hydrogen energy is an effective way to practice green development and promote industrial transformation and upgrading, which is conducive to ensuring my country's energy security.

[0003] At present, the technologies of hydrogen production and supply, such as coal-to-hydrogen, natural gas-to-hydrogen, byproduct hydrogen refining, and renewable energy-to-hydrogen, are relatively mature, while the high cost of hydrogen storage and transportation is a key link that affects the competitiveness of the hydrogen energy market at present and in the future. With the large-scale development of fuel cell vehicles in the future, the demand for hydrogen will increase. Distributed on-site hydrogen production to achieve in-station hydrogen supply is a feasible solution to dilute the cost of hydrogen use, and can also reduce the cost and safety risks caused by hydrogen transportation.

[0004] Natural gas hydrogen production is one of the main sources of industrial hydrogen. The most commonly used technology is steam reforming, which is also used in the development of distributed natural gas hydrogen production technology. Natural gas steam reforming mainly produces the following three reactions: CH 4 + 2H 2 O = CO 2 + 4H 2 (1) CO + H 2 O = CO 2 + 3H 2 (2) CH 4 + H 2 O = CO + H 2 (3) From reaction equations (1-3), it can be seen that high temperature and low pressure conditions are conducive to the conversion of methane into hydrogen. To achieve a 90% methane conversion rate, the reaction needs to be at a temperature higher than 900-1000°C. Therefore, natural gas steam reforming hydrogen production requires a high-temperature combustion furnace. Usually, PSA desorbed gas and (or) natural gas directly burned after product hydrogen purification are used for heating. High-temperature open flame heating increases the safety risks of distributed natural gas hydrogen production equipment and also increases the energy consumption of hydrogen production.

[0005] At present, developing a small self-heating and efficient hydrogen production reactor suitable for distributed hydrogen production equipment to avoid the use of high-temperature combustion furnaces is one of the key issues that need to be solved in the development of distributed hydrogen production equipment. Traditional methane steam reforming needs to react in a radiation furnace above 900°C, providing reaction heat through high-temperature radiation and improving the reaction equilibrium conversion rate.

[0006] Traditional industrial steam reforming hydrogen production uses a radiation furnace for heating and recovers waste heat in the convection section. However, there are problems such as large footprint of the reaction device, low energy utilization rate, and inability to achieve in-situ separation of the products. Summary of the invention

[0007] The purpose of the present invention is to overcome the problems of the prior art that the hydrogen production reaction device occupies a large area, has low energy utilization rate, low hydrogen production reaction conversion rate, high reaction temperature, requires open flame heating, and cannot achieve in-situ separation of products. A hydrogen production reaction system and application and a method for producing hydrogen from methane are provided, which can achieve in-situ separation of reaction products, improve conversion rate, and reduce reaction temperature. It has the advantages of low energy consumption, simple process, easy industrialization and miniaturization of the device. Furthermore, the production capacity of the device can be enlarged by connecting multiple integrated reaction equipment in parallel.

[0008] In order to achieve the above object, the present invention provides a hydrogen production reaction system on one hand, wherein the hydrogen production reaction system comprises an integrated reaction device, and the integrated reaction device comprises: A separation unit, a hydrogen production reaction unit and a heat supply unit are nested from the inside out, wherein the heat supply unit is used to provide heat for the reaction of the hydrogen production reaction unit, and the separation unit is used to separate the reacted material into at least two outputs.

[0009] The second aspect of the present invention provides the use of the hydrogen production reaction system of the present invention in methane hydrogen production, wherein the hydrogen production scale of the hydrogen production reaction system is 1-10Nm 3 / h.

[0010] A third aspect of the present invention provides a method for producing hydrogen from methane, the method using the hydrogen production reaction system of the present invention, the method comprising: A heating material is fed into the heating unit, a mixed raw material of methane and water is fed into the hydrogen production reaction unit to generate a hydrogen-containing product, and hydrogen in the hydrogen-containing product is separated by a separation unit.

[0011] The above technical scheme adopts the hydrogen production reaction system including the integrated reaction equipment of the present invention, integrates heat supply-heat absorption-separation, can realize in-situ separation of reaction products, has the advantages of low energy consumption, simple process, easy industrialization and miniaturization of equipment. Furthermore, the hydrogen production method of the present invention can realize the catalytic oxidation of fuel gas to directly supply heat for hydrogen production reaction, avoids the use of high-temperature heating furnaces, avoids open flames, reduces reaction temperature and energy consumption, and improves heat transfer efficiency, methane conversion rate and the safety and reliability of the hydrogen production reaction system. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 It is an integrated reaction device used to illustrate the specific implementation part of the present invention; Figure 2 yes Figure 1 A top view of Figure 3 It is used to illustrate the hydrogen production reaction system of the specific implementation part of the present invention.

[0013] Description of Reference Numerals I is a separation chamber, II is a reaction chamber, III is a heating chamber, a1 is a feed port; a2 is a discharge port; a3 is a carrying gas inlet; a4 is a discharge port; a5 is a material inlet; a6 is a material outlet; a7 is a temperature measuring element for the reaction chamber; a8 is a temperature measuring element for the heating chamber; b2 is a reaction shell; b1 is a heating shell; b3 is a separation shell; c1 is an integrated reaction device; c2 is a second heat exchanger; c3 is a desalted water pump; c4 is a third heat exchanger; c5 is a first heat exchanger; c6 is a membrane separation permeation side back pressure valve; c7 is a pressure swing adsorption device; c8 is a reforming reaction side back pressure valve; c9 is an air blower; c10 is a gas mixer; c11 is a high temperature circulation fan; c25 is a branch pipe; c71 is a desorption gas outlet; f3 is a heating material feed pipeline; c47 is a first pipeline.

[0014] The process flow includes: the raw desalted water is vaporized by heat exchange with the catalytic oxidation outlet flue gas in the third heat exchanger c4, and then mixed with the raw natural gas to obtain a mixed raw gas, which is preheated to the reaction temperature by the catalytic oxidation outlet flue gas in the second heat exchanger c2 and then enters the feed port a1 of the integrated reaction equipment c1. The high-temperature outlet gas of the outlet a2 is directly used as a catalytic oxidation raw gas after being reduced in pressure by the back pressure valve c8 on the reforming reaction side. The permeate gas in the tubular membrane assembly is preheated by the first heat exchanger c5 to recover the heat and then enters the pressure swing adsorption device c7 to purify the fuel cell grade hydrogen, and the desorbed gas is used as another catalytic oxidation raw gas. Part of the fuel gas (such as methane) supplemented through the heating material feed pipeline f3 is used as the third catalytic oxidation raw gas, and each combustible gas is mixed with air in the gas mixer c1 and enters the material inlet a5. The high-temperature flue gas discharged from the material outlet a6 is preheated by the second heat exchanger c2 to mix the raw material gas and recover part of the heat. Most of it (for example, 90%) is returned to the material inlet a5 as circulating gas, and a small part goes to the third heat exchanger c4 to heat the desalted water and then discharged on site. DETAILED DESCRIPTION

[0015] The specific embodiments of the present invention are described in detail below in conjunction with the accompanying drawings.It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention and are not intended to limit the present invention.The endpoints and any values ​​of the scope disclosed in this article are not limited to the precise scope or value, and these scopes or values ​​should be understood to include values ​​close to these scopes or values.For numerical ranges, between the endpoint values ​​of each scope, between the endpoint values ​​of each scope and a separate point value, and between separate point values ​​can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be considered to be specifically disclosed in this article.

[0016] In the present invention, unless otherwise specified, directional words such as "up, down, top, bottom" are usually used with reference to the directions shown in the drawings or are used to describe the relative positional relationships of components in the vertical, perpendicular or gravity direction. "Inside" and "outside" usually refer to the inside and outside of a chamber relative to the chamber or the radial inside and outside relative to the center of a circle.

[0017] In one aspect, the present invention provides a hydrogen production reaction system, the hydrogen production reaction system comprises an integrated reaction device, the integrated reaction device c1 comprises: The separation unit, hydrogen production reaction unit and heating unit are nested from the inside out, wherein the heating unit is used to provide heat for the reaction of the hydrogen production reaction unit, and the separation unit is used to separate the reacted material into at least two outputs.

[0018] The hydrogen production reaction system including the integrated reaction equipment of the present invention integrates heat supply-heat absorption-separation, can realize in-situ separation of reaction products, can improve conversion rate, and reduce reaction temperature, and has the advantages of low energy consumption, simple process, easy industrialization and miniaturization of equipment.

[0019] In some embodiments of the present invention, the hydrogen production reaction unit includes a reaction shell b2 and a reaction chamber II formed around the reaction shell b2; the heating unit includes a heating shell b1, and the heating shell b1 is configured to wrap the reaction shell b2 with a gap, and the gap forms a heating chamber III for circulating or storing a heating medium; the separation unit includes a separation element arranged in the reaction chamber II, and the separation element can separate the reaction chamber into two spaces, so that a part of the reacted material passes through the separation element to be discharged, and the other part is discharged from the original reaction chamber; Preferably, the separation element has a separation chamber I formed by surrounding a separation shell b3, and the separation shell b3 allows a portion of the reacted material to be discharged from the reaction chamber II, and the rest to be discharged from the separation chamber I.

[0020] It should be noted that the reaction chamber and the heating chamber are both independently sealed chambers, each of which is provided with an inlet and outlet for logistics. The overall shape of the reaction chamber, the heating chamber and the separation chamber can be cylindrical, spherical or other shaped cavities that can be nested inside and outside.

[0021] like Figure 1 As shown, in some embodiments of the present invention, the integrated reaction equipment is configured as a column, including a cylindrical separation shell b3, a cylindrical closed reaction shell b2 and a cylindrical closed heating shell b1 that are nested from the inside to the outside. It can be understood that the cross-section of the column of the present invention can be circular, elliptical or polygonal; in some embodiments of the present invention, the upper and lower ends of the separation shell b3, the heating shell b1 and the reaction shell b2 can be sealed and connected to the upper sealing plate and the lower sealing plate respectively by welding, wherein the upper sealing plate is connected to a carrying gas inlet a3, which is connected to the top of the separation shell b3, and the lower sealing plate is connected to a discharge port a4, which is connected to the bottom of the separation shell b3. It can be understood that the The carrying gas inlet a3 can introduce a carrying gas, such as nitrogen, on the permeation side of the membrane assembly; the heating shell b1 is provided with a material inlet a5 and a material outlet a6 connected to the heating chamber III, and the upper sealing plate and the lower sealing plate are respectively provided with a feed port a1 and a discharge port a2 connected to the reaction chamber II, wherein the discharge port a2 is connected to the material inlet a5, wherein the heating chamber can adopt catalytic combustion to achieve non-open flame heating to avoid the use of a high-temperature heating furnace and avoid open flame. Combined with the structural form of the present invention, the heat transfer efficiency can be improved, the energy consumption can be reduced, and the safety and reliability of the reactor can be improved. For example, in the catalytic hydrogen production from methane, the tail gas after hydrogen is separated from the reaction product can be used as a raw material for catalytic combustion through the connected discharge port a2 and material inlet a5.

[0022] To avoid short-circuiting of the material flow into the cavity, it is understood that the material inlet and outlet can be set as follows Figure 1 As shown, the feed port a1 and the discharge port a2 are respectively located on the upper sealing plate and the lower sealing plate connected to the reaction shell b2, and the orthographic projections on the horizontal plane are arranged symmetrically at 180°. Similarly, the material inlet a5 and the material outlet a6 are respectively located at the upper and lower ends of the side of the heating shell, and the orthographic projections on the horizontal plane are arranged symmetrically at 180°.

[0023] In some embodiments of the present invention, the outer diameter of the heating shell b1 is 10-15 cm, and the height is 40-60 cm.

[0024] In some embodiments of the present invention, the width of the annular gap formed between the reaction housing b2 and the heating housing b1 is preferably 1 to 5 cm, more preferably 2 to 3 cm.

[0025] In some embodiments of the present invention, the separation housing b3 is configured as a tubular membrane module, and preferably the tubular membrane module comprises a porous tubular substrate and a membrane covering the surface of the porous tubular substrate.

[0026] In some embodiments of the present invention, the porous tubular substrate material is selected from porous ceramics or porous stainless steel. It should be noted that the porous ceramics or porous stainless steel tubular substrates in the present invention can be obtained commercially, and the present invention will not elaborate on this.

[0027] In some embodiments of the present invention, the outer diameter of the porous tubular substrate is 2-5 cm.

[0028] In some embodiments of the present invention, the film is an alloy film formed by Pd and another precious metal, and preferably the other precious metal is selected from one of gold, silver or ruthenium; in the embodiments of the present invention, only the palladium-silver alloy film is used as an example to illustrate the advantages of the present invention, but the present invention is not limited to this.

[0029] In some embodiments of the present invention, the film is an alloy film formed by Pd and another noble metal formed by chemical plating.

[0030] In some embodiments of the present invention, the thickness of the film is 3-10 μm, preferably 4-6 μm.

[0031] When the present invention is applied to hydrogen production from methane, the tubular membrane assembly of the present invention can achieve balanced pull of the methane reforming reaction, and achieving the same outlet methane conversion rate can significantly reduce the thermodynamic equilibrium temperature and the reactor operating temperature, thereby improving the operating stability and life of the separation membrane.

[0032] In some embodiments of the present invention, a detection port for the heating chamber temperature measuring element a8 to extend into is provided on the heating shell b1; a detection port for the reaction chamber temperature measuring element a7 to extend into is provided on the reaction shell b2. Preferably, the detection port of the reaction shell b2 and the discharge port a2 are located on the same straight line in the height direction, so that both the real-time temperature at the outlet can be monitored and the bed temperature distribution in the height direction can be determined by moving the thermocouple upward; preferably, the heating chamber temperature measuring element a8 and the reaction chamber temperature measuring element a7 are thermocouples.

[0033] In some embodiments of the present invention, the hydrogen production reaction system includes a purification device for purifying the output of the hydrogen production reaction unit or the separation unit in the integrated reaction device c1; specifically, Figure 3 As shown, the purification equipment includes a pressure swing adsorption device (PSA) c7 connected to the discharge port a4, and the desorption gas outlet c71 of the pressure swing adsorption device c7 is connected to the heating chamber III. For example, methane and water are used as raw materials to produce hydrogen in the reaction chamber, and the residual gas after the product is separated online by the tubular membrane assembly is directly used as a feed for catalytic oxidation in the heating chamber. The crude product hydrogen separated from the tubular membrane assembly is recovered by the heat recovery module and then enters the pressure swing adsorption device (PSA) c7 for adsorption purification. The purified hydrogen is discharged into the subsequent processing process, and the remaining desorption gas is discharged from the desorption gas outlet c71 to the heating chamber III as a heating material. The present invention has no special requirements for the pressure swing adsorption device (PSA), and the conventional pressure swing adsorption device (PSA) and operation method can be used in the present invention, which will not be repeated here.

[0034] In some embodiments of the present invention, the hydrogen production reaction system includes at least two integrated reaction devices c1, and each of the integrated reaction devices c1 is connected in series and / or in parallel.

[0035] In some embodiments of the present invention, the hydrogen production reaction unit is a reforming reaction unit, the heat supply unit is a catalytic oxidation reaction heat supply unit, and the separation unit is a membrane permeation separation unit.

[0036] In some embodiments of the present invention, Figure 3 As shown, the hydrogen production reaction system includes a heat exchange device, which is used to collect the heat of the discharged material in the integrated reaction device c1 to preheat the feed material of the integrated reaction device c1.

[0037] In some embodiments of the present invention, the hot medium channel of the heat exchange device is preferably connected to the material outlet a6 of the heat supply unit, and the cold medium channel of the heat exchange device is connected to the hydrogen production raw material feed channel of the hydrogen production reaction unit.

[0038] For example, in some embodiments of the present invention, Figure 3 As shown, the heat exchange device includes a first heat exchanger c5, a second heat exchanger c2 and a third heat exchanger c4, wherein: The discharge port a4 is connected to the feed port of the pressure swing adsorption device c7 through the first pipeline c47. The first heat exchanger c5 is installed on the first pipeline and the hot medium channel (for example, the shell side) of the first heat exchanger is connected to the first pipeline c47. The cold medium channel of the first heat exchanger c5 is connected to the material inlet a5 of the heating chamber III, so that the discharge material of the separation chamber I and the feed material of the heating chamber II can exchange heat. Air can be introduced into the cold medium channel of the first heat exchanger c5, and the air is first preheated by the discharge material of the separation chamber I and then enters the heating chamber, so that the reaction raw materials can be provided when a catalytic combustion reaction occurs in the heating chamber to provide heat.

[0039] The hot medium channel of the second heat exchanger c2 is connected to the material outlet a6, and the cold medium channel of the second heat exchanger c2 is connected to the feed port a1 of the reaction chamber II, so that the discharge material of the heating chamber III and the feed material of the reaction chamber II can exchange heat; the hot medium channel of the third heat exchanger c4 is connected to the hot medium channel of the second heat exchanger c2, and the cold medium channel of the third heat exchanger c4 is connected to the cold medium channel of the second heat exchanger c2 and along the flow direction of the reaction material, and the cold medium channel of the third heat exchanger c4 is located upstream of the cold medium channel of the second heat exchanger c2; for example, Figure 3 As shown, when natural gas and desalted water are used to produce hydrogen, the desalted water feed pipeline feeds the desalted water into the reaction chamber through the desalted water pump c3, first passes through the third heat exchanger for the first preheating, and then mixes with the feed natural gas to form a stream, which then passes through the second heat exchanger for the second preheating and then enters the feed port a1; wherein, the heat medium of the second heat exchanger c2 comes from the hot flue gas discharged from the material outlet a6 of the heating chamber, and is divided into two streams after flowing out of the second heat exchanger c2, one stream enters the third heat exchanger for gasifying the desalted water and then is discharged, and the other stream returns to the material inlet a5 of the heating chamber through the branch pipe c25.

[0040] In some embodiments of the present invention, in order to achieve more uniform and efficient heat supply, the hydrogen production reaction system is provided with a gas mixer c10, the outlet of the gas mixer c10 is connected to the material inlet a5, and the gas mixer c10 is connected to the branch pipe c25, the desorption gas outlet c71 of the pressure swing adsorption device c7, the outlet a2 of the reaction chamber II, the cold medium channel of the first heat exchanger c5 and the heating material feed pipeline f3.

[0041] It is understandable that in order to achieve safe production, Figure 3 As shown, an oxygen online analyzer is respectively arranged on the pipelines of the material outlet a6 and the material inlet a5 of the heating chamber, and the gas composition can be made to meet the safety requirements by adjusting the flue gas circulation volume.

[0042] It is understandable that in the present invention, various parts can be added with various pipelines, valves, pumps, fans or instruments as needed, and can be used as follows: Figure 3The configuration shown in the figure is not specifically required by the present invention and will not be described in detail here.

[0043] In view of the problems of low conversion rate, high reaction temperature, open flame heating, difficulty in miniaturization and high energy consumption of the existing natural gas steam reforming hydrogen production reaction, the second aspect of the present invention provides the application of the hydrogen production reaction system of the present invention in methane hydrogen production. By enlarging the hydrogen production reaction system of the present invention, the hydrogen production scale of the hydrogen production reaction system can be adjusted to 1.0~10Nm 3 / h, for example, the production capacity of the device can be enlarged by connecting multiple integrated reaction devices in parallel.

[0044] The third aspect of the present invention provides a method for producing hydrogen, which adopts the methane hydrogen production reaction system of the present invention, and the method comprises: The heating material is fed into the heating unit, and a mixed raw material of methane and water (hydrogen production raw material) is fed into the hydrogen production reaction unit to generate a hydrogen-containing product, and the hydrogen in the hydrogen-containing product is separated by the separation unit.

[0045] In the present invention, there are no special requirements for the source and composition of the hydrogen production raw materials. The following exemplary description is not intended to limit the scope of the present invention. In some embodiments of the present invention, the hydrogen production raw materials include methane and water, and the water is selected from desalted water, and the desalted water meets the requirements for direct current furnace water in the national standard GB / T12145-2016.

[0046] In some embodiments of the present invention, the molar ratio of water to methane in the mixed raw material is controlled to be 1: 1 to 3: 1, more preferably 1.5: 1 to 3: 1. In the embodiments of the present invention, the molar ratio of water to methane is only 3.0 as an example to illustrate the advantages of the present invention, but the present invention is not limited thereto.

[0047] In some embodiments of the present invention, the gas volume space velocity is preferably controlled at 400-1500 h / min based on carbon. -1 , more preferably 500~1000h -1 .

[0048] In some embodiments of the present invention, the methane treatment capacity is preferably 0.5~3.0Nm 3 / h, more preferably 1.0~2.5Nm 3 / h.

[0049] In some embodiments of the present invention, the hydrogen production raw material is preferably preheated to 400-490° C., preferably 450-485° C. before entering the hydrogen production reaction unit. In the embodiments of the present invention, the advantages of the present invention are illustrated by only taking the hydrogen production raw material preheated to 460-468° C. before entering the hydrogen production reaction unit, but the present invention is not limited thereto.

[0050] In some embodiments of the present invention, the reaction pressure is preferably controlled at 1.0-3.0 MPa, more preferably 1.6-2.0 MPa.

[0051] In some embodiments of the present invention, the pressure difference between the inside and outside of the separation unit (preferably a tubular membrane module) is maintained at 0.5-1.5 MPa, more preferably 1.0-1.5 MPa, which has the advantages of taking into account both membrane separation efficiency and membrane flux. The hydrogen production catalyst is filled between the reaction shell b2 and the tubular membrane assembly. In the present invention, conventional catalysts for hydrogen production from methane are applicable to the present invention. The following exemplary description does not limit the scope of the present invention. In some embodiments of the present invention, the active component of the hydrogen production catalyst is nickel, the carrier is alumina, and the auxiliary agent contains at least one of lithium, sodium, potassium, magnesium, calcium, copper, cerium, zinc and other elements. In the embodiment of the present invention, only Ni / Al with a Ni content of 15wt% is filled in the reaction chamber. 2 O 3 The catalyst, wherein the promoter is lanthanum (component content 1 wt%), is used as an example to illustrate the advantages of the present invention, but the present invention is not limited thereto.

[0052] In order to achieve heating without open flames, in some embodiments of the present invention, a catalytic oxidation catalyst is loaded between the heating shell b1 and the reaction shell b2. The catalytic oxidation catalyst includes an active component and a carrier. The active component of the catalytic oxidation catalyst includes a precious metal or a non-precious metal catalyst, preferably one or more of platinum, palladium, ruthenium, nickel, manganese, iron, and cobalt metals. In the embodiment of the present invention, only Pt / Al with a Pt loading of 0.5wt% is loaded in the heating cavity. 2 O 3 The catalyst and the auxiliary agent are ruthenium (component content 0.1wt%) as an example to illustrate the advantages of the present invention, but the present invention is not limited thereto.

[0053] The hydrogen production method of the present invention adopts the hydrogen production reaction system of the present invention, which is sequentially divided into a catalytic oxidation heating area (heating chamber III), a reforming reaction area (reaction chamber II) and a membrane permeation area (separation chamber I) from the outer layer to the inner layer. The desalted water and natural gas after vaporization and preheating enter the reforming reaction area to undergo a methane reforming reaction, and the permeation membrane assembly (tubular membrane assembly) in the bed layer realizes the in-situ separation of hydrogen. The hydrogen is purified by pressure swing adsorption to obtain product fuel cell hydrogen. The catalytic oxidation heating area is arranged in the outer layer of the reforming reaction area to realize efficient heating. The PSA desorbed gas and the reforming reaction outlet (discharge port a2) gas enter the catalytic oxidation to recover its chemical energy. The present invention can realize heat recovery of high-temperature product gas and flue gas, and reduce process energy consumption. There is no open flame in the whole process, and the use of a high-temperature heating furnace is avoided, which greatly reduces the reaction temperature, improves the heat transfer efficiency, reduces energy consumption, and improves the process safety.

[0054] The advantages of the present invention will be described below by way of examples, but the present invention is not limited thereto.

[0055] Example 1 Use Figure 1-Figure 3 The reaction system shown in the figure has an outer diameter of 13 cm and a height of 50 cm for the heating shell b1. The width of the annular gap formed between the reaction shell b2 and the heating shell b1 is 2 cm. A purchased porous ceramic tube with an outer diameter of 5 cm is used as the substrate. The tube length is 40 cm. A tubular membrane assembly with a palladium-silver alloy composite membrane with a thickness of 5 μm is obtained by chemical plating. The tubular membrane assembly is installed in the reaction chamber and a graphite gasket is used to seal the upper and lower pipe openings and the connection positions with the carrying gas inlet a3 and the discharge port a4. The reaction chamber is filled with Ni / Al with a Ni content of 15 wt%. 2 O 3 Catalyst, wherein the promoter is lanthanum (1wt%), and the heating chamber is filled with Pt / Al with a Pt loading of 0.5wt% 2 O 3 Catalyst, the auxiliary agent is ruthenium (0.1wt%). Figure 3 As shown in the process, the feed amount of raw methane is 2.2Nm 3 / h, and the molar ratio of water to methane is controlled to be 3.0. The desalted water is heated to vaporization in the third heat exchanger c4 and then mixed with natural gas. The mixed raw gas is preheated to 460~468℃ in the second heat exchanger c2 and enters the reforming reaction bed. The gas volume space velocity is controlled at 1000h in terms of carbon. -1 . The gas at the outlet a2 is about 515℃, and the gas at the side outlet a4 of the membrane permeation is 420~480℃. The gas at the outlet a4 of the permeation side is cooled to 40℃ after the heat is recovered by the first heat exchanger c5, and then purified by pressure swing adsorption c7 to obtain fuel cell grade hydrogen. The reforming reaction pressure is controlled at 2.0MPa by the back pressure valve c8 on the reforming reaction side, and the pressure difference between the inside and outside of the tubular membrane assembly is controlled at about 1.0MPa by the back pressure valve c6 on the membrane separation permeation side. PSA desorption gas and high-temperature outlet gas at the outlet a2 are used as catalytic oxidation raw gas. The temperature of the reforming reaction outlet a2 is adjusted between 500~520℃ by supplementing the fuel methane feed amount. The flue gas at the catalytic oxidation outlet is used to preheat the reforming reaction raw gas. Most of the flue gas (90%) after cooling is returned to the catalytic oxidation inlet as circulating gas, and a small part is used to vaporize desalted water, and then discharged on site.

[0056] Example 2 Use Figure 1-Figure 3The reaction system shown in the figure has an outer diameter of 10 cm and a height of 50 cm. The width of the annular gap formed between the reaction shell b2 and the heating shell b1 is 4 cm. A purchased porous ceramic tube with an outer diameter of 2 cm is used as the substrate. The tube length is 40 cm. A tubular membrane assembly with a palladium-silver alloy composite membrane with a thickness of 4 μm is obtained by chemical plating. The tubular membrane assembly is installed in the reaction chamber and a graphite gasket is used to seal the upper and lower pipe openings and the connection positions with the carrying gas inlet a3 and the discharge port a4. The reaction chamber is filled with Ni / Al with a Ni content of 15 wt%. 2 O 3 Catalyst, wherein the promoter is lanthanum (1wt%), and the heating chamber is filled with Pt / Al with a Pt loading of 0.5wt% 2 O 3 Catalyst, the auxiliary agent is ruthenium (0.1wt%). Figure 3 As shown in the process, the feed amount of raw methane is 0.6Nm 3 / h, and the molar ratio of water to methane is controlled to be 3.0. The desalted water is heated to vaporization in the third heat exchanger c4 and then mixed with natural gas. The mixed raw gas is preheated to 460~468℃ in the second heat exchanger c2 and enters the reforming reaction bed. The gas volume space velocity is controlled at 1000h in terms of carbon. -1 . The gas at the outlet a2 is about 515℃, and the gas at the side outlet a4 of the membrane permeation is 420~480℃. The gas at the outlet a4 of the permeation side is cooled to 40℃ after recovering heat through the first heat exchanger c5, and then enters the pressure swing adsorption c7 for purification to obtain fuel cell grade hydrogen. The reforming reaction pressure is controlled at 2.0MPa by the back pressure valve c8 on the reforming reaction side, and the pressure difference between the inside and outside of the tubular membrane assembly is controlled at about 1.0MPa by the back pressure valve c6 on the membrane separation permeation side. PSA desorption gas and high-temperature outlet gas at the outlet a2 are used as catalytic oxidation raw gas. The temperature of the reforming reaction outlet a2 is adjusted between 500~520℃ by supplementing the fuel methane feed amount. The flue gas at the catalytic oxidation outlet is used to preheat the reforming reaction raw gas. Most of the flue gas after cooling (about 90%) is returned to the catalytic oxidation inlet as circulating gas, and a small part is used to vaporize desalted water, and then discharged on site.

[0057] Example 3 Use Figure 1-Figure 3 The reaction system shown in the figure has an outer diameter of 15 cm and a height of 40 cm for the heating shell b1. The width of the annular gap formed between the reaction shell b2 and the heating shell b1 is 3 cm. A purchased porous ceramic tube with an outer diameter of 5 cm is used as the substrate. The tube length is 40 cm. A tubular membrane assembly with a palladium-silver alloy composite membrane with a thickness of 4 μm is obtained by chemical plating. The tubular membrane assembly is installed in the reaction chamber and a graphite gasket is used to seal the upper and lower pipe openings and the connection positions with the carrying gas inlet a3 and the discharge port a4. The reaction chamber is filled with Ni / Al with a Ni content of 15 wt%. 2 O 3Catalyst, wherein the promoter is lanthanum (1wt%), and the heating chamber is filled with Pt / Al with a Pt loading of 0.5wt% 2 O 3 Catalyst, the auxiliary agent is ruthenium (0.1wt%). Figure 3 As shown in the process, the feed amount of raw methane is 1.76Nm 3 / h, and the molar ratio of water to methane is controlled to be 3.0. The desalted water is heated to vaporization in the third heat exchanger c4 and then mixed with natural gas. The mixed raw gas is preheated to 460~468℃ in the second heat exchanger c2 and enters the reforming reaction bed. The gas volume space velocity is controlled at 1000h in terms of carbon. -1 . The gas at the outlet a2 is about 515℃, and the gas at the side outlet a4 of the membrane permeation is 420~480℃. The gas at the outlet a4 of the permeation side is cooled to 40℃ after the heat is recovered by the first heat exchanger c5, and then purified by pressure swing adsorption c7 to obtain fuel cell grade hydrogen. The reforming reaction pressure is controlled at 2.0MPa by the back pressure valve c8 on the reforming reaction side, and the pressure difference between the inside and outside of the tubular membrane assembly is controlled at about 0.8MPa by the back pressure valve c6 on the membrane separation permeation side. PSA desorption gas and high-temperature outlet gas at the outlet a2 are used as catalytic oxidation raw gas. The temperature of the reforming reaction outlet a2 is adjusted between 500~520℃ by supplementing the fuel methane feed amount. The flue gas at the catalytic oxidation outlet is used to preheat the reforming reaction raw gas. Most of the flue gas (90%) after cooling is returned to the catalytic oxidation inlet as circulating gas, and a small part is used to vaporize desalted water, and then discharged on site.

[0058] Example 4 Use Figure 1-Figure 3 The reaction system shown in the figure has an outer diameter of 13 cm and a height of 50 cm for the heating shell b1. The width of the annular gap formed between the reaction shell b2 and the heating shell b1 is 2 cm. A purchased porous ceramic tube with an outer diameter of 5 cm is used as the substrate. The tube length is 40 cm. A tubular membrane assembly with a palladium-silver alloy composite membrane with a thickness of 5 μm is obtained by chemical plating. The tubular membrane assembly is installed in the reaction chamber and a graphite gasket is used to seal the upper and lower pipe openings and the connection positions with the carrying gas inlet a3 and the discharge port a4. The reaction chamber is filled with Ni / Al with a Ni content of 15 wt%. 2 O 3 Catalyst, wherein the promoter is lanthanum (1wt%), and the heating chamber is filled with Pt / Al with a Pt loading of 0.5wt% 2 O 3 Catalyst, the auxiliary agent is ruthenium (0.1wt%). Figure 3 As shown in the process, the feed amount of raw methane is 4.4Nm 3 / h, and the molar ratio of water to methane is controlled to be 3.0. The desalted water is heated to vaporization in the third heat exchanger c4 and then mixed with natural gas. The mixed raw gas is preheated to 460~468℃ in the second heat exchanger c2 and enters the reforming reaction bed. The gas volume space velocity is controlled at 2000h in terms of carbon. -1 . The gas at the outlet a2 is about 515℃, and the gas at the side outlet a4 of the membrane permeation is 420~480℃. The gas at the outlet a4 of the permeation side is cooled to 40℃ after the heat is recovered by the first heat exchanger c5, and then purified by pressure swing adsorption c7 to obtain fuel cell grade hydrogen. The reforming reaction pressure is controlled at 2.0MPa by the back pressure valve c8 on the reforming reaction side, and the pressure difference between the inside and outside of the tubular membrane assembly is controlled at about 0.8MPa by the back pressure valve c6 on the membrane separation permeation side. PSA desorption gas and high-temperature outlet gas at the outlet a2 are used as catalytic oxidation raw gas. The temperature of the reforming reaction outlet a2 is adjusted between 500~520℃ by supplementing the fuel methane feed amount. The flue gas at the catalytic oxidation outlet is used to preheat the reforming reaction raw gas. Most of the flue gas (90%) after cooling is returned to the catalytic oxidation inlet as circulating gas, and a small part is used to vaporize desalted water, and then discharged on site.

[0059] Example 5 Use Figure 1-Figure 3 The reaction system shown in the figure has an outer diameter of 13 cm and a height of 50 cm for the heating shell b1. The width of the annular gap formed between the reaction shell b2 and the heating shell b1 is 2 cm. A purchased porous ceramic tube with an outer diameter of 5 cm and a tube length of 40 cm is used. A tubular membrane assembly with a palladium-silver alloy composite membrane with a thickness of 10 μm is obtained by chemical plating. The tubular membrane assembly is installed in the reaction chamber and a graphite gasket is used to seal the upper and lower pipe openings and the connection positions with the carrying gas inlet a3 and the discharge port a4. The reaction chamber is filled with Ni / Al with a Ni content of 15 wt%. 2 O 3 Catalyst, wherein the promoter is lanthanum (1wt%), and the heating chamber is filled with Pt / Al with a Pt loading of 0.5wt% 2 O 3 Catalyst, the auxiliary agent is ruthenium (0.1wt%). Figure 3 As shown in the process, the feed amount of raw methane is 2.2Nm 3 / h, and the molar ratio of water to methane is controlled to be 3.0. The desalted water is heated to vaporization in the third heat exchanger c4 and then mixed with natural gas. The mixed raw gas is preheated to 460~468℃ in the second heat exchanger c2 and enters the reforming reaction bed. The gas volume space velocity is controlled at 1000h in terms of carbon. -1. The gas at the outlet a2 is about 515℃, and the gas at the side outlet a4 of the membrane permeation is 420~480℃. The gas at the outlet a4 of the permeation side is cooled to 40℃ after the heat is recovered by the first heat exchanger c5, and then purified by pressure swing adsorption c7 to obtain fuel cell grade hydrogen. The reforming reaction pressure is controlled at 2.0MPa by the back pressure valve c8 on the reforming reaction side, and the pressure difference between the inside and outside of the tubular membrane assembly is controlled at about 1.0MPa by the back pressure valve c6 on the membrane separation permeation side. PSA desorption gas and high-temperature outlet gas at the outlet a2 are used as catalytic oxidation raw gas. The temperature of the reforming reaction outlet a2 is adjusted between 500~520℃ by supplementing the fuel methane feed amount. The flue gas at the catalytic oxidation outlet is used to preheat the reforming reaction raw gas. Most of the flue gas (90%) after cooling is returned to the catalytic oxidation inlet as circulating gas, and a small part is used to vaporize desalted water, and then discharged on site.

[0060] Comparative Example 1 Different from Example 1, no tubular membrane assembly is used in the reactor in the process, and the reforming reaction product gas enters the PSA for purification to obtain fuel cell hydrogen after cooling. All the PSA desorbed gas is used as a catalytic oxidation raw material, which will result in excess heat supply. The reforming reaction outlet temperature is controlled by controlling the amount of desorbed gas introduced into the catalytic oxidation bed, which is consistent with Example 1, and there is no need to introduce additional fuel methane gas.

[0061] Comparative Example 2 Different from Example 1, the heating unit of the present invention is not arranged outside the reaction unit in the integrated reaction equipment c1, but traditional electric heating is used to provide heat for the reaction, and the control reaction parameters are consistent with those in Example 1.

[0062] Table 1 Comparison of energy consumption and material consumption of the embodiment and the comparative example Serial number Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Carbon volume space velocity, (h-1) 1000 1000 1000 2000 1000 1000 1000 Film thickness, (μm) 5 4 4 5 10 0 5 Pressure difference between inside and outside of membrane, (MPa) 1.0 1.0 1.2 1.2 1.0 - 1.0 Average temperature of feed inlet a1, (℃) 464 468 464 460 464 468 464 Average temperature of discharge port a2, (℃) 515 515 515 515 515 515 515 Average temperature of material outlet a6, (℃) 530 530 530 530 530 530 - Methane conversion rate, (%) 92 92.5 93 55 65 16 92 Methane consumption per cubic meter of H2 fuel 0.11 Nm3CH4 0.13 Nm3CH4 0.13 Nm3CH4 0.01 Nm3CH4 0.03 Nm3CH4 0 Nm3CH4 0.87 KWh Methane consumption per cubic meter of H2 raw material 0.29 Nm3CH4 0.28 Nm3CH4 0.28 Nm3CH4 0.49 Nm3CH4 0.41 Nm3CH4 2.51 Nm3CH4 0.29 Nm3CH4 In the embodiments of the present invention and the comparative examples, H 2 The fuel methane consumption refers to the methane fed through the heating material feed pipeline f3.

[0063] The preferred embodiments of the present invention are described in detail above in conjunction with the accompanying drawings, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various specific technical features in any appropriate manner. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations. However, these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A hydrogen production reaction system, characterized in that: The hydrogen production reaction system comprises an integrated reaction device, and the integrated reaction device (c1) comprises: A separation unit, a hydrogen production reaction unit and a heat supply unit are nested from the inside out, wherein the heat supply unit is used to provide heat for the reaction of the hydrogen production reaction unit, and the separation unit is used to separate the hydrogen-containing product after the reaction into at least two outputs.

2. The hydrogen production reaction system according to claim 1, characterized in that: The hydrogen production reaction unit comprises a reaction shell (b2) and a reaction chamber (II) formed around the reaction shell (b2); The heating unit comprises a heating shell (b1), wherein the heating shell (b1) is configured to wrap the reaction shell (b2) with a gap, wherein the gap forms a heating cavity (III) for circulating or storing a heating medium; The separation unit comprises a separation member arranged in the reaction chamber (II); and / or The material outlet (a2) of the hydrogen production reaction unit is communicated with the material inlet (a5) of the heat supply unit.

3. The hydrogen production reaction system according to claim 2, characterized in that: The separation element comprises a separation chamber (I) formed by a separation shell (b3), wherein the separation shell (b3) comprises a material having a separation function; The integrated reaction device comprises a cylindrical separation shell (b3), a cylindrical reaction shell (b2) and a cylindrical heating shell (b1) which are nested from inside to outside; Preferably, the outer diameter of the heating shell (b1) is 10-15 cm and the height is 40-60 cm; and / or The width of the annular gap formed between the reaction housing (b2) and the heating housing (b1) is preferably 1 to 5 cm, more preferably 2 to 3 cm.

4. The hydrogen production reaction system according to any one of claims 1 to 3, characterized in that: The hydrogen production reaction system comprises: A heat exchange device, used for collecting heat of the discharged material in the integrated reaction device (c1) to preheat the feed material of the integrated reaction device (c1), preferably, the hot medium channel of the heat exchange device is connected to the material outlet (a6) of the heating unit, and the cold medium channel of the heat exchange device is connected to the hydrogen production raw material feed channel of the hydrogen production reaction unit; and / or The hydrogen production reaction system comprises at least two of the integrated reaction devices (c1), and each of the integrated reaction devices (c1) is connected in series and / or in parallel; and / or The hydrogen production reaction unit is a reforming reaction unit, the heat supply unit is a catalytic oxidation reaction heat supply unit, and the separation unit is a membrane permeation separation unit.

5. The hydrogen production reaction system according to claim 4, characterized in that: The separation housing (b3) is configured as a tubular membrane assembly, and the tubular membrane assembly preferably comprises a porous tubular substrate and a membrane covering the surface of the porous tubular substrate; Preferably, the porous tubular substrate material is selected from porous ceramic or porous stainless steel; and / or Preferably, the outer diameter of the porous tubular substrate is 2 to 5 cm.

6. The hydrogen production reaction system according to claim 5, characterized in that: The film is an alloy film formed by Pd and another noble metal, and the other noble metal is preferably selected from one of gold, silver or ruthenium; and / or The film is an alloy film formed by Pd and another noble metal after chemical plating; and / or The thickness of the film is 3-10 μm, preferably 4-6 μm.

7. The hydrogen production reaction system according to claim 6, characterized in that: The hydrogen production reaction system comprises a purification device for purifying the output of the hydrogen production reaction unit or the separation unit in the integrated reaction device (c1); Preferably, the purification equipment comprises a pressure swing adsorption device (c7) connected to the discharge port (a4) of the separation unit, and the desorption gas outlet (c71) of the pressure swing adsorption device (c7) is connected to the heating chamber (III).

8. Application of the hydrogen production reaction system according to any one of claims 1 to 7 in methane hydrogen production, wherein the hydrogen production scale of the hydrogen production reaction system is 1 to 10 Nm 3 / h.

9. A method for producing hydrogen from methane, characterized in that: The method adopts the hydrogen production reaction system according to any one of claims 1 to 7, and the method comprises: A heating material is fed into the heating unit, a mixed raw material of methane and water is fed into the hydrogen production reaction unit to generate a hydrogen-containing product, and hydrogen in the hydrogen-containing product is separated by a separation unit.

10. The method according to claim 9, wherein: The molar ratio of water to methane in the mixed raw material is controlled in the range of 1:1 to 3:1, preferably 1.5:1 to 3:1; and / or The gas volume space velocity is controlled at 400~1500h-1 in terms of carbon -1 , preferably 500~1000h -1 ; and / or Methane processing capacity is 0.5~3.0Nm 3 / h, preferably 1.0~2.5Nm 3 / h; and / or The heat exchange equipment is used to preheat the hydrogen production reaction raw materials with the heat output from the heating unit; and / or The hydrogen production raw material is preheated to 400-490°C, preferably 450-485°C before entering the hydrogen production reaction unit; and / or The reaction pressure is controlled at 1.0~3.0MPa, preferably 1.6~2.0Mpa; and / or The pressure difference between the inside and outside of the separation unit is maintained at 0.5~1.5MPa, preferably 1.0~1.5MPa.

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