Methanol reforming hydrogen production equipment

Abstract

The invention provides methanol reforming hydrogen production equipment which is characterized in that liquid metal is arranged in a heat exchange cavity, a baffle is arranged in the heat exchange cavity in the vertical direction and divides the heat exchange cavity into a first area and a second area, and the upper side and the lower side of the baffle and the inner wall of the heat exchange cavity are arranged at intervals; the first heating device is arranged at the bottom of the first area; the gasification pipe and the reaction pipe are both arranged in the second area, the reaction pipe is located below the gasification pipe, the first end of the gasification pipe penetrates out of the box body and is provided with a liquid inlet, and an outlet of the gasification pipe is communicated with an inlet of the reaction pipe; the purification pipe is arranged in the first area and located above the first heating device, an outlet of the reaction pipe is communicated with an inlet of the purification pipe, and the second end of the purification pipe penetrates out of the box body and is provided with a pure hydrogen outlet. According to the technical scheme provided by the invention, the problem that the heat transfer efficiency of the methanol reforming hydrogen production equipment is affected due to the fact that mineral oil serving as a heat exchange medium is easy to deteriorate after being used for a long time in related technologies can be solved.

Description

Technical Field

[0001] The present invention relates to the technical field of methanol reforming hydrogen production equipment, and in particular to a methanol reforming hydrogen production equipment. Background Art

[0002] The safe and efficient storage of hydrogen has always been a world-class problem. Since methanol has the advantages of high hydrogen storage density (12.5wt%) and convenient storage and transportation, the use of methanol to store hydrogen has gradually become a hot spot for hydrogen storage and transportation. At present, the production of hydrogen from methanol is very mature in technology and has been widely used in chemical industry, metallurgy, electronics industry, transportation and other fields. Methanol production of hydrogen is carried out by methanol steam reforming reaction. Specifically, methanol and water vapor are subjected to gas phase catalytic reforming reaction to generate crude hydrogen under certain temperature, certain pressure and catalyst conditions. The volume content of H2 in crude hydrogen is about 65%, and the rest are impurities that need to be removed (CO, CO2, H2O, etc.). A specific purification process is used to obtain pure hydrogen gas that meets the product purity requirements from crude hydrogen.

[0003] In the related art, the methanol steam reforming hydrogen production reaction is an endothermic reaction. The methanol reforming hydrogen production device is provided with a heat transfer oil system and uses heat transfer oil as a heat exchange medium to provide the methanol reforming hydrogen production device with the heat required for the reaction process.

[0004] However, in the related art, thermal oil is generally mineral oil, which is prone to decomposition, aging and coking when used under high temperature conditions for a long time, affecting the heat transfer efficiency of the system. Summary of the invention

[0005] The present invention provides a methanol reforming hydrogen production device to solve the problem in the related art that mineral oil as a heat exchange medium is prone to deterioration after long-term use, thereby affecting the heat transfer efficiency of the methanol reforming hydrogen production device.

[0006] The present invention provides a methanol reforming hydrogen production device, which comprises: a liquid metal box, comprising a box body and a baffle, the box body having a heat exchange cavity, the heat exchange cavity being provided with liquid metal, the baffle being arranged in the heat exchange cavity along the up and down direction, the upper side and the lower side of the baffle being spaced apart from the inner wall of the heat exchange cavity, the left side and the right side of the baffle being connected to the inner wall of the heat exchange cavity, the baffle dividing the heat exchange cavity into a first area and a second area; a first heating device being arranged at the bottom of the first area; a gasification pipe being arranged in the second area, the first end of the gasification pipe passing through the box body and A liquid inlet is provided, and a gas outlet is provided at the second end of the gasification tube; a reaction tube is provided in the second area, the reaction tube is located below the gasification tube, a reaction inlet is provided at the first end of the reaction tube, a reaction outlet is provided at the second end of the reaction tube, and the gas outlet is connected to the reaction inlet; a purification tube is provided in the first area, the purification tube is located above the first heating device, a purification inlet is provided at the first end of the purification tube, the second end of the purification tube passes through the box body and is provided with a pure hydrogen outlet, an impurity gas outlet is also provided on the purification tube, and the reaction outlet is connected to the purification inlet.

[0007] Furthermore, the liquid metal box also includes a turbulent structure arranged in the heat exchange cavity.

[0008] Furthermore, the spoiler structure includes: a first driving impeller, which is arranged in the first area and drives the liquid metal in the first area to move from bottom to top; and / or a second driving impeller, which is arranged in the second area and drives the liquid metal in the second area to move from top to bottom.

[0009] Furthermore, the spoiler structure also includes at least two layers of spoiler groups arranged in the up-down direction, each layer of the spoiler structure includes at least two spoilers arranged in the left-right direction, the spoilers are arranged on the baffle, and the at least two spoilers of the spoiler group are alternately arranged with the at least two spoilers of the spoiler group located downstream thereof.

[0010] Furthermore, the first heating device includes a first heating valve, a temperature measuring component, a control component and at least two layers of first heating tubes arranged in the up and down directions, a first heating valve is arranged at the entrance of each layer of first heating tubes, the temperature measuring component is arranged between two adjacent layers of first heating tubes and above the topmost first heating tube, and the control component is respectively connected to the temperature measuring component and the first heating valve signal to control the opening size of the first heating valve according to the temperature measurement result of the temperature measuring component.

[0011] Furthermore, the methanol reforming hydrogen production equipment also includes a methanol replenishing pipe and a tail gas exhaust pipe, the first end of the methanol replenishing pipe and the first end of the tail gas exhaust pipe both pass through the box body, the second end of the methanol replenishing pipe and the impurity gas outlet are both connected to the inlet of the first heating pipe, and the outlet of the first heating pipe can be connected to the second end of the tail gas exhaust pipe.

[0012] Furthermore, the methanol reforming hydrogen production equipment also includes a second heating device, which includes a second heating valve and a second heating tube arranged in the second area and located below the reaction tube, the outlet of the first heating tube is connected to the inlet of the second heating tube, the second heating valve is arranged between the first heating tube and the second heating tube, and the outlet of the second heating tube is connected to the second end of the exhaust gas exhaust pipe.

[0013] Furthermore, the liquid level of the liquid metal is higher than the vaporization tube, the purification tube and the baffle, and there is a gap between the liquid level of the liquid metal and the top wall of the heat exchange chamber to form a gas chamber, wherein an inert gas inlet and an exhaust port connected to the gas chamber are provided at the upper end of the box body; and / or, the methanol reforming hydrogen production equipment also includes a gas pressure monitoring device arranged in the gas chamber.

[0014] Further, the purification tube includes an outer tube, an inner tube and a sealing plate, the inner tube is at least one tube that passes through the outer tube, the inner tube is made of hydrogen separation material, the purification inlet is arranged at the inlet of the inner tube, the impurity gas outlet is arranged at the outlet of the inner tube, the sealing plate is arranged at the inlet of the outer tube and is connected to the inner wall of the outer tube and the outer wall of the inner tube, the pure hydrogen outlet is arranged at the outlet of the outer tube and is located between the inner wall of the outer tube and the outer wall of the inner tube; and / or, the box body includes a box body main body and an upper cover plate detachably arranged at the upper end of the box body main body.

[0015] Furthermore, the methanol reforming hydrogen production equipment includes a plurality of reaction tubes and a plurality of purification tubes, both of which extend in the left-right direction, and the plurality of reaction tubes are arranged in an array, and the plurality of purification tubes are arranged in an array; the methanol reforming hydrogen production equipment includes at least two gasification tubes arranged in the transverse direction, and the gasification tube includes at least two gasification tube sections arranged in the up-down direction, and the gasification tube section extends in the left-right direction, and the outlet of the gasification tube section is connected with the inlet of the gasification tube section located below and adjacent to it, the liquid inlet is arranged at the inlet of the gasification tube located at the top, and the gas outlet is arranged at the outlet of the gasification tube located at the bottom; a liquid metal discharge port is arranged at the lower end of the box body; and the box body is made of stainless steel.

[0016] By applying the technical solution of the present invention, a methanol reforming hydrogen production equipment comprises a liquid metal box, a first heating device, a gasification tube, a reaction tube and a purification tube. During the use of the methanol reforming hydrogen production equipment, the first heating device is used to heat the liquid metal in the heat exchange chamber, and the liquid metal in the heat exchange chamber is used as the heat exchange medium of the methanol reforming hydrogen production equipment. A mixture of liquid methanol and water is input from a liquid inlet to the gasification tube, and the liquid metal in the heat exchange chamber is used to heat the gasification tube, so that the liquid methanol and water mixture is gasified in the gasification tube, and the gas outlet outputs the gaseous methanol and water mixture, and the gaseous methanol and water mixture enters the reaction inlet, and the liquid metal in the heat exchange chamber is used to heat the reaction tube, so that the gaseous methanol and water mixture undergoes a reforming reaction, and the reaction outlet outputs a reforming reaction product, and the reforming reaction product enters the purification inlet, and the liquid metal in the heat exchange chamber is used to heat the purification tube, so that the pure hydrogen outlet of the purification tube outputs pure hydrogen, and the impurity gas outlet of the purification tube outputs purified tail gas. Among them, the liquid metal in the heat exchange chamber is used as the heat exchange medium of the methanol reforming hydrogen production equipment. Compared with the use of heat transfer oil as the heat exchange medium of the methanol reforming hydrogen production equipment, the use of liquid metal as the heat exchange medium can avoid the problem of over-temperature aging or coking failure of the heat exchange medium, avoid the deterioration of the heat exchange medium, and ensure the heat transfer efficiency of the methanol reforming hydrogen production equipment. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The drawings constituting a part of the present application are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0018] Figure 1 A cross-sectional view of a methanol reforming hydrogen production device provided according to an embodiment of the present invention is shown;

[0019] Figure 2 A cross-sectional view from another perspective of a methanol reforming hydrogen production device provided in accordance with an embodiment of the present invention is shown;

[0020] Figure 3 A cross-sectional view from another perspective of the methanol reforming hydrogen production equipment provided according to an embodiment of the present invention is shown.

[0021] The above drawings include the following reference numerals:

[0022] 10. Liquid metal box; 11. Box body; 111. Heat exchange chamber; 1111. Liquid metal; 1112. First area; 1113. Second area; 1114. Gas chamber; 12. Baffle;

[0023] 20. first heating device; 21. first heating pipe; 211. first heating branch pipe; 2111. heating pipe section;

[0024] 30. Gasification pipe; 31. Liquid inlet; 32. Gas outlet; 33. Gasification pipe section;

[0025] 40. reaction tube; 41. reaction inlet; 42. reaction outlet;

[0026] 50. Purification tube; 51. Purification inlet; 52. Pure hydrogen outlet; 53. Impurity gas outlet; 54. Outer tube; 55. Inner tube; 56. Sealing plate;

[0027] 60. spoiler structure; 61. first driving impeller; 62. second driving impeller; 63. spoiler set; 631. spoiler;

[0028] 80. Exhaust gas discharge pipe;

[0029] 90. Second heating device; 92. Second heating tube; 921. Second heating branch tube. DETAILED DESCRIPTION

[0030] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is by no means intended to limit the present invention and its application or use. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0031] like Figures 1 to 3As shown, an embodiment of the present invention provides a methanol reforming hydrogen production device, which includes a liquid metal box 10, a first heating device 20, a vaporization tube 30, a reaction tube 40 and a purification tube 50. The liquid metal box 10 includes a box body 11 and a baffle 12. The box body 11 has a heat exchange cavity 111, and liquid metal 1111 is arranged in the heat exchange cavity 111. The baffle 12 is arranged in the heat exchange cavity 111 along the up and down direction. The upper side and the lower side of the baffle 12 are both spaced from the inner wall of the heat exchange cavity 111, and the left side and the right side of the baffle 12 are connected to the inner wall of the heat exchange cavity 111. The baffle 12 divides the heat exchange cavity 111 into a first area 1112 and a second area 1113. The first heating device 20 is arranged at the bottom of the first area 1112, and the vaporization tube 30 is arranged at the bottom of the second area In the domain 1113, the first end of the gasification tube 30 passes through the box body 11 and is provided with a liquid inlet 31, and the second end of the gasification tube 30 is provided with a gas outlet 32. The reaction tube 40 is arranged in the second area 1113, the reaction tube 40 is located below the gasification tube 30, the first end of the reaction tube 40 is provided with a reaction inlet 41, the second end of the reaction tube 40 is provided with a reaction outlet 42, and the gas outlet 32 ​​is connected to the reaction inlet 41. The purification tube 50 is arranged in the first area 1112, the purification tube 50 is located above the first heating device 20, the first end of the purification tube 50 is provided with a purification inlet 51, the second end of the purification tube 50 passes through the box body 11 and is provided with a pure hydrogen outlet 52, the purification tube 50 is also provided with an impurity gas outlet 53, and the reaction outlet 42 is connected to the purification inlet 51.

[0032] The methanol reforming hydrogen production equipment provided in this embodiment is applied. During the use of the methanol reforming hydrogen production equipment, the first heating device 20 is used to heat the liquid metal 1111 in the heat exchange chamber 111, and the liquid metal 1111 in the heat exchange chamber 111 is used as the heat exchange medium of the methanol reforming hydrogen production equipment. The mixture of liquid methanol and water is input from the liquid inlet 31 to the gasification tube 30, and the liquid metal 1111 in the heat exchange chamber 111 is used to heat the gasification tube 30, so that the mixture of liquid methanol and water is gasified in the gasification tube 30, and the gas is discharged. Port 32 outputs a gaseous mixture of methanol and water, which enters the reaction inlet 41, and the liquid metal 1111 in the heat exchange chamber 111 is used to heat the reaction tube 40, so that the gaseous mixture of methanol and water undergoes a reforming reaction, and the reaction outlet 42 outputs the reforming reaction product, which enters the purification inlet 51, and the liquid metal 1111 in the heat exchange chamber 111 is used to heat the purification tube 50, so that the pure hydrogen outlet 52 of the purification tube 50 outputs pure hydrogen, and the impurity gas outlet 53 of the purification tube 50 outputs purified tail gas. Among them, the liquid metal 1111 in the heat exchange chamber 111 is used as the heat exchange medium of the methanol reforming hydrogen production equipment. Since the liquid metal 1111 has the advantages of good thermal conductivity and stable performance, compared with using heat transfer oil as the heat exchange medium of the methanol reforming hydrogen production equipment, the liquid metal 1111 is used as the heat exchange medium to avoid the problems of over-temperature aging or coking failure of the heat exchange medium, avoid the deterioration of the heat exchange medium, and do not need regular cleaning to reduce the operation and maintenance cost, thereby ensuring the heat transfer efficiency of the methanol reforming hydrogen production equipment.

[0033] The gasification tube 30 and the reaction tube 40 are both arranged in the second area 1113, and the reaction tube 40 is located below the gasification tube 30. Since the heat absorbed by the gasification of the mixture of liquid methanol and water is lower than the heat absorbed by the reforming reaction of the mixture of gaseous methanol and water, the pressure difference formed by the temperature difference and density difference of the liquid metal 1111 in different areas can be used to drive the liquid metal 1111 in the second area 1113 to move downward, and since the upper and lower sides of the baffle 12 are in contact with the exchange The inner walls of the heat chamber 111 are arranged at intervals so that the liquid metal 1111 in the first area 1112 is connected with the liquid metal 1111 in the second area 1113. The movement of the liquid metal 1111 in the second area 1113 is used to move the liquid metal 1111 in the first area 1112 upward, thereby making full use of the pressure difference formed by the temperature difference and density difference of the liquid metal 1111 in different areas to drive the liquid metal 1111 to circulate autonomously, thereby improving the temperature uniformity in the heat exchange chamber 111.

[0034] Furthermore, since the purification temperature required for the purification tube 50 to purify the reforming reaction product is greater than the vaporization temperature required for the vaporization of the liquid methanol and water mixture and the reaction temperature required for the reforming reaction of the gaseous methanol and water mixture, the first heating device 20 is arranged at the bottom of the first area 1112, and the purification tube 50 is arranged in the first area 1112 and located above the first heating device 20, so that the purification tube 50 first contacts the liquid metal 1111 with the highest temperature in the heat exchange chamber 111, thereby meeting the use requirements of the purification tube 50.

[0035] Specifically, the first heating device 20 heats the liquid metal 1111 in the heat exchange chamber 111, and the liquid metal 1111 flows upward and contacts the purification tube 50, maintaining the high temperature environment in the area where the purification tube 50 is located. After that, the liquid metal 1111 goes over the upper side of the baffle 12 and enters the second area 1113, and the liquid metal 1111 contacts the gasification tube 30. The liquid metal 1111 provides heat for gasifying the liquid methanol and water mixture in the gasification tube 30, and the temperature of the liquid metal 1111 is reduced. The temperature of the liquid metal 1111 continues to decrease, and the density of the liquid metal 1111 continues to increase. The liquid metal 1111 flows downward, and contacts the reaction tube 40. The liquid metal 1111 provides heat for the reforming reaction of the gaseous methanol and water mixture in the reaction tube 40. The temperature of the liquid metal 1111 continues to decrease, and the density continues to increase. The liquid metal 1111 goes over the lower side of the baffle 12 and enters the first area 1112. The liquid metal 1111 contacts the first heating device 20 again, and the liquid metal 1111 absorbs the heat provided by the first heating device 20.

[0036] It should be noted that the gas outlet 32 ​​is connected to the reaction inlet 41 , and the reaction outlet 42 is connected to the purification inlet 51 . The two pipelines can be connected from outside the box 11 or inside the box 11 .

[0037] It should be noted that the impurity gas outlet 53 can be located outside the box 11 or inside the box 11. When the impurity gas outlet 53 is located inside the box 11, the impurity gas outlet 53 can be connected to the first heating device 20, and the purified tail gas discharged from the impurity gas outlet 53 is burned in the first heating device 20 to provide heat. When the impurity gas outlet 53 is located outside the box 11, the impurity gas outlet 53 can be connected to the first heating device 20, and the purified tail gas discharged from the impurity gas outlet 53 is burned in the first heating device 20 to provide heat, or the impurity gas outlet 53 can be connected to the tail gas treatment structure.

[0038] like Figures 1 to 3 As shown, the liquid metal box 10 further includes a spoiler structure 60 disposed in the heat exchange cavity 111. The spoiler structure 60 disposed in the heat exchange cavity 111 is used to improve the fluidity of the liquid metal 1111 in the heat exchange cavity 111 and improve the temperature uniformity in the heat exchange cavity 111.

[0039] like Figures 1 to 3 As shown, the spoiler structure 60 includes a first driving impeller 61 and a second driving impeller 62. The first driving impeller 61 is arranged in the first area 1112 and drives the liquid metal 1111 in the first area 1112 to move from bottom to top. The second driving impeller 62 is arranged in the second area 1113 and drives the liquid metal 1111 in the second area 1113 to move from top to bottom. Thus, the flow rate of the liquid metal 1111 in the first area 1112 and the second area 1113 is increased by using the first driving impeller 61 and the second driving impeller 62 rotating at a low speed.

[0040] like Figure 2 and Figure 3 As shown, the spoiler structure 60 further includes at least two layers of spoiler plates 63 arranged in the up-down direction, each layer of the spoiler structure 60 includes at least two spoilers 631 arranged in the left-right direction, the spoilers 631 are arranged on the baffle 12, and the at least two spoilers 631 of the spoiler plate group 63 are staggered with the at least two spoilers 631 of the spoiler plate group 63 located downstream thereof. Since the at least two spoilers 631 of the spoiler plate group 63 are staggered with the at least two spoilers 631 of the spoiler plate group 63 located downstream thereof, when the liquid metal 1111 flows in the heat exchange chamber 111, the liquid metal 1111 can be diverted and mixed by the spoiler effect of at least two layers of spoiler plates 63, so that the temperature of the liquid metal 1111 is more uniform, and the problem of the catalyst agglomeration and deactivation in the reaction tube 40 caused by the concentration of cold and heat in the reaction tube 40 is avoided, thereby extending the life of the reaction tube 40 and improving the performance of the reaction tube 40.

[0041] Specifically, the front and rear surfaces of the baffle 12 are both provided with spoiler groups 63, and the front and rear surfaces are both provided with spoiler groups 63. The spoiler groups 63 arranged on the front surface of the baffle 12 and the spoiler groups 63 arranged on the rear surface of the baffle 12 may be at the same height.

[0042] like Figure 2As shown, the first heating device 20 includes a first heating valve, a temperature measuring component, a control component, and at least two layers of first heating tubes 21 arranged in the vertical direction. A first heating valve is provided at the entrance of each layer of first heating tubes 21. The temperature measuring component is provided between two adjacent layers of first heating tubes 21 and above the top first heating tube 21. The control component is respectively connected to the temperature measuring component and the first heating valve signal to control the opening size of the first heating valve according to the temperature measurement result of the temperature measuring component. The above structure can be used to control at least two layers of first heating tubes 21 in layers. According to the temperature of the liquid metal 1111 above each layer of first heating tubes 21, the opening size of the first heating valve at the entrance of the first heating tube 21 of the layer is adjusted. If the temperature of the liquid metal 1111 above the first heating tube 21 does not meet the equipment requirements, the opening size of the first heating valve at the entrance of the first heating tube 21 of the layer is increased until the temperature of the liquid metal 1111 above the first heating tube 21 meets the equipment requirements.

[0043] It should be noted that the first heating tube 21 may include at least two first heating branch tubes 211 connected in series, and the first heating tube 21 may also include at least two first heating branch tubes 211 connected in parallel.

[0044] Wherein, when the first heating pipe 21 includes at least two first heating branch pipes 211 connected in parallel, the first heating branch pipe 211 includes at least two heating pipe sections 2111 arranged in the up-down direction, the heating pipe section 2111 extends in the left-right direction, and the outlet of the heating pipe section 2111 is connected to the inlet of the heating pipe section 2111 located below and adjacent to it. The first heating branch pipe 211 with the above structure can fully utilize the first heating branch pipe 211 to heat the liquid metal.

[0045] like Figure 3 As shown, the methanol reforming hydrogen production equipment further includes a methanol supplementary pipe and an exhaust gas discharge pipe 80. The first end of the methanol supplementary pipe and the first end of the exhaust gas discharge pipe 80 both pass through the housing 11. The second end of the methanol supplementary pipe and the impurity gas outlet 53 are both connected to the inlet of the first heating pipe 21. The outlet of the first heating pipe 21 can be connected to the second end of the exhaust gas discharge pipe 80. The purified exhaust gas discharged from the impurity gas outlet 53 is burned in the first heating pipe 21 to provide heat, and the methanol supplementary pipe is used to supplement fuel for the first heating pipe 21. The exhaust gas discharge pipe 80 is used to discharge the combustion exhaust gas generated at the outlet of the first heating pipe 21.

[0046] like Figure 1 and Figure 2As shown, the methanol reforming hydrogen production equipment further includes a second heating device 90, the second heating device 90 includes a second heating valve and a second heating tube 92 arranged in the second area 1113 and located below the reaction tube 40, the outlet of the first heating tube 21 is connected to the inlet of the second heating tube 92, the second heating valve is arranged between the first heating tube 21 and the second heating tube 92, and the outlet of the second heating tube 92 is connected to the second end of the tail gas exhaust pipe 80. When the methanol reforming hydrogen production equipment is started at low temperature, the first heating valve and the second heating valve are opened, and the solid liquid metal in the heat exchange chamber 111 is heated and melted by the first heating tube 21 and the second heating tube 92 at the same time. During the use of the methanol reforming hydrogen production equipment, the second heating valve is closed, and the liquid metal 1111 in the heat exchange chamber 111 is heated only by the first heating device 20, so as to avoid the second heating device 90 interfering with the flow of the liquid metal in the heat exchange chamber 111.

[0047] like Figure 1 As shown, the liquid level of the liquid metal 1111 is higher than the vaporization tube 30, the purification tube 50 and the baffle 12, and there is a gap between the liquid level of the liquid metal 1111 and the top wall of the heat exchange chamber 111 to form a gas chamber 1114, wherein the upper end of the box body 11 is provided with an inert gas inlet and an exhaust port connected to the gas chamber 1114. Protective gas (such as nitrogen, argon, etc.) is filled into the gas chamber 1114 through the inert gas inlet, and air is exhausted through the exhaust port, so that the gas chamber 1114 forms an oxygen-free atmosphere to prevent the liquid metal from being oxidized.

[0048] Furthermore, the gas cavity 1114 is used to absorb the volume expansion and contraction of the liquid metal 1111 during the temperature increase and decrease process.

[0049] In this embodiment, the methanol reforming hydrogen production equipment further includes a gas pressure monitoring component disposed in the gas chamber 1114. The gas pressure monitoring component is used to detect the gas pressure of the gas chamber 1114 to improve the safety of the equipment.

[0050] like Figure 2As shown, the purification tube 50 includes an outer tube 54, an inner tube 55 and a sealing plate 56. The inner tube 55 is at least one tube that penetrates the outer tube 54. The inner tube 55 is made of hydrogen separation material. The purification inlet 51 is arranged at the inlet of the inner tube 55. The impurity gas outlet 53 is arranged at the outlet of the inner tube 55. The sealing plate 56 is arranged at the inlet of the outer tube 54 and connected to the inner wall of the outer tube 54 and the outer wall of the inner tube 55. The pure hydrogen outlet 52 is arranged at the outlet of the outer tube 54 and located between the inner wall of the outer tube 54 and the outer wall of the inner tube 55. The reforming reaction product is introduced into the purification inlet 51 at the inlet of the inner tube 55, and the hydrogen molecules enter the interlayer between the inner tube 55 and the outer tube 54 through the tube wall of the inner tube 55. The pure hydrogen is discharged from the pure hydrogen outlet 52 arranged at the outlet of the outer tube 54 and located between the inner wall of the outer tube 54 and the outer wall of the inner tube 55, and the purified tail gas is discharged from the impurity gas outlet 53 arranged at the outlet of the inner tube 55. It should be noted that the tube wall of the inner tube 55 only allows hydrogen molecules to pass through and intercepts other impurity gases. This inner tube belongs to the prior art in this field.

[0051] It should be noted that the hydrogen separation material includes materials such as metal palladium, palladium alloy or niobium-based alloy.

[0052] In this embodiment, the box body 11 includes a box body and an upper cover plate detachably arranged on the upper end of the box body. By opening the upper cover plate, liquid metal can be filled into the heat exchange cavity 111, and the liquid metal in solid form can be filled at this time.

[0053] like Figure 1 As shown, the methanol reforming hydrogen production equipment includes a plurality of reaction tubes 40 and a plurality of purification tubes 50, both of which extend in the left-right direction, and the plurality of reaction tubes 40 are arranged in an array, and the plurality of purification tubes 50 are arranged in an array. The plurality of reaction tubes 40 and the plurality of purification tubes 50 of the above structure can improve the efficiency of the methanol reforming hydrogen production equipment in reforming the mixture of gaseous methanol and water and the efficiency of purifying the reforming reaction product.

[0054] like Figure 1 and Figure 3 As shown, the methanol reforming hydrogen production equipment includes at least two gasification pipes 30 arranged in the transverse direction, and the gasification pipe 30 includes at least two gasification pipe sections 33 arranged in the up-down direction, and the gasification pipe section 33 extends in the left-right direction. The outlet of the gasification pipe section 33 is connected with the inlet of the gasification pipe section 33 located below and adjacent to it, and the liquid inlet 31 is arranged at the inlet of the gasification pipe 30 located at the top, and the gas outlet 32 ​​is arranged at the outlet of the gasification pipe section 33 located at the bottom. The gasification pipe 30 with the above structure can fully gasify the liquid methanol and water mixture in the gasification pipe 30, and can also improve the gasification efficiency of the methanol reforming hydrogen production equipment for the liquid methanol and water mixture.

[0055] In this embodiment, a liquid metal discharge port is provided at the lower end of the box body 11. By opening the liquid metal discharge port, the liquid metal 1111 can be discharged, which is convenient for equipment maintenance and replacement of liquid metal.

[0056] In this embodiment, the box body 11 is made of stainless steel.

[0057] In this embodiment, the reaction tube 40 is filled with a copper-zinc-aluminum catalyst, and the copper-zinc-aluminum catalyst is in the shape of spherical particles or honeycomb columns. The copper-zinc-aluminum catalyst is doped with a precious metal (one of palladium or platinum) with a content of less than 0.1% (wt%) to improve the high-temperature stability of the copper-zinc-aluminum catalyst. The first heating tube 21 and the second heating tube 92 are both filled with a precious metal catalyst, and the active component of the precious metal catalyst is one of palladium or platinum, and the precious metal catalyst is in the shape of spherical particles or honeycomb columns.

[0058] In this embodiment, the liquid metal 1111 is a lead-bismuth alloy (melting point is about 125° C.), wherein the bismuth content is between 48% (at%) and 63% (at%), and the volume of the liquid metal 1111 is 0.3 m 3 The length and height of the box body 11 are both 1 m, the height of the box body 11 is 0.5 m, and the height of the gas chamber 14 is 0.05 m.

[0059] In this embodiment, the working temperature of the liquid metal 1111 is 300-350°C, the working pressure of the liquid metal 1111 is normal pressure, the maximum working temperature of the first heating device 20 and the second heating device 90 is 400°C, and the working pressure of the first heating device 20 and the second heating device 90 is normal pressure. The working pressure of the inner tube 55, the vaporization tube 30 and the reaction tube 40 is 2.0MPa, the working pressure of the interlayer between the inner tube 55 and the outer tube 54 is 1.0MPa, the diameters of the purification tube 50, the vaporization tube 30, the first heating tube 21 and the second heating tube 92 are all 40mm, and the diameter of the reaction tube 40 is 30mm.

[0060] In this embodiment, there are 40 purification tubes 50, which are arranged in an array of 10 layers and 4 columns. There are 40 reaction tubes 40, which are arranged in an array of 8 layers and 5 columns. There are 20 gasification tubes 30, which are arranged in an array of 5 layers and 4 columns. There are 3 first driving impellers 61 and 3 second driving impellers 62 arranged in the left-right direction. There are 4 layers of first heating tubes 21, and each layer of first heating tubes 21 includes 4 first heating branch tubes 211. There is 1 layer of second heating tubes 92, and each layer of second heating tubes 92 includes 4 second heating branch tubes 921.

[0061] The methanol reforming hydrogen production equipment provided in this embodiment has the following beneficial effects:

[0062] (1) Liquid metal 1111 in heat exchange chamber 111 is used as heat exchange medium of methanol reforming hydrogen production equipment. Liquid metal 1111 has the advantages of good thermal conductivity and stable performance. Compared with using heat transfer oil as heat exchange medium of methanol reforming hydrogen production equipment, using liquid metal 1111 as heat exchange medium can avoid the problem of over-temperature aging or coking failure of heat exchange medium, avoid deterioration of heat exchange medium, and reduce operation and maintenance costs without regular cleaning, thereby ensuring the heat transfer efficiency of methanol reforming hydrogen production equipment;

[0063] (2) Compared with using heat transfer oil as the heat exchange medium of methanol reforming hydrogen production equipment, liquid metal 1111 is used as the heat exchange medium, and the first heating device 20, the gasification tube 30, the reaction tube 40 and the purification tube 50 are all tubular structures and are arranged in the same box 11. The overall structure is simple and compact, easy to process and manufacture, and suitable for small distributed and mobile hydrogen production and supply scenarios;

[0064] (3) The baffle plate 12 is used to separate the heat exchange chamber 111 into a first area 1112 and a second area 1113, and combined with the arrangement positions of the first heating device 20, the gasification tube 30, the reaction tube 40 and the purification tube 50, a pressure difference is formed, so that the liquid metal can circulate naturally, thereby improving the temperature uniformity in the heat exchange chamber 111.

[0065] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present application. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, it indicates the presence of features, steps, operations, devices, components and / or combinations thereof.

[0066] Unless otherwise specifically stated, the relative arrangement, numerical expressions and numerical values ​​of the parts and steps set forth in these embodiments do not limit the scope of the present invention. Meanwhile, it should be understood that, for ease of description, the sizes of the various parts shown in the accompanying drawings are not drawn according to the actual proportional relationship. The technology, method and equipment known to those of ordinary skill in the relevant art may not be discussed in detail, but in appropriate cases, the technology, method and equipment should be considered as a part of the specification. In all examples shown and discussed here, any specific value should be interpreted as being merely exemplary, rather than as a limitation. Therefore, other examples of exemplary embodiments may have different values. It should be noted that similar reference numerals and letters represent similar items in the following drawings, and therefore, once a certain item is defined in an accompanying drawing, it does not need to be further discussed in subsequent drawings.

[0067] In the description of the present invention, it is necessary to understand that the directions or positional relationships indicated by directional words such as "front, back, up, down, left, right", "lateral, up and down, vertical, horizontal" and "top, bottom" are usually based on the directions or positional relationships shown in the drawings. They are only for the convenience of describing the present invention and simplifying the description. Unless otherwise specified, these directional words do not indicate or imply that the devices or elements referred to must have a specific direction or be constructed and operated in a specific direction. Therefore, they cannot be understood as limiting the scope of protection of the present invention. The directional words "inside and outside" refer to the inside and outside relative to the contours of each component itself.

[0068] For ease of description, spatially relative terms such as "above", "above", "on the upper surface of", "above", etc. may be used here to describe the spatial positional relationship between a device or feature and other devices or features as shown in the figure. It should be understood that spatially relative terms are intended to include different orientations of the device in use or operation in addition to the orientation described in the figure. For example, if the device in the accompanying drawings is inverted, the device described as "above other devices or structures" or "above other devices or structures" will be positioned as "below other devices or structures" or "below other devices or structures". Thus, the exemplary term "above" can include both "above" and "below". The device can also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatially relative descriptions used here are interpreted accordingly.

[0069] In addition, it should be noted that the use of terms such as "first" and "second" to limit components is only for the convenience of distinguishing the corresponding components. If not otherwise stated, the above terms have no special meaning and therefore cannot be understood as limiting the scope of protection of the present invention.

[0070] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A methanol reforming hydrogen production equipment, characterized in that: The methanol reforming hydrogen production equipment comprises: A liquid metal box (10) comprises a box body (11) and a baffle (12), wherein the box body (11) has a heat exchange cavity (111), liquid metal (1111) is arranged in the heat exchange cavity (111), the baffle (12) is arranged in the heat exchange cavity (111) along the up and down direction, the upper side and the lower side of the baffle (12) are both spaced apart from the inner wall of the heat exchange cavity (111), the left side and the right side of the baffle (12) are both connected to the inner wall of the heat exchange cavity (111), and the baffle (12) divides the heat exchange cavity (111) into a first area (1112) and a second area (1113); A first heating device (20) is arranged at the bottom of the first area (1112); a gasification pipe (30) disposed in the second area (1113); a first end of the gasification pipe (30) passing through the box body (11) and provided with a liquid inlet (31); and a second end of the gasification pipe (30) provided with a gas outlet (32); a reaction tube (40) disposed in the second area (1113), the reaction tube (40) being located below the gasification tube (30), a reaction inlet (41) being disposed at a first end of the reaction tube (40), a reaction outlet (42) being disposed at a second end of the reaction tube (40), and the gas outlet (32) being connected to the reaction inlet (41); A purification tube (50) is arranged in the first area (1112). The purification tube (50) is located above the first heating device (20). A purification inlet (51) is arranged at the first end of the purification tube (50). The second end of the purification tube (50) passes through the box (11) and is provided with a pure hydrogen outlet (52). An impurity gas outlet (53) is also arranged on the purification tube (50). The reaction outlet (42) is connected to the purification inlet (51).

2. The methanol reforming hydrogen production equipment according to claim 1, characterized in that: The liquid metal box (10) further comprises a flow disturbance structure (60) arranged in the heat exchange cavity (111).

3. The methanol reforming hydrogen production equipment according to claim 2, characterized in that: The spoiler structure (60) comprises: a first driving impeller (61), disposed in the first region (1112) and driving the liquid metal (1111) in the first region (1112) to move from bottom to top; and / or, A second driving impeller (62) is disposed in the second region (1113) and drives the liquid metal (1111) in the second region (1113) to move from top to bottom.

4. The methanol reforming hydrogen production equipment according to claim 2, characterized in that: The spoiler structure (60) further comprises at least two layers of spoiler panels (63) arranged in the up-down direction, each layer of the spoiler structure (60) comprises at least two spoilers (631) arranged in the left-right direction, the spoilers (631) being arranged on the baffle (12), and the at least two spoilers (631) of the spoiler panel group (63) being arranged alternately with the at least two spoilers (631) of the spoiler panel group (63) located downstream thereof.

5. The methanol reforming hydrogen production equipment according to claim 1, characterized in that: The first heating device (20) comprises a first heating valve, a temperature measuring component, a control component and at least two layers of first heating tubes (21) arranged in the up-down direction, a first heating valve is arranged at the entrance of each layer of the first heating tubes (21), the temperature measuring component is arranged between two adjacent layers of the first heating tubes (21) and above the topmost first heating tube (21), and the control component is respectively connected to the temperature measuring component and the first heating valve signal to control the opening size of the first heating valve according to the temperature measurement result of the temperature measuring component.

6. The methanol reforming hydrogen production equipment according to claim 5, characterized in that: The methanol reforming hydrogen production equipment also includes a methanol replenishing pipe and an exhaust gas exhaust pipe (80), the first end of the methanol replenishing pipe and the first end of the exhaust gas exhaust pipe (80) both pass through the box (11), the second end of the methanol replenishing pipe and the impurity gas outlet (53) are both connected to the inlet of the first heating pipe (21), and the outlet of the first heating pipe (21) can be connected to the second end of the exhaust gas exhaust pipe (80).

7. The methanol reforming hydrogen production equipment according to claim 6, characterized in that: The methanol reforming hydrogen production equipment also includes a second heating device (90), the second heating device (90) includes a second heating valve and a second heating tube (92) arranged in the second area (1113) and located below the reaction tube (40), the outlet of the first heating tube (21) is connected to the inlet of the second heating tube (92), the second heating valve is arranged between the first heating tube (21) and the second heating tube (92), and the outlet of the second heating tube (92) is connected to the second end of the exhaust gas exhaust pipe (80).

8. The methanol reforming hydrogen production equipment according to any one of claims 1 to 7, characterized in that: The liquid level of the liquid metal (1111) is higher than the vaporization tube (30), the purification tube (50) and the baffle (12); a gap is formed between the liquid level of the liquid metal (1111) and the top wall of the heat exchange chamber (111) to form a gas chamber (1114); Wherein, the upper end of the box body (11) is provided with an inert gas inlet and an exhaust port which are connected to the gas chamber (1114); and / or, The methanol reforming hydrogen production equipment also includes a gas pressure monitoring component arranged in the gas chamber (1114).

9. The methanol reforming hydrogen production equipment according to any one of claims 1 to 7, characterized in that: The purification tube (50) comprises an outer tube (54), an inner tube (55) and a sealing plate (56); the inner tube (55) is at least one tube penetrating the outer tube (54); the inner tube (55) is made of a hydrogen separation material; the purification inlet (51) is arranged at the inlet of the inner tube (55); the impurity gas outlet (53) is arranged at the outlet of the inner tube (55); the sealing plate (56) is arranged at the inlet of the outer tube (54) and connected to the inner wall of the outer tube (54) and the outer wall of the inner tube (55); the pure hydrogen outlet (52) is arranged at the outlet of the outer tube (54) and located between the inner wall of the outer tube (54) and the outer wall of the inner tube (55); and / or, The box body (11) comprises a box body main body and an upper cover plate detachably arranged on the upper end of the box body main body.

10. The methanol reforming hydrogen production equipment according to any one of claims 1 to 7, characterized in that: The methanol reforming hydrogen production equipment comprises a plurality of the reaction tubes (40) and a plurality of the purification tubes (50), the reaction tubes (40) and the purification tubes (50) both extend in the left-right direction, the plurality of the reaction tubes (40) are arranged in an array, and the plurality of the purification tubes (50) are arranged in an array; The methanol reforming hydrogen production equipment comprises at least two gasification pipes (30) arranged in a transverse direction, the gasification pipe (30) comprises at least two gasification pipe sections (33) arranged in the up-down direction, the gasification pipe section (33) extends in the left-right direction, the outlet of the gasification pipe section (33) is connected to the inlet of the gasification pipe section (33) located below and adjacent to the gasification pipe section (33), the liquid inlet (31) is arranged at the inlet of the gasification pipe (30) located at the top, and the gas outlet (32) is arranged at the outlet of the gasification pipe (30) located at the bottom; The lower end of the box body (11) is provided with a liquid metal discharge port; The box body (11) is made of stainless steel.

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