Integrated device for catalytic reforming of methanol steam
By designing an integrated device that combines the key equipment of the methanol steam reforming system, the problem of large independent footprint of individual equipment is solved, and the system is made more compact and methanol is removed more efficiently.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- SICHUAN CHUANGDA XINNENG TECH CO LTD
- Filing Date
- 2025-06-17
- Publication Date
- 2026-06-16
AI Technical Summary
Existing methanol steam catalytic reforming systems are independent and occupy a large area, lacking integrated design.
Design an integrated device including a shell and a first tube extending axially. The shell is divided into a first heat exchange chamber and a water washing chamber. The first tube passes through the heat exchange chamber and the water washing chamber. The catalyst reacts in the first tube. The converted gas contacts demineralized water in the water washing chamber to remove methanol. The device integrates a vaporizer, a superheater, a reactor, and a water washing tower.
This invention achieves a compact methanol steam reforming system, reduces floor space, effectively removes methanol from the reforming gas, and improves system integration and methanol removal efficiency.
Smart Images
Figure CN224358405U_ABST
Abstract
Description
Technical Field
[0001] This utility model relates to the field of methanol-to-hydrogen technology, and in particular to an integrated device for methanol steam catalytic reforming. Background Technology
[0002] A methanol steam catalytic reforming system typically comprises several interconnected devices, such as a vaporizer, superheater, reactor, heat exchanger, water cooler, and water scrubbing tower. The feedstock for this hydrogen production system includes methanol and demineralized water (dissolved from the methanol in the reformed gas) in the water scrubbing tower. After vaporization in the vaporizer, the feedstock is further heated in the superheater before entering the reactor for methanol steam reforming. The resulting reformed gas contains H2, CO2, CO, H2O, and trace amounts of methanol. After cooling, the reformed gas enters the water scrubbing tower, where the demineralized water dissolves and removes methanol from the reformed gas. These devices in a methanol steam reforming hydrogen production system are usually independent and require a large floor space. Utility Model Content
[0003] To solve the above-mentioned technical problems, this utility model provides an integrated device for methanol vapor catalytic reforming.
[0004] This disclosed integrated apparatus for methanol vapor catalytic reforming includes a housing and a plurality of first tubes extending axially within the housing. The housing is at least divided into a first heat exchange chamber and a water washing chamber arranged axially. The first heat exchange chamber contains a heat-conducting medium, and the water washing chamber contains demineralized water. The first tubes extend through the first heat exchange chamber and into the water washing chamber. A catalyst is disposed within the section of the first tube located in the first heat exchange chamber. The catalyst is used for the methanol vapor catalytic reforming reaction, and the heat-conducting medium provides heat for the catalytic reforming reaction. The first tubes are in fluid communication with the water washing chamber, allowing the reformed gas generated by the catalytic reforming reaction to pass through the demineralized water in the water washing chamber to remove methanol before flowing out of the integrated apparatus. The demineralized water containing dissolved methanol serves as part of the feedstock for the catalytic reforming reaction.
[0005] Optionally, the washing chamber is equipped with at least one packing material selected from Pall rings and step rings to assist in the removal of methanol from the converted gas. Optionally, the flow path of the converted gas in the demineralized water is not less than 20 cm.
[0006] Optionally, the feedstock for the catalytic reforming reaction also includes additional methanol. The first heat exchange chamber is also provided with several second tubes extending axially along the shell. The feedstock for the catalytic reforming reaction flows through the second tubes to absorb heat before entering the first tube for the catalytic reforming reaction.
[0007] Optionally, the cavity divided by the shell further includes a communicating cavity, which is located on one side of the first heat exchange cavity and away from the water washing cavity, and the second tube communicates with the first tube through the communicating cavity. Preferably, the shell includes a large-diameter portion and a small-diameter portion, a plurality of second tubes are disposed in the large-diameter portion, and the plurality of second tubes are disposed on the outer periphery of a plurality of first tubes. Further, the cavity divided by the shell further includes a second heat exchange cavity, which is located on one side of the first heat exchange cavity and close to the water washing cavity, and the second heat exchange cavity is in fluid communication with the second tube, and the first tube also extends through the second heat exchange cavity. Wherein, the shell further includes a transition section disposed between the large-diameter portion and the small-diameter portion, the second heat exchange cavity is defined at least by the transition section and a portion of the small-diameter portion adjacent to the transition section, and the first tube also extends through the second heat exchange cavity, the feedstock for the catalytic reforming reaction flows through the second heat exchange cavity, absorbs heat from the conversion gas and enters the second tube. Optionally, the cavity divided by the shell further includes a third heat exchange cavity, which is located between the second heat exchange cavity and the water washing cavity, and the first tube also extends through the third heat exchange cavity. The third heat exchange chamber is used to contain circulating water for cooling the converted gas.
[0008] Optionally, the heat transfer medium is heat transfer oil. A baffle is provided in the first heat exchange cavity to increase the flow path of the heat transfer oil. The portion of the shell that defines the first heat exchange cavity is provided with a heat transfer medium inlet and a heat transfer medium outlet. The heat transfer medium inlet is located in the upper part of the first heat exchange cavity, and the heat transfer medium outlet is located in the lower part of the first heat exchange cavity.
[0009] Optionally, at least one of the first heat exchange chamber, the second heat exchange chamber, and the third heat exchange chamber is provided with a baffle plate arranged along the axial direction, which is used to increase the flow path of the medium in the chamber.
[0010] The features and advantages of this disclosure include:
[0011] The integrated device for methanol vapor catalytic reforming disclosed herein has a compact structure. By setting a first heat exchange chamber in the upper part of the integrated device and a water washing chamber in the lower part, multiple devices (or units) for the methanol vapor reforming hydrogen production system can be integrated into one unit, reducing the floor space required. Through a reasonable structural arrangement, the methanol-to-water conversion gas unit, such as the vaporizer, superheater, reactor, cooler, and water washing tower, can be integrated into the integrated device. In the lower part of the integrated device, the converted gas is introduced into the demineralized water stored in the water washing chamber, where the methanol in the converted gas is removed by dissolution, and the remaining poorly soluble gases such as H2, CO2, and CO float to the upper part of the water washing chamber and are discharged. This part has a simple structure and good formaldehyde removal effect. In addition, in the integrated device with a third heat exchange chamber, the temperature of the downward flowing converted gas gradually decreases, and the water vapor in the converted gas gradually condenses into liquid water, which can flow downward and collect in the water washing chamber, serving as a feedstock along with the demineralized water. Attached Figure Description
[0012] To more clearly illustrate the technical solutions in the embodiments of this disclosure, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this disclosure. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0013] Figure 1 A schematic diagram of the integrated apparatus and hydrogen production system for methanol vapor catalytic reforming disclosed herein is shown.
[0014] Figure 2 A schematic diagram is shown showing the first, second, and third pipelines of the hydrogen production system disclosed herein, in which analytical devices, flow meters, etc. are installed.
[0015] Explanation of reference numerals in the attached figures:
[0016] 100 - Integrated device, 101 - Heat transfer medium inlet, 102 - Heat transfer medium outlet, 103 - Demineralized water inlet, 104 - Demineralized water outlet, 105 - Converted gas outlet, 107 - Raw material inlet, 108 - Circulating water inlet, 109 - Circulating water outlet;
[0017] 10-Shell, 11-Large diameter section, 12-Small diameter section, 13-Transition section;
[0018] 21-First partition, 22-Spacer ring, 23-Second partition, 24-Third partition, 25-Fourth partition;
[0019] 31-First heat exchange chamber, 32-Water washing chamber, 33-Connecting chamber, 34-Second heat exchange chamber, 35-Third heat exchange chamber;
[0020] 41 - First tube, 42 - Second tube;
[0021] 51-Baffle plate;
[0022] 200-Hydrogen production system, 201-Heat transfer oil, 202-Desalinated water, 203-Converted gas, 204-Circulating water, 205-New methanol, 206-Circulating liquid, 207-Raw material;
[0023] 211-First pipeline, 212-Second pipeline, 213-Third pipeline, 214-First pump, 215-Second pump, 216-Regulating valve, 217-Buffer tank;
[0024] 221-First flow meter, 222-First analysis device, 223-Second flow meter, 224-Second analysis device. Detailed Implementation
[0025] The technical solutions of the embodiments of this disclosure will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this disclosure, and not all of them. Based on the embodiments of this disclosure, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this disclosure.
[0026] In describing this invention, when one or more components are described as being connected, linked, fixed, coupled, attached, or otherwise interconnected, such interconnection may be a direct interconnection between components or an indirect interconnection, such as by using one or more intermediate components.
[0027] refer to Figure 1 This disclosure provides an integrated apparatus 100 for methanol vapor catalytic reforming, and a methanol vapor reforming hydrogen production system 200 including the integrated apparatus 100. The integrated apparatus 100 includes a housing 10 and a plurality of first pipes 41 disposed within the housing and extending axially along the housing. In use of the integrated apparatus and the hydrogen production system, the axial direction of the housing specifically refers to the height direction. The integrated apparatus 100 also includes at least one partition, dividing the housing 10 into at least an axially arranged first heat exchange chamber 31 and a water washing chamber 32, with the first pipes 41 extending through the first heat exchange chamber 31 and extending to the water washing chamber 32. The water washing chamber 32 is located downstream of the first heat exchange chamber 31 along the flow direction of the reformed gas. The first heat exchange chamber 31 is used to contain a heat-conducting medium, and the water washing chamber 32 is used to contain demineralized water.
[0028] The first tube 41, located within the first heat exchange chamber 31, houses a catalyst used for the catalytic reforming reaction of methanol vapor. The heat transfer medium provides heat for the catalytic reforming reaction. The first tube 41 is in fluid communication with the water washing chamber 32, allowing the reformed gas generated in the reforming reaction to pass through the demineralized water in the water washing chamber 32 to remove methanol before exiting the integrated device 100. The demineralized water containing dissolved methanol flowing out of the water washing chamber 32 serves as part of the raw material for the reforming reaction.
[0029] Specifically, see Figure 1 The portion of the housing 10 that defines the first heat exchange chamber 31 is provided with a heat transfer medium inlet 101 and a heat transfer medium outlet 102. Preferably, the heat transfer medium inlet 101 is located away from the water washing chamber 32, while the heat transfer medium outlet 102 is located close to the water washing chamber 32. Specifically, the heat transfer medium is flue gas, heat transfer oil, etc., and heat transfer oil 201 will be used as an example for the following description.
[0030] Specifically, see [link to relevant documentation] Figure 1The portion of the shell 10 defining the washing chamber 32 is provided with a demineralized water inlet 103, a demineralized water outlet 104, and a converted gas outlet 105. Preferably, the demineralized water inlet 103 is located at the upper part of the washing chamber 32, the demineralized water outlet 104 is located at the bottom of the washing chamber 32, and the converted gas outlet 105 is located at the upper part of the washing chamber 32. More preferably, the position of the converted gas outlet 105 is higher than the position of the demineralized water inlet 103. A first pipe 41 can extend to the bottom of the washing chamber 32, and both ends of the first pipe 41 are provided with openings. The converted gas after the reaction flows out from the bottom opening of the first pipe 41 and enters the demineralized water in the washing chamber 32. During the upward floating process, the converted gas comes into full contact with the demineralized water, which can dissolve and remove methanol in the converted gas. The converted gas floats and accumulates at the top of the washing chamber 32, and then flows out of the washing chamber 32 from the converted gas outlet 105. There are no specific requirements for the position of the demineralized water liquid level, as long as it is lower than the converted gas outlet 105. Preferably, the position of the demineralized water liquid level is lower than the demineralized water inlet 103. The conversion gas outlet of the first pipe 41 is located at its bottom end or side wall. When using the integrated device 100, the conversion gas outlet of the first pipe 41 is submerged in demineralized water. Preferably, the flow path of the conversion gas in the demineralized water is not less than 20 cm to ensure that the methanol in the conversion gas is fully dissolved in the demineralized water. Preferably, a level gauge can be installed to monitor the depth of the demineralized water to ensure that the methanol in the conversion gas is fully dissolved. Preferably, the conversion gas outlet of the first pipe 41 is kept at a certain distance from the bottom of the washing chamber, for example, 20 cm, to prevent the conversion gas from flowing away from the demineralized water outlet 104. Optionally, several small holes can be opened on the side wall of the first pipe 41 near the bottom. These small holes can be immersed in the demineralized water to facilitate the diffusion of the conversion gas from the small holes to the surrounding area, increase the contact area with the demineralized water, and reduce the gas flow velocity at the end, further preventing the conversion gas from flowing away from the demineralized water outlet 104.
[0031] In some embodiments, the washing chamber 32 is further provided with packing material to assist in the removal of methanol from the converted gas. Specifically, at least one packing material such as Pall rings or step rings can be used. By providing a large, constantly renewed gas-liquid contact surface in the washing chamber, the packing material can greatly accelerate the rate and efficiency of methanol dissolving from the gas phase to the aqueous phase (deionized water).
[0032] In the integrated device 100 disclosed herein, the section of the first pipe 41 located in the first heat exchange chamber 31, the first heat exchange chamber, and the heat exchange medium belong to the reactor unit of the hydrogen production system. The section of the first pipe 41 located in the water washing chamber 32, the water washing chamber 32, and the demineralized water belong to the demineralized water washing unit of the hydrogen production system (functionally similar to a water washing tower). That is, the integrated device 100 integrates the reactor and water washing tower of the hydrogen production system, making the hydrogen production system more compact and saving floor space. Furthermore, the lower part of the integrated device 100 introduces the converted gas into the demineralized water stored in the water washing chamber, thereby removing methanol from the converted gas through dissolution. The remaining undissolved gases such as H2, CO2, and CO float to the upper part of the water washing chamber and are discharged. This part has a simple structure and good formaldehyde removal effect.
[0033] Specifically, the feedstock for the reforming reaction also includes newly added methanol. The demineralized water containing dissolved methanol flowing out of the water washing chamber 32, along with the newly added methanol 205, serves as the feedstock for the reforming reaction. In some embodiments, the first heat exchange chamber 31 is further provided with several second pipes 42 extending axially along the shell, where the demineralized water containing dissolved methanol and the newly added methanol 205 serve as feedstock 207 (see...). Figure 2 After absorbing heat through the second pipe 42, the feedstock 207 enters the first pipe 41 for reforming reaction. When the feedstock 207 passes through the section of the second pipe 42 located in the first heat exchange chamber 31, it can absorb heat from the heat transfer oil, so that the feedstock 207 flowing out of the second pipe 42 reaches the temperature of 240-280°C required for catalytic reforming reaction.
[0034] Optionally, the integrated device 100 includes a plurality of partitions, the number of which may be two, three, or four. The cavity of the housing 10 separated by the plurality of partitions may also include any one, two, or three of the following: a connecting cavity 33, a second heat exchange cavity 34, and a third heat exchange cavity 35.
[0035] Specifically, in Figure 1 In the illustrated embodiment, the cavity divided by the housing 10 further includes a communicating cavity 33, which is disposed on the side of the first heat exchange cavity 31 away from the water washing cavity 32. The second pipe 42 is connected to the first pipe 41 through the communicating cavity 33. Preferably, a plurality of second pipes 42 are disposed on the outer periphery of a plurality of first pipes 41.
[0036] Specifically, see Figure 1The shell 10 is constructed in a cylindrical shape. A connecting cavity 33, a first heat exchange cavity 31, and a water washing cavity 32 are sequentially arranged axially from top to bottom within the shell 10. Specifically, the connecting cavity 33 is located at the top of the shell 10, the water washing cavity 32 is located at the bottom of the shell 10, and the first heat exchange cavity 31 is located between the connecting cavity 33 and the water washing cavity 32. Preferably, the shell 10 includes a large-diameter portion 11 and a small-diameter portion 12. A plurality of second pipes 42 are disposed in the large-diameter portion 11, and the water washing cavity 32 is located in the small-diameter portion. Specifically, a first partition 21 is provided near the top end of the large-diameter portion 11. The upper side of the first partition 21 is the connecting cavity 33, and the lower side of the first partition 21 is the first heat exchange cavity 31.
[0037] Optionally, in some embodiments, the partitioned cavity of the housing 10 further includes a second heat exchange cavity 34, which is disposed on the side of the first heat exchange cavity 31 near the water washing cavity 32 (i.e., the lower side of the first heat exchange cavity 31), and the second heat exchange cavity 34 is in fluid communication with the second pipe 42. The first pipe 41 also extends through the second heat exchange cavity 34, and the housing 10 is provided with a raw material inlet 107 in fluid communication with the second heat exchange cavity 34. In some embodiments, when the demineralized water containing dissolved methanol and the newly added methanol flow through the second heat exchange cavity 34 as raw materials, they absorb heat from the conversion gas flowing through the first pipe 41 and are converted into gaseous methanol and water vapor. The gaseous methanol and water vapor flow into the second pipe 42 and absorb heat again from the heat transfer oil to achieve superheating and temperature rise. In other embodiments, when the raw material flows through the second heat exchange chamber 34, it absorbs heat from the conversion gas flowing through the first pipe 41 and is preheated. The preheated raw material then flows upward along the second pipe 42, absorbing heat from the heat transfer oil, causing it to change from a liquid to a gaseous state (i.e., gaseous methanol and water vapor). The gaseous methanol and water vapor continue to absorb heat from the heat transfer oil, achieving superheating before flowing out of the second pipe 42. The heat transfer oil 201 enters the first heat exchange chamber from the heat transfer medium inlet 101. The flow direction of the heat transfer oil 201 is opposite to that of the raw material in the second pipe 42, which facilitates heat exchange between the heat transfer oil and the raw material. Furthermore, the temperature of the heat transfer oil decreases as it flows through the first chamber, thus allowing the heat transfer oil to continuously heat the upward-flowing raw material, causing it to vaporize and superheat to meet the requirements of subsequent reactions. Additionally, the superheated gaseous methanol and water vapor enter the first pipe 41 and flow downward, absorbing heat from the heat transfer oil and undergoing a catalytic reforming reaction under the action of a catalyst. Specifically, this catalytic reforming reaction includes a methanol cracking reaction and a water-gas shift reaction. Since the heat absorbed by the methanol cracking reaction is greater than the heat released by the water-gas shift reaction, the catalytic reforming reaction is, overall, an endothermic reaction.
[0038] Preferably, the raw material inlet 107 is located at the lower part of the second heat exchange chamber 34, which is conducive to the convection of the raw material in the second heat exchange chamber 34 and the conversion gas in the first pipe 41 to achieve sufficient heat exchange.
[0039] Specifically, a second partition 23 is provided inside the casing 10. The upper side of the second partition 23 is the first heat exchange chamber 31, and the lower side of the second partition 23 is the second heat exchange chamber 34. Optionally, the second partition 23 is located in the large-diameter portion 11, and the second heat exchange chamber 34 extends from the large-diameter portion 11 to the small-diameter portion 12. See also... Figure 1 The housing 10 further includes a transition section 13 disposed between the large-diameter portion 11 and the small-diameter portion 12, and the second heat exchange cavity 34 is defined at least by the transition section and a portion of the small-diameter portion adjacent to the transition section. In some embodiments, the second heat exchange cavity 34 is defined by the transition section, a portion of the large-diameter portion adjacent to the transition section, and a portion of the small-diameter portion.
[0040] By configuring the shell 10 into a large-diameter section 11, a transition section 13, and a small-diameter section 12, the integrated device 100 can save shell material and reduce material costs while meeting usage requirements. The transition section 13 in the shell 10 facilitates the smooth guidance of the reforming reaction feedstock to the second tube and further reduces shell material requirements.
[0041] Optionally, the lower end of the second tube 42 may extend to the second heat exchange chamber 34, and the upper end of the second tube 42 may extend to the connecting chamber 33. The upper end of the first tube may also extend to the connecting chamber 33; no specific limitation is made here. Preferably, the second tube 42 is only provided in the first heat exchange chamber 31, that is, one end of the second tube 42 extends to the first partition 21, and the other end extends to the second partition 23. Preferably, the upper end of the first tube 41 extends to the first partition 21, and a partition ring 22 is provided on the upper side of the first partition 21. The partition ring 22 is used to guide the raw material into the first tube 41. Specifically, the partition ring 22 may be constructed as a column or a cone.
[0042] Optionally, in some embodiments, the cavity divided by the housing 10 further includes a third heat exchange cavity 35, which is located between the second heat exchange cavity 34 and the water washing cavity 32, and the first pipe 41 extends through the third heat exchange cavity 35. Specifically, the small-diameter portion 12 is provided with a third partition 24 and a fourth partition 25 along the axial direction. The second heat exchange cavity 34 is located above the third partition 24, and the third heat exchange cavity 35 is located between the third partition 24 and the fourth partition 25. The water washing cavity 32 is located below the fourth partition 25. The portion of the small-diameter portion 12 that restricts the third heat exchange cavity 35 (i.e., the sidewall of the third heat exchange cavity 35) is provided with a circulating water inlet 108 and a circulating water outlet 109. Circulating water enters the third heat exchange cavity 35 from the circulating water inlet 108, absorbs the heat of the converted gas in the first pipe 41, and then flows out from the circulating water outlet 109. The converted gas is cooled down and then enters the water washing cavity. Preferably, along the flow direction of the converted gas, the circulating water inlet 108 is located downstream of the circulating water outlet 109, which is beneficial for convective heat transfer.
[0043] Optionally, in some embodiments, baffles 51 may be provided inside one, two, or all three of the first heat exchange cavity 31, the second heat exchange cavity 34, and the third heat exchange cavity 35 to increase the flow path of the fluid inside the cavity and facilitate sufficient heat exchange. Specifically, the baffles 51 in the first heat exchange cavity 31, the second heat exchange cavity 34, and the third heat exchange cavity 35 may be arranged axially.
[0044] When the integrated device 100 of this disclosure is equipped with a second heat exchange chamber 34, the raw material can be heated by high-temperature reformed gas, which is beneficial for both system energy recovery and reducing the temperature of the reformed gas. When the integrated device 100 is equipped with a third heat exchange chamber, the reformed gas can be directly cooled by circulating water, allowing the cooled reformed gas to directly enter the water washing chamber. The integrated device 100 of this disclosure has a compact structure. By setting the first heat exchange chamber at its upper part and the water washing chamber at its lower part, multiple devices used in the methanol steam reforming hydrogen production system can be integrated, reducing the floor space required. Through a reasonable structural arrangement, the vaporizer, superheater, reactor, cooler, and methanol removal unit are integrated into the integrated device 100.
[0045] See also Figure 1 The hydrogen production system 200 also includes a first pipeline 211, a second pipeline 212, and a third pipeline 213. The first pipeline 211 is used to transport demineralized water containing dissolved methanol flowing from the washing chamber 32; the second pipeline 212 is used to transport newly added methanol 205; and the third pipeline 213, connected to the first and second pipelines, is used to transport the newly added methanol 205 and the demineralized water containing dissolved methanol together to the second heat exchange chamber 34. Specifically, one end of each of the three pipelines is connected: the other end of the first pipeline 211 is connected to the demineralized water outlet 104, and the other end of the third pipeline 213 is connected to the raw material inlet 107. More specifically, the first pipeline 211 is equipped with a first pump 214, and the second pipeline 212 is equipped with a second pump 215.
[0046] The following is combined with Figure 1The following describes the methanol steam reforming process for hydrogen production in the hydrogen production system 200. Demineralized water 203 enters the water washing chamber 32 through the demineralized water inlet 103, and the demineralized water 203 stored in the water washing chamber 32 is maintained at a certain liquid level. Demineralized water containing methanol dissolved in the converted gas flows out of the water washing chamber 32 through the demineralized water outlet 104, and enters the third pipeline 213 under pressure from the first pump 214 via the first pipeline 211. Newly added methanol 205 enters the third pipeline 213 under pressure from the second pump 215 via the second pipeline 212. The newly added methanol 205 and the demineralized water containing dissolved methanol are mixed in the third pipeline 213 as feedstock for hydrogen production, and then enter the second heat exchange chamber 34 through the feedstock inlet 107. After absorbing heat from the converted gas in the first pipe 41, it vaporizes and enters the second pipe 42. After vaporization, the raw material continues to absorb heat from the heat transfer oil in the second pipe 42, and enters the first pipe 41 through the connecting cavity 33. Under the action of the catalyst and absorbing heat from the heat transfer oil, it undergoes a methanol vapor reforming reaction, generating H2, CO2, and a trace amount of CO gas. The generated gas contains unreacted H2O and a small amount of methanol, forming the reformed gas. The high-temperature reformed gas flows downward along the first pipe 41. When it flows through the second heat exchange cavity 34, part of the heat of the reformed gas is recovered and reused for heating the raw material. When it flows through the third heat exchange cavity 35, the circulating water absorbs the heat in the reformed gas, cooling it to the target value. Specifically, the target value ranges from 30 to 45°C. The cooled reformed gas continues to flow to the water washing cavity 32, where it dissolves and removes methanol in the demineralized water, then floats and accumulates at the top of the water washing cavity. The methanol-removed reformed gas 203 flows out from the reformed gas outlet 105.
[0047] In the integrated device 100 equipped with a third heat exchange chamber 35, the temperature of the downward-flowing conversion gas gradually decreases, and the liquid water that is gradually condensed from the water vapor in the conversion gas can flow downward and collect in the water washing chamber, and be used as raw material along with the demineralized water.
[0048] It should be noted that, in some embodiments, the third heat exchange chamber 35 of the integrated device 100 in the hydrogen production system 200 is not essential. The integrated device 100 includes a housing 10, a plurality of first pipes 41 and a plurality of second pipes 42, the first pipes 41 and the second pipes 42 being in fluid communication and extending axially within the housing 10. The first pipes 41 and the second pipes 42 are connected not only through a connecting cavity 33, but also through pipes or the like. The housing 10 is at least divided into a first heat exchange chamber 31, a second heat exchange chamber 34 and a water washing chamber 32 arranged sequentially along the axial direction. The first heat exchange chamber 31 is used to contain a heat-conducting medium, the second heat exchange chamber 34 is used to contain raw materials for the reforming reaction, and the water washing chamber 32 is used to contain demineralized water. The first pipes 41 extend through the first heat exchange chambers 31 and 34 to the water washing chamber 32; the second pipes 42 are disposed within the first heat exchange chamber 31 and are in communication with the second heat exchange chamber 34. The first pipe 41, located within the first heat exchange chamber 31, houses a catalyst used for methanol vapor reforming. The heat transfer medium provides heat for the reforming reaction and the raw material flowing through the second pipe 42. The portion of the shell 10 defining the water washing chamber 32 includes a demineralized water inlet 103, a demineralized water outlet 104, and a converted gas outlet 105. The portion of the shell 10 defining the second heat exchange chamber 34 includes a raw material inlet 107. The two ends of the first pipeline 211 are connected to the demineralized water outlet 104 and the third pipeline 213, respectively. The second pipeline 212 is connected to the third pipeline 213, which is also connected to the raw material inlet 107. The first pipe 41 is in fluid communication with the water washing chamber 32, allowing the converted gas generated from the reforming reaction to pass through the demineralized water in the water washing chamber to remove methanol before flowing out of the integrated device from the converted gas outlet 105. The demineralized water containing dissolved methanol, transported by the first pipeline 211, and the newly added methanol, transported by the second pipeline 212, serve as raw materials entering the second heat exchange chamber 34 via the third pipeline 213.
[0049] The hydrogen production system 200 disclosed herein can be equipped with three pipelines to transport demineralized water containing dissolved methanol and newly added methanol as raw materials for reforming reaction to the integrated unit 100 for reforming reaction, thus simplifying the pipeline setup.
[0050] See Figure 2 For ease of description, the demineralized water containing dissolved methanol flowing out of the washing chamber 32 is referred to as circulating liquid 206, and the mixture of circulating liquid 206 and newly added methanol 205 is referred to as raw material 207. In some embodiments, the hydrogen production system 200 of this disclosure further includes a first analysis device 221 disposed on the third pipeline 213 and a regulating valve 216 disposed on the second pipeline 212. The concentration of raw material 207 can be obtained through the first analysis device 221, and the regulating valve 216 is used to regulate the flow rate of newly added methanol 205. During the operation of the hydrogen production system 200, the methanol concentration of raw material 207 can be adjusted to the target methanol concentration value by adjusting the regulating valve 216. By setting the first analysis device 221 and the regulating valve 216, the hydrogen production system 200 can automatically batch the raw materials.
[0051] Optionally, the second pipeline 212 is also equipped with a first flow meter 222, which measures the flow rate of newly added methanol 205 entering the hydrogen production system 200. During the adjustment process, the flow rate of newly added methanol 205 entering the system can be measured from the first flow meter 222, which is beneficial for quickly feeding back the opening of the regulating valve 216 and facilitating the control of the methanol concentration of the raw material.
[0052] In the hydrogen production system 200, some methanol in the feedstock 207 entering the first pipe 41 is unreacted, and the amount of unreacted methanol fluctuates with the reaction temperature, meaning the methanol concentration in the circulating liquid 206 fluctuates with the reaction temperature. To maintain system stability, the methanol concentration in the feedstock 207 entering the system is kept constant. Since the concentration of newly added methanol 205 is constant, the amount of newly added methanol 205 required by the system needs to be dynamically adjusted according to the methanol concentration in the circulating liquid 206.
[0053] See also Figure 2 Optionally, in some embodiments, the hydrogen production system 200 of this disclosure further includes a second analysis device 223 and a second flow meter 224 disposed on the first pipeline 211. The methanol concentration in the circulating liquid 206 can be obtained through the second analysis device 223, and the flow meter 224 can measure the flow rate of the circulating liquid 206 entering the hydrogen production system 200. The hydrogen production system 200 obtains the methanol concentration in the circulating liquid 206 from the second analysis device 223, obtains the flow rate of the circulating liquid 206 from the second flow meter 224, and calculates the required flow rate of the additional methanol 205 based on the target value of the methanol concentration of the raw material 207, the methanol concentration of the circulating liquid 206, and the flow rate, thereby adjusting the regulating valve 216 so that the methanol concentration of the raw material 207 measured by the first analysis device 221 is the target value of the methanol concentration.
[0054] Optionally, in some embodiments, the second pipeline 212 may be equipped with a third analysis device (not shown in the figure), from which the concentration of the newly added methanol 205 can be obtained, which can further improve the methanol concentration control accuracy of the system feedstock 207.
[0055] Specifically, the first analytical device 221, the second analytical device 223, and the third analytical device can be configured as concentration meters, allowing the hydrogen production system 200 to directly obtain the concentrations of the corresponding liquids from these devices, namely, the concentrations of the feed liquid 207, the circulating liquid 206, and the newly added methanol 205. Alternatively, the first analytical device 221, the second analytical device 223, and the third analytical device can be configured as density meters, allowing the hydrogen production system 200 to indirectly obtain the liquid concentration by obtaining the liquid density. In some embodiments, the second analytical device 223 and the second metering device 224 are provided by mass flow meters.
[0056] Preferably, in some embodiments, a buffer tank 217 is also provided on the third pipeline 213. The circulating liquid 206 and the newly added methanol 205 flow into the buffer tank 217, mix, and then flow into the second heat exchange chamber 34. The buffer tank 217 facilitates the uniform mixing of the circulating liquid 206 and the newly added methanol 205, which is beneficial for subsequent reactions. Specifically, along the flow direction of the raw material 207, the mixing tank 217 is located upstream of the first analytical device 221.
[0057] The above descriptions are merely a few embodiments of this disclosure. Those skilled in the art can make various modifications or variations to the embodiments of this disclosure based on the content disclosed in the application documents without departing from the spirit and scope of this disclosure.
Claims
1. An integrated unit for methanol steam catalytic reforming, characterized in that, include: The housing and a plurality of first tubes disposed within the housing and extending axially along the housing, the housing being at least divided into a first heat exchange chamber and a water washing chamber arranged axially, the first heat exchange chamber being used to contain a heat-conducting medium, the water washing chamber being used to contain demineralized water, and the first tubes extending through the first heat exchange chamber and extending into the water washing chamber. The first tube is equipped with a catalyst in the tube section located in the first heat exchange chamber. The catalyst is used for methanol vapor catalytic reforming reaction, and the heat transfer medium provides heat for the catalytic reforming reaction. The first tube is in fluid communication with the water washing chamber, so that the converted gas generated by the catalytic reforming reaction is demineralized in the water washing chamber to remove methanol before flowing out of the integrated device. And the desalinated water containing dissolved methanol is used as part of the raw material for the catalytic reforming reaction.
2. The integrated device according to claim 1, characterized in that, The washing chamber is equipped with at least one packing material, namely Pall rings and step rings, to assist in the removal of methanol from the conversion gas.
3. The integrated device according to claim 1, characterized in that, The flow path of the converted gas in the demineralized water is not less than 20 cm.
4. The integrated device according to claim 3, characterized in that, The feedstock for the catalytic reforming reaction also includes newly added methanol. The first heat exchange chamber is also provided with several second tubes extending axially along the shell. The feedstock for the catalytic reforming reaction flows through the second tubes to absorb heat before entering the first tube for the catalytic reforming reaction.
5. The integrated device according to claim 4, characterized in that, The cavity divided by the housing also includes a connecting cavity, which is located on one side of the first heat exchange cavity and away from the water washing cavity, and the second pipe is connected to the first pipe through the connecting cavity.
6. The integrated device according to claim 5, characterized in that, The housing includes a large-diameter portion and a small-diameter portion, the plurality of second tubes are disposed in the large-diameter portion, and the plurality of second tubes are disposed on the outer periphery of the plurality of first tubes.
7. The integrated device according to claim 6, characterized in that, The cavity divided by the housing also includes a second heat exchange cavity, which is disposed on one side of the first heat exchange cavity and close to the water washing cavity. The second heat exchange cavity is in fluid communication with the second pipe, and the first pipe also extends through the second heat exchange cavity. The housing further includes a transition section disposed between the large-diameter portion and the small-diameter portion. The second heat exchange chamber is defined at least by the transition section and a portion of the small-diameter portion adjacent to the transition section. The first tube also extends through the second heat exchange chamber. The feedstock for the catalytic reforming reaction flows through the second heat exchange chamber and enters the second tube after absorbing heat from the conversion gas.
8. The integrated device according to claim 7, characterized in that, The cavity divided by the housing also includes a third heat exchange cavity, which is located between the second heat exchange cavity and the water washing cavity, and the first tube extends through the third heat exchange cavity; The third heat exchange chamber is used to contain circulating water for cooling the converted gas.
9. The integrated device according to any one of claims 1 to 8, characterized in that, The heat transfer medium is heat transfer oil. A baffle plate is provided in the first heat exchange cavity to increase the flow path of the heat transfer oil. The portion of the shell that defines the first heat exchange cavity is provided with a heat transfer medium inlet and a heat transfer medium outlet. The heat transfer medium inlet is located in the upper part of the first heat exchange cavity, and the heat transfer medium outlet is located in the lower part of the first heat exchange cavity.
10. The integrated device according to any one of claims 1 to 8, characterized in that, At least one of the first heat exchange cavity, the second heat exchange cavity, and the third heat exchange cavity is provided with a baffle plate arranged along the axial direction, which is used to increase the flow path of the medium in the cavity.