CN118387835A - Tandem reforming conversion hydrogen production device and reforming conversion hydrogen production method - Google Patents
Tandem reforming conversion hydrogen production device and reforming conversion hydrogen production method Download PDFInfo
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- CN118387835A CN118387835A CN202410367673.4A CN202410367673A CN118387835A CN 118387835 A CN118387835 A CN 118387835A CN 202410367673 A CN202410367673 A CN 202410367673A CN 118387835 A CN118387835 A CN 118387835A
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- 238000002407 reforming Methods 0.000 title claims abstract description 118
- 239000001257 hydrogen Substances 0.000 title claims abstract description 89
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 89
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 228
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 121
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims description 74
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
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- 239000000203 mixture Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910014779 CaAl4 Inorganic materials 0.000 claims description 3
- 229910003303 NiAl2O4 Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910001650 dmitryivanovite Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
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- 229910001707 krotite Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 abstract description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 238000000629 steam reforming Methods 0.000 description 9
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- 238000005984 hydrogenation reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 229910000480 nickel oxide Inorganic materials 0.000 description 1
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- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention relates to the technical field of reforming hydrogen production, in particular to a serial reforming shift hydrogen production device which comprises a steam generator, and a gas mixing valve, a reforming reactor, a heat exchanger, a high-temperature water gas shift reactor, a low-temperature water gas shift reactor and a draught fan which are sequentially communicated. The reforming reactor, the high-temperature water gas shift reactor and the low-temperature water gas shift reactor are cylindrical reactors; the cylindrical reactor comprises an outer cylinder vertically arranged, an inner cylinder vertically arranged in the outer cylinder, an electric heater arranged in the inner cylinder and an annular separation net horizontally arranged outside the inner cylinder. In addition, the invention also relates to a reforming conversion hydrogen production method. The invention provides the surplus energy of the high-temperature reforming gas and water gas shift reactor to the reforming reactor and the steam generator through the heat exchanger, improves the utilization rate of energy, and has the advantages of high raw material treatment efficiency, high space utilization rate, stable operation, easy maintenance and the like.
Description
Technical Field
The invention relates to the technical field of reforming hydrogen production, in particular to a serial reforming conversion hydrogen production device and a reforming conversion hydrogen production method.
Background
Along with the rapid promotion of the urban and industrialized progress of China, the demand of energy sources for China society is rapidly increased. The hydrogen energy has the advantages of high heat value, zero emission, reproducibility, wide sources and the like, and plays a key role in the process of changing the energy production mode and the consumption mode thereof and in the process of converting the traditional energy structure into the new energy structure.
Methane reforming is an important source of hydrogen energy. Methane is also a greenhouse gas, and after reforming, methane is converted into synthesis gas hydrogen gas, so that clean utilization of methane gas can be realized, and the synthesis gas can be further used for Fischer-Tropsch synthesis for synthesizing methanol or other organic compounds. In various utilization modes of methane, the methane steam reforming process is mature, has long history and wide application in the field of chemical synthesis, and is a main mode of industrial hydrogen production at present. Steam reforming of methane is currently used as a means of methane conversion for large-scale applications, which not only converts methane into synthesis gas for hydrogen production, but also provides a rich raw material for downstream industrial production.
Wherein, the catalytic reforming reaction in the methane steam reforming reactor is mainly as follows:
the water gas shift reaction is a typical plant for a methane steam reforming process, with the aim of eliminating CO and also increasing the yield of hydrogen, and occurs as follows:
catalytic reforming and water gas shift processes are the core processes in methane reforming shift hydrogen production processes. At present, a fixed bed reaction chamber is mostly adopted in a methane steam reforming device, and a catalytic device is relatively simple, so that the problems of more energy consumption, lower hydrogen yield and the like exist. Moreover, the temperature required for the water gas shift reaction is lower than that required for the reforming reaction, and the large temperature difference in the two processes easily causes a great deal of heat waste.
Chinese patent CN1 616343a discloses a detachable sample plate type reforming hydrogen production reactor, which belongs to a fixed bed structure, and aims to improve the problem of uneven temperature distribution of a reaction chamber, the problem of space of a reaction system and the problem of heat transfer resistance by combining a plurality of different cavities, thereby improving the reaction efficiency and the reaction selectivity. The device has compact structure, can meet the requirement of small-scale hydrogen production, but the internal space of the reaction chamber main body is relatively narrow, the internal structure of the reaction chamber is complex, and the manufacturing and maintenance cost is higher.
Chinese patent CN11 2607705A discloses a hydrogen production device by steam methane reforming and a process, the device connects a hydrodesulfurization device, a reaction chamber for hydrogen production by steam methane reforming, a low-temperature steam shift reaction chamber, a separator and a pressure swing adsorption device in turn, which improves the efficiency of the hydrogen production device by reforming, but the channel design of the reaction chamber is complicated, the applicability of the reaction chamber to different raw gases is poor, the loading of reforming catalyst is complex, and the equipment maintenance and guarantee are possibly difficult.
Disclosure of Invention
First, the technical problem to be solved
In view of the above-mentioned shortcomings and drawbacks of the prior art, the present invention provides an energy-efficient serial reforming shift hydrogen production apparatus and reforming shift hydrogen production method.
(II) technical scheme
In order to achieve the aim, the serial reforming conversion hydrogen production device comprises a steam generator, a gas mixing valve, a reforming reactor, a heat exchanger, a high-temperature water gas conversion reactor, a low-temperature water gas conversion reactor and an induced draft fan which are sequentially communicated; the inlets of the gas mixing valves are connected with the outlet of the steam generator and the raw material gas supply device;
The outlet of the steam generator is also communicated with the high-temperature water gas shift reactor and the low-temperature water gas shift reactor; heat exchangers are arranged between the reforming reactor and the high-temperature water gas shift reactor and between the high-temperature water gas shift reactor and the low-temperature water gas shift reactor, and heat recovery outlets of the heat exchangers are respectively communicated with the steam generator and the reforming reactor;
The reforming reactor, the high-temperature water gas shift reactor and the low-temperature water gas shift reactor are all cylindrical reactors; the cylindrical reactor comprises an outer cylinder vertically arranged, an inner cylinder vertically arranged in the outer cylinder, an electric heater arranged in the inner cylinder and an annular separation net horizontally arranged outside the inner cylinder, wherein an air inlet, an air outlet and a catalyst filling opening are formed in the outer cylinder, a reaction chamber is formed between the outer cylinder and the inner cylinder, and the separation net is at least one and the outer edge of the separation net is close to the inner surface of the outer cylinder.
Optionally, a plurality of thermocouples are arranged on the outer surface of the inner cylinder at intervals;
and/or a plurality of the separation nets are distributed at intervals to divide the reaction chamber into a plurality of reaction sections, wherein one separation net is fixed at the bottom end of the inner cylinder.
Optionally, the cylindrical reactor further comprises a rotating shaft, the inner cylinder is fixedly arranged on the rotating shaft, and the rotating shaft is rotatably arranged on the end face of the outer cylinder; the rotary shaft comprises an inlet section and an outlet section which are opposite to each other, the inlet section and the outlet section are hollow pipes, an air inlet is formed in the inlet section, and an air outlet and an air collecting hole are formed in the outlet section.
Optionally, baffles or irregular protrusions are arranged on the inner surface of the outer cylinder at intervals.
Optionally, the reaction chamber of the reforming reactor is filled with a spherical solid nickel-based catalyst with the diameter of 10-20 mm, and the spherical solid nickel-based catalyst comprises a compound formed by any one or more of Ni/Al2O3、Ni/CaAl2O4、Ni/CaAl4O7、Ni/Ca3Al2O6 and Ni/Ca 12Al14O33;
The reaction chamber of the high temperature water gas shift reactor is filled with a spherical solid iron-based catalyst with the diameter of 10-20 mm, and the spherical solid iron-based catalyst comprises a compound formed by any one or more of Fe/MoC, fe/Al 2O3 and Fe/CaAl 4O7;
The reaction chamber of the low temperature water gas shift reactor is filled with spherical solid copper-based catalyst with the diameter of 10-20 mm, and the spherical solid copper-based catalyst comprises Cu/ZnO and/or Cu/Al 2O3.
Optionally, the inner cylinders are heat conduction cylinders with the thickness of 4-6 mm; the outer cylinder is a high-temperature-resistant heat-insulating cylinder with the thickness of 4-6 mm.
Optionally, the electric heater comprises electric heating wires which are uniformly and longitudinally arranged.
Further, the invention also provides a reforming conversion hydrogen production method which is implemented based on the serial reforming conversion hydrogen production device and comprises the following steps of:
S1, filling catalysts in a reforming reactor, a high-temperature water gas shift reactor and a low-temperature water gas shift reactor respectively, introducing nitrogen into the reforming reactor to discharge air, and heating the reforming reactor, the high-temperature water gas shift reactor and the low-temperature water gas shift reactor to a reaction temperature;
S2, after the reforming reactor, the high-temperature water gas shift reactor and the low-temperature water gas shift reactor reach the reaction temperature, respectively introducing nitrogen-hydrogen mixed gas to reduce the catalysts filled in the reforming reactor, the high-temperature water gas shift reactor and the low-temperature water gas shift reactor; introducing nitrogen after reduction to remove residual hydrogen in each reaction chamber;
S3, starting a steam generator, a heat exchanger and an induced draft fan, and introducing raw material gas and steam into the gas mixing valve at a preset flow rate, wherein the raw material gas contacts with a catalyst in each reaction chamber and reacts;
S4, the heat exchanger recovers heat in the reformed gas, is used for preheating the steam generator or the raw gas of the reforming reactor, and the cooled reformed gas sequentially enters the high-temperature water gas shift reactor and the low-temperature water gas shift reactor to generate water gas shift reaction, so that the synthesis gas containing hydrogen is obtained.
Optionally, the hydrogen content in the components of the nitrogen-hydrogen mixture used for the reduction catalyst is 10% -80%.
Optionally, the reaction temperature in the reforming reactor is 700-900 ℃, the water-carbon ratio is 1-5, and the gas-carbon airspeed is 5000-30000 h -1; the reaction temperature in the high-temperature water gas shift reactor is 320-450 ℃; the reaction temperature in the low-temperature water gas shift reactor is 150-250 ℃.
(III) beneficial effects
The technical scheme of the invention provides the serial reforming conversion hydrogen production device, which omits complex pretreatment equipment, improves the energy utilization efficiency of the device, and enables the methane reforming conversion hydrogen production reaction to be efficiently and stably carried out. Steam from the steam generator and purified natural gas or methane are uniformly mixed through a gas mixing valve and then enter a reaction chamber of a reforming reactor, raw material gas is heated to the required reforming temperature in the reaction chamber in an electric heating mode, then a reforming reaction is carried out under the catalysis of a catalyst required for reforming to obtain reformed gas with higher temperature, after the reformed gas enters a high-temperature water gas shift reactor and a low-temperature water gas shift reactor, the water gas shift reaction is carried out to improve the content of hydrogen in the synthetic gas, and hydrogen-rich synthetic gas with higher hydrogen content can be obtained after multiple shifts. The high-temperature reformed gas obtained by the reforming reactor can recover the contained energy after being cooled by the heat exchanger, and is used for preheating the steam generator or the reforming reactor gas, so that the heat efficiency of the system can be improved.
Compared with the prior device, the invention combines the reforming reactor and the multiple water gas shift reactor, provides the redundant energy of the high-temperature reforming gas and the water gas shift reactor for the reforming reactor and the steam generator through the heat exchanger, improves the utilization ratio of the energy, provides the energy-saving and efficient reforming shift hydrogen production device, has the advantages of high energy utilization ratio, high raw material treatment efficiency, high space utilization ratio, stable operation, easy maintenance and the like, and has wide application prospect in the fields of methane reforming equipment, hydrogenation stations and the like.
The device of the invention is optimized in the aspect of the design of the reaction chamber and the catalyst filling method, and has the following beneficial effects:
(1) The reactor of the device adopts cylindrical arrangement to form multi-layer annular heat flow distribution, so that uniform heat transfer and sufficient supply of heat required by reaction can be ensured; in addition, the outer cylinder is a high-temperature-resistant heat-insulating cylinder, so that heat loss can be reduced.
(2) The catalyst with different characteristics can be matched with each other by sectionally filling the catalyst with different types, so that the optimal utilization of the catalytic effect of the catalyst is realized.
(3) The heat exchanger can recycle the energy contained in the high-temperature gas, so that the heat can be recycled, the energy consumption is reduced, and the heat efficiency of the reaction chamber is improved.
(4) The rotating shaft can perform variable frequency rotation in the operation process, so that the catalyst and equipment collide with each other, carbon deposition on the catalyst can be timely shaken off, and the deactivation problem of the catalyst caused by carbon deposition can be relieved.
(5) Compared with a single-tube fixed bed reaction chamber, the reaction chamber has higher thermal efficiency, is higher than the current actual factory operation technology level, and is not only suitable for on-site hydrogenation stations, but also suitable for hydrogenation systems of marine transportation means in coastal areas.
(6) The reforming conversion hydrogen production device provided by the invention has the advantages of simple process flow, convenience in operation, high reliability, strong adaptability, high starting speed and low later maintenance cost.
Drawings
FIG. 1 is a technical scheme of a serial reforming shift hydrogen plant of the present invention;
FIG. 2 is a schematic structural view of a cartridge reactor of the present invention.
[ Reference numerals description ]
1: A steam generator; 2: a gas mixing valve; 3: a reforming reactor; 4: a heat exchanger; 5: a high temperature water gas shift reactor; 6: a low temperature water gas shift reactor; 7: an induced draft fan; 8: an inlet section; 9: a catalyst loading port; 10: an inner cylinder; 11: an electric heater; 12: an outer cylinder; 13: a reaction chamber; 14: a baffle; 15: a thermocouple; 16: a screen; 17: an outlet section; 18: and a gas collecting hole.
Detailed Description
The invention will be better explained by the following detailed description of the embodiments with reference to the drawings.
It should be noted that all directional indicators (such as up, down, left, right, front, and rear … …) in the embodiments of the present invention are merely used to explain the relative positional relationship, movement, etc. between the components in a particular posture (as shown in the drawings), and if the particular posture is changed, the directional indicator is changed accordingly.
Furthermore, descriptions such as those referred to as "first," "second," and the like, are provided for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implying an order of magnitude of the indicated technical features in the present disclosure. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
In the present invention, unless specifically stated and limited otherwise, the terms "connected," "affixed," and the like are to be construed broadly, and for example, "affixed" may be a fixed connection, a removable connection, or an integral body; "coupled" may be mechanical or electrical; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
Referring to fig. 1, the present invention provides a serial reforming shift hydrogen production device, which comprises a steam generator 1, a gas mixing valve 2, a reforming reactor 3, a heat exchanger 4, a high temperature water gas shift reactor 5, a low temperature water gas shift reactor 6 and an induced draft fan 7. The inlet of the gas mixing valve 2 is connected with the outlet of the steam generator 1 and the raw material gas supply device, the gas mixing valve 2, the reforming reactor 3, the high-temperature water gas shift reactor 5, the low-temperature water gas shift reactor 6 and the induced draft fan 7 are sequentially communicated, and specifically, the raw material gas and steam generated by the steam generator 1 are fully mixed through the gas mixing valve 2 and then are introduced into the reforming reactor 3. The outlet of the steam generator 1 is also connected to the high temperature water gas shift reactor 5 and the low temperature water gas shift reactor 6, i.e. the steam generated by the steam generator 1 can also be provided to the high temperature water gas shift reactor 5 and the low temperature water gas shift reactor 6. Heat exchangers 4 are arranged on communication pipelines between the reforming reactor 3 and the high-temperature water gas shift reactor 5 and between the high-temperature water gas shift reactor 5 and the low-temperature water gas shift reactor 6, wherein the heat exchangers 4 comprise heat recovery channels and heat supply channels which can mutually exchange heat, the heat supply channels are communicated with the communication pipelines, and the heat recovery channels are respectively communicated to the steam generator 1 and the reforming reactor 3 through heat recovery outlets after absorbing heat. The heat exchanger 4 can recycle the energy contained in the high-temperature gas, so that the heat can be recycled, thereby reducing the energy consumption and improving the heat efficiency of the device.
The reforming reactor 3, the high-temperature water gas shift reactor 5 and the low-temperature water gas shift reactor 6 are all cylindrical reactors, and in the preferred embodiment, the three reactors are all the same in size and are sequentially and coaxially arranged along the vertical direction, and the three reactors can adopt the same transmission shaft for transmission, so that the transmission mode is simplified, and the production and manufacturing cost of equipment can be reduced. Referring to fig. 2, the cartridge reactor includes an outer cartridge 12 vertically disposed, an inner cartridge 10 vertically disposed in the outer cartridge 12, an electric heater 11 disposed in the inner cartridge 10, and an annular barrier 16 horizontally disposed outside the inner cartridge 10, wherein both the inner cartridge 10 and the outer cartridge 12 may be cylindrical hollow cartridges with both ends sealed and coaxially disposed to ensure stable operation. The outer cylinder 12 is provided with an air inlet, an air outlet and a catalyst filling opening 9, and in addition, the bottom of the outer cylinder 12 is provided with a residue outlet which can discharge carbon deposition and residues generated in the reaction process. An annular reaction chamber 13 is formed between the outer cylinder 12 and the inner cylinder 10, at least one partition net 16 is provided, the inner edge of the partition net 16 is fixed on the outer surface of the inner cylinder 10, and the outer edge is close to the inner surface of the outer cylinder 12. Wherein, the separation net 16 can be a stainless steel net, and the reaction chamber 13 can be divided into a plurality of reaction sections by a plurality of separation nets 16 which are distributed at intervals, wherein one separation net 16 is fixed at the bottom end of the inner cylinder 10.
When reforming and converting to produce hydrogen, the desulfurized natural gas/methane and the like and the steam from the steam generator 1 are uniformly mixed through the gas mixing valve 2 and preheated, and the preheated natural gas/methane and the steam are introduced into the reaction chamber 13 of the reforming reactor 3 through the gas inlet, so that the water-carbon ratio can be adjusted in the reaction process, and the reformed gas can be obtained after being heated to the required temperature in the reforming reactor 3, and then the reformed gas is fully contacted with the catalyst to produce methane steam reforming reaction. The high-temperature reformed gas after the reforming reaction sequentially enters a high-temperature water gas shift reactor 5 and a low-temperature water gas shift reactor 6 to carry out water gas shift reaction (both are exothermic reactions, waste heat can be recovered by the heat exchanger 4), and then the hydrogen-rich synthetic gas is discharged through a draught fan 7. And then, the hydrogen-rich synthetic gas enters a pressure swing adsorption separation system (the existing device) for gas separation and purification, and the pure hydrogen is separated and purified, and the low-value combustible gas remains.
The invention combines the reforming reactor 3 and the multiple water gas shift reactors, and provides the excess energy of the high-temperature reforming gas and the water gas shift reactors for the reforming reactor 3 and the steam generator 1 through the heat exchanger 4, thereby having the advantages of high energy utilization rate, high raw material treatment efficiency, high space utilization rate, stable operation, easy maintenance and the like, and having wide application prospects in the fields of methane reforming equipment, hydrogenation stations and the like.
Further, in a preferred embodiment, the cartridge reactor may further include a rotation shaft on which the inner cylinder 10 is fixedly disposed, the rotation shaft being rotatably mounted on an end surface of the outer cylinder 12, i.e., the inner cylinder 10 is rotatably mounted between the end surfaces of the outer cylinder 12 by the rotation shaft, and the rotation shaft may have a predetermined rotation speed of 1 to 5r/min and may be driven to perform variable frequency rotation by a variable frequency motor. Specifically, the rotary shaft penetrates from the head end to the tail end of the outer cylinder 12, the rotary shaft is rotatably supported by a pair of bearings at the two axial ends and is dynamically sealed at the end face of the outer cylinder 12, and the end face of the inner cylinder 10 is hermetically fixed on the rotary shaft and rotates along with the rotary shaft, so that the vibration mixing effect on the catalyst is enhanced, the raw material gas can fully contact with the catalyst, and carbon deposition on the catalyst is reduced. Furthermore, referring again to fig. 2, baffles 14 or irregular protrusions may be disposed at intervals on the inner surface of the outer tub 12, and the baffles may be isosceles trapezoid stainless steel plates having a thickness of 5mm to further enhance the vibration mixing effect. In addition, the electric heater 11 is disposed inside the inner cylinder 10, and a conductive slip ring may be provided near a bearing of the rotating shaft, and a power line may be connected to the electric heater 11 through the conductive slip ring and then through the inside of the rotating shaft to supply power to the electric heater 11.
Wherein the air inlet and the air outlet can be formed on the end face of the outer cylinder 12, and in a preferred embodiment, the rotating shaft comprises an inlet section 8 and an outlet section 17 (which are both parts close to the dynamic sealing structure), the inlet section 8 and the outlet section 17 are hollow pipes, the inlet section 8 is provided with the air inlet, and the outlet section 17 is provided with the air outlet and the air outlet hole 18. The rotating shaft can be a complete shaft, and the middle part of the rotating shaft and the hollow pipe at the end part are separated by a partition plate so as to prevent gas from directly flowing from the inlet section 8 to the outlet section 17; alternatively, the rotary shaft may comprise only the inlet section 8 and the outlet section 17 coaxially arranged, and the end surfaces of the inlet section 8 and the outlet section 17 are fixed to the corresponding end surfaces of the inner cylinder 10, respectively. Among them, the inner diameter of the rotary shaft is 150 to 250mm (preferably 200 mm), and may preferably be a stainless steel tube. At the top of the reaction chamber 13, a connecting pipeline can be communicated with the reaction chamber 13 through a hollow pipe and an air inlet positioned in the outer cylinder 12, so as to form an air inlet channel; at the bottom of the reaction chamber 13, the reaction chamber 13 is communicated with the connecting pipeline through a hollow pipe through an air outlet positioned in the outer barrel 12, so that an air outlet channel is formed, a concise air path is formed, and the air is conveniently discharged. After being uniformly mixed by the gas mixing valve 2, the raw material gas and the steam enter the reaction chamber 13 from the gas inlet of the inlet section 8 of the reforming reactor 3, and after a series of reactions, the raw material gas and the steam are externally connected to the induced draft fan 7 from the gas outlet on the outlet section 17 of the low-temperature water gas shift reactor 6.
In addition, a plurality of thermocouples 15 can be arranged on the outer surface of the inner barrel 10 at intervals, so that the independent monitoring of the temperature of each reaction chamber 13 or each reaction section is realized, and the sectional temperature accurate control can be realized by matching with the electric heater 11. The electric heater 11 comprises electric heating wires which are uniformly and longitudinally arranged, and the power of the electric heating wires can be controlled by a temperature controller so as to realize higher temperature rising rate and more accurate temperature control effect.
The inner cylinder 10 is a heat conduction cylinder with the thickness of 4-6 mm (preferably 5 mm), is made of metal materials mainly made of ferrochrome or ceramic materials mainly made of alumina, and can form multi-layer annular heat flow distribution by adopting cylindrical arrangement so as to ensure uniform heat transfer and sufficient supply of heat required by reaction. The outer cylinder 12 is a high-temperature resistant heat-insulating cylinder with the thickness of 4-6 mm (preferably 5 mm), and mainly takes ceramic fiber as a main material, thereby playing a role in heat preservation and heat insulation and reducing heat loss.
In reforming shift hydrogen production, each reaction section of the reaction chamber 13 of each reactor can be filled with a catalyst, and the catalysts in adjacent reaction sections of the same reaction chamber 13 may be the same or different. The catalyst with different characteristics can be mutually matched by filling the catalyst with different types in the sections, so that the optimal utilization of the catalytic effect of the catalyst is realized. The rotating shaft can be driven by the variable frequency motor to perform variable frequency rotation in the operation process, so that the catalyst and equipment collide with each other, carbon deposition on the catalyst can be timely shaken off, and the deactivation problem of the catalyst caused by carbon deposition can be relieved.
Wherein, the reaction chamber 13 of the reforming reactor 3 is filled with a spherical solid nickel-based catalyst with a diameter of 10-20 mm (preferably 10mm, 15mm or 20 mm), and the spherical solid nickel-based catalyst comprises a compound composed of any one or more of Ni/Al2O3、Ni/CaAl2O4、Ni/CaAl4O7、Ni/Ca3Al2O6 and Ni/Ca 12Al14O33. And the diameter of the spherical catalyst is larger than the pore diameter of the mesh 16 supporting the corresponding catalyst. For example, when the reaction chamber 13 of the reforming reactor 3 is partitioned into a first reaction section on the left and a second reaction section on the right, the left screen 16 is a stainless steel screen having a pore diameter of 15mm, the first reaction section is filled with 15L of a spherical Ni/CaAl 4O7 catalyst having a diameter of 20mm (Ni content of 14 wt%) and the right screen 16 is a stainless steel screen having a pore diameter of 8mm, the second reaction section is filled with 15L of a spherical NiAl 2O3 catalyst having a diameter of 10mm (Ni content of 14 wt%), the reforming reactor 3 may be erected at the time of operation, and then the second reaction section is filled from the catalyst filling port 9, and then the first reaction section is filled.
In addition, the reaction chamber 13 of the high temperature water gas shift reactor 5 is filled with a spherical solid iron-based catalyst having a diameter of 10 to 20mm (may preferably be 10mm, 15mm or 20 mm), and the spherical solid iron-based catalyst includes a composite composed of any one or more of Fe/MoC, fe/Al 2O3 and Fe/CaAl 4O7. The reaction chamber 13 of the low temperature water gas shift reactor 6 is filled with a spherical solid copper-based catalyst having a diameter of 10 to 20mm (which may be preferably 10mm, 15mm or 20 mm), the spherical solid copper-based catalyst comprising Cu/ZnO and/or Cu/Al 2O3.
Furthermore, the invention also provides a reforming conversion hydrogen production method which is implemented based on the serial reforming conversion hydrogen production device, and specifically comprises the following steps:
S1, respectively filling corresponding catalysts in a reforming reactor 3, a high-temperature water gas shift reactor 5 and a low-temperature water gas shift reactor 6, introducing high-purity nitrogen into the reforming reactor 3 to discharge air, and simultaneously heating the reforming reactor 3, the high-temperature water gas shift reactor 5 and the low-temperature water gas shift reactor 6 to a reaction temperature;
S2, after the reforming reactor 3, the high-temperature water gas shift reactor 5 and the low-temperature water gas shift reactor 6 reach the reaction temperature, respectively introducing nitrogen-hydrogen mixed gas, and reducing the catalysts filled in the reforming reactor 3, the high-temperature water gas shift reactor 5 and the low-temperature water gas shift reactor 6; high-purity nitrogen is introduced after reduction to remove residual hydrogen in each reaction chamber 13;
S3, starting the steam generator 1, the heat exchanger 4 and the induced draft fan 7, and introducing raw material gas and steam into the gas mixing valve 2 at a preset flow rate, wherein the raw material gas fully contacts with the catalyst in each reaction chamber 13 and reacts;
s4, the heat exchanger 4 recovers heat in the high-temperature reformed gas, is used for preheating the raw gas of the steam generator 1 or the reforming reactor 3, and the cooled reformed gas sequentially enters the high-temperature water gas shift reactor 5 and the low-temperature water gas shift reactor 6 to generate water gas shift reaction, so that the synthesis gas with higher hydrogen content is obtained.
The raw gas may include a gas rich in methane, air, water vapor and a nitrogen-hydrogen mixture, the components of the reaction gas for performing the steam reforming reaction of methane may include CO 2, CO, etc., and the source of methane may be natural gas, biogas, pyrolysis gas, gasification gas or coke oven gas. Before reforming reaction, introducing nitrogen-hydrogen mixed gas to reduce the catalyst filled in the reforming reactor 3, so that the active component nickel in the catalyst is reduced from nickel oxide to nickel simple substance, and the hydrogen content in the nitrogen-hydrogen mixed gas used in the reduction catalyst is 10% -80%.
In addition, the reaction temperature in the reforming reactor 3 may be 700 to 900 ℃, specifically 700 to 750 ℃, 800 ℃, 850 ℃, 900 ℃, etc., the water-carbon ratio may be 1 to 5, and the gas-carbon space velocity may be 5000 to 30000h -1; the reaction temperature in the high temperature water gas shift reactor 5 may be 320 to 450 ℃, specifically 320 ℃, 350 ℃, 400 ℃, 450 ℃ and the like; the reaction temperature in the low-temperature water gas shift reactor 6 may be 150 to 250 ℃, specifically 150 ℃, 200 ℃, 250 ℃ and the like. Specifically, a heat exchanger 4 between the reforming reactor 3 and the high-temperature water gas shift reactor 5 carries out heat recovery and cooling to 320-450 ℃ on the reformed gas with the temperature of more than 700 ℃; the heat exchanger 4 between the high temperature water gas shift reactor 5 and the low temperature water gas shift reactor 6 cools the recovered heat of the high temperature water gas shift gas at 320-450 ℃ to 150-250 ℃, and the recovered heat is supplied to the steam generator 1 and the reforming reactor 3. Wherein, the water-carbon ratio refers to the ratio of the total number of water vapor molecules to the total number of carbon atoms in the feed in unit time. The carbon space velocity refers to the flow of carbon treated per unit time over a unit volume of catalyst.
The following describes in detail the process flow of reforming shift hydrogen production using a serial reforming shift hydrogen production apparatus by specific examples, in which apparatus having substantially the same structure is used.
Example 1
The inner diameter of each reaction chamber 13 is 500mm, the outer diameter is 600mm, the height is 1600mm, the inner cylinder 10 between the electric heater 11 and the reaction chamber 13 is made of heat conducting material ferrochrome alloy, and the thickness is 5mm; the inner diameter of the inlet section 8 and the outlet section 17 is 200mm, and the stainless steel is made of stainless steel with the thickness of 8 mm; the electric heater 11 has a diameter of 490mm and a height of 1500mm, and gaps are reserved between the upper and lower ends of the inner cylinder 10 and the upper and lower ends of the outer cylinder 12 as gas channels so as to be respectively communicated with the gas inlet and the gas outlet; the outer cylinder 12 is made of ceramic fiber which is a high temperature resistant heat insulating material and has a thickness of 5 mm.
The natural gas after desulfurization and purification and the steam generated by the steam generator 1 are fully mixed by the gas mixing valve 2 and then are introduced into the reaction chamber 13 of the reforming reactor 3. Wherein, 15L of spherical Ni/CaAl 4O7 catalyst with the diameter of 15mm (the Ni content is 14 wt%) is filled in the reaction chamber 13 of the reforming reactor 3. The water-carbon ratio is 3, the carbon space velocity is 10000h -1, the methane flow entering the gas mixing valve 2 is 2500L/min, and the steam flow is 7500L/min. The raw material gas is heated to more than 700 ℃ and then subjected to methane steam reforming reaction to obtain reformed gas, the reformed gas after the reforming reaction enters a high-temperature water gas shift reactor 5 after primary heat exchange, 10L of Fe/CaAl 4O7 catalyst with the diameter of 15mm (the content of Fe is 15 wt%) is filled in the high-temperature water gas shift reactor 5, the high-temperature water gas shift reaction is carried out at 400 ℃, 10L of Cu/ZnO catalyst with the diameter of 15mm (the content of Cu is 15 wt%) is filled in a low-temperature water gas shift reactor 6, the low-temperature water gas shift reaction is carried out at 200 ℃, and energy is provided for the reforming reactor 3 and the steam generator 1 through a heat exchanger 4.
The methane conversion rate of the reformed gas is 90.8%, the hydrogen yield is 72.4%, and the thermal efficiency is 73.9%; the hydrogen content in the obtained high-temperature reformed gas is 62.3%, the hydrogen content in the synthesis gas obtained after the high-temperature water gas conversion is 74.0%, and the hydrogen content in the hydrogen-rich synthesis gas obtained after the low-temperature water gas conversion is 83.2%.
Example 2
Example 2 used the same reaction apparatus as example 1 except that the composition of the feed gas was changed, wherein the feed gas was changed to purified biogas (gas composition: 75% ch 4-21％CO2-4％N2), and the reforming reaction was changed from methane steam reforming to methane steam-carbon dioxide double reforming.
The reaction chamber 13 of the reforming reactor 3 was filled with 20L of a spherical Ni/CaAl 4O7 catalyst (Ni content: 14 wt%) having a diameter of 15mm, the high temperature water gas shift reactor 5 was filled with 10L of a Fe/CaAl 4O7 catalyst (Fe content: 15 wt%) having a diameter of 15mm, and the low temperature water gas shift reactor 6 was filled with I0L of a Cu/ZnO catalyst (Cu content: 15 wt%) having a diameter of 15 mm. The temperature of the reaction chamber 13 of the reforming reactor 3 is controlled to 800 ℃, the temperature of the high-temperature water gas reforming reactor is controlled to 400 ℃, and the temperature of the low-temperature water gas reforming reactor is controlled to 200 ℃; the reforming reaction water-carbon ratio is 1:1, the carbon airspeed is 6000h -1, the flow rate of methane entering the gas mixing valve 2 is 2083L/min, and the flow rate of the steam is 2000L/min. The raw material gas is subjected to reforming reaction in the reaction chamber 13 of the reforming reactor 3 under the action of a catalyst, and a hydrogen product is obtained through a subsequent process. In example 2, the methane conversion rate was 97.7%, the hydrogen yield was 85.1%, the thermal efficiency was 78.3%, the hydrogen content in the obtained high-temperature reformed gas was 58.9%, the hydrogen content in the synthesis gas obtained after the high-temperature water gas shift was 72.7%, and the hydrogen content in the hydrogen-rich synthesis gas obtained after the low-temperature water gas shift was 83.0%, thereby realizing the high-value utilization of methane gas.
Example 3
Example 3 the same reaction apparatus, feed gas, catalyst and reaction conditions were used as in example 1, except that the inner cylinder 10 was rotated at a speed of 5r/min in example 3.
The reaction chamber 13 of the reforming reactor 3 was filled with 15L of a spherical Ni/CaAl 4O7 catalyst (Ni content: 14 wt%) having a diameter of 15 mm. The inner cylinder rotates at a speed of 5r/min, the water-carbon ratio is 3, the carbon space velocity is 10000h -1, the flow rate of methane entering the gas mixing valve 2 is 2500L/min, and the flow rate of steam is 7500L/min; 10L of Fe/CaAl 4O7 catalyst with the diameter of 15mm (the Fe content is 15 wt%) is filled in the high-temperature water gas shift reactor 5, and the high-temperature water gas shift reaction is carried out at 400 ℃; the low temperature water gas shift reactor 6 was charged with 10L of Cu/ZnO catalyst (Cu content 15 wt%) having a diameter of 15 mm. The methane conversion rate of the reformed gas is 97.6%, the hydrogen yield is 80.4%, and the thermal efficiency is 78.1%; the hydrogen content in the obtained high-temperature reformed gas is 68.7%, the hydrogen content in the synthesis gas obtained after the high-temperature water gas conversion is 83.1%, and the hydrogen content in the hydrogen-rich synthesis gas obtained after the low-temperature water gas conversion is 86.7%.
It should be understood that the above description of the specific embodiments of the present invention is only for illustrating the technical route and features of the present invention, and is for enabling those skilled in the art to understand the present invention and implement it accordingly, but the present invention is not limited to the above-described specific embodiments. All changes or modifications that come within the scope of the appended claims are intended to be embraced therein.
Claims (10)
1. A tandem reforming shift hydrogen plant comprising: the steam generator (1) is sequentially communicated with a gas mixing valve (2), a reforming reactor (3), a heat exchanger (4), a high-temperature water gas shift reactor (5), a low-temperature water gas shift reactor (6) and a draught fan (7); the inlets of the gas mixing valves (2) are connected with the outlet of the steam generator (1) and the raw material gas supply device;
The outlet of the steam generator (1) is also communicated with the high-temperature water gas shift reactor (5) and the low-temperature water gas shift reactor (6); a heat exchanger (4) is arranged between the reforming reactor (3) and the high-temperature water gas shift reactor (5) and between the high-temperature water gas shift reactor (5) and the low-temperature water gas shift reactor (6), and the heat recovery outlet of the heat exchanger (4) is respectively communicated with the steam generator (1) and the reforming reactor (3);
The reforming reactor (3), the high-temperature water gas shift reactor (5) and the low-temperature water gas shift reactor (6) are cylindrical reactors; the cylindrical reactor comprises an outer cylinder (12) which is vertically placed, an inner cylinder (10) which is vertically arranged in the outer cylinder (12), an electric heater (11) which is arranged in the inner cylinder (10) and an annular separation net (16) which is horizontally arranged outside the inner cylinder (10), wherein an air inlet, an air outlet and a catalyst filling opening (9) are formed in the outer cylinder (12), a reaction chamber (13) is formed between the outer cylinder (12) and the inner cylinder (10), and the separation net (16) is at least one and the outer edge of the separation net is close to the inner surface of the outer cylinder (12).
2. The series reforming conversion-conversion hydrogen plant as defined in claim 1, characterized in that a plurality of thermocouples (15) are arranged at intervals on the outer surface of the inner tube (10);
and/or a plurality of the separation nets (16) are distributed at intervals to divide the reaction chamber (13) into a plurality of reaction sections, wherein one separation net (16) is fixed at the bottom end of the inner cylinder (10).
3. The tandem reforming conversion hydrogen plant as defined in claim 1 or 2, characterized in that the cylindrical reactor further comprises a rotary shaft on which the inner cylinder (10) is fixedly provided, the rotary shaft being rotatably mounted on an end face of the outer cylinder (12); the rotary shaft comprises an inlet section (8) and an outlet section (17) which are opposite to each other, the inlet section (8) and the outlet section (17) are hollow pipes, an air inlet is formed in the inlet section (8), and an air outlet and an air collecting hole (18) are formed in the outlet section (17).
4. The tandem reforming conversion hydrogen plant as defined in claim 1 or 2, wherein baffles (14) or irregular projections are arranged at intervals on the inner surface of the outer tub (12).
5. The tandem reforming shift hydrogen plant according to claim 1 or 2, characterized in that the reaction chamber (13) of the reforming reactor (3) is filled with a spherical solid nickel-based catalyst having a diameter of 10 to 20mm, the spherical solid nickel-based catalyst comprising a complex composed of any one or more of Ni/Al2O3、Ni/CaAl2O4、Ni/CaAl4O7、Ni/Ca3Al2O6 and Ni/Ca 12Al14O33;
The reaction chamber (13) of the high-temperature water gas shift reactor (5) is filled with a spherical solid iron-based catalyst with the diameter of 10-20 mm, and the spherical solid iron-based catalyst comprises a compound formed by any one or more of Fe/MoC, fe/Al 2O3 and Fe/CaAl 4O7;
The reaction chamber (13) of the low temperature water gas shift reactor (6) is filled with a spherical solid copper-based catalyst with the diameter of 10-20 mm, and the spherical solid copper-based catalyst comprises Cu/ZnO and/or Cu/Al 2O3.
6. The series reforming conversion hydrogen plant as defined in claim 1 or 2, wherein the inner cylinders (10) are heat conductive cylinders each having a thickness of 4 to 6 mm; the outer cylinder (12) is a high-temperature resistant heat insulation cylinder with the thickness of 4-6 mm.
7. A series reforming shift hydrogen plant as defined in claim 1 or 2, characterized in that the electric heater (11) comprises electric heating wires uniformly longitudinally arranged.
8. A reforming shift hydrogen production method implemented based on the serial reforming shift hydrogen production apparatus according to any one of claims 1 to 7, characterized by comprising the steps of:
S1, filling catalysts in a reforming reactor (3), a high-temperature water gas shift reactor (5) and a low-temperature water gas shift reactor (6) respectively, introducing nitrogen into the reforming reactor (3) to discharge air, and heating the reforming reactor (3), the high-temperature water gas shift reactor (5) and the low-temperature water gas shift reactor (6) to a reaction temperature;
S2, after the reforming reactor (3), the high-temperature water gas shift reactor (5) and the low-temperature water gas shift reactor (6) reach the reaction temperature, introducing nitrogen-hydrogen mixed gas respectively, and reducing the catalysts filled in the reforming reactor (3), the high-temperature water gas shift reactor (5) and the low-temperature water gas shift reactor (6); introducing nitrogen after reduction to remove residual hydrogen in each reaction chamber (13);
S3, starting a steam generator (1), a heat exchanger (4) and an induced draft fan (7), and introducing raw material gas and steam into the gas mixing valve (2) at a preset flow rate, wherein the raw material gas contacts with a catalyst in each reaction chamber (13) and reacts;
s4, the heat exchanger (4) is used for recovering heat in the reformed gas and preheating the raw gas of the steam generator (1) or the reforming reactor (3), and the cooled reformed gas sequentially enters the high-temperature water gas shift reactor (5) and the low-temperature water gas shift reactor (6) to generate water gas shift reaction, so that the synthesis gas containing hydrogen is obtained.
9. The reforming conversion to hydrogen process as defined in claim 8, wherein the hydrogen content of the nitrogen-hydrogen mixture used in the reduction catalyst is 10% to 80%.
10. The reforming shift hydrogen production method as defined in claim 8, wherein the reaction temperature in the reforming reactor (3) is 700 to 900 ℃, the water-carbon ratio is 1 to 5, and the gas-carbon space velocity is 5000 to 30000h -1; the reaction temperature in the high-temperature water gas shift reactor (5) is 320-450 ℃; the reaction temperature in the low-temperature water gas shift reactor (6) is 150-250 ℃.
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