CN117658074B - Reforming reaction device with carbon deposit resistance function and application method thereof - Google Patents
Reforming reaction device with carbon deposit resistance function and application method thereof Download PDFInfo
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
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Abstract
The invention relates to a reforming reaction device with an anti-carbon function and a use method thereof. The device comprises a reforming reaction component, an adsorption reactor, a condenser, a first outlet, a second outlet, a three-way valve and a conversion pipe, wherein the upper end of the reforming reactor of the reforming reaction component is connected with the lower end of the adsorption reactor through the condenser, the condenser is connected with the first outlet, the upper end of the adsorption reactor is connected with the second outlet through the three-way valve, the three-way valve is communicated with a third pipeline through the conversion pipe, and the reforming reactor and the adsorption reactor are both arranged in an independent heating furnace. According to the invention, through the carbon elimination reaction comprising the C+CO 2→2CO;(9)C+O2→CO2;(10)C+H2O→CO+H2 in the formula (8), when the reforming reaction is not performed, the carbon elimination reaction (formula (8)) is induced by introducing CO 2 into the reforming reactor, so that the regeneration of the reforming catalyst is promoted, the temperature gradient in the reactor is relieved, and meanwhile, the collection and recycling of the byproduct CO 2 are realized.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a reforming reaction device with an anti-carbon function and a use method thereof.
Background
The advanced catalytic technology at present is a key field of competitive research and a high point of preemptive science and technology in all countries of the world, plays an important role in modern production, and the catalytic reactor is core equipment in the catalytic technology, has great influence on catalytic efficiency due to design and selection, and has the following general problems for the existing reforming reaction system.
Firstly, the traditional reforming reactor has simple design, mainly a cylindrical or flat cylindrical single shell, granular catalyst is filled in the shell or an integral catalyst with corresponding shape is packaged in the shell, however, for the steam reforming reaction with strong heat absorption, the reforming reactor with simple structure has temperature gradient, so that the temperature of the catalyst in the reactor is lower than that of the catalyst close to the shell of the reactor, and carbon deposition and byproducts are easy to generate.
Secondly, most reforming reaction systems do not capture and utilize reaction byproducts, for example, methane steam reforming, the main reaction is represented by formula (1), the ideal product is synthesis gas, namely CO and H 2 (molar ratio 1:3), however, during the reaction, byproduct CO 2 is inevitably generated, as shown in formulas (2) and (3), and excessive CO 2 not only can reduce the purity of the synthesis gas, but also can influence the reaction balance and prevent the forward progress of the reaction.
(1)CH4+H2O→CO+3H2
(2)CH4+3H2O→CO+CO2+5H2
(3)CH4+2H2O→CO2+4H2
Notably, the cause of catalyst coking in methane reforming reactions is complex, and the main reactions involved include formulas (4) - (7).
(4)2CO→C+CO2
(5)CH4→C+2H2
(6)CO+H2→C+H2O
(7)CO2+2H2→2H2O+C
For several reasons mentioned above, in order to prevent the catalyst from depositing carbon, it is common to operate with a high water-carbon ratio (2.5 to 3.5) or to frequently replace the catalyst, which increases the energy consumption of the reaction process and increases the reaction cost.
Disclosure of Invention
In order to solve the technical problems, the invention provides a reforming reaction device with an anti-carbon deposition function and a use method thereof, wherein the carbon elimination reaction comprises a C+CO 2→2CO;(9)C+O2→CO2;(10)C+H2O→CO+H2 in a formula (8), and when the reforming reaction is not performed, CO 2 is introduced into a reforming reactor to induce the carbon elimination reaction (formula (8)), so that the regeneration of a reforming catalyst is promoted, the temperature gradient in the reactor is relieved, and meanwhile, the collection and the reuse of a byproduct CO 2 are realized.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a reforming reaction device with an anti-carbon function comprises a reforming reaction component, an adsorption reactor, a condenser, a first outlet, a second outlet, a three-way valve, a conversion pipe and a heating component.
The reforming reaction component comprises a methane reservoir, a deionized water reservoir, a throttle, a steam generator, a first pipeline, a second pipeline, a third pipeline, a mixer, a reforming reactor and a circulating pipeline, wherein the deionized water reservoir, the throttle and the steam generator are sequentially connected through the pipelines, the methane reservoir and the steam generator are respectively connected into the mixer through the first pipeline and the second pipeline, and the mixer is connected into the lower end of the reforming reactor through the third pipeline; the reforming reactor is internally provided with a porous spiral duct and a first metal net, the first metal net is arranged at the lower end inside the reforming reactor, the upper end of the first metal net is filled with a reforming catalyst, the porous spiral duct is spirally arranged inside the reforming reactor from bottom to top, and the lower end of the porous spiral duct is connected with a third pipeline; the upper end of the circulating pipeline is communicated with the upper end of a porous spiral conduit in the reforming reactor, the lower end of the circulating pipeline is connected with a third pipeline, and a first two-way valve is arranged on the circulating pipeline;
The upper end of the reforming reactor is connected with the lower end of the adsorption reactor through a condenser, the condenser is connected with the first outlet, the upper end of the adsorption reactor is connected with the second outlet through a three-way valve, the three-way valve is communicated with a third pipeline through a conversion pipe, and the reforming reactor and the adsorption reactor are both arranged in an independent heating furnace; the heating component comprises a heat exchanger and a heat tracing belt, the heat exchanger is arranged on a pipeline between the reforming reactor and the condenser, the heat exchanger is arranged on a first pipeline and a second pipeline, and the heat tracing belt is coated on the second pipeline; the adsorption reactor is internally provided with a second metal net and a gas sharing plate, the second metal net is arranged at the lower end inside the adsorption reactor, the adsorbent is filled at the upper end of the second metal net, and the gas sharing plate is arranged at the lower end of the second metal net.
The condenser is provided with a first outlet, a second two-way valve is arranged at the joint of the condenser and the first outlet, a third two-way valve is arranged at the joint of the condenser and the adsorption reactor, and a filter is arranged at the joint of the three-way valve and the second outlet.
Further, the gas equally dividing plate at least comprises two groups, the holes close to the center of the shaft on the two groups of gas equally dividing plates are dense and small in aperture, and the holes at the edge are few and large in aperture.
The invention also provides a using method of the reforming reaction device with the carbon deposit resistance function, which comprises the following steps:
s1: initial temperature rising stage of reforming reactor: the first two-way valve is opened, the second two-way valve and the third two-way valve are closed, and the three-way ball valve is communicated with the filter and the adsorption reactor; deionized water enters a throttle from a deionized water storage, the water inflow is regulated to control the water-carbon ratio, the deionized water is vaporized into water vapor through a steam generator and enters a second pipeline, a heat tracing belt is started at the same time, and the temperature of the second pipeline is regulated to about 110 ℃; methane enters the first pipeline through a methane storage; the two gases enter the mixer at the same time, the uniformly mixed reaction gas enters the porous spiral conduit in the reforming reactor from bottom to top through the third pipeline, and is continuously migrated from the holes of the porous spiral conduit and diffused to the surface of the reforming catalyst in the flowing process; starting a heating furnace outside the reforming reactor, and increasing the temperature of the reforming reactor; at this time, the reaction gas does not have high enough energy to react with the catalyst, so that the gas in the porous spiral conduit needs to flow into the circulating pipeline from the upper end of the porous spiral conduit and flow back into the third pipeline until the reforming reactor reaches the target temperature;
S2: methane steam reforming reaction stage: after the reforming reactor reaches the target temperature, the second two-way valve and the third two-way valve are opened, and the three-way ball valve is communicated with the filter and the adsorption reactor; the uniformly mixed reaction gas enters a porous spiral conduit in the reforming reactor from bottom to top through a third pipeline, is continuously removed from the holes of the porous spiral conduit and is diffused to the surface of a reforming catalyst in the flowing process, and is subjected to reforming reaction with the inner surface of the catalyst at the reaction temperature; at the moment, the reaction space velocity is higher, the reaction gas in the porous spiral duct does not diffuse out of the hole to react with the catalyst, and the redundant gas flows back to the third pipeline through the circulating pipeline to participate in reforming reaction together with the newly-inflowing gas; the reaction product with higher temperature flows out from the top of the reforming reactor and then enters the heat exchanger to preheat the water vapor in the second pipeline and the methane in the first pipeline, so that the self temperature is reduced; the reaction product flowing through the heat exchanger continuously flows into the condenser to further reduce the temperature, and the water vapor in the reaction product is discharged from the first outlet after being cooled; the dehydrated reaction products enter an adsorption reactor from bottom to top, the reaction products are uniformly distributed in the radial direction of the reactor through a gas sharing plate, so that CO 2 in the subsequent reaction products can be fully adsorbed by an adsorbent, the gas after adsorption and purification flows through a filter to remove catalyst or adsorbent dust, the obtained pure synthetic gas flows out from a second outlet, and CO 2 is timely removed from the reaction products, so that the synthetic gas can be purified;
S3: the reforming catalyst and the adsorbent are regenerated simultaneously: the second two-way valve is opened, the first two-way valve and the third two-way valve are closed, and the three-way ball valve is communicated with the conversion pipe and the adsorption reactor; starting a heating furnace outside the reforming reactor and a heating furnace outside the adsorption reactor, and respectively increasing the temperature to the target temperature; in the heating process, CO 2 desorbed from the adsorbent flows into the reforming reactor, and continuously migrates from the holes of the porous spiral conduit and diffuses to the surface of the reforming catalyst in the CO 2 flowing process, carbon deposit on the reforming catalyst reacts with the inflow CO 2 to generate CO, and flows out of the first outlet, CO can be collected at the first outlet, and after the reaction is continued for a period of time, the reforming catalyst and the adsorbent are regenerated.
Further, in S2, if the reaction space velocity is low, the reaction gas in the porous spiral conduit diffuses out of the pores to react with the catalyst, and the first communication valve can be closed, so that recirculation from the circulation pipeline is not required, and the reacted product flows out from the top of the reforming reactor.
Further, S4: and (3) adsorbent regeneration: the third two-way valve is closed, and the three-way ball valve is communicated with the filter and the adsorption reactor; starting a heating furnace outside the adsorption reactor, and increasing the temperature to a target temperature; in the heating process, CO 2 adsorbed and saturated in the adsorbent can be gradually desorbed, the desorbed CO 2 is filtered to remove adsorbent dust, pure CO 2 flows out from the second outlet, CO 2 can be collected at the second outlet, and the adsorbent can be regenerated after the reaction is continued for a period of time.
Compared with the prior art, the invention has the advantages that:
The methane can generate CO 2 by-products in the reforming process, and CO 2 generated by the reforming reaction can be adsorbed by the technology; the porous spiral conduit in the reforming reactor is beneficial to the uniform diffusion of the reaction gas in the reforming reactor and promotes the reaction of the reaction gas and the reforming catalyst; when the reaction space velocity is higher, unreacted gas can be continuously returned to the third pipeline to react with the reforming catalyst again, so that the reforming efficiency is improved; the steam is removed by condensation of the reaction product generated by methane reforming, and then the reaction product enters a CO2 adsorption reactor to avoid the interference of H 2 O on the adsorption performance of the CO 2 adsorbent.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of the connection of the structures in the device of the present invention;
FIG. 2 is a schematic view of a gas distribution plate structure according to the present invention;
fig. 3 is a flow chart of the main steps of the method of the present invention.
Wherein: 1. reforming reaction means; 10. a methane storage; 11. a deionized water storage; 12. a throttle; 13. a steam generator; 14. a first pipe; 15. a second pipe; 16. a third conduit; 17. a mixer; 18. a reforming reactor; 181. a porous helical catheter; 182. a first metal mesh; 183. a reforming catalyst; 19. a circulation pipe; 191. a first two-way valve; 2. an adsorption reactor; 21. a second metal mesh; 22. a gas equally dividing plate; 23. an adsorbent; 3. a condenser; 31. a second two-way valve; 32. a third two-way valve; 4. a first outlet; 5. a second outlet; 6. a three-way valve; 61. a filter; 7. a switching tube; 8. a heating member; 81. a heat exchanger; 82. heat is carried along with the belt.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the invention, are within the scope of the invention.
Specific embodiments of the present invention will be described below with reference to the accompanying drawings:
As shown in fig. 1 to 3, a reforming reaction device having an anti-carbon function includes a reforming reaction member 1, an adsorption reactor 2, a condenser 3, a first outlet 4, a second outlet 5, a three-way valve 6, a switching tube 7, and a heating member 8.
The reforming reaction member 1 comprises a methane reservoir, a deionized water reservoir, a throttle 12, a steam generator 13, a first pipeline 14, a second pipeline 15, a third pipeline 16, a mixer 17, a reforming reactor 18 and a circulating pipeline 19, wherein the deionized water reservoir, the throttle 12 and the steam generator 13 are sequentially connected through pipelines, the methane reservoir and the steam generator 13 are respectively connected into the mixer 17 through the first pipeline 14 and the second pipeline 15, and the mixer 17 is connected into the lower end of the reforming reactor 18 through the third pipeline 16; the reforming reactor 18 is internally provided with a porous spiral conduit 181 and a first metal mesh 182, the first metal mesh 182 is arranged at the lower end of the inside of the reforming reactor 18, the upper end of the first metal mesh 182 is filled with a reforming catalyst 183, the porous spiral conduit 181 is spirally arranged in the reforming reactor 18 from bottom to top, and the lower end of the porous spiral conduit 181 is connected with the third pipeline 16; the upper end of the circulating pipeline 19 is communicated with the upper end of a porous spiral conduit 181 in the reforming reactor 18, the lower end of the circulating pipeline 19 is connected with the third pipeline 16, and a first two-way valve 191 is arranged on the circulating pipeline 19;
The upper end of the reforming reactor 18 is connected with the lower end of the adsorption reactor 2 through a condenser 3, the condenser 3 is connected with the first outlet 4, the upper end of the adsorption reactor 2 is connected with the second outlet 5 through a three-way valve 6, the three-way valve 6 is communicated with a third pipeline 16 through a conversion pipe 7, and the reforming reactor 18 and the adsorption reactor 2 are both arranged in independent heating furnaces; the heating member 8 includes a heat exchanger 81 and a heat tracing band 82, the heat exchanger 81 is disposed on a pipe between the reforming reactor 18 and the condenser 3, the heat exchanger 81 is disposed on the first pipe 14 and the second pipe 15, and the heat tracing band 82 is coated on the second pipe 15; the adsorption reactor 2 is internally provided with a second metal net 21 and a gas sharing plate 22, the second metal net 21 is arranged at the lower end of the inside of the adsorption reactor 2, the upper end of the second metal net 21 is filled with an adsorbent 23, and the gas sharing plate 22 is arranged at the lower end of the second metal net 21.
The second two-way valve 31 is arranged at the joint of the condenser 3 and the first outlet 4, the third two-way valve 32 is arranged at the joint of the condenser 3 and the adsorption reactor 2, and the filter 61 is arranged at the joint of the three-way valve 6 and the second outlet 5.
Further, the gas dividing plate 22 includes at least two groups, and the holes near the center of the shaft on the two groups of gas dividing plates 22 are dense and have small hole diameters, and the holes at the edge are few and have large hole diameters.
Description of the working mode of the invention:
The reforming reaction device with the carbon deposit resistance function adopting the structure is characterized in that a first metal net 182 at the lower end of the reforming reactor 18 is used for supporting a reforming catalyst 183, and the reforming catalyst 183 can be a Ni-based catalyst or a noble metal catalyst. The perforated spiral pipe 181 penetrating the reforming reactor 18 has a plurality of through holes in its wall, and the number of holes and the pore size can be adjusted according to the flow rate of the reaction gas. The lower end of the adsorption reactor 2 comprises two layers of gas sharing plates 22, wherein the holes in the center of the upper shaft of the gas sharing plates 22 are dense, the holes in the edges are small, the holes in the edges are large, the positions and the hole orientations of the two layers of gas sharing plates 22 are not limited, and the gas inlet is uniformly distributed in the radial direction of the adsorption reactor 2 and can fully react with the adsorbent 23. The second metal mesh 21 is arranged at the upper end of the gas equipartition plate 22 and used for supporting the adsorbent 23, and the adsorbent 23 can be molecular sieve, modified silica gel, modified calcium oxide, etc. The reforming reactor 18 and the adsorption reactor 2 are both arranged in independent heating furnaces, and the temperature of the reforming reactor and the adsorption reactor can be adjusted according to the reaction requirements.
In the steam reforming reaction, the reforming catalyst 183 is deactivated by oxidation of the active components when in contact with O 2, so that methane is introduced before the temperature-raising reaction to keep the catalyst in a reducing atmosphere, and the dry methane gas causes carbon deposition of the catalyst after the temperature is higher than 200 ℃, so that the scheme of heating the catalyst after simultaneously introducing methane and steam is adopted.
The invention relates to a method for using a reforming reaction device with an anti-carbon function and the steps:
S1: initial warm-up phase of reforming reactor 18: the first two-way valve 191 is opened, the second two-way valve 31 and the third two-way valve 32 are closed, and the three-way ball valve is communicated with the filter 61 and the adsorption reactor 2; deionized water enters a throttle 12 from a deionized water storage 11, the water inflow is regulated to control the water-carbon ratio, the deionized water is vaporized into water vapor through a steam generator 13 and enters a second pipeline 15, a heat tracing belt 82 is started, and the temperature of the second pipeline 15 is regulated to about 110 ℃; methane enters the first conduit 14 via the methane storage 10; the two gases enter the mixer 17 at the same time, the uniformly mixed reaction gas enters the porous spiral conduit 181 in the reforming reactor 18 from bottom to top through the third pipeline 16, and continuously migrates out of the pores of the porous spiral conduit 181 and diffuses to the surface of the reforming catalyst 183 in the flowing process; starting a heating furnace outside the reforming reactor 18, and increasing the temperature of the reforming reactor 18; at this time, since the reaction gas does not have high enough energy to react with the catalyst, the gas in the porous spiral pipe 181 needs to flow into the circulation pipe 19 from the upper end of the porous spiral pipe 181 and flow back into the third pipe 16 until the reforming reactor 18 reaches the target temperature;
S2: methane steam reforming reaction stage: after the reforming reactor 18 reaches the target temperature, the second two-way valve 31 and the third two-way valve 32 are opened, and the three-way ball valve is communicated with the filter 61 and the adsorption reactor 2; the uniformly mixed reaction gas enters the porous spiral conduit 181 in the reforming reactor 18 from bottom to top through the third pipeline 16, is continuously migrated from the pores of the porous spiral conduit 181 and is diffused to the surface of the reforming catalyst 183 in the flowing process, and is subjected to reforming reaction with the inner surface of the catalyst at the reaction temperature; at this time, the reaction space velocity is high, the reaction gas in the porous spiral conduit 181 does not diffuse out of the pores to react with the catalyst, and the redundant gas flows back to the third pipeline 16 through the circulating pipeline 19 to participate in the reforming reaction together with the newly inflowing gas; at this time, if the reaction space velocity is low, the reaction gas in the porous spiral conduit 181 is diffused outside the pores to react with the catalyst, the first communication valve can be closed, recirculation from the circulation pipeline 19 is not needed, and the reacted product flows out from the top of the reforming reactor 18; the reaction product with higher temperature flows out from the top of the reforming reactor 18 and enters the heat exchanger 81 to preheat the water vapor in the second pipeline 15 and the methane in the first pipeline 14, so as to reduce the temperature of the reaction product; the reaction product after flowing through the heat exchanger 81 continuously flows into the condenser 3 to further reduce the temperature, and the water vapor in the reaction product is discharged from the first outlet 4 after being cooled; the dehydrated reaction product enters the adsorption reactor 2 from bottom to top, the reaction product is uniformly distributed in the radial direction of the reactor through the gas sharing plate 22, so that CO 2 in the subsequent reaction product can be fully adsorbed by the adsorbent 23, the gas after adsorption purification flows through the filter 61 to remove the catalyst or the dust of the adsorbent 23, the obtained pure synthetic gas flows out from the second outlet 5, and the CO 2 is timely removed from the reaction product, so that the synthetic gas can be purified;
S3: the reforming catalyst 183 is regenerated simultaneously with the adsorbent 23: the second two-way valve 31 is opened, the first two-way valve 191 and the third two-way valve 32 are closed, and the three-way ball valve is communicated with the conversion pipe 7 and the adsorption reactor 2; starting a heating furnace outside the reforming reactor 18 and a heating furnace outside the adsorption reactor 2, and respectively raising the temperatures to target temperatures; during the heating process, the CO 2 desorbed from the adsorbent 23 flows into the reforming reactor 18, and continuously migrates from the pores of the porous spiral pipe 181 and diffuses to the surface of the reforming catalyst 183 during the flow of the CO 2, so that carbon deposits on the reforming catalyst 183 react with the inflow CO 2 to generate CO, and flow out from the first outlet 4, where the CO can be collected, and after the reaction continues for a period of time, both the reforming catalyst 183 and the adsorbent 23 are regenerated.
S4: regenerating the adsorbent 23: the third two-way valve 32 is closed, and the three-way ball valve is communicated with the filter 61 and the adsorption reactor 2; starting a heating furnace outside the adsorption reactor 2, and increasing the temperature to a target temperature; during the heating process, the saturated CO 2 adsorbed in the adsorbent 23 is gradually desorbed, the desorbed CO 2 passes through the filter 61 to remove dust from the adsorbent 23, pure CO 2 flows out from the second outlet 5, the CO 2 can be collected at the second outlet 5, and the adsorbent 23 can be regenerated after the reaction is continued for a period of time.
The invention has the beneficial effects that:
1. The methane can generate CO 2 byproducts in the reforming process, and the CO 2 generated by the reforming reaction can be adsorbed by the technology, so that the method has the following beneficial effects: 1) The synthetic gas can be purified, and the cleanliness of the product is improved; 2) The method is favorable for breaking the balance of the reforming reaction and promoting the reforming reaction to continuously proceed to the direction of generating the synthesis gas; 3) Capturing CO 2 in the product, and reducing carbon emission in the synthesis gas preparation process; 4) When the adsorbent 23 is saturated in adsorption, the desorption of CO 2 can be promoted by heating, so that the CO 2 adsorbent 23 is regenerated; 5) When the reforming catalyst 183 is seriously coked, the regeneration of the reforming catalyst 183 may be promoted by inducing a carbon elimination reaction by introducing CO 2 into the reforming reactor 18.
2. The porous spiral conduit 181 in the reforming reactor 18 has the following advantageous effects: 1) Facilitating uniform diffusion of the reactant gas within the reforming reactor 18 and promoting sufficient reaction of the reactant gas with the reforming catalyst 183; 2) Because the reforming is a strong endothermic reaction, a temperature gradient exists in the reforming catalyst 183 in the reforming reactor 18, the temperature of the reforming catalyst 183 in the reforming reactor 18 is lower than that of a catalyst close to the shell of the reforming reactor 18, carbon deposition and byproducts are easy to generate, a metal conduit is directly connected with the bottom of the reforming reactor 18, the materials are stainless steel with high heat conductivity, the porous spiral conduit 181 is almost isothermal with the shell of the reforming reactor 18 and approaches the set temperature of the reaction furnace, the porous spiral conduit 181 penetrates through the inside of the reforming reactor 18, heat can be supplemented to the reforming catalyst 183 in the reforming reactor 18, and the effective performance of the reforming reaction is ensured; 3) When the reaction space velocity is high, the reaction gas in the porous spiral conduit 181 does not diffuse out of the pores to react with the catalyst, and the unreacted gas can continue to flow back to the third pipeline 16 to react with the reforming catalyst 183 again, so that the reforming efficiency is improved.
3. The steam is removed by condensation of the reaction product generated by methane reforming, and then the reaction product enters the CO 2 adsorption reactor 2 to avoid the interference of H 2 O on the adsorption performance of the adsorbent 23.
The CO 2 adsorption reactor 2 is provided with two layers of gas distribution plates with holes, so that the uniform distribution of the gas entering the reactor can be effectively ensured, and the gas can be promoted to fully react with the adsorbent 23.
The above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (4)
1. The reforming reaction device with the carbon deposit resistance function comprises a reforming reaction component, wherein the reforming reaction component comprises a methane storage, a deionized water storage, a restrictor, a steam generator, a first pipeline, a second pipeline, a third pipeline, a mixer and a reforming reactor, the deionized water storage, the restrictor and the steam generator are sequentially connected through the pipelines, the methane storage and the steam generator are respectively connected into the mixer through the first pipeline and the second pipeline, the mixer is connected into the lower end of the reforming reactor through the third pipeline, the reaction device further comprises an adsorption reactor, a condenser, a first outlet, a second outlet, a three-way valve and a conversion pipe, the three-way valve is a three-way ball valve, the upper end of the reforming reactor is connected with the lower end of the adsorption reactor through the condenser, the condenser is connected with the first outlet, the upper end of the adsorption reactor is connected with the second outlet through the three-way valve, the three-way valve is communicated with the third pipeline through the conversion pipe, and the reforming reactor and the adsorption reactor are both arranged in an independent heating furnace; the reforming reactor is internally provided with a porous spiral duct and a first metal net, the first metal net is arranged at the lower end inside the reforming reactor, the upper end of the first metal net is filled with a reforming catalyst, the porous spiral duct is spirally arranged inside the reforming reactor from bottom to top, and the lower end of the porous spiral duct is connected with a third pipeline; the reforming reaction component further comprises a circulating pipeline, the upper end of the circulating pipeline is communicated with the upper end of the porous spiral conduit in the reforming reactor, the lower end of the circulating pipeline is connected with a third pipeline, and a first two-way valve is arranged on the circulating pipeline; the reaction device further comprises a heating component, the heating component comprises a heat exchanger and a heat tracing belt, the heat exchanger is arranged on a pipeline between the reforming reactor and the condenser, the heat exchanger is arranged on a first pipeline and a second pipeline, and the heat tracing belt is coated on the second pipeline; the adsorption reactor is internally provided with a second metal net and a gas sharing plate, the second metal net is arranged at the lower end inside the adsorption reactor, the adsorbent is filled at the upper end of the second metal net, and the gas sharing plate is arranged at the lower end of the second metal net; the gas equally dividing plate at least comprises two groups, the holes on the gas equally dividing plate, which are close to the center of the shaft, are dense and have small apertures, and the holes on the edge are few and have large apertures.
2. The reforming reaction device with anti-carbon function according to claim 1, wherein: the junction of condenser and first export is equipped with the second two-way valve, the junction of condenser and adsorption reactor is equipped with the third two-way valve, the junction of three-way valve and second export is equipped with the filter.
3. The method for using a reforming reaction device having an anti-coking function according to any one of claims 1 to 2, characterized in that: the method comprises the following steps:
S1: initial temperature rising stage of reforming reactor: the first two-way valve is opened, the second two-way valve and the third two-way valve are closed, and the three-way ball valve is communicated with the filter and the adsorption reactor; deionized water enters a throttle from a deionized water storage, the water inflow is regulated to control the water-carbon ratio, the deionized water is vaporized into water vapor through a steam generator and enters a second pipeline, a heat tracing belt is started at the same time, and the temperature of the second pipeline is regulated to 110 ℃; methane enters the first pipeline through a methane storage; the two gases enter the mixer at the same time, the uniformly mixed reaction gas enters the porous spiral conduit in the reforming reactor from bottom to top through the third pipeline, and is continuously migrated from the holes of the porous spiral conduit and diffused to the surface of the reforming catalyst in the flowing process; starting a heating furnace outside the reforming reactor, and increasing the temperature of the reforming reactor; at this time, the reaction gas does not have high enough energy to react with the catalyst, so that the gas in the porous spiral conduit needs to flow into the circulating pipeline from the upper end of the porous spiral conduit and flow back into the third pipeline until the reforming reactor reaches the target temperature;
S2: methane steam reforming reaction stage: after the reforming reactor reaches the target temperature, the second two-way valve and the third two-way valve are opened, and the three-way ball valve is communicated with the filter and the adsorption reactor; the uniformly mixed reaction gas enters a porous spiral conduit in the reforming reactor from bottom to top through a third pipeline, is continuously removed from the holes of the porous spiral conduit and is diffused to the surface of a reforming catalyst in the flowing process, and is subjected to reforming reaction with the inner surface of the catalyst at the reaction temperature; at the moment, the reaction space velocity is higher, the reaction gas in the porous spiral duct does not diffuse out of the hole to react with the catalyst, and the redundant gas flows back to the third pipeline through the circulating pipeline to participate in reforming reaction together with the newly-inflowing gas; the reaction product with higher temperature flows out from the top of the reforming reactor and then enters the heat exchanger to preheat the water vapor in the second pipeline and the methane in the first pipeline, so that the self temperature is reduced; the reaction product flowing through the heat exchanger continuously flows into the condenser to further reduce the temperature, and the water vapor in the reaction product is discharged from the first outlet after being cooled; the dehydrated reaction products enter an adsorption reactor from bottom to top, the reaction products are uniformly distributed in the radial direction of the reactor through a gas sharing plate, CO 2 in the subsequent reaction products is ensured to be fully adsorbed by an adsorbent, the gas after adsorption and purification flows through a filter to remove catalyst or adsorbent dust, and the obtained pure synthesis gas flows out from a second outlet;
S3: the reforming catalyst and the adsorbent are regenerated simultaneously: the second two-way valve is opened, the first two-way valve and the third two-way valve are closed, and the three-way ball valve is communicated with the conversion pipe and the adsorption reactor; starting a heating furnace outside the reforming reactor and a heating furnace outside the adsorption reactor, and respectively increasing the temperature to the target temperature; in the heating process, CO 2 desorbed from the adsorbent flows into the reforming reactor, and continuously migrates from the holes of the porous spiral conduit and diffuses to the surface of the reforming catalyst in the CO 2 flowing process, carbon deposit on the reforming catalyst reacts with the inflow CO 2 to generate CO, and flows out of the first outlet, CO is collected here, and after the reaction is continued for a period of time, both the reforming catalyst and the adsorbent are regenerated.
4. A method of use according to claim 3, wherein: further comprising S4: and (3) adsorbent regeneration: the third two-way valve is closed, and the three-way ball valve is communicated with the filter and the adsorption reactor; starting a heating furnace outside the adsorption reactor, and increasing the temperature to a target temperature; in the heating process, CO 2 adsorbed and saturated in the adsorbent can be gradually desorbed, the desorbed CO 2 is filtered to remove adsorbent dust, pure CO 2 flows out from the second outlet, CO 2 is collected at the second outlet, and the adsorbent is regenerated after the reaction is continued for a period of time.
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| JP2002179403A (en) * | 2000-12-07 | 2002-06-26 | Isuzu Ceramics Res Inst Co Ltd | Natural gas reforming system and natural gas reforming apparatus |
| CN101559924A (en) * | 2009-05-26 | 2009-10-21 | 清华大学 | Methane vapor reforming hydrogen production process and devices thereof |
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| CN100491235C (en) * | 2007-05-25 | 2009-05-27 | 清华大学 | Circulating fluidized bed methane steam reforming hydrogen production reaction process and reaction device |
| JP2009298620A (en) * | 2008-06-11 | 2009-12-24 | Ihi Corp | Glycerin reforming apparatus and reforming method therefor |
| KR102750305B1 (en) * | 2022-03-24 | 2025-01-09 | 한국에너지기술연구원 | Continuous syngas-production method and syngas-production system comprising regeneration of reforming catalysts deactivated by coking |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002179403A (en) * | 2000-12-07 | 2002-06-26 | Isuzu Ceramics Res Inst Co Ltd | Natural gas reforming system and natural gas reforming apparatus |
| CN101559924A (en) * | 2009-05-26 | 2009-10-21 | 清华大学 | Methane vapor reforming hydrogen production process and devices thereof |
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