CN218709194U - Natural gas steam reforming hydrogen production system - Google Patents
Natural gas steam reforming hydrogen production system Download PDFInfo
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- CN218709194U CN218709194U CN202221763567.0U CN202221763567U CN218709194U CN 218709194 U CN218709194 U CN 218709194U CN 202221763567 U CN202221763567 U CN 202221763567U CN 218709194 U CN218709194 U CN 218709194U
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Abstract
The utility model discloses a natural gas steam reforming hydrogen production system, including natural gas preheater, reborner and well change stove, take place the reforming conversion reaction in the reborner and produce the transformation gas, change the reaction in taking place in the well change stove and produce in the transformation gas, should become the reaction and be used for getting rid of in a large number CO in the transformation gas, wherein, the reborner is equipped with converting tube and transformation gas export, and the transformation gas export is fluid intercommunication to natural gas preheater and well stove in proper order in the downstream direction. Based on the utility model discloses a system design, the additional indirect heating equipment that is relevant with transformation gas and high temperature flue gas outside the reborner is small in quantity, equipment layout retrencies, can reduce entire system's area.
Description
Technical Field
The utility model relates to a natural gas steam reforming hydrogen production system, in particular to a small-scale natural gas steam reforming hydrogen production system.
Background
In the existing natural gas steam reforming hydrogen production system, raw material natural gas can enter a reformer after being preheated by a plurality of heat exchange devices so as to meet the temperature requirement of catalytic reforming reaction; the reformed gas flowing out of the reforming furnace is required to be reduced to a certain temperature through the additional heat exchange device and then enters the medium-grade furnace so as to meet the temperature requirement of the medium-grade furnace.
For example, CN11401427A discloses a modular natural gas reforming hydrogen production machine and a method for producing hydrogen by using the same, referring to fig. 1, a raw material gas is preheated by a natural gas preheater and then preheated by a heat exchange type shift reactor, the raw material gas is mixed with water vapor to form a mixed gas, and the mixed gas needs to exchange heat with a reformed gas by a wound steam superheater before entering a reforming reformer (i.e., the reformed gas flowing out of the reformer needs to be reduced to a certain temperature by an additional heat exchange device and then enters the shift furnace); the process flow is complex, and the number of equipment is large, so that the whole natural gas steam reforming hydrogen production system not only occupies a large area, but also has high equipment cost.
For small and medium-sized natural gas hydrogen production devices, the purpose of miniaturization cannot be realized by simply reducing the scale of the traditional natural gas hydrogen production process.
SUMMERY OF THE UTILITY MODEL
In order to solve the technical problem, the utility model provides a natural gas steam reforming hydrogen production system which can simplify the process flow.
A natural gas steam reforming hydrogen production system comprises a natural gas preheater, a reformer and a shift converter, wherein reforming conversion reaction occurs in the reformer to generate reformed gas, shift reaction occurs in the shift converter to generate shift gas, and the shift reaction is used for largely removing CO in the reformed gas; the reforming furnace is provided with a reforming pipe and a reforming gas outlet, and the reforming gas outlet is sequentially communicated with the natural gas preheater and the converter in a downstream direction.
Preferably, the hydrogen production system further comprises a desalted water preheater, and the converter is fluidly connected in a downstream direction to the desalted water preheater.
Furthermore, the hydrogen production system also comprises a water-cooling separator, wherein the water-cooling separator is provided with an integrated water-cooling tube array, so that medium transformed gas flowing out of the desalted water preheater is separated by the water-cooling separator to obtain dry-basis converted gas.
Further, the hydrogen production system also comprises a pressure swing adsorption unit which is communicated with the water-cooled separator in an upstream direction through fluid so as to separate and extract the dry-based converted gas to obtain the product hydrogen and desorbed gas.
Particularly, an air self-preheating type burner is arranged in the reformer, a high-temperature flue gas outlet is formed in the upper portion of the reformer, and the air self-preheating type burner is in fluid communication with the high-temperature flue gas outlet, so that high-temperature flue gas after air preheating flows out of the reformer from the high-temperature flue gas outlet.
Further, the hydrogen production system also comprises a flue gas steam generator, and the high-temperature flue gas outlet is sequentially communicated with the flue gas steam generator and the atmosphere in a downstream direction.
Further, the hydrogen production system also includes a desulfurization unit and a mixer, the desulfurization unit being fluidly connected to the natural gas preheater in an upstream direction; the mixer is fluidly coupled in an upstream direction to the desulfurization unit and the flue gas steam generator, respectively, and the mixer is fluidly coupled in a downstream direction directly to the reformer tube.
Features and advantages of the present disclosure include:
based on the utility model discloses a natural gas steam reforming hydrogen manufacturing system, the raw materials natural gas only carries out the heat exchange with the reborner gas that flows from the reborner and realizes preheating the raw materials natural gas and cooling to the reborner gas through the natural gas preheater, directly gets into the reborner after the raw materials natural gas through the natural gas preheater mixes with the steam. Other heat exchange equipment related to the mixed gas and the reformed gas is not arranged outside the reforming furnace, so that the process flow is simplified, the number of the heat exchange equipment is reduced, and the occupied area of the whole system can be reduced.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present disclosure, the drawings required to be used in the description of the embodiments are briefly introduced below, and it is apparent that the drawings in the description below are only some embodiments of the present disclosure, and it is obvious for those skilled in the art that other drawings may be obtained according to the drawings without creative efforts.
FIG. 1 shows a schematic diagram of a natural gas steam reforming hydrogen production system and process;
figure 2 shows a schematic diagram of a reformer tube and its heat exchange process for the raw gas mixture and the reformed gas.
Description of reference numerals:
110-natural gas preheater, 112-raw natural gas, 120-desulfurization unit;
210-desalted water preheater, 212-desalted water, 220-flue gas steam generator, 224-steam;
310-mixer, 314-raw material gas mixture, 314 a-raw material gas mixture of the first heat exchange area, 314 b-raw material gas mixture of the second heat exchange area;
410-a blower;
500-reformer, 510-burner, 512-fuel gas, 514-high temperature flue gas, 514 a-high temperature flue gas outlet, 516-atmosphere, 520-reformer tube, 522-first heat transfer zone, 524-reformed gas, 524 a-intermediate reformed gas/reformed gas of second heat transfer zone, 524 b-reformed gas of first heat transfer zone, 524 c-reformed gas outlet, 526-second heat transfer zone, 526 a-catalyst bed;
610-medium changing furnace, 614-medium changing gas;
710-water-cooled separator, 712-circulating water inflow, 714-dry-based reformed gas, 716-circulating water return and 718-process condensate;
810-pressure swing adsorption unit, 812-stripping gas, 814-product hydrogen.
Detailed Description
The technical solutions in the embodiments of the present disclosure will be clearly and completely described below with reference to the drawings in the embodiments of the present disclosure, and it is obvious that the described embodiments are only a part of the embodiments of the present disclosure, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments disclosed herein without making any creative effort, shall fall within the protection scope of the present disclosure.
Referring to fig. 1, a schematic diagram of a system for producing hydrogen by steam reforming of natural gas and a flow method thereof is shown. The natural gas steam reforming hydrogen production system mainly comprises: the natural gas preheater 110 and the desulfurization unit 120 pre-treating the raw natural gas 112, the desalted water preheater 210 and the flue gas steam generator 220 pre-treating the desalted water 212, the mixer 310 mixing the steam generated from the flue gas steam generator 220 and the raw natural gas 112 treated by the desulfurization unit 120 to generate the raw mixed gas 314, and the reformer 500, the shift converter 610, the water-cooled separator 710 and the pressure swing adsorption unit 810.
Referring now to fig. 1, a system for producing hydrogen by steam reforming of natural gas and the process steps included therein will be described.
In the first step, feed natural gas 112 is preheated and desulfurized.
The raw material natural gas 112 after the compression treatment is preheated to 300-400 ℃ by the natural gas preheater 110 and then enters the desulfurization unit 120, so that the sulfur content in the raw material natural gas 112 is reduced to below 0.2 PPm.
In the second step, the desalted water 212 is preheated and vaporized.
The desalted water 212 is preheated to 100-200 ℃ by the desalted water preheater 210, and the preheated desalted water is produced into steam 224 by the flue gas steam generator 220.
In the third step, the desulfurized feed natural gas 112 is mixed with steam 224.
The steam 224 is mixed with the desulfurized feed natural gas 112 by the mixer 310 in a ratio of 3. The temperature of the raw material mixed gas 314 output by the mixer is 150-350 ℃, and the pressure is 0.6-2.5 MPa; preferably, the temperature of the raw mixed gas 314 output by the mixer is 250 ℃ and the pressure is 1.0MPa. The raw material gas mixture 314 from the mixer 310 directly enters a reformer tube 520 (described in detail below) of the reformer 500; directly as described herein, means that no heat exchange device is required between the mixer 310 and the reforming pipe 520 to provide the preheating function for the raw material gas mixture 314.
And fourthly, reforming conversion reaction and waste heat utilization.
The reforming conversion reaction is performed in the reformer 500, and the reformer 500 is provided with a plurality of reforming tubes 520 and a burner 510. The combustor 510 combusts fuel, including fuel gas 512 and desorbed gas 812 (described in detail in the eighth step below), and generates high temperature flue gas that provides the heat required for the steam reforming reaction in the reformer tubes 520. Wherein air (combustion-supporting gas) required for the combustion reaction is blown by the blower 410.
In some preferred embodiments, the burner 510 is an air self-preheating type burner. The preheating of the air is accomplished inside the burner 510, which is provided by the high temperature flue gases produced by the combustion reaction.
Disposed within the shift pipe 520 is a catalyst bed 526a (see FIG. 2), which may be a nickel-based catalyst. The raw material mixed gas 314 undergoes a catalytic reforming reaction in the conversion pipe 520 to mainly generate CO and H2, and converted gas 524 is obtained; the reformed gas 524 consists primarily of methane, hydrogen, CO2, and H2O. The reformer 500 is provided with a reformed gas outlet 524c, and the reformed gas 524 flowing out of the reformed gas outlet 524c is at a temperature of 350 to 550 c (preferably 450 c) and a pressure of 0.6 to 2.5MPa (preferably 1.0 MPa).
According to the system and process design of the present disclosure, inside the reformer 500, the high temperature flue gas generated by the combustion reaction is used only to provide heat for the air preheating process and the steam reforming reaction process, and the temperature of the flue gas exiting the reformer 500 is 450 to 750 ℃, preferably 650 ℃, without other additional flue gas heat exchange lines or heat exchange devices.
The reformer 500 is provided at an upper portion thereof with a high temperature flue gas outlet 514a, the air is in fluid communication with the high temperature flue gas outlet 514a from the preheating type burner, and the high temperature flue gas preheated by the air in the burner 510 directly flows out of the reformer 500 from the high temperature flue gas outlet 514 a. The temperature of the high temperature flue gas 514 flowing out of the reformer 500 is 450-750 ℃, and the high temperature flue gas 514 directly enters the flue gas steam generator 220 in the second step to provide heat for the steam gasification of the preheated desalted water. The temperature of the high-temperature flue gas 514 is reduced to 150-250 ℃ after heat exchange in the flue gas steam generator 220, and then the high-temperature flue gas is directly exhausted to the atmosphere 516; the term "directly" as used herein means that no other heat exchange device is provided between the flue gas steam generator and the atmosphere for reducing the temperature of the high temperature flue gas.
Based on the system and the process design disclosed by the invention, the quantity of heat exchange equipment for high-temperature flue gas is small, the equipment layout is simplified, and the complexity of the whole process and the occupied area of the system can be reduced.
Fifthly, the heat exchange of the converted gas and the medium-temperature shift reaction are carried out.
The reformed gas 524 directly enters the natural gas preheater 110 from the reformed gas outlet 524c, and the reformed gas 524 directly enters the medium converter 610 after being preheated by the natural gas preheater 110; reforming CO and H in gas 524 2 O is reacted with a catalyst (e.g., iron-based catalyst) in the converter to remove CO from the converted gas in a large amount and produce mainly H 2 And CO 2 Obtaining medium converted gas 614 with higher hydrogen content than converted gas 524; directly as described herein, means that no additional heat exchange devices for reducing the temperature of reformed gas 524 are provided between reformed gas outlet 524c and natural gas preheater 100, and between natural gas preheater 110 and medium transformer 610. The medium shift gas mainly comprises methane, hydrogen, a small amount of CO and CO 2 And H 2 And O, the temperature of the medium gas 614 flowing out of the medium gas furnace 610 is 350-450 ℃.
Specifically, the reformed gas 524 increases the temperature of the raw natural gas flowing through the natural gas preheater to 300 to 400 ℃, and decreases the temperature of the reformed gas after preheating the raw natural gas to 300 to 400 ℃.
Sixthly, gas changing and heat exchanging.
The medium-grade gas 614 flowing out of the medium-grade furnace 610 further exchanges heat through the desalted water preheater 210, so that the temperature of the medium-grade gas 614 is reduced to 100-200 ℃. Specifically, the medium temperature gas 614 preheats the desalted water flowing through the desalted water preheater to 100-200 ℃, and the medium temperature gas after preheating the desalted water is reduced to 100-200 ℃.
And step seven, water cooling separation.
The medium shift gas 614 enters a water-cooled separator 710 provided with water-cooled tubes at about 100-200 ℃, and circulating water inlet 712 and circulating water return 716 pass through the water-cooled tubes to enable H in the medium shift gas 614 to pass through 2 O is condensed into process condensate 718 and the other components in the process gas 614 are separated to form the dry converted gas 714. The dry-based reformed gas 714 mainly contains methane, hydrogen, CO and CO 2 And trace amount of H 2 O。
And step eight, pressure swing adsorption.
The dry-based reformed gas 714 is separated and purified by a pressure swing adsorption unit 810 to obtain desorbed gas 812 and a product hydrogen 814 with yield of more than 80%. Wherein the main component of the desorption gas 812 comprises a large amount of CO 2 Methane, CO, H 2 And trace amount of H 2 Together, the stripping gas 812 and the fuel gas 512 serve as the fuel for the combustion reaction in the combustor 510.
In some preferred embodiments, referring to a reformer tube and a schematic of the process for exchanging heat between the raw gas mixture and the reformate gas therein as shown in figure 2, the reformer tube 520 has a first heat exchange zone 522 and a second heat exchange zone 526.
The second heat transfer zone 526 is located downstream of the first heat transfer zone 522 in the flow direction of the raw gas mixture 314. The raw material mixed gas 314 with the temperature of about 200-400 ℃ enters the first heat exchange area 522, the raw material mixed gas 314a in the first heat exchange area 522 and the converted gas 524b entering the first heat exchange area after the reforming conversion reaction are finished carry out first heat exchange to obtain temperature increase, and the temperature of the raw material mixed gas after the first heat exchange is about 300-500 ℃. In the second heat transfer area 526, the raw material mixed gas 314b entering the second heat transfer area after being heated by the first heat exchange is further subjected to second heat exchange with the intermediate reformed gas 524a in the reforming conversion reaction area. After the second heat exchange, the temperature of the raw material gas mixture 314b flowing out of the second heat exchange area reaches 450 to 650 ℃, preferably 550 to 600 ℃. The raw gas mixture flows out of the second heat exchange area and then enters the catalyst bed 526a in the conversion pipe 520 to undergo the reforming conversion reaction. The temperature of the raw material mixed gas 314 is increased from 200-400 ℃ to 450-650 ℃, the contribution ratio of the first heat exchange to the raw material mixed gas is about 40%, and the contribution ratio of the second heat exchange to the raw material mixed gas is about 60%.
The first heat transfer zone 522 is located downstream of the second heat transfer zone 526 in the flow direction of the reformed gas produced by the reforming conversion reaction. The intermediate reformed gas 524a produced during the reforming conversion reaction is subjected to the second heat exchange with the raw material mixed gas 314b in the second heat exchange zone 526; the intermediate reformed gas 524a flows through the catalyst bed 526a of the second heat exchange zone 526 to obtain reformed gas 524b after reforming conversion is completed, and the temperature of the reformed gas 524b flowing out of the conversion pipe 520 and/or the conversion furnace 500 is 350-550 ℃ after the reformed gas 524b exchanges heat with the raw material mixed gas 314 a. The reformed gas 524 flows out of the reformer 500, exchanges heat through the natural gas preheater 110, and enters the shift converter 610 to undergo shift reaction.
The present disclosure preheats the raw material gas mixture by using the heat of the reformed gas 524b generated after the reforming conversion reaction and the intermediate reformed gas 524a generated during the reforming conversion reaction in the reforming tubes in a divisional, staged, and divided manner, without separately providing a heat exchange device for the preheating function of the raw material gas mixture 314 outside the reformer 500; the reformed gas produced by the reforming conversion reaction is sufficiently heat-exchanged with the raw material mixed gas in a divided manner, in stages and in a divided ratio before flowing out of the reformer. Therefore, before the raw material mixed gas flows into the conversion pipe, an independent preheating device is not required to be arranged, the internal structure of the conversion furnace 500 is simplified, the production and processing difficulty of the conversion furnace 500 is reduced, the volume of the conversion furnace 500 is reduced, the equipment layout of the whole system is simplified, and the occupied area of the whole system is reduced.
In conclusion, the system and the method for preparing hydrogen by reforming natural gas steam can simplify the whole flow and pipeline arrangement of the hydrogen preparation process, and reduce the total occupied area of equipment and the investment of equipment cost.
The above description is only a few embodiments of the present disclosure, and those skilled in the art can make various changes or modifications to the embodiments of the present disclosure without departing from the spirit and scope of the present disclosure based on the disclosure of the application document.
Claims (7)
1. A natural gas steam reforming hydrogen production system comprises a natural gas preheater, a reformer and a shift converter, wherein reforming conversion reaction occurs in the reformer to generate reformed gas, and shift reaction occurs in the shift converter to generate shift gas, and the reformer is characterized in that the reformer is provided with a reformer tube and a reformed gas outlet, and the reformed gas outlet is sequentially communicated with the natural gas preheater and the shift converter in a downstream direction.
2. The natural gas steam reforming hydrogen production system of claim 1, further comprising a desalted water preheater, the converter being fluidly connected in a downstream direction to the desalted water preheater.
3. The system for producing hydrogen by reforming natural gas with steam as claimed in claim 2, wherein an air self-preheating burner is arranged in the reformer, a high-temperature flue gas outlet is arranged at the upper part of the reformer, and the air self-preheating burner is in fluid communication with the high-temperature flue gas outlet, so that the high-temperature flue gas after air preheating flows out of the reformer from the high-temperature flue gas outlet.
4. The system for hydrogen production by steam reforming of natural gas as claimed in claim 3, further comprising a flue gas steam generator, the high temperature flue gas outlet being in turn fluidly connected in a downstream direction to the flue gas steam generator and the atmosphere.
5. The system for producing hydrogen by steam reforming of natural gas as claimed in claim 4, further comprising a desulfurization unit and a mixer; the desulfurization unit is fluidly connected to the natural gas preheater in an upstream direction; the mixer is fluidly coupled in an upstream direction to the desulfurization unit and the flue gas steam generator, respectively, and the mixer is fluidly coupled in a downstream direction directly to the reformer tube.
6. The system for producing hydrogen by reforming natural gas with steam as claimed in claim 2, further comprising a water-cooled separator provided with an integrated water-cooled tube array, so that the medium transformed gas flowing out of the desalted water preheater is separated by the water-cooled separator to obtain a dry-basis reformed gas.
7. The system for hydrogen production by steam reforming of natural gas as claimed in claim 6, further comprising a pressure swing adsorption unit fluidly connected to the water-cooled separator in an upstream direction for separating and purifying the dry-based reformed gas to produce hydrogen product and desorbed gas.
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| CN202221763567.0U CN218709194U (en) | 2022-07-07 | 2022-07-07 | Natural gas steam reforming hydrogen production system |
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| CN202221763567.0U CN218709194U (en) | 2022-07-07 | 2022-07-07 | Natural gas steam reforming hydrogen production system |
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| CN218709194U true CN218709194U (en) | 2023-03-24 |
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