CN218261977U - Hydrocarbon steam reforming hydrogen production system - Google Patents
Hydrocarbon steam reforming hydrogen production system Download PDFInfo
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- CN218261977U CN218261977U CN202222188633.2U CN202222188633U CN218261977U CN 218261977 U CN218261977 U CN 218261977U CN 202222188633 U CN202222188633 U CN 202222188633U CN 218261977 U CN218261977 U CN 218261977U
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Abstract
The utility model discloses a hydrocarbon steam reforming hydrogen production system, including reborner and well change stove, take place the reforming conversion reaction in the reborner and produce the transformation gas, change the reaction 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 direct fluid intercommunication of transformation gas export becomes the stove. Based on the utility model discloses a system design, the heat exchange 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
The present application claims priority from chinese patent application No. 202221719902.7, entitled "hydrocarbon steam reforming hydrogen production system," filed by chinese patent office at 29/6/2022, the entire contents of which are incorporated herein by reference.
Technical Field
The utility model relates to a hydrocarbon steam reforming hydrogen production system, in particular to a small-scale hydrocarbon steam reforming hydrogen production system.
Background
In the existing natural gas steam reforming hydrogen production system, raw material mixed gas needs to be preheated by an independent heat exchange device before entering a reforming converter; the reformed gas flowing out of the reforming furnace is required to be reduced to a certain temperature through an independent heat exchange device and then enters the middle-variable furnace; the flue gas temperature of reformer output is too high, may lead to heat waste, also may lead to the increase of indirect heating equipment.
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. The existing natural gas steam reforming hydrogen production process has the main problems that: (1) The process flow is long, the number of equipment is large, the device scale is large, the occupied area is large, and the equipment investment is high; (2) The waste heat collection reutilization rate is not high, and the flue outlet temperature is too high in the hydrogen production process, so that much heat is wasted, and the energy consumption is high.
SUMMERY OF THE UTILITY MODEL
In order to solve at least one technical problem, the utility model provides a hydrogen production system by hydrocarbon steam reforming.
A hydrocarbon steam reforming hydrogen production system comprises 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; wherein, the reformer is provided with a reformer tube and a reformed gas outlet, and the reformed gas outlet is directly communicated with the medium converter in a fluid way.
Preferably, the hydrocarbon steam reforming hydrogen production system is a natural gas steam reforming hydrogen production system; the hydrogen production system also comprises a natural gas preheater and a desalted water preheater, wherein the downstream of the medium transformer furnace is sequentially communicated with the natural gas preheater and the desalted water preheater in a fluid mode, so that medium transformer gas generated by the medium transformer furnace sequentially passes through the natural gas preheater and the desalted water preheater to exchange heat.
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 directly and fluidly communicated with the flue gas steam generator, so that the temperature of the high-temperature flue gas flowing out of the flue gas steam generator is 150-250 ℃.
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 system design, the heat exchange 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.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present disclosure, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present disclosure, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 shows a schematic diagram of a hydrocarbon steam reforming hydrogen production system and hydrogen production flow 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 hydrogen production by steam reforming of hydrocarbons and a flow method thereof are shown, wherein the system is suitable for hydrogen production by steam reforming of hydrocarbon gases such as natural gas, methane, biogas, liquefied petroleum gas and the like. The following specifically describes a steam reforming hydrogen production system and a process thereof, taking natural gas as an example of the hydrocarbon gas as the raw material.
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 passes through the flue gas steam generator 220 to generate steam 224.
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 gas mixture 314.
And step four, 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 250 to 450 deg.c (preferably 350 deg.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.
The fifth step, the middle variation reaction.
The reformed gas 524 directly enters the shift converter 610 from the reformed gas outlet 524c, and CO and H in the reformed gas 524 2 O is reacted by 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 equipment is provided between the reformed gas outlet 524c and the intermediate converter 610 to reduce the temperature of the reformed gas 524. 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 cooking gas 614 flowing out of the medium cooking furnace 610 is 350-450 ℃.
Sixthly, gas changing and heat exchanging.
The medium shift gas 614 flowing out of the medium shift furnace 610 further exchanges heat with the natural gas preheater 110 and the desalted water preheater 210 in order to lower the temperature of the medium shift gas 614 to 100 to 200 ℃. Specifically, the medium temperature gas is preheated to 300-400 ℃ through the natural gas flowing through the natural gas preheater 110, and the medium temperature after the natural gas is preheated is reduced to 250-350 ℃; the desalted water flowing through the desalted water preheater is continuously preheated to 100-200 ℃, and the temperature of the medium temperature after the desalted water is preheated 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 the temperature of 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 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, O, 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 400-600 ℃. 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 550 to 750 ℃, preferably 650 to 700 ℃. 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. Increasing the temperature of the raw material mixed gas 314 from 200-400 ℃ to 550-750 ℃, wherein the first heat exchange contributes more than 50%, particularly more than 55%, and particularly about 57% to the raw material mixed gas; the proportion of contribution of the second heat exchange thereto is below 50%, in particular about 43%.
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 area 526; the reformed gas 524b after reforming conversion is obtained after the intermediate reformed gas 524a flows through the catalyst bed 526a of the second heat exchange zone 526, and the temperature of the reformed gas 524 flowing out of the conversion pipe 520 and/or the conversion furnace 500 is 250-450 ℃ 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 and directly enters the middle-variable furnace 610 for middle-variable reaction; directly as described herein, means that no equipment for further reducing the temperature of the reformed gas 524 is required between the reformer 500 and the midrange furnace 610.
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; before the reformed gas generated by reforming conversion reaction flows out of the reformer, the reformed gas is fully subjected to heat exchange with the raw material mixed gas in regions, stages and proportions. Therefore, before the raw material mixed gas flows into the conversion pipe, a separate preheating device is not needed to be arranged, and after the converted gas flows out of the conversion furnace, the converted gas can directly enter the converter to carry out the next conversion reaction without an additional heat exchange device; not only simplifies the internal structure of the reformer 500, reduces the production and processing difficulty of the reformer 500, reduces the volume of the reformer 500, but also simplifies the equipment layout of the whole system and reduces the occupied area of the whole system.
In conclusion, the hydrogen production system and the hydrogen production method by reforming the hydrocarbon steam can simplify the overall flow and pipeline arrangement of the hydrogen production 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 according to the disclosure of the application document without departing from the spirit and scope of the present disclosure.
Claims (7)
1. A hydrocarbon steam reforming hydrogen production system comprises a reformer and a shift converter, wherein a reforming conversion reaction occurs in the reformer to generate a reformed gas, a shift reaction occurs in the shift converter to generate a shift gas, and the shift reaction is used for largely removing CO in the reformed gas.
2. The hydrocarbon steam reforming hydrogen production system of claim 1, wherein the hydrocarbon steam reforming hydrogen production system is a natural gas steam reforming hydrogen production system; the system also comprises a natural gas preheater and a desalted water preheater, wherein the downstream of the medium transformer furnace is sequentially communicated with the natural gas preheater and the desalted water preheater in a fluid mode, and medium transformer gas generated by the medium transformer furnace is sequentially subjected to heat exchange through the natural gas preheater and the desalted water preheater.
3. The system for producing hydrogen by reforming hydrocarbon steam as claimed in claim 2, wherein an air self-preheating burner is disposed in the reformer, and a high-temperature flue gas outlet is disposed 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 preheating the air flows out of the reformer from the high-temperature flue gas outlet.
4. The system for hydrogen production by steam reforming of hydrocarbons of claim 3, further comprising a flue gas steam generator, wherein the high temperature flue gas outlet is directly fluidly connected to the flue gas steam generator such that the temperature of the high temperature flue gas exiting the flue gas steam generator is between 150 ℃ and 250 ℃.
5. The system for producing hydrogen by steam reforming of hydrocarbons 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 steam reforming of hydrocarbons as claimed in claim 2, further comprising a water-cooled separator provided with an integrated water-cooled array pipe, so that the medium reformed 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 hydrocarbons 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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202221719902 | 2022-06-29 | ||
| CN2022217199027 | 2022-06-29 |
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| Publication Number | Publication Date |
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| CN218261977U true CN218261977U (en) | 2023-01-10 |
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| CN202222188633.2U Active CN218261977U (en) | 2022-06-29 | 2022-08-19 | Hydrocarbon steam reforming hydrogen production system |
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