CN114522508B - Hydrogen adsorber regeneration system and method thereof - Google Patents
Hydrogen adsorber regeneration system and method thereof Download PDFInfo
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- CN114522508B CN114522508B CN202210432597.1A CN202210432597A CN114522508B CN 114522508 B CN114522508 B CN 114522508B CN 202210432597 A CN202210432597 A CN 202210432597A CN 114522508 B CN114522508 B CN 114522508B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0407—Constructional details of adsorbing systems
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0454—Controlling adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/16—Hydrogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Abstract
The invention provides a hydrogen adsorber regeneration system and a method thereof, wherein the regeneration system comprises: the first gas supply unit is used for supplying hydrogen to be treated; the adsorption unit is connected with the first gas supply unit and comprises at least two first adsorbers and second adsorbers which can be switched to use, and the second adsorber is regenerated when the first adsorber is used for adsorption; the regeneration gas supply unit is connected with the adsorption unit and is used for supplying regeneration gas to the second adsorber so as to discharge impurity gas generated when the second adsorber is regenerated by the regeneration gas; the high-purity hydrogen supply unit is connected with the adsorption unit and used for supplying high-purity hydrogen with a preset temperature range to the second adsorber so as to discharge the regeneration gas in the second adsorber by using the high-purity hydrogen; and the discharge unit is connected with the adsorption unit and is used for discharging at least the impurity gas and the regeneration gas in the second adsorber. The application provides a hydrogen adsorber regeneration system can improve the regeneration degree of depth of hydrogen adsorber.
Description
Technical Field
The embodiment of the invention relates to the technical field of hydrogen liquefaction, in particular to a hydrogen adsorber regeneration system and a method thereof.
Background
Utilization of hydrogen energy can solve sustainability, pollutant emissions, and energy safety issues. In recent years, hydrogen energy has been widely used in the fields of national defense, aerospace, large scientific engineering research, low-temperature superconduction, electronic chips, energy chemical industry, metallurgy and energy transportation. However, the cost of commercial application of hydrogen energy is high due to storage and transportation issues of hydrogen energy. As is known, Liquefied Hydrogen (LH)2) Has an energy density of almost 4.5 times that of compressed hydrogen at 200bar, and if a large amount of hydrogen can be transported from a remote location to a municipal hydrogen refueling station, the manner of storage and transportation of the liquid becomes particularly attractive, and therefore, a hydrogen liquefaction system is implementedThe key to converting hydrogen gas to liquid hydrogen.
In the hydrogen liquefaction system, because the boiling point of hydrogen is extremely low (about 253 ℃), other various gases not only become liquid, but also most of the gases become solid in the process of hydrogen liquefaction, and particularly, solid oxygen is easy to accumulate at the inlet of a throttling valve or the inner surface of a rough pipeline, so that the solid oxygen explosion is easy to cause, and serious personal safety and property loss are caused. Therefore, in order to remove solid impurities generated in the hydrogen liquefaction process, one or more stages of hydrogen adsorbers are required in the hydrogen liquefaction system to purify the raw hydrogen (hydrogen to be liquefied) or the recycle hydrogen (refrigerant). However, in a low-temperature working environment, the hydrogen adsorber is very easy to adsorb and saturate, and when the adsorber is saturated, impurities cannot be continuously removed, so that impurity gas in the hydrogen enters a downstream system to be solidified, frozen, blocked and accumulated, thereby generating overpressure of the system and explosion risk caused by accumulated solid oxygen. Therefore, the hydrogen adsorber is the key for ensuring the safe and stable operation of the hydrogen liquefaction system.
In the prior art, when a hydrogen adsorber is saturated in adsorption and needs to be regenerated, the regeneration depth is low, so that the safe operation of a hydrogen liquefaction system and the purity of liquid hydrogen are influenced.
Therefore, there is a need for a hydrogen adsorber regeneration system and method thereof to solve the above problems.
Disclosure of Invention
The embodiment of the invention provides a hydrogen adsorber regeneration system and a method thereof, which can improve the regeneration depth of a hydrogen adsorber.
In a first aspect, an embodiment of the present invention provides a hydrogen adsorber regeneration system, including:
a first gas supply unit for supplying hydrogen to be processed including raw hydrogen to be used for liquefaction and hydrogen to be used for a refrigeration cycle;
the adsorption unit is connected with the first gas supply unit and comprises at least two first adsorbers and second adsorbers which can be switched to use, and the second adsorbers are regenerated when the first adsorbers adsorb;
a regeneration gas supply unit connected to the adsorption unit, for supplying a regeneration gas to the second adsorber to discharge an impurity gas generated during regeneration of the second adsorber by the regeneration gas;
the high-purity hydrogen supply unit is connected with the adsorption unit and used for supplying high-purity hydrogen with a preset temperature range to the second adsorber so as to discharge the regeneration gas in the second adsorber by using the high-purity hydrogen, and the preset temperature range is at least higher than the temperature of the hydrogen to be processed;
and the discharge unit is connected with the adsorption unit and is used for discharging at least the impurity gas and the regeneration gas in the second adsorber.
In one possible design, the first gas supply unit includes a first pipeline, a second pipeline, a first valve and a second valve disposed on the first pipeline, a first pressure transmitter, a second pressure transmitter, a third valve and a fourth valve disposed on the second pipeline, a third pressure transmitter, and a fourth pressure transmitter;
the first valve and the second valve are used for controlling the on-off of the hydrogen to be treated in the first pipeline, and the third valve and the fourth valve are used for controlling the on-off of the hydrogen to be treated in the second pipeline;
the first pressure transmitter and the second pressure transmitter are used for monitoring the pressure of the hydrogen to be processed in the first pipeline, and the third pressure transmitter and the fourth pressure transmitter are used for monitoring the pressure of the hydrogen to be processed in the second pipeline.
In one possible design, the first adsorber is disposed on the first pipeline, the first valve and the first pressure transmitter are disposed at one end of the first adsorber, and the second valve and the second pressure transmitter are disposed at the other end of the first adsorber;
the second adsorber is arranged on the second pipeline, the third valve and the third pressure transmitter are arranged at one end of the second adsorber, and the fourth valve and the fourth pressure transmitter are arranged at the other end of the second adsorber;
and the first adsorber and the second adsorber are switched between adsorption and regeneration by controlling the opening and closing of the first valve, the second valve, the third valve and the fourth valve.
In one possible design, a first temperature transmitter and a second temperature transmitter are respectively arranged on the first adsorber and the second adsorber;
the first temperature transmitter is used for monitoring the temperature of the first adsorber, and the second temperature transmitter is used for monitoring the temperature of the second adsorber.
In one possible design, the regeneration gas supply unit includes a first supply line, a first supply valve, a second supply valve, and a third supply valve;
the first supply valve is arranged at the inlet end of the first supply pipeline and is connected with the second supply valve and the third supply valve in series respectively, and the first supply valve is used for controlling the total on-off of the regeneration gas;
the second supply valve and the third supply valve are connected in parallel; wherein the second supply valve is connected with the outlet end of the first adsorber, the third supply valve is connected with the outlet end of the second adsorber, and the regeneration gas is supplied to the first adsorber or the second adsorber by controlling the opening and closing of the second supply valve and the third supply valve.
In one possible design, the inlet end of the first supply line is provided with a heating device and a third temperature transmitter; the heating device is used for heating the regenerated gas, and the third temperature transmitter is used for monitoring the heating temperature of the regenerated gas.
In one possible design, the high purity hydrogen supply unit includes a second supply line and a fourth supply valve, the fourth supply valve being disposed at an inlet end of the second supply line;
the second supply line and the first supply line communicate with each other, and share the second supply valve and the third supply valve with the regeneration gas supply unit;
and supplying high-purity hydrogen to the first adsorber or the second adsorber by controlling the opening and closing of the second supply valve and the third supply valve.
In one possible design, the bleed unit includes a first bleed line, a first bleed valve and a second bleed valve disposed on the first bleed line;
the first and second bleed valves are connected in parallel; wherein the first discharge valve is connected with the inlet end of the first adsorber, and the second discharge valve is connected with the inlet end of the second adsorber;
and discharging impurity gas and regeneration gas in the first adsorber and the second adsorber by controlling the opening and closing of the first discharge valve and the second discharge valve.
In one possible design, the bleed unit further includes a second bleed line and a third bleed valve disposed on the second bleed line; one end of the second bleed line is communicated with the first bleed line, and the other end of the second bleed line is communicated with the first supply line and the second supply line;
and discharging the hydrogen which is used for primarily cooling the first adsorber or the second adsorber and is higher than the preset temperature by controlling the opening and closing of the third discharge valve, the second supply valve and the third supply valve.
In a second aspect, an embodiment of the present invention further provides a method for regenerating a hydrogen adsorber, including:
providing hydrogen to be treated by using the first gas supply unit;
supplying a regeneration gas to a second adsorber of the adsorption unit using the regeneration gas supply unit to discharge an impurity gas generated when the second adsorber is regenerated using the regeneration gas;
supplying high-purity hydrogen to a second adsorber of the adsorption unit using the high-purity hydrogen supply unit to discharge a regeneration gas in the second adsorber using the high-purity hydrogen;
and at least discharging the impurity gas and the regeneration gas in the second adsorber by using the discharging unit.
The application provides a hydrogen adsorber regeneration system, through setting up high-purity hydrogen supply unit, to the high-purity hydrogen that the hydrogen adsorber that needs regeneration provides the temperature for predetermineeing temperature range to utilize the regeneration gas of this high-purity hydrogen in with the adsorber to discharge, rather than utilize the regeneration gas in the microthermal pending hydrogen discharge adsorber, so can prevent that the adsorber that has regenerated adsorbs the regeneration gas again under microthermal environment. Therefore, the hydrogen adsorber regeneration system provided by the application can improve the regeneration depth of the hydrogen adsorber.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a system schematic of a hydrogen adsorber regeneration system provided by an embodiment of the present invention;
FIG. 2 is a schematic flow diagram of a method for regenerating a hydrogen adsorber in accordance with an embodiment of the present invention.
Reference numerals:
1-a first air supply unit;
11-a first conduit;
111-a first valve;
112-a second valve;
113-a first pressure transmitter;
114-a second pressure transmitter;
12-a second conduit;
121-a third valve;
122-a fourth valve;
123-a third pressure transmitter;
124-a fourth pressure transmitter;
2-an adsorption unit;
21-a first adsorber;
22-a second adsorber;
23-a first temperature transmitter;
24-a second temperature transmitter;
3-a regeneration gas supply unit;
31-a first supply line;
32-a first supply valve;
33-a second supply valve;
34-a third supply valve;
35-a heating device;
36-a third temperature transmitter;
4-a high purity hydrogen supply unit;
41-a second supply line;
42-a fourth supply valve;
5-a bleed-off unit;
51-a first bleed line;
52-a first bleed valve;
53-a second bleed valve;
54-a second bleed line;
55-third bleed valve.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions in the embodiments of the present invention will be described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention, and based on the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without creative efforts belong to the scope of the present invention.
As described above, in the prior art, the regeneration depth of the hydrogen adsorber is too low, which affects the safe operation of the hydrogen liquefaction system and the purity of the liquid hydrogen.
In view of the above problems, the inventors have found that this is caused by replacing the regeneration gas in the hydrogen adsorber with the low-temperature hydrogen to be treated after the completion of the regeneration of the hydrogen adsorber. The hydrogen adsorber is easy to have adsorption reaction in the low-temperature working environment, so that the low-temperature hydrogen to be treated (such as 80K) is directly used for replacing the regeneration gas in the adsorber, the regenerated adsorber is caused to adsorb the regeneration gas again, and the regeneration depth of the adsorber is reduced.
In order to solve the above problems, the inventor proposes that a path of high-purity hydrogen with a preset temperature range can be added to a hydrogen liquefaction system to replace the regenerated gas in the hydrogen adsorber, so as to improve the regeneration depth of the hydrogen adsorber.
As shown in fig. 1, an embodiment of the present invention provides a hydrogen adsorber regeneration system, comprising:
a first gas supply unit 1 for supplying hydrogen to be treated including raw hydrogen to be used for liquefaction and hydrogen to be used for a refrigeration cycle;
an adsorption unit 2 connected to the first gas supply unit 1, including at least two first adsorbers 21 and second adsorbers 22 that can be switched to use, wherein the second adsorbers 22 are regenerated when the first adsorbers 21 perform adsorption;
a regeneration gas supply unit 3 connected to the adsorption unit 2, for supplying a regeneration gas to the second adsorber 22 to discharge an impurity gas generated during regeneration of the second adsorber 22 by the regeneration gas;
a high-purity hydrogen supply unit 4 connected to the adsorption unit 2, for supplying high-purity hydrogen to the second adsorber 22 in a preset temperature range, which is at least higher than the temperature of the hydrogen to be processed, to discharge the regeneration gas from the second adsorber 22 by using the high-purity hydrogen;
and a discharge unit 5 connected to the adsorption unit 2, for discharging at least the impurity gas and the regeneration gas in the second adsorber 22.
In the embodiment, the high-purity hydrogen supply unit 4 is arranged to supply the high-purity hydrogen with the temperature within the preset temperature range to the hydrogen adsorber to be regenerated, and the high-purity hydrogen is used for discharging the regeneration gas in the adsorber instead of discharging the regeneration gas in the adsorber by using the low-temperature hydrogen to be treated, so that the regenerated adsorber can be prevented from adsorbing the regeneration gas again in the low-temperature environment. Therefore, the hydrogen adsorber regeneration system provided by the embodiment can improve the regeneration depth of the hydrogen adsorber.
On one hand, because hydrogen belongs to flammable and explosive gas, if the temperature of high-purity hydrogen is too high, explosion danger is easy to occur; on the other hand, since the hydrogen adsorber has a strong adsorbability in a low-temperature environment, if the temperature of the high-purity hydrogen is too low (for example, lower than 200K), the regeneration gas remaining in the hydrogen adsorber is easily adsorbed, and the regeneration depth of the adsorber is affected. Therefore, it is necessary to limit the temperature range of the high-purity hydrogen gas, which is preferably 20 to 35 ℃, i.e., normal temperature, and which is easily available without separate heating or cooling, while not causing the risk of explosion and re-adsorption of the regeneration gas. Of course, the preset temperature range is a preferable mode, and the user can also select other high-purity hydrogen with the temperature higher than that of the hydrogen to be treated, and the safety or the regeneration effect is slightly poor.
In addition, in this embodiment, the high-purity hydrogen is preferably hydrogen with a purity higher than 99.999%, and the hydrogen with the purity is easy to prepare, has a low cost, and meets the use requirement (impurities are not introduced to affect the purity of the hydrogen to be processed), and of course, a user may select hydrogen with other purity, which is not limited in this application.
In addition, the hydrogen adsorber regeneration system provided by the embodiment is suitable for any one stage of hydrogen adsorbers of raw material hydrogen or refrigeration cycle hydrogen, such as a first-stage adsorber and a second-stage adsorber, wherein the first-stage adsorber is used for removing most of impurity gases such as oxygen, nitrogen, hydrocarbons and the like, and the second-stage adsorber is used for removing impurity gases such as neon and the like. When multiple stages of adsorbers are present in the regeneration system, the adsorbers share the regeneration gas supply unit 3, the high purity hydrogen supply unit 4, and the bleed unit 5.
In some embodiments, the regeneration gas may be nitrogen or helium, preferably nitrogen, because nitrogen is chemically stable, non-flammable, non-explosive, and economical, and other gases may be used by the user, which is not limited herein.
In some embodiments, the first gas supply unit 1 includes a first pipeline 11, a second pipeline 12, a first valve 111 and a second valve 112 disposed on the first pipeline, a first pressure transmitter 113, a second pressure transmitter 114, a third valve 121 and a fourth valve 122 disposed on the second pipeline, a third pressure transmitter 123, a fourth pressure transmitter 124;
the first valve 111 and the second valve 112 are used for controlling the on-off of the hydrogen to be treated in the first pipeline 11, and the third valve 121 and the fourth valve 122 are used for controlling the on-off of the hydrogen to be treated in the second pipeline 12; for example, when the first valve 111 and the second valve 112 are closed and the third valve 121 and the fourth valve 122 are opened, the hydrogen to be treated is allowed to pass through the second pipeline 12, while the first adsorber 21 is in standby and the second adsorber 22 is in operation.
The first pressure transmitter 113 and the second pressure transmitter 114 are used to monitor the pressure of the hydrogen gas to be processed in the first pipeline 11, and the third pressure transmitter 123 and the fourth pressure transmitter 124 are used to monitor the pressure of the hydrogen gas to be processed in the second pipeline 12. The working states of the two adsorbers can be obtained in real time through the pressures monitored by the four pressure transmitters, for example, whether the first adsorber 21 is saturated by adsorption can be judged by calculating the pressure difference between the first pressure transmitter 113 and the second pressure transmitter 114, and for example, the charging pressure and the discharging pressure of the first adsorber 21 can be judged through the pressure value of the first pressure transmitter 113, so as to effectively control the regeneration operation of the regeneration system.
In some embodiments, a first adsorber 21 is disposed on the first pipeline 11, a first valve 111 and a first pressure transmitter 113 are disposed at one end of the first adsorber 21, and a second valve 112 and a second pressure transmitter 114 are disposed at the other end of the first adsorber 21;
the second adsorber 22 is arranged on the second pipeline 12, the third valve 121 and the third pressure transmitter 123 are arranged at one end of the second adsorber 22, and the fourth valve 122 and the fourth pressure transmitter 124 are arranged at the other end of the second adsorber 22;
the first adsorber 21 and the second adsorber 22 are switched between adsorption and regeneration by controlling the opening and closing of the first valve 111, the second valve 112, the third valve 121, and the fourth valve 122.
In some embodiments, the first adsorber 21 and the second adsorber 22 are provided with a first temperature transmitter 23 and a second temperature transmitter 24, respectively; wherein a first temperature transmitter 23 is used to monitor the temperature of the first adsorber 21 and a second temperature transmitter 24 is used to monitor the temperature of the second adsorber 22. Therefore, the working temperature, the regeneration temperature and the precooling temperature of the hydrogen to be processed and the adsorber can be obtained in real time, and the stable operation of the system is further ensured.
In some embodiments, the regeneration gas supply unit 3 includes a first supply line 31, a first supply valve 32, a second supply valve 33, and a third supply valve 34;
a first supply valve 32 is disposed at an inlet end of the first supply line 31, and is connected in series with a second supply valve 33 and a third supply valve 34, respectively, and the first supply valve 32 is used for controlling the total on-off of the regeneration gas;
the second supply valve 33 and the third supply valve 34 are connected in parallel; the second supply valve 33 is connected to the outlet of the first adsorber 21, the third supply valve 34 is connected to the outlet of the second adsorber 22, and the regeneration gas is supplied to the first adsorber 21 or the second adsorber 22 by controlling the opening and closing of the second supply valve 33 and the third supply valve 34. For example, when regeneration of the second adsorber 22 is required, the regeneration gas may be introduced into the second adsorber 22 by closing the second supply valve 33 and opening the first supply valve 32 and the third supply valve 34.
In general, the hydrogen adsorber has the characteristics of high-pressure low-temperature adsorption and low-pressure high-temperature regeneration, and therefore, the regeneration gas in the present embodiment is preferably a low-pressure regeneration gas, for example, 0.7MPa nitrogen.
Of course, in the initial hydrogen replacement stage, the adsorber may be regenerated using low-pressure normal-temperature regeneration gas in order to prevent the replaced hydrogen from exploding, and after the hydrogen is completely discharged, the adsorber needs to be continuously regenerated using high-temperature regeneration gas in order to ensure the regeneration depth.
Therefore, in some embodiments, the inlet end of the first supply line 31 is provided with a heating device 35 to heat the regeneration gas by the heating device 35, for example, to 65 ℃, and of course, the first supply line 31 may be provided with a third temperature transmitter 36 to monitor the heating temperature of the regeneration gas in real time.
In some embodiments, the heating device 35 may be an electric heater or other device with heating function, and the application does not specifically limit the type of the heating device and the heating temperature, and the user may determine the heating device autonomously according to actual needs.
In some embodiments, the high purity hydrogen supply unit 4 includes a second supply line 41 and a fourth supply valve 42, the fourth supply valve 42 being disposed at an inlet end of the second supply line 41;
the second supply line 41 and the first supply line 31 communicate with each other, sharing the second supply valve 33 and the third supply valve 34 with the regeneration gas supply unit 3;
by controlling the opening and closing of the second supply valve 33 and the third supply valve 34, high purity hydrogen gas is supplied to the first adsorber 21 or the second adsorber 22.
In this embodiment, when the regeneration is completed and the regeneration gas in the second adsorber 22 needs to be exhausted, the first supply valve 32 and the second supply valve 33 are closed, and the fourth supply valve 42 and the third supply valve 34 are opened to allow the high-purity hydrogen gas to be introduced into the second adsorber 22, thereby performing the regeneration gas replacement.
In this embodiment, since the second supply line 41 and the first supply line 31 communicate with each other and the second supply valve 33 and the third supply valve 34 are shared, the system can be simplified, and cost can be saved.
In some embodiments, the relief unit 5 comprises a first relief line 51, a first relief valve 52 and a second relief valve 53 provided on the first relief line 51;
the first bleed valve 52 and the second bleed valve 53 are connected in parallel; wherein, the first discharge valve 52 is connected with the inlet end of the first adsorber 21, and the second discharge valve 53 is connected with the inlet end of the second adsorber 22; the impurity gas and the regeneration gas in the first adsorber 21 and the second adsorber 22 are purged by controlling the opening and closing of the first purge valve 52 and the second purge valve 53. For example, during the hydrogen replacement phase or the regeneration gas replacement phase, the impurity gas and the regeneration gas in the second adsorber 22 may be purged by closing the first purge valve 52 and opening the second purge valve 53.
In the hydrogen liquefaction system, the standby regenerators are all in a cold standby state, so that after replacement of the regenerators is completed, preliminary precooling needs to be carried out on regenerated adsorbers, and precooled gas can adopt hydrogen to be treated. Generally, after the preliminary pre-cooling of the hydrogen to be processed is completed, the temperature of the hydrogen is higher than the normal operating temperature, for example, the normal operating temperature is 80K, and the temperature of the hydrogen after participating in the pre-cooling is 200K, at this time, if the part of the hydrogen is directly discharged into the downstream liquefaction system, the temperature fluctuation of the downstream liquefaction system may be caused.
To avoid the above problem, in some embodiments, the relief unit 5 further comprises a second relief line 54 and a third relief valve 55 provided on the second relief line 54; one end of the second drain line 54 communicates with the first drain line 51, and the other end of the second drain line 54 communicates with the first supply line 31 and the second supply line 41; the hydrogen to be treated which is higher than the preset temperature after the primary cooling of the first adsorber 21 or the second adsorber 22 is discharged by controlling the opening and closing of the third discharge valve 55, the second supply valve 33 and the third supply valve 34.
For example, when preliminary pre-cooling of the second adsorber 22 is required, the fourth valve 122 is closed, the third valve 121 (which may be partially opened, for example, 20% of the total opening degree), the third supply valve 34, and the third drain valve 55 are opened, so that a small amount of hydrogen to be treated passes through, and preliminary pre-cooling of the second adsorber 22 is performed, where the pre-cooled hydrogen is discharged through the drain line, thereby avoiding temperature fluctuation of the downstream liquefaction system. In the pre-cooling process, the temperature of the second adsorber 22 is monitored by the second temperature transmitter 24, when the temperature of the second temperature transmitter 24 is close to the normal operating temperature (for example, the temperature of the second temperature transmitter 24 is higher than the normal operating temperature by about 10-20K), the preliminary pre-cooling is completed, the third supply valve 34 and the third release valve 55 are closed, and the hydrogen used for pre-cooling is discharged to a downstream system, so as to avoid waste of low-temperature hydrogen.
Therefore, in the present embodiment, by providing the second bleed line 54 and the third bleed valve 55, the hydrogen used for cooling is bled and discharged in the initial cooling stage, which can avoid temperature fluctuation of the downstream liquefaction system, and the third bleed valve 55 is closed in the deep cooling stage, so that the hydrogen used for precooling is discharged to the downstream system, and waste of the hydrogen can be avoided.
In some embodiments, in order to realize the on-line automatic switching of the hydrogen adsorber regeneration system, all the valves in this application are preferably pneumatic valves or electric valves, and of course, valves with interlocking functions such as hydraulic valves, etc., and the application does not specifically limit the control form of the valves.
In addition, in order to adjust the flow rate of the hydrogen to be processed in real time according to the user requirement and ensure the stability of the regeneration system, the first valve 111 and the third valve 121 in the embodiments of the present application are preferably valves having a regulating function, so as to adjust the opening degree of the valves according to the actual requirement. The valves other than the first valve 111 and the third valve 121 are preferably shut-off valves, such as ball valves or butterfly valves, so that the system can respond quickly when the system needs to switch adsorbers, thereby ensuring the stability and safety of the system. Of course, the above only provides a preferred mode of the valve, and the user can also determine the valve form by himself according to the needs, and the application is not limited in particular. Besides, in order to guarantee the service life of the valve, in the low temperature unit, a low temperature resistant valve is preferred, and in the high temperature unit, a high temperature resistant valve is preferred, which is not specifically limited in this application.
In addition, the regeneration system shown in fig. 1 only realizes automatic switching and regeneration of the hydrogen adsorber, and ensures continuous operation of the hydrogen liquefaction system and safety of the device, and in addition, the system may further include other devices required for normal operation, such as valves, pipelines, temperature meters, and pressure meters, and thus, the present application is not repeated.
As shown in fig. 2, an embodiment of the present invention provides a method for regenerating a hydrogen adsorber, the method including:
a step 102 of supplying a regeneration gas to the second adsorber 22 of the adsorption unit 2 by the regeneration gas supply unit 3 to discharge an impurity gas generated during regeneration of the second adsorber 22 by the regeneration gas;
a step 104 of supplying high-purity hydrogen to the second adsorber 22 of the adsorption unit 2 by the high-purity hydrogen supply unit 4 to discharge the regeneration gas in the second adsorber 22 by the high-purity hydrogen;
at least the impurity gas and the regeneration gas in the second adsorber 22 are purged 106 using the purge unit 5.
The regeneration scheme of the regeneration system of the present application will be described in detail below, taking the regeneration of the second adsorber 22 as an example:
step A, switching the adsorbers, opening a first valve 111 and a second valve 112, and switching the first adsorber 21 to a working state; the third valve 121 and the fourth valve 122 are closed, and the second adsorber 22 is switched to the regeneration state.
Step B, releasing the hydrogen to be processed, keeping the first release valve 52, the second supply valve 33, the third supply valve 34, the fourth supply valve 42, the first supply valve 32 and the third release valve 55 closed, and opening the second release valve 53 until the third pressure transmitter 123 reaches the micro-positive pressure, thereby completing the hydrogen release. In this step, the micro-positive pressure is maintained to prevent the external air from entering the adsorber and the pipeline to cause explosion.
And step C, replacing and regenerating the regeneration gas, maintaining the opening state of the second relief valve 53, opening the first supply valve 32 and the third supply valve 34, introducing the low-pressure normal-temperature regeneration gas, starting the heating device 35 after a preset time, heating the regeneration gas to a regeneration temperature design value (such as 65 ℃), and enabling the heated regeneration gas to flow through the second adsorber 22 until the temperature of the second temperature transmitter 24 is close to the regeneration temperature design value. At this time, the dew point of the bleed gas is detected, and if the detected dew point temperature does not exceed the design value, indicating that regeneration is completed, the heating device 35 is stopped, the regeneration gas at normal temperature is continuously introduced until the temperature of the second temperature transmitter 24 approaches the ambient temperature, and the first supply valve 32, the third supply valve 34, and the second bleed valve 53 are closed. In this step, the preset time may be determined according to an empirical value, and the main purpose is to completely discharge the hydrogen in the second adsorber 22, so as to avoid explosion risk caused by introducing high-temperature regeneration gas. In addition, the normal temperature regeneration gas is continuously introduced after the regeneration is completed, so as to reduce the temperature of the second adsorber 22, and avoid the explosion risk after the normal temperature hydrogen is introduced in the step D.
And D, replacing hydrogen, opening the second relief valve 53, observing the third pressure transmitter 123, closing the second relief valve 53 when the pressure of the third pressure transmitter 123 reaches the micro-positive pressure, opening the fourth supply valve 42 and the third supply valve 34 to start hydrogen pressurization until the pressure of the third pressure transmitter 123 reaches the normal operating pressure, closing the fourth supply valve 42 and the third supply valve 34, and opening the second relief valve 53 to start pressure relief until the pressure of the third pressure transmitter 123 reaches the micro-positive pressure. And D, repeating the step D, finishing hydrogen charging and discharging replacement, and closing the fourth supply valve 42, the third supply valve 34 and the second discharge valve 53. By adopting the step, the regeneration depth of the adsorber can be improved.
Step E, pre-cooling, namely opening the third valve 121 by a certain opening degree (for example, not more than 20% of the normal opening degree so as to avoid affecting the normal operation of the downstream liquefaction system), opening the third supply valve 34 and the third discharge valve 55, observing the second temperature transmitter 24, and closing the third supply valve 34 and the third discharge valve 55 when the second temperature transmitter 24 reaches a preliminary pre-cooling set value (for example, the temperature difference between the second temperature transmitter 24 and the normal operating temperature is not more than 20K); the fourth valve 122 is fully opened until the second temperature transmitter 24 reaches a set point for deep pre-cooling end (e.g., the second temperature transmitter 24 is not more than 3K from the normal operating temperature), the pre-cooling end, and the third valve 121 and the fourth valve 122 are closed.
Step F, cold standby, the second adsorber 22 enters the cold standby state, and the regeneration process ends.
It should be noted that before performing adsorber regeneration, it is necessary to determine whether the current adsorber is saturated by adsorption, and if not, the current adsorber continues to operate without switching to the standby adsorber; if yes, the standby adsorber is started, and the current adsorber is closed and regenerated.
In some embodiments, the method for determining whether the current adsorber is saturated by adsorption includes at least four methods:
first, sampling and analyzing whether the oxygen content or other impurity content at the outlet of the current adsorber exceeds a set value, for example, if the impurity content such as nitrogen content, argon content or oxygen content exceeds the set value, the automatic switching and regeneration of the adsorber are started in an interlocking way. The set value of the content of each impurity may be specifically set according to experience and the requirement for the purity of hydrogen, and is not specifically limited in the present application.
And secondly, judging according to the pressure drop of the inlet and the outlet of the current adsorber, and if the pressure drop exceeds a set value, starting the automatic switching and regeneration of the adsorber in an interlocking manner. In this kind of mode, the pressure drop can be calculated according to the pressure value of adsorber entry pressure sensor and the pressure value of export pressure sensor and obtain, also can read through the differential pressure gauge, and this application does not do not specifically limit.
Third, automatic switching and regeneration is performed at regular intervals, such as 7 days after continuous adsorber operation.
Fourth, automatic switching and regeneration is actively initiated in the control room for other reasons, such as system pressure instability or current adsorber attachment equipment requiring service.
It is understood that the method for regenerating a hydrogen adsorber provided in this embodiment and the system for regenerating a hydrogen adsorber provided in the foregoing embodiments have the same advantages, and therefore, the detailed description thereof is omitted.
In summary, the embodiments of the present invention have at least the following advantages:
1. by arranging the high-purity hydrogen supply unit 4, high-purity hydrogen at normal temperature is supplied to the hydrogen adsorber to be regenerated, and the high-purity hydrogen is used for discharging the regenerated gas in the adsorber instead of discharging the regenerated gas in the adsorber by using low-temperature hydrogen to be treated, so that the regenerated adsorber can be prevented from adsorbing the regenerated gas again in a low-temperature environment, and the regeneration depth of the hydrogen adsorber is further improved.
2. By providing the second bleed line 54 and the third bleed valve 55 in the bleed unit 5, the hydrogen gas (e.g., hydrogen gas having a temperature above 20K higher than the normal operating temperature) after the preliminary precooling of the regenerated adsorber can be discharged through the second bleed line 54 instead of being directly discharged into the downstream liquefaction system, thereby avoiding causing temperature fluctuations in the downstream liquefaction system.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an …" does not exclude the presence of other similar elements in a process, method, article, or apparatus that comprises the element.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present 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 solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A hydrogen adsorber regeneration system, comprising:
a first gas supply unit (1) for supplying hydrogen to be treated including raw hydrogen to be used for liquefaction and hydrogen to be used for a refrigeration cycle; the temperature of the hydrogen to be treated is 80K;
the adsorption unit (2) is connected with the first gas supply unit (1), comprises at least two first adsorbers (21) and second adsorbers (22) which can be switched to use, and regenerates the second adsorbers (22) when the first adsorbers (21) adsorb;
a regeneration gas supply unit (3) connected to the adsorption unit (2) and configured to supply a regeneration gas to the second adsorber (22) to discharge an impurity gas generated during regeneration of the second adsorber (22) by the regeneration gas;
a high-purity hydrogen supply unit (4) connected to the adsorption unit (2) and configured to supply high-purity hydrogen to the second adsorber (22) within a predetermined temperature range to discharge the regeneration gas from the second adsorber (22) by using the high-purity hydrogen, wherein the predetermined temperature range is at least higher than the temperature of the hydrogen to be processed; the preset temperature range of the high-purity hydrogen is 20-35 ℃, and the high-purity hydrogen with the temperature of 20-35 ℃ is used for preventing the adsorber from adsorbing the regeneration gas again;
a bleed unit (5) connected to the adsorption unit (2) for bleeding at least the impurity gas and the regeneration gas from the second adsorber (22).
2. The regeneration system of claim 1, wherein the first gas supply unit comprises a first pipeline (11), a second pipeline (12), a first valve (111) and a second valve (112) disposed on the first pipeline, a first pressure transmitter (113), a second pressure transmitter (114), a third valve (121) and a fourth valve (122) disposed on the second pipeline, a third pressure transmitter (123), a fourth pressure transmitter (124);
the first valve (111) and the second valve (112) are used for controlling the on-off of the hydrogen to be treated in the first pipeline (11), and the third valve (121) and the fourth valve (122) are used for controlling the on-off of the hydrogen to be treated in the second pipeline (12);
the first pressure transmitter (113) and the second pressure transmitter (114) are used for monitoring the pressure of the hydrogen to be treated in the first pipeline (11), and the third pressure transmitter (123) and the fourth pressure transmitter (124) are used for monitoring the pressure of the hydrogen to be treated in the second pipeline (12).
3. The regeneration system according to claim 2, wherein the first adsorber (21) is provided on the first pipe (11), the first valve (111) and the first pressure transmitter (113) are provided at one end of the first adsorber (21), and the second valve (112) and the second pressure transmitter (114) are provided at the other end of the first adsorber (21);
the second adsorber (22) is arranged on the second pipeline (12), the third valve (121) and the third pressure transmitter (123) are arranged at one end of the second adsorber (22), and the fourth valve (122) and the fourth pressure transmitter (124) are arranged at the other end of the second adsorber (22);
the first adsorber (21) and the second adsorber (22) are switched between adsorption and regeneration by controlling the opening and closing of the first valve (111), the second valve (112), the third valve (121), and the fourth valve (122).
4. Regeneration system according to claim 3, characterized in that the first adsorber (21) and the second adsorber (22) are provided with a first temperature transmitter (23) and a second temperature transmitter (24), respectively;
the first temperature transmitter (23) is used for monitoring the temperature of the first adsorber (21), and the second temperature transmitter (24) is used for monitoring the temperature of the second adsorber (22).
5. Regeneration system according to claim 4, characterized in that the regeneration gas supply unit (3) comprises a first supply line (31), a first supply valve (32), a second supply valve (33) and a third supply valve (34);
the first supply valve (32) is arranged at the inlet end of the first supply pipeline (31) and is respectively connected with the second supply valve (33) and the third supply valve (34) in series, and the first supply valve (32) is used for controlling the total on-off of the regeneration gas;
the second supply valve (33) and the third supply valve (34) are connected in parallel; wherein the second supply valve (33) is connected to an outlet end of the first adsorber (21), the third supply valve (34) is connected to an outlet end of the second adsorber (22), and the regeneration gas is supplied to the first adsorber (21) or the second adsorber (22) by controlling opening and closing of the second supply valve (33) and the third supply valve (34).
6. Regeneration system according to claim 5, wherein the inlet end of the first supply line (31) is provided with a heating device (35) and a third temperature transmitter (36); the heating device (35) is used for heating the regenerated gas, and the third temperature transmitter (36) is used for monitoring the heating temperature of the regenerated gas.
7. The regeneration system according to claim 6, wherein the high purity hydrogen supply unit (4) comprises a second supply line (41) and a fourth supply valve (42), the fourth supply valve (42) being provided at an inlet end of the second supply line (41);
the second supply line (41) and the first supply line (31) being in communication with each other, the second supply valve (33) and the third supply valve (34) being shared with the regeneration gas supply unit (3);
and supplying high-purity hydrogen to the first adsorber (21) or the second adsorber (22) by controlling the opening and closing of the second supply valve (33) and the third supply valve (34).
8. Regeneration system according to claim 7, wherein the bleed unit (5) comprises a first bleed line (51), a first bleed valve (52) and a second bleed valve (53) arranged on the first bleed line (51);
the first bleed valve (52) and the second bleed valve (53) are connected in parallel; wherein the first bleed valve (52) is connected to the inlet side of the first adsorber (21) and the second bleed valve (53) is connected to the inlet side of the second adsorber (22);
and discharging the impurity gas and the regeneration gas in the first adsorber (21) and the second adsorber (22) by controlling the opening and closing of the first discharge valve (52) and the second discharge valve (53).
9. Regeneration system according to claim 8, wherein the relief unit (5) further comprises a second relief line (54) and a third relief valve (55) arranged on the second relief line (54); one end of the second drain line (54) communicates with the first drain line (51), and the other end of the second drain line (54) communicates with the first supply line (31) and the second supply line (41);
and discharging the hydrogen gas which is higher than the preset temperature after the primary cooling of the first adsorber (21) or the second adsorber (22) by controlling the opening and closing of the third discharge valve (55), the second supply valve (33) and the third supply valve (34).
10. A method for regenerating a hydrogen adsorber, the method being applied to a hydrogen adsorber regeneration system according to any one of claims 1 to 9, the method comprising:
providing hydrogen to be treated by using the first gas supply unit (1);
supplying a regeneration gas to a second adsorber (22) of the adsorption unit (2) by the regeneration gas supply unit (3) to discharge an impurity gas generated when the second adsorber (22) is regenerated by the regeneration gas;
supplying high-purity hydrogen to a second adsorber (22) of the adsorption unit (2) by means of the high-purity hydrogen supply unit (4) in order to discharge the regeneration gas in the second adsorber (22) by means of the high-purity hydrogen;
-bleeding off at least the impurity gas and the regeneration gas in the second adsorber (22) by means of the bleed unit (5).
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