CN112919414A - Low-pressure flushing regeneration pressure swing adsorption hydrogen purification system and hydrogen purification method - Google Patents

Low-pressure flushing regeneration pressure swing adsorption hydrogen purification system and hydrogen purification method Download PDF

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CN112919414A
CN112919414A CN202110275325.0A CN202110275325A CN112919414A CN 112919414 A CN112919414 A CN 112919414A CN 202110275325 A CN202110275325 A CN 202110275325A CN 112919414 A CN112919414 A CN 112919414A
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pressure
adsorption
pipeline
flushing
adsorption tower
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陈健
卜令兵
王键
张宏宇
赵洪法
张崇海
周晓烽
穆永峰
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Southwest Research and Desigin Institute of Chemical Industry
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    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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    • B01D53/00Separation 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
    • B01D53/02Separation 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
    • B01D53/04Separation 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
    • B01D53/0454Controlling adsorption
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/02Separation 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
    • B01D53/04Separation 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
    • B01D53/047Pressure swing adsorption
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75Multi-step processes
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
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    • B01D2259/40003Methods relating to valve switching
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2259/00Type of treatment
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    • B01D2259/40007Controlling pressure or temperature swing adsorption
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2259/40011Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40013Pressurization
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    • B01D2259/40032Depressurization with three sub-steps
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
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    • B01D2259/414Further details for adsorption processes and devices using different types of adsorbents
    • B01D2259/4141Further details for adsorption processes and devices using different types of adsorbents within a single bed
    • B01D2259/4143Further details for adsorption processes and devices using different types of adsorbents within a single bed arranged as a mixture
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
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Abstract

The invention discloses a system and a method for purifying hydrogen by low-pressure flushing regeneration pressure swing adsorption, which solve the technical problems of low hydrogen recovery rate or high investment in the prior art. The hydrogen purification system comprises an adsorption tower, first to ninth program control valves, a raw material gas conveying pipeline, a flushing pipeline, a reverse gas release pipeline, a flushing inlet pipeline, a forward gas release pipeline, a second pressure equalizing/third pressure equalizing pipeline, a fourth pressure equalizing pipeline, a first pressure equalizing and final pressure increasing pipeline, a product gas outward conveying pipeline, vacuumizing equipment and pipelines. The hydrogen purification method is characterized in that each adsorption tower sequentially carries out pressure swing adsorption and hydrogen purification through repeated circulation steps comprising an adsorption step, a forward pressure reduction step, a reverse pressure reduction step, a low-pressure flushing regeneration step and a reverse pressure increasing step. When the adsorption tower is in the low-pressure flushing step, the invention vacuumizes to ensure that the flushing regeneration pressure is lower than the regeneration pressure of the normal-pressure flushing process, the flushing efficiency is higher, and the adsorbent is regenerated more thoroughly, thereby improving the dynamic adsorption capacity of the adsorbent and improving the hydrogen recovery rate.

Description

Low-pressure flushing regeneration pressure swing adsorption hydrogen purification system and hydrogen purification method
Technical Field
The invention belongs to the technical field of pressure swing adsorption and purification of gases, and particularly relates to a system and a method for purifying hydrogen through pressure swing adsorption by low-pressure flushing regeneration.
Background
The pressure swing adsorption hydrogen purification technology is widely applied to the fields of petroleum, chemical industry, energy and the like, and with the development of industrial technology, a pressure swing adsorption hydrogen purification system becomes a main unit of a large-scale industrial system, and the scale of the pressure swing adsorption hydrogen purification system is gradually increased, and the hydrogen production per hour is dozens of ten thousand cubic meters.
The pressure swing adsorption hydrogen purification technology utilizes the difference of adsorption capacity of an adsorbent to different gases, and the characteristics that the adsorption capacity is increased along with the increase of adsorption pressure and is reduced along with the reduction of the adsorption pressure, and the hydrogen is purified by adsorbing at high pressure and desorbing and regenerating at low pressure. One of the two regeneration modes of the common adsorbent is normal-pressure flushing regeneration, namely, the adsorbent is flushed and regenerated by utilizing part of hydrogen under normal pressure, and the regeneration pressure is 0.02-0.05 MPag; the other regeneration mode is evacuation regeneration, namely, a vacuum pump is used for vacuumizing the adsorption tower, the adsorbent is regenerated under the vacuum condition, and the regeneration pressure is-0.08 MPag to-0.095 MPa. Wherein, the quantity of the adsorption towers for the flushing regeneration process is small, the investment is low, but the recovery rate of the hydrogen is relatively low; and the evacuation regeneration process needs more pressure equalizing times, and the evacuation process generally has more than 2 steps of pressure equalizing than the flushing process, so that the number of adsorption towers is more, the investment is higher, and the recovery rate of hydrogen is relatively higher.
The purpose of the research of the pressure swing adsorption hydrogen extraction process is to improve the efficiency and the regeneration, and the patent CN210874700U adopts a high-pressure regeneration process to improve the traditional flushing regeneration pressure from 0.02-0.05 MPag to 0.1-0.3 MPag, so that the pressurization energy consumption of desorption gas can be reduced, however, the high-pressure flushing process can reduce the regeneration effect of an adsorbent and reduce the hydrogen recovery rate; in order to improve the regeneration effect of the evacuation process, a plurality of patents disclose that the purge gas is introduced at the later stage of the evacuation step, that is, the evacuation purge process is used to enhance the regeneration of the adsorbent at the later stage of the evacuation, for example, the patent CN110052114A uses a process in which evacuation and purge are performed simultaneously at the middle and later stages of the evacuation stage, and the evacuation process and the purge process can be switched at the same time, for example, patent technologies such as CN1151957C, CN109276973A, CN109529534A, CN110252083A, CN211635878U introduce the evacuation purge step after the evacuation step, however, the improvement is still based on evacuation regeneration, and more pressure equalization times, lower regeneration pressure and larger vacuum pump are still needed than in the purge process. How to increase the efficiency of the flushing regeneration process remains a problem to be solved.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a system and a method for purifying hydrogen by pressure swing adsorption with low-pressure flushing regeneration, which solve the technical problems of low hydrogen recovery rate and high investment of evacuation regeneration process in the prior art with normal-pressure flushing regeneration process.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a low-pressure flushing regeneration pressure swing adsorption hydrogen purification system comprises at least three adsorption towers, a raw material gas conveying pipeline which is connected into the adsorption towers and is provided with a first program control valve 10X, a flushing outlet pipeline provided with a second program control valve 20X, a reverse gas release pipeline provided with a third program control valve 30X, a flushing inlet pipeline which is connected out of the adsorption towers and is provided with a fourth program control valve 40X, a forward discharge pipeline provided with a fifth program control valve 50X, a second pressure equalizing/third pressure equalizing pipeline provided with a seventh program control valve 70X, a fourth pressure equalizing pipeline provided with a sixth program control valve 60X, a first pressure equalizing and final boosting pipeline provided with an eighth program control valve 80X, and a product gas output pipeline provided with a ninth program control valve 90X; the flushing outlet pipeline is provided with a vacuumizing device, and a pipeline is communicated between the flushing inlet pipeline and the sequential discharging pipeline.
Furthermore, a forward-discharge regulating valve is arranged on the pipeline.
Furthermore, the first pressure equalizing and final boosting pipeline is communicated with the product gas output pipeline through a final-charging regulating valve.
A hydrogen purification method of a low-pressure flushing regeneration pressure swing adsorption hydrogen purification system adopts at least three adsorption towers to respectively carry out pressure swing adsorption hydrogen purification through repeated circulation steps, and each adsorption tower sequentially comprises an adsorption step, a forward depressurization step, a reverse depressurization step, a low-pressure flushing regeneration step and a reverse pressurization step through the repeated circulation steps.
Further, the adsorption step is that the raw material gas enters the adsorption tower from the feed end of the adsorption tower under the pressure of 1.0-7.0 MPa, non-hydrogen impurities are adsorbed by the adsorbent, and a hydrogen product flows out from the discharge end of the adsorption tower.
Further, the forward pressure reduction step is that the gas in the adsorption tower flows out of the adsorption tower along the gas flow direction during adsorption, the pressure in the adsorption tower is reduced, the forward pressure reduction step comprises at least two pressure reduction processes, and the forward pressure reduction step comprises a pressure equalizing pressure reduction step and a forward release step of providing flushing regeneration gas for the regeneration adsorption tower.
Further, the reverse pressure reduction step is that the gas in the adsorption tower flows out of the adsorption tower against the gas flow direction during adsorption, the pressure in the adsorption tower is reduced, and the reverse pressure reduction step comprises at least one pressure reduction process.
Furthermore, the low-pressure flushing regeneration step is to flush the adsorption tower from the outlet end of the adsorption tower against the gas flow direction during adsorption, the impurities adsorbed in the adsorption tower are desorbed under low pressure and flow out of the adsorption tower along with the flushing gas, and in the process, the vacuumizing equipment vacuumizes the adsorption tower in the low-pressure flushing regeneration step to ensure that the internal pressure of the adsorption tower is-0.06-0.005 MPa, preferably-0.035-0.005 MPa.
Further, the reverse pressure increasing step comprises a pressure equalizing and increasing step and a final pressure increasing step, wherein the pressure equalizing and increasing step is an adsorption tower after regeneration is completed, and the gas in the forward pressure decreasing step is used for reversely increasing the pressure of the adsorption tower; and in the final pressure boosting step, the pressure of the adsorption tower is boosted to the adsorption pressure by utilizing product gas or raw gas in the adsorption tower completing the pressure equalizing and boosting step.
Furthermore, the adsorption tower is filled with a molecular sieve adsorbent, or a composite adsorption bed consisting of one or more of molecular sieve, activated alumina, activated carbon and silica gel.
Compared with the prior art, the invention has the following beneficial effects:
the invention has simple structure, scientific and reasonable design and convenient use, and when the adsorption tower is in the flushing step, the adsorption tower is vacuumized, so that the pressure for flushing regeneration is lower than the regeneration pressure of the normal-pressure flushing process, the flushing efficiency is higher, and the adsorbent can be regenerated more thoroughly, thereby improving the dynamic adsorption capacity of the adsorbent and the hydrogen recovery rate, wherein the hydrogen recovery rate can be improved by more than 4 percent, and the processing capacity of the unit adsorbent is improved by more than 30 percent.
Drawings
FIG. 1 is a flow diagram of a system for purifying hydrogen by pressure swing adsorption with low-pressure flushing and regeneration (taking 10 towers as an example) according to the present invention.
FIG. 2 is a graph showing the pressure change in the low-pressure-purged regenerative adsorption tower according to the present invention.
Wherein, the names corresponding to the reference numbers are:
1-raw material gas conveying pipeline, 2-flushing pipeline, 3-reverse gas discharging pipeline, 4-flushing inlet pipeline, 5-forward discharging pipeline, 6-fourth pressure equalizing pipeline, 7-second pressure equalizing/third pressure equalizing pipeline, 8-first pressure equalizing and final boosting pipeline, 9-product gas output pipeline, 10-final filling regulating valve, 11-forward discharging regulating valve, 12-vacuumizing equipment, 13-adsorption tower and 14-pipeline.
A first program control valve 10X, a second program control valve 20X, a third program control valve 30X, a fourth program control valve 40X, a fifth program control valve 50X, a sixth program control valve 60X, a seventh program control valve 70X, an eighth program control valve 80X, and a ninth program control valve 90X. Wherein X in 10X, 20X, 30X, 40X, 50X, 60X, 70X, 80X, and 90X is the number of the adsorption tower, and correspondingly, 10X, 20X, 30X, 40X, 50X, 60X, 70X, 80X, and 90X are the numbers of the program control valves, as shown in fig. 1, 10X, 20X, 30X, 40X, 50X, 60X, 70X, 80X, and 90X corresponding to adsorption tower T03 are respectively 103, 203, 303, 403, 503, 603, 703, 803, 903, and 10X, 20X, 30X, 40X, 50X, 60X, 70X, 80X, and 90X corresponding to adsorption tower T10 are respectively 110, 210, 310, 410, 510, 610, 710, 810, and 910, and so on.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation or be constructed and operated in a particular orientation, and thus, it should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; of course, mechanical connection and electrical connection are also possible; alternatively, they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
As shown in fig. 1 and 2, the system for purifying hydrogen through pressure swing adsorption with low pressure flushing and regeneration provided by the present invention comprises at least three adsorption towers 13, a raw material gas delivery pipeline 1 connected to the adsorption towers 13 and provided with a first program control valve 10X, a flushing outlet pipeline 2 provided with a second program control valve 20X, a reverse gas discharge pipeline 3 provided with a third program control valve 30X, a flushing inlet pipeline 4 connected from the adsorption towers 13 and provided with a fourth program control valve 40X, a forward discharge pipeline 5 provided with a fifth program control valve 50X, a second pressure equalizing/third pressure equalizing pipeline 7 provided with a seventh program control valve 70X, a fourth pressure equalizing pipeline 6 provided with a sixth program control valve 60X, a first pressure equalizing and final pressure increasing pipeline 8 provided with an eighth program control valve 80X, and a product gas output pipeline 9 provided with a ninth program control valve 90X; the flushing pipeline 2 is provided with a vacuum pumping device 12, a pipeline 14 is communicated between the flushing inlet pipeline 4 and the forward discharging pipeline 5, the pipeline 14 is provided with a forward discharging regulating valve 11, and the first pressure equalizing and final boosting pipeline 8 is communicated with the product gas output pipeline 9 through a final charging regulating valve 10.
The invention has simple structure, scientific and reasonable design and convenient use, and when the adsorption tower is in the flushing step, the adsorption tower is vacuumized, so that the pressure for flushing regeneration is lower than the regeneration pressure of the normal-pressure flushing process, the flushing efficiency is higher, and the adsorbent can be regenerated more thoroughly, thereby improving the dynamic adsorption capacity of the adsorbent and the hydrogen recovery rate, wherein the hydrogen recovery rate can be improved by more than 4 percent, and the processing capacity of the unit adsorbent is improved by more than 30 percent.
The invention provides a method for purifying hydrogen by using a low-pressure flushing regeneration pressure swing adsorption hydrogen purification system, which adopts at least three adsorption towers to carry out pressure swing adsorption hydrogen purification through repeated circulation steps, wherein a molecular sieve adsorbent is filled in the adsorption towers, or the molecular sieve and one or more of activated alumina, activated carbon and silica gel form a composite adsorption bed, and each adsorption tower undergoes repeated circulation steps, namely an adsorption step, a forward depressurization step, a reverse depressurization step, a low-pressure flushing regeneration step and a reverse pressurization step in sequence. Wherein, the adsorption step is that the raw material gas enters the adsorption tower from the feed end of the adsorption tower under the pressure of 1.0-7.0 MPa, non-hydrogen impurities are adsorbed by the adsorbent, and a hydrogen product flows out from the discharge end of the adsorption tower; the forward depressurization step is that gas in the adsorption tower flows out of the adsorption tower along the gas flow direction during adsorption, the pressure in the adsorption tower is reduced, the forward depressurization step comprises at least two depressurization processes, and the forward depressurization step comprises a pressure equalizing depressurization step and a forward release step of providing flushing regeneration gas for the regeneration adsorption tower; the reverse pressure reduction step is that the gas in the adsorption tower flows out of the adsorption tower against the flow direction of the gas during adsorption, the pressure in the adsorption tower is reduced, and the reverse pressure reduction step comprises at least one pressure reduction process; the low-pressure flushing regeneration step is that the regenerated gas is flushed from the outlet end of the adsorption tower against the gas flow direction during adsorption, the impurities adsorbed in the adsorption tower are desorbed under low pressure and flow out of the adsorption tower along with the flushing gas, and in the process, the vacuumizing equipment vacuumizes the adsorption tower in the flushing regeneration step to ensure that the internal pressure of the adsorption tower is-0.06-0.005 MPa, preferably-0.035-0.005 MPa; the reverse pressure increasing step comprises a pressure equalizing and increasing step and a final pressure increasing step, the pressure equalizing and increasing step is an adsorption tower after regeneration is completed, and the gas in the forward pressure reducing step is used for reversely increasing the pressure of the adsorption tower; and in the final pressure boosting step, the pressure of the adsorption tower is boosted to the adsorption pressure by utilizing product gas or raw gas in the adsorption tower completing the pressure equalizing and boosting step.
By adopting the method, when the adsorption tower is in the flushing step, the adsorption tower is vacuumized, so that the pressure for flushing regeneration is lower than the regeneration pressure of a normal-pressure flushing process, the flushing efficiency is higher, the adsorbent is regenerated more thoroughly, the dynamic adsorption capacity of the adsorbent is improved, the hydrogen recovery rate can be improved by more than 4 percent, and the processing capacity of the unit adsorbent is improved by more than 30 percent. The evacuation device used in the present invention is preferably a vacuum pump.
In order to make the technical solution better understood by those skilled in the art, a 10-tower example will now be described in detail. The following concentration percentages are used as mole percentages, pressure gauge, and absolute pressures unless explicitly indicated.
As shown in fig. 1, the system for purifying hydrogen by low-pressure flushing regeneration pressure swing adsorption of the present invention includes ten adsorption towers 13, a raw material gas delivery pipeline 1, a product gas output pipeline 9, a reverse gas release pipeline 3, a flushing output pipeline 2, a first pressure equalizing and final pressure increasing pipeline 8, a second pressure equalizing/third pressure equalizing pipeline 7, a fourth pressure equalizing pipeline 6, a forward discharge pipeline 5, a flushing input pipeline 4, program control valves 101 to 910, a final filling regulating valve HV101, a forward discharge regulating valve PV101, and an evacuation device 12.
The 10-tower embodiment adopts a 10-2-4/P flow, the process time sequence and the on-off state of a valve of the adsorption tower T01 are shown in Table 1, namely 10 adsorption towers, 2 adsorption towers are used for simultaneous adsorption, 4 steps of pressure equalization and low-pressure flushing regeneration. The cycle process taking the adsorption column T01 as an example is as follows (for convenience of description, the adsorption column 13 will be described below using specific column numbers, that is, the adsorption column 13 will be described as adsorption column T01, adsorption column T02, adsorption column T03, adsorption column T04, adsorption column T05, adsorption column T06, adsorption column T07, adsorption column T08, adsorption column T09 and adsorption column T10 according to the specific involved adsorption columns):
step 1 adsorption step (a): step 1 to step 4, the raw material gas flows into the adsorption tower T01 through the raw material gas conveying pipeline 1 and the first program control valve 101, impurities are adsorbed by the adsorbent in the adsorption tower T01, and the hydrogen is sent out of the system through the ninth program control valve 901 and the product gas external conveying pipeline 9, so that the product gas is obtained.
Step 2 first pressure equalizing and reducing step (1D): step 5, closing the first programmable valve 101 and the ninth programmable valve 901, opening the eighth programmable valve 801 and the eighth programmable valve 804, communicating the adsorption tower T01 and the adsorption tower T04 through the first pressure equalizing and final boosting pipeline 8, and performing first pressure equalizing on the adsorption tower T01 and the adsorption tower T04, namely, the adsorption tower T01 is a first pressure equalizing and reducing step, and the adsorption tower T04 is a first pressure equalizing and increasing step.
Step 3, a second pressure equalizing and reducing step (2D): step 6, the eighth programmable valve 801 is closed, the seventh programmable valve 701 and the seventh programmable valve 705 are opened, the adsorption tower T01 and the adsorption tower T05 are communicated through a second pressure equalizing/third pressure equalizing pipeline 7, the adsorption tower T01 and the adsorption tower T05 perform second pressure equalizing, namely, the adsorption tower T01 is a second pressure equalizing and reducing step, and the adsorption tower T05 is a second pressure equalizing and increasing step.
Step 4, a third pressure equalizing and reducing step (3D): step 7, closing the seventh programmable valve 705, opening the seventh programmable valve 706, communicating the adsorption tower T01 with the adsorption tower T06 through a second pressure equalizing/third pressure equalizing pipeline 7, and performing third pressure equalizing on the adsorption tower T01 and the adsorption tower T06, namely, the adsorption tower T01 is a third pressure equalizing and reducing step, and the adsorption tower T06 is a third pressure equalizing and increasing step.
Step 5, a fourth pressure equalizing and reducing step (4D): step 8, closing the seventh programmable valve 701 and the seventh programmable valve 706, opening the sixth programmable valve 601 and the sixth programmable valve 607, communicating the adsorption tower T01 with the adsorption tower T07 through a fourth pressure equalizing pipeline 6, and carrying out fourth pressure equalization on the adsorption tower T01 and the adsorption tower T07, namely, the adsorption tower T01 is a fourth pressure equalizing and reducing step, and the adsorption tower T07 is a fourth pressure equalizing and increasing step.
Step 6 (PP): 9-10 of the step sequence, the sixth programmable valve 601 and the sixth programmable valve 607 are closed, the fifth programmable valve 501 and the forward release regulating valve 11(PV101) are opened, the adsorption tower T01 is communicated with the adsorption towers T08, T09 and T10 through a forward release pipeline 5, and the forward release step of the adsorption tower T01 is used for providing flushing regeneration gas for the adsorption towers T08, T09 and T10.
Step 7 reverse discharge step (D): in step 11, the fifth programmable valve 501 is closed, the third programmable valve 301 is opened, and the gas in the adsorption tower T01 flows out of the system through the reverse gas discharge pipeline 3 in the direction opposite to the adsorption direction, and is partially adsorbed and desorbed in the reverse discharge step.
Process 8 low pressure rinse step (PV): and (12-15), closing the third programmable valve 301, opening the second programmable valve 201 and the fourth programmable valve 401, receiving the cis-gassing gas from the adsorption towers T02, T03 and T04 by the adsorption tower T01, backwashing the adsorption beds against the gas flow direction during adsorption, and discharging the flushing waste gas out of the system through the low-pressure flushing pipeline 2 and the vacuumizing device 12. In the whole flushing process, the vacuumizing device 12 vacuumizes the adsorption tower T01, so that the pressure of the adsorption tower T01 is-0.06-0.005 MPa, preferably-0.035-0.005 MPag during flushing.
Step 9 a fourth voltage equalizing and boosting step (4R): step 16, the second programmable valve 201 and the fourth programmable valve 401 are closed, the sixth programmable valve 601 and the sixth programmable valve 605 are opened, the adsorption tower T01 and the adsorption tower T05 are communicated through a fourth pressure equalizing pipeline 6, the adsorption tower T01 and the adsorption tower T05 perform fourth pressure equalizing, that is, the adsorption tower T01 is a fourth pressure equalizing and boosting step, and the adsorption tower T05 is a fourth pressure equalizing and boosting step.
Step 10 third pressure equalizing and raising step (3R): step 17, closing the sixth programmable valve 601 and the sixth programmable valve 605, opening the seventh programmable valve 701 and the seventh programmable valve 706, communicating the adsorption tower T01 and the adsorption tower T06 through the second pressure equalizing/third pressure equalizing pipeline 7, and performing third pressure equalizing on the adsorption tower T01 and the adsorption tower T06, that is, the adsorption tower T01 is a third pressure equalizing step, and the adsorption tower T06 is a third pressure equalizing step.
Step 11 second uniform pressure increasing step (2R): step 18, the seventh programmable valve 706 is closed, the seventh programmable valve 707 is opened, the adsorption tower T01 and the adsorption tower T07 are communicated through the second pressure equalizing/third pressure equalizing pipeline 7, the adsorption tower T01 and the adsorption tower T07 perform second pressure equalizing, that is, the adsorption tower T01 is a second pressure equalizing and boosting step, and the adsorption tower T07 is a second pressure equalizing and depressurizing step.
Step 12 first pressure equalizing and raising step (1R): step 19, closing the seventh programmable valve 701 and the seventh programmable valve 707, opening the eighth programmable valve 801 and the eighth programmable valve 808, communicating the adsorption tower T01 and the adsorption tower T08 through the first pressure equalizing and final boosting pipeline 8, and performing first pressure equalizing on the adsorption tower T01 and the adsorption tower T08, namely, the adsorption tower T01 is a first pressure equalizing and boosting step, and the adsorption tower T08 is a first pressure equalizing and depressurizing step.
Procedure 13 final pressure increasing step (FR): step 20, the eighth programmable valve 808 is closed, the final charge regulating valve 10(HV101) is opened, the adsorption tower T01 is communicated with the product gas export pipeline 9 through the first pressure equalizing and final boosting pipeline 8, the adsorption tower T01 is finally boosted with the product gas, and the pressure of the adsorption tower T01 is raised to the adsorption pressure.
TABLE 1 EXAMPLE 1 timing and T01 valve switching schedule
Figure BDA0002976397960000081
Figure BDA0002976397960000091
Note: a: adsorption step, 1D: a first pressure equalizing and reducing step, 2D: a second pressure equalizing and reducing step, 3D: a third pressure equalizing and reducing step, 4D: a fourth pressure equalizing and reducing step, PP: step D: reverse amplification step, PV: low-pressure flushing step, 4R: a fourth voltage equalizing and boosting step, 3R: a third voltage-equalizing and boosting step, 2R: a second voltage equalizing and boosting step, 1R: a first voltage equalizing and boosting step, FR: and finally, a pressure rising step.
The experiment verifies that a simulation experiment is carried out in a laboratory, the experimental process is 10 < -2 > -4/P, the flow chart is shown in figure 1, the pressure of the raw material gas is 2.5MPa, and the regeneration pressure is-0.035 MPa-0.005 MPa; the raw material gas composition is as follows: h2:N2:CO:CH4:CO277:1:5:9:8, purity of hydrogen gas of product is more than or equal to 99.9%, CO is less than or equal to 10ppmv, CO2Less than or equal to 10ppmv, the adsorbent adopts two adsorbents of a molecular sieve and activated carbon, the pressure change curve in the adsorption tower is shown in figure 2 (flushing pressure-0.03 MPa), the system operation performance under different flushing regeneration pressures is shown in table 2, namely, the low-pressure flushing process is compared with normal-pressure (0.02-0.05 MPa) flushing, the system performance is obviously improved, the recovery rate of hydrogen is 4.3 percentage points higher than that of hydrogen in flushing regeneration at 0.03MPa, and the treatment capacity of the unit adsorbent is improved by 32%.
TABLE 2 Performance of the device at different flushing pressures
Figure BDA0002976397960000092
Figure BDA0002976397960000101
Finally, it should be noted that: the above embodiments are only preferred embodiments of the present invention to illustrate the technical solutions of the present invention, but not to limit the technical solutions, and certainly not to limit the patent scope of the present invention; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; that is, the technical problems to be solved by the present invention, which are not substantially changed or supplemented by the spirit and the concept of the main body of the present invention, are still consistent with the present invention and shall be included in the scope of the present invention; in addition, the technical scheme of the invention is directly or indirectly applied to other related technical fields, and the technical scheme is included in the patent protection scope of the invention.

Claims (10)

1. A low-pressure flushing regeneration pressure swing adsorption hydrogen purification system is characterized by comprising at least three adsorption towers (13), a raw material gas conveying pipeline (1) which is connected into the adsorption towers (13) and provided with a first program control valve 10X, a flushing outlet pipeline (2) provided with a second program control valve 20X, a reverse gas release pipeline (3) provided with a third program control valve 30X, a flushing inlet pipeline (4) which is connected from the inside of the adsorption towers (13) and provided with a fourth program control valve 40X, a forward discharge pipeline (5) provided with a fifth program control valve 50X, a second pressure equalizing/third pressure equalizing pipeline (7) provided with a seventh program control valve 70X, a fourth pressure equalizing pipeline (6) provided with a sixth program control valve 60X, a first pressure equalizing and final pressure increasing pipeline (8) provided with an eighth program control valve 80X and a product gas outer conveying pipeline (9) provided with a ninth program control valve 90X; the flushing pipeline (2) is provided with a vacuum pumping device (12), and a pipeline (14) is communicated between the flushing inlet pipeline (4) and the forward discharge pipeline (5).
2. The system for purifying hydrogen by pressure swing adsorption with low pressure flush regeneration according to claim 1, wherein the pipeline (14) is provided with a sequential control valve (11).
3. A low pressure flush regeneration pressure swing adsorption hydrogen purification system as claimed in claim 1 wherein the first pressure equalization and final boost line (8) is in communication with the product gas export line (9) through a final charge control valve (10).
4. The method for purifying hydrogen in a system for pressure swing adsorption and purification of hydrogen according to any one of claims 1 to 3, wherein at least three adsorption towers are used for pressure swing adsorption and purification of hydrogen through repeated circulation steps, and each adsorption tower is subjected to repeated circulation steps, namely an adsorption step, a forward depressurization step, a reverse depressurization step, a low-pressure flushing and regeneration step and a reverse pressurization step in sequence.
5. A method for purifying hydrogen as claimed in claim 4, wherein the adsorption step is carried out by feeding the raw material gas into the adsorption tower from the feed end of the adsorption tower under a pressure of 1.0MPa to 7.0MPa, adsorbing the non-hydrogen impurities by the adsorbent, and discharging the hydrogen product from the discharge end of the adsorption tower.
6. The method of purifying hydrogen as claimed in claim 4, wherein the forward pressure-reducing step is a step in which the gas in the adsorption column flows out of the adsorption column along the flow direction of the gas during adsorption, the pressure in the adsorption column is reduced, the forward pressure-reducing step comprises at least two pressure-reducing processes, and the forward pressure-reducing step comprises a pressure-equalizing pressure-reducing step and a forward pressure-reducing step of supplying a purge regeneration gas to the regeneration adsorption column.
7. The method of purifying hydrogen as claimed in claim 4, wherein the reverse pressure-reducing step is a step of flowing the gas in the adsorption column out of the adsorption column against the flow of the gas during adsorption, and the pressure in the adsorption column is reduced, and the reverse pressure-reducing step comprises at least one pressure-reducing process.
8. The method for purifying hydrogen according to claim 4, wherein the low-pressure flushing regeneration step is to flush the adsorption tower with the regeneration gas from the outlet end of the adsorption tower against the gas flow direction during adsorption, the impurities adsorbed in the adsorption tower are desorbed at a low pressure and flow out of the adsorption tower with the flushing gas, and the adsorption tower is evacuated by the evacuation device during the flushing regeneration step to have an internal pressure of-0.06 to 0.005MPa, preferably-0.035 to 0.005 MPa.
9. A method for purifying hydrogen as claimed in claim 4, wherein the reverse pressure increasing step comprises a pressure equalizing and increasing step and a final pressure increasing step, the pressure equalizing and increasing step is a regenerated adsorption tower, and the gas in the forward pressure decreasing step is used for reversely increasing the pressure of the adsorption tower; and in the final pressure boosting step, the pressure of the adsorption tower is boosted to the adsorption pressure by utilizing product gas or raw gas in the adsorption tower completing the pressure equalizing and boosting step.
10. The method for purifying hydrogen according to claim 4, wherein the adsorption column is filled with a molecular sieve adsorbent, or the molecular sieve and one or more of activated alumina, activated carbon and silica gel form a composite adsorption bed.
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