CN111545014A - Method for removing argon in hydrogen through pressure swing adsorption - Google Patents

Method for removing argon in hydrogen through pressure swing adsorption Download PDF

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Publication number
CN111545014A
CN111545014A CN202010401488.4A CN202010401488A CN111545014A CN 111545014 A CN111545014 A CN 111545014A CN 202010401488 A CN202010401488 A CN 202010401488A CN 111545014 A CN111545014 A CN 111545014A
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adsorption
adsorption tower
pressure
hydrogen
tower
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陈志诚
黎佳荣
杨坤
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Hangzhou Branch Of Beijing Zhongke Fuhai Low Temperature Technology Co ltd
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Hangzhou Branch Of Beijing Zhongke Fuhai Low Temperature Technology Co ltd
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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
    • B01D53/047—Pressure swing adsorption
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40086—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by using a purge gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0001—Separation or purification processing
    • C01B2210/0009—Physical processing
    • C01B2210/0014—Physical processing by adsorption in solids
    • C01B2210/0015—Physical processing by adsorption in solids characterised by the adsorbent
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0078—Noble gases
    • C01B2210/0082—Argon

Abstract

The invention belongs to the field of purification, and particularly relates to a method for removing argon from hydrogen through pressure swing adsorption. The invention solves the problem of large energy consumption in the prior art, and utilizes a plurality of adsorption towers for step pressure reduction and step pressure rise to recycle pressure, thereby not only improving the pressure swing adsorption efficiency, but also ensuring the stable purity.

Description

Method for removing argon in hydrogen through pressure swing adsorption
Technical Field
The invention belongs to the field of purification, and particularly relates to a method for removing argon in hydrogen through pressure swing adsorption.
Background
At normal temperature and pressure, hydrogen is a gas which is extremely easy to burn, colorless, transparent, odorless and tasteless and is difficult to dissolve in water. Hydrogen is the least dense gas known in the world, and its density is only 1/14 for air, i.e., hydrogen is at 1 atm and 0 deg.C, and its density is 0.089 g/L. Therefore, the hydrogen can be used as filling gas for the airship and the hydrogen balloon (because the hydrogen has flammability and low safety, the airship is filled with helium at present). Hydrogen is the relatively least molecular weight species and is used primarily as a reducing agent. With the increasingly strict environmental regulations and the good combustion performance of hydrogen, the market in the future has a huge potential demand for hydrogen. The purity of hydrogen is highly desirable in industrial processes, such as the electronics industry where purity levels of greater than 99.999% are required, and in some cases even higher. Therefore, the hydrogen-containing raw gas needs to be separated and purified to meet different production requirements. However, the current process mainly comprises a membrane separation method, low-temperature adsorption separation and low-temperature rectification, wherein the membrane separation method has large pressure loss and large energy consumption and is difficult to realize industrial production, and the low-temperature adsorption separation and low-temperature rectification method needs a large amount of cold energy and can be extremely high.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for removing argon from hydrogen through pressure swing adsorption, which solves the problem of high energy consumption in the prior art, and utilizes a plurality of adsorption towers for step pressure reduction and step pressure increase to recycle pressure, thereby not only improving the pressure swing adsorption efficiency, but also ensuring the stable purity.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a method for removing argon from hydrogen by pressure swing adsorption comprises introducing hydrogen as raw material into an adsorption system, performing alternate adsorption treatment to realize continuous discharge of product gas, wherein the adsorption system adopts a multi-stage pressure-equalizing method cyclic regeneration system.
The raw material hydrogen adopts hydrogen containing argon, and the content concentration of the argon is from PPM level to percentage level.
The adsorption system comprises a plurality of adsorption towers, and the adsorption towers form a continuous adsorption regeneration circulating system.
And a complete adsorption-regeneration cycle is formed in each adsorption tower, and the method comprises the following specific steps:
step 1, adding raw material hydrogen into an adsorption tower from the bottom of the tower, adsorbing argon through an adsorption bed in the adsorption tower, and discharging hydrogen serving as product gas through the top of the tower; when the mass transfer front of argon reaches the reserved section of the bed layer outlet, the feed valve and the outlet valve of the adsorption tower are closed, the adsorption is stopped, and at the moment, the adsorption tower enters the regeneration process;
step 2, introducing gas at the tail end of an adsorption bed of the adsorption tower into the next adsorption tower to form a pressure equalizing and reducing process, wherein the high-purity hydrogen which is adsorbed at the top end of the adsorption tower is recycled into the next adsorption tower in the process to ensure the sufficient recycling of the hydrogen;
step 3, disconnecting the adsorption tower after the pressure of the adsorption tower and the next adsorption tower is leveled, communicating the top end of the adsorption tower into a downstream gas release tank, collecting the hydrogen subjected to pressure equalizing treatment at the top end of the adsorption tower into the downstream gas release tank to achieve the effect of recovering the product gas, and simultaneously serving as an adsorbent regeneration gas source in the subsequent process; in the process, the argon and the hydrogen at the bottom layer flow from bottom to top and continuously rise until the adsorption front reaches the outlet of the adsorption bed;
step 4, the bottom of the adsorption tower is communicated with a desorption gas buffer tank, the pressure is reduced against the adsorption direction until the pressure in the adsorption tower is reduced to the normal pressure, and in the process, a large amount of argon is desorbed from the adsorbent under the action of pressure and enters the desorption gas buffer tank;
step 5, introducing the gas in the normal gas release tank into the adsorption tower against the adsorption direction, performing desorption treatment on an adsorption bed in the adsorption tower, flushing impurities in the adsorption bed, and flushing desorbed gas into a desorbed gas buffer tank;
step 6, connecting the adsorption tower with the next adsorption tower to be regenerated after flushing to form pressure equalizing and boosting treatment, wherein in the process, high-purity hydrogen on the upper layer of other adsorption towers to be regenerated is used for boosting treatment, so that the pressure in the adsorption towers can be increased, meanwhile, the hydrogen in dead spaces of other adsorption towers is recovered, and the pressure equalizing and boosting treatment is repeatedly carried out with different adsorption towers with regeneration;
step 7, introducing product hydrogen into the adsorption tower after the pressure equalizing and boosting treatment until the pressure of the adsorption tower reaches the adsorption pressure;
the adsorption-regeneration cycle can be completed once through the treatment.
After pressure equalizing and boosting processing for multiple times, the pressure of the adsorption tower is greatly increased after pressure equalizing processing of other adsorption towers to be regenerated, but a certain distance exists between the pressure of the adsorption tower and the adsorption pressure, and the pressure of the adsorption tower is directly increased by utilizing product gas until the pressure of the adsorption tower reaches the adsorption pressure.
The multi-stage pressure equalizing method of the adsorption system comprises a plurality of adsorption towers, and each adsorption tower alternately carries out adsorption-regeneration circulation to realize continuous separation and purification of gas.
The alternative adsorption treatment adopts a high-selectivity adsorbent, the argon adsorption capacity of the adsorbent is far higher than that of hydrogen, the separation coefficient reaches more than 10, the adsorbent adopts a molecular sieve, and the molecular sieve contains a large number of micropores with the diameter of several angstroms.
From the above description, it can be seen that the present invention has the following advantages:
1. the invention solves the problem of large energy consumption in the prior art, and utilizes a plurality of adsorption towers for step pressure reduction and step pressure rise to recycle pressure, thereby not only improving the pressure swing adsorption efficiency, but also ensuring the stable purity.
2. The invention utilizes the recycling of the adsorption tower to fully utilize the residual high-purity hydrogen, thereby greatly improving the recovery rate of the hydrogen and reducing the pressure loss.
3. The method provided by the invention can be used for arranging different numbers of adsorption tower combinations according to the product requirements to form continuous discharge of product gas, and continuous cyclic use of the adsorption towers is realized by utilizing an adsorption regeneration system.
Drawings
FIG. 1 is a flow chart of an embodiment of the present invention.
Detailed Description
With reference to fig. 1, a specific embodiment of the present invention is described in detail, but the present invention is not limited in any way by the claims.
Example 1
A method for removing argon from hydrogen by pressure swing adsorption comprises the steps of introducing raw material hydrogen into an adsorption system, and performing alternate adsorption treatment to realize continuous discharge of product gas, wherein the adsorption system adopts a three-stage pressure-equalizing method cyclic regeneration system.
The raw material hydrogen adopts hydrogen containing argon, and the content concentration of the argon is from PPM level to percentage level.
The adsorption system comprises five adsorption towers, and the five adsorption towers form a continuous adsorption regeneration circulating system.
And a complete adsorption-regeneration cycle is formed in each adsorption tower, and the method comprises the following specific steps:
step 1, adding raw material hydrogen into an adsorption tower from the bottom of the tower, adsorbing argon through an adsorption bed in the adsorption tower, and discharging hydrogen serving as product gas through the top of the tower; when the mass transfer front of argon reaches the reserved section of the bed layer outlet, the feed valve and the outlet valve of the adsorption tower are closed, the adsorption is stopped, and at the moment, the adsorption tower enters the regeneration process;
step 2, introducing gas at the tail end of an adsorption bed of the adsorption tower into the next adsorption tower to form a pressure equalizing and reducing process, wherein the high-purity hydrogen which is adsorbed at the top end of the adsorption tower is recycled into the next adsorption tower in the process to ensure the sufficient recycling of the hydrogen;
step 3, disconnecting the adsorption tower after the pressure of the adsorption tower and the next adsorption tower is leveled, communicating the top end of the adsorption tower into a downstream gas release tank, collecting the hydrogen subjected to pressure equalizing treatment at the top end of the adsorption tower into the downstream gas release tank to achieve the effect of recovering the product gas, and simultaneously serving as an adsorbent regeneration gas source in the subsequent process; in the process, the argon and the hydrogen at the bottom layer flow from bottom to top and continuously rise until the adsorption front reaches the outlet of the adsorption bed;
step 4, the bottom of the adsorption tower is communicated with a desorption gas buffer tank, the pressure is reduced against the adsorption direction until the pressure in the adsorption tower is reduced to the normal pressure, and in the process, a large amount of argon is desorbed from the adsorbent under the action of pressure and enters the desorption gas buffer tank;
step 5, introducing the gas in the normal gas release tank into the adsorption tower against the adsorption direction, performing desorption treatment on an adsorption bed in the adsorption tower, flushing impurities in the adsorption bed, and flushing desorbed gas into a desorbed gas buffer tank;
step 6, connecting the adsorption tower with the next adsorption tower to be regenerated after flushing to form pressure equalizing and boosting treatment, wherein in the process, high-purity hydrogen on the upper layer of other adsorption towers to be regenerated is used for boosting treatment, so that the pressure in the adsorption towers can be increased, meanwhile, the hydrogen in dead spaces of other adsorption towers is recovered, and the pressure equalizing and boosting treatment is repeatedly carried out with different adsorption towers with regeneration;
step 7, introducing product hydrogen into the adsorption tower after the pressure equalizing and boosting treatment until the pressure of the adsorption tower reaches the adsorption pressure;
the adsorption-regeneration cycle can be completed once through the treatment.
After pressure equalizing and boosting processing for multiple times, the pressure of the adsorption tower is greatly increased after pressure equalizing processing of other adsorption towers to be regenerated, but a certain distance exists between the pressure of the adsorption tower and the adsorption pressure, and the pressure of the adsorption tower is directly increased by utilizing product gas until the pressure of the adsorption tower reaches the adsorption pressure.
As shown in fig. 1, the three-stage pressure equalization method of the adsorption system includes five adsorption towers, and includes the following steps:
step 1, introducing raw material hydrogen into a first adsorption tower through a raw material gas buffer tank, adsorbing the raw material hydrogen by an adsorption bed in the first adsorption tower, directly discharging high-purity hydrogen serving as product hydrogen through the top end of the first adsorption tower, and directly adsorbing argon in the hydrogen by an adsorbent on the adsorption bed;
when the adsorption front edge of the argon reaches a certain height of the adsorption bed, closing an air inlet valve and an air outlet valve of the first adsorption tower, and stopping the input of the raw material hydrogen and the output of the product hydrogen; at the moment, the argon adsorbed by the adsorbent bed is still a certain distance away from the outlet of the adsorbent bed;
step 2, introducing raw material hydrogen into a second adsorption tower to perform adsorption treatment in the step 1, simultaneously opening an outlet end of the first adsorption tower and an outlet end of a third adsorption tower subjected to second-stage boosting equalization treatment, performing first-stage pressure equalization treatment, continuously moving an adsorption front edge of argon towards an outlet of an adsorption bed in the pressure equalization process, simultaneously transferring hydrogen above the adsorption bed into the third adsorption tower, and disconnecting the outlet ends after the pressures of the first adsorption tower and the third adsorption tower are leveled, wherein the adsorption front edge of the argon does not reach the outlet of the adsorption bed;
step 3, communicating the outlet end of the first adsorption tower with the outlet end of a fourth adsorption tower subjected to third-stage boosting equalization treatment, carrying out second-stage equalization treatment until the pressures of the first adsorption tower and the fourth adsorption tower are equalized, and disconnecting the connection in the outlet end, wherein in the equalization process, the argon adsorption front edge of the first adsorption tower moves towards the outlet of the adsorption bed until the pressures are equalized, the distance between the argon adsorption front edge and the outlet is shortened, but the argon adsorption front edge does not reach the outlet;
step 4, communicating the outlet end of the first adsorption tower with the outlet end of a fifth adsorption tower which is just washed, carrying out third-stage pressure equalizing treatment until the pressure of the first adsorption tower and the pressure of the fifth adsorption tower are equalized, and disconnecting the outlet end, wherein the front edge of the argon adsorption of the first adsorption tower moves towards the outlet of the adsorption bed and is further close to the outlet in the pressure equalizing process;
step 5, the outlet end of the first adsorption tower is communicated with the forward-discharging tank, and the gas of the first adsorption tower is introduced into the forward-discharging tank until a certain pressure is reached; disconnecting the forward-discharging tank from the outlet end of the first adsorption tower;
step 6, reversely reducing the pressure of a feed inlet of the first adsorption tower and a desorption gas buffer tank, desorbing most impurities of the adsorption bed, and discharging desorption gas into the desorption gas buffer tank;
step 7, communicating the first adsorption tower with a forward discharge tank, flushing an adsorption bed by hydrogen in the forward discharge tank, further reducing impurity partial pressure, and ensuring full regeneration of an adsorbent; when the pressure in the sequential discharge tank reaches a certain value, closing the communicating structure and finishing flushing;
step 8, communicating the outlet end of the first adsorption tower after flushing with the outlet end of a second adsorption tower which just finishes the second stage pressure equalizing treatment, performing third stage pressure boosting treatment, and closing the communication of the outlet sections after the pressure of the first adsorption tower and the pressure of the second adsorption tower are equalized;
step 9, communicating the outlet end of the first adsorption tower with the outlet end of a third adsorption tower which just finishes the first-stage pressure equalizing treatment, performing second-stage pressure boosting treatment, and closing the communication of the outlet sections after the pressures of the first adsorption tower and the third adsorption tower are equalized;
step 10, communicating the outlet end of the first adsorption tower with the outlet end of a fourth adsorption tower which just finishes adsorption, performing first-stage pressure boosting treatment, and closing the communication of the outlet sections after the pressure of the first adsorption tower and the pressure of the fourth adsorption tower are balanced;
step 11, communicating the first adsorption tower with product hydrogen, and raising the pressure in the first adsorption tower to adsorption pressure by the product hydrogen;
at this point, the first adsorption tower is used in the subsequent adsorption process after completing the adsorption-regeneration process.
The five adsorption towers are used in a staggered mode in the adsorption-regeneration process, and the purity of the discharged sample gas is guaranteed not to fluctuate in circulation.
The method is realized by a pressure swing adsorption device which mainly comprises 1 raw material gas buffer tank V01, 5 adsorption towers V02A-E, 1 product gas buffer tank V03, 1 forward-discharging tank V04, 1 desorption gas buffer tank V05 and a series of program control valves.
The first adsorption tower V02A is taken as an example to illustrate each process step and the process thereof in one cycle period. (all the opening and closing actions of the program control valve are finished by the microcomputer control)
Adsorption:
the programmable valves KV01A and KV02A were opened (other programmable valves connected to the first adsorption column V02A were closed, the same below).
The raw material hydrogen enters a first adsorption tower V02A from KV01A, Ar is adsorbed, and H2And taking the obtained product out of the tower through KV02A, and closing KV01A and KV02A when the adsorption front of Ar moves to a certain position of the adsorption tower, so that the input of raw material gas and the output of products are stopped. At this time, a section of the adsorbent which does not adsorb impurities is still left in the first adsorption tower V02A from the adsorption front to the outlet end.
First stage pressure equalization drop:
KV05A and KV05C were opened.
After the adsorption step of the first adsorption tower V02A is stopped, the first adsorption tower V02C is connected with the outlet end of the third adsorption tower V02C to perform the first stage pressure equalization, and the adsorption front of the first adsorption tower V02A advances towards the outlet end in the pressure equalization process but does not reach the outlet end. When the pressures of the two adsorption towers are basically equal, the valve KV05A is closed, and the first pressure equalization reduction step is finished.
Second-stage pressure equalization drop:
KV04A and KV04D are started.
After the first pressure equalization decreasing step of the first adsorption tower V02A is stopped, the second pressure equalization step is performed by connecting the fourth adsorption tower V02D, which has just finished the second pressure equalization increasing step, to the outlet side, and the adsorption front of the first adsorption tower V02A continues to advance toward the outlet side during the pressure equalization process, but does not reach the outlet side. When the pressures of the two adsorption towers are basically equal, the valve KV04D is closed, and the second stage pressure equalization reduction step is finished.
Third stage pressure equalization drop:
and opening the program control valve KV04E, and continuing to open the valve KV 04A.
After the second-stage pressure equalization decreasing step of the first adsorption tower V02A is stopped, the third-stage pressure equalization is performed by connecting the second adsorption tower V02E, which has just finished the flushing step, to the outlet end thereof, and after the pressure equalization step is finished, the adsorption front of the first adsorption tower V02A is further close to the outlet end thereof. When the pressures of the two adsorption towers are basically equal, closing the valve KV04A, and finishing the third stage pressure equalization reduction step.
Forward pressure reduction:
KV06A and KV07 are started.
After the third-stage pressure equalization reduction step of the first adsorption tower V02A is stopped, forward purge gas in the first adsorption tower V02A is discharged to a forward purge tank V04 through valves KV06A and KV07, and when the pressure of the first adsorption tower V02A is reduced to a set value, valves KV06A and KV07 are closed, and the forward purge step is ended.
And (3) reverse pressure release:
valve KV03A was opened.
After the forward discharge of the first adsorption tower V02A is finished, the pressure is reduced in the reverse direction of the adsorption, most impurities in the adsorbent are desorbed, and when the pressure of the tower is reduced to a set value, the reverse discharge is finished.
Washing:
the opening valve KV08 and the regulating valves HV03, KV06A and KV03A are continuously opened.
The first adsorption tower V02A is flushed by using the cis-bleeding gas of the cis-bleeding tank V03, so that the impurity partial pressure in the first adsorption tower V02A is further reduced, and the adsorbent is fully regenerated. When the pressure of the cis-releasing tank V04 is reduced to a specified value, the valves KV08, KV03A and KV06A and the regulating valve HV03 are closed, and the flushing step is finished.
Third-stage pressure equalization rising:
valve KV04A was opened, and valve KV04B was continued to be opened.
The first adsorption tower V02A and the second adsorption tower V02B which just finishes the second stage pressure equalization reduction step are connected at outlet ends for third stage pressure equalization, the pressure of the first adsorption tower V02A rises during the pressure equalization, when the pressures of the two adsorption towers are basically equal, the valve 04 KV04B is closed, and the third stage pressure equalization rise step is finished.
Second-stage pressure equalization rising:
valve KV04C was opened, and valve KV04A was continued to be opened.
The first adsorption tower V02A and the third adsorption tower V02C which has just finished the first pressure equalization decreasing step are connected at the outlet ends for the second stage pressure equalization, the pressure of the first adsorption tower V02A is increased during the pressure equalization, when the pressures of the two adsorption towers are basically equal, the valve KV04A is closed, and the second stage pressure equalization increasing step is finished.
First-stage pressure equalization rising:
the valves KV05A and KV05D were opened.
The first adsorption tower V02A and the fourth adsorption tower V02D which is just finished the adsorption step are connected by outlet ends to perform first-stage pressure equalization, the pressure of the first adsorption tower V02A is increased in the pressure equalization process, when the pressures of the two adsorption towers are basically equal, the valve KV05D is closed, and the first-stage pressure equalization increasing step is finished (the valve KV05A is continuously opened for the final pressure increasing step of the next step of the first adsorption tower V02A).
And (3) final boosting:
and opening the final-charging regulating valve HV04, the programmable valve KV10 and the programmable valve KV05A continuously.
After three pressure equalization and pressure rise steps, the first adsorption tower V02A is finally pressurized by using product gas through flow limitation by an adjusting valve HV04 to gradually reach the adsorption pressure. When the pressure is close to the adsorption pressure, the valves KV05A and HV04 are closed, and the final charging step is finished.
At this point, the adsorption and regeneration processes of the first adsorption tower V02A are all completed, and the next cycle is performed.
The alternative adsorption treatment adopts a high-selectivity adsorbent, the argon adsorption capacity of the adsorbent is far higher than that of hydrogen, the separation coefficient reaches 12, the adsorbent adopts a molecular sieve, and the molecular sieve contains a large number of micropores with the diameter of several angstroms.
Example 2
A method for removing argon from hydrogen by pressure swing adsorption comprises the steps of introducing raw material hydrogen into an adsorption system, and performing alternate adsorption treatment to realize continuous discharge of product gas, wherein the adsorption system adopts a two-stage pressure-equalizing method cyclic regeneration system.
The two-stage pressure equalizing method of the adsorption system comprises four adsorption towers and comprises the following specific steps:
step 1, introducing raw material hydrogen into a first adsorption tower through a raw material gas buffer tank, adsorbing the raw material hydrogen by an adsorption bed in the first adsorption tower, directly discharging high-purity hydrogen serving as product hydrogen through the top end of the first adsorption tower, and directly adsorbing argon in the hydrogen by an adsorbent on the adsorption bed;
when the adsorption front edge of the argon reaches a certain height of the adsorption bed, closing an air inlet valve and an air outlet valve of the first adsorption tower, and stopping the input of the raw material hydrogen and the output of the product hydrogen; at the moment, the argon adsorbed by the adsorbent bed is still a certain distance away from the outlet of the adsorbent bed;
step 2, introducing raw material hydrogen into a second adsorption tower to perform adsorption treatment in the step 1, simultaneously opening an outlet end of the first adsorption tower and an outlet end of a third adsorption tower subjected to second-stage boosting equalization treatment, performing first-stage pressure equalization treatment, continuously moving an adsorption front edge of argon towards an outlet of an adsorption bed in the pressure equalization process, simultaneously transferring hydrogen above the adsorption bed into the third adsorption tower, and disconnecting the outlet ends after the pressures of the first adsorption tower and the third adsorption tower are leveled, wherein the adsorption front edge of the argon does not reach the outlet of the adsorption bed;
step 3, communicating the outlet end of the first adsorption tower with the outlet end of a fourth adsorption tower subjected to third-stage pressure boosting equalization treatment, carrying out second-stage pressure equalization treatment until the pressure of the first adsorption tower and the pressure of the fourth adsorption tower are equalized, and disconnecting the outlet end, wherein in the pressure equalization process, the front edge of argon adsorption of the first adsorption tower moves towards the outlet of the adsorption bed and is close to the outlet;
step 4, the outlet end of the first adsorption tower is communicated with the forward-discharging tank, and the gas of the first adsorption tower is introduced into the forward-discharging tank until a certain pressure is reached; disconnecting the forward-discharging tank from the outlet end of the first adsorption tower;
step 5, reversely reducing the pressure of a feed inlet of the first adsorption tower and a desorption gas buffer tank, desorbing most impurities of the adsorption bed, and discharging desorption gas into the desorption gas buffer tank;
step 6, communicating the first adsorption tower with a forward discharge tank, flushing an adsorption bed by hydrogen in the forward discharge tank, further reducing impurity partial pressure, and ensuring full regeneration of an adsorbent; when the pressure in the sequential discharge tank reaches a certain value, closing the communicating structure and finishing flushing;
step 7, the outlet end of the first adsorption tower after being washed is communicated with the outlet end of a second adsorption tower which just finishes the first-stage pressure equalizing treatment, the second-stage pressure boosting treatment is carried out, and the communication of the outlet sections is closed after the pressures of the first adsorption tower and the second adsorption tower are equalized;
step 8, communicating the outlet end of the first adsorption tower with the outlet end of a third adsorption tower which just finishes adsorption, performing first-stage pressure boosting treatment, and closing the communication of the outlet sections after the pressure of the first adsorption tower and the pressure of the third adsorption tower are balanced;
step 9, communicating the first adsorption tower with product hydrogen, and raising the pressure in the first adsorption tower to adsorption pressure by the product hydrogen;
at this point, the first adsorption tower is used in the subsequent adsorption process after completing the adsorption-regeneration process.
The four adsorption towers are used in a staggered mode in the adsorption-regeneration process, and the purity of the discharged sample gas is guaranteed not to fluctuate in circulation.
The alternative adsorption treatment adopts a high-selectivity adsorbent, the argon adsorption capacity of the adsorbent is far higher than that of hydrogen, the separation coefficient reaches 15, the adsorbent adopts a molecular sieve, and the molecular sieve contains a large number of micropores with the diameter of several angstroms.
Example 1-2 pressure swing adsorption treatment was carried out as described above, with the following data:
Figure BDA0002489640810000101
in summary, the invention has the following advantages:
1. the invention solves the problem of large energy consumption in the prior art, and utilizes a plurality of adsorption towers for step pressure reduction and step pressure rise to recycle pressure, thereby not only improving the pressure swing adsorption efficiency, but also ensuring the stable purity.
2. The invention utilizes the recycling of the adsorption tower to fully utilize the residual high-purity hydrogen, thereby greatly improving the recovery rate of the hydrogen and reducing the pressure loss.
3. The method provided by the invention can be used for arranging different numbers of adsorption tower combinations according to the product requirements to form continuous discharge of product gas, and continuous cyclic use of the adsorption towers is realized by utilizing an adsorption regeneration system.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.

Claims (5)

1. A method for removing argon in hydrogen by pressure swing adsorption is characterized in that: introducing raw material hydrogen into an adsorption system, and performing alternate adsorption treatment to realize continuous discharge of product gas, wherein the adsorption system adopts a multistage pressure equalization method cyclic regeneration system.
2. The pressure swing adsorption process for removing argon from hydrogen of claim 1, wherein: the raw material hydrogen adopts hydrogen containing argon, and the content concentration of the argon is from PPM level to percentage level.
3. The pressure swing adsorption process for removing argon from hydrogen of claim 1, wherein: the adsorption system is formed by a plurality of adsorption towers to form a continuous adsorption regeneration circulating system.
4. The pressure swing adsorption process for removing argon from hydrogen of claim 3, wherein: and a complete adsorption-regeneration cycle is formed in each adsorption tower, and the method comprises the following specific steps:
step 1, adding raw material hydrogen into an adsorption tower from the bottom of the tower, adsorbing argon through an adsorption bed in the adsorption tower, and discharging hydrogen serving as product gas through the top of the tower; when the mass transfer front of argon reaches the reserved section of the bed layer outlet, the feed valve and the outlet valve of the adsorption tower are closed, the adsorption is stopped, and at the moment, the adsorption tower enters the regeneration process;
step 2, introducing gas at the tail end of an adsorption bed of the adsorption tower into the next adsorption tower to form a pressure equalizing and reducing process, wherein the high-purity hydrogen which is adsorbed at the top end of the adsorption tower is recycled into the next adsorption tower in the process to ensure the sufficient recycling of the hydrogen;
step 3, disconnecting the adsorption tower after the pressure of the adsorption tower and the next adsorption tower is leveled, communicating the top end of the adsorption tower into a downstream gas release tank, collecting the hydrogen subjected to pressure equalizing treatment at the top end of the adsorption tower into the downstream gas release tank to achieve the effect of recovering the product gas, and simultaneously serving as an adsorbent regeneration gas source in the subsequent process;
step 4, communicating the bottom of the adsorption tower with a desorption gas buffer tank, and carrying out pressure reduction treatment against the adsorption direction until the pressure in the adsorption tower is reduced to the normal pressure;
step 5, introducing the gas in the normal gas release tank into the adsorption tower against the adsorption direction, performing desorption treatment on an adsorption bed in the adsorption tower, flushing impurities in the adsorption bed, and flushing desorbed gas into a desorbed gas buffer tank;
step 6, connecting the adsorption tower with the next adsorption tower to be regenerated after flushing is finished to form pressure equalizing and boosting treatment;
step 7, introducing product hydrogen into the adsorption tower after the pressure equalizing and boosting treatment until the pressure of the adsorption tower reaches the adsorption pressure;
the adsorption-regeneration cycle can be completed once through the treatment.
5. The pressure swing adsorption process for removing argon from hydrogen of claim 4, wherein: the multi-stage pressure equalizing method of the adsorption system comprises a plurality of adsorption towers, and each adsorption tower alternately carries out adsorption-regeneration circulation to realize continuous separation and purification of gas.
CN202010401488.4A 2020-05-13 2020-05-13 Method for removing argon in hydrogen through pressure swing adsorption Pending CN111545014A (en)

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Application publication date: 20200818