CN111482050A - Hydrogen purification device and method - Google Patents
Hydrogen purification device and method Download PDFInfo
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- CN111482050A CN111482050A CN202010542820.9A CN202010542820A CN111482050A CN 111482050 A CN111482050 A CN 111482050A CN 202010542820 A CN202010542820 A CN 202010542820A CN 111482050 A CN111482050 A CN 111482050A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/56—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with multiple filtering elements, characterised by their mutual disposition
- B01D46/62—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with multiple filtering elements, characterised by their mutual disposition connected in series
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- 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
- C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
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- 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
Abstract
The invention provides a hydrogen purification device and a method, wherein the device comprises a first filter, a feed gas enters from an air inlet end, and a first intermediate gas is discharged from an air outlet end; the adsorption tower group is connected with the first filter through a pipeline with a first valve and comprises at least two adsorption towers, and the adsorption towers are in an adsorption state and a desorption regeneration state; the air inlet end enters first intermediate air, and the air outlet end discharges second intermediate air; the second filter is connected with the adsorption tower group through a pipeline with a second valve, the gas inlet end enters second intermediate gas, and the gas outlet end discharges third intermediate gas; the pressure swing adsorption unit is connected with the second filter, the gas inlet end of the pressure swing adsorption unit enters third intermediate gas, the gas outlet end of the pressure swing adsorption unit discharges product hydrogen and the gas to be analyzed, and part of the gas to be analyzed is conveyed to the adsorption tower in a desorption regeneration state; the application prolongs the service life of the adsorbent in the pressure swing adsorption unit and improves the purity and recovery rate of the product hydrogen.
Description
Technical Field
The invention relates to the technical field of hydrogen purification in petrochemical industry, in particular to a hydrogen purification device and a hydrogen purification method.
Background
Along with the aggravation of the heavy oil and the inferior oil of the refinery, the environmental protection requirement is stricter and stricter, the hydrogen demand of the refinery is larger and larger, and the hydrogen becomes the essential production raw material of the refinery. At present, the hydrogen of a refinery is mainly obtained by the modes of hydrogen production, hydrogen byproduct reforming, hydrogen recovery from hydrogen-rich tail gas and the like, wherein the hydrogen-rich tail gas recovery is an important way for obtaining cheap hydrogen by the refinery.
The hydrogen-rich gas in the refinery has wide sources, such as ethylene cracking gas, reformed tail gas, catalytic dry gas, coking dry gas and the like, and has high hydrogen content and high recovery value. At present, Pressure Swing Adsorption (PSA) purification is an important hydrogen recovery technology.
Pressure swing adsorption, as a separation technique, has been increasingly widely used in petrochemical, metallurgical and other industries. It is suitable for treating various complex mixed gases, can remove various impurity components in raw material gas by one step, and can make the purity of product gas be very high. The pressure swing adsorption technology is based on physical adsorption of the internal surface of the adsorbent to gas molecules, raw gas passes through an adsorbent bed under pressure, impurity components with high boiling points relative to hydrogen are selectively adsorbed, and hydrogen with low boiling point components is difficult to adsorb and passes through the adsorbent bed to achieve separation of hydrogen and the impurity components. The separated hydrogen is product gas, and the impurity component gas is analysis gas.
Because the hydrogen-rich tail gas of the refinery has complex components, the hydrogen-rich tail gas often contains a small amount of heavy components of C5 and above, and the heavy components of C5 and above belong to very easy-to-adsorb components. Adopt pressure swing adsorption technique also to handle this type of rich hydrogen tail gas for PSA device, easily cause C5 and above heavy hydrocarbon component to accumulate on the adsorbent in the PSA device, easily form capillary condensation after the absorption, occupy the adsorbent hole, hardly resolve out, cause the activity decline of adsorbent, reduce the adsorption efficiency of adsorbent to influence PSA device to the recovery purity and the rate of recovery of hydrogen.
As the operating time of the pressure swing adsorption unit is extended, the performance index of the adsorbent is gradually reduced, resulting in a reduction in the yield and purity of the product hydrogen, and thus in an increase in hydrogen loss. To improve the performance of the adsorbent, hot nitrogen regeneration of the adsorbent is required, which consumes both steam and nitrogen and results in the hydrogen purification plant having to stop producing.
In the prior art, the dosage of the protective agent is generally increased in the pressure swing adsorption device so as to prolong the failure time of the adsorbent. Thus, not only is the cost increased, but also the problems of C5 and above component accumulation and difficulty in adsorbent regeneration in the pressure swing adsorption device are not fundamentally solved.
Disclosure of Invention
In view of the above, the invention provides a hydrogen purification apparatus and method, which improve the recovery purity and recovery rate of the product hydrogen, and prolong the service life of the adsorbent in the PSA apparatus.
According to an aspect of the present invention, there is provided a hydrogen purification apparatus, the apparatus including:
the feed gas enters the first filter at the gas inlet end of the first filter, and the first intermediate gas is discharged from the gas outlet end of the first filter;
the adsorption tower group is connected with the first filter through a pipeline with a first valve, and comprises at least two adsorption towers, wherein the adsorption towers are in an adsorption state and a desorption regeneration state; the gas inlet end of the adsorption tower group enters the first intermediate gas, and the gas outlet end of the adsorption tower group discharges a second intermediate gas; one adsorption tower in the adsorption tower group is in an adsorption state, and the other adsorption towers are in a desorption regeneration state;
the second filter is connected with the adsorption tower group through a pipeline with a second valve, the gas inlet end of the second filter enters the second intermediate gas, and the gas outlet end of the second filter discharges a third intermediate gas; when the adsorption tower is in an adsorption state, the first valve and the second valve are both opened; when the adsorption tower is in a desorption regeneration state, the first valve and the second valve are both closed; and
and the pressure swing adsorption unit is connected with the second filter, the gas inlet end of the pressure swing adsorption unit enters the third intermediate gas, the gas outlet end of the pressure swing adsorption unit respectively discharges product hydrogen and the gas to be desorbed, and part of the gas to be desorbed is conveyed to the adsorption tower in a desorption regeneration state in the adsorption tower group.
Preferably, in the adsorption tower group, the first adsorption tower working in the adsorption state and the second adsorption tower working in the desorption regeneration state are replaced in working state.
Preferably, a part of the desorbed gas is respectively delivered to the adsorption towers in the desorption and regeneration state in the adsorption tower group through a pipeline with a third valve and a pipeline with a fourth valve, and when the pressure in the adsorption towers in the desorption and regeneration state reaches a first preset threshold value, the third valve is opened; when the temperature in the adsorption tower in the desorption regeneration state reaches a second preset threshold value, the third valve is closed, and the fourth valve is opened; when the temperature reaches a third preset threshold value, the fourth valve is closed; the second preset threshold is greater than the third preset threshold.
Preferably, the pressure swing adsorption unit is respectively connected with the adsorption tower group through a first pipeline and a second pipeline, and the first pipeline directly conveys part of the desorbed gas to the adsorption tower in the desorption regeneration state in the adsorption tower group; and the second pipeline heats part of the analysis gas to a preset temperature through a heater and then conveys the analysis gas to the adsorption tower in a desorption regeneration state in the adsorption tower group.
Preferably, the device further comprises a tail gas exhaust unit, and the tail gas exhaust unit is respectively connected with the adsorption tower set and the pressure swing adsorption unit.
Preferably, a third pipeline is arranged between the gas outlet end of the adsorption tower in the adsorption state and the gas outlet end of the adsorption tower in the desorption regeneration state, the third pipeline has a connection and disconnection state, when the third pipeline is connected, the adsorption tower in the adsorption state is connected with the adsorption tower in the desorption regeneration state, and when the third pipeline is disconnected, the adsorption tower in the adsorption state is disconnected with the adsorption tower in the desorption regeneration state.
Preferably, the first filter is connected to each adsorption tower of the adsorption tower group, the second filter is connected to each adsorption tower of the adsorption tower group, the first filter is used for filtering solid particles and liquid, and the second filter is used for filtering dust.
According to another aspect of the present invention, there is provided a hydrogen purification method for purifying hydrogen using the above hydrogen purification apparatus, the method comprising the steps of:
providing a raw material gas;
filtering the feed gas by using a first filter to obtain a first intermediate gas;
adsorbing the first intermediate gas by using an adsorption tower in an adsorption state in the adsorption tower group, and discharging a second intermediate gas; the other adsorption towers in the adsorption tower group are all in the desorption regeneration state;
filtering the second intermediate gas by using a second filter to obtain a third intermediate gas;
and separating the third intermediate gas by using a pressure swing adsorption unit to obtain a product hydrogen gas and a gas to be analyzed, and conveying part of the gas to be analyzed to the adsorption tower in a desorption regeneration state in the adsorption tower group.
Preferably, the delivering of a part of the desorption gas to the adsorption tower in the desorption regeneration state in the adsorption tower group includes:
heating part of the analysis gas to a second preset temperature, and then conveying the analysis gas to an adsorption tower in a desorption regeneration state in the adsorption tower group;
and directly conveying part of the analysis gas to the adsorption tower in the desorption regeneration state in the adsorption tower group.
Preferably, the method further comprises the step of:
and communicating the adsorption tower in the adsorption state with the adsorption tower in the desorption regeneration state in the adsorption tower group.
Compared with the prior art, the invention has the beneficial effects that:
the hydrogen purification device and the method provided by the invention realize that C5 and above heavy hydrocarbon components are removed before feed gas enters the pressure swing adsorption unit through the front-mounted adsorption tower group capable of continuously working, improve the quality of the feed gas of the pressure swing adsorption unit and prolong the service life of an adsorbent in the pressure swing adsorption unit; on the other hand, the impurity accumulation of the adsorbent in the pressure swing adsorption unit is reduced, and the activity and adsorption performance of the adsorbent are improved, so that the purity and recovery rate of the product hydrogen are improved; the application also realizes continuous and uninterrupted production of hydrogen purification.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic structural diagram of a hydrogen purification apparatus according to an embodiment of the present invention;
fig. 2 is a schematic flow chart of a hydrogen purification method disclosed in the embodiment of the invention.
Detailed Description
Example embodiments will now be described more fully with reference to the accompanying drawings. Example embodiments may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of example embodiments to those skilled in the art. The same reference numerals in the drawings denote the same or similar structures, and thus their repetitive description will be omitted.
As shown in fig. 1, the present invention discloses a hydrogen purification apparatus, which comprises a raw gas supply unit 101, a first filter 102, an adsorption tower set 103, a second filter 104, a pressure swing adsorption unit 105, a tail gas discharge unit 106, and a product hydrogen recovery unit 107. Wherein, the raw material gas providing unit 101 is used for providing raw material gas for the hydrogen purification device. The off-gas discharge unit 106 is connected to the adsorption column group 103 and the pressure swing adsorption unit 105, respectively. The raw gas supply unit 101 communicates with the first filter 102. The first filter 102 is used to filter out impurities such as solid particles and liquid in the feed gas. The raw gas enters the first filter 102 at the inlet end and the first intermediate gas exits the first filter at the outlet end. That is, the raw material gas enters the first filter 102 from the inlet end of the first filter 102 for the first stage filtration, and after filtration, a first intermediate gas is obtained and discharged.
The adsorption tower set 103 is connected to the first filter 102 through a pipeline having a first valve, that is, each adsorption tower in the adsorption tower set 103 is connected to the first filter 102 through a pipeline having a first valve. The adsorption tower group 103 includes at least two adsorption towers, and all the adsorption towers have an adsorption state and a desorption regeneration state. The gas inlet end of the adsorption tower set 103 enters the first intermediate gas, and the gas outlet end discharges the second intermediate gas. One adsorption tower in the adsorption tower group 103 is in an adsorption state, and the other adsorption towers are in a desorption regeneration state.
Specifically, as shown in fig. 1, in the present embodiment, the adsorption tower group 103 includes two adsorption towers, a first adsorption tower 1031 and a second adsorption tower 1032, respectively. The first valve is valve 1A or valve 1B. Each adsorption tower is connected to the first filter 102 through a pipe, for example, the first adsorption tower 1031 is connected to the first filter 102 through a pipe having a valve 1A, and the second adsorption tower 1032 is connected to the first filter 102 through a pipe having a valve 1B. The valve 1A and the valve 1B respectively open or close corresponding pipelines.
The adsorption tower is used for adsorbing heavy hydrocarbon gas with C5 and above components, namely gas with the number of adsorbed carbon atoms being more than or equal to 5. Most of the heavy hydrocarbon gas of C5 and components above C5 is removed by the adsorption column group 103. Thus, the C5 and the heavy hydrocarbon gas in the feed gas are removed before the feed gas enters the PSA device, namely the pressure swing adsorption unit 105, the gas quality in the pressure swing adsorption unit 105 is improved, the service life of the adsorbent in the pressure swing adsorption unit 105 is effectively prolonged, and the maintenance cost of the adsorbent is reduced.
In the adsorption tower group 103, the first adsorption tower 1031 operating in the adsorption state and the second adsorption tower 1032 operating in the desorption regeneration state perform the operation state replacement, that is, alternate switching, and the switching process is realized by valves in all pipelines. Specifically, for example, when the duration of the adsorption state of the first adsorption tower 1031 reaches the first preset time, which indicates that the adsorption of the heavy hydrocarbon gas having components of C5 and C5 by the first adsorption tower 1031 is close to saturation, and new heavy hydrocarbon gas cannot be continuously adsorbed, the adsorption state of the first adsorption tower 1031 is switched to the desorption regeneration state. At this time, the duration that the second adsorption tower 1032 is in the desorption regeneration state also corresponds to the first preset time, the desorption of the heavy hydrocarbon gas adsorbed on the adsorbent in the second adsorption tower 1032 is completed, and then the desorption regeneration state of the second adsorption tower 1032 is switched to the adsorption state.
Accordingly, when the second adsorption tower 1032 is in the adsorption state for the first preset time, which indicates that the adsorption of the heavy hydrocarbon gas by the second adsorption tower 1032 is close to saturation, the second adsorption tower 1032 is switched from the adsorption state to the desorption regeneration state. Correspondingly, the first adsorption tower 1031 is now in desorption complete and is switched from the desorption regeneration state to the adsorption state. The first preset time is set according to the relevant data about the adsorption saturation time of the adsorbent, and the first preset time may be 8 hours in this embodiment, which is not limited in this application.
The second filter 104 is connected to the adsorption tower set 103 through a pipeline having a second valve, that is, each adsorption tower in the adsorption tower set 103 is connected to the second filter 104 through a pipeline having a second valve. The second intermediate air is introduced into the second filter 104 at the air inlet end and the third intermediate air is discharged at the air outlet end. When the adsorption tower is in an adsorption state, the first valve and the second valve are both opened. When the adsorption tower is in a desorption regeneration state, the first valve and the second valve are both closed. In this embodiment, the second filter 104 is used to filter dust.
Specifically, in this embodiment, the second valve is the valve 2A or the valve 2B. The valve 2A and the valve 2B respectively open or close the corresponding pipelines. The first adsorption tower 1031 is connected to the second filter 104 through a pipe having a valve 2A, and the second adsorption tower 1032 is connected to the second filter 104 through a pipe having a valve 2B. When the first adsorption tower 1031 is in the adsorption state, the valves 1A and 2A are opened, and the valves 1B and 2B are both closed. When the first adsorption tower 1031 is in the desorption regeneration state, both the valve 1A and the valve 2A are closed, and both the valves 1B and 2B are opened.
The pressure swing adsorption unit 105 is connected to the second filter 104. The gas inlet end of the pressure swing adsorption unit 105 enters the third intermediate gas, and the gas outlet end discharges the product hydrogen and the desorbed gas. The desorption gas is the gas of the impurity component. Part of the above-mentioned desorbed gas is sent to the adsorption tower in the desorption regeneration state in the above-mentioned adsorption tower group 103, and is used for the adsorption tower to desorb the above-mentioned heavy hydrocarbon gas adsorbed on the adsorbent.
Specifically, the pressure swing adsorption unit 105 is a PSA apparatus for separating the third intermediate gas and simultaneously obtaining the product hydrogen and the desorbed gas. The pressure swing adsorption unit 105 has two gas outlet ends, one of which is connected to the product hydrogen recovery unit 107, and the product hydrogen is discharged to the product hydrogen recovery unit 107. And the other gas outlet end discharges the resolved gas. The pressure swing adsorption unit 105 can be implemented by using the prior art, and the details thereof are not repeated herein.
Part of the desorption gas is supplied to the adsorption tower in the desorption regeneration state in the adsorption tower group 103 through a pipeline with a third valve and a pipeline with a fourth valve, respectively. And when the pressure in the adsorption tower in the desorption regeneration state reaches a first preset threshold value, the third valve is opened. When the temperature in the adsorption tower in the desorption regeneration state reaches a second preset threshold value, the third valve is closed, and the fourth valve is opened. And when the temperature in the adsorption tower in the desorption regeneration state reaches a third preset threshold value, the fourth valve is closed. The second preset threshold is greater than the third preset threshold. Illustratively, in this embodiment, the first preset threshold is 0.05MPag, the second preset threshold is 200 ℃, and the third preset threshold is 25 ℃, which is not limited in this application. In this embodiment, the third valve is 5A, and the fourth valve is 6A.
In this embodiment, each adsorption tower in the adsorption tower group 103 is connected to the off-gas discharge unit 106 through a pipeline with a valve. Referring to fig. 1, the first adsorption tower 1031 is connected through the off-gas line take-off unit 106 having the valve 4A, and the second adsorption tower 1032 is connected through the off-gas line take-off unit 106 having the valve 4B. In the present embodiment, the first adsorption tower 1031 is in the adsorption state, and the second adsorption tower 1032 is in the desorption regeneration state.
The desorption regeneration process of the adsorption tower in the desorption regeneration state sequentially comprises four steps: respectively comprising a pressure reduction step, a hot blowing step, a cold blowing step and a pressure increasing step. For example, when the second adsorption tower 1032 starts to perform the pressure reduction step, referring to fig. 1, the valve 4B is opened, and the high pressure gas in the second adsorption tower 1032 is discharged to the off-gas discharge unit 106 through the lines S5 and S6, so that the pressure in the second adsorption tower 1032 is reduced. Meanwhile, the first adsorption tower 1031 is in an adsorption state, and the pressure swing adsorption unit 105 is continuously discharging the desorbed gas. Therefore, it is necessary to open the valve 7A simultaneously with the opening of the valve 4B in order to discharge the decomposed gas. At this time, the analysis gas passes through the line S1, the line S4, and the line S6 in this order, is output to the exhaust gas discharge unit 106, and is discharged from the exhaust gas discharge unit 106.
The pressure swing adsorption unit 105 is connected to the adsorption tower unit 103 through a first line and a second line, respectively. And when the pressure in the adsorption tower in the desorption regeneration state reaches a first preset threshold value or the opening time of the valve 4B exceeds a second preset time, starting to execute the hot blowing step. At this time, the valve 4B and the valve 7A are closed, the third valve 5A and the valve 3B are opened, and a part of the desorbed gas discharged from the pressure swing adsorption unit 105 is heated to a predetermined temperature by the heater 108 on the second pipeline, and then is supplied to the adsorption tower in the desorption regeneration state in the adsorption tower group 103. Referring to fig. 1, in this step of the present embodiment, the desorption gas is sent to the second adsorption tower 1032 through the lines S1 and S3 in this order. The preset temperature is equal to the second preset threshold. Desorption gas after the heating makes second adsorption tower 1032 be in a high temperature environment, and the desorption is carried out to the adsorbed heavy hydrocarbon gas on the adsorbent of being convenient for.
And when the execution time of the hot blowing step reaches a third preset time, starting to execute the cold blowing step. At this time, the third valve 5A and the valve 7A are closed, the fourth valve 6A, the valve 3B, and the valve 4B are opened, and part of the analysis gas discharged from the pressure swing adsorption unit 105 is directly supplied to the adsorption tower in the desorption regeneration state in the adsorption tower group 103 through the first pipeline. Referring to fig. 1, in this step of the present embodiment, the desorption gas is sequentially sent to the second adsorption tower 1032 through the lines S1 and S2, the gas in the second adsorption tower 1032 is cooled and blown, and the cooled desorption gas is discharged from the hydrogen purification apparatus through the lines S5 and S6 and the off-gas discharge unit 106. Because second adsorption tower 1032 is in high temperature low pressure environment this moment, inside gas is comparatively active, does benefit to the desorption. Through analyzing gas and cold blowing to inside, can be with heavy hydrocarbon gas desorption discharge second adsorption tower 1032. Until the execution time of the cold blowing step reaches the fourth preset time, at which time the temperature in the second adsorption tower 1032 drops to the above third preset threshold, and the fourth valve 6A and the valve 4B are closed.
The boosting step is then started. In this embodiment, a third pipeline is disposed between the gas outlet end of the adsorption tower in the adsorption state and the gas outlet end of the adsorption tower in the desorption regeneration state. The third line has on and off states. When the third pipeline is communicated, the adsorption tower in the adsorption state is communicated with the adsorption tower in the desorption regeneration state. When the third pipeline is disconnected, the adsorption tower in the adsorption state and the adsorption tower in the desorption regeneration state are disconnected. Referring to fig. 1, in the pressure increasing step, the valve 3B, the valve 3A, and the valve 7A are opened, and the first adsorption tower 1031 and the second adsorption tower 1032 are communicated to form the third line. Since the gas in the first adsorption tower 1031 is high-pressure gas, the second adsorption tower 1032 is also switched to a high-pressure atmosphere after the communication. When the execution time of the pressure increasing step reaches the fifth preset time, the valve 3B and the valve 3A are closed, and the pressure increase in the second adsorption tower 1032 is completed. At this time, the second adsorption tower 1032 realizes desorption regeneration, realizes cyclic utilization of the adsorption tower, and also realizes continuous operation of the whole hydrogen purification device.
Since the first adsorption tower 1031 and the second adsorption tower 1032 need to be replaced in operation state in order to ensure the continuity of the operation of the entire hydrogen purification apparatus. Therefore, when the pressure increase of the second adsorption tower 1032 is completed, the adsorbent in the first adsorption tower 1031 is not saturated yet, that is, the adsorption state operation time of the first adsorption tower 1031 is not yet reached to the first preset time, then the second adsorption tower 1032 waits until the adsorption state operation time of the first adsorption tower 1031 is reached to the first preset time, and the operation state is not replaced.
For example, the second preset time may be 10 minutes, the third preset time may be 230 minutes, the fourth preset time may be 3 hours, and the fifth preset time may be 10 minutes. This is not limited by the present application.
It should be noted that, when the first adsorption tower 1031 is currently in the desorption regeneration state and the second adsorption tower 1032 is currently in the adsorption state, or when two or more adsorption towers are included in the adsorption tower group 103, the above operation principle needs to be adjusted accordingly. This application is not described in detail herein. All valves in the hydrogen purification device are used for realizing disconnection or connection of the pipeline.
As shown in fig. 2, an embodiment of the present invention further provides a hydrogen purification method, which uses the hydrogen purification apparatus disclosed in any of the above embodiments to purify hydrogen. The detailed structural features and advantages of the hydrogen purification apparatus can be referred to the description of the above embodiments, and will not be described herein. The hydrogen purification method comprises the following steps:
s10, providing raw material gas;
s20, filtering the raw material gas by using a first filter to obtain a first intermediate gas;
s30, adsorbing the first intermediate gas by an adsorption tower in an adsorption state in the adsorption tower group, and discharging a second intermediate gas; the rest adsorption towers in the adsorption tower group are all in the desorption regeneration state;
s40, filtering the second intermediate gas by a second filter to obtain a third intermediate gas;
and S50, separating the third intermediate gas by using a pressure swing adsorption unit to obtain a product hydrogen gas and a gas to be analyzed, and conveying part of the gas to be analyzed to the adsorption tower in a desorption regeneration state in the adsorption tower group.
Wherein, step S50 includes the steps of:
heating part of the analysis gas to a second preset temperature, and then conveying the analysis gas to the adsorption tower in a desorption regeneration state in the adsorption tower group;
and directly conveying part of the analysis gas to the adsorption tower in the desorption regeneration state in the adsorption tower group.
In another embodiment of the present invention, the above hydrogen purification method further comprises the steps of:
and S60, communicating the adsorption tower in the adsorption state with the adsorption tower in the desorption regeneration state in the adsorption tower group.
To facilitate an understanding of the invention, a specific embodiment thereof is set forth below. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The following examples illustrate a refinery with a feed gas flow of 2500Nm3The hydrogen purification is carried out by analyzing the working conditions of 2.2MPa pressure and 35 ℃ temperature, and the advantages of the hydrogen purification device and method disclosed by the invention are illustrated.
The product hydrogen composition pairs for each of the prior art and the present application are shown in table 1 below.
TABLE 1 comparison of the composition of the product hydrogen of the prior art and the present application
The results for hydrogen purity and recovery of the respective products of the prior art and the present application are shown in table 2 below.
TABLE 2 comparison of product Hydrogen purity and recovery rates of the prior art and the present application
| Item | Prior Art | This application |
| Product hydrogen purity (V%) | 98.7 | 99.5 |
| Product hydrogen recovery rate (V%) | 84.3 | 88.6 |
Wherein, the calculation formula of the hydrogen recovery rate of the product is as follows:
as can be seen from table 1, the hydrogen purification apparatus and method of the present invention can completely remove components of C5 and C5 in the feed gas before the feed gas enters the pressure swing adsorption unit, thereby improving the quality of the feed gas in the pressure swing adsorption unit, reducing the accumulation of heavy hydrocarbon gas on the adsorbent in the pressure swing adsorption unit, and prolonging the service life of the adsorbent.
Compare and utilize steam and nitrogen gas to regenerate the adsorbent of pressure swing adsorption unit in prior art, the desorption regeneration of adsorbent in the adsorption tower can be realized to desorption gas that this application utilized discharged, has practiced thrift the cost.
And compare in prior art and must make pressure swing adsorption unit stop work carry out the desorption operation, this application has an adsorption tower in guaranteeing the adsorption tower group and adsorbs, carries out desorption regeneration to other adsorption towers, has realized the continuous uninterrupted production of hydrogen purification.
As can be seen from Table 2, the product hydrogen purity is improved from 98.7% in the prior art to 99.5% in the present application, and the product hydrogen recovery is improved from 84.3% in the prior art to 88.6% in the present application. The recovery rate is improved by 4.3 percent, which is equivalent to more 70Nm of recovered hydrogen3Calculated according to the annual operation time 8400h, about 59 ten thousand parts of hydrogen can be expected to be recovered in one year, and the hydrogen price is 2 yuan/Nm3And (3) calculating to increase the direct economic benefit by 118 ten thousand yuan per year.
In summary, the hydrogen purification apparatus and method of the present invention have at least the following advantages:
the hydrogen purification device and method disclosed in the embodiment realize removal of heavy hydrocarbon components of C5 and above before the feed gas enters the pressure swing adsorption unit through the pre-adsorption tower set capable of continuously working, improve the quality of the feed gas of the pressure swing adsorption unit, and prolong the service life of the adsorbent in the pressure swing adsorption unit; on the other hand, the impurity accumulation of the adsorbent in the pressure swing adsorption unit is reduced, and the activity and adsorption performance of the adsorbent are improved, so that the purity and recovery rate of the product hydrogen are improved; the application also realizes continuous and uninterrupted production of hydrogen purification.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. A hydrogen purification apparatus, characterized in that the apparatus comprises:
the feed gas enters the first filter at the gas inlet end of the first filter, and the first intermediate gas is discharged from the gas outlet end of the first filter;
the adsorption tower group is connected with the first filter through a pipeline with a first valve, and comprises at least two adsorption towers, wherein the adsorption towers are in an adsorption state and a desorption regeneration state; the gas inlet end of the adsorption tower group enters the first intermediate gas, and the gas outlet end of the adsorption tower group discharges a second intermediate gas; one adsorption tower in the adsorption tower group is in an adsorption state, and the other adsorption towers are in a desorption regeneration state;
the second filter is connected with the adsorption tower group through a pipeline with a second valve, the gas inlet end of the second filter enters the second intermediate gas, and the gas outlet end of the second filter discharges a third intermediate gas; when the adsorption tower is in an adsorption state, the first valve and the second valve are both opened; when the adsorption tower is in a desorption regeneration state, the first valve and the second valve are both closed; and
and the pressure swing adsorption unit is connected with the second filter, the gas inlet end of the pressure swing adsorption unit enters the third intermediate gas, the gas outlet end of the pressure swing adsorption unit respectively discharges product hydrogen and the gas to be desorbed, and part of the gas to be desorbed is conveyed to the adsorption tower in a desorption regeneration state in the adsorption tower group.
2. The hydrogen purification apparatus according to claim 1, wherein the first adsorption tower operating in the adsorption state and the second adsorption tower operating in the desorption regeneration state are replaced in the adsorption tower group.
3. The hydrogen purification apparatus according to claim 1, wherein a portion of the desorbed gas is supplied to the adsorption columns in the adsorption column group in the desorption regeneration state through a pipeline having a third valve and a pipeline having a fourth valve, respectively, and the third valve is opened when the pressure in the adsorption columns in the desorption regeneration state reaches a first preset threshold value; when the temperature in the adsorption tower in the desorption regeneration state reaches a second preset threshold value, the third valve is closed, and the fourth valve is opened; when the temperature reaches a third preset threshold value, the fourth valve is closed; the second preset threshold is greater than the third preset threshold.
4. The hydrogen purification apparatus according to claim 1, wherein the pressure swing adsorption unit is connected to the adsorption column group through a first pipeline and a second pipeline, respectively, and the first pipeline directly delivers part of the desorbed gas to the adsorption columns in the adsorption column group in a desorption regeneration state; and the second pipeline heats part of the analysis gas to a preset temperature through a heater and then conveys the analysis gas to the adsorption tower in a desorption regeneration state in the adsorption tower group.
5. The hydrogen purification apparatus according to claim 1, further comprising a tail gas discharge unit connected to the adsorption column set and the pressure swing adsorption unit, respectively.
6. The hydrogen purification apparatus according to claim 1, wherein a third line is provided between the gas outlet end of the adsorption tower in the adsorption state and the gas outlet end of the adsorption tower in the desorption regeneration state, the third line having on and off states, the adsorption tower in the adsorption state and the adsorption tower in the desorption regeneration state being in communication when the third line is on, and the adsorption tower in the adsorption state and the adsorption tower in the desorption regeneration state being in disconnection when the third line is off.
7. The hydrogen purification apparatus according to claim 1, wherein the first filter is connected to each adsorption tower of the adsorption tower group, and the second filter is connected to each adsorption tower of the adsorption tower group, the first filter being for filtering solid particles and liquid, and the second filter being for filtering dust.
8. A method for purifying hydrogen gas, characterized by purifying hydrogen gas using the hydrogen purification apparatus according to any one of claims 1 to 7, the method comprising the steps of:
providing a raw material gas;
filtering the feed gas by using a first filter to obtain a first intermediate gas;
adsorbing the first intermediate gas by using an adsorption tower in an adsorption state in the adsorption tower group, and discharging a second intermediate gas; the other adsorption towers in the adsorption tower group are all in the desorption regeneration state;
filtering the second intermediate gas by using a second filter to obtain a third intermediate gas;
and separating the third intermediate gas by using a pressure swing adsorption unit to obtain a product hydrogen gas and a gas to be analyzed, and conveying part of the gas to be analyzed to the adsorption tower in a desorption regeneration state in the adsorption tower group.
9. The method of purifying hydrogen as claimed in claim 8, wherein said feeding of a portion of said desorbed gas to an adsorption column in a desorption regeneration state in said adsorption column group comprises:
heating part of the analysis gas to a second preset temperature, and then conveying the analysis gas to an adsorption tower in a desorption regeneration state in the adsorption tower group;
and directly conveying part of the analysis gas to the adsorption tower in the desorption regeneration state in the adsorption tower group.
10. The method for purifying hydrogen as claimed in claim 8, further comprising the steps of:
and communicating the adsorption tower in the adsorption state with the adsorption tower in the desorption regeneration state in the adsorption tower group.
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