WO2022119376A1 - Method for separation and purification of hydrogen from decomposed mixed gas of ammonia - Google Patents

Method for separation and purification of hydrogen from decomposed mixed gas of ammonia Download PDF

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WO2022119376A1
WO2022119376A1 PCT/KR2021/018220 KR2021018220W WO2022119376A1 WO 2022119376 A1 WO2022119376 A1 WO 2022119376A1 KR 2021018220 W KR2021018220 W KR 2021018220W WO 2022119376 A1 WO2022119376 A1 WO 2022119376A1
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pressure
adsorption
adsorption tower
ammonia
hydrogen
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PCT/KR2021/018220
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French (fr)
Korean (ko)
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조순행
김인백
임삼목
박주현
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주식회사 젠스엔지니어링
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Publication of WO2022119376A1 publication Critical patent/WO2022119376A1/en

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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
    • C01B3/56—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
    • 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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • 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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/047—Decomposition of ammonia
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/16—Controlling the process
    • C01B2203/1628—Controlling the pressure
    • 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
    • C01B2210/0053—Hydrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to an adsorption separation method for separating and purifying hydrogen from a decomposed mixed gas of ammonia, and more particularly, to a pressure of 4 or more units filled with an adsorbent in the adsorption step of a mixed gas containing hydrogen, nitrogen and undecomposed ammonia After passing through a swing adsorption device to adsorb nitrogen and ammonia to the adsorbent, hydrogen that is not adsorbed is discharged to the upper part of the adsorption tower to produce purified hydrogen, and the nitrogen and ammonia adsorbed to the adsorbent are removed by reducing the pressure to atmospheric pressure ( It relates to an adsorption separation method for separating and purifying hydrogen from a decomposed mixed gas of ammonia using the Pressure Swing Adsorption (PSA) method and the Vacuum Pressure Swing Adsorption (VPSA) method, which removes the pressure by reducing the pressure to vacuum.
  • PSA Pressure Swing Adsorption
  • VPSA Vacuum Pressure Swing Ad
  • the pressure swing adsorption process is a process of separating a mixed gas using the adsorption selectivity of the adsorbent to the adsorbent.
  • the adsorbent is regenerated by desorbing the adsorbed component. In order to sufficiently regenerate the adsorbent, it is cleaned at low pressure with high-purity weak adsorption components, and raw material gas or product gas is used to pressurize the adsorption pressure.
  • PSA Pressure Swing Adsorption
  • a technology and method for removing impurities using various adsorbents and producing hydrogen, and a technology and method for producing nitrogen and oxygen in air have been commercialized.
  • Ammonia differs from the above method in that it does not contain carbon and thus does not emit carbon dioxide.
  • Japanese Patent Laid-Open No. 2008-238180 discloses an ammonia decomposition catalyst using a catalyst, a method for preparing the same, and a method for treating ammonia.
  • the conventional ammonia decomposition catalyst does not produce more than 99.9% of hydrogen, and a technique for removing nitrogen and ammonia from hydrogen containing nitrogen and ammonia and purifying more than 99.9% of hydrogen has not been disclosed.
  • the present inventors have made diligent efforts to separate and purify hydrogen at 99.9% or more from the mixed gas containing hydrogen, nitrogen, and undecomposed ammonia obtained by decomposing ammonia.
  • the mixed gas containing hydrogen, nitrogen, and undecomposed ammonia In the adsorption step, nitrogen and ammonia are adsorbed to the adsorbent by passing through 4 or more pressure swing adsorption devices filled with adsorbent, and then the hydrogen that is not adsorbed is discharged to the top of the adsorption tower to produce purified hydrogen,
  • the pressure swing adsorption method to remove ammonia under reduced pressure to atmospheric pressure
  • the vacuum pressure swing adsorption method to remove ammonia by reducing the pressure to vacuum pressure
  • the present invention is (a) passing a decomposed mixed gas of ammonia containing hydrogen, nitrogen and undecomposed ammonia through a pressure swing adsorption device equipped with an adsorption tower filled with nitrogen and ammonia selective adsorbent to obtain the adsorbent adsorbing nitrogen and ammonia, and discharging hydrogen that is not adsorbed to the upper portion of the adsorption tower to separate hydrogen; and (b) performing a pressure swing adsorption (PSA) method in which nitrogen and ammonia adsorbed to the adsorbent are desorbed and discharged by reducing the pressure of the adsorption tower to atmospheric pressure, or the pressure of the adsorption tower is reduced to a vacuum pressure to perform a vacuum pressure swing adsorption (VPSA) method in which nitrogen and ammonia are desorbed and discharged by It provides a method for separation and purification of
  • PSA pressure swing adsorption
  • PSA pressure swing adsorption
  • VPSA vacuum pressure swing adsorption
  • V-1, V-2, V-3, V-4 adsorption tower
  • T-1 99.9% or more hydrogen storage tank from which nitrogen and ammonia have been removed
  • T-2 Mixed gas storage tank containing nitrogen and ammonia
  • the present invention selectively adsorbs nitrogen and ammonia in an adsorption tower filled with nitrogen and ammonia selective adsorbent for a mixed gas containing hydrogen, nitrogen, and undecomposed ammonia obtained by decomposing ammonia, and uses an adsorbent for pressure swing adsorption and vacuum pressure It was confirmed that nitrogen and ammonia were removed from the mixed gas by the swing adsorption method and that hydrogen of 99.9% or more could be purified and produced.
  • the present invention is (a) passing through a pressure swing adsorption device equipped with an adsorption tower filled with nitrogen and ammonia selective adsorbent to pass the decomposed mixed gas of ammonia including hydrogen, nitrogen and undecomposed ammonia to the adsorbent.
  • PSA pressure swing adsorption
  • VPSA vacuum pressure swing adsorption
  • the step (b) comprises: (i) a pressure equalization step of equalizing the pressure between the two adsorption towers by supplying the gas discharged by reducing the pressure of the adsorption tower to another adsorption tower; (ii) a countercurrent depressurization step of depressurizing the pressure in the adsorption tower where the pressure equalization step is completed to atmospheric pressure to discharge nitrogen and ammonia present in the adsorption tower; (iii) a desorption step of desorbing nitrogen and ammonia by vacuuming the pressure of the adsorption tower where the countercurrent depressurization step has been completed; (iv) a pressure equalization step of equalizing the pressure between the two adsorption towers by supplying a gas discharged by co-current depressurizing the adsorption tower where the adsorption step of (a) has been completed to the adsorption tower where the desorption step has been completed; and (v) introducing a part of hydrogen produced in the adsorption tower
  • a washing supply step for washing impurities generated in the adsorbent charged in the adsorption tower may be added and performed.
  • the (i) exhaust gas of the adsorption tower where the pressure equalization step has been completed is supplied to the adsorption tower and supplied as the washing gas of the adsorption tower, and the (ii) countercurrent depressurization step is started. It may be a step of cleaning nitrogen and ammonia present in the adsorption tower by supplying a gas to be used.
  • pressure equalization step - washing supply step - (ii) countercurrent pressure reduction step can be carried out in the order.
  • step (b) is a preferred embodiment, (i) a pressure equalization step of equalizing the pressure between the two adsorption towers by supplying the gas discharged by reducing the pressure of the adsorption tower to another adsorption tower; (ii) a cleaning supply step of supplying the exhaust gas of the adsorption tower where the pressure equalization step has been completed to the adsorption tower and supplying it to the cleaning gas of the adsorption tower; (iii) a countercurrent depressurization step of depressurizing the pressure to atmospheric pressure in the adsorption tower where the washing supply step has been completed to discharge nitrogen and ammonia present in the adsorption tower; (iv) vacuuming the pressure of the adsorption tower where the countercurrent depressurization step has been completed to desorb nitrogen and ammonia, and receiving the gas discharged from the adsorption tower of the (ii) cleaning supply step to wash nitrogen and ammonia present in the adsorption tower desorption step; (v) a pressure equalization
  • a mixed gas of hydrogen, nitrogen, and ammonia is introduced into an adsorption tower filled with a nitrogen and ammonia selective adsorbent to selectively apply nitrogen and ammonia in the mixed gas to the nitrogen and ammonia selective adsorbent an adsorption step of adsorbing and discharging non-adsorbed hydrogen from the adsorption tower to produce;
  • a cleaning supply step of reducing the pressure of the adsorption tower where the pressure equalization step has been completed by co-current, supplying the discharged gas to the adsorption tower in the desorption step, and supplying it as a cleaning gas of the
  • the present invention is an apparatus and method for purifying and producing 99.9% or more of hydrogen by removing a mixed gas containing hydrogen, nitrogen, and ammonia by a pressure swing adsorption method and a vacuum pressure swing adsorption method.
  • the hydrogen mixed gas containing 25% nitrogen and 5 ⁇ 3,000ppm ammonia is passed through a pressure swing adsorption device filled with an adsorbent and a vacuum pressure swing adsorption device to selectively adsorb nitrogen and ammonia and separate and not adsorb.
  • Product hydrogen that is not produced is emitted and produced.
  • the adsorbed nitrogen and ammonia are removed under reduced pressure to atmospheric pressure or removed under reduced pressure to vacuum pressure.
  • the present invention manufactures and operates an adsorption device using 4 adsorption towers to purify hydrogen from a mixed gas containing hydrogen, nitrogen, and undecomposed ammonia obtained by decomposing ammonia, or installs a vacuum pump to increase the recovery rate of nitrogen and ammonia You can build and operate a device that removes it.
  • a pressure swing adsorption device and a vacuum pressure swing adsorption device and operation method which are adsorption separation methods for removing nitrogen and ammonia from a mixed gas containing hydrogen, nitrogen, and ammonia and purifying 99.9% or more of hydrogen, will be described in detail.
  • the adsorption separation process of the present invention is a process using four adsorption towers, and in FIG. 1, the adsorption step - pressure equalization step - washing supply step - countercurrent pressure reduction - pressure equalization step - pressure accumulation step are operated. The cleaning supply stage-countercurrent pressure reduction-desorption stage-pressure equalization stage-pressure accumulation stage is operated.
  • FIGS. 1 and 2 A method and apparatus according to the present invention will be described in detail with reference to FIGS. 1 and 2 .
  • the adsorption step, the pressure equalization step, the cleaning supply step, the countercurrent depressurization step, the desorption step and the pressure accumulation step are sequentially performed and are operated repeatedly.
  • the operation in each of the adsorption towers is, when operating the 4 pressure swing adsorption device, the (a) mixed gas of hydrogen, nitrogen, and ammonia is introduced into the adsorption tower filled with nitrogen and ammonia selective adsorbents. an adsorption step of selectively adsorbing nitrogen and ammonia in the mixed gas and discharging hydrogen that is not adsorbed from the adsorption tower to produce;
  • the adsorption tower where the pressure equalization step has been completed consists of an accumulating step of introducing a part of hydrogen produced in the adsorption tower in the adsorption step to fill the pressure of the adsorption tower up to the pressure of the adsorption step, and reducing the pressure to the vacuum pressure (e) ) the desorption step was excluded.
  • the adsorption tower in which the pressure equalization step has been completed may include a pressure accumulating step of (a) introducing a portion of hydrogen produced in the adsorption tower in the adsorption step to fill the pressure of the adsorption tower to the pressure of the adsorption step.
  • adsorption tower in the adsorption tower, four or more adsorption towers may be arranged in parallel with each other. Preferably, four adsorption towers may be arranged in parallel with each other.
  • the adsorption step, the pressure equalization step, the washing supply step, the countercurrent pressure reduction step, the desorption step and the pressure accumulation step are performed at the same time by the operation of at least four adsorption towers during the at least 4 bed process.
  • the adsorption step, the pressure equalization step, the cleaning supply step, the countercurrent pressure reduction step, and the pressure accumulation step are repeatedly performed in different steps at the same time in the four adsorption towers, and the vacuum pressure swing adsorption device is used.
  • the adsorption step, the pressure equalization step, the washing supply step, the countercurrent pressure reduction step, the desorption step, and the pressure accumulation step may be repeatedly performed in different steps at the same time in the four adsorption towers.
  • the adsorption separation method may constitute a method of performing (c) the washing supply step, and may also constitute an adsorption separation method excluding the washing supply step (c).
  • the pressure in step (g), may also be accumulated by supplying a raw material. That is, in the (g) pressure accumulation step, the pressure may be accumulated by supplying a feed, or the pressure may be accumulated using a product gas.
  • the nitrogen and ammonia selective adsorbent may be at least one selected from the group consisting of activated carbon, alumina, zeolite, silica and MOF adsorbent.
  • the adsorption step (a) may be performed under a pressure condition of 0 to 30 barG.
  • the countercurrent decompression step of steps (d) and (f) may be performed under 0 to 3 barG conditions.
  • the (e) desorption step may be performed under -1 to 3 barG conditions.
  • Tables 1 and 2 show a process for purifying 99.9% or more of hydrogen by introducing a hydrogen-nitrogen-ammonia mixed gas into the adsorption separation process.
  • Table 1 shows the operation steps of the pressure swing adsorption device using four adsorption towers
  • Table 2 shows the operating steps of the vacuum pressure swing adsorption device using four adsorption towers.
  • an adsorption step in each of the four adsorption towers (V-1, V-2, V-3, V-4), an adsorption step, a pressure equalization step, a washing supply step, a countercurrent pressure reduction step, a desorption step, and a pressure accumulation step It can be operated by performing
  • FIG. 1 shows a 4-bed pressure swing adsorption device composed of four main adsorption towers (V-1,2,3,4).
  • control valves are attached to control the gas flow in each operation step, and the main adsorption tower is configured to remove nitrogen and ammonia by reducing the pressure to atmospheric pressure.
  • the operation of the device for refining and producing hydrogen goes through the following operation steps.
  • nitrogen and ammonia which are strongly adsorbed components, are adsorbed by the adsorption tower, and unadsorbed hydrogen is discharged through the valve (6) to the hydrogen storage (T-1).
  • the exhaust gas of the adsorption tower (V-4) to be used is supplied to the adsorption tower (V-3) through the valve (21) and valve (15) to partially pressurize the adsorption tower (V-3).
  • the adsorption tower (V-4) turns the exhaust gas into the washing gas of the adsorption tower (V-2) while reducing the co-current pressure through the valve (22).
  • a cleaning supply step of supplying is performed, and the adsorption tower (V-2) opens the valve (10) to receive the gas supplied from the adsorption tower (V-4) to clean the adsorbent.
  • the adsorption tower (V-2) performs countercurrent pressure reduction to atmospheric pressure through the valve (8) and valve (25). It is used to clean the adsorbent by receiving a cleaning gas while performing countercurrent pressure reduction.
  • the adsorption tower (V-3) closes the valve (15) and opens the valve (17) to introduce the product gas in a counter-current flow, thereby accumulating the pressure of the tower to the adsorption pressure.
  • the valves 7, 10, 22, and 25 of the adsorption tower (V-2) where countercurrent depressurization is completed and the adsorption tower (V-4) where the cleaning supply stage is completed are closed and the valve (9) is closed.
  • the secondary pressure equalization proceeds as the valve 21 is opened, and the remaining adsorption towers proceed with the existing performing steps.
  • the adsorption tower (V-1) and the adsorption tower (V-2) close the valve (1) and the valve (6), and open the valve (3) to perform the first equalization pressure
  • the adsorption tower (V-3) closes the valve (17)
  • the adsorption tower (V-4) closes the valve (21)
  • the valve (20) the countercurrent pressure reduction step is performed to atmospheric pressure by opening the valve 25 .
  • the adsorption tower (V-1) closes the valve (3) and opens the valve (4) to reduce the co-current pressure while removing the exhaust gas from the adsorption tower (V-)
  • a cleaning supply step of sending the cleaning gas to 4) is performed, and the adsorption tower (V-4) receives the gas supplied from the adsorption tower (V-1) by opening the valve (22) to clean the adsorbent.
  • the adsorption tower (V-4) performs countercurrent pressure reduction to atmospheric pressure through the valve 20 and the valve 25 to atmospheric pressure. It is used to clean the adsorbent by receiving a cleaning gas while performing countercurrent pressure reduction.
  • the adsorption tower (V-2) closes the valve (3) and opens the valve (11) to introduce the product gas in a counter-current flow, thereby accumulating the pressure of the tower to the adsorption pressure.
  • the valve (4), valve (20), valve (22), and valve (25) of the adsorption tower (V-4) where countercurrent depressurization is finished and the adsorption tower (V-1) where the cleaning supply step is completed are closed, and valve (3) is closed.
  • the secondary pressure equalization proceeds as the valve 21 is opened, and the remaining adsorption towers proceed with the existing performing steps.
  • the adsorption tower (V-3) and the adsorption tower (V-4) close the valve 13 and 18, and open the valve 3 to perform the first equalization pressure
  • the adsorption tower (V-2) closes the valve 11, and opens the valve 7 and 12 to perform the adsorption step
  • the adsorption tower (V-1) closes the valve 3
  • the valve (2) the countercurrent pressure reduction step is performed to atmospheric pressure by opening the valve 25 .
  • the adsorption tower (V-3) closes the valve (15) and opens the valve (16) to co-currently pressure reduce the exhaust gas to the adsorption tower (V-)
  • a cleaning supply step of sending a cleaning gas to 1) is performed, and the adsorption tower (V-1) receives the gas supplied from the adsorption tower (V-3) by opening the valve (4) to clean the adsorbent.
  • the adsorption tower (V-1) performs countercurrent pressure reduction to atmospheric pressure through the valve 20 and the valve 25 to atmospheric pressure. It is used to clean the adsorbent by receiving a cleaning gas while performing countercurrent pressure reduction.
  • the adsorption tower (V-4) closes the valve (21) and opens the valve (23) to introduce the product gas in a counter-current flow, thereby accumulating the pressure of the tower to the adsorption pressure.
  • the valve (2), valve (4), valve (10), and valve (25) of the adsorption tower (V-1) where countercurrent depressurization has been completed and the washing supply step (V-3) are closed, and valve (3) is closed.
  • the secondary pressure equalization proceeds as the valve 15 is opened, and the remaining adsorption towers proceed with the existing performing steps.
  • the adsorption tower (V-1) and the adsorption tower (V-2) close the valve 7 and 12, and open the valve 9 to perform the first equalization pressure
  • the adsorption tower (V-4) closes the valve 23, and opens the valve 19 and valve 24 to perform the adsorption step
  • the adsorption tower (V-3) closes the valve 15, the valve 14
  • the countercurrent pressure reduction step is performed to atmospheric pressure by opening the valve 25 .
  • the adsorption tower (V-2) closes the valve (9) and opens the valve (10) to co-current pressure reduce the exhaust gas to the adsorption tower (V-)
  • a cleaning supply step of sending the cleaning gas to 3) is performed, and the adsorption tower (V-3) receives the gas supplied from the adsorption tower (V-2) by opening the valve (16) to clean the adsorbent.
  • the adsorption tower (V-3) performs countercurrent pressure reduction to atmospheric pressure through the valve 14 and the valve 25 to atmospheric pressure. It is used to clean the adsorbent by receiving a cleaning gas while performing countercurrent pressure reduction.
  • the adsorption tower (V-1) closes the valve (3) and opens the valve (5) to introduce the product gas in a counter-current flow, thereby accumulating the pressure of the tower to the adsorption pressure.
  • the valves 10, 14, 16, and 25 of the adsorption tower (V-3) where countercurrent depressurization has been completed and the washing supply step (V-2) of the adsorption tower (V-2) are closed, and the valve (9) is closed. ), the secondary pressure equalization proceeds as the valve 15 is opened, and the remaining adsorption towers proceed with the existing performing steps.
  • This operation is alternately continued in the four adsorption towers, forming one cycle, and continuous operation is performed.
  • FIG. 2 shows a 4-bed vacuum pressure swing adsorption device composed of four main adsorption towers (V-1,2,3,4).
  • control valves are attached to control the gas flow in each operation step, and it consists of a vacuum pump to remove nitrogen by lowering the vacuum pressure from the main adsorption tower.
  • the operation of the device for refining and producing hydrogen goes through the following operation steps.
  • nitrogen and ammonia which are strongly adsorbed components, are adsorbed by the adsorption tower, and unadsorbed hydrogen is discharged through the valve (6) to the hydrogen storage (T-1).
  • the exhaust gas of the adsorption tower (V-4) to be used is supplied to the adsorption tower (V-3) through the valve (15) and valve (21) to partially pressurize the adsorption tower (V-3).
  • the adsorption tower (V-4) turns the exhaust gas into the washing gas of the adsorption tower (V-2) while reducing the co-current pressure through the valve (22).
  • a cleaning supply step of supplying is performed, and the adsorption tower (V-2) opens the valve (10) to receive the gas supplied from the adsorption tower (V-4) to clean the adsorbent.
  • the adsorption tower (V-2) performs vacuum desorption using a vacuum pump by opening the valve 26 after the countercurrent pressure reduction to atmospheric pressure is completed. While performing vacuum desorption, a cleaning gas is supplied and used to clean the adsorbent.
  • the adsorption tower (V-3) closes the valve (15) and opens the valve (17) to introduce the product gas in a counter-current flow, thereby accumulating the pressure of the tower to the adsorption pressure.
  • the valves 8, 10, 22, and 26 of the adsorption tower (V-2) where the vacuum desorption is completed and the adsorption tower (V-4) where the cleaning supply stage is completed are closed, and the valve (9) is closed. ), the valve 21 is opened, and the secondary pressure equalization proceeds, and the remaining adsorption towers proceed with the existing steps.
  • the adsorption tower (V-1) and the adsorption tower (V-2) close the valve (1) and the valve (6), and open the valve (3) to perform the first equalization pressure
  • the adsorption tower (V-3) closes the valve (17)
  • the adsorption tower (V-4) closes the valve (21)
  • the valve (20) the countercurrent pressure reduction step is performed to atmospheric pressure by opening the valve 25 .
  • the adsorption tower (V-1) closes the valve (3) and opens the valve (4) to reduce the co-current pressure while removing the exhaust gas from the adsorption tower (V-)
  • a cleaning supply step of sending a cleaning gas to 4) is performed, and the adsorption tower (V-4) receives the gas supplied from the adsorption tower (V-1) by opening the valve (22) to clean the adsorbent.
  • the adsorption tower (V-4) performs vacuum desorption using a vacuum pump by opening the valve 26 after the countercurrent pressure reduction to atmospheric pressure is completed.
  • a cleaning gas is supplied and used to clean the adsorbent.
  • the adsorption tower (V-2) closes the valve (3) and opens the valve (11) to introduce the product gas in a counter-current flow, thereby accumulating the pressure of the tower to the adsorption pressure.
  • the valve (4), valve (20), valve (22), and valve (26) of the adsorption tower (V-4) where the vacuum desorption is completed and the adsorption tower (V-1) where the cleaning supply step is completed are closed and the valve (3) ), the valve 21 is opened, and the secondary pressure equalization proceeds, and the remaining adsorption towers proceed with the existing steps.
  • the adsorption tower (V-3) and the adsorption tower (V-4) close the valve 13 and 18, and open the valve 15 to perform the first equalization pressure
  • the adsorption tower (V-2) closes the valve 11, and opens the valve 7 and 12 to perform the adsorption step
  • the adsorption tower (V-1) closes the valve 3
  • the valve (2) the countercurrent pressure reduction step is performed to atmospheric pressure by opening the valve 25 .
  • the adsorption tower (V-3) closes the valve (15) and opens the valve (16) to co-currently pressure reduce the exhaust gas to the adsorption tower (V-)
  • a cleaning supply step of sending a cleaning gas to 1) is performed, and the adsorption tower (V-1) receives the gas supplied from the adsorption tower (V-3) by opening the valve (4) to clean the adsorbent.
  • the adsorption tower (V-1) performs vacuum desorption using a vacuum pump by opening the valve 26 after the counter-current pressure reduction to atmospheric pressure is completed.
  • a cleaning gas is supplied and used to clean the adsorbent.
  • the adsorption tower (V-4) closes the valve (21) and opens the valve (23) to introduce the product gas in a counter-current flow, thereby accumulating the pressure of the tower to the adsorption pressure.
  • the valves (2), valves (4), valves (16), and valves (26) of the adsorption tower (V-1) where vacuum desorption has been completed and the washing supply step (V-3) are closed and valve (3) is closed.
  • the secondary pressure equalization proceeds as the valve 15 is opened, and the remaining adsorption towers proceed with the existing performing steps.
  • the adsorption tower (V-1) and the adsorption tower (V-2) close the valve 7 and 12, and open the valve 9 to perform the first equalization pressure
  • the adsorption tower (V-4) closes the valve 23, and opens the valve 19 and the valve 24 to perform the adsorption step
  • the adsorption tower (V-3) closes the valve 15, the valve 11 and the valve 25 is opened to perform a countercurrent pressure reduction step to atmospheric pressure.
  • the adsorption tower (V-2) closes the valve (9) and opens the valve (10) to co-currently pressure reduce the exhaust gas to the adsorption tower (V-)
  • a cleaning supply step of sending the cleaning gas to 3) is performed, and the adsorption tower (V-3) receives the gas supplied from the adsorption tower (V-2) by opening the valve (16) to clean the adsorbent.
  • the adsorption tower (V-3) performs vacuum desorption using a vacuum pump by opening the valve 26 after the countercurrent pressure reduction to atmospheric pressure is completed.
  • a cleaning gas is supplied and used to clean the adsorbent.
  • the adsorption tower (V-1) closes the valve (3) and opens the valve (5) to introduce the product gas in a counter-current flow, thereby accumulating the pressure of the tower to the adsorption pressure.
  • the valve 10, 14, valve 16, and valve 26 of the adsorption tower (V-3) where vacuum desorption is completed and the adsorption tower (V-2) where the cleaning supply step is completed are closed, and the valve (9) is closed. ) and the valve 15 are opened, the secondary pressure equalization proceeds, and the remaining adsorption towers proceed with the existing execution steps.
  • This operation is alternately continued in the four adsorption towers to form one cycle, and continuous operation is performed. It is produced by purifying 99.9% or more of hydrogen through the same operation as above.
  • Example 2 Example of atmospheric pressure desorption hydrogen purification from 75% hydrogen + 25% nitrogen + 5ppm ammonia mixed gas
  • the performance of the process according to the present invention was compared using the pressure swing adsorption device of the four adsorption towers for purifying hydrogen from a mixed gas containing 75% hydrogen, 25% nitrogen, and 5 ppm ammonia.
  • the pressure in the adsorption step was 2-20 barG, and the pressure in the counter-current decompression step was normal pressure.
  • the adsorption temperature the following results were obtained at ambient temperature.
  • Nitrogen remaining in the product hydrogen was detected at 100 ppm or less, and ammonia was removed and not detected.
  • Example 3 Example of hydrogen purification using vacuum pressure swing adsorption from 75% hydrogen + 25% nitrogen + 5 ppm ammonia mixed gas
  • the performance of the process according to the present invention was compared using a vacuum pressure swing adsorption device of 4 adsorption towers for purifying hydrogen from a mixed gas containing 75% hydrogen, 25% nitrogen, and 5 ppm ammonia.
  • the pressure in the adsorption step was 2 to 20 barG
  • the pressure in the desorption step was (-)1 to (-)0.1 barG.
  • the adsorption temperature the following results were obtained at an ambient temperature of 25 to 32 °C.
  • Nitrogen remaining in the product hydrogen was detected at 100 ppm or less, and ammonia was removed and not detected.
  • Both the pressure swing adsorption device and the vacuum pressure swing adsorption device for purifying hydrogen from a mixed gas containing 75% hydrogen, 25% nitrogen, and 5ppm ammonia were purified and produced more than 99.9% of hydrogen, and the nitrogen concentration was detected below 100pm, Ammonia was removed and was not detected.
  • Example 4 Example of atmospheric pressure desorption hydrogen purification from 74.7% hydrogen + 25% nitrogen + 3,000 ppm mixed gas
  • the performance of the process according to the present invention was compared using the pressure swing adsorption device of the four adsorption towers for purifying hydrogen from a mixed gas containing 74.7% hydrogen, 25% nitrogen, and 3,000 ppm ammonia.
  • the pressure in the adsorption step was 2-20 barG, and the pressure in the counter-current decompression step was normal pressure.
  • the adsorption temperature the following results were obtained at an ambient temperature of 25 to 32 °C.
  • Nitrogen remaining in the product hydrogen was detected at 100 ppm or less, and ammonia was removed and not detected.
  • Example 5 Example of hydrogen purification using vacuum pressure swing adsorption from 74.7% hydrogen + 25% nitrogen + 3,000 ppm mixed gas
  • the performance of the process according to the present invention was compared using a vacuum pressure swing adsorption device of 4 adsorption towers for purifying hydrogen from a mixed gas containing 74.7% hydrogen, 25% nitrogen, and 3,000 ppm ammonia.
  • the pressure in the adsorption step was 2 to 20 barG
  • the pressure in the desorption step was (-)1 to (-)0.1 barG.
  • the adsorption temperature the following results were obtained at an ambient temperature of 25 to 32 °C.
  • Nitrogen remaining in the product hydrogen was detected at 100 ppm or less, and ammonia was removed and not detected.
  • Both the pressure swing adsorption device and the vacuum pressure swing adsorption device that purify hydrogen from a mixed gas containing 74.7% hydrogen, 25% nitrogen, and 3,000 ppm ammonia purified and produced more than 99.9% of hydrogen, and the nitrogen concentration was detected below 100pm. , ammonia was removed and was not detected.

Abstract

The present invention relates to a pressure swing adsorption process, which is an adsorption separation method for purifying hydrogen from a mixed gas in which hydrogen and nitrogen, obtained by decomposing ammonia, and undecomposed ammonia, are contained. After nitrogen and ammonia are adsorbed onto adsorbents, from hydrogen gas containing nitrogen and ammonia, by allowing same to pass through four or more pressure swing adsorption devices filled with the adsorbents, unadsorbed hydrogen is discharged to the upper portion of an adsorption tower to produce purified hydrogen, and hydrogen can be purified and produced from a mixed gas in which hydrogen and nitrogen, obtained by decomposing ammonia, and undecomposed ammonia, are contained, by using a pressure swing adsorption (PSA) process for removing the nitrogen and ammonia adsorbed onto the adsorbents by reducing the pressure to atmospheric pressure, and a vacuum pressure swing adsorption (VPSA) process for removing the adsorbed nitrogen and ammonia by reducing the pressure to vacuum pressure.

Description

암모니아의 분해 혼합가스로부터 수소의 분리 및 정제방법Separation and purification method of hydrogen from ammonia decomposition mixed gas
본 발명은 암모니아의 분해 혼합가스로부터 수소를 분리·정제하는 흡착분리방법에 관한 것으로서, 보다 상세하게는 수소, 질소 및 미분해 암모니아가 포함된 혼합가스를 흡착단계에서 흡착제가 충진된 4기 이상의 압력스윙 흡착장치에 통과시켜 흡착제에 질소와 암모니아를 흡착시킨 후 흡착되지 않는 수소는 흡착탑 상부로 배출하여 정제된 수소를 생산하고, 흡착제에 흡착된 질소와 암모니아는 대기압까지 감압하여 제거하는 압력스윙흡착(Pressure Swing Adsorption, PSA)법과 진공압력까지 감압하여 제거하는 진공압력스윙흡착(Vacuum Pressure Swing Adsorption, VPSA)법을 이용하여 암모니아의 분해 혼합가스로부터 수소를 분리·정제하는 흡착분리방법에 관한 것이다.The present invention relates to an adsorption separation method for separating and purifying hydrogen from a decomposed mixed gas of ammonia, and more particularly, to a pressure of 4 or more units filled with an adsorbent in the adsorption step of a mixed gas containing hydrogen, nitrogen and undecomposed ammonia After passing through a swing adsorption device to adsorb nitrogen and ammonia to the adsorbent, hydrogen that is not adsorbed is discharged to the upper part of the adsorption tower to produce purified hydrogen, and the nitrogen and ammonia adsorbed to the adsorbent are removed by reducing the pressure to atmospheric pressure ( It relates to an adsorption separation method for separating and purifying hydrogen from a decomposed mixed gas of ammonia using the Pressure Swing Adsorption (PSA) method and the Vacuum Pressure Swing Adsorption (VPSA) method, which removes the pressure by reducing the pressure to vacuum.
일반적으로 압력스윙흡착공정은 흡착제에 대한 흡착질의 흡착 선택도를 이용하여 혼합가스를 분리하는 공정으로서 약흡착성분과 강흡착성분을 분리하는 흡착스텝은 높은 압력에서 이루어지며, 흡착탑의 압력을 떨어뜨려서 흡착된 성분을 탈착하여 흡착제를 재생한다. 흡착제를 충분히 재생하기 위해서 고순도의 약흡착성분으로 저압에서 세정을 하고 흡착압력으로 가압하기 위해서 원료가스나 제품가스를 사용한다. 일반적으로 압력스윙 흡착법(Pressure Swing Adsorption, PSA)에서는 다양한 흡착제를 이용하여 불순물을 제거하고 수소를 생산하는 기술과 방법, 공기 중에서 질소, 산소를 생산하는 기술과 방법이 상용화되어 있다.In general, the pressure swing adsorption process is a process of separating a mixed gas using the adsorption selectivity of the adsorbent to the adsorbent. The adsorbent is regenerated by desorbing the adsorbed component. In order to sufficiently regenerate the adsorbent, it is cleaned at low pressure with high-purity weak adsorption components, and raw material gas or product gas is used to pressurize the adsorption pressure. In general, in Pressure Swing Adsorption (PSA), a technology and method for removing impurities using various adsorbents and producing hydrogen, and a technology and method for producing nitrogen and oxygen in air have been commercialized.
종래에는 미래 에너지 중 하나인 수소를 생산하기 위해 석유화학산업이나 제철산업에서 발생하는 부생가스로부터 수소 생산 또는 천연가스 개질 방식을 통한 수소 생산 또는 수전해 시스템 방식을 이용하여 수소를 생산하는 기술과 방법을 사용하고 있다. 부생가스, 천연가스 개질, 수전해 시스템으로부터 얻은 수소는 일산화탄소, 이산화탄소, 메탄 등 불순물을 함유하고 있어 수소 압력스윙흡착(Pressure Swing Adsorption, PSA)을 이용한 흡착분리장치를 이용하여 99.9% 이상의 고순도 수소를 정제한 후 생산하고 있다. 현재 진행되고 있는 수소를 정제하는 기술로서, 수소 함유 혼합 가스로부터 99.9% 이상의 고순도 수소를 정제하는 압력스윙흡착공정의 생산성을 높이기 위한 운전방법으로서, 한국공개특허 제2000-0051347호에 높은 생산성을 갖는 수소 압력변동흡착 공정에 관하여 기술되어 있다.Conventionally, in order to produce hydrogen, which is one of the future energy, hydrogen production from by-product gas generated in the petrochemical industry or steel industry, hydrogen production through natural gas reforming method, or technology and method for producing hydrogen using a water electrolysis system method is using Hydrogen obtained from by-product gas, natural gas reforming, and water electrolysis systems contains impurities such as carbon monoxide, carbon dioxide, and methane, so it is possible to obtain high-purity hydrogen of more than 99.9% using an adsorption separation device using hydrogen pressure swing adsorption (PSA). It is produced after purification. As a technology for purifying hydrogen currently in progress, it is an operation method for increasing the productivity of a pressure swing adsorption process for purifying high-purity hydrogen of 99.9% or more from a hydrogen-containing mixed gas. A hydrogen pressure swing adsorption process is described.
최근에는 탄소를 함유하고 있지 않은 암모니아를 분해하여 생산한 수소를 연료전지용으로 이용하는 연구가 진행되고 있다. 암모니아는 상기 방식과 다르게 탄소를 함유하고 있지 않아 이산화탄소를 배출하지 않는 방식으로 차이를 가지고 있다. 일본공개특허 제2008-238180호에는 촉매를 사용하여 암모니아 분해 촉매, 그 제조방법 및 암모니아 처리방법이 기술되어 있다.Recently, research using hydrogen produced by decomposing ammonia that does not contain carbon for fuel cells is being conducted. Ammonia differs from the above method in that it does not contain carbon and thus does not emit carbon dioxide. Japanese Patent Laid-Open No. 2008-238180 discloses an ammonia decomposition catalyst using a catalyst, a method for preparing the same, and a method for treating ammonia.
그러나, 암모니아를 분해하는 과정에서 100%의 효율로 수소와 질소로 분해되지 않아 분해 반응한 다음 수소와 질소, 미분해 암모니아가 포함된 혼합가스가 생성된다. 수소기술 분야 ISO 국제표준 번호 ISO 14687-2에 따르면 연료전지 내에 질소는 허용농도 100ppm 이하, 암모니아 허용농도는 0.1ppm 이하에 해당된다. 연료전지에 필요로 하는 수소는 질소와 암모니아를 제거하여 99.97% 이상의 수소를 요구하고 있다.However, in the process of decomposing ammonia, it is not decomposed into hydrogen and nitrogen with 100% efficiency, so a decomposition reaction is performed, and then a mixed gas containing hydrogen, nitrogen, and undecomposed ammonia is generated. According to ISO International Standard No. ISO 14687-2 in the field of hydrogen technology, nitrogen in a fuel cell has an allowable concentration of 100 ppm or less and ammonia is 0.1 ppm or less. The hydrogen required for the fuel cell is 99.97% or more hydrogen by removing nitrogen and ammonia.
이와 같이, 종래의 암모니아 분해 촉매는 99.9% 이상의 수소를 생산하지 못하며, 질소와 암모니아가 포함된 수소에서 질소와 암모니아를 제거하고 99.9%이상의 수소를 정제하는 기술은 공개된 바가 없다.As such, the conventional ammonia decomposition catalyst does not produce more than 99.9% of hydrogen, and a technique for removing nitrogen and ammonia from hydrogen containing nitrogen and ammonia and purifying more than 99.9% of hydrogen has not been disclosed.
이에, 본 발명자들은 암모니아를 분해하여 얻은 수소와 질소, 미분해 암모니아가 포함된 혼합가스로부터 99.9% 이상으로 수소를 분리·정제하기 위하여 예의 노력한 결과, 수소와 질소, 미분해 암모니아가 포함된 혼합가스를 흡착단계에서 흡착제가 충진된 4기 이상의 압력스윙 흡착장치에 통과시켜 흡착제에 질소와 암모니아를 흡착시킨 후 흡착되지 않는 수소는 흡착탑 상부로 배출하여 정제된 수소를 생산하고, 흡착제에 흡착된 질소와 암모니아는 대기압까지 감압하여 제거하는 압력스윙 흡착법과 진공압력까지 감압하여 제거하는 진공압력스윙 흡착법을 이용할 경우, 암모니아를 분해하여 얻은 수소와 질소, 미분해 암모니아가 포함된 혼합가스로부터 수소를 흡착분리방법으로 정제할 수 있다는 것을 확인하고, 본 발명을 완성하게 되었다.Accordingly, the present inventors have made diligent efforts to separate and purify hydrogen at 99.9% or more from the mixed gas containing hydrogen, nitrogen, and undecomposed ammonia obtained by decomposing ammonia. As a result, the mixed gas containing hydrogen, nitrogen, and undecomposed ammonia In the adsorption step, nitrogen and ammonia are adsorbed to the adsorbent by passing through 4 or more pressure swing adsorption devices filled with adsorbent, and then the hydrogen that is not adsorbed is discharged to the top of the adsorption tower to produce purified hydrogen, In the case of using the pressure swing adsorption method to remove ammonia under reduced pressure to atmospheric pressure and the vacuum pressure swing adsorption method to remove ammonia by reducing the pressure to vacuum pressure, the method for adsorption separation of hydrogen from a mixed gas containing hydrogen, nitrogen and undecomposed ammonia obtained by decomposing ammonia It was confirmed that it can be purified, and the present invention was completed.
발명의 요약Summary of the invention
본 발명의 목적은 암모니아를 분해하여 얻은 수소와 질소, 미분해 암모니아가 포함된 혼합가스로부터 질소와 암모니아를 제거하고 수소를 99.9% 이상으로 정제할 수 있는 방법 및 장치를 제공하는데 있다.It is an object of the present invention to provide a method and apparatus capable of removing nitrogen and ammonia from a mixed gas containing hydrogen, nitrogen, and undecomposed ammonia obtained by decomposing ammonia and purifying hydrogen to 99.9% or more.
상기 목적을 달성하기 위하여, 본 발명은 (a) 수소, 질소 및 미분해 암모니아를 포함하는 암모니아의 분해 혼합가스를 질소 및 암모니아 선택성 흡착제가 충진된 흡착탑이 구비된 압력스윙 흡착장치에 통과시켜 상기 흡착제에 질소와 암모니아를 흡착시키고, 흡착되지 않는 수소를 흡착탑 상부로 배출하여 수소를 분리하는 단계; 및 (b) 상기 흡착탑의 압력을 대기압까지 감압하여 상기 흡착제에 흡착된 질소와 암모니아를 탈착시켜 배출하는 압력스윙흡착(Pressure Swing Adsorption, PSA)법을 수행하거나, 상기 흡착탑의 압력을 진공압력까지 감압하여 질소와 암모니아를 탈착시켜 배출하는 진공압력스윙흡착(Vacuum Pressure Swing Adsorption, VPSA)법을 수행하거나, 상기 PSA법을 수행한 다음, VPSA법을 수행하는 단계를 포함하는 암모니아의 분해 혼합가스로부터 수소의 분리 및 정제방법을 제공한다.In order to achieve the above object, the present invention is (a) passing a decomposed mixed gas of ammonia containing hydrogen, nitrogen and undecomposed ammonia through a pressure swing adsorption device equipped with an adsorption tower filled with nitrogen and ammonia selective adsorbent to obtain the adsorbent adsorbing nitrogen and ammonia, and discharging hydrogen that is not adsorbed to the upper portion of the adsorption tower to separate hydrogen; and (b) performing a pressure swing adsorption (PSA) method in which nitrogen and ammonia adsorbed to the adsorbent are desorbed and discharged by reducing the pressure of the adsorption tower to atmospheric pressure, or the pressure of the adsorption tower is reduced to a vacuum pressure to perform a vacuum pressure swing adsorption (VPSA) method in which nitrogen and ammonia are desorbed and discharged by It provides a method for separation and purification of
도 1은 본 발명의 일 실시예에 따른 수소-질소-암모니아 가스에서 수소를 생산하기 위한 4bed 압력스윙흡착(Pressure Swing Adsorption, PSA) 공정도이다.1 is a 4bed pressure swing adsorption (PSA) process diagram for producing hydrogen from hydrogen-nitrogen-ammonia gas according to an embodiment of the present invention.
도 2는 본 발명의 일 실시예에 따른 수소-질소-암모니아 가스에서 수소를 생산하기 위한 4bed 진공압력스윙흡착(Vacuum Pressure Swing Adsorption, VPSA) 공정도이다.2 is a 4bed vacuum pressure swing adsorption (VPSA) process diagram for producing hydrogen from hydrogen-nitrogen-ammonia gas according to an embodiment of the present invention.
* 부호의 설명 ** Explanation of symbols *
1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26: 밸브1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26: valve
27: 유량계27: flow meter
28: 진공펌프28: vacuum pump
V-1, V-2, V-3, V-4: 흡착탑V-1, V-2, V-3, V-4: adsorption tower
T-1: 질소와 암모니아가 제거된 99.9% 이상의 수소 저장탱크T-1: 99.9% or more hydrogen storage tank from which nitrogen and ammonia have been removed
T-2: 질소와 암모니아가 포함된 혼합가스 저장탱크T-2: Mixed gas storage tank containing nitrogen and ammonia
발명의 상세한 설명 및 구체적인 구현예DETAILED DESCRIPTION OF THE INVENTION AND SPECIFIC EMBODIMENTS OF THE INVENTION
다른 식으로 정의되지 않는 한, 본 명세서에서 사용된 모든 기술적 및 과학적 용어들은 본 발명이 속하는 기술 분야에서 숙련된 전문가에 의해서 통상적으로 이해되는 것과 동일한 의미를 갖는다. 일반적으로, 본 명세서에서 사용된 명명법은 본 기술 분야에서 잘 알려져 있고 통상적으로 사용되는 것이다.Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is those well known and commonly used in the art.
본 발명은 암모니아를 분해하여 얻은 수소와 질소, 미분해 암모니아가 포함된 혼합가스를 질소, 암모니아 선택성 흡착제가 충진된 흡착탑에서 질소와 암모니아를 선택적으로 흡착시켜 분리하고 흡착제를 이용한 압력스윙흡착과 진공압력스윙 흡착법에 의하여 상기 혼합가스로부터 질소, 암모니아를 제거하고 99.9% 이상의 수소를 정제하여 생산할 수 있는 것을 확인하였다.The present invention selectively adsorbs nitrogen and ammonia in an adsorption tower filled with nitrogen and ammonia selective adsorbent for a mixed gas containing hydrogen, nitrogen, and undecomposed ammonia obtained by decomposing ammonia, and uses an adsorbent for pressure swing adsorption and vacuum pressure It was confirmed that nitrogen and ammonia were removed from the mixed gas by the swing adsorption method and that hydrogen of 99.9% or more could be purified and produced.
따라서, 본 발명은 일 관점에서 (a) 수소, 질소 및 미분해 암모니아를 포함하는 암모니아의 분해 혼합가스를 질소 및 암모니아 선택성 흡착제가 충진된 흡착탑이 구비된 압력스윙 흡착장치에 통과시켜 상기 흡착제에 질소와 암모니아를 흡착시키고, 흡착되지 않는 수소를 흡착탑 상부로 배출하여 수소를 분리하는 단계; 및 (b) 상기 흡착탑의 압력을 대기압까지 감압하여 상기 흡착제에 흡착된 질소와 암모니아를 탈착시켜 배출하는 압력스윙흡착(Pressure Swing Adsorption, PSA)법을 수행하거나, 상기 흡착탑의 압력을 진공압력까지 감압하여 질소와 암모니아를 탈착시켜 배출하는 진공압력스윙흡착(Vacuum Pressure Swing Adsorption, VPSA)법을 수행하거나, 상기 PSA법을 수행한 다음, VPSA법을 수행하는 단계를 포함하는 암모니아의 분해 혼합가스로부터 수소의 분리 및 정제방법에 관한 것이다.Accordingly, in one aspect, the present invention is (a) passing through a pressure swing adsorption device equipped with an adsorption tower filled with nitrogen and ammonia selective adsorbent to pass the decomposed mixed gas of ammonia including hydrogen, nitrogen and undecomposed ammonia to the adsorbent. and adsorbing ammonia, and discharging non-adsorbed hydrogen to the upper portion of the adsorption tower to separate hydrogen; and (b) performing a pressure swing adsorption (PSA) method in which nitrogen and ammonia adsorbed to the adsorbent are desorbed and discharged by reducing the pressure of the adsorption tower to atmospheric pressure, or the pressure of the adsorption tower is reduced to a vacuum pressure to perform a vacuum pressure swing adsorption (VPSA) method in which nitrogen and ammonia are desorbed and discharged by It relates to a method for separation and purification of
본 발명에 있어서, 상기 (b) 단계는 (i) 상기 흡착탑의 압력을 감압하여 배출한 가스를 다른 흡착탑으로 공급하여 두 흡착탑 사이에 압력을 균등화하는 균압단계; (ii) 상기 균압단계가 종료된 흡착탑에 압력을 상압으로 감압시켜 흡착되어 있는 흡착탑에 존재하는 질소와 암모니아를 배출하는 향류감압단계; (iii) 상기 향류감압단계가 종료된 흡착탑의 압력을 진공으로 하여 질소와 암모니아를 탈착시키는 탈착단계; (iv) 상기 탈착단계가 종료된 흡착탑에 (a)의 흡착단계가 종료된 흡착탑을 병류감압하여 배출되는 가스를 공급하여 두 흡착탑 사이에 압력을 균등화하는 균압단계; 및 (v) 상기 균압단계가 종료된 흡착탑에 상기 (a) 흡착단계에 있는 흡착탑의 생산되는 수소 일부를 도입하여 흡착탑의 압력을 흡착단계 압력까지 채워주는 축압단계를 수행할 수 있다.In the present invention, the step (b) comprises: (i) a pressure equalization step of equalizing the pressure between the two adsorption towers by supplying the gas discharged by reducing the pressure of the adsorption tower to another adsorption tower; (ii) a countercurrent depressurization step of depressurizing the pressure in the adsorption tower where the pressure equalization step is completed to atmospheric pressure to discharge nitrogen and ammonia present in the adsorption tower; (iii) a desorption step of desorbing nitrogen and ammonia by vacuuming the pressure of the adsorption tower where the countercurrent depressurization step has been completed; (iv) a pressure equalization step of equalizing the pressure between the two adsorption towers by supplying a gas discharged by co-current depressurizing the adsorption tower where the adsorption step of (a) has been completed to the adsorption tower where the desorption step has been completed; and (v) introducing a part of hydrogen produced in the adsorption tower in the (a) adsorption step to the adsorption tower where the pressure equalization step has been completed to fill the pressure of the adsorption tower to the pressure of the adsorption step.
여기서, 흡착분리 방법 중 상기 (i) 단계 이후에 상기 흡착탑에 충진된 흡착제에 생성된 불순물을 세정하기 위한 세정공급단계를 추가하여 수행할 수 있다. 상기 세정공급단계는 상기 (i) 균압단계가 종료된 흡착탑의 배출 가스를 흡착탑으로 공급하여 흡착탑의 세정가스로 공급하며, 상기 (ii) 향류감압단계가 시작되는 흡착탑에 세정공급단계의 흡착탑에서 배출되는 가스를 공급하여 흡착탑에 존재하는 질소와 암모니아를 세정하는 단계일 수 있다. (i) 균압단계- 세정공급단계-(ii) 향류감압단계의 순서로 수행할 수 있다.Here, in the adsorption separation method, after step (i), a washing supply step for washing impurities generated in the adsorbent charged in the adsorption tower may be added and performed. In the washing supply step, the (i) exhaust gas of the adsorption tower where the pressure equalization step has been completed is supplied to the adsorption tower and supplied as the washing gas of the adsorption tower, and the (ii) countercurrent depressurization step is started. It may be a step of cleaning nitrogen and ammonia present in the adsorption tower by supplying a gas to be used. (i) pressure equalization step - washing supply step - (ii) countercurrent pressure reduction step can be carried out in the order.
또한, 상기 (b) 단계는 바람직한 실시예로서, (i) 상기 흡착탑의 압력을 감압하여 배출한 가스를 다른 흡착탑으로 공급하여 두 흡착탑 사이에 압력을 균등화하는 균압단계; (ii) 상기 균압단계가 종료된 흡착탑의 배출 가스를 흡착탑으로 공급하여 흡착탑의 세정가스로 공급하는 세정공급단계; (iii) 상기 세정공급단계가 종료된 흡착탑에 압력을 상압으로 감압시켜 흡착되어 있는 흡착탑에 존재하는 질소와 암모니아를 배출하는 향류감압단계; (iv) 상기 향류감압단계가 종료된 흡착탑의 압력을 진공으로 하여 질소와 암모니아를 탈착시키고, 상기 (ii) 세정공급단계의 흡착탑에서 배출되는 가스를 공급받아 흡착탑에 존재하는 질소와 암모니아를 세정하는 탈착단계; (v) 상기 탈착단계가 종료된 흡착탑에 (a)의 흡착단계가 종료된 흡착탑을 병류감압하여 배출되는 가스를 공급하여 두 흡착탑 사이에 압력을 균등화하는 균압단계; 및 (vi) 상기 균압단계가 종료된 흡착탑에 상기 (a) 흡착단계에 있는 흡착탑의 생산되는 수소 일부를 도입하여 흡착탑의 압력을 흡착단계 압력까지 채워주는 축압단계를 수행할 수 있다.In addition, the step (b) is a preferred embodiment, (i) a pressure equalization step of equalizing the pressure between the two adsorption towers by supplying the gas discharged by reducing the pressure of the adsorption tower to another adsorption tower; (ii) a cleaning supply step of supplying the exhaust gas of the adsorption tower where the pressure equalization step has been completed to the adsorption tower and supplying it to the cleaning gas of the adsorption tower; (iii) a countercurrent depressurization step of depressurizing the pressure to atmospheric pressure in the adsorption tower where the washing supply step has been completed to discharge nitrogen and ammonia present in the adsorption tower; (iv) vacuuming the pressure of the adsorption tower where the countercurrent depressurization step has been completed to desorb nitrogen and ammonia, and receiving the gas discharged from the adsorption tower of the (ii) cleaning supply step to wash nitrogen and ammonia present in the adsorption tower desorption step; (v) a pressure equalization step of equalizing the pressure between the two adsorption towers by supplying the gas discharged by co-current depressurizing the adsorption tower where the adsorption step of (a) has been completed to the adsorption tower where the desorption step has been completed; and (vi) introducing a part of hydrogen produced in the adsorption tower in the (a) adsorption step to the adsorption tower where the pressure equalization step has been completed to fill the pressure of the adsorption tower to the pressure of the adsorption step.
본 발명의 바람직한 일 실시예에 의하면, (a) 수소와 질소, 암모니아의 혼합가스를 질소, 암모니아 선택성 흡착제가 충진된 흡착탑으로 도입하여 질소, 암모니아 선택성 흡착제에 상기 혼합가스 내 질소와 암모니아를 선택적으로 흡착시키고 상기 흡착탑으로부터 흡착되지 않는 수소를 배출하여 생산하는 흡착단계; (b) 상기 흡착단계가 종료된 흡착탑의 압력을 원료가스의 흐름과 같은 방향인 병류(竝流, co-current flow)로 감압하여 배출한 수소를 다른 흡착탑으로 공급하여 두 흡착탑 사이에 압력을 균등화 하는 균압 단계; (c) 상기 균압단계가 종료된 흡착탑의 압력을 병류로 감압하고 배출되는 가스를 탈착단계에 있는 흡착탑으로 공급하여 흡착탑의 세정가스로 공급하는 세정공급 단계; (d) 상기 세정공급단계가 종료된 흡착탑에 압력을 향류(向流, countercurrent flow)로 대기압까지 감압하여 흡착되어 있는 질소, 암모니아를 제거하는 향류감압단계; (e) 상기 향류감압단계가 종료된 흡착탑으로 세정공급단계에 있는 흡착탑에서 배출되는 가스를 도입하여 흡착탑에 존재하는 질소, 암모니아를 진공압력까지 감압하여 제거하는 탈착단계; (f) 상기 탈착단계가 종료된 흡착탑의 출구로 병류감압하는 다른 흡착탑의 배출가스를 향류로 도입하여 가압하는 균압단계; (g) 상기 균압단계가 종료된 흡착탑은 (a) 흡착단계에 있는 흡착탑의 생산되는 수소 일부를 도입하여 흡착탑의 압력을 흡착단계 압력까지 채워주는 축압단계로 구성되어 암모니아를 분해하여 얻은 수소와 질소, 미분해 암모니아가 포함된 혼합가스로부터 수소를 정제하는 흡착분리방법인 압력스윙 흡착법과 진공압력스윙 흡착법을 제공한다.According to a preferred embodiment of the present invention, (a) a mixed gas of hydrogen, nitrogen, and ammonia is introduced into an adsorption tower filled with a nitrogen and ammonia selective adsorbent to selectively apply nitrogen and ammonia in the mixed gas to the nitrogen and ammonia selective adsorbent an adsorption step of adsorbing and discharging non-adsorbed hydrogen from the adsorption tower to produce; (b) equalize the pressure between the two adsorption towers by reducing the pressure of the adsorption tower where the adsorption step has been completed in a co-current flow, which is the same direction as the flow of the raw material gas, and supplying the discharged hydrogen to another adsorption tower pressure equalization step; (c) a cleaning supply step of reducing the pressure of the adsorption tower where the pressure equalization step has been completed by co-current, supplying the discharged gas to the adsorption tower in the desorption step, and supplying it as a cleaning gas of the adsorption tower; (d) a countercurrent pressure reducing step of removing adsorbed nitrogen and ammonia by reducing the pressure to atmospheric pressure in a countercurrent flow to the adsorption tower where the washing supply step has been completed; (e) a desorption step of introducing the gas discharged from the adsorption tower in the washing supply step to the adsorption tower where the countercurrent depressurization step has been completed, and removing nitrogen and ammonia present in the adsorption tower under reduced pressure to a vacuum pressure; (f) a pressure equalization step of introducing and pressurizing the exhaust gas of another adsorption tower co-currently depressurized to the outlet of the adsorption tower where the desorption step has been completed; (g) the adsorption tower where the pressure equalization step has been completed consists of an accumulating step of introducing a part of hydrogen produced in the adsorption tower in the adsorption step to fill the pressure of the adsorption tower to the pressure of the adsorption step, and hydrogen and nitrogen obtained by decomposing ammonia , provides a pressure swing adsorption method and a vacuum pressure swing adsorption method, which are adsorption separation methods for purifying hydrogen from a mixed gas containing undecomposed ammonia.
이하, 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 수소와 질소, 암모니아가 포함된 혼합가스를 압력스윙 흡착법과 진공압력스윙 흡착법에 의하여 제거하여 99.9% 이상의 수소를 정제하여 생산하는 장치와 방법이다.The present invention is an apparatus and method for purifying and producing 99.9% or more of hydrogen by removing a mixed gas containing hydrogen, nitrogen, and ammonia by a pressure swing adsorption method and a vacuum pressure swing adsorption method.
먼저 25% 정도의 질소와 5~3,000ppm 정도의 암모니아가 포함된 수소 혼합가스로부터 흡착제가 충진된 압력스윙 흡착장치와 진공압력스윙 흡착장치에 통과시켜 질소와 암모니아를 선택적으로 흡착시켜 분리하고 흡착되지 않는 제품 수소는 배출되어 생산한다. 흡착된 질소와 암모니아는 대기압까지 감압하여 제거 또는 진공압력까지 감압하여 제거된다.First, the hydrogen mixed gas containing 25% nitrogen and 5~3,000ppm ammonia is passed through a pressure swing adsorption device filled with an adsorbent and a vacuum pressure swing adsorption device to selectively adsorb nitrogen and ammonia and separate and not adsorb. Product hydrogen that is not produced is emitted and produced. The adsorbed nitrogen and ammonia are removed under reduced pressure to atmospheric pressure or removed under reduced pressure to vacuum pressure.
본 발명은 암모니아를 분해하여 얻은 수소와 질소, 미분해 암모니아가 포함된 혼합가스로부터 수소를 정제하기 위하여 흡착탑 4기를 이용하여 흡착장치를 제작하고 운전하거나 회수율을 높이기 위하여 진공펌프를 설치하여 질소와 암모니아 제거하는 장치를 제작하고 운전할 수 있다.The present invention manufactures and operates an adsorption device using 4 adsorption towers to purify hydrogen from a mixed gas containing hydrogen, nitrogen, and undecomposed ammonia obtained by decomposing ammonia, or installs a vacuum pump to increase the recovery rate of nitrogen and ammonia You can build and operate a device that removes it.
이하 수소와 질소, 암모니아가 포함된 혼합가스에서 질소, 암모니아를 제거하고 99.9% 이상의 수소를 정제하는 흡착분리방법인 압력스윙 흡착장치와 진공압력스윙 흡착장치와 운전방법에 대하여 상세히 설명한다.Hereinafter, a pressure swing adsorption device and a vacuum pressure swing adsorption device and operation method, which are adsorption separation methods for removing nitrogen and ammonia from a mixed gas containing hydrogen, nitrogen, and ammonia and purifying 99.9% or more of hydrogen, will be described in detail.
본 발명의 흡착분리공정은 흡착탑 4기를 이용한 공정으로 도 1에서는 흡착단계-균압단계-세정공급단계-향류감압-균압단계-축압단계로 구성되어 운전이 되고, 도 2에서는 흡착단계-균압단계-세정공급단계-향류감압-탈착단계-균압단계-축압단계로 구성되어 운전이 된다.The adsorption separation process of the present invention is a process using four adsorption towers, and in FIG. 1, the adsorption step - pressure equalization step - washing supply step - countercurrent pressure reduction - pressure equalization step - pressure accumulation step are operated. The cleaning supply stage-countercurrent pressure reduction-desorption stage-pressure equalization stage-pressure accumulation stage is operated.
도 1 및 도 2를 참조하여 본 발명에 의한 방법 및 장치를 상세하게 설명한다.A method and apparatus according to the present invention will be described in detail with reference to FIGS. 1 and 2 .
상호 병렬 배치되어 있으면서, 질소와 암모니아 선택성 흡착제가 각각 충진된 적어도 4개의 흡착탑의 흡착분리 공정에 의하여 수소-질소-암모니아 혼합가스로부터 질소와 암모니아를 제거하고 수소를 생산하는 방법으로서, 상기 각각의 흡착탑은 4기(4bed) 공정일 때는 흡착단계, 균압단계, 세정공급단계, 향류감압단계, 탈착단계 및 축압단계로 순차적으로 수행되면서 반복하여 운전된다.A method of removing nitrogen and ammonia from a hydrogen-nitrogen-ammonia mixed gas and producing hydrogen by an adsorption separation process of at least four adsorption towers arranged in parallel with each other and each filled with nitrogen and ammonia selective adsorbents, wherein each of the adsorption towers In the case of a 4 bed process, the adsorption step, the pressure equalization step, the cleaning supply step, the countercurrent depressurization step, the desorption step and the pressure accumulation step are sequentially performed and are operated repeatedly.
이때 상기 각각의 흡착탑에서의 운전은, 4기 압력스윙흡착 장치를 운전 시에는 상기 (a) 수소와 질소, 암모니아의 혼합가스를 질소, 암모니아 선택성 흡착제가 충진된 흡착탑으로 도입하여 질소, 암모니아 선택성 흡착제에 상기 혼합가스 내 질소와 암모니아를 선택적으로 흡착시키고 상기 흡착탑으로부터 흡착되지 않는 수소를 배출하여 생산하는 흡착단계;At this time, the operation in each of the adsorption towers is, when operating the 4 pressure swing adsorption device, the (a) mixed gas of hydrogen, nitrogen, and ammonia is introduced into the adsorption tower filled with nitrogen and ammonia selective adsorbents. an adsorption step of selectively adsorbing nitrogen and ammonia in the mixed gas and discharging hydrogen that is not adsorbed from the adsorption tower to produce;
(b) 상기 흡착단계가 종료된 흡착탑의 압력을 원료가스의 흐름과 같은 방향인 병류로 감압하여 배출한 수소를 다른 흡착탑으로 공급하여 두 흡착탑 사이에 압력을 균등화 하는 균압 단계;(b) a pressure equalization step of equalizing the pressure between the two adsorption towers by reducing the pressure of the adsorption tower where the adsorption step has been completed in a co-current flow in the same direction as the flow of the raw material gas and supplying the discharged hydrogen to another adsorption tower;
(c) 상기 균압단계가 종료된 흡착탑의 압력을 병류로 감압하고 배출되는 가스를 탈착단계에 있는 흡착탑으로 공급하여 흡착탑의 세정가스로 공급하는 세정공급 단계;(c) a cleaning supply step of reducing the pressure of the adsorption tower where the pressure equalization step has been completed by co-current, supplying the discharged gas to the adsorption tower in the desorption step, and supplying it as a cleaning gas of the adsorption tower;
(d) 상기 세정공급단계가 종료된 흡착탑에 압력을 향류로 대기압까지 감압하여 흡착되어 있는 질소, 암모니아를 제거하는 향류감압단계;(d) a countercurrent pressure reducing step of removing the adsorbed nitrogen and ammonia by reducing the pressure to atmospheric pressure in a countercurrent manner in the adsorption tower where the washing supply step has been completed;
(f) 상기 탈착단계가 종료된 흡착탑의 출구로 병류감압하는 다른 흡착탑의 배출가스를 향류로 도입하여 가압하는 균압단계;(f) a pressure equalization step of introducing and pressurizing the exhaust gas of another adsorption tower co-currently depressurized to the outlet of the adsorption tower where the desorption step has been completed;
(g) 상기 균압단계가 종료된 흡착탑은 (a) 흡착단계에 있는 흡착탑의 생산되는 수소 일부를 도입하여 흡착탑의 압력을 흡착단계 압력까지 채워주는 축압단계로 구성되었고, 진공 압력까지 감압하는 (e) 탈착단계는 제외되었다.(g) the adsorption tower where the pressure equalization step has been completed consists of an accumulating step of introducing a part of hydrogen produced in the adsorption tower in the adsorption step to fill the pressure of the adsorption tower up to the pressure of the adsorption step, and reducing the pressure to the vacuum pressure (e) ) the desorption step was excluded.
도 1에 상기 공정을 나타내었다.1 shows the process.
4기(4bed) 진공압력스윙흡착 장치를 운전 시에는When operating a 4 bed vacuum pressure swing adsorption device,
(a) 수소와 질소, 암모니아의 혼합가스를 질소, 암모니아 선택성 흡착제가 충진된 흡착탑으로 도입하여 질소, 암모니아 선택성 흡착제에 상기 혼합가스 내 질소와 암모니아를 선택적으로 흡착시키고 상기 흡착탑으로부터 흡착되지 않는 수소를 배출하여 생산하는 흡착단계;(a) introducing a mixed gas of hydrogen, nitrogen, and ammonia into an adsorption tower filled with a nitrogen and ammonia selective adsorbent to selectively adsorb nitrogen and ammonia in the mixed gas to the nitrogen and ammonia selective adsorbent, and hydrogen that is not adsorbed from the adsorption tower Adsorption step to produce by discharging;
(b) 상기 흡착단계가 종료된 흡착탑의 압력을 원료가스의 흐름과 같은 방향인 병류로 감압하여 배출한 수소를 다른 흡착탑으로 공급하여 두 흡착탑 사이에 압력을 균등화 하는 균압 단계;(b) a pressure equalization step of equalizing the pressure between the two adsorption towers by reducing the pressure of the adsorption tower where the adsorption step has been completed in a co-current flow in the same direction as the flow of the raw material gas and supplying the discharged hydrogen to another adsorption tower;
(c) 상기 균압단계가 종료된 흡착탑의 압력을 병류로 감압하고 배출되는 가스를 탈착단계에 있는 흡착탑으로 공급하여 흡착탑의 세정가스로 공급하는 세정공급 단계;(c) a cleaning supply step of reducing the pressure of the adsorption tower where the pressure equalization step has been completed by co-current, supplying the discharged gas to the adsorption tower in the desorption step, and supplying it as a cleaning gas of the adsorption tower;
(d) 상기 세정공급단계가 종료된 흡착탑에 압력을 향류로 대기압까지 감압하여 흡착되어 있는 질소, 암모니아를 제거하는 향류감압단계;(d) a countercurrent pressure reducing step of removing the adsorbed nitrogen and ammonia by reducing the pressure to atmospheric pressure in a countercurrent manner in the adsorption tower where the washing supply step has been completed;
(e) 상기 향류감압단계가 종료된 흡착탑으로 세정공급단계에 있는 흡착탑에서 배출되는 가스를 도입하여 흡착탑에 존재하는 질소, 암모니아를 진공압력까지 감압하여 제거하는 탈착단계;(e) a desorption step of introducing the gas discharged from the adsorption tower in the washing supply step to the adsorption tower where the countercurrent depressurization step has been completed, and removing nitrogen and ammonia present in the adsorption tower under reduced pressure to a vacuum pressure;
(f) 상기 탈착단계가 종료된 흡착탑의 출구로 병류감압하는 다른 흡착탑의 배출가스를 향류로 도입하여 가압하는 균압단계;(f) a pressure equalization step of introducing and pressurizing the exhaust gas of another adsorption tower co-currently depressurized to the outlet of the adsorption tower where the desorption step has been completed;
(g) 상기 균압단계가 종료된 흡착탑은 (a) 흡착단계에 있는 흡착탑의 생산되는 수소 일부를 도입하여 흡착탑의 압력을 흡착단계 압력까지 채워주는 축압단계를 포함하여 구성될 수 있다.(g) The adsorption tower in which the pressure equalization step has been completed may include a pressure accumulating step of (a) introducing a portion of hydrogen produced in the adsorption tower in the adsorption step to fill the pressure of the adsorption tower to the pressure of the adsorption step.
도 2에 상기 공정을 나타내었다.2 shows the process.
본 발명에 있어서, 상기 흡착탑은 4개 이상의 흡착탑이 상호 병렬로 배치될 수 있다. 바람직하게는 4개의 흡착탑이 상호병렬로 배치될 수 있다. In the present invention, in the adsorption tower, four or more adsorption towers may be arranged in parallel with each other. Preferably, four adsorption towers may be arranged in parallel with each other.
여기서, 상기 수소-질소-암모니아 분리 방법은 상기 적어도 4bed 공정 시 적어도 4개의 흡착탑의 운전에 의하여 동일 시점에 흡착단계, 균압단계, 세정공급단계, 향류감압단계, 탈착단계 및 축압단계를 각각 수행할 수 있다.Here, in the hydrogen-nitrogen-ammonia separation method, the adsorption step, the pressure equalization step, the washing supply step, the countercurrent pressure reduction step, the desorption step and the pressure accumulation step are performed at the same time by the operation of at least four adsorption towers during the at least 4 bed process. can
다시 말하면, 압력스윙 흡착장치를 사용할 경우에 4개의 흡착탑에서 흡착단계, 균압단계, 세정공급단계, 향류감압단계 및 축압단계가 동일한 시점에 서로 상이한 단계로 반복하여 수행하며, 진공압력스윙 흡착장치를 사용할 경우에 4개의 흡착탑에서 흡착단계, 균압단계, 세정공급단계, 향류감압단계, 탈착단계 및 축압단계가 동일한 시점에 서로 상이한 단계로 반복하여 수행할 수 있다.In other words, when a pressure swing adsorption device is used, the adsorption step, the pressure equalization step, the cleaning supply step, the countercurrent pressure reduction step, and the pressure accumulation step are repeatedly performed in different steps at the same time in the four adsorption towers, and the vacuum pressure swing adsorption device is used. When used, the adsorption step, the pressure equalization step, the washing supply step, the countercurrent pressure reduction step, the desorption step, and the pressure accumulation step may be repeatedly performed in different steps at the same time in the four adsorption towers.
본 발명에 있어서, 상기 흡착분리 방법은 (c) 세정공급단계 수행하는 방법을 구성할 수 있으며, (c) 세정공급단계를 제외한 흡착분리 방법도 구성할 수 있다.In the present invention, the adsorption separation method may constitute a method of performing (c) the washing supply step, and may also constitute an adsorption separation method excluding the washing supply step (c).
본 발명에 있어서, 상기 (g) 단계는 원료 공급에 의해서도 축압할 수 있다. 즉, 상기 (g) 축압 단계는 원료(feed)를 공급하여 축압하거나 제품 가스(product)를 이용하여 축압할 수 있다.In the present invention, in step (g), the pressure may also be accumulated by supplying a raw material. That is, in the (g) pressure accumulation step, the pressure may be accumulated by supplying a feed, or the pressure may be accumulated using a product gas.
본 발명에 있어서, 상기 질소 및 암모니아 선택성 흡착제는 활성탄, 알루미나, 제올라이트, 실리카 및 MOF 흡착제로 구성된 군에서 1종 이상 선택될 수 있다.In the present invention, the nitrogen and ammonia selective adsorbent may be at least one selected from the group consisting of activated carbon, alumina, zeolite, silica and MOF adsorbent.
본 발명에 있어서, 상기 (a) 흡착단계는 0~30 barG의 압력 조건하에서 수행될 수 있다. 상기 상기 (d) 및 (f) 단계의 향류감압단계는 0~3barG 조건하에서 수행될 수 있다. 상기 (e) 탈착단계는 -1~3 barG 조건하에서 수행될 수 있다.In the present invention, the adsorption step (a) may be performed under a pressure condition of 0 to 30 barG. The countercurrent decompression step of steps (d) and (f) may be performed under 0 to 3 barG conditions. The (e) desorption step may be performed under -1 to 3 barG conditions.
본 발명에 의하여 0.1~5,000 ppm 이상 암모니아가 포함된 혼합가스로부터 암모니아와 질소가 제거된 최종 농도가 99.9% 이상인 수소를 얻을 수 있다.According to the present invention, it is possible to obtain hydrogen having a final concentration of 99.9% or more from which ammonia and nitrogen are removed from a mixed gas containing 0.1 to 5,000 ppm or more of ammonia.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It goes without saying that such variations and modifications fall within the scope of the appended claims.
[실시예][Example]
실시예 1: 수소-질소-암모니아 혼합가스의 흡착분리방법Example 1: Adsorption separation method of hydrogen-nitrogen-ammonia mixed gas
수소-질소-암모니아 혼합가스를 흡착분리공정에 도입하여 99.9% 이상의 수소를 정제하여 생산하는 공정을 표 1 및 표 2에 나타내었다.Tables 1 and 2 show a process for purifying 99.9% or more of hydrogen by introducing a hydrogen-nitrogen-ammonia mixed gas into the adsorption separation process.
표 1은 4기의 흡착탑을 이용한 압력스윙 흡착장치의 운전단계이며, 표 2는 4기의 흡착탑을 이용한 진공압력스윙 흡착장치의 운전단계이다. 표 1, 표 2에 나타낸 바와 같이 4개의 흡착탑(V-1, V-2, V-3, V-4)에서 각각 흡착단계, 균압단계, 세정공급단계, 향류감압단계, 탈착단계 및 축압단계를 수행하여 운전될 수 있다.Table 1 shows the operation steps of the pressure swing adsorption device using four adsorption towers, and Table 2 shows the operating steps of the vacuum pressure swing adsorption device using four adsorption towers. As shown in Tables 1 and 2, in each of the four adsorption towers (V-1, V-2, V-3, V-4), an adsorption step, a pressure equalization step, a washing supply step, a countercurrent pressure reduction step, a desorption step, and a pressure accumulation step It can be operated by performing
Figure PCTKR2021018220-appb-img-000001
Figure PCTKR2021018220-appb-img-000001
Figure PCTKR2021018220-appb-img-000002
Figure PCTKR2021018220-appb-img-000002
도 1은 4개의 주 흡착탑(V-1,2,3,4)으로 구성된 4bed 압력스윙 흡착장치를 도시하였다.1 shows a 4-bed pressure swing adsorption device composed of four main adsorption towers (V-1,2,3,4).
각 운전스텝에서 기체의 흐름을 조절하는 조절밸브가 25개 부착되며, 주 흡착탑에서 대기압까지 감압하여 질소와 암모니아를 제거하는 구성으로 되어 있다.25 control valves are attached to control the gas flow in each operation step, and the main adsorption tower is configured to remove nitrogen and ammonia by reducing the pressure to atmospheric pressure.
수소를 정제하여 생산하는 장치의 운전은 다음의 운전 스텝을 거치게 된다. 밸브(1)를 통하여 흡착탑(V-1)으로 공급된 가스 중에 강흡착성분인 질소와 암모니아는 흡착탑에 흡착되고 흡착되지 않은 수소는 밸브(6)를 통하여 배출되어 수소 저장소(T-1)에 들어간다. 흡착이 끝난 흡착탑(V-2)은 밸브(8), 밸브(25)를 통하여 대기압까지 향류 감압되며, 흡착탑(V-3), 흡착탑(V-4)은 1차균압을 수행하는데, 병류감압되는 흡착탑(V-4)의 배출가스는 밸브(21), 밸브(15)를 통하여 흡착탑(V-3)로 공급되어 흡착탑(V-3)을 부분가압하는데 사용된다. 흡착탑(V-4)와 흡착탑(V-3)의 1차균압이 종료한 후에 흡착탑(V-4)는 밸브(22)를 통하여 병류감압하면서 배출가스를 흡착탑(V-2)의 세정가스로 공급하는 세정공급단계를 수행하고, 흡착탑(V-2)는 밸브(10)을 열어서 흡착탑(V-4)로부터 공급되는 가스를 받아서 흡착제를 세정한다. 이때, 흡착탑(V-2)은 밸브(8), 밸브(25)를 통하여 대기압까지 향류감압을 수행한다. 향류갑압을 수행하면서 세정가스를 공급받아 흡착제를 세정하는데 사용한다. 흡착탑(V-3)은 밸브(15)를 닫고 밸브(17)를 열어서 제품가스를 향류로 도입하여 탑의 압력을 흡착압력까지 축압한다. 다음 스텝에서는 향류감압이 끝난 흡착탑(V-2)과 세정공급단계가 끝난 흡착탑(V-4)의 밸브(7), 밸브(10), 밸브(22), 밸브(25)가 닫히고 밸브(9), 밸브(21)가 열리면서 2차 균압이 진행되며, 나머지 흡착탑들은 기존의 수행단계를 진행한다. 흡착탑(V-1)에서 흡착단계가 종료되면 흡착탑(V-1)과 흡착탑(V-2)은 밸브(1), 밸브(6)를 닫고, 밸브(3)를 열어서 1차균압을 수행하고, 흡착탑(V-3)은 밸브(17)를 닫고, 밸브(13)와 밸브(18)를 열어서 흡착단계를 수행하며, 흡착탑(V-4)은 밸브(21)를 닫고, 밸브(20), 밸브(25)를 열어서 대기압까지 향류감압단계를 수행한다.The operation of the device for refining and producing hydrogen goes through the following operation steps. In the gas supplied to the adsorption tower (V-1) through the valve (1), nitrogen and ammonia, which are strongly adsorbed components, are adsorbed by the adsorption tower, and unadsorbed hydrogen is discharged through the valve (6) to the hydrogen storage (T-1). go in The adsorption tower (V-2), which has been adsorbed, is reduced countercurrently to atmospheric pressure through the valve (8) and valve (25), and the adsorption tower (V-3) and the adsorption tower (V-4) perform primary equalization, co-current pressure reduction The exhaust gas of the adsorption tower (V-4) to be used is supplied to the adsorption tower (V-3) through the valve (21) and valve (15) to partially pressurize the adsorption tower (V-3). After the primary equalization of the adsorption tower (V-4) and the adsorption tower (V-3) is completed, the adsorption tower (V-4) turns the exhaust gas into the washing gas of the adsorption tower (V-2) while reducing the co-current pressure through the valve (22). A cleaning supply step of supplying is performed, and the adsorption tower (V-2) opens the valve (10) to receive the gas supplied from the adsorption tower (V-4) to clean the adsorbent. At this time, the adsorption tower (V-2) performs countercurrent pressure reduction to atmospheric pressure through the valve (8) and valve (25). It is used to clean the adsorbent by receiving a cleaning gas while performing countercurrent pressure reduction. The adsorption tower (V-3) closes the valve (15) and opens the valve (17) to introduce the product gas in a counter-current flow, thereby accumulating the pressure of the tower to the adsorption pressure. In the next step, the valves 7, 10, 22, and 25 of the adsorption tower (V-2) where countercurrent depressurization is completed and the adsorption tower (V-4) where the cleaning supply stage is completed are closed and the valve (9) is closed. ), the secondary pressure equalization proceeds as the valve 21 is opened, and the remaining adsorption towers proceed with the existing performing steps. When the adsorption step is completed in the adsorption tower (V-1), the adsorption tower (V-1) and the adsorption tower (V-2) close the valve (1) and the valve (6), and open the valve (3) to perform the first equalization pressure, , the adsorption tower (V-3) closes the valve (17), opens the valve (13) and the valve (18) to perform the adsorption step, the adsorption tower (V-4) closes the valve (21), the valve (20) , the countercurrent pressure reduction step is performed to atmospheric pressure by opening the valve 25 .
흡착탑(V-1)과 흡착탑(V-2)의 1차균압이 종료된 후에 흡착탑(V-1)은 밸브(3)를 닫고 밸브(4)를 열어 병류감압하면서 배출가스를 흡착탑(V-4)에 세정가스로 보내는 세정공급단계를 수행하고, 흡착탑(V-4)은 밸브(22)을 열어서 흡착탑(V-1)로부터 공급되는 가스를 받아서 흡착제를 세정한다. 이때, 흡착탑(V-4)은 대기압까지 밸브(20), 밸브(25)를 통하여 대기압까지 향류감압을 수행한다. 향류갑압을 수행하면서 세정가스를 공급받아 흡착제를 세정하는데 사용한다. 흡착탑(V-2)은 밸브(3)를 닫고 밸브(11)를 열어서 제품가스를 향류로 도입하여 탑의 압력을 흡착압력까지 축압한다. 다음 스텝에서는 향류감압이 끝난 흡착탑(V-4)과 세정공급단계가 끝난 흡착탑(V-1)의 밸브(4), 밸브(20), 밸브(22), 밸브(25)가 닫히고 밸브(3), 밸브(21)가 열리면서 2차 균압이 진행되며, 나머지 흡착탑들은 기존의 수행단계를 진행한다. 흡착탑(V-3)에서 흡착단계가 종료되면 흡착탑(V-3)과 흡착탑(V-4)은 밸브(13), 밸브(18)를 닫고, 밸브(3)를 열어서 1차균압을 수행하고, 흡착탑(V-2)은 밸브(11)를 닫고, 밸브(7), 밸브(12)를 열어서 흡착단계를 수행하며, 흡착탑(V-1)는 밸브(3)를 닫고, 밸브(2), 밸브(25)를 열어서 대기압까지 향류감압단계를 수행한다. 흡착탑(V-3)과 흡착탑(V-4)의 1차균압이 종료한 후에 흡착탑(V-3)은 밸브(15)를 닫고 밸브(16)를 열어 병류감압하면서 배출가스를 흡착탑(V-1)에 세정가스로 보내는 세정공급단계를 수행하고, 흡착탑(V-1)은 밸브(4)를 열어서 흡착탑(V-3)으로부터 공급되는 가스를 받아서 흡착제를 세정한다. 이때, 흡착탑(V-1)은 대기압까지 밸브(20), 밸브(25)를 통하여 대기압까지 향류감압을 수행한다. 향류갑압을 수행하면서 세정가스를 공급받아 흡착제를 세정하는데 사용한다. 흡착탑(V-4)은 밸브(21)를 닫고 밸브(23)을 열어서 제품가스를 향류로 도입하여 탑의 압력을 흡착압력까지 축압한다. 다음 스텝에서는 향류감압이 끝난 흡착탑(V-1)과 세정공급단계가 끝난 흡착탑(V-3)의 밸브(2), 밸브(4), 밸브(10), 밸브(25)가 닫히고 밸브(3), 밸브(15)가 열리면서 2차 균압이 진행되며, 나머지 흡착탑들은 기존의 수행단계를 진행한다. 흡착탑(V-2)에서 흡착단계가 종료되면 흡착탑(V-1)과 흡착탑(V-2)은 밸브(7), 밸브(12)을 닫고, 밸브(9)를 열어서 1차균압을 수행하고, 흡착탑(V-4)은 밸브(23)를 닫고, 밸브(19), 밸브(24)를 열어서 흡착단계를 수행하며, 흡착탑(V-3)는 밸브(15)을 닫고, 밸브(14), 밸브(25)을 열어서 대기압까지 향류감압단계를 수행한다. 흡착탑(V-1)과 흡착탑(V-2)의 1차균압이 종료한 후에 흡착탑(V-2)은 밸브(9)을 닫고 밸브(10)를 열어 병류감압하면서 배출가스를 흡착탑(V-3)에 세정가스로 보내는 세정공급단계를 수행하고, 흡착탑(V-3)은 밸브(16)를 열어서 흡착탑(V-2)으로부터 공급되는 가스를 받아서 흡착제를 세정한다. 이때, 흡착탑(V-3)은 대기압까지 밸브(14), 밸브(25)를 통하여 대기압까지 향류감압을 수행한다. 향류갑압을 수행하면서 세정가스를 공급받아 흡착제를 세정하는데 사용한다. 흡착탑(V-1)은 밸브(3)를 닫고 밸브(5)를 열어서 제품가스를 향류로 도입하여 탑의 압력을 흡착압력까지 축압한다. 다음 스텝에서는 향류감압이 끝난 흡착탑(V-3)과 세정공급단계가 끝난 흡착탑(V-2)의 밸브(10), 밸브(14), 밸브(16), 밸브(25)이 닫히고 밸브(9), 밸브(15)가 열리면서 2차 균압이 진행되며, 나머지 흡착탑들은 기존의 수행단계를 진행한다.After the primary equalization of the adsorption tower (V-1) and the adsorption tower (V-2) is completed, the adsorption tower (V-1) closes the valve (3) and opens the valve (4) to reduce the co-current pressure while removing the exhaust gas from the adsorption tower (V-) A cleaning supply step of sending the cleaning gas to 4) is performed, and the adsorption tower (V-4) receives the gas supplied from the adsorption tower (V-1) by opening the valve (22) to clean the adsorbent. At this time, the adsorption tower (V-4) performs countercurrent pressure reduction to atmospheric pressure through the valve 20 and the valve 25 to atmospheric pressure. It is used to clean the adsorbent by receiving a cleaning gas while performing countercurrent pressure reduction. The adsorption tower (V-2) closes the valve (3) and opens the valve (11) to introduce the product gas in a counter-current flow, thereby accumulating the pressure of the tower to the adsorption pressure. In the next step, the valve (4), valve (20), valve (22), and valve (25) of the adsorption tower (V-4) where countercurrent depressurization is finished and the adsorption tower (V-1) where the cleaning supply step is completed are closed, and valve (3) is closed. ), the secondary pressure equalization proceeds as the valve 21 is opened, and the remaining adsorption towers proceed with the existing performing steps. When the adsorption step is completed in the adsorption tower (V-3), the adsorption tower (V-3) and the adsorption tower (V-4) close the valve 13 and 18, and open the valve 3 to perform the first equalization pressure, , the adsorption tower (V-2) closes the valve 11, and opens the valve 7 and 12 to perform the adsorption step, and the adsorption tower (V-1) closes the valve 3, and the valve (2) , the countercurrent pressure reduction step is performed to atmospheric pressure by opening the valve 25 . After the primary equalization of the adsorption tower (V-3) and the adsorption tower (V-4) is completed, the adsorption tower (V-3) closes the valve (15) and opens the valve (16) to co-currently pressure reduce the exhaust gas to the adsorption tower (V-) A cleaning supply step of sending a cleaning gas to 1) is performed, and the adsorption tower (V-1) receives the gas supplied from the adsorption tower (V-3) by opening the valve (4) to clean the adsorbent. At this time, the adsorption tower (V-1) performs countercurrent pressure reduction to atmospheric pressure through the valve 20 and the valve 25 to atmospheric pressure. It is used to clean the adsorbent by receiving a cleaning gas while performing countercurrent pressure reduction. The adsorption tower (V-4) closes the valve (21) and opens the valve (23) to introduce the product gas in a counter-current flow, thereby accumulating the pressure of the tower to the adsorption pressure. In the next step, the valve (2), valve (4), valve (10), and valve (25) of the adsorption tower (V-1) where countercurrent depressurization has been completed and the washing supply step (V-3) are closed, and valve (3) is closed. ), the secondary pressure equalization proceeds as the valve 15 is opened, and the remaining adsorption towers proceed with the existing performing steps. When the adsorption step is completed in the adsorption tower (V-2), the adsorption tower (V-1) and the adsorption tower (V-2) close the valve 7 and 12, and open the valve 9 to perform the first equalization pressure, , the adsorption tower (V-4) closes the valve 23, and opens the valve 19 and valve 24 to perform the adsorption step, the adsorption tower (V-3) closes the valve 15, the valve 14 , the countercurrent pressure reduction step is performed to atmospheric pressure by opening the valve 25 . After the primary equalization of the adsorption tower (V-1) and the adsorption tower (V-2) is completed, the adsorption tower (V-2) closes the valve (9) and opens the valve (10) to co-current pressure reduce the exhaust gas to the adsorption tower (V-) A cleaning supply step of sending the cleaning gas to 3) is performed, and the adsorption tower (V-3) receives the gas supplied from the adsorption tower (V-2) by opening the valve (16) to clean the adsorbent. At this time, the adsorption tower (V-3) performs countercurrent pressure reduction to atmospheric pressure through the valve 14 and the valve 25 to atmospheric pressure. It is used to clean the adsorbent by receiving a cleaning gas while performing countercurrent pressure reduction. The adsorption tower (V-1) closes the valve (3) and opens the valve (5) to introduce the product gas in a counter-current flow, thereby accumulating the pressure of the tower to the adsorption pressure. In the next step, the valves 10, 14, 16, and 25 of the adsorption tower (V-3) where countercurrent depressurization has been completed and the washing supply step (V-2) of the adsorption tower (V-2) are closed, and the valve (9) is closed. ), the secondary pressure equalization proceeds as the valve 15 is opened, and the remaining adsorption towers proceed with the existing performing steps.
이와 같은 동작이 4개의 흡착탑에서 교대로 계속되며 한 주기를 형성하며 연속운전이 이루어진다. This operation is alternately continued in the four adsorption towers, forming one cycle, and continuous operation is performed.
도 2는 4개의 주 흡착탑(V-1,2,3,4)으로 구성된 4bed 진공압력스윙 흡착장치를 도시하였다.2 shows a 4-bed vacuum pressure swing adsorption device composed of four main adsorption towers (V-1,2,3,4).
각 운전스텝에서 기체의 흐름을 조절하는 조절밸브가 26개 부착되며, 주 흡착탑에서 진공압력까지 낮추어 질소를 제거시키기 위한 진공펌프로 구성되어 있다.26 control valves are attached to control the gas flow in each operation step, and it consists of a vacuum pump to remove nitrogen by lowering the vacuum pressure from the main adsorption tower.
수소를 정제하여 생산하는 장치의 운전은 다음의 운전 스텝을 거치게 된다. 밸브(1)를 통하여 흡착탑(V-1)으로 공급된 가스 중에 강흡착성분인 질소와 암모니아는 흡착탑에 흡착되고 흡착되지 않은 수소는 밸브 (6)을 통하여 배출되어 수소 저장소(T-1)에 들어간다. 흡착이 끝난 흡착탑(V-2)은 밸브(8), 밸브(25)를 통하여 대기압까지 향류 감압되며, 흡착탑(V-3), 흡착탑(V-4)은 1차균압을 수행하는데, 병류감압되는 흡착탑(V-4)의 배출가스는 밸브(15), 밸브(21)를 통하여 흡착탑(V-3)로 공급되어 흡착탑(V-3)을 부분가압하는데 사용된다. 흡착탑(V-4)와 흡착탑(V-3)의 1차균압이 종료한 후에 흡착탑(V-4)는 밸브(22)를 통하여 병류감압하면서 배출가스를 흡착탑(V-2)의 세정가스로 공급하는 세정공급단계를 수행하고, 흡착탑(V-2)는 밸브(10)을 열어서 흡착탑(V-4)로부터 공급되는 가스를 받아서 흡착제를 세정한다. 이때, 흡착탑(V-2)은 대기압까지 향류감압이 완료된 후 밸브(26)을 열어 진공펌프를 사용하여 진공탈착을 수행한다. 진공탈착을 수행하면서 세정가스를 공급받아 흡착제를 세정하는데 사용한다. 흡착탑(V-3)은 밸브(15)을 닫고 밸브(17)을 열어서 제품가스를 향류로 도입하여 탑의 압력을 흡착압력까지 축압한다. 다음 스텝에서는 진공탈착이 끝난 흡착탑(V-2)과 세정공급단계가 끝난 흡착탑(V-4)의 밸브(8), 밸브(10), 밸브(22), 밸브(26)이 닫히고 밸브(9), 밸브(21)이 열리면서 2차 균압이 진행되며, 나머지 흡착탑들은 기존의 수행단계를 진행한다. 흡착탑(V-1)에서 흡착단계가 종료되면 흡착탑(V-1)와 흡착탑(V-2)는 밸브(1), 밸브(6)을 닫고, 밸브(3)를 열어서 1차균압을 수행하고, 흡착탑(V-3)은 밸브(17)을 닫고, 밸브(13), 밸브(18)을 열어서 흡착단계를 수행하며, 흡착탑(V-4)는 밸브(21)을 닫고, 밸브(20), 밸브(25)을 열어서 대기압까지 향류감압단계를 수행한다. The operation of the device for refining and producing hydrogen goes through the following operation steps. In the gas supplied to the adsorption tower (V-1) through the valve (1), nitrogen and ammonia, which are strongly adsorbed components, are adsorbed by the adsorption tower, and unadsorbed hydrogen is discharged through the valve (6) to the hydrogen storage (T-1). go in The adsorption tower (V-2), which has been adsorbed, is reduced countercurrently to atmospheric pressure through the valve (8) and valve (25), and the adsorption tower (V-3) and the adsorption tower (V-4) perform primary equalization, co-current pressure reduction The exhaust gas of the adsorption tower (V-4) to be used is supplied to the adsorption tower (V-3) through the valve (15) and valve (21) to partially pressurize the adsorption tower (V-3). After the primary equalization of the adsorption tower (V-4) and the adsorption tower (V-3) is completed, the adsorption tower (V-4) turns the exhaust gas into the washing gas of the adsorption tower (V-2) while reducing the co-current pressure through the valve (22). A cleaning supply step of supplying is performed, and the adsorption tower (V-2) opens the valve (10) to receive the gas supplied from the adsorption tower (V-4) to clean the adsorbent. At this time, the adsorption tower (V-2) performs vacuum desorption using a vacuum pump by opening the valve 26 after the countercurrent pressure reduction to atmospheric pressure is completed. While performing vacuum desorption, a cleaning gas is supplied and used to clean the adsorbent. The adsorption tower (V-3) closes the valve (15) and opens the valve (17) to introduce the product gas in a counter-current flow, thereby accumulating the pressure of the tower to the adsorption pressure. In the next step, the valves 8, 10, 22, and 26 of the adsorption tower (V-2) where the vacuum desorption is completed and the adsorption tower (V-4) where the cleaning supply stage is completed are closed, and the valve (9) is closed. ), the valve 21 is opened, and the secondary pressure equalization proceeds, and the remaining adsorption towers proceed with the existing steps. When the adsorption step is completed in the adsorption tower (V-1), the adsorption tower (V-1) and the adsorption tower (V-2) close the valve (1) and the valve (6), and open the valve (3) to perform the first equalization pressure, , the adsorption tower (V-3) closes the valve (17), opens the valve (13), and opens the valve (18) to perform the adsorption step, the adsorption tower (V-4) closes the valve (21), the valve (20) , the countercurrent pressure reduction step is performed to atmospheric pressure by opening the valve 25 .
흡착탑(V-1)와 흡착탑(V-2)의 1차균압이 종료한 후에 흡착탑(V-1)은 밸브(3)을 닫고 밸브(4)를 열어 병류감압하면서 배출가스를 흡착탑(V-4)에 세정가스로 보내는 세정공급단계를 수행하고, 흡착탑(V-4)는 밸브(22)을 열어서 흡착탑(V-1)로부터 공급되는 가스를 받아서 흡착제를 세정한다. 이때, 흡착탑(V-4)은 대기압까지 향류감압이 완료된 후 밸브(26)을 열어 진공펌프를 사용하여 진공탈착을 수행한다. 진공탈착을 수행하면서 세정가스를 공급받아 흡착제를 세정하는데 사용한다. 흡착탑(V-2)은 밸브(3)을 닫고 밸브(11)을 열어서 제품가스를 향류로 도입하여 탑의 압력을 흡착압력까지 축압한다. 다음 스텝에서는 진공탈착이 끝난 흡착탑(V-4)과 세정공급단계가 끝난 흡착탑(V-1)의 밸브(4), 밸브(20), 밸브(22), 밸브(26)이 닫히고 밸브(3), 밸브(21)이 열리면서 2차 균압이 진행되며, 나머지 흡착탑들은 기존의 수행단계를 진행한다. 흡착탑(V-3)에서 흡착단계가 종료되면 흡착탑(V-3)와 흡착탑(V-4)은 밸브(13), 밸브(18)을 닫고, 밸브(15)를 열어서 1차균압을 수행하고, 흡착탑(V-2)은 밸브(11)를 닫고, 밸브(7), 밸브(12)을 열어서 흡착단계를 수행하며, 흡착탑(V-1)는 밸브(3)을 닫고, 밸브(2), 밸브(25)을 열어서 대기압까지 향류감압단계를 수행한다. 흡착탑(V-3)과 흡착탑(V-4)의 1차균압이 종료한 후에 흡착탑(V-3)은 밸브(15)을 닫고 밸브(16)을 열어 병류감압하면서 배출가스를 흡착탑(V-1)에 세정가스로 보내는 세정공급단계를 수행하고, 흡착탑(V-1)은 밸브(4)를 열어서 흡착탑(V-3)으로부터 공급되는 가스를 받아서 흡착제를 세정한다. 이때, 흡착탑(V-1)은 대기압까지 향류감압이 완료된 후 밸브(26)을 열어 진공펌프를 사용하여 진공탈착을 수행한다. 진공탈착을 수행하면서 세정가스를 공급받아 흡착제를 세정하는데 사용한다. 흡착탑(V-4)는 밸브(21)을 닫고 밸브(23)을 열어서 제품가스를 향류로 도입하여 탑의 압력을 흡착압력까지 축압한다. 다음 스텝에서는 진공탈착이 끝난 흡착탑(V-1)과 세정공급단계가 끝난 흡착탑(V-3)의 밸브(2), 밸브(4), 밸브(16), 밸브(26)이 닫히고 밸브(3), 밸브(15)가 열리면서 2차 균압이 진행되며, 나머지 흡착탑들은 기존의 수행단계를 진행한다. 흡착탑(V-2)에서 흡착단계가 종료되면 흡착탑(V-1)과 흡착탑(V-2)은 밸브(7), 밸브(12)를 닫고, 밸브(9)를 열어서 1차균압을 수행하고, 흡착탑(V-4)은 밸브(23)를 닫고, 밸브(19), 밸브(24)을 열어서 흡착단계를 수행하며, 흡착탑(V-3)은 밸브(15)를 닫고, 밸브(11)와 밸브(25)를 열어서 대기압까지 향류감압단계를 수행한다. 흡착탑(V-1)과 흡착탑(V-2)의 1차균압이 종료한 후에 흡착탑(V-2)은 밸브(9)를 닫고 밸브(10)를 열어 병류감압하면서 배출가스를 흡착탑(V-3)에 세정가스로 보내는 세정공급단계를 수행하고, 흡착탑(V-3)은 밸브(16)를 열어서 흡착탑(V-2)으로부터 공급되는 가스를 받아서 흡착제를 세정한다. 이때, 흡착탑(V-3)은 대기압까지 향류감압이 완료된 후 밸브(26)를 열어 진공펌프를 사용하여 진공탈착을 수행한다. 진공탈착을 수행하면서 세정가스를 공급받아 흡착제를 세정하는데 사용한다. 흡착탑(V-1)은 밸브(3)를 닫고 밸브(5)를 열어서 제품가스를 향류로 도입하여 탑의 압력을 흡착압력까지 축압한다. 다음 스텝에서는 진공탈착이 끝난 흡착탑(V-3)과 세정공급단계가 끝난 흡착탑(V-2)의 밸브(10), 밸브(14), 밸브(16) 및 밸브(26)가 닫히고 밸브(9)와 밸브(15)가 열리면서 2차 균압이 진행되며, 나머지 흡착탑들은 기존의 수행단계를 진행한다.After the primary pressure equalization of the adsorption tower (V-1) and the adsorption tower (V-2) is completed, the adsorption tower (V-1) closes the valve (3) and opens the valve (4) to reduce the co-current pressure while removing the exhaust gas from the adsorption tower (V-) A cleaning supply step of sending a cleaning gas to 4) is performed, and the adsorption tower (V-4) receives the gas supplied from the adsorption tower (V-1) by opening the valve (22) to clean the adsorbent. At this time, the adsorption tower (V-4) performs vacuum desorption using a vacuum pump by opening the valve 26 after the countercurrent pressure reduction to atmospheric pressure is completed. While performing vacuum desorption, a cleaning gas is supplied and used to clean the adsorbent. The adsorption tower (V-2) closes the valve (3) and opens the valve (11) to introduce the product gas in a counter-current flow, thereby accumulating the pressure of the tower to the adsorption pressure. In the next step, the valve (4), valve (20), valve (22), and valve (26) of the adsorption tower (V-4) where the vacuum desorption is completed and the adsorption tower (V-1) where the cleaning supply step is completed are closed and the valve (3) ), the valve 21 is opened, and the secondary pressure equalization proceeds, and the remaining adsorption towers proceed with the existing steps. When the adsorption step is completed in the adsorption tower (V-3), the adsorption tower (V-3) and the adsorption tower (V-4) close the valve 13 and 18, and open the valve 15 to perform the first equalization pressure, , the adsorption tower (V-2) closes the valve 11, and opens the valve 7 and 12 to perform the adsorption step, the adsorption tower (V-1) closes the valve 3, and the valve (2) , the countercurrent pressure reduction step is performed to atmospheric pressure by opening the valve 25 . After the primary equalization of the adsorption tower (V-3) and the adsorption tower (V-4) is completed, the adsorption tower (V-3) closes the valve (15) and opens the valve (16) to co-currently pressure reduce the exhaust gas to the adsorption tower (V-) A cleaning supply step of sending a cleaning gas to 1) is performed, and the adsorption tower (V-1) receives the gas supplied from the adsorption tower (V-3) by opening the valve (4) to clean the adsorbent. At this time, the adsorption tower (V-1) performs vacuum desorption using a vacuum pump by opening the valve 26 after the counter-current pressure reduction to atmospheric pressure is completed. While performing vacuum desorption, a cleaning gas is supplied and used to clean the adsorbent. The adsorption tower (V-4) closes the valve (21) and opens the valve (23) to introduce the product gas in a counter-current flow, thereby accumulating the pressure of the tower to the adsorption pressure. In the next step, the valves (2), valves (4), valves (16), and valves (26) of the adsorption tower (V-1) where vacuum desorption has been completed and the washing supply step (V-3) are closed and valve (3) is closed. ), the secondary pressure equalization proceeds as the valve 15 is opened, and the remaining adsorption towers proceed with the existing performing steps. When the adsorption step is completed in the adsorption tower (V-2), the adsorption tower (V-1) and the adsorption tower (V-2) close the valve 7 and 12, and open the valve 9 to perform the first equalization pressure, , the adsorption tower (V-4) closes the valve 23, and opens the valve 19 and the valve 24 to perform the adsorption step, the adsorption tower (V-3) closes the valve 15, the valve 11 and the valve 25 is opened to perform a countercurrent pressure reduction step to atmospheric pressure. After the primary equalization of the adsorption tower (V-1) and the adsorption tower (V-2) is completed, the adsorption tower (V-2) closes the valve (9) and opens the valve (10) to co-currently pressure reduce the exhaust gas to the adsorption tower (V-) A cleaning supply step of sending the cleaning gas to 3) is performed, and the adsorption tower (V-3) receives the gas supplied from the adsorption tower (V-2) by opening the valve (16) to clean the adsorbent. At this time, the adsorption tower (V-3) performs vacuum desorption using a vacuum pump by opening the valve 26 after the countercurrent pressure reduction to atmospheric pressure is completed. While performing vacuum desorption, a cleaning gas is supplied and used to clean the adsorbent. The adsorption tower (V-1) closes the valve (3) and opens the valve (5) to introduce the product gas in a counter-current flow, thereby accumulating the pressure of the tower to the adsorption pressure. In the next step, the valve 10, 14, valve 16, and valve 26 of the adsorption tower (V-3) where vacuum desorption is completed and the adsorption tower (V-2) where the cleaning supply step is completed are closed, and the valve (9) is closed. ) and the valve 15 are opened, the secondary pressure equalization proceeds, and the remaining adsorption towers proceed with the existing execution steps.
이와 같은 동작이 4개의 흡착탑에서 교대로 계속되어 한 주기를 형성하며 연속운전이 이루어진다. 상기와 같은 운전으로 99.9% 이상의 수소를 정제하여 생산한다.This operation is alternately continued in the four adsorption towers to form one cycle, and continuous operation is performed. It is produced by purifying 99.9% or more of hydrogen through the same operation as above.
실시예 2: 75% 수소 + 25% 질소 + 5ppm 암모니아 혼합가스로부터 대기압 탈착 수소정제 예Example 2: Example of atmospheric pressure desorption hydrogen purification from 75% hydrogen + 25% nitrogen + 5ppm ammonia mixed gas
수소 75%, 질소 25%, 암모니아 5ppm를 함유하고 있는 혼합가스로부터 수소를 정제하는 4기 흡착탑의 압력스윙흡착 장치를 사용하여 본 발명에 따른 공정의 성능을 비교하였다. 흡착단계의 압력은 2~20barG이었고, 향류감압단계의 압력은 상압이었다. 흡착온도는 대기온도에서 다음과 같은 결과를 얻을 수 있었다.The performance of the process according to the present invention was compared using the pressure swing adsorption device of the four adsorption towers for purifying hydrogen from a mixed gas containing 75% hydrogen, 25% nitrogen, and 5 ppm ammonia. The pressure in the adsorption step was 2-20 barG, and the pressure in the counter-current decompression step was normal pressure. As for the adsorption temperature, the following results were obtained at ambient temperature.
제품수소의 순도= 99.99%Purity of product hydrogen = 99.99%
제품 수소에 잔류한 질소는 100 ppm 이하 검출되었고, 암모니아는 제거되어 검출되지 않았다. Nitrogen remaining in the product hydrogen was detected at 100 ppm or less, and ammonia was removed and not detected.
실시예 3: 75% 수소 + 25% 질소 + 5ppm 암모니아 혼합가스로부터 진공압력 스윙흡착을 이용한 수소정제 예Example 3: Example of hydrogen purification using vacuum pressure swing adsorption from 75% hydrogen + 25% nitrogen + 5 ppm ammonia mixed gas
수소 75%, 질소 25%, 암모니아 5ppm를 함유하고 있는 혼합가스로부터 수소를 정제하는 4기 흡착탑의 진공압력스윙흡착 장치를 사용하여 본 발명에 따른 공정의 성능을 비교하였다. 흡착단계의 압력은 2~20barG이었고, 탈착단계의 압력은 (-)1~(-)0.1barG이었다. 흡착온도는 대기온도 25~32℃에서 다음과 같은 결과를 얻을 수 있었다.The performance of the process according to the present invention was compared using a vacuum pressure swing adsorption device of 4 adsorption towers for purifying hydrogen from a mixed gas containing 75% hydrogen, 25% nitrogen, and 5 ppm ammonia. The pressure in the adsorption step was 2 to 20 barG, and the pressure in the desorption step was (-)1 to (-)0.1 barG. As for the adsorption temperature, the following results were obtained at an ambient temperature of 25 to 32 °C.
제품수소의 순도= 99.99%Purity of product hydrogen = 99.99%
제품 수소에 잔류한 질소는 100 ppm 이하 검출되었고, 암모니아는 제거되어 검출되지 않았다. Nitrogen remaining in the product hydrogen was detected at 100 ppm or less, and ammonia was removed and not detected.
수소 75%, 질소 25%, 암모니아 5ppm를 함유하고 있는 혼합가스로부터 수소를 정제하는 압력스윙 흡착장치와 진공압력스윙 흡착장치 모두 99.9% 이상의 수소를 정제하여 생산했으며, 질소 농도는 100pm 이하 검출되었고, 암모니아는 제거되어 검출되지 않았다.Both the pressure swing adsorption device and the vacuum pressure swing adsorption device for purifying hydrogen from a mixed gas containing 75% hydrogen, 25% nitrogen, and 5ppm ammonia were purified and produced more than 99.9% of hydrogen, and the nitrogen concentration was detected below 100pm, Ammonia was removed and was not detected.
실시예 4: 74.7% 수소 + 25% 질소 + 3,000ppm 혼합가스로부터 대기압 탈착 수소정제 예Example 4: Example of atmospheric pressure desorption hydrogen purification from 74.7% hydrogen + 25% nitrogen + 3,000 ppm mixed gas
74.7% 수소, 25% 질소, 3,000ppm 암모니아를 함유하고 있는 혼합가스로부터 수소를 정제하는 4기 흡착탑의 압력스윙흡착 장치를 사용하여 본 발명에 따른 공정의 성능을 비교하였다. 흡착단계의 압력은 2~20barG이었고, 향류감압단계의 압력은 상압이었다. 흡착온도는 대기온도 25~32℃에서 다음과 같은 결과를 얻을 수 있었다.The performance of the process according to the present invention was compared using the pressure swing adsorption device of the four adsorption towers for purifying hydrogen from a mixed gas containing 74.7% hydrogen, 25% nitrogen, and 3,000 ppm ammonia. The pressure in the adsorption step was 2-20 barG, and the pressure in the counter-current decompression step was normal pressure. As for the adsorption temperature, the following results were obtained at an ambient temperature of 25 to 32 °C.
제품수소의 순도= 99.99%Purity of product hydrogen = 99.99%
제품 수소에 잔류한 질소는 100 ppm 이하 검출되었고, 암모니아는 제거되어 검출되지 않았다. Nitrogen remaining in the product hydrogen was detected at 100 ppm or less, and ammonia was removed and not detected.
실시예 5: 74.7% 수소 + 25% 질소 + 3,000ppm 혼합가스로부터 진공압력 스윙흡착을 이용한 수소정제 예Example 5: Example of hydrogen purification using vacuum pressure swing adsorption from 74.7% hydrogen + 25% nitrogen + 3,000 ppm mixed gas
74.7% 수소, 25% 질소, 3,000ppm 암모니아를 함유하고 있는 혼합가스로부터 수소를 정제하는 4기 흡착탑의 진공압력스윙흡착 장치를 사용하여 본 발명에 따른 공정의 성능을 비교하였다. 흡착단계의 압력은 2~20barG 이었고, 탈착단계의 압력은 (-)1~(-)0.1barG이었다. 흡착온도는 대기온도 25~32℃에서 다음과 같은 결과를 얻을 수 있었다.The performance of the process according to the present invention was compared using a vacuum pressure swing adsorption device of 4 adsorption towers for purifying hydrogen from a mixed gas containing 74.7% hydrogen, 25% nitrogen, and 3,000 ppm ammonia. The pressure in the adsorption step was 2 to 20 barG, and the pressure in the desorption step was (-)1 to (-)0.1 barG. As for the adsorption temperature, the following results were obtained at an ambient temperature of 25 to 32 °C.
제품수소의 순도= 99.99%Purity of product hydrogen = 99.99%
제품 수소에 잔류한 질소는 100 ppm 이하 검출되었고, 암모니아는 제거되어 검출되지 않았다. Nitrogen remaining in the product hydrogen was detected at 100 ppm or less, and ammonia was removed and not detected.
74.7% 수소, 25% 질소, 3,000ppm 암모니아를 함유하고 있는 혼합가스로부터 수소를 정제하는 압력스윙 흡착장치와 진공압력스윙 흡착장치 모두 99.9% 이상의 수소를 정제하여 생산했으며, 질소 농도는 100pm 이하 검출되었고, 암모니아는 제거되어 검출되지 않았다.Both the pressure swing adsorption device and the vacuum pressure swing adsorption device that purify hydrogen from a mixed gas containing 74.7% hydrogen, 25% nitrogen, and 3,000 ppm ammonia purified and produced more than 99.9% of hydrogen, and the nitrogen concentration was detected below 100pm. , ammonia was removed and was not detected.
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서 이러한 구체적 기술은 단지 바람직한 실시양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서, 본 발명의 실질적인 범위는 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.As the specific parts of the present invention have been described in detail above, for those of ordinary skill in the art, it is clear that these specific descriptions are only preferred embodiments, and the scope of the present invention is not limited thereby. will be. Accordingly, it is intended that the substantial scope of the invention be defined by the claims and their equivalents.
본 발명에 따라서 암모니아를 분해하여 얻은 수소와 질소, 미분해 암모니아가 포함된 혼합가스로부터 질소와 암모니아를 제거하고 수소 정제하여 생산할 때, 99.9% 이상의 수소를 얻는 효과를 얻을 수 있다.According to the present invention, when hydrogen and nitrogen obtained by decomposing ammonia and nitrogen and ammonia are removed from the mixed gas containing undecomposed ammonia and produced by hydrogen purification, it is possible to obtain the effect of obtaining 99.9% or more of hydrogen.
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서 이러한 구체적 기술은 단지 바람직한 실시양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서, 본 발명의 실질적인 범위는 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.As the specific parts of the present invention have been described in detail above, for those of ordinary skill in the art, it is clear that these specific descriptions are only preferred embodiments, and the scope of the present invention is not limited thereby. will be. Accordingly, it is intended that the substantial scope of the invention be defined by the claims and their equivalents.

Claims (9)

  1. 다음 단계를 포함하는 암모니아의 분해 혼합가스로부터 수소의 분리 및 정제방법:A method for separating and purifying hydrogen from a mixed gas of decomposition of ammonia comprising the following steps:
    (a) 수소, 질소 및 미분해 암모니아를 포함하는 암모니아의 분해 혼합가스를 질소 및 암모니아 선택성 흡착제가 충진된 흡착탑이 구비된 압력스윙 흡착장치에 통과시켜 상기 흡착제에 질소와 암모니아를 흡착시키고, 흡착되지 않는 수소를 흡착탑 상부로 배출하여 수소를 분리하는 단계; 및(a) passing the decomposed mixed gas of ammonia containing hydrogen, nitrogen and undecomposed ammonia through a pressure swing adsorption device equipped with an adsorption tower filled with nitrogen and ammonia selective adsorbent to adsorb nitrogen and ammonia to the adsorbent, and not to be adsorbed separating hydrogen by discharging hydrogen to the upper portion of the adsorption tower; and
    (b) 상기 흡착탑의 압력을 대기압까지 감압하여 상기 흡착제에 흡착된 질소와 암모니아를 탈착시켜 배출하는 압력스윙흡착(Pressure Swing Adsorption, PSA)법을 수행하거나, 상기 흡착탑의 압력을 진공압력까지 감압하여 질소와 암모니아를 탈착시켜 배출하는 진공압력스윙흡착(Vacuum Pressure Swing Adsorption, VPSA)법을 수행하거나, 상기 PSA법을 수행한 다음, VPSA법을 수행하는 단계.(b) performing a pressure swing adsorption (PSA) method for desorbing and discharging nitrogen and ammonia adsorbed on the adsorbent by reducing the pressure of the adsorption tower to atmospheric pressure, or by reducing the pressure of the adsorption tower to vacuum pressure Performing a vacuum pressure swing adsorption (VPSA) method for desorbing and discharging nitrogen and ammonia, or performing the PSA method and then performing the VPSA method.
  2. 제1항에 있어서, 상기 (b) 단계는According to claim 1, wherein the step (b)
    (i) 상기 흡착탑의 압력을 감압하여 배출한 가스를 다른 흡착탑으로 공급하여 두 흡착탑 사이에 압력을 균등화하는 균압단계;(i) a pressure equalization step of equalizing the pressure between the two adsorption towers by supplying the gas discharged by reducing the pressure of the adsorption tower to another adsorption tower;
    (ii) 상기 균압단계가 종료된 흡착탑에 압력을 상압으로 감압시켜 흡착되어 있는 흡착탑에 존재하는 질소와 암모니아를 배출하는 향류감압단계;(ii) a countercurrent depressurization step of depressurizing the pressure in the adsorption tower where the pressure equalization step is completed to atmospheric pressure to discharge nitrogen and ammonia present in the adsorption tower;
    (iii) 상기 향류감압단계가 종료된 흡착탑의 압력을 진공으로 하여 질소와 암모니아를 탈착시키는 탈착단계;(iii) a desorption step of desorbing nitrogen and ammonia by vacuuming the pressure of the adsorption tower where the countercurrent depressurization step has been completed;
    (iv) 상기 탈착단계가 종료된 흡착탑에 (a)의 흡착단계가 종료된 흡착탑을 병류감압하여 배출되는 가스를 공급하여 두 흡착탑 사이에 압력을 균등화하는 균압단계; 및(iv) a pressure equalization step of equalizing the pressure between the two adsorption towers by supplying a gas discharged by co-current depressurizing the adsorption tower where the adsorption step of (a) has been completed to the adsorption tower where the desorption step has been completed; and
    (v) 상기 균압단계가 종료된 흡착탑에 상기 (a) 흡착단계에 있는 흡착탑의 생산되는 수소 일부를 도입하여 흡착탑의 압력을 흡착단계 압력까지 채워주는 축압단계를 수행하는 것을 특징으로 하는 암모니아의 분해 혼합가스로부터 수소의 분리 및 정제방법.(v) introducing a part of hydrogen produced in the adsorption tower in the (a) adsorption step to the adsorption tower where the pressure equalization step has been completed, and performing an accumulating step of filling the pressure of the adsorption tower to the pressure of the adsorption step. Decomposition of ammonia, characterized in that Separation and purification method of hydrogen from mixed gas.
  3. 제1항에 있어서, 상기 흡착탑은 4개 또는 4개 이상의 흡착탑이 상호 병렬로 배치된 것을 특징으로 하는 암모니아의 분해 혼합가스로부터 수소의 분리 및 정제방법.[Claim 2] The method of claim 1, wherein in the adsorption tower, four or four or more adsorption towers are arranged in parallel with each other.
  4. 제2항에 있어서, 각각의 흡착탑의 운전에 의하여 동일 시점에 흡착단계, 균압단계, 향류감압단계 및 축압단계가 각각 수행되는 것을 특징으로 하는 암모니아의 분해 혼합가스로부터 수소의 분리 및 정제방법.The method of claim 2, wherein the adsorption step, the pressure equalization step, the countercurrent pressure reduction step, and the pressure accumulation step are respectively performed at the same time by the operation of each adsorption tower.
  5. 제2항에 있어서, 상기 (i) 단계 이후에 상기 흡착탑에 충진된 흡착제에 생성된 불순물을 세정하기 위한 세정공급단계를 추가하여 수행하고,The method according to claim 2, wherein after step (i), a cleaning supply step for cleaning impurities generated in the adsorbent charged in the adsorption tower is added and performed,
    상기 세정공급단계는 The cleaning supply step
    상기 (i) 균압단계가 종료된 흡착탑의 배출 가스를 흡착탑으로 공급하여 흡착탑의 세정가스로 공급하며, 상기 (ii) 향류감압단계가 시작되는 흡착탑에 세정공급단계의 흡착탑에서 배출되는 가스를 공급하여 흡착탑에 존재하는 질소와 암모니아를 세정하는 것을 특징으로 하는 암모니아의 분해 혼합가스로부터 수소의 분리 및 정제방법.The (i) exhaust gas of the adsorption tower where the pressure equalization step has been completed is supplied to the adsorption tower and supplied as the cleaning gas of the adsorption tower, and the gas discharged from the adsorption tower of the cleaning supply step is supplied to the adsorption tower where the countercurrent depressurization step starts. A method for separating and purifying hydrogen from a decomposed mixed gas of ammonia, characterized in that the nitrogen and ammonia present in the adsorption tower are washed.
  6. 제2항에 있어서, 상기 (vi) 단계는 원료 공급에 의해서도 축압하는 것을 특징으로 하는 암모니아의 분해 혼합가스로부터 수소의 분리 및 정제방법.The method of claim 2, wherein in step (vi), the pressure is also accumulating by supplying a raw material.
  7. 제1항에 있어서, 상기 질소 및 암모니아 선택성 흡착제는 활성탄, 알루미나, 제올라이트, 실리카 및 MOF 흡착제로 구성된 군에서 1종 이상 선택되는 것을 특징으로 하는 암모니아의 분해 혼합가스로부터 수소의 분리 및 정제방법.The method of claim 1, wherein the nitrogen and ammonia selective adsorbent is at least one selected from the group consisting of activated carbon, alumina, zeolite, silica and MOF adsorbent.
  8. 제1항에 있어서, 흡착제를 탈착시키는 방법은 압력스윙흡착법(PSA), 온도스윙흡착법(TSA), 또는 압력과 온도 두가지 모두 스윙하는 압력온도스윙흡착법(PTSA)로 수행하는 것을 특징으로 하는 암모니아의 분해 혼합가스로부터 수소의 분리 및 정제방법.The method of claim 1, wherein the method for desorbing the adsorbent is a pressure swing adsorption method (PSA), a temperature swing adsorption method (TSA), or a pressure-temperature swing adsorption method (PTSA) in which both pressure and temperature swing. Separation and purification method of hydrogen from cracked gas mixture.
  9. 제1항에 있어서, 0.1~5,000 ppm 이상 암모니아가 포함된 혼합가스로부터 암모니아와 질소를 제거하여, 최종 수소가 99.9% 이상인 것을 특징으로 하는 암모니아의 분해 혼합가스로부터 수소의 분리 및 정제방법.The method of claim 1, wherein the final hydrogen is 99.9% or more by removing ammonia and nitrogen from the mixed gas containing 0.1 to 5,000 ppm or more of ammonia.
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