WO2022099350A1 - A process and plant for producing ultrahigh-purity hydrogen from low-grade hydrogen gas - Google Patents

A process and plant for producing ultrahigh-purity hydrogen from low-grade hydrogen gas Download PDF

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WO2022099350A1
WO2022099350A1 PCT/AU2021/051278 AU2021051278W WO2022099350A1 WO 2022099350 A1 WO2022099350 A1 WO 2022099350A1 AU 2021051278 W AU2021051278 W AU 2021051278W WO 2022099350 A1 WO2022099350 A1 WO 2022099350A1
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hydrogen
pressure
adsorption
gas
vol
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PCT/AU2021/051278
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English (en)
French (fr)
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Lefu TAO
Penny XIAO
Ming Sheng Liu
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Dimer Technologies Pty Ltd
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Priority claimed from AU2020904141A external-priority patent/AU2020904141A0/en
Application filed by Dimer Technologies Pty Ltd filed Critical Dimer Technologies Pty Ltd
Priority to CN202180074382.0A priority Critical patent/CN116390797A/zh
Priority to AU2021377152A priority patent/AU2021377152B2/en
Publication of WO2022099350A1 publication Critical patent/WO2022099350A1/en

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    • 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
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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    • B01D2256/16—Hydrogen
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    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
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Definitions

  • High purity hydrogen (H 2 ) is traditional industrial gas for various industrial processing, aerospace, and medical uses it also seriously promises emerging hydrogenenergy applications.
  • the dynamic developing hydrogen-energy fuel cells offer a broad range of benefits, including minimizing the CO 2 emission, powering the fuel cell vehicles, and enabling power-to-H 2 as an energy transition & storage.
  • a minimum H 2 purity of 99.97 vol% is required.
  • the impurities in H 2 are strictly confined within certain levels, such as CH 4 below 100 ppm, total HCs (except for CH 4 ) below 2 ppm, O 2 below 5 ppm, N 2 below 300 ppm, CO 2 below 2 ppm, and CO below 0.2 ppm.
  • the predictable surge and applications of hydrogen fuel cells are demanding effective and efficient production of ultrahigh purity hydrogen gas.
  • the present invention relates to a vacuum-pressure swing adsorption (VPSA) process and multiple columns plant corresponding to the said VPSA process for producing ultrahigh-purity hydrogen gas (>99.997 vol%) from a low-grade hydrogen gas stream (>95 vol%).
  • VPSA vacuum-pressure swing adsorption
  • PSA pressure swing adsorption
  • a typical PSA system contains multiple adsorption columns (also called ‘beds’), and each separate adsorption column operates in a programmed and purposeful sequence, which is called the PSA cycle.
  • PSA cycles comprise a number of well-known steps, and a specific PSA application requires skilled personnel to combine the known steps in a suitable manner to achieve the desired separation target.
  • These known steps include but are not limited to: feed and adsorption step, co-current pressurising equalization step, co-current providing purge step, counter-current blow down and desorption step, counter-current pressurising equalization step, and re-pressurisation step.
  • Cryo-TSA process requires chilling the feed hydrogen gas and the adsorption column to the liquid nitrogen temperature (-196 °C).
  • the adsorbents adsorb the impurities at such temperature and meanwhile obtain high purity hydrogen with > 99.999 vol% as the effluent product.
  • the temperature in the adsorption column needs to be heated to normal environmental temperature. Because of the large temperature swing range and the usage of the cryogenic agent, such processes, compared to the traditional PSA processes, require exceptionally high energy consumption, special consideration of the construction materials, and an extra control mechanism for the liquid system.
  • Palladium-based alloy membrane is exclusively selective to hydrogen at elevated temperature (400 to 500 °C). This feature can be exploited by a well-designed device to produce ultrahigh purity hydrogen products containing more than 99.999 vol% H 2 . However, the high cost and low production amount of the palladium membrane prevent such processes from popularity for mass production of ultrahigh purity hydrogen.
  • Hydrogen purification via metal hydride is a chemical adsorption process, using metal alloy to chemically react with hydrogen to form metal hydride. Most of the hydrogen is separated from the impurity by fixing in the solid phase, while the impurity leaves with the gas phase. Thereafter, ultrahigh purity hydrogen (>99.999 vol%) can be collected by decomposing the metal hydride, which is the reverse reaction of the hydride forming reaction.
  • the main issue of such a process is the stability of the metal alloy. The performance of the metal alloy will quickly decay after a few adsorption/release cycles so that frequent maintenance and adsorbent replacement is required.
  • This invention presents a technical pathway to innovate the well-established PSA steps into new PSA cycles to achieve ultrahigh purity hydrogen gas, although the product specification of this invention is over-qualified for the purpose of obtaining ultra-high purity hydrogen gas and the negative temperatures applied in this invention requires substantial extra energy consumption.
  • the present invention has been proposed under the circumstances described above. It is to provide a process and multiple columns’ pressure-vacuum swing adsorption (VPSA) plant for producing hydrogen with a purity of over 99.997 vol% from a feed gas containing 95.0 vol% to 99.9 vol% hydrogen and one or more impurities.
  • the plant comprises six or more parallel adsorption columns, five control valves for each column, a feed gas buffer tank, a product gas buffer tank, and a vacuum pump.
  • the process to achieve vacuum-pressure swing adsorption cycles in the said plant includes three or more co-current pressure reduction steps and three or more counter-current pressurization steps and one step of vacuum purge.
  • FIG.l is a schematic diagram showing a six-bed VPSA system for carrying out the VPSA process to purify high pure hydrogen of the present invention.
  • FIG.2 is a process & flow diagram showing the 12-step VPSA cycles in the invented six-bed VPSA system.
  • the first aspect of the present invention there is a provided process for purifying the low-grade hydrogen gas to ultra-high purity hydrogen by vacuumpressure swing adsorption using six or more adsorption columns each filled with adsorbents.
  • Each adsorption column is programmed to repeatedly perform the same sequential cycle of twelve steps. However, at one certain moment, they are operated at different steps so that they can be synchronized to satisfy the continuous utilisation of the feed hydrogen gas and provide continuous production of ultrahigh purity hydrogen.
  • the process described below is conducted by focusing on one of the six adsorption columns.
  • the repeatedly performed cycle of steps includes:
  • (g) desorption step the content in the adsorption column forcedly flows countercurrent out of the bottom of the adsorption column, while the evacuation force is provided by the vacuum pump connected to the adsorption column. All the extracted gas is regarded as the desorption gas product.
  • No.3 counter-current pressurising equalization step from the top of the adsorption column, a gas stream from another adsorption column, which is undertaking a No.3 cocurrent depressurising equalization step, flows counter-current to pressurise the column until pressures within two connected adsorption columns reach the same level;
  • No.2 counter-current pressurising equalization step from the top of the adsorption column, a gas stream from another adsorption column, which is undertaking the No.2 co-current depressurising equalization step, flows counter-current to pressurise the column until pressures within two connected adsorption columns reach the same level.
  • No.l counter-current pressurising equalization step from the top of the adsorption column, a gas stream from another adsorption column, which is undertaking the No.l co-current depressurising equalization step, flows counter-current to pressurise the column until pressures within two connected adsorption columns reach the same level.
  • (1) product gas re-pressurising step from the top of the adsorption column, a gas stream from the product buffer gas tank flows counter-current to pressurise the column. After (1) step, the adsorption column will again operate (a) step to conduct another PSA cycle.
  • ultra-high purity hydrogen gas product > 99.997 vol%) is obtained via the described vacuum-pressure swing adsorption process.
  • the feed pure hydrogen gas to be purified by said process contains 95.0 vol% to 99.9 vol% hydrogen, balanced with minor components including nitrogen (N 2 ), oxygen (O 2 ), methane (CH 4 ), hydrocarbons (HCs), carbon dioxide (CO 2 ) and carbon monoxide (CO), and the feed pure hydrogen gas is at a gauge pressure within a range of 1.2 MPa to 3.0 MPa.
  • the vacuum pump vacuums the adsorption column to the absolute pressure level of 10-50 kPa at Step (g) desorption and Step (h) counter-current purge.
  • the adsorption column each comprises a layer of activated carbon (first adsorbent), or the similar, filling at the upstream portion in the flow direction of the feed pure hydrogen gas at a percentage of 25 to 75 %, and a calculated layer of zeolite-based adsorbent (second adsorbent), or the similar, filling at the downstream portion in the flow direction of the feed pure hydrogen gas at a percentage of 25 to 75 %.
  • Suitable activated carbons include but are not limited to coconut shell activated carbon.
  • Suitable zeolite-based adsorbents include but are not limited to the 5A, CaX, LiX, 13X, LiA zeolites.
  • the recovery of hydrogen which is defined as the total molar amount of hydrogen within the ultra-high purity hydrogen product (> 99.997 vol%) divided by the molar amount of hydrogen within the feed pure hydrogen gas, is considerably high by the described process, commonly greater than 85 %, and more preferably, greater than 90%. This is generally much higher than other published H 2 -PSA processes for ultrahigh H 2 production which normally achieve the hydrogen recovery rate in the range of 60% to 80%.
  • the usage of the vacuum pump is another important feature of the present invention.
  • increasing the regeneratability of the adsorbent can always increase the performance of an adsorption process.
  • a more powerful regeneration driving force which in this case is a vacuum, is needed to deeply clean the impurity adsorbed on the adsorbents in each VPSA cycle, and therewith, enables the adsorbents to adsorb most new impurities in the next adsorption cycle.
  • a purpose-built plant i.e. a VPSA plant using six adsorption columns filled with designed adsorbents, can purify the low-grade pure hydrogen gas to ultrahigh purity hydrogen of 99.997% or higher.
  • This VPSA plant can achieve the process according to the first aspect of the present invention, and hence has the same advantages as those described above with respect to the present invention.
  • Example section shows the examples of the application of the present invention.
  • Adsorption columns 1, 2, 3, 4, 5, and 6 are provided in parallel to each other.
  • the adsorption columns are configured to generate a product gas discharging in path 10 by adsorbing, using adsorbents, adsorption target components other than the hydrogen components from the feed gas supplying in path 8.
  • the feed gas supply path 8 for supplying a feed gas is connecting the feed gas buffer tank 8a to the lower portion of the six adsorption columns.
  • Feed gas supply valves la, 2a, 3a, 4a, 5a, and 6a on the feed supply path of each adsorption column open and close the feed gas supply to the corresponding individual adsorption column.
  • the desorption path 9 for discharging the desorption gas is connected to the lower portion of the six adsorption columns.
  • a vacuum pump 7 is installed on the desorption path to reduce the pressure in the desorption path to an absolute pressure value of 10 to 50 KPa.A.
  • Desorption gas discharge valves lb, 2b, 3b, 4b, 5b, and 6b on the desorption path of the corresponding adsorption column open and close the desorption gas discharging path to the vacuum pump 7.
  • a side-path control valve 7a is parallel connected to the vacuum pump.
  • the side-path control valve 7a is programmed to open the discharging side path when the absolute pressure within the desorption discharge path is higher than a value of 0.11 MPa. A, otherwise, close the side path when the absolute pressure within the desorption discharge path is lower than 0.11 MPa.
  • the off-gas side of vacuum pump 7 is connected to the desorption gas buffer tank 9a.
  • the product gas path 10 for providing a product hydrogen gas is connecting between the upper portions of the six adsorption columns and the product gas buffer tank 10a.
  • Product gas valves If, 2f, 3f, 4f, 5f, and 6f on the product gas path of each adsorption column open and close the product gas discharging path of the corresponding adsorption column to the product gas buffer tank.
  • two sets of pressure-equalization adjustment valves are connected to the upper portion of the adsorption column.
  • pressure-equalization adjustment valves 1c, 2c, 3c, 4c, 5c, and 6c control the communication pattern between any of the two adsorption columns by opening/closing the corresponding adjustment valves.
  • pressure-equalization adjustment valves Id, 2d, 3d, 4d, 5d, and 6d control the communication pattern between any of the two adsorption columns by opening/closing the corresponding adjustment valves.
  • the first pressureequalization path 11 is used for the No.3 pressure-equalization steps and the purge steps
  • the second pressure-equalization path 12 is used for the No.2 and No.l pressure-equalization steps.
  • Another set of valves, le, 2e, 3e, 4e, 5e, and 6e connect the product gas buffer tank 10a and the adsorption columns on the re-pressurisation path 13.
  • the re-pressurisation valves le, 2e, 3e, 4e, 5e, and 6e open and close the corresponding re-pressurisation path allowing the ultra-high purity of hydrogen gas in the product gas tank to backflow to the adsorption columns to pressurise the column to feed pressure.
  • the 12-step VPSA cycle shown can be therewith implemented to purify a pure hydrogen feed gas obtaining an ultra-high purity hydrogen product. Specifically, all 12 steps are controlled to perform in six respective adsorption columns in parallel. The following 12- step VPS A cycle is illustrated.
  • Step (a) the adsorption column 1 is undertaking the first feed and adsorption step. Specifically, the feed hydrogen gas is introduced to the bottom of the adsorption column 1 to adsorb most of the impurity by switching on control valve la. Meanwhile, the product gas valve If is open to discharge a purified hydrogen gas from the top of the adsorption column 1 as the high purity of hydrogen product.
  • the adsorption column 4 is undertaking the desorption step, that the desorption gas product is evacuated from the bottom of the adsorption column 4 by the vacuum pump 7 via the opened desorption valve 4b.
  • the pressure within the adsorption column 4 decreases to the desorption pressure which is decided by the power of the vacuum pump.
  • the adsorption column 3 and adsorption column 5 are performing the No. 3 pressure equalization step using the pressure equalization path 11. Specifically, the adsorption column 5 is providing a co-current gas stream via the opening pressure equalization valve 5c, in a result that the pressure within the adsorption column 5 decreases. The adsorption column 3 is receiving a gas stream counter-current via the opening pressure equalization valve 3c, in a result that the pressure within the adsorption column 3 increases.
  • pressure equalization step is that the pressure within the adsorption column 5 which is relatively higher at the initial stage of Step (a), and the pressure within the adsorption column 3 which is relatively lower at the initial stage of Step (a) reach to the same level at the end stage of Step (a).
  • the adsorption column 2 and adsorption column 6 are performing the No. 1 pressure equalization step using the pressure equalization path 12. Specifically, the adsorption column 6 is providing a co-current gas stream via the opening pressure equalization valve 6d, in a result that the pressure within the adsorption column 6 decreases. The adsorption column 2 is receiving a gas stream counter-current via the opening pressure equalization valve 2d, in a result that the pressure within the adsorption column 2 increases.
  • pressure equalization step is that the pressure within the adsorption column 6 which is relatively higher at the initial stage of Step (a), and the pressure within the adsorption column 2 which is relatively lower at the initial stage of Step (a) reach to the same level at the end stage of Step (a).
  • Step (b) the adsorption column 1 is in the second feed and adsorption step, which is similar to Step (a) by opening the feed gas valve la and the product gas valve If.
  • the adsorption column 2 is carrying out the re-pressurisation step.
  • High purity of hydrogen product gas is introduced from the product gas buffer tank to the adsorption column 2 through re-pressurisation line 13 by opening the re-pressurisation valve 2e.
  • the pressure within the adsorption column 2 increases to the same level as the feed gas at the end stage of Step (b).
  • the adsorption column 4 is performing the purge step, while the adsorption column 5 is in the co-current providing purge step. Specifically, the desorption gas valve 4b is kept opening following Step (a) to continuously withdraw the desorption gas out of the adsorption column 4. At the same time, another gas stream from the adsorption column 5 is introduced via the pressure equalization valve 4c and the first pressure equalization path 11. The pressure equalization valve 5c is opened for the gas content in the adsorption column 5 flowing out to purge the adsorption column 4.
  • Step (b) With such interaction between the adsorption column 4 and 5, the pressure within the adsorption column 5 at the end stage of Step (b) decreases to a certain level above the desorption pressure, while the pressure within the adsorption column 4 is maintained at the desorption pressure.
  • the adsorption column 3 and adsorption column 6 are performing the No. 2 pressure equalization step using the pressure equalization path 12. Specifically, the adsorption column 6 is providing a co-current gas stream via the opening pressure equalization valve 6d, in a result that the pressure within the adsorption column 6 decreases. The adsorption column 3 is receiving a counter-current gas stream via the opening pressure equalization valve 3d, in a result that the pressure within the adsorption column 2 increases.
  • pressure equalization step is that the pressure within the adsorption column 6 which is relatively higher at the initial stage of Step (b), and the pressure within the adsorption column 3 which is relatively lower at the initial stage of Step (b) reach to the same level at the end stage of Step (b).
  • Step (a) and Step (b) includes all 12 steps of the VPSA cycle: the feed and adsorption step, the feed and the providing re-pressurisation step, the No. 1 pressure equalization step, the No. 2 pressure equalization step, the No. 3 pressure equalization step, the desorption step, the vacuum purge and providing purge step, although performed by different adsorption columns.
  • Step (a) and Step (b) is the basic “building block unit” and can be expanded to produce the whole VPSA cycle by switching adsorption columns to perform every individual step.
  • Step (c) and Step (d) the adsorption column 1 is performing the No. 1 pressure equalization step and No. 2 pressure equalization step similar as the adsorption column 6 performs in Step (a) and Step (b).
  • Step (e) and Step (f) the adsorption column 1 is performing the No. 3 pressure equalization step and co-current providing purge step similar as the adsorption column 5 performs in Step (a) and Step (b).
  • Step (g) and Step (h) the adsorption column 1 is performing the desorption step and purge step similar as the adsorption column 4 performs in Step (a) and Step (b).
  • Step (i) and Step (j) the adsorption column 1 is performing the No.
  • Step (k) and Step (1) the adsorption column 1 is performing the No. 1 pressure equalization step and re-pressurisation step as the adsorption column 2 performs in Step (a) and Step (b). Thereafter, the adsorption column 1 can repeat the feed and adsorption step in Step (a) and Step (b) again to restart the VPSA cycle.
  • the adsorption column 2 to 6 are performing in the same manner as the adsorption column 1, switching operation patterns through Step (a) to Step (1) to finish a complete VPSA cycle.
  • the sequential proceeding of adsorption process steps is governed by orderly switching on/off the program-controlled valves.
  • the program-controlled valves in the embodiment can be controlled remotely or wirelessly through an automatic control and communication system.
  • the device of the present invention includes an automatic control system, such as a programmable logic controller (PLC) with a communication module or a distributed control system (DCS) with a communication module. That skilled personnel can remotely/wirelessly control the device of the present invention through an automatic PLC/DCS control system according to the requirements of gas separation.
  • PLC programmable logic controller
  • DCS distributed control system
  • the present invention is not limited to the embodiment.
  • the specific VPSA method and apparatus to produce an ultra-high purity of hydrogen referring to this invention can be further modified in various ways without deviating from the scope of the present invention.
  • six adsorption columns are described above, the number of adsorption columns is not limited to six.
  • various sets of pressure equalization steps, purge step, desorption step, vacuum purge step, and product re -pressurisation steps can perform the same and provide the same advantage of the present invention.
  • a feed gas of pure hydrogen gas introduced from a refinery SMR hydrogen-PSA system is further purified to ultra-high pure hydrogen gas by the method described in the foregoing embodiment. Specifically, hydrogen purification is performed under the following conditions. [0059] [Table 1]
  • Adsorbent 1 Activated carbon
  • the six adsorption columns are in a cylinder shape with the same diameter of 0.8 m.
  • the height of the adsorbent packing section is 3.0 m, where coconut shell-based activated carbon is filled at the lower portion of the packing section for 1.5 m, and zeolite 5A is filled at the higher portion of the packing section for the other 1.5 m.
  • the feed pure hydrogen gas from a purified refinery hydrogen-rich off-gas contains 99.3170 vol% of hydrogen with various minor impurities.
  • the feed gas is supplied at a volumetric flow rate of 3500 Nm3/hr.
  • the adsorption pressure (maximum pressure) in the adsorption step is 3 MPa (absolute pressure: this holds true in every case of the pressures described hereinafter), and the desorption pressure achieved by the vacuum pump is 20 KPa.A. Table 1 above discloses the operating conditions and the VPSA process performance.
  • a feed gas with a hydrogen purity of 95.3601 vol% from the hydrogen-rich off gas of ethane reforming processes is further purified to a high purity hydrogen gas by the method described in the foregoing embodiment. Specifically, hydrogen purification is performed under the following conditions.
  • Adsorbent 1 Activated carbon
  • This example shows that the present process and device can produce ultra-high purity hydrogen product gas (>99.997 vol%) when the feed gas is with lower hydrogen purity (around 95 vol%) and in lower feed pressure (1.2 MPa).

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US20070199446A1 (en) * 2006-02-28 2007-08-30 Golden Timothy C Production of carbon monoxide-free hydrogen and helium from a high-purity source
US20190275460A1 (en) * 2018-05-29 2019-09-12 Sichuan Techairs Co., Ltd. Method of Purifying and Recycling Normal-pressure Waste Hydrogen by Full Temperature Range Pressure Swing Adsorption (FTrPSA) in Manufacturing Process of Semiconductor
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US20070199446A1 (en) * 2006-02-28 2007-08-30 Golden Timothy C Production of carbon monoxide-free hydrogen and helium from a high-purity source
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EP3733264A1 (en) * 2019-05-02 2020-11-04 Casale Sa A pressure swing adsorption process for producing hydrogen and carbon dioxide

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CN115259087A (zh) * 2022-07-29 2022-11-01 广西柳州钢铁集团有限公司 一种创建预判机制提高氢气纯度的制氢操作方法及系统
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