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Hydrogen purification

January 01, 1970

Hydrogen purification is any technology used to purify hydrogen. The impurities in hydrogen gas depend on the source of the H2, e.g., petroleum, coal, electrolysis, etc. The required purity is determined by the application of the hydrogen gas. For example, ultra-high purified hydrogen is needed for applications like proton exchange membrane fuel cells.[1]

Purification technologies edit

Low temperature methods edit

The default large-scale purification of H2 produced in oil refineries exploits its very low boiling point of −253 °C. Most impurities have boiling points well above this temperature. Low temperature methods can be complemented by scrubbing to remove particular impurities.[1]

Palladium membrane hydrogen purifiers edit

Hydrogen can be purified by passing through a membrane composed of palladium and silver. This alloy with a ca. 3:1 ratio for Pd:Ag is more structural robust than pure Pd, which is the active comonent that allows the selective diffusion of H2 through it. Diffusion is faster near 300 °C. This method has been used for purification of hydrogen on a laboratory scale, but not in industry. Silver-palladium membranes are unstable toward alkenes and sulfur-containing compounds.[1]

Dense thin-metal membrane purifiers are compact, relatively inexpensive and simple to use.[2][3][4]

Pressure swing adsorption edit

Pressure swing adsorption is used for the removal of carbon dioxide (CO2) as the final step in the large-scale commercial synthesis of hydrogen. It can also remove methane, carbon monoxide, nitrogen, moisture and in some cases, argon, from hydrogen.

Applications edit

Metalorganic vapour phase epitaxy edit

Hydrogen purifiers are used in metalorganic vapour phase epitaxy reactors for LED production.[5]

PEM fuel cells edit

Fuel cell electric vehicles commonly use polymer electrolyte membrane fuel cells (PEMFC) that are susceptible to a range of impurities. Impurities impact PEMFC using a range of mechanisms, these may include poisoning the anode hydrogen oxidation reaction catalysts, reducing the ionic conductivity of the ionomer and membrane, altering wetting behaviour of components or blocking porosity in diffusion media. The impact of some impurities like carbon monoxide, formic acid, or formaldehyde is reversible with PEMFC performance recovering once the supply of impurity is removed. Other impurities, for example sulphurous compounds, may cause irreversible degradation.[6] The permissible limits of hydrogen impurities are shown below.

Fuel Quality Specification For Gasseous Hydrogen Supplied to PEMFC Road Vehicles [7]
Maximum Permissible Concentration / μmol mol−1
Total non-hydrogen gasses 300
Water 5
Total Hydrocarbons Except Methane [Carbon atom basis] 2
Methane 100
Oxygen 5
Helium 300
Nitrogen 300
Argon 300
Carbon Dioxide 2
Carbon Monoxide 0.2
Total Sulphur Compounds [Sulphur atom basis] 0.004
Formaldehyde 0.2
Formic Acid 0.2
Ammonia 0.1
Halogenated Compounds [Halogen ion basis] 0.05
Maximum Particulate Concentration 1 mg kg−1

Efforts to assess the compliance of hydrogen supplied by hydrogen refuelling stations against the ISO-14687 standard have been performed.[8][9][10] While the hydrogen was generally found to be 'good'[8] violations of the standard have been reported, most frequently for nitrogen, water and oxygen.

Combustion engines and appliances edit

Combustion applications are generally more tolerant of hydrogen impurities than PEFMC, as such the ISO-14687 standard for permissible impurities is less strict.[11] This standard has itself been criticised with revisions proposed to make it more lenient and therefore suitable for hydrogen distributed through a repurposed gas network.[12]

Fuel Quality Specification For Gaseous Hydrogen Supplied to Combustion Engines and Appliances [13]
Impurity Maximum Permissible Concentration / μmol mol−1
Total non-hydrogen gasses 20 000
Water Non-condensing
Total Hydrocarbons [Carbon atom basis] 100
Carbon Monoxide 1
Sulphur [Sulphur atom basis] 2
Combined water, oxygen, nitrogen, argon 19 000
Permanent Particulates Shall not contain an amount sufficient to cause damage.

Sources of impurities edit

The presence of impurities in hydrogen depends on the feedstock and the production process. Hydrogen produced by electrolysis of water may routinely include trace oxygen and water. Hydrogen produced by reforming of hydrocarbons contains carbon dioxide and carbon monoxide as well as sulphur compounds.[12] Some impurities may be added deliberately, for example odorants to aid detection of gas leaks.[14]

Methods for analysis edit

As the permissible concentrations for many impurities are very low this sets stringent demands on the sensitivity of the analytical methods. Moreover, the high reactivity of some impurities requires use of a properly passivated sampling and analytical systems.[15] Sampling of hydrogen of is challenging and care must be taken to ensure that impurities are not introduced to the sample and that impurities do not absorb on or react within the sampling equipment, there are currently different methods for sampling but rely on filling a gas cylinder from the refuelling nozzle of a refuelling station.[16] Efforts are underway to standardise and compare sampling strategies.[17][18] A combination of different instruments is needed to assess hydrogen samples for all of the components listed in ISO 14687-2.[19] Techniques suitable for individual impurities are indicated in the table below.

Example Analytical Methods for Asessing The Concentration of Impurities in Hydrogen[20][21]
Impurity Possible Analytical Methods Detection Limits
Total non-hydrogen gasses
Water Quartz crystal microbalance

or CRDS

1.3 or 0.030
Total Hydrocarbons Except Methane [Carbon atom basis] GC-Methaniser-FID 0.1
Methane GC-Methaniser-FID, GC-EPD 0.1
Oxygen GC-PDHID, GC-EPD 0.3
Helium GC-TCD 10
Nitrogen GC-PDHID, GC-EPD 1
Argon GC-PDHID, GC-EPD 0.3
Carbon Dioxide GC-Methaniser-FID, GC-EPD 0.02
Carbon Monoxide GC-Methaniser-FID, GC-EPD 0.02
Total Sulphur Compounds [Sulphur atom basis] GC-SCD, GC-EPD 0.001
Formaldehyde GC-Methaniser-FID 0.1
Formic Acid FTIR 0.2
Ammonia GC-MS or UV-visible spectroscopy or FTIR 1 or 0.03 or 0.1
Halogenated Compounds (Halogen Ion Equivalent) TD-GC-MS 0.016

Techniques such as electrochemical sensors [22][23] and mass spectrometry.[24]

See also edit

References edit

  1. ^ a b c Häussinger, Peter; Lohmüller, Reiner; Watson, Allan M. (2011). "Hydrogen, 3. Purification". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.o13_o04. ISBN 978-3-527-30385-4.
  2. ^ Hydrogen purification membranes
  3. ^ Dense metal membranes for hydrogen purifying
  4. ^ Han, Jae-Yun; Kim, Chang-Hyun; Kim, Sang-Ho; Kim, Dong-Won (2014). "Development of Pd Alloy Hydrogen Separation Membranes with Dense/Porous Hybrid Structure for High Hydrogen Perm-Selectivity". Advances in Materials Science and Engineering. 2014: 1–10. doi:10.1155/2014/438216.
  5. ^ "Hydrogen purifiers proving vital to LED production". III-Vs Review. 19 (5): 19. June 2006. doi:10.1016/S0961-1290(06)71698-2.
  6. ^ X. Cheng, Z. Shi, N. Glass, L. Zhang, J. Zhang, D. Song, Z.-S. Liu, H. Wang and J. Shen (2007). "A review of PEM hydrogen fuel cell contamination:Impacts, mechanisms, and mitigation". Journal of Power Sources. 165 (2): 739–756. Bibcode:2007JPS...165..739C. doi:10.1016/j.jpowsour.2006.12.012. S2CID 95246225.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  7. ^ "ISO 14687:2019". Retrieved 2021-10-18.
  8. ^ a b Aarhaug, Thor Anders; Kjos, Ole; Bacquart, Thomas; Valter, Vladimir; Optenhostert, Thomas (2021-08-18). "Assessment of hydrogen quality dispensed for hydrogen refuelling stations in Europe". International Journal of Hydrogen Energy. HYDROGEN ENERGY SYSTEMS. 46 (57): 29501–29511. doi:10.1016/j.ijhydene.2020.11.163. hdl:11250/3025287. ISSN 0360-3199. S2CID 230535934.
  9. ^ Aarhaug, Thor A.; Kjos, Ole S.; Ferber, Alain; Hsu, Jong Pyong; Bacquart, Thomas (2020). "Mapping of Hydrogen Fuel Quality in Europe". Frontiers in Energy Research. 8: 307. doi:10.3389/fenrg.2020.585334. hdl:11250/2770289. ISSN 2296-598X.
  10. ^ "HYDRAITE public report D3.1 | HYDRAITE". Retrieved 2021-10-18.
  11. ^ "ISO 14687:2019". Retrieved 2021-10-18.
  12. ^ a b "WP2 Report Hydrogen Purity". Hy4Heat. Retrieved 2021-10-18.
  13. ^ "ISO 14687:2019". Retrieved 2021-10-18.
  14. ^ "Hydrogen Odorant and Leak Detection Project Closure Report" (PDF).
  15. ^ Bacquart, Thomas; Moore, Niamh; Hart, Nick; Morris, Abigail; Aarhaug, Thor A.; Kjos, Ole; Aupretre, Fabien; Colas, Thibault; Haloua, Frederique; Gozlan, Bruno; Murugan, Arul (2020-02-14). "Hydrogen quality sampling at the hydrogen refuelling station – lessons learnt on sampling at the production and at the nozzle". International Journal of Hydrogen Energy. 22nd World Hydrogen Energy Conference. 45 (8): 5565–5576. doi:10.1016/j.ijhydene.2019.10.178. hdl:11250/2689927. ISSN 0360-3199. S2CID 213820032.
  16. ^ Arrhenius, Karine; Aarhaug, Thor; Bacquart, Thomas; Morris, Abigail; Bartlett, Sam; Wagner, Lisa; Blondeel, Claire; Gozlan, Bruno; Lescornez, Yann; Chramosta, Nathalie; Spitta, Christian (2021-10-11). "Strategies for the sampling of hydrogen at refuelling stations for purity assessment". International Journal of Hydrogen Energy. 46 (70): 34839–34853. doi:10.1016/j.ijhydene.2021.08.043. hdl:11250/3010363. ISSN 0360-3199. S2CID 239636011.
  17. ^ Practice for Sampling of High Pressure Hydrogen and Related Fuel Cell Feed Gases, ASTM International, doi:10.1520/d7606-17, retrieved 2021-11-01
  18. ^ DIN ISO/TS 22002-3:2017-09, retrieved 2021-11-01
  19. ^ Murugan, Arul; Brown, Andrew S. (2015-03-22). "Review of purity analysis methods for performing quality assurance of fuel cell hydrogen". International Journal of Hydrogen Energy. 40 (11): 4219–4233. doi:10.1016/j.ijhydene.2015.01.041. ISSN 0360-3199.
  20. ^ "Hydrogen purity". NPLWebsite. Retrieved 2021-10-18.
  21. ^ Bacquart, Thomas; Arrhenius, Karine; Persijn, Stefan; Rojo, Andrés; Auprêtre, Fabien; Gozlan, Bruno; Moore, Niamh; Morris, Abigail; Fischer, Andreas; Murugan, Arul; Bartlett, Sam (2019-12-31). "Hydrogen fuel quality from two main production processes: Steam methane reforming and proton exchange membrane water electrolysis". Journal of Power Sources. 444: 227170. Bibcode:2019JPS...44427170B. doi:10.1016/j.jpowsour.2019.227170. ISSN 0378-7753. S2CID 208754564.
  22. ^ Mukundan, Rangachary (2020). "Development of an Electrochemical Hydrogen Contaminant Detector". Journal of the Electrochemical Society. 167 (14): 147507. Bibcode:2020JElS..167n7507M. doi:10.1149/1945-7111/abc43a. S2CID 226341724.
  23. ^ Noda, Z.; Hirata, K.; Hayashi, A.; Takahashi, T.; Nakazato, N.; Saigusa, K.; Seo, A.; Suzuki, K.; Ariura, S.; Shinkai, H.; Sasaki, K. (2017-02-02). "Hydrogen pump-type impurity sensors for hydrogen fuels". International Journal of Hydrogen Energy. 42 (5): 3281–3293. doi:10.1016/j.ijhydene.2016.12.066. ISSN 0360-3199.
  24. ^ "HydrogenSense". www.vandf.com. Retrieved 2021-10-27.

External links edit

  • 3 industrial hydrogen purifier systems 2007-07-15 at the Wayback Machine
  • Power and Energy, Inc.
  • Setting a new benchmark for hydrogen delivery

January 01, 1970
hydrogen, purification, technology, used, purify, hydrogen, impurities, hydrogen, depend, source, petroleum, coal, electrolysis, required, purity, determined, application, hydrogen, example, ultra, high, purified, hydrogen, needed, applications, like, proton, . Hydrogen purification is any technology used to purify hydrogen The impurities in hydrogen gas depend on the source of the H2 e g petroleum coal electrolysis etc The required purity is determined by the application of the hydrogen gas For example ultra high purified hydrogen is needed for applications like proton exchange membrane fuel cells 1 Contents 1 Purification technologies 1 1 Low temperature methods 1 2 Palladium membrane hydrogen purifiers 1 3 Pressure swing adsorption 2 Applications 2 1 Metalorganic vapour phase epitaxy 2 2 PEM fuel cells 2 3 Combustion engines and appliances 3 Sources of impurities 4 Methods for analysis 5 See also 6 References 7 External linksPurification technologies editLow temperature methods edit The default large scale purification of H2 produced in oil refineries exploits its very low boiling point of 253 C Most impurities have boiling points well above this temperature Low temperature methods can be complemented by scrubbing to remove particular impurities 1 Palladium membrane hydrogen purifiers edit Hydrogen can be purified by passing through a membrane composed of palladium and silver This alloy with a ca 3 1 ratio for Pd Ag is more structural robust than pure Pd which is the active comonent that allows the selective diffusion of H2 through it Diffusion is faster near 300 C This method has been used for purification of hydrogen on a laboratory scale but not in industry Silver palladium membranes are unstable toward alkenes and sulfur containing compounds 1 Dense thin metal membrane purifiers are compact relatively inexpensive and simple to use 2 3 4 Pressure swing adsorption edit Pressure swing adsorption is used for the removal of carbon dioxide CO2 as the final step in the large scale commercial synthesis of hydrogen It can also remove methane carbon monoxide nitrogen moisture and in some cases argon from hydrogen Applications editMetalorganic vapour phase epitaxy edit Hydrogen purifiers are used in metalorganic vapour phase epitaxy reactors for LED production 5 PEM fuel cells edit Fuel cell electric vehicles commonly use polymer electrolyte membrane fuel cells PEMFC that are susceptible to a range of impurities Impurities impact PEMFC using a range of mechanisms these may include poisoning the anode hydrogen oxidation reaction catalysts reducing the ionic conductivity of the ionomer and membrane altering wetting behaviour of components or blocking porosity in diffusion media The impact of some impurities like carbon monoxide formic acid or formaldehyde is reversible with PEMFC performance recovering once the supply of impurity is removed Other impurities for example sulphurous compounds may cause irreversible degradation 6 The permissible limits of hydrogen impurities are shown below Fuel Quality Specification For Gasseous Hydrogen Supplied to PEMFC Road Vehicles 7 Maximum Permissible Concentration mmol mol 1 Total non hydrogen gasses 300 Water 5 Total Hydrocarbons Except Methane Carbon atom basis 2 Methane 100 Oxygen 5 Helium 300 Nitrogen 300 Argon 300 Carbon Dioxide 2 Carbon Monoxide 0 2 Total Sulphur Compounds Sulphur atom basis 0 004 Formaldehyde 0 2 Formic Acid 0 2 Ammonia 0 1 Halogenated Compounds Halogen ion basis 0 05 Maximum Particulate Concentration 1 mg kg 1 Efforts to assess the compliance of hydrogen supplied by hydrogen refuelling stations against the ISO 14687 standard have been performed 8 9 10 While the hydrogen was generally found to be good 8 violations of the standard have been reported most frequently for nitrogen water and oxygen Combustion engines and appliances edit Combustion applications are generally more tolerant of hydrogen impurities than PEFMC as such the ISO 14687 standard for permissible impurities is less strict 11 This standard has itself been criticised with revisions proposed to make it more lenient and therefore suitable for hydrogen distributed through a repurposed gas network 12 Fuel Quality Specification For Gaseous Hydrogen Supplied to Combustion Engines and Appliances 13 Impurity Maximum Permissible Concentration mmol mol 1 Total non hydrogen gasses 20 000 Water Non condensing Total Hydrocarbons Carbon atom basis 100 Carbon Monoxide 1 Sulphur Sulphur atom basis 2 Combined water oxygen nitrogen argon 19 000 Permanent Particulates Shall not contain an amount sufficient to cause damage Sources of impurities editThe presence of impurities in hydrogen depends on the feedstock and the production process Hydrogen produced by electrolysis of water may routinely include trace oxygen and water Hydrogen produced by reforming of hydrocarbons contains carbon dioxide and carbon monoxide as well as sulphur compounds 12 Some impurities may be added deliberately for example odorants to aid detection of gas leaks 14 Methods for analysis editAs the permissible concentrations for many impurities are very low this sets stringent demands on the sensitivity of the analytical methods Moreover the high reactivity of some impurities requires use of a properly passivated sampling and analytical systems 15 Sampling of hydrogen of is challenging and care must be taken to ensure that impurities are not introduced to the sample and that impurities do not absorb on or react within the sampling equipment there are currently different methods for sampling but rely on filling a gas cylinder from the refuelling nozzle of a refuelling station 16 Efforts are underway to standardise and compare sampling strategies 17 18 A combination of different instruments is needed to assess hydrogen samples for all of the components listed in ISO 14687 2 19 Techniques suitable for individual impurities are indicated in the table below Example Analytical Methods for Asessing The Concentration of Impurities in Hydrogen 20 21 Impurity Possible Analytical Methods Detection Limits Total non hydrogen gasses Water Quartz crystal microbalance or CRDS 1 3 or 0 030 Total Hydrocarbons Except Methane Carbon atom basis GC Methaniser FID 0 1 Methane GC Methaniser FID GC EPD 0 1 Oxygen GC PDHID GC EPD 0 3 Helium GC TCD 10 Nitrogen GC PDHID GC EPD 1 Argon GC PDHID GC EPD 0 3 Carbon Dioxide GC Methaniser FID GC EPD 0 02 Carbon Monoxide GC Methaniser FID GC EPD 0 02 Total Sulphur Compounds Sulphur atom basis GC SCD GC EPD 0 001 Formaldehyde GC Methaniser FID 0 1 Formic Acid FTIR 0 2 Ammonia GC MS or UV visible spectroscopy or FTIR 1 or 0 03 or 0 1 Halogenated Compounds Halogen Ion Equivalent TD GC MS 0 016 Techniques such as electrochemical sensors 22 23 and mass spectrometry 24 See also editGas separation Hydrogen pinch Membrane gas separation Membrane reactor 45 Home Power 67 October November 1998 home electrolyzers Hydrogen station Hydrogen fuel Proton exchange membrane fuel cell MetroHyVe2 Project Hydraite Project National Physical Laboratory Hydrogen PurityReferences edit a b c Haussinger Peter Lohmuller Reiner Watson Allan M 2011 Hydrogen 3 Purification Ullmann s Encyclopedia of Industrial Chemistry doi 10 1002 14356007 o13 o04 ISBN 978 3 527 30385 4 Hydrogen purification membranes Dense metal membranes for hydrogen purifying Han Jae Yun Kim Chang Hyun Kim Sang Ho Kim Dong Won 2014 Development of Pd Alloy Hydrogen Separation Membranes with Dense Porous Hybrid Structure for High Hydrogen Perm Selectivity Advances in Materials Science and Engineering 2014 1 10 doi 10 1155 2014 438216 Hydrogen purifiers proving vital to LED production III Vs Review 19 5 19 June 2006 doi 10 1016 S0961 1290 06 71698 2 X Cheng Z Shi N Glass L Zhang J Zhang D Song Z S Liu H Wang and J Shen 2007 A review of PEM hydrogen fuel cell contamination Impacts mechanisms and mitigation Journal of Power Sources 165 2 739 756 Bibcode 2007JPS 165 739C doi 10 1016 j jpowsour 2006 12 012 S2CID 95246225 a href Template Cite journal html title Template Cite journal cite journal a CS1 maint multiple names authors list link ISO 14687 2019 Retrieved 2021 10 18 a b Aarhaug Thor Anders Kjos Ole Bacquart Thomas Valter Vladimir Optenhostert Thomas 2021 08 18 Assessment of hydrogen quality dispensed for hydrogen refuelling stations in Europe International Journal of Hydrogen Energy HYDROGEN ENERGY SYSTEMS 46 57 29501 29511 doi 10 1016 j ijhydene 2020 11 163 hdl 11250 3025287 ISSN 0360 3199 S2CID 230535934 Aarhaug Thor A Kjos Ole S Ferber Alain Hsu Jong Pyong Bacquart Thomas 2020 Mapping of Hydrogen Fuel Quality in Europe Frontiers in Energy Research 8 307 doi 10 3389 fenrg 2020 585334 hdl 11250 2770289 ISSN 2296 598X HYDRAITE public report D3 1 HYDRAITE Retrieved 2021 10 18 ISO 14687 2019 Retrieved 2021 10 18 a b WP2 Report Hydrogen Purity Hy4Heat Retrieved 2021 10 18 ISO 14687 2019 Retrieved 2021 10 18 Hydrogen Odorant and Leak Detection Project Closure Report PDF Bacquart Thomas Moore Niamh Hart Nick Morris Abigail Aarhaug Thor A Kjos Ole Aupretre Fabien Colas Thibault Haloua Frederique Gozlan Bruno Murugan Arul 2020 02 14 Hydrogen quality sampling at the hydrogen refuelling station lessons learnt on sampling at the production and at the nozzle International Journal of Hydrogen Energy 22nd World Hydrogen Energy Conference 45 8 5565 5576 doi 10 1016 j ijhydene 2019 10 178 hdl 11250 2689927 ISSN 0360 3199 S2CID 213820032 Arrhenius Karine Aarhaug Thor Bacquart Thomas Morris Abigail Bartlett Sam Wagner Lisa Blondeel Claire Gozlan Bruno Lescornez Yann Chramosta Nathalie Spitta Christian 2021 10 11 Strategies for the sampling of hydrogen at refuelling stations for purity assessment International Journal of Hydrogen Energy 46 70 34839 34853 doi 10 1016 j ijhydene 2021 08 043 hdl 11250 3010363 ISSN 0360 3199 S2CID 239636011 Practice for Sampling of High Pressure Hydrogen and Related Fuel Cell Feed Gases ASTM International doi 10 1520 d7606 17 retrieved 2021 11 01 DIN ISO TS 22002 3 2017 09 retrieved 2021 11 01 Murugan Arul Brown Andrew S 2015 03 22 Review of purity analysis methods for performing quality assurance of fuel cell hydrogen International Journal of Hydrogen Energy 40 11 4219 4233 doi 10 1016 j ijhydene 2015 01 041 ISSN 0360 3199 Hydrogen purity NPLWebsite Retrieved 2021 10 18 Bacquart Thomas Arrhenius Karine Persijn Stefan Rojo Andres Aupretre Fabien Gozlan Bruno Moore Niamh Morris Abigail Fischer Andreas Murugan Arul Bartlett Sam 2019 12 31 Hydrogen fuel quality from two main production processes Steam methane reforming and proton exchange membrane water electrolysis Journal of Power Sources 444 227170 Bibcode 2019JPS 44427170B doi 10 1016 j jpowsour 2019 227170 ISSN 0378 7753 S2CID 208754564 Mukundan Rangachary 2020 Development of an Electrochemical Hydrogen Contaminant Detector Journal of the Electrochemical Society 167 14 147507 Bibcode 2020JElS 167n7507M doi 10 1149 1945 7111 abc43a S2CID 226341724 Noda Z Hirata K Hayashi A Takahashi T Nakazato N Saigusa K Seo A Suzuki K Ariura S Shinkai H Sasaki K 2017 02 02 Hydrogen pump type impurity sensors for hydrogen fuels International Journal of Hydrogen Energy 42 5 3281 3293 doi 10 1016 j ijhydene 2016 12 066 ISSN 0360 3199 HydrogenSense www vandf com Retrieved 2021 10 27 External links edit3 industrial hydrogen purifier systems Archived 2007 07 15 at the Wayback Machine Power and Energy Inc Setting a new benchmark for hydrogen delivery Retrieved from https en wikipedia org w index php title Hydrogen purification amp oldid 1223324517, wikipedia, wiki, book, books, library,

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