Heat and Mass Transfer

, Volume 55, Issue 11, pp 3179–3187 | Cite as

Improved desorption performance of NaA zeolite by rare earth (Re = La, Nd) ion exchange

  • Bingqiong Tan
  • Yanshu Luo
  • Xiaoyun Bi
  • Xianghui Liang
  • Shuangfeng Wang
  • Xuenong Gao
  • Zhengguo Zhang
  • Yutang FangEmail author


With a characteristic of type I water adsorption isotherms, NaA zeolite has been considered as a very promising candidate for the utilization in adsorptive rotary wheel dehumidification system for deep dehumidification. However, high desorption temperature of the zeolite is not conducive to the system energy saving. In this research, the La-modified, Nd-modified and the binary La/Nd-modified NaA zeolites were synthesized by microwave-assisted ionexchangemethod to reduce the desorption temperature. The structural and the composition of the modified products were characterized using X-ray diffraction (XRD) and X-ray Energy Dispersive Spectrometry (EDS), and their adsorption/desorption performances were evaluated by static adsorption, thermogravimetry (TG) and temperature programmed desorption (TPD). TG results exhibited that, Nd-modified zeolite with the highest ion-exchange degree (α) of 63.35% was more effective in reducing the desorption temperature of NaA zeolite. TPD analysis also demonstrated that the binary modified adsorbent had a lower desorption activation energy (Ed), which indicates that the binary modified zeolite as deep dehumidification adsorbent has an excellent desorption performance.


NaA zeolite Rare earth Ion-exchange Desorption performance Deep dehumidification 



This work was supported by the National Natural Science Foundation of China [No. 51536003, 21471059].

Compliance with ethical standards

Conflict of interest

On behalf of all authors, the corresponding author states that there is no conflict of interest.


  1. 1.
    Enteria N, Mizutani K (2011) The role of the thermally activated desiccant cooling technologies in the issue of energy and environment. Renew Sust Energ Rev 15:2095–2122Google Scholar
  2. 2.
    Madhiyanon T, Adirekrut S, Sathitruangsak P, Soponronnarit S (2007) Integration of a rotary desiccant wheel into a hot-air drying system: Drying performance and product quality studies. Chem Eng Process Process Intensif 46:282–290Google Scholar
  3. 3.
    T. Hachimaki (2003) Hollow fiber membrane dehumidification device, Google PatentsGoogle Scholar
  4. 4.
    Min J, Webb RL (2000) Condensate carryover phenomena in dehumidifying, finned-tube heat exchangers. Exp Thermal Fluid Sci 22:175–182Google Scholar
  5. 5.
    Tso CY, Chao CY (2012) Activated carbon, silica-gel and calcium chloride composite adsorbents for energy efficient solar adsorption cooling and dehumidification systems. Int J Refrig 35:1626–1638Google Scholar
  6. 6.
    Fang YT, Hu YH, Liang XH, Wang SF, Zuo SQ, Gao XN, Zhang ZG (2018) Microwave hydrothermal synthesis and performance of NaA zeolite monolithic adsorbent with honeycomb ceramic matrix. Microporous Mesoporous Mater 259:116–122Google Scholar
  7. 7.
    Rambhad KS, Walke PV, Tidke DJ (2016) Solid desiccant dehumidification and regeneration methods-A review. Renew Sust Energ Rev 59:73–83Google Scholar
  8. 8.
    Jain S, Bansal P (2007) Performance analysis of liquid desiccant dehumidification systems. Int J Refrig 30:861–872Google Scholar
  9. 9.
    Fang Y, Liu T, Zhang Z, Gao X (2014) Silica gel adsorbents doped with Al, Ti, and Co ions improved adsorption capacity, thermal stability and aging resistance. Renew Energy 63:755–761Google Scholar
  10. 10.
    Beck J, Vartuli J, Roth WJ, Leonowicz M, Kresge C, Schmitt K, Chu C, Olson DH, Sheppard E, McCullen S (1992) A new family of mesoporous molecular sieves prepared with liquid crystal templates. J Am Chem Soc 114:10834–10843Google Scholar
  11. 11.
    Katiyar A, Yadav S, Smirniotis PG, Pinto NG (2006) Synthesis of ordered large pore SBA-15 spherical particles for adsorption of biomolecules. J Chromatogr A 1122:13–20Google Scholar
  12. 12.
    Kakiuchi H, Shimooka S, Iwade M, Oshima K, Yamazaki M, Terada S, Watanabe H, Takewaki T (2005) Novel water vapor adsorbent FAM-Z01 and its applicability to an adsorption heat pump. Kagaku Kogaku Ronbunshu 31:361–364Google Scholar
  13. 13.
    Oshima K, Yamazaki M, Takewaki T, Kakiuchi H, Kodama A (2006) Application of novel FAM adsorbents in a desiccant system. Kagaku Kogaku Ronbunshu 32:518–523Google Scholar
  14. 14.
    Ammann J, Michel B, Ruch PW (2019) Characterization of transport limitations in SAPO-34 adsorbent coatings for adsorption heat pumps. Int J Heat Mass Tran 129:18–27Google Scholar
  15. 15.
    Yuan ZX, Zhang X, Wang WC, Du CX, Liu Z, Chen YC (2018) Experimental study on desorption characteristics of SAPO-34 and ZSM-5 zeolite. Heat Mass Transf 54:895–902Google Scholar
  16. 16.
    Ji J, Wang R, Li L (2007) New composite adsorbent for solar-driven fresh water production from the atmosphere. Desalination 212:176–182Google Scholar
  17. 17.
    Shimooka S, Oshima K, Hidaka H, Takewaki T, Kakiuchi H, Kodama A, Kubota M, Matsuda H (2007) The evaluation of direct cooling and heating desiccant device coated with FAM. Journal of chemical engineering of Japan 40:1330–1334Google Scholar
  18. 18.
    Kim H, Yang S, Rao SR, Narayanan S, Kapustin EA, Furukawa H, Umans AS, Yaghi OM, Wang EN (2017) Water harvesting from air with metal-organic frameworks powered by natural sunlight. Science 356:430–432Google Scholar
  19. 19.
    Furukawa H, Gandara F, Zhang YB, Jiang JC, Queen WL, Hudson MR, Yaghi OM (2014) Water Adsorption in Porous Metal-Organic Frameworks and Related Materials. J Am Chem Soc 136:4369–4381Google Scholar
  20. 20.
    Seo YK, Yoon JW, Lee JS, Hwang YK, Jun CH, Chang JS, Wuttke S, Bazin P, Vimont A, Daturi M, Bourrelly S, Llewellyn PL, Horcajada P, Serre C, Ferey G (2012) Energy-Efficient Dehumidification over Hierachically Porous Metal-Organic Frameworks as Advanced Water Adsorbents. Adv Mater 24:806Google Scholar
  21. 21.
    Henninger SK, Ernst SJ, Gordeeva L, Bendix P, Frohlich D, Grekova AD, Bonaccorsi L, Aristov Y, Jaenchen J (2017) New materials for adsorption heat transformation and storage. Renew Energy 110:59–68Google Scholar
  22. 22.
    Tan BQ, Luo YS, Liang XH, Wang SF, Gao XN, Zhang ZG, Fang YT (2019) Mixed-Solvothermal Synthesis of MIL-101(Cr) and Its Water Adsorption/Desorption Performance. Ind Eng Chem Res 58:2983–2990Google Scholar
  23. 23.
    Solovyeva MV, Gordeeva LG, Krieger TA, Aristov YI (2018) MOF-801 as a promising material for adsorption cooling: Equilibrium and dynamics of water adsorption. Energ Convers Manage 174:356–363Google Scholar
  24. 24.
    Jeremias F, Khutia A, Henninger SK, Janiak C (2012) MIL-100(Al, Fe) as water adsorbents for heat transformation purposes-a promising application. J Mater Chem 22:10148–10151Google Scholar
  25. 25.
    Frohlich D, Pantatosaki E, Kolokathis PD, Markey K, Reinsch H, Baumgartner M, van der Veen MA, De Vos DE, Stock N, Papadopoulos GK, Henninger SK, Janiak C (2016) Water adsorption behaviour of CAU-10-H: a thorough investigation of its structure-property relationships. J Mater Chem A 4:11859–11869Google Scholar
  26. 26.
    Kummer H, Jeremias F, Warlo A, Fuldner G, Frohlich D, Janiak C, Glaser R, Henninger SK (2017) A Functional Full-Scale Heat Exchanger Coated with Aluminum Fumarate Metal-Organic Framework for Adsorption Heat Transformation. Ind Eng Chem Res 56:8393–8398Google Scholar
  27. 27.
    Kalmutzki MJ, Diercks CS, Yaghi OM (2018) Metal-Organic Frameworks for Water Harvesting from Air. Adv Mater 30Google Scholar
  28. 28.
    Higgins FM (2002) Modelling the effect of water on cation exchange in zeolite A. J Mater Chem 12:124–131Google Scholar
  29. 29.
    Holmberg BA, Wang H, Yan YS (2004) High silica zeolite Y nanocrystals by dealumination and direct synthesis. Microporous Mesoporous Mater 74:189–198Google Scholar
  30. 30.
    Janchen J, Stach H (2014) Shaping adsorption properties of nano-porous molecular sieves for solar thermal energy storage and heat pump applications. Sol Energy 104:16–18Google Scholar
  31. 31.
    Herzog TH, Jaenchen J, Kontogeorgopoulos EM, Lutz W (2014) Steamed zeolites for heat pump applications and solar driven thermal adsorption storage. Enrgy Proced 48:380–383Google Scholar
  32. 32.
    Ristic A, Fischer F, Hauer A, Logar NZ (2018) Improved performance of binder-free zeolite Y for low-temperature sorption heat storage. J Mater Chem A 6:11521–11530Google Scholar
  33. 33.
    Athens GL, Shayib RM, Chmelka BF (2009) Functionalization of mesostructured inorganic-organic and porous inorganic materials. Curr Opin Colloid In 14:281–292Google Scholar
  34. 34.
    Janchen J, Ackermann D, Stach H, Brosicke W (2004) Studies of the water adsorption on Zeolites and modified mesoporous materials for seasonal storage of solar heat. Sol Energy 76:339–344Google Scholar
  35. 35.
    Li XS, Narayanan S, Michaelis VK, Ong TC, Keeler EG, Kim H, Mckay IS, Griffin RG, Wang EN (2015) Zeolite Y adsorbents with high vapor uptake capacity and robust cycling stability for potential applications in advanced adsorption heat pumps. Microporous Mesoporous Mater 201:151–159Google Scholar
  36. 36.
    Aprea P, de Gennaro B, Gargiulo N, Peluso A, Liguori B, Iucolano F, Caputo D (2016) Sr-, Zn- and Cd-exchanged zeolitic materials as water vapor adsorbents for thermal energy storage applications. Appl Therm Eng 106:1217–1224Google Scholar
  37. 37.
    FANG Y, GUO J, LI D, GAO X (2011) Characterization and performance of rare-earth modified molecular sieve. CIESC Journal:6Google Scholar
  38. 38.
    Zhang L, Liu H, Li X, Xie S, Wang Y, Xin W, Liu S, Xu L (2010) Differences between ZSM-5 and ZSM-11 zeolite catalysts in 1-hexene aromatization and isomerization. Fuel Process Technol 91:449–455Google Scholar
  39. 39.
    Pan HH, Ming-Yuan HE, Song JQ, Tian HP, Zhu YX (2007) Study on lanthanum cation location in LaY Zeolite. Acta Pet Sin 23:87–91Google Scholar
  40. 40.
    Yoshikawa N, Mikoshiba S, Sumi T, Taniguchi S (2017) Model experimental study on Cs removal from clay minerals by ion exchange under microwave irradiation. Chem Eng Process Process Intensif 115:56–62Google Scholar
  41. 41.
    Akdeniz Y, Ulku S (2007) Microwave effect on ion-exchange and structure of clinoptilolite. J Porous Mat 14:55–60Google Scholar
  42. 42.
    Helfferich FG (1995) Ion exchange, Courier CorporationGoogle Scholar
  43. 43.
    Kissinger HE (1957) Reaction Kinetics in Differential Thermal Analysis. Anal Chem 29:1702–1706Google Scholar
  44. 44.
    Xu C, Zhou C, Wang S, Huang A (2019) Copper-exchanged LTA zeolite membranes with enhanced water flux for ethanol dehydration. Chin Chem Lett. Google Scholar
  45. 45.
    Onyango MS, Kojima Y, Aoyi O, Bernardo EC, Matsuda H (2004) Adsorption equilibrium modeling and solution chemistry dependence of fluoride removal from water by trivalent-cation-exchanged zeolite F-9. J Colloid Interf Sci 279:341–350Google Scholar
  46. 46.
    Alby D, Salles F, Fullenwarth J, Zajac J (2018) On the use of metal cation-exchanged zeolites in sorption thermochemical storage: Some practical aspects in reference to the mechanism of water vapor adsorption. Sol Energ Mat Sol C 179:223–230Google Scholar
  47. 47.
    Walton KS, Abney MB, Douglas LeVan M (2006) CO2 adsorption in Y and X zeolites modified by alkali metal cation exchange. Microporous Mesoporous Mater 91:78–84Google Scholar
  48. 48.
    Li X, Li Z, Xia QB, Xi HX (2007) Effects of pore sizes of porous silica gels on desorption activation energy of water vapour. Appl Therm Eng 27:869–876Google Scholar
  49. 49.
    Jacobs PA, Mortier WJ (1982) An attempt to rationalize stretching frequencies of lattice hydroxyl groups in hydrogen-zeolites. Zeolites 2:226–230Google Scholar
  50. 50.
    Yu MX, Li Z, Xia QB, Xi HX, Wang SW (2007) Desorption activation energy of dibenzothiophene on the activated carbons modified by different metal salt solutions. Chem Eng J 132:233–239Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Key Laboratory of Enhanced Heat Transfer and Energy Conservation, The Ministry of Education, School of Chemistry and Chemical EngineeringSouth China University of TechnologyGuangzhouChina

Personalised recommendations