Skip to main content
SpringerLink
Log in

Adsorption properties of BEA zeolites and their aluminum phosphate extrudates for purification of isomaltose

  • Published:
Adsorption Aims and scope Submit manuscript

Abstract

The disaccharide isomaltose is produced via an enzymatic reaction and is adsorbed to BEA zeolite. This reaction integrated adsorption can be achieved as fluidized bed as well as fixed bed. We investigated isotherms, adsorption enthalpies and sorption kinetics of BEA zeolite and extrudates with a novel aluminum phosphate sintermatrix. These extrudates contain 50% (w/w) of BEA 150 zeolites (Si/Al = 75) as primary crystals. BET-surface for extrudates is 245 m2⋅g−1 and 487 m2⋅g−1 for zeolite. Extrudates show a monomodal macropore structure with a maximum at 90 nm. All isotherms show a type I shape. For lower equilibrium concentrations, which occur during the enzymatic reaction, Henry’s law is applied and compared to a Langmuir model. Adsorption equilibrium constant K i,L calculated from Langmuir for extrudates at 4 °C is 64.7 mL⋅g−1 and more than twice as high as obtained from Henry’s law with K i is 26.8 mL⋅g−1. Adsorption on extrudates at 4 °C is much stronger than on zeolite crystals where the Henry coefficient K i is 17.1 mL⋅g−1. Adsorption enthalpy Δh Ad calculated from van’t Hoff plot with the Henry equation is −44.3 kJ⋅mol−1 for extrudates and −29.6 kJ⋅mol−1 for zeolite crystals. Finally, the kinetics for ad- and desorption were calculated from the initial slope. The diffusion rate for ad- and desorption on extrudates were in the same range while adsorption on zeolites is three orders of magnitudes faster than desorption.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

Abbreviations

A :

External area of adsorbent, m2

b i :

Langmuir parameter for component i, L⋅g−1

c e :

Equilibrium concentration, g⋅L−1

c i :

Initial concentration, g⋅L−1

d crit :

Critical diameter of a molecule, nm

d cry,ex :

Diameter of primary crystals in extrudates, nm

d cry :

Diameter of zeolite crystals, μm

dp :

Diameter of pores, nm

D :

Diffusion coefficient, m2⋅s−1

Δh Ad :

Adsorption enthalpy, kJ⋅mol−1

K i :

Henry coefficient for component i, mL⋅g−1

K i,L :

Adsorption equilibrium constant calculated from Langmuir parameters, mL⋅g−1

l ex :

Length of extrudates, mm

m Ad :

Mass of adsorbent, g

m 0 :

Mass of solvent, g

q 0 :

Loading at t=0 s, mg⋅g−1

q i :

Loading of component i, mg⋅g−1

q s :

Saturation loading of water, mg⋅g−1

q i,max  :

Saturation loading of component i, mg⋅g−1

\(q_{i}^{\mathrm{Ex}}\) :

Excess loading of component i, mg⋅g−1

q t :

Loading at t, mg⋅g−1

q ∞ :

Loading at equilibrium, mg⋅g−1

r cry,ex :

Radius of primary crystals in extrudates, nm

r cry :

Radius of zeolite crystals, μm

r ex :

Radius of extrudates, mm

R :

Ideal gas constant 8.3144, J⋅K−1⋅mol−1

t :

Time, s

T :

Absolute temperature, K

V :

Volume of adsorbent, m3

V L :

Volume of liquid solvent during adsorption, mL

ϑ :

Temperature, °C

References

  • Baerlocher, C., McCusker, L.B., Olson, D.H.: Atlas of Zeolite Framework Types. Elsevier, Amsterdam (2007)

    Google Scholar 

  • Berensmeier, S., Buchholz, K.: Separation of isomaltose from high sugar concentrated enzyme reaction mixture by dealuminated [beta]-zeolite. Sep. Purif. Technol. 38, 129–138 (2004)

    Article  CAS  Google Scholar 

  • Breck, D.W.: Zeolite Molecular Sieves. Wiley, New York (1974)

    Google Scholar 

  • Buchholz, K., Seibel, J.: Enzymatic oligosaccharide synthesis. In: Flickinger, M.C. (ed.) Encyclopedia of Industrial Biotechnology. Bioprocess, Bioseparation, and Cell Technology, vol. 6, pp. 2049–2054. Wiley-Blackwell, Oxford (2010)

    Google Scholar 

  • Buttersack, C.: Separation by adsorption chromatography or membranes. Zuckerind. 124, 846–858 (1999)

    CAS  Google Scholar 

  • Buttersack, C., Fornefett, I., Mahrholz, J., Buchholz, K.: Specific adsorption from aqueous phase on apolar zeolites. In: Hakze Chon, S.-K.I.a.Y.S.U. (ed.) Progress in Zeolite and Microporous Materials, Proceedings of the 11th International Zeolite Conference. Stud. Surf. Sci. Catalysis, vol. 82(2), pp. 1723–1730. Elsevier, Amsterdam (1997)

    Chapter  Google Scholar 

  • Buttersack, C., Perlberg, A.: 18-O-02—Amino acids in BEA type channels. Stud. Surf. Sci. Catal. 135, 143 (2001)

    Article  Google Scholar 

  • Buttersack, C., Rudolph, H., Mahrholz, J., Buchholz, K.: High specific interaction of polymers with the pores of hydrophobic zeolites. Langmuir 12, 3101–3106 (1996)

    Article  CAS  Google Scholar 

  • Buttersack, C., Wach, W., Buchholz, K.: Specific adsorption of saccharides by dealuminated Y-zeolites. J. Phys. Chem. 97, 11861–11864 (1993)

    Article  CAS  Google Scholar 

  • Buttersack, C., Wach, W., Buchholz, K.: Adsorption of glucose and fructose containing disaccharides on different faujasites. In: Weitkamp, H.G.K.J., Pfeifer, H., Hölderich, W. (eds.) Zeolites and Related Microporous Materials: State of the Art 1994, Proceedings of the 10th International Zeolite Conference. Stud. Surf. Sci. Catalysis, vol. 84, pp. 1363–1371. Elsevier, Amsterdam (1994)

    Chapter  Google Scholar 

  • Chen, N.Y., Degnan, T.F., Smith, C.M.: Molecular Transport and Reaction in Zeolites. VCH, New York (1994)

    Google Scholar 

  • Diercks, R., Arndt, J.-D., Freyer, S., Geier, R., Machhammer, O., Schwartze, J., Volland, M.: Raw material changes in the chemical industry. Chem. Eng. Technol. 31, 631–637 (2008)

    Article  CAS  Google Scholar 

  • Ergezinger, M., Bohnet, M., Berensmeier, S., Bucholz, K.: Integrated enzymatic synthesis and adsorption of isomaltose in a multiphase fluidized bed reactor. Eng. Life Sci. 6, 481–487 (2006)

    Article  CAS  Google Scholar 

  • Erhardt, F.A.: Tailor-made biocatalysts for integrated adsorption and synthesis of saccharides in a multiphase reactor. Ph.D. Thesis, Technische Universität Braunschweig, Germany (2008)

  • Fornefett, I.: Adsorption und Chromatographie von Kohlenhydraten und anderen Hydroxyverbindungen an Zeolithen. Ph.D. Thesis, Technische Universität Braunschweig, Germany, Papierflieger, Clausthal-Zellerfeld (1999)

  • Freiding, J., Patcas, F.-C., Kraushaar-Czarnetzki, B.: Extrusion of zeolites: properties of catalysts with a novel aluminium phosphate sintermatrix. Appl. Catal. A, Gen. 328, 210–218 (2007)

    Article  CAS  Google Scholar 

  • Garg, D.R., Ruthven, D.M.: The effect of the concentration dependence of diffusivity on zeolitic sorption curves. Chem. Eng. Sci. 27, 417–423 (1972)

    Article  CAS  Google Scholar 

  • Heper, M., Türker, L., Kincal, N.S.: Sodium, ammonium, calcium, and magnesium forms of zeolite Y for the adsorption of glucose and fructose from aqueous solutions. J. Colloid Interface Sci. 306, 11–15 (2007)

    Article  CAS  Google Scholar 

  • Hicks, K.B., Symanski, E.V., Pfeffer, P.E.: Synthesis and high-performance liquid chromatography of maltulose and cellobiulose. Carbohydr. Res. 112, 37 (1983)

    Article  CAS  Google Scholar 

  • Holtkamp, M., Erhardt, F.A., Jördening, H.-J., Scholl, S.: Reaction-integrated separation of isomaltose by ad- and desorption on zeolite. Chem. Eng. Process., Process Intensif. 48, 852–858 (2009)

    Article  CAS  Google Scholar 

  • Jördening, H.-J., Erhardt, F.A., Holtkamp, M., Buchholz, K., Scholl, S.: Verfahrens- und Katalysatordesign als Aufarbeitungsstrategie für die enzymatische Darstellung von Isomaltose. Chem. Ing. Tech. 80, 867–874 (2008)

    Article  Google Scholar 

  • Kiyosawa, K.: The volumes of hydrated glucose, sucrose and raffinose molecules, and the osmotic pressures of these aqueous saccharide solutions as measured by the freezing-point-depression method. Bull. Chem. Soc. Jpn. 61, 633–642 (1988)

    Article  CAS  Google Scholar 

  • Langmuir, I.: The adsorption of gases on plane surfaces of glass, mica and platinum. J. Am. Chem. Soc. 40, 1361–1403 (1918)

    Article  CAS  Google Scholar 

  • Lima, P.M., Gonçalves, C.V., Cavalcante, C.L. Jr., Cardoso, D.: Sorption kinetics of linear paraffins in zeolite BEA nanocrystals. Microporous Mesoporous Mater. 116, 352–357 (2008)

    Article  CAS  Google Scholar 

  • Miyake, T., Sakai, S., Shibuya, T.: Process for producing a high-purity isomaltose, USA, Patent 4,521,252 (1985)

  • Moore, R.M., Katzer, J.R.: Counterdiffusion of liquid hydrocarbons in type Y zeolite: effect of molecular size, molecular type, and direction of diffusion. AIChE J. 18, 816–824 (1972)

    Article  CAS  Google Scholar 

  • Newsam, J.M., Treacy, M.M.J., Koetsier, W.T., Gruyter, C.B.D.: Structural characterization of zeolite beta. Proc. R. Soc. Lond. A 420, 375–405 (1988)

    Article  CAS  Google Scholar 

  • Pereira, C.S., Kony, D., Baron, R., Müller, M., van Gunsteren, W.F., Hünenberger, P.H.: Conformational and dynamical properties of disaccharides in water: a molecular dynamics study. Biophys. J. 90, 4337–4344 (2006)

    Article  CAS  Google Scholar 

  • Pigman, W., Horton, D.: The Carbohydrates/Chemistry and Biochemistry, vol. 2(A). Academic Press, New York (1970)

    Google Scholar 

  • Reitmeier, S.J., Gobin, O.C., Jentys, A., Lercher, J.A.: Enhancement of sorption processes in the zeolite H-ZSM5 by postsynthetic surface modification. Angew. Chem., Int. Ed. Engl. 48, 533–538 (2009)

    Article  CAS  Google Scholar 

  • Ruthven, D.M.: Principles of Adsorption and Adsorption Processes. Wiley, New York (1984)

    Google Scholar 

  • Schulthess, C.P., Dey, D.K.: Estimation of Langmuir constants using linear and nonlinear least squares regression analyses. Soil Sci. Soc. Am. J. 60, 433–441 (1996)

    Article  CAS  Google Scholar 

  • Seeberger, P.H., Werz, D.B.: Synthesis and medical applications of oligosaccharides. Nature 446, 1046–1051 (2007)

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institute for Chemical and Thermal Process Engineering, Technische Universität Braunschweig, Langer Kamp 7, 38106, Braunschweig, Germany

    Manuel Holtkamp & Stephan Scholl

Authors
  1. Manuel Holtkamp
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Stephan Scholl
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Stephan Scholl.

Additional information

Presented at FoA 10—10th International Conference on Fundamentals of Adsorption.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Holtkamp, M., Scholl, S. Adsorption properties of BEA zeolites and their aluminum phosphate extrudates for purification of isomaltose. Adsorption 17, 801–811 (2011). https://doi.org/10.1007/s10450-011-9339-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10450-011-9339-1

Keywords

Search

Navigation