Adsorption

, Volume 21, Issue 4, pp 307–320 | Cite as

Saturation loadings on 13X (faujasite) zeolite above and below the critical conditions. Part I: alkane data evaluation and modeling

  • Alaa Al Mousa
  • Dana Abouelnasr
  • Kevin F. Loughlin
Article

Abstract

The saturation loadings for subcritical adsorption of n-, iso- and neo alkanes C1–C8 in 13X zeolite are modeled using the modified Rackett model of Spencer and Danner (J Chem Eng Data 17:236–240, 1972) for the saturated liquid densities combined with crystallographic data for the 13X zeolite. For validation of this model, alkane adsorption data in the literature is first critically evaluated and then compared to the model. The saturation loading of each isotherm that approaches saturation is extracted from the data. Log–log plots are used to determine whether each isotherm is near saturation; isotherms that exhibit a \(({{\partial \text{ \ ln \ } q)} \mathord{\left/ ({\vphantom {{\partial { \ ln \ } q} {\partial { \ ln \ }p}}} \right. \kern-0pt} {\partial \text { \ ln \ }p}})\) slope of zero at their maximum pressure point are assumed to be saturated. Isotherms not fulfilling this criterion are deemed unsaturated and not considered further. The theoretical equation satisfactorily models the available experimental data for the n- alkanes. However, steric factors are required for the model to fit iso alkanes and neo-pentane. For supercritical temperatures, no model presently exists to explain the data. However, the data are satisfactorily modeled with an equation of the form qmax = 8.5 ± 2.5 g/100 g.

Keywords

Alkanes C1–C8 13X zeolite Sorbate densities Saturation loadings Sorbate molar volumes Critical conditions 

List of symbols

Variables

MW

Molecular weight (g/mol)

Pc

Critical pressure (kPa)

Pr

Reduced pressure

q

Zeolite loading (g/100 g zeolite crystal)

qmax

Maximum zeolite loading (g/100 g zeolite crystal)

qmax,c

Theoretical maximum zeolite loading at the critical temperature, defined by Eq. 5 (g/100 g zeolite crystal)

R

Gas constant (8314 kPa-cm3/gmol.K)

Tc

Critical temperature (K)

TCAR

Critical adsorbate reduced temperature (K)

Tr

Reduced temperature

Vsat

Saturated liquid volume (cm3/g)

ZRA

Rackett parameter

Greek letters

Γ

Normalized loading, dimensionless, calculated in Eqs. 6 and 7

εZ

Crystallographic 13X zeolite void fraction, 0.428 (Breck 1974, p. 133)

λ

Steric factor, used in Eq. 8

ρsat

Sorbate liquid density, g adsorbate/cm3)

ρZ

Zeolite 13X crystallographic density, 1.43 g/cm3, (Breck 1974, p. 133)

Notes

Acknowledgments

This is a detailed manuscript of a paper presented at the Fall 2011 conference of AICHE. The authors wish to acknowledge the support of the American University of Sharjah and the California State University at Bakersfield during this study. The authors also wish to acknowledge anonymous reviewers for their comments on steric factors.

Supplementary material

10450_2015_9672_MOESM1_ESM.tif (89 kb)
Fig. S1 qmax calculated from Rackett’s equation and crystal properties for n-alkanes C1 through C8 as a function of reduced temperature. A dashed line is used when Tr is above the TCAR for 5A zeolite (Loughlin and Abouelnasr 2009) for the given species. (TIF 90 kb)
10450_2015_9672_MOESM2_ESM.tif (103 kb)
Fig. S2a Methane isotherms before screening. Labels are reduced temperatures. Isotherms in grey are inconsistent with others, and so are screened out. Deleted points are in grey. (TIF 104 kb)
10450_2015_9672_MOESM3_ESM.tif (106 kb)
Fig. S2b Methane isotherms after screening. Labels are reduced temperatures. Isotherms that attain saturation have a solid line. Isotherms that are not near saturation have a dotted line. (TIF 106 kb)
10450_2015_9672_MOESM4_ESM.tif (92 kb)
Fig. S2c Log-log plot of methane isotherms. Labels are reduced temperatures. Isotherms that attain saturation have a solid line. Isotherms that are not near saturation have a dotted line. (TIF 93 kb)
10450_2015_9672_MOESM5_ESM.tif (112 kb)
Fig. S3a Ethane isotherms. Labels are reduced temperatures. Isotherms that attain saturation have a solid line. Isotherms that are not near saturation have a dotted line. (TIF 113 kb)
10450_2015_9672_MOESM6_ESM.tif (111 kb)
Fig. S3b Log–log plot of ethane isotherms. Labels are reduced temperatures. Isotherms that attain saturation have a solid line. Isotherms that are not near saturation have a dotted line. (TIF 111 kb)
10450_2015_9672_MOESM7_ESM.tif (149 kb)
Fig. S4a Propane isotherms before screening. Labels are reduced temperatures. Isotherms in grey are inconsistent with others and so are screened out. Deleted points are in grey. Isotherms that attain saturation have a solid line. Isotherms that are not near saturation have a dotted line. (TIF 150 kb)
10450_2015_9672_MOESM8_ESM.tif (122 kb)
Fig. S4b Log–log plot of propane isotherms. Labels are reduced temperatures. Isotherms that attain saturation have a solid line. Isotherms that are not near saturation have a dotted line. (TIF 122 kb)
10450_2015_9672_MOESM9_ESM.tif (46 kb)
Fig. S5a n Butane isotherms. Labels are reduced temperatures. Isotherms that attain saturation have a solid line. (TIF 47 kb)
10450_2015_9672_MOESM10_ESM.tif (42 kb)
Fig. S5b Log–log plot of n butane isotherms. Labels are reduced temperatures. Isotherms that attain saturation have a solid line. (TIF 42 kb)
10450_2015_9672_MOESM11_ESM.tif (113 kb)
Fig. S6a Butane isotherms. Labels are reduced temperatures. Isotherms in grey are inconsistent with others, and so are screened out. Isotherms that attain saturation have a solid line. (TIF 113 kb)
10450_2015_9672_MOESM12_ESM.tif (99 kb)
Fig. S6b Log–log plot of iso butane isotherms. Labels are reduced temperatures. Isotherms that attain saturation have a solid line. (TIF 99 kb)
10450_2015_9672_MOESM13_ESM.tif (48 kb)
Fig. S7a n Pentane isotherms. Labels are reduced temperatures. Isotherms that attain saturation have a solid line. (TIF 49 kb)
10450_2015_9672_MOESM14_ESM.tif (42 kb)
Fig. S7b Log–log plot of n pentane isotherms. Labels are reduced temperatures. Isotherms that attain saturation have a solid line. (TIF 42 kb)
10450_2015_9672_MOESM15_ESM.tif (48 kb)
Fig. S8a iso Pentane isotherms. Labels are reduced temperatures. Isotherms that attain saturation have a solid line. (TIF 49 kb)
10450_2015_9672_MOESM16_ESM.tif (43 kb)
Fig. S8b Log–log plot of iso pentane isotherms. Labels are reduced temperatures. Isotherms that attain saturation have a solid line. (TIF 43 kb)
10450_2015_9672_MOESM17_ESM.tif (50 kb)
Fig. S9a neo Pentane isotherms. Labels are reduced temperatures. Isotherms that attain saturation have a solid line. (TIF 50 kb)
10450_2015_9672_MOESM18_ESM.tif (46 kb)
Fig. S9b Log–log plot of neo pentane isotherms. Labels are reduced temperatures. Isotherms that attain saturation have a solid line. (TIF 47 kb)
10450_2015_9672_MOESM19_ESM.tif (53 kb)
Fig. S10a n Hexane isotherms. Labels are reduced temperatures. Isotherms that are deleted are in grey. Isotherms that attain saturation have a solid line. (TIF 53 kb)
10450_2015_9672_MOESM20_ESM.tif (47 kb)
Fig. S10b Log–llog plot of n hexane isotherms. Labels are reduced temperatures. Isotherms that attain saturation have a solid line. (TIF 48 kb)
10450_2015_9672_MOESM21_ESM.tif (93 kb)
Fig. S11a n Heptane isotherms. Labels are reduced temperatures. Deleted points are in grey. Isotherms that attain saturation have a solid line. (TIF 93 kb)
10450_2015_9672_MOESM22_ESM.tif (85 kb)
Fig. S11b Log–log plot of n heptane isotherms. Labels are reduced temperatures. Isotherms that attain saturation have a solid line. (TIF 85 kb)
10450_2015_9672_MOESM23_ESM.tif (41 kb)
Fig. S12a n Octane isotherms before screening. Labels are reduced temperatures. Isotherms that attain saturation have a solid line. Data points in grey are deleted. (TIF 41 kb)
10450_2015_9672_MOESM24_ESM.tif (38 kb)
Fig. S12b Log–log plot of n octane isotherms. Labels are reduced temperatures. Isotherms that attain saturation have a solid line. (TIF 39 kb)
10450_2015_9672_MOESM25_ESM.tif (44 kb)
Fig. S13a iso Octane isotherms. Labels are reduced temperatures. Isotherms that attain saturation have a solid line. Data points in grey are deleted. (TIF 45 kb)
10450_2015_9672_MOESM26_ESM.tif (42 kb)
Fig. S13b Log–log plot of iso octane isotherms. Labels are reduced temperatures. Isotherms that attain saturation have a solid line. (TIF 43 kb)
10450_2015_9672_MOESM27_ESM.tif (72 kb)
Fig. S14 qmax vs. Tr for all alkanes. Bounding-lines for supercritical are at 6 and 11 g/100 g. (TIF 73 kb)
10450_2015_9672_MOESM28_ESM.tif (68 kb)
Fig. S15a Solid line is the theoretical plot of normalized parameter Г against reduced temperature, Eq. 6. Points are Γ derived from the observed values for qmax, per Eq. 7. (TIF 69 kb)
10450_2015_9672_MOESM29_ESM.tif (63 kb)
Fig. S15b Same as Figure 15a, but with Barrer and Sutherland data removed. (TIF 63 kb)
10450_2015_9672_MOESM30_ESM.tif (69 kb)
Fig. S15c Solid line is the theoretical plot of normalized parameter Г against reduced temperature, Eq. 6. Points are Γ derived from the observed values for qmax, per Eq. 7, for only branched alkanes. (TIF 69 kb)
10450_2015_9672_MOESM31_ESM.tif (67 kb)
Fig. S15d Solid line is the theoretical plot of normalized parameter Г against reduced temperature, Eq. 6. Points are Γ derived from the observed values for qmax, corrected by the steric factor per Eq. 7, for only branched alkanes. (TIF 68 kb)
10450_2015_9672_MOESM32_ESM.tif (69 kb)
Fig. S16 The model and observed qmax for all three isomers of pentane. The model for neo pentane with a steric factor of 0.8 is indicated by a dotted line. (TIF 69 kb)

References

  1. Al Mousa, A., Abouelnasr, M., Loughlin, K.: Saturated loadings on 13X (faujasite) zeolite above and below the critical conditions. Part II: unsaturated and cyclic hydrocarbons data evaluation and modeling, Adsorption (2015a). doi: 10.1007/s10450-015-9671-y
  2. Al Mousa, A., Abouelnasr, M., Loughlin, K.: Saturation loadings on 13X (faujasite) zeolite above and below the critical conditions. Part III: inorganic, and ethyl acetate data evaluation and modeling, unpublished work, (2015b)Google Scholar
  3. Barrer, R., Sutherland, J.W.: Inclusion complexes of faujasite with paraffins and permanent gases. Proc. R. Soc. Lond. A 237(1211), 439–463 (1956)CrossRefGoogle Scholar
  4. Breck, D.: Zeolite Molecular Sieves; Structure, Chemistry and Use. Wiley, New York (1974)Google Scholar
  5. Campo, M., Baptista, M., Ribeiro, A., Ferreira, A., Santos, J., Lutz, C., Rodrigues, A.: Gas phase SMB for propane/propylene separation using enhanced 13X zeolite beads. Adsorption 20, 61–75 (2014)CrossRefGoogle Scholar
  6. Campo, M., Ribeiro, A., Ferreira, A., Santos, J., Lutz, C., Loueiro, J.A.: New 13X zeolite for propylene/propane separation by vacuum swing adsorption. Sep. Purif. Technol. 103, 60–70 (2013)CrossRefGoogle Scholar
  7. Cavenati, S., Grande, C., Rodrigues, A.: Adsorption equilibrium of methane, carbon dioxide, and nitrogen on zeolite 13X at high pressures. J. Chem. Eng. Data 49(4), 1095–1101 (2004)CrossRefGoogle Scholar
  8. CHERIC. http:www.cheric.org/kdb/research/hcprop/cmpsrch.phpe. Accessed 27 Mar 2012
  9. Da Silva, F., Rodrigues, A.: Adsorption equilibria and kinetics for propylene and propane over 13X and 4A zeolite pellets. Ind. Eng. Chem. Res. 38(5), 2051–2057 (1999)CrossRefGoogle Scholar
  10. Hyun, S., Danner, R.P.: Equilibrium adsorption of ethane, ethylene, isobutane, carbon dioxide, and their binary mixtures on 13X molecular sieves. J. Chem. Eng. Data 27(2), 196–200 (1982)CrossRefGoogle Scholar
  11. Lamia, N., Wolff, L., Leflaive, P., Sa Gomes, P.: Propane/propylene separation by simulated moving bed I. Adsorption of propane, propylene and isobutane in pellets of 13X zeolite. Sep. Sci. Technol. 42(12), 2539–2566 (2007)CrossRefGoogle Scholar
  12. Lopes, F.V., Grande, C.A., Ribeiro, A.M., Loureiro, J.M., Evaggelos, O., Nikolakis, V., Rodrigues, A.E.: Adsorption of H2, CO2, CH4, CO, N2 and H2O in activated carbon and zeolite for hydrogen production. Sep. Sci. Technol. 44(5), 1045–1073 (2009)CrossRefGoogle Scholar
  13. Loughlin, K.F., Abouelnasr, D.M.: Sorbate densities on 5A zeolite above and below the critical conditions: n alkane data evaluation and modeing. Adsorption 15, 521–533 (2009)CrossRefGoogle Scholar
  14. Loughlin, K., Hasanain, M., Abdul-Rehman, H.: Quaternary, ternary, binary, and pure component sorption on zeolites. 2. light alkanes on Linde 5A and 13X zeolites at moderate to high pressures. Ind. Eng. Chem. Res. 29(7), 1535–1546 (1990)CrossRefGoogle Scholar
  15. Narin, G., Martins, V.F., Campo, M.R.A., Ferreira, A., Santos, J.C., Rodrigues, A.E.: Light olefins/paraffins separation with 13X zeolite binderless beads. Sep. Purif. Technol. 133, 452–475 (2014)CrossRefGoogle Scholar
  16. Rolniak, P.D., Kobayashi, R.: Adsorption of methane and several mixtures of methane and carbon dioxide at elevated pressures and near ambient temperatures on 5A and 13X molecular sieves by tracer perturbation chromatography. AIChE J. 26(4), 616–625 (1980)CrossRefGoogle Scholar
  17. Ruthven, D., Doetsch, I.: Diffusion of hydrocarbons in 13X zeolite. AIChE J. 22(5), 882–886 (1976)CrossRefGoogle Scholar
  18. Salem, M.M., Braeuer, P., Szombathely, M.V., Heuchel, M., Harting, P., Quitzsch, K.: Thermodynamics of high-pressure adsorption of argon, nitrogen, and methane on microporous adsorbents. Langmuir 14(12), 3376–3389 (1998)CrossRefGoogle Scholar
  19. Spencer, C., Danner, R.: Improved equation for prediction of saturated liquid density. J. Chem. Eng. Data 17(2), 236–240 (1972)CrossRefGoogle Scholar
  20. van Miltenburg, A., Gascon, J., Zhu, W., Kapteijn, F., Moulijn, J.A.: Propylene/propane mixture adsorption on faujasite sorbents. Adsorption 14(2–3), 309–321 (2008)CrossRefGoogle Scholar
  21. Vermesse, J., Vidal, D., Malbrunot, P.: Gas adsorption on zeolites at high pressure. Langmuir 12(17), 4190–4196 (1996)CrossRefGoogle Scholar
  22. Zhdanov, S.P., Kiselev, A.V., Pavlova, L.F.: Adsorption of benzene and n-hexane and their liquid solutions by 10X and 13X zeolites. Kinet. Katal. 3(3), 391–394 (1962)Google Scholar

Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  • Alaa Al Mousa
    • 1
  • Dana Abouelnasr
    • 2
    • 3
  • Kevin F. Loughlin
    • 2
  1. 1.Petrofac International LtdSharjahUAE
  2. 2.Department of Chemical EngineeringAmerican University of SharjahSharjahUAE
  3. 3.California State University at BakersfieldBakersfieldUSA

Personalised recommendations