Adsorption

, Volume 24, Issue 1, pp 81–94 | Cite as

Saturation loadings on 13X (Faujasite) zeolite above and below the critical conditions. Part IV: inorganic multi-atomic species, halocarbons and oxygenated hydrocarbons data evaluation and modeling

  • Kevin F. Loughlin
  • Dana Abouelnasr
  • Alaa al Mousa
Article
  • 44 Downloads

Abstract

The saturation loadings for subcritical adsorption of multi-atomic inorganic species, halocarbons and oxygenated hydrocarbons on 13X zeolite are modeled using the modified Rackett model of Spencer and Danner (J. Chem. Eng. Data 17(2):236–240, 1972) for the saturated liquid densities combined with crystallographic data for the 13X zeolite. A similar equation is used for supercritical adsorption involving supercritical adsorbate densities and crystallographic data for the 13X zeolite employing a different f(Tr) expression than used by Spencer and Danner. Adsorption data from the literature are first critically evaluated and then compared to the model. Log–log plots are used to determine whether each isotherm is near saturation; isotherms that exhibit a \(\left( {\partial \ln q} \right)/\left( {\partial \ln p} \right)\) slope of zero at the maximum pressure point are assumed to be saturated (capillary condensation points are deleted). The highest loading is used from each isotherm that approaches saturation. Unsaturated isotherms are not considered further. The theoretical equation satisfactorily models the available experimental data for the data that is subcritical except for water and methanol. However, steric factors are required in the model for tetrafluoromethane, sulfur hexafluoride and the aldehydes. The adsorption data for ethyl acetate is questionable. A significant amount of data in the supercritical region (tetrafluouromethane, and hexafluoroethane) revealed a decreasing trend with increasing Tr. For this data a f(Tr) is modeled using TCAR and the slope of the decreasing linear plot against Tr. The physical phenomenom causing this effect is attributed to increasing molecular vibration in the cavity reducing the total molecular loading with temperature rise.

Keywords

Inorganic species Halocarbons 13X zeolite Sorbate densities Saturation loadings Sorbate molar volumes 

Nomenclature

b

Dimensionless slope of f(Tr) plot versus saturation loading

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

Reduced critical adsorbate temperature

Tr

Reduced temperature

Vβ cage

Volume of the β cage, 150 Å3

Vlarge cage

Volume of the large cage, 900 Å3

Zc

Critical compressibility

ZRA

Rackett parameter

Greek letters

Γ

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

εZ

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

λ

Steric factor, used in Eq. 7

ρZ

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

Notes

Acknowledgements

The authors wish to acknowledge the support of the American University of Sharjah.

Supplementary material

10450_2017_9916_MOESM1_ESM.png (110 kb)
Fig. S1 qmax calculated from Rackett’s equation and crystal properties for 13X zeolite as a function of reduced temperature (PNG 109 KB)
10450_2017_9916_MOESM2_ESM.png (57 kb)
Fig. S2a Water isotherms. Reduced temperatures are indicated as labels. Isotherms in grey are inconsistent with others, and so are screened out. Isotherms that attain saturation have an unbroken line. Isotherms that have not attained or approached saturation have a dotted line (PNG 57 KB)
10450_2017_9916_MOESM3_ESM.png (51 kb)
Fig. S2b Water isotherms for studies of the first group. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line (PNG 51 KB)
10450_2017_9916_MOESM4_ESM.png (60 kb)
Fig. S2c Water isotherms for studies of the second group. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line. Isotherms that have not attained or approached saturation have a dotted line (PNG 59 KB)
10450_2017_9916_MOESM5_ESM.png (49 kb)
Fig. S2d Log–log plot of water isotherms for studies of the first group. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line. Isotherms that have not attained or approached saturation have a dotted line (PNG 48 KB)
10450_2017_9916_MOESM6_ESM.png (57 kb)
Fig. S2e Log-log plot of water isotherms for studies of the second group. Reduced temperatures are indicated as labels. Isotherms in grey are inconsistent with others, and so are screened out. Isotherms that attain saturation have an unbroken line. Isotherms that have not attained or approached saturation have a dotted line (PNG 57 KB)
10450_2017_9916_MOESM7_ESM.png (43 kb)
Fig. S3a Ammonia isotherms. Reduced temperatures are indicated as labels. Isotherms in grey are inconsistent with others, and so are screened out. Isotherms that attain saturation have an unbroken line. Isotherms that have not attained or approached saturation have a dotted line. Data points that are deleted are in grey (PNG 43 KB)
10450_2017_9916_MOESM8_ESM.png (29 kb)
Fig. S3b Log-log plot of ammonia isotherms. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line. Isotherms that have not attained or approached saturation have a dotted line (PNG 28 KB)
10450_2017_9916_MOESM9_ESM.png (41 kb)
Fig. S4a Sulfur hexafluoride isotherms. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line. Isotherms that have not attained or approached saturation have a dotted line (PNG 40 KB)
10450_2017_9916_MOESM10_ESM.png (16 kb)
Fig. S4b Log-log plot of sulfur hexafluoride isotherms. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line. Isotherms that have not attained or approached saturation have a dotted line (PNG 15 KB)
10450_2017_9916_MOESM11_ESM.png (35 kb)
Fig. S5a Dichloromethane (C2H2Cl2) isotherm. Reduced temperature is indicated as a label. The Isotherm has attained saturation and has an unbroken line (PNG 35 KB)
10450_2017_9916_MOESM12_ESM.png (9 kb)
Fig. S5b Log-log plot of dichloromethane (C2H2Cl2) isotherm. Reduced temperature is indicated as a label. The Isotherm has attained saturation and has an unbroken lin (PNG 9 KB)
10450_2017_9916_MOESM13_ESM.png (47 kb)
Fig. S6a Tetrafluouromethane (CF4) isotherms. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line. Isotherms that have not attained or approached saturation have a dotted line (PNG 46 KB)
10450_2017_9916_MOESM14_ESM.png (36 kb)
Fig. S6b Log-log plot of Tetrafluouromethane (CF4) isotherms. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line. Isotherms that have not attained or approached saturation have a dotted line (PNG 36 KB)
10450_2017_9916_MOESM15_ESM.png (25 kb)
Fig. S7a Hexafluouroethane (C2F6) isotherms. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line. Isotherms that have not attained or approached saturation have a dotted line (PNG 25 KB)
10450_2017_9916_MOESM16_ESM.png (31 kb)
Fig. S7b Log-log plot of hexafluoroethane (C2F6) isotherms. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line. Isotherms that have not attained or approached saturation have a dotted line. Data points that are deleted are in grey (PNG 31 KB)
10450_2017_9916_MOESM17_ESM.png (18 kb)
Fig. S8a Perfluorodimethylcyclohexane (C8F16) isotherms. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line. Isotherms that have not attained or approached saturation have a dotted line. Data points that are deleted are in grey (PNG 17 KB)
10450_2017_9916_MOESM18_ESM.png (35 kb)
Fig. S8b Log-log plot of perfluorodimethylcyclohexane (C8F16) isotherms. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line (PNG 35 KB)
10450_2017_9916_MOESM19_ESM.png (10 kb)
Fig. S9a Isotherms for other halocarbons. Labels designate species and reduced temperatures. Isotherms that attain saturation have an unbroken line. Data points that are deleted are in grey (PNG 10 KB)
10450_2017_9916_MOESM20_ESM.png (24 kb)
Fig. S9b Log-log plot of isotherms for other halocarbons. Labels designate species and reduced temperature. Isotherms that attain saturation have an unbroken line (PNG 23 KB)
10450_2017_9916_MOESM21_ESM.png (17 kb)
Fig. S10a Methanol isotherms. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line (PNG 16 KB)
10450_2017_9916_MOESM22_ESM.png (20 kb)
Fig. S10b Log-log plot of methanol isotherms. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line (PNG 20 KB)
10450_2017_9916_MOESM23_ESM.png (23 kb)
Fig. S11a Acetaldehyde (CH3CHO) isotherms. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line (PNG 22 KB)
10450_2017_9916_MOESM24_ESM.png (8 kb)
Fig. S11b Log-log plot of acetaldehyde (CH3CHO) isotherms. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line (PNG 7 KB)
10450_2017_9916_MOESM25_ESM.png (15 kb)
Fig. S12a Propionaldehyde (C2H5CHO) isotherms. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line. Data points that are deleted are in grey (PNG 15 KB)
10450_2017_9916_MOESM26_ESM.png (8 kb)
Fig. S12b Log-log plot of propionaldehyde (C2H5CHO) isotherms. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line (PNG 7 KB)
10450_2017_9916_MOESM27_ESM.png (23 kb)
Fig. S13a Butyraldehyde (C3H7CHO) isotherms. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line. Data points that are deleted are in grey (PNG 22 KB)
10450_2017_9916_MOESM28_ESM.png (8 kb)
Fig. S13b Log-log plot of butyraldehyde (C3H7CHO) isotherms. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line (PNG 7 KB)
10450_2017_9916_MOESM29_ESM.png (15 kb)
Fig. S14a Ethyl acetate isotherms. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line. Isotherms that have not attained or approached saturation have a dotted line (PNG 15 KB)
10450_2017_9916_MOESM30_ESM.png (19 kb)
Fig. S14b Log-log plot of ethyl acetate isotherms. Reduced temperatures are indicated as labels. Isotherms that attain saturation have an unbroken line. Isotherms that have not attained or approached saturation have a dotted line (PNG 19 KB)
10450_2017_9916_MOESM31_ESM.png (17 kb)
Fig. S15a Plot of water data in the subcritical regions, with predicted model. The data for water do not fit the model and are correlated (PNG 17 KB)
10450_2017_9916_MOESM32_ESM.png (22 kb)
Fig. S15b Plot of ammonia and sulfur hexafluoride data in the subcritical and supercritical regions, with predicted model. The data for SF6 is regressed using a steric factor (PNG 22 KB)
10450_2017_9916_MOESM33_ESM.png (21 kb)
Fig. S15c Plot of C8F16 data in the subcritical region, with predicted model. The data lie between two isomers of the model (PNG 20 KB)
10450_2017_9916_MOESM34_ESM.png (43 kb)
Fig. S15d Data for hydrogenated halocarbons, except for C8F16, in the subcritical and supercritical regions, with predicted model. The data is correlated in the supercritical region (PNG 42 KB)
10450_2017_9916_MOESM35_ESM.png (25 kb)
Fig. S15e Plot of methanol data in the subcritical region, with predicted model. The data do not fit the model and are correlated (PNG 25 KB)
10450_2017_9916_MOESM36_ESM.png (12 kb)
Fig. S15f Plot of aldehyde data in the subcritical region, with predicted model. The data for all three aldehydes are regressed using steric factors (PNG 11 KB)
10450_2017_9916_MOESM37_ESM.png (33 kb)
Fig. S15g Plot of ethyl acetate in the subcritical region, with predicted model. All the data appear erroneous (PNG 33 KB)
10450_2017_9916_MOESM38_ESM.png (14 kb)
Fig. S16a Gamma plot for all species (with steric factor where applicable) except water, methanol and ethyl acetate (PNG 13 KB)
10450_2017_9916_MOESM39_ESM.png (16 kb)
Fig. S16b Gamma plot for water and methanol (PNG 16 KB)

References

  1. Abouelnasr, D., Loughlin, K. F., Al Mousa, A.: Saturation loadings on 13X (faujasite) zeolite above and below the critical conditions. Part III: Inorganic monatomic and diatomic species data evaluation and modeling. Adsorption 23, 945–961 (2017)CrossRefGoogle Scholar
  2. Ahn, N. G., Kang, S. W., Min, B. H., Suh, S. S.: Adsorption isotherms of tetrafluoromethane and hexafluoroethane on various adsorbents. J. Chem. Eng. Data. 51(2), 451–456 (2006)CrossRefGoogle Scholar
  3. Aittomäki, A., Härkönen, M.: Zeolite heat pump—adsorption of methanol in synthetic zeolites 13X, 4A and 5A. Int. J. Refrige. 9(4), 240–244 (1986)CrossRefGoogle Scholar
  4. Akgun, U.: Prediction of adsorption equilibria of gases. Dissertation, The Technische Universitat Munchen, Munchen, Germany (2006)Google Scholar
  5. Akgun, U., Mersmann, A.: Prediction of single component adsorption isotherms on microporous adsorbents. Adsorption 14, 323–333 (2008)CrossRefGoogle Scholar
  6. Al Mousa, A., Abouelnasr, D. M., Loughlin, K. F.: Saturation loadings on 13X (faujasite) zeolite above and below the critical conditions. Part I: Alkane data evaluation and modeling. Adsorption 21, 307–320 (2015a)CrossRefGoogle Scholar
  7. Al Mousa, A., Abouelnasr, D. M., Loughlin, K. F.: Saturation loadings on 13X (faujasite) zeolite above and below the critical conditions. Part II: Unsaturated and cyclic hydrocarbons data evaluation and modeling. Adsorption 21, 321–332 (2015b)CrossRefGoogle Scholar
  8. Barrer, R. M., Reucroft, P. J.: Inclusion of fluorine compounds in Faujasite. I. The physical state of the occluded molecules. Proc. R. Soc. London A 258(No. 1295), 431–448 (1960)CrossRefGoogle Scholar
  9. Bielanski, A., Hajduk, J.: Adsorption of ammonia on active-carbon and 13X molecular-sieve under high-pressure. Przemysl Chem. 65(9), 476–478 (1986)Google Scholar
  10. Breck, D.: Zeolite molecular sieves; structure, chemistry and use. Wiley, New York (1974)Google Scholar
  11. CHERIC. Retrieved from https://www.cheric.org/kdb/research/hcprop/cmpsrch.phpe (2012). Accessed 2012
  12. Cortés, F. B., Chejne, F., Carrasco-Marín, F., Moreno-Castilla, C., Pérez-Cadenas, A. F.: Water adsorption on zeolite 13X: comparison of the two methods based on mass spectrometry and thermogravimetry. Adsorption. 16(3), 141–146 (2010)CrossRefGoogle Scholar
  13. DeBoer, J. H.: The dynamical character of adsorption, 2 edn. Oxford Press, London (1968)Google Scholar
  14. Deng, H., Yi, H., Tang, X., Yu, Q., Ning, P., Yang, L.: Adsorption equilibrium for sulfur dioxide, nitric oxide, carbon dioxide, nitrogen on 13X and 5A zeolites. Chem. Eng. J. 188, 77–85 (2012)CrossRefGoogle Scholar
  15. Dirar, H. Q., Loughlin, K. F.: Intrinsic adsorption properties of CO2 on 5A and 13X zeolite. Adsorption. 19(6), 1149–1163 (2013)CrossRefGoogle Scholar
  16. Doonan, C. J., Tranchemontagne, D. J., Glover, T. G., Hunt, J. R., Yaghi, O. M.: Exceptional ammonia uptake by a covalent organic framework. Nat. Chem. 2(3), 235–238 (2010)CrossRefGoogle Scholar
  17. Ferreira, D., Magalhães, R., Taveira, P., & Mendes, A.: Effective adsorption equilibrium isotherms and breakthroughs of water vapor and carbon dioxide on different adsorbents. Ind. Eng. Chem. Res. 50(17), 10201–10210 (2011)CrossRefGoogle Scholar
  18. Ghosh, T. K., Hines, A. L.: Adsorption of acetaldehyde, propionaldehyde, and butyraldehyde on molecular sieve 13X. Sep. Sci. Technol. 26(7), 931–945 (1991)CrossRefGoogle Scholar
  19. Grace Davison: Sylobead Adsorbents for Process Applications (2015). https://grace.com/general-industrial/en-us/Documents/sylobead_br_E_2010_f100222_web.pdf
  20. Helminen, J., Helenius, J., Paatero, E., Turunen, I.: Adsorption equilibria of ammonia gas on inorganic and organic sorbents at 298.15 K. J. Chem. Eng. Data. 46(2), 391–399 (2001)CrossRefGoogle Scholar
  21. Kim, J. H., Lee, C. H., Kim, W. S., Lee, J. S., Kim, J. T., Suh, J. K., Lee, J. M.: Adsorption equilibria of water vapor on alumina, zeolite 13X, and a zeolite X/activated carbon composite. J. Chem. Eng. Data. 48(1), 137–141 (2003)CrossRefGoogle Scholar
  22. Kim, K.-M., Oh, H.-T., Lim, S.-J., Park, Y., Lee, C.-H.: Adsorption equilibria of water vapor on zeolite 3A, zeolite 13X, and dealuminated Y zeolite. J. Chem. Eng. Data. 61, 1547–1554 (2016)CrossRefGoogle Scholar
  23. 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
  24. 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
  25. Manjare, S. D., Ghoshal, A. K.: Adsorption equilibrium studies for ethyl acetate vapor and E-Merck 13X molecular sieve system. Sep. Purif. Technol. 51(2), 118–125 (2006)CrossRefGoogle Scholar
  26. Mette, B., Kerskes, H., Drück, H., Müller-Steinhagen, H.: Experimental and numerical investigations on the water vapor adsorption isotherms and kinetics of binderless zeolite 13X. Int. J. Heat Mass Transfer. 71, 555–561 (2014)CrossRefGoogle Scholar
  27. Rege, S. U., Yang, R., Buzanowski, M. A.: Sorbents for air prepurification in air separation. Chem. Eng. Sci. 55(21), 4827–4838 (2000)CrossRefGoogle Scholar
  28. Ruthven, D., Doetsch, I.: Diffusion of hydrocarbons in 13X zeolite. AlChE J. 22(5), 882–886 (1976)CrossRefGoogle Scholar
  29. Ryu, Y. K., Lee, S. J., Kim, J. W., Leef, C. H.: Adsorption equilibrium and kinetics of H2O on zeolite 13X. Korean J. Chem. Eng. 18(4), 525–530 (2001)CrossRefGoogle Scholar
  30. Shiflett, M. B., Corbin, D. R., Yokozeki, A.: Comparison of the sorption of trifluoromethane (R-23) on zeolites and in an ionic liquid. Adsorpt. Sci. Technol. 31(1), 59–83 (2013)CrossRefGoogle Scholar
  31. Siperstein, F. R., Myers, A. L.: Mixed gas adsorption. AIChEJ. 47(5), 1141–1159 (2001)CrossRefGoogle Scholar
  32. Spencer, C., Danner, R.: Improved equation for prediction of saturated liquid density. J. Chem. Eng. Data. 17(2), 236–240 (1972)CrossRefGoogle Scholar
  33. Wang, Y., LeVan, M. D.: Adsorption equilibrium of carbon dioxide and water vapor on zeolites 5A and 13X and silica gel: pure components. J. Chem. Eng. Data. 54(10), 2839–2844 (2009)CrossRefGoogle Scholar
  34. Wang, C. M., Chung, T. W., Huang, C. M., Wu, H.: Adsorption equilibria of acetate compounds on activated carbon, silica gel, and 13X zeolite. J. Chem. Eng. Data. 50(3), 811–816 (2005)CrossRefGoogle Scholar
  35. Zhu, R., Han, B., Lin, M., Yu, Y.: Experimental investigation on an adsorption system for producing chilled water. Int. J. Refrige. 15(1), 31–34 (1992)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2017

Authors and Affiliations

  • Kevin F. Loughlin
    • 1
  • Dana Abouelnasr
    • 1
  • Alaa al Mousa
    • 2
  1. 1.Department of Chemical EngineeringAmerican University of SharjahUniversity City, SharjahUnited Arab Emirates
  2. 2.Petrofac International, Ltd.SharjahUnited Arab Emirates

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