Thermodynamics Research Center / ThermoML | Journal of Chemical and Engineering Data

Density, Viscosity, and Surface Tension of Liquid Phase Beckmann Rearrangement Mixtures

Zuidhof, K. T.[Klaas T.], Croon, M. H. J. M. d.[Mart H.J.M. de], Schouten, J. C.[Jaap C.], Tinge, J. T.[Johan T.]
J. Chem. Eng. Data 2015, 60, 4, 1056-1062
ABSTRACT
We have determined the density, dynamic viscosity, and surface tension of liquid phase Beckmann rearrangement mixtures, consisting of e-caprolactam and fuming oleum. These important properties have been measured in wide ranges of both temperature and molar ratios of acid and e-caprolactam, covering conditions that are of relevance for industrial production of e-caprolactam from cyclohexanone oxime, i.e., T = (293 to 393) K and ([H2SO4] + [SO3])/[e-caprolactam] = (1.4 to 2.6). The results were correlated as functions of temperature and composition. The density of oleum/e-caprolactam mixtures shows a linear relationship with both temperature and composition. A modification of the traditional Reynolds model proved to be the most suitable way to represent the dynamic viscosity of these Beckmann rearrangement mixtures. The reduction of the surface tension with temperature is described with a power law expression, while the decrease of the surface tension with increasing molar ratios of acid over e-caprolactam is described with a linear relationship. These results can be applied to design liquid phase Beckmann rearrangement processes on both large scale and microscale.
Compounds
# Formula Name
1 H2O4S sulfuric acid
2 O3S sulfur trioxide
3 C6H11NO 1-aza-2-cycloheptanone
Datasets
The table above is generated from the ThermoML associated json file (link above). POMD and RXND refer to PureOrMixture and Reaction Datasets. The compound numbers are included in properties, variables, and phases, if specificied; the numbers refer to the table of compounds on the left.
Type Compound-# Property Variable Constraint Phase Method #Points
  • POMD
  • 3
  • 2
  • 1
  • Mass density, kg/m3 ; Liquid
  • Mass fraction - 3; Liquid
  • Mass fraction - 1; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Pycnometric method
  • 24
  • POMD
  • 3
  • 2
  • 1
  • Viscosity, Pa*s ; Liquid
  • Mass fraction - 3; Liquid
  • Mass fraction - 1; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Concentric cylinders viscometry
  • 72
  • POMD
  • 3
  • 2
  • 1
  • Surface tension liquid-gas, N/m ; Liquid
  • Mass fraction - 3; Liquid
  • Mass fraction - 1; Liquid
  • Temperature, K; Liquid
  • Liquid
  • Air at 1 atmosphere
  • Maximal bubble pressure
  • 33