Izák P.

: Pervaporation of liquid organic mixtures

Supervisor: doc. M. Šípek
This PhD thesis deals with a description of transport parameters during
pervaporation of binary liquid mixture through non-porous polymer membrane. The
main task of this work is the application of the model that would be able to describe the
transport of the penetrant in the membrane. The influence of the C-number of aliphatic
alcohols on transport parameters is also under study.
It was necessary to determine experimentally the concentration dependent
density of the membrane, pure component vapor sorption isotherms, the dependence of
pure component diffusion coefficients on their relative pressure and the dependence of
the solubility of liquid binary mixture in a membrane. All dependencies were
mathematically described and than introduced into Maxwell-Stefan equations.
Literature survey shows that these equations represent the most practical model
for the description of pervaporation process. A modified Maxwell-Stefan model takes
into accounts the non-ideal multicomponent solubility effect, concentration dependent
diffusion coefficients of all permeating components, concentration dependent density of
the membrane and diffusion coupling. The model was experimentally verified by using
the liquid binary mixtures (methanol, ethanol, propan-1-ol, butan-1-ol, pentan-1-ol,
hexan-1-ol with toluene) and the low-density polyethylene membrane at 25°C.
To describe concentration dependence of the membrane density we used a
device, which is able to measure the extension of the polymer membrane during
swelling continuously, while the membrane is immersed in liquid. This device was
developed at the Department of Physical Chemistry of the Institute of Chemical-
Technology in Prague.
The sorption apparatus with quartz spring balance was also constructed for
suitable measuring of vapor sorption isotherms and vapor sorption kinetics of pure
solvents. All measured sorption isotherms increased exponentially with increasing
relative pressure of the solvent.
Our results show that the solubility of toluene in PE membrane is in one order of
magnitude higher than the solubility of aliphatic alcohols. From our vapor sorption
measurements we observed an increase of mass fraction of the solvent in the
membrane with increasing C-number.
The diffusion coefficients of all aliphatic alcohols increase exponentially with the
increase of their relative pressure. Swelling of the polyethylene membrane, during
which the solvent extends polyethylene chains and therefore the penetrants can pass
through the network more easily, could cause this increase.
The values of diffusion coefficient obtained for toluene pass maximum in the
dependence on relative pressure. Forming of clusters at higher relative pressure
probably causes the decrease of the diffusion coefficient of toluene with its relative
pressure.
In order to establish the composition of the sorbed phase in the polyethylene
membrane, which differs from that of the bulk equilibrium solution, two different
experiments were performed and compared: interferometry and permittivity
measurements in all measured systems in PE membrane. Both used methods show a
negligible solubility of aliphatic alcohols in comparison with toluene. Much higher
solubility of toluene and its diffusion coefficient (bigger than the one of aliphatic
alcohols) are responsible for good separation of these binary compounds by PE
membrane.
Pervaporation data for all six systems were measured in order to calculate
coupled diffusion coefficient and to compare the model with the experiment.
The data are described by the experimental dependencies of the weight fraction
of toluene in permeate, partial fluxes of permeates, enrichment factor and separation
factor on the weight fraction of toluene in retentate. The azeotropic mixtures were
separated by pervaporation in the whole concentration range.
The dependencies of pervaporation fluxes and weight fraction of toluene in
permeate on concentration of toluene in the retentate are compared with the
calculations based on the 1st Fick’s law with constant diffusion coefficient and a modified
Maxwell-Stefan model.
As the toluene concentration in retentate was becoming higher, the
pervaporation flux through the polyethylene membrane was increasing exponentially.
We did not find any influence of the C-number in the alcohol molecule on
pervaporation flux through the membrane.
The separation process in all measured binary mixtures is most successful in
cases, where there is a small amount of toluene in alcohol. The mixture with the highest
separation factor, i.e. in which the separation is most efficient, is hexan-1-ol with
toluene.
The experimental error in all experimental data does not exceed 5% of the total
value.
 It turns out that the strong non-ideal solubility and diffusivity behavior of the
measured liquid binary mixture components in polyethylene membrane and diffusive
coupling effects play the dominant roles in the pervaporation process. Therefore the
results based on the 1st Fick’s law with constant diffusion coefficient are completely
unsatisfactory.
An essential improvement of the model description can be achieved by
introduction of the concentration dependence of all diffusion coefficients, the density of
the membrane and diffusion coupling using Maxwell-Stefan model with one additional
adjustable parameter. These diffusion coupling coefficients were calculated using
Newton iterative method.
Our results show that this model is able to describe the performance of a
pervaporation membrane for given separation problems very well.