DEMOCRATIC AND POPULAR ALGERIAN REPUBLIC

MINISTRY OF HIGHER EDUCATION AND RESEARCH

SCIENTIFIC
UNIVERSITY OF SCIENCE AND TECHNOLOGY
D'ORAN MOHAMED BOUDIAF USTO-MB
DEPARTMENT OF CHEMICAL ENGINEERING

MODULE: ADSORPTION AND SEPARATION PROCESSES

MEMBRANES

PART II: MEMBRANE SEPARATION PROCESSES

CHAPTER 4: GENERALITIES AND DEFINITIONS

2020/2021 Presented by: Dr. A. Elaziouti

 History
The main stages of the discovery of membrane processes:

1748: discovery by Abbot Nollet of the selectively permeable membrane;

1829: start of Graham's work on dialysis and gas permeation;
1861: conception by Graham of the first dialysis machine;
1887: laws on diffusion by Van't Hoff and osmotic pressure law;
1900: production of the first artificial membranes and beginning of studies
industrial applications;
1950: production of the first cellulose acetate membranes by REID in
the University of Florida for seawater desalination (reverse osmosis);
1967: emergence of spiral flat modules and hollow fiber modules;
1978: development of the first composite mineral tubular membrane
in the USA;
1982-1987: development of ultrafiltration and microfiltration
tangential in the industry;
1987-1993: development of nanofiltration, pervaporation,
electrodialysis
 GENERAL PRINCIPLE OF MEMBRANE FILTRATION

. Membrane filtration is a physical separation process in the liquid phase.

It is based on the principle of permeation through a semipermeable membrane.
This permselective membrane, according to its intrinsic characteristics and its
mode of use, constitutes a barrier allowing (or favoring) certain
material transfers and limiting others (figure 1)
.,

. The driving forces that allow permeation through the membrane can be
the diffusion of one of the two phases (active transport) but also the
differentials of pressures ∆P, of concentrations ∆C, of electric potentials ∆E
(passive transport) old temperature ∆T.

. Depending on the size of its pores, the filtration membrane constitutes a

absolute physical barrier for molecules or particles larger than
a certain threshold.

. It is the main advantage of membrane filtration in comparison.

to conventional treatments. Indeed, they consist of a filtration on
granular media (sand and/or activated carbon), which does not constitute an absolute filter.

. Unlike membrane filtration, the quality of the water filtered by the process
Traditional largely depends on the treated raw water.
. At the end of a membrane filtration operation, two phases are
obtained:
. the retentate (or concentrate) in which the molecules are concentrated
and/or particles retained by the membrane;
. the permeate, free from retained molecules and/or particles.

Figure I.1: Membrane sélective

Membrane techniques with pressure gradient
. Tangential microfiltration (TMF)⇒ a process that implements
microporous membranes (the pore size is between 0.1 and 10µ.
⇒ Depending on the applications, the membranes used are of different natures.
knowledge: Ceramic, Organic polymer, Titanium dioxide coated stainless steel.
solution to be treated circulates parallel to the surface of the membrane and a pressure
Transmembrane of some bars is applied.
. Ultrafiltration (UF)⇒ a membrane process allowing solvent extraction
(generally water) and ionic or molecular solutes of a solution
containing macronutrients.⇒ The size of the pores ranges from 1 to 100 nm.
The solution to be processed flows parallel to the surface of the membrane and a
a transmembrane pressure of a few bars is applied. The molecules of
Molecular weight greater than 5000-10000 D are retained by membranes.
. Nanofiltration (NF)⇒ a baromembrane separation technique covering a
separation domain between ultrafiltration (UF) and reverse osmosis (RO).⇒ She
uses membranes with pore diameters close to 1 nanometer. This
the technique allows to extract from the water at the same time as monovalent ions
as well as substances whose molecular weight does not exceed approximately 200D.
The applied transmembrane pressure is on the order of 10 to 25 bars. In agro-
In the industry, nanofiltration is used to concentrate solutions while
ensuring partial demineralization.
. Reverse osmosis (RO)⇒ a separation technique using membranes
densities allowing the extraction of pure water from a solution containing salts
(to see other dissolved substances).⇒ The pressures at play must be
sufficient to reverse the osmotic flow (several tens of bars).
 Areas of membrane filtration
. The main filtration areas based on the average pore size of the
membranes, as well as the correspondence with the retained molecules and particles
are represented in the figure2

Figure 2 - Situation of membrane separation techniques in

function of the size of the retained particles
 Filtration
. Membrane processes are separation processes used for
extract, concentrate, purify or separate compounds contained in a
mixture in a liquid or gaseous phase. Here we will only consider the phase
liquids.

. Membrane processes with pressure gradient allow the filtration of a

liquid medium with membranes whose pore diameter determines the size of
retained compounds.

. The membrane plays the role of a selective barrier that allows the passage of
some compounds and block others. The driving force is the difference in
pression.

. Unlike classic filtration where the flow of liquid is

perpendicular to the filtering middle (frontal filtration), here the flow of the
The mixture to be filtered is parallel to the membrane. This is tangential filtration.
Thus we avoid the accumulation on the surface of the membrane of particles or
molecules that remain suspended in the liquid.
. The frontal filtration is
also appreciated for the fact
that this technology is
compact and therefore more
easily sterilizable
what a circuit does
intervene several
pumps.

Fig 3: Presentation of the functioning of front filtration

. Tangential filtration
is on the other hand used
quasi systematically
when fluids have
of material rates in
high suspensions.

Fig 4: Presentation of the functioning of tangential filtration

MF and UF membranes are microporous while the OI membranes and
Not considered as such, NF membranes can belong to
one or the other of these categories depending on their cutoff threshold. The
The transfer mechanisms are then different (see figure 7). For the membranes
microporous, the molecules are separated by sieve effect, while in the case
dense membranes, the molecules are separated by differences in solubility and
mobility in the surface membrane material

Figure 5: Molecular transport through microporous and dense membranes

Operating parameters of a membrane filtration process
Figure 2–Schematic diagram
of a separation process
membranous

PA-PRPressure drop (Pa)

QRTangential flow (m3/s)
QPFront flow (m)3/s)
QASupply flow (m)3/s

. Transmembrane pressure (TMP) (Pa): Acting force of the characterized operation

by the average supply pressures, PA, and retentat,PR, which is subtracted from
the permeate compartment pressure, PP.

. Permeation flow (m3/s,m2Process productivity defined by permeate flow rate

divided by airflow membrane (flux density). This flux also represents the speed
average of the fluid perpendicular to the surface of the membrane.

. Taux de rejet (ou taux de retention)(%): Sélectivité du procédé : un taux de rejet de 1

means that the solute is perfectly retained by the membrane (mass concentration
in the permeate CP= 0) while a rejection rate of 0 corresponds to a non-solute
retained, identical concentration in permeate CPand the tornadoR(CP=CR).

. Conversion rate (%): Fraction of liquid flow that passes through the membrane
 Note
. The permeate flux is related to the pressure applied. In the case of filtration of
solvent only, the flow can be expressed in terms of pressure
transmembrane according to Darcy's law:

withJ: the permeate flow (m3/s,m2);

Qpthe permeate flow rate (m3/s);
S: surface of the membrane (m2);
ΔP: the transmembrane pressure (Pa);
μ: the viscosity of the liquid (Pa.s);
R: the resistance of the membrane to the passage of the liquid (m-1)

. The intrinsic resistance of a membrane corresponds to its ability to

last to resist the flow forces of a fluid through its defects
(pores). Its expression is presented by the following equation derived from the law of
Darcy. According to this law, the flow (J) of a fluid through a carpet
the filter is proportional to the pressure difference (ΔP or TMP) and
inversely proportional to the resistance of the carpet (R) and to the viscosity (μ) of
fluid
. Ultrafiltration, the effectiveness of the
membrane is generally
characterized by the cutoff threshold
(cut-off), which can be defined as
being the molar mass M (g/mol)
corresponding to a retention
high (90% most often) of a
determined macromolecule (figure).
It is measured atthe helpof compounds
models, most often from
polyethylene glycol (PEG).
Figure 6: Determination of the cut-off threshold (Molecular Weight Cut-off) of a membrane
ultrafiltration, from a screening curve

. Generally, for a family of standard molecules, the curve is plotted.

f(M). This means that one obtains a different curve for each family of molecules.
standards. On the other hand, if we trace in relation to the hydrodynamic radius, a
unique curve TR = f(radius) is obtained. The hydrodynamic radius is given
by the following relationship:
Avecrhydhydrodynamic radius of the molecule (m);
η: intrinsic viscosity of the solution (m3g-1);
M: molar mass (g mol-1);
N: Avogadro's number (mol)-1),
Table 2–Order of magnitude of permeabilities

Table 3–Order of magnitude of flux density

volume of the different membrane techniques