1 Describe working principle of membrane distillation,

adsorption distillation
1.1 Membrane distillation
1.1.1 Introduction
MD is a thermally driven process, in which water vapour transport occurs through a nonwetted
porous hydrophobic membrane. The term MD comes from the similarity between conventional
distillation process and its membrane variant as both technologies are based on the vapour-liquid
equilibrium for separation and both of them require the latent heat of evaporation for the phase
change from liquid to vapour which is achieved by heating the feed solution. The driving force
for MD process is given by the vapour pressure gradient which is generated by a temperature
difference across the membrane. As the driving force is not a pure thermal driving force,
membrane distillation can be held at a much lower temperature than conventional thermal
distillation. The hydrophobic nature of the membrane prevents penetration of the pores by
aqueous solutions due to surface tensions, unless a trans membrane pressure higher than the
membrane liquid entry pressure (LEP) is applied. Therefore, liquid/vapour interfaces are formed
at the entrances of each pore.

1.1.2 Membrane configuration

1.1.2.1 Direct Contact Membrane Distillation (DCMD)
In this configuration (figure 1), the hot solution (feed) is in direct contact with the hot membrane
side surface. Therefore, evaporation takes place at the feed-membrane surface. The vapour is
moved by the pressure difference across the membrane to the permeate side and condenses inside
the membrane module. Because of the hydrophobic characteristic, the feed cannot penetrate the
membrane (only the gas phase exists inside the membrane pores). DCMD is the simplest MD
configuration, and is widely employed in desalination processes and concentration of aqueous
solutions in food industries, or acids manufacturing. The main drawback of this design is the heat
lost by conduction.
Figure 1. Direct Contact Membrane Distillation (DCMD)

1.1.2.2 Air Gap Membrane Distillation (AGMD)

The schematic of the Air Gap Membrane Distillation (AGMD) is shown in Fig. 2. The feed
solution is in direct contact with the hot side of the membrane surface only. Stagnant air is
introduced between the membrane and the condensation surface. The vapour crosses the air gap
to condense over the cold surface inside the membrane cell. The benefit of this design is the
reduced heat lost by conduction. However, additional resistance to mass transfer is created,
which is considered a disadvantage. This configuration is suitable for desalination and removing
volatile compounds from aqueous solutions.

Figure 2. Air Gap Membrane Distillation (AGMD)

1.1.2.3 Sweeping Gas Membrane Distillation (SGMD)

In Sweeping Gas Membrane Distillation (SGMD), as the schematic diagram in Fig.3 shows, inert
gas is used to sweep the vapour at the permeate membrane side to condense outside the
membrane module. There is a gas barrier, like in AGMD, to reduce the heat loss, but this is not
stationary, which enhances the mass transfer coefficient. This configuration is useful for
removing volatile compounds from aqueous solution. The main disadvantage of this
configuration is that a small volume of permeate diffuses in a large sweep gas volume, requiring
a large condenser. It is worthwhile stating that AGMD and SGMD can be combined in a process
called thermostatic sweeping gas membrane distillation (TSGMD). The inert gas in this case is
passed through the gap between the membrane and the condensation surface. Part of vapor is
condensed over the condensation surface (AGMD) and the remainder is condensed outside the
membrane cell by external condenser.
 Figure 3. Sweeping Gas Membrane Distillation (SGMD).

1.1.2.4 Vacuum Membrane Distillation (VMD)

The schematic diagram of this module is shown in Fig. 4. In VMD configuration, a pump is used
to create a vacuum in the permeate membrane side. Condensation takes place outside the
membrane module. The heat lost by conduction is negligible, which is considered a great
advantage. This type of MD is used to separate aqueous volatile solutions.

Figure 4. Vacuum Membrane Distillation (VMD)

1.1.3 Working principle

MD is a process mainly suited for applications in which water is the major component present in
the feed solution to be treated and refers to a thermally driven transport of vapor through
nonwetted porous hydrophobic membranes, the driving force being the partial pressure
difference between each side of the membrane pores.

The liquid feed to be treated by MD is maintained in direct contact with one side of the
membrane without penetrating its dry pores unless a trans membrane pressure higher than the
membrane liquid entry pressure [i.e., liquid entry pressure or breakthrough pressure (LEP)] is
applied. In fact, the hydrophobic nature of the membrane prevents liquid solutions from entering
its pores due to the surface tension forces. As a result, liquid–vapor interfaces are formed at the
entrances of the membrane pores. Various MD modes differing in the technology applied to
establish the driving force can be used. The differences between them are localized only in the
permeate side. The MD driving force may be maintained with one of the four following
possibilities applied in the permeate side.as we discussed before:

An aqueous solution colder than the feed solution is maintained in direct contact with the
permeate side of the membrane giving rise to the configuration known as Direct Contact
Membrane Distillation (DCMD). Both the feed and permeate aqueous solutions are
circulated tangentially to the membrane surfaces by means of circulating pumps or are stirred
inside the membrane cell by means of a magnetic stirrer. In this case the trans membrane
temperature difference induces a vapor pressure difference. Consequently, volatile molecules
evaporate at the hot liquid/vapor interface, cross the membrane pores in vapor phase and
condense in the cold liquid/vapor interface inside the membrane module. A DCMD with
 liquid gap is another DCMD variant, in which a stagnant cold liquid, frequently distilled
water, is kept in direct contact with the permeate side of the membrane.

Figure a. DCMD and DCMD with liquid gap

Vacuum is applied in the permeate side of the membrane module by means of a vacuum
pump. The applied vacuum pressure is lower than the saturation pressure of volatile
molecules to be separated from the feed solution. In this case, condensation takes place
outside of the membrane module. This MD configuration is termed Vacuum Membrane
Distillation (VMD).

Figure b. VMD
A stagnant air gap is interposed between the membrane and a condensation surface. In this
case, the evaporated volatile molecules cross both the membrane pores and the air gap to
finally condense over a cold surface inside the membrane module. This MD configuration is
called Air Gap Membrane Distillation (AGMD).

Figure d. AGMD
 A cold inert gas sweeps the permeate side of the membrane carrying the vapour molecules
and condensation takes place outside the membrane module. This type of configuration is
termed Sweeping Gas Membrane Distillation (SGMD). In this configuration, due to the heat
transferred from the feed side through the membrane, the sweeping gas temperature in the
permeate side increases considerably along the membrane module length. A SGMD variant
termed Thermostatic Sweeping Gas Membrane Distillation (TSGMD) has been proposed
recently. In this mode of SGMD the increase in the gas temperature is minimized by using a
cold wall in the permeate side.

Figure c. SGMD and thermostatic SGMD

1.2 Adsorption distillation

1.2.1 Introduction
In this type of separation method active adsorbents are added to the distillation column as
separating agent.Example: separation of water and ethanol using molecular sieves as adsorbent.
The water rich feed is separated in first distillation column where pure water obtained as bottom
product and water-ethanol azeotrope as overhead vapour product. The azeotropic mixture is sent
to adsorption column where water is primarily adsorbed by molecular sieve.

Figure 5.Typical example of adsorption distillation process

1.2.2 Working principle

There are two types of adsorption distillation

1.2.2.1 Fixed-bed adsorption distillation (FAD )

It involves replacement of the inert packing material in packed-bed distillation column by an
active packing material. in FAD molecular sieves or ion-exchange resins as the separating agents
can be used for the separation of the mixture with close boiling point or azeotropic point.
Furthermore, FAD is an extremely environment-friendly process because no extra organic
 solution is introduced except the components to be separated, and thus there doesn't exist solvent
loss, unlike azeotropic distillation and extractive distillation.

Comparison of FAD and extractive distillation

Comparison of adsorption distillation and extractive distillation for separating ethanol and water
is very attractive because adsorption distillation is an attractive "new" technique and extractive
distillation is an "old" technique. The most commonly used separating agentsin the extractive
distillation are ethylene glycol, the mixture of ethylene glycol and one salt, CaCl2 and N, N-
dimethylformamide. Today, azeortopic distillation is almost replaced by extractive distillation for
separating ethanol and water. So it is unadvisable to use azeortopic distillation for separating
ethanol and water. Comparison of adsorption distillation and extractive distillation is made on
the basis of process experiment and vapor-liquid equilibrium (VLE )experiment. According to
some reports the following experiment was made in laboratory to see the result of extractive
distillation and adsorption distillation for separating ethanol and water.

The extractive distillation column was composed of three sections:

i. rectifying section of 30 mm (diameter) x 800 mm (height)

ii. stripping section of 30 mm (diameter) * 400 mm (height) and
iii. scrubbing section of 30 mm (diameter) * 150 mm (height).

The solvent recovery column was composed of two sections:

( I ) rectifying section of 30 mm (diameter) x 650 mm (height)

(II) stripping section of 30 mm (diameter) x 300 mm (height). The two columns were packed by
a type of ring-shape packing with the size of 4 mm (width) x 4 mm (height). The theoretical
plates are determined by use of the system of n-heptane and methylcyclohexane at infinite reflux,
having 18 theoretical plates (including reboiler and condenser) for extractive distillation column
and 14 theoretical plates (including reboiler and condenser) for solvent recovery column.

In the extractive distillation process experiment, the mixture of ethylene glycol and CaCl2 was
used as the separating agent. The reagents, ethylene glycol and CaCl2, , were of analytical purity.

Composition analyses of the samples withdrawn from the top of extractive distillation column
were done by a gas chromatography (type Shimadzu GC-14B) equipped with a thermal
conductivity detector. Porapark Q was used as the fixed agent of the column packing, and
hydrogen as the carrier gas. The column packing was 160 °C and the detector 160 °C. The data
were dealt with by a SC 1100 workstation. In terms of peak area of the components, the sample
compositions could be deduced

The experimental results of extractive distillation column are given in Table 1, where the feed
concentration is ethanol of 0.3576 mole fraction and water of 0.6424 mole fraction. It is shown
that high-purity of ethanol (above 99.0%wt), up to 0.9835 mole fraction (almost 99.5%wt), was
obtained under low solvent/feed volume ratio 2.0 and low reflux ratio 0.5, which means that the
mixture of ethylene glycol and CaCl2 as the separating agent is very effective for the separation
of ethanol and water by extractive distillation and has been governed in industry for a long time.
Figure 6: The double-column process for extractive distillation

In order to test the effect of molecular sieves and ion-exchange resins on the separation of
ethanol and water in the adsorption distillation column, a set of experimental apparatus wase
stablished. The column was composed of two sections, ( I ) 30 mm (diameter) x 600 mm (height)
and (II) 30 mm (diameter) x 600 mm (height). The first section was firstly filled with stainless
steel ring-shape packing with the size of 3 mm width and 3 mm height, then filled with 3 A
sphere-shape molecular sieves with the diameter of 4-6 mm, and finally filled with ion-exchange
resins (the type is D072 Styrene-DVB composed of the anion RSO3" and the cation Na+.) with
the diameter of 1.20 - 1.30 mm. The second section was always filled with stainless steel ring-
shape packing with the size of 3 mm width and 3 mm height in both experiments.

In the beginning the feed mixture entered into the bottom tin with 2500 ml. Then the batch
distillation column started to run. In the experiment it was assumed that the bottom and top
concentration was keep constant because the operation time wasn't too long and concentration
change in the bottom tin was negligible.
Figure 7. Experimental apparatus used for separating ethanol and water by adsorption distillation

Under the infinite reflux condition, the experimental results are given in Table 2 where x1 and
X2 are molar fraction of ethanol and water in the liquid phase, respectively, and T is temperature
(K). The fresh molecular sieves and ion-exchange resins are used and not replaced during the
operation.

It can be seen from the above table that the enhancement of molecular sieves and ion-exchange
resins on the separation of ethanol and water is very limited, and high-purity of ethanol (above
99.0%wt) can't be obtained, at most up to 0.8463 mole fraction (94.8%wt) and 0.8205 mole
fraction (93.8%wt) respectively in the case study. Therefore, although adsorption distillation, in
which the solid separating agent is used and the operation process is simple, may be attractive, it
seems to be unattractive in the actual distillation process.

1.2.2.2 Suspension adsorption distillation

Suspension adsorption distillation doesn’t involve replacement of internals of distillation.
Although SAD looks like SCD, in SAD the tiny solid particles are used as the adsorption agent
and blended with liquid phase in the column. In SCD the tiny solid particles are used as catalyst.

Sometimes adsorption distillation is coupled with extractive distillation, and is applied in a same
column. This kind of adsorption distillation also can be called adsorption extractive distillation.
The only difference from extractive distillation is that the separating agent is the mixture of
particle and liquid solvent. The whole process is unchanged, just the two-column extractive
distillation process. Consequently, the merits of both extractive distillation and adsorption
distillation are completely exhibited

The most significance of employing adsorption distillation is that the gas-liquid mass transport is
enhanced by adding the tiny solid particles, which correspondingly improves the tray efficiency
for tray columns. However, when adding solid particles to liquid phase, the packed column is
prone to be jammed. From this viewpoint, the tray column is more suitable for SAD. However,
SAD has its own drawback. For instance, it is difficult to run the distillation column again while
the solid particles are dispositted after a long time. This should be noted in the operation.

2 Describe advantages and limitations of Azeotropic

distillation, Extractive distillation, Membrane distillation and
Adsorption distillation
2.1 Azeotropic distillation
2.1.1 Introduction
Azeotropic distillation is accomplished by adding to the liquid phase, a volatile third component,
which changes the volatility of one of the two components more than the other so that the
components are separated by distillation. The two components to be separated often are close
boiling point components which do or do not azeotrope in the binary mixture, but sometimes
they are components which do azeotrope although they aren't close boiling point components. It
is likely that in some cases, one system can be separated either by azeotropic distillation or by
extractive distillation, for instance, alcohol/water, acid/water, etc.

The added third component, sometimes called the entrainer, may form a ternary azeotrope with the two
components being separated. However, it must be sufficiently volatile from the solution so that it is taken
overhead with one of the two components in the azeotropic distillation column. If the entrainer and the
component taken overhead separate into two liquid phases when the vapor overhead is condensed, the
entrainer phase is refluxed back to the column. The other phase can be fractionated to remover the
dissolved entrainer and the residual amount of the other component before it is discarded in the solvent
(entrainer) recovery column). Alternatively, this second liquid phase is recycled to some appropriate place
in the main process scheme.

Figure 8. double-column process for homogeneous and heterogeneous azeotropic distillation

2.1.2 Advantages Azeotropic distillation