Batch distillation

Main article: Batch distillation

A batch still showing the separation of A and B.

Heating an ideal mixture of two volatile substances A and B (with A having the higher
volatility, or lower boiling point) in a batch distillation setup (such as in an apparatus depicted
in the opening figure) until the mixture is boiling results in a vapor above the liquid which
contains a mixture of A and B. The ratio between A and B in the vapor will be different from
the ratio in the liquid: the ratio in the liquid will be determined by how the original mixture was
prepared, while the ratio in the vapor will be enriched in the more volatile compound, A (due
to Raoult's Law, see above). The vapor goes through the condenser and is removed from the
system. This in turn means that the ratio of compounds in the remaining liquid is now different
from the initial ratio (i.e. more enriched in B than the starting liquid).

The result is that the ratio in the liquid mixture is changing, becoming richer in component B.
This causes the boiling point of the mixture to rise, which in turn results in a rise in the
temperature in the vapor, which results in a changing ratio of A : B in the gas phase (as
distillation continues, there is an increasing proportion of B in the gas phase). This results in a
slowly changing ratio A : B in the distillate.

If the difference in vapor pressure between the two components A and B is large (generally
expressed as the difference in boiling points), the mixture in the beginning of the distillation is
highly enriched in component A, and when component A has distilled off, the boiling liquid is
enriched in component B.

[edit]Continuous distillation
Main article: Continuous distillation
Continuous distillation is an ongoing distillation in which a liquid mixture is continuously
(without interruption) fed into the process and separated fractions are removed continuously
as output streams as time passes during the operation. Continuous distillation produces at
least two output fractions, including at least one volatile distillate fraction, which has boiled
and been separately captured as a vapor condensed to a liquid. There is always a bottoms
(or residue) fraction, which is the least volatile residue that has not been separately captured
as a condensed vapor.

Continuous distillation differs from batch distillation in the respect that concentrations should
not change over time. Continuous distillation can be run at a steady state for an arbitrary
amount of time. For any source material of specific composition, the main variables that affect
the purity of products in continuous distillation are the reflux ratio and the number of
theoretical equilibrium stages (practically, the number of trays or the height of packing).
Reflux is a flow from the condenser back to the column, which generates a recycle that allows
a better separation with a given number of trays. Equilibrium stages are ideal steps where
compositions achieve vapor-liquid equilibrium, repeating the separation process and allowing
better separation given a reflux ratio. A column with a high reflux ratio may have fewer stages,
but it refluxes a large amount of liquid, giving a wide column with a large holdup. Conversely,
a column with a low reflux ratio must have a large number of stages, thus requiring a taller
column.

[edit]General improvements
Both batch and continuous distillations can be improved by making use of a fractionating
column on top of the distillation flask. The column improves separation by providing a larger
surface area for the vapor and condensate to come into contact. This helps it remain at
equilibrium for as long as possible. The column can even consist of small subsystems ('trays'
or 'dishes') which all contain an enriched, boiling liquid mixture, all with their own vapor-liquid
equilibrium.

There are differences between laboratory-scale and industrial-scale fractionating columns, but
the principles are the same. Examples of laboratory-scale fractionating columns (in increasing
efficiency) include:

 Air condenser
 Vigreux column (usually laboratory scale only)
 Packed column (packed with glass beads, metal pieces, or other chemically inert
material)
 Spinning band distillation system.

[edit]Laboratory scale distillation

Laboratory scale distillations are almost exclusively run as batch distillations. The device used
in distillation, sometimes referred to as a still, consists at a minimum of a reboileror pot in
which the source material is heated, a condenser in which the heated vapour is cooled back
to the liquid state, and a receiver in which the concentrated or purified liquid, called
the distillate, is collected. Several laboratory scale techniques for distillation exist (see
also distillation types).

[edit]Simple distillation
In simple distillation, all the hot vapors produced are immediately channeled into a
condenser that cools and condenses the vapors. Therefore, the distillate will not be pure – its
composition will be identical to the composition of the vapors at the given temperature and
pressure, and can be computed from Raoult's law.

As a result, simple distillation is usually used only to separate liquids whose boiling points
differ greatly (rule of thumb is 25 °C),[13] or to separate liquids from involatile solids or oils. For
these cases, the vapor pressures of the components are usually sufficiently different that
Raoult's law may be neglected due to the insignificant contribution of the less volatile
component. In this case, the distillate may be sufficiently pure for its intended purpose.

[edit]Fractional distillation
Main article: Fractional distillation
For many cases, the boiling points of the components in the mixture will be sufficiently close
that Raoult's law must be taken into consideration. Therefore, fractional distillationmust be
used in order to separate the components by repeated vaporization-condensation cycles
within a packed fractionating column. This separation, by successive distillations, is also
referred to as rectification.[14]

As the solution to be purified is heated, its vapors rise to the fractionating column. As it rises,
it cools, condensing on the condenser walls and the surfaces of the packing material. Here,
the condensate continues to be heated by the rising hot vapors; it vaporizes once more.
However, the composition of the fresh vapors are determined once again by Raoult's law.
Each vaporization-condensation cycle (called a theoretical plate) will yield a purer solution of
the more volatile component.[15] In reality, each cycle at a given temperature does not occur at
exactly the same position in the fractionating column; theoretical plate is thus a concept rather
than an accurate description.

More theoretical plates lead to better separations. A spinning band distillation system uses a
spinning band of Teflon or metal to force the rising vapors into close contact with the
descending condensate, increasing the number of theoretical plates.[16]

[edit]Steam distillation
Main article: Steam distillation
Like vacuum distillation, steam distillation is a method for distilling compounds which are
heat-sensitive.[17] The temperature of the steam is easier to control than the surface of a
heating element, and allows a high rate of heat transfer without heating at a very high
temperature. This process involves bubbling steam through a heated mixture of the raw
material. By Raoult's law, some of the target compound will vaporize (in accordance with its
partial pressure). The vapor mixture is cooled and condensed, usually yielding a layer of oil
and a layer of water.

Steam distillation of various aromatic herbs and flowers can result in two products;
an essential oil as well as a watery herbal distillate. The essential oils are often used in
perfumery and aromatherapy while the watery distillates have many applications
in aromatherapy, food processing and skin care.

Dimethyl sulfoxide usually boils at 189 °C. Under a vacuum, it distills off into the receiver at only 70 °C.
Perkin triangle distillation setup
1: Stirrer bar/anti-bumping granules 2: Still pot 3: Fractionating column 4:Thermometer/Boiling point
temperature 5:Teflon tap 1 6: Cold finger 7: Cooling water out 8: Cooling water in 9: Teflon tap
2 10:Vacuum/gas inlet 11: Teflon tap 3 12: Still receiver
[edit]Vacuum distillation
Main article: Vacuum distillation
Some compounds have very high boiling points. To boil such compounds, it is often better to
lower the pressure at which such compounds are boiled instead of increasing the
temperature. Once the pressure is lowered to the vapor pressure of the compound (at the
given temperature), boiling and the rest of the distillation process can commence. This
technique is referred to as vacuum distillation and it is commonly found in the laboratory in
the form of the rotary evaporator.

This technique is also very useful for compounds which boil beyond their decomposition
temperature at atmospheric pressure and which would therefore be decomposed by any
attempt to boil them under atmospheric pressure.

Molecular distillation is vacuum distillation below the pressure of 0.01 torr.[18] 0.01 torr is one
order of magnitude above high vacuum, where fluids are in the free molecular flow regime,
i.e. the mean free path of molecules is comparable to the size of the equipment. The gaseous
phase no longer exerts significant pressure on the substance to be evaporated, and
consequently, rate of evaporation no longer depends on pressure. That is, because the
continuum assumptions of fluid dynamics no longer apply, mass transport is governed by
molecular dynamics rather than fluid dynamics. Thus, a short path between the hot surface
and the cold surface is necessary, typically by suspending a hot plate covered with a film of
feed next to a cold plate with a line of sight in between. Molecular distillation is used
industrially for purification of oils.

[edit]Air-sensitive vacuum distillation

Some compounds have high boiling points as well as being air sensitive. A simple vacuum
distillation system as exemplified above can be used, whereby the vacuum is replaced with
an inert gas after the distillation is complete. However, this is a less satisfactory system if one
desires to collect fractions under a reduced pressure. To do this a "cow" or "pig" adaptor can
be added to the end of the condenser, or for better results or for very air sensitive compounds
a Perkin triangle apparatus can be used.

The Perkin triangle, has means via a series of glass or Teflon taps to allows fractions to be
isolated from the rest of the still, without the main body of the distillation being removed from
either the vacuum or heat source, and thus can remain in a state of reflux. To do this, the
sample is first isolated from the vacuum by means of the taps, the vacuum over the sample is
then replaced with an inert gas (such as nitrogen or argon) and can then be stoppered and
removed. A fresh collection vessel can then be added to the system, evacuated and linked
back into the distillation system via the taps to collect a second fraction, and so on, until all
fractions have been collected.

[edit]Short path distillation

Short path vacuum distillation apparatus with vertical condenser (cold finger), to minimize the distillation
path; 1: Still pot with stirrer bar/anti-bumping granules 2: Cold finger – bent to direct condensate 3: Cooling
water out 4: cooling water in 5: Vacuum/gas inlet 6: Distillate flask/distillate.

Short path distillation is a distillation technique that involves the distillate travelling a short
distance, often only a few centimeters, and is normally done at reduced pressure.[19] A classic
example would be a distillation involving the distillate travelling from one glass bulb to
another, without the need for a condenser separating the two chambers. This technique is
often used for compounds which are unstable at high temperatures or to purify small amounts
of compound. The advantage is that the heating temperature can be considerably lower (at
reduced pressure) than the boiling point of the liquid at standard pressure, and the distillate
only has to travel a short distance before condensing. A short path ensures that little
compound is lost on the sides of the apparatus. The Kugelrohr is a kind of a short path
distillation apparatus which often contain multiple chambers to collect distillate fractions.

[edit]Zone distillation
Zone distillation is a distillation process in long container with partial melting of refined matter
in moving liquid zone and condensation of vapor in the solid phase at condensate pulling in
cold area. The process is worked in theory. When zone heater is moving from the top to the
bottom of the container then solid condensate with irregular impurity distribution is forming.
Then most pure part of the condensate may be extracted as product. The process may be
iterated many times by moving (without turnover) the received condensate to the bottom part
of the container on the place of refined matter. The irregular impurity distribution in the
condensate (that is efficiency of purification) increases with number of repetitions of the
process. Zone distillation is a distillation analog of zone recrystallization. Impurity distribution
in the condensate is described by known equations of zone recrystallization with various
numbers of iteration of process – with replacement distribution efficient k of crystallization on
separation factor α of distillation. (Literature: Kravchenko, A.I. Zone distillation: a new method
of refining // Problems of atomic science and technology, 2011. – N. 6 – Series: “Vacuum,
pure materials, superconductors” (19). – P. 24-26. [in Russian]. – [1])

[edit]Other types

 The process of reactive distillation involves using the reaction vessel as the still. In
this process, the product is usually significantly lower-boiling than its reactants. As the
product is formed from the reactants, it is vaporized and removed from the reaction
mixture. This technique is an example of a continuous vs. a batch process; advantages
include less downtime to charge the reaction vessel with starting material, and less
workup.
 Catalytic distillation is the process by which the reactants are catalyzed while being
distilled to continuously separate the products from the reactants. This method is used to
assist equilibrium reactions reach completion.
 Pervaporation is a method for the separation of mixtures of liquids by partial
vaporization through a non-porous membrane.
 Extractive distillation is defined as distillation in the presence of a miscible, high
boiling, relatively non-volatile component, the solvent, that forms no azeotrope with the
other components in the mixture.
 Flash evaporation (or partial evaporation) is the partial vaporization that occurs when
a saturated liquid stream undergoes a reduction in pressure by passing through a
throttlingvalve or other throttling device. This process is one of the simplest unit
operations, being equivalent to a distillation with only one equilibrium stage.
 Codistillation is distillation which is performed on mixtures in which the two
compounds are not miscible.

The unit process of evaporation may also be called "distillation":

 In rotary evaporation a vacuum distillation apparatus is used to remove

bulk solvents from a sample. Typically the vacuum is generated by a water aspirator or
a membrane pump.
 In a kugelrohr a short path distillation apparatus is typically used (generally in
combination with a (high) vacuum) to distill high boiling (> 300 °C) compounds. The
apparatus consists of an oven in which the compound to be distilled is placed, a receiving
portion which is outside of the oven, and a means of rotating the sample. The vacuum is
normally generated by using a high vacuum pump.

Other uses:

 Dry distillation or destructive distillation, despite the name, is not truly distillation, but
rather a chemical reaction known as pyrolysis in which solid substances are heated in an
 inert or reducing atmosphere and any volatile fractions, containing high-boiling liquids
and products of pyrolysis, are collected. The destructive distillation of wood to
givemethanol is the root of its common name – wood alcohol.
 Freeze distillation is an analogous method of purification using freezing instead of
evaporation. It is not truly distillation, but a recrystallization where the product is
the mother liquor, and does not produce products equivalent to distillation. This process
is used in the production of ice beer and ice wine to increase ethanol and sugar content,
respectively. It is also used to produce applejack. Unlike distillation, freeze distillation
concentrates poisonous congeners rather than removing them.

[edit]Azeotropic distillation
Main article: Azeotropic distillation
Interactions between the components of the solution create properties unique to the solution,
as most processes entail nonideal mixtures, where Raoult's law does not hold. Such
interactions can result in a constant-boiling azeotrope which behaves as if it were a pure
compound (i.e., boils at a single temperature instead of a range). At an azeotrope, the
solution contains the given component in the same proportion as the vapor, so that
evaporation does not change the purity, and distillation does not effect separation. For
example,ethyl alcohol and water form an azeotrope of 95.6% at 78.1 °C.

If the azeotrope is not considered sufficiently pure for use, there exist some techniques to
break the azeotrope to give a pure distillate. This set of techniques are known asazeotropic
distillation. Some techniques achieve this by "jumping" over the azeotropic composition (by
adding an additional component to create a new azeotrope, or by varying the pressure).
Others work by chemically or physically removing or sequestering the impurity. For example,
to purify ethanol beyond 95%, a drying agent or a (desiccant such aspotassium carbonate)
can be added to convert the soluble water into insoluble water of crystallization. Molecular
sieves are often used for this purpose as well.

Immiscible liquids, such as water and toluene, easily form azeotropes. Commonly, these
azeotropes are referred to as a low boiling azeotrope because the boiling point of the
azeotrope is lower than the boiling point of either pure component. The temperature and
composition of the azeotrope is easily predicted from the vapor pressure of the pure
components, without use of Raoult's law. The azeotrope is easily broken in a distillation set-
up by using a liquid-liquid separator (a decanter) to separate the two liquid layers that are
condensed overhead. Only one of the two liquid layers is refluxed to the distillation set-up.

High boiling azeotropes, such as a 20 weight percent mixture of hydrochloric acid in water,
also exist. As implied by the name, the boiling point of the azeotrope is greater than the
boiling point of either pure component.

To break azeotropic distillations and cross distillation boundaries, such as in the DeRosier
Problem, it is necessary to increase the composition of the light key in the distillate.

[edit]Breaking an azeotrope with unidirectional pressure

manipulation
The boiling points of components in an azeotrope overlap to form a band. By exposing an
azeotrope to a vacuum or positive pressure, it's possible to bias the boiling point of one
component away from the other by exploiting the differing vapour pressure curves of each;
the curves may overlap at the azeotropic point, but are unlikely to be remain identical further
along the pressure axis either side of the azeotropic point. When the bias is great enough, the
two boiling points no longer overlap and so the azeotropic band disappears.

This method can remove the need to add other chemicals to a distillation, but it has two
potential drawbacks.

Under negative pressure, power for a vacuum source is needed and the reduced boiling
points of the distillates requires that the condenser be run cooler to prevent distillate vapours
being lost to the vacuum source. Increased cooling demands will often require additional
energy and possibly new equipment or a change of coolant.

Alternatively, if positive pressures are required, standard glassware can not be used, energy
must be used for pressurization and there is a higher chance of side reactions occurring in the
distillation, such as decomposition, due to the higher temperatures required to effect boiling.

A unidirectional distillation will rely on a pressure change in one direction, either positive or
negative.

[edit]Pressure-swing distillation
Further information: Pressure-Swing Distillation (section on the main Azeotrope page)
This section may be confusing or unclear to readers. Please
help clarify the section; suggestions may be found on the talk
page. (May 2009)

Pressure-swing distillation is essentially the same as the unidirectional distillation used to

break azeotropic mixtures, but here both positive and negative pressures may be employed.
[clarification needed]

This has an important impact on the selectivity of the distillation and allows a chemist[citation
needed]
to optimize a process such that fewer extremes of pressure and temperature are
required and less energy is consumed. This is particularly important in commercial
applications.

Pressure-swing distillation is employed during the industrial purification of ethyl acetate after
its catalytic synthesis from ethanol.

[edit]Industrial distillation
Typical industrial distillation towers
Main article: Continuous distillation
Large scale industrial distillation applications include both batch and continuous fractional,
vacuum, azeotropic, extractive, and steam distillation. The most widely used industrial
applications of continuous, steady-state fractional distillation are in petroleum
refineries,petrochemical and chemical plants and natural gas processing plants.

Industrial distillation[14][20] is typically performed in large, vertical cylindrical columns known

as distillation towers or distillation columns with diameters ranging from about 65
centimeters to 16 meters and heights ranging from about 6 meters to 90 meters or more.
When the process feed has a diverse composition, as in distilling crude oil, liquid outlets at
intervals up the column allow for the withdrawal of different fractions or products having
different boiling points or boiling ranges. The "lightest" products (those with the lowest boiling
point) exit from the top of the columns and the "heaviest" products (those with the highest
boiling point) exit from the bottom of the column and are often called the bottoms.

Diagram of a typical industrial distillation tower

Industrial towers use reflux to achieve a more complete separation of products. Reflux refers
to the portion of the condensed overhead liquid product from a distillation or fractionation
tower that is returned to the upper part of the tower as shown in the schematic diagram of a
typical, large-scale industrial distillation tower. Inside the tower, the downflowing reflux liquid
provides cooling and condensation of the upflowing vapors thereby increasing the efficiency
of the distillation tower. The more reflux that is provided for a given number of theoretical
plates, the better the tower's separation of lower boiling materials from higher boiling
materials. Alternatively, the more reflux that is provided for a given desired separation, the
fewer the number of theoretical plates required.

Such industrial fractionating towers are also used in air separation, producing
liquid oxygen, liquid nitrogen, and high purity argon. Distillation of chlorosilanes also enables
the production of high-purity silicon for use as a semiconductor.
Section of an industrial distillation tower showing detail of trays with bubble caps

Design and operation of a distillation tower depends on the feed and desired products. Given
a simple, binary component feed, analytical methods such as the McCabe-Thiele method[14]
[21]
or the Fenske equation[14] can be used. For a multi-component feed, simulation models are
used both for design and operation. Moreover, the efficiencies of the vapor-liquid contact
devices (referred to as "plates" or "trays") used in distillation towers are typically lower than
that of a theoretical 100% efficient equilibrium stage. Hence, a distillation tower needs more
trays than the number of theoretical vapor-liquid equilibrium stages.

In modern industrial uses, a packing material is used in the column instead of trays when low
pressure drops across the column are required. Other factors that favor packing are: vacuum
systems, smaller diameter columns, corrosive systems, systems prone to foaming, systems
requiring low liquid holdup and batch distillation. Conversely, factors that favor plate columns
are: presence of solids in feed, high liquid rates, large column diameters, complex columns,
columns with wide feed composition variation, columns with a chemical reaction, absorption
columns, columns limited by foundation weight tolerance, low liquid rate, large turn-down ratio
and those processes subject to process surges.
Large-scale, industrial vacuum distillation column[22]

This packing material can either be random dumped packing (1–3" wide) such asRaschig
rings or structured sheet metal. Liquids tend to wet the surface of the packing and the vapors
pass across this wetted surface, where mass transfer takes place. Unlike conventional tray
distillation in which every tray represents a separate point of vapor-liquid equilibrium, the
vapor-liquid equilibrium curve in a packed column is continuous. However, when modeling
packed columns, it is useful to compute a number of "theoretical stages" to denote the
separation efficiency of the packed column with respect to more traditional trays. Differently
shaped packings have different surface areas and void space between packings. Both of
these factors affect packing performance.

Another factor in addition to the packing shape and surface area that affects the performance
of random or structured packing is the liquid and vapor distribution entering the packed bed.
The number of theoretical stages required to make a given separation is calculated using a
specific vapor to liquid ratio. If the liquid and vapor are not evenly distributed across the
superficial tower area as it enters the packed bed, the liquid to vapor ratio will not be correct
in the packed bed and the required separation will not be achieved. The packing will appear
to not be working properly. The height equivalent of a theoretical plate (HETP) will be greater
than expected. The problem is not the packing itself but the mal-distribution of the fluids
entering the packed bed. Liquid mal-distribution is more frequently the problem than vapor.
The design of the liquid distributors used to introduce the feed and reflux to a packed bed is
critical to making the packing perform to it maximum efficiency. Methods of evaluating the
effectiveness of a liquid distributor to evenly distribute the liquid entering a packed bed can be
found in references.[23][24]Considerable work as been done on this topic by Fractionation
Research, Inc. (commonly known as FRI).[25]

[edit]Multi-effect distillation
The goal of multi-effect distillation is to increase the energy efficiency of the process, for use
in desalination, or in some cases one stage in the production of ultrapure water. The number
of effects is proportional to the kW·h/m3 of water recovered figure, and refers to the volume of
water recovered per unit of energy compared with single-effect distillation. One effect is
roughly 636 kW·h/m3.

 Multi-stage flash distillation Can achieve more than 20 effects with thermal energy
input, as mentioned in the article.

 Vapor compression evaporation Commercial large-scale units can achieve around 72

effects with electrical energy input, according to manufacturers.

There are many other types of multi-effect distillation processes, including one referred to as
simply multi-effect distillation (MED), in which multiple chambers, with intervening heat
exchangers, are employed.

[edit]Distillation in food processing

[edit]Distilled beverages
Main article: Distilled beverage
Carbohydrate-containing plant materials are allowed to ferment, producing a dilute solution of
ethanol in the process. Spirits such as whiskey and rum are prepared by distilling these dilute
solutions of ethanol. Components other than ethanol, including water, esters, and other
alcohols, are collected in the condensate, which account for the flavor of the beverage.