Вы находитесь на странице: 1из 15

# Flash Separation

## Separations of liquid and condensable vapour mixtures are highly important in

chemical industry. Typically, a reactor produces a host of products with high selectivity for
the desired product. Downstream of the reactor, the reactor effluents are processed to
separate and produce the desired product with high purity. Separations are often done
upstream of the reactor, too. They consume 50-90% of total operating and capital costs of a
chemical plant. Therefore, it is imperative that they be designed and operated to achieve a
‘high’ purity of the desired product at a ‘low’ cost.

## Distillation is by far the widest applied separation technique in chemical industry.

The U.S. Department of Energy estimates that there are upwards of 40,000 distillation
columns in North America consuming about 40% of the total energy used in operating
chemical plants (White, ‘Optimize Energy Use in Distillation,’ Chemical Engineering
Progress, March 2012, 35-41).

In this course, we will learn how distillation works in chemical industry. Simply put,
distillation involves heating a liquid mixture until it starts to boil. More volatile components
are vaporized; this vapour, rich in more volatile component, is condensed to form a liquid
with high purity of that component. The residue is a liquid containing more of less volatile
component.

Vapour-liquid equilibrium is central to flash and other types of distillation. This topic was
covered in your Thermodynamics courses. We will review it here quickly.

## Vapour phase At equilibrium, temperatures,

pressures and chemical
potentials are same for both
Liquid phase phases.

Ideal mixtures: Raoult’s law is applicable for these mixtures. If total pressure is , mole
fractions in gas and liquid phases of component, i, are and , respectively, is
vapour pressure at temperature T, then,

## For a binary mixture, a bubble point curve can be generated using

and

66
For a given, and , find that satisfies the above equation. This temperature is bubble
point temperature. Compute to get the mole fraction of the component 1 in vapour phase.

## For a binary mixture, a bubble point curve can be generated using

Equilibrium T-x-y diagram and x-y diagram are shown below for benzene-toluene system at
1 atm.

Draw a plot similar to above when the difference between the volatilities of the two
components is very high

67
Draw a plot similar to above when the difference between the volatilities of the two
components is very high

For non-ideal liquid systems, how is the equation modified for predicting bubble and dew
point temperatures? Write it below.

68
Acetone—water system (activity coefficients are >1 for this system)

Liquid mixtures could deviate positively or negatively from Raoult’s law. They could exhibit
azeotrope also.

What is an azeotrope?

## Sometimes, , for ideal solutions, is also used to describe and calculate

equilibrium data. Evidently, is a distribution factor for component . It is the ratio of mole
fraction of component i in vapour phase to its mole fraction in liquid phase. is a function of
temperature and pressure. This kind of equilibrium representation using is more
prevalent for mixtures containing highly volatile and very low volatile components. A couple
of examples are: mixture of hydrogen/benzene and methane/octane. Here, hydrogen is
extremely volatile compared to benzene and methane is exceedingly volatile compared to
octane.

## Representation of equilibrium by using values is used in the design of flash separators.

Look up De Priester Charts by searching for them in google.com. Figure out how to read the
charts to get values for hydrocarbons for a given temperature and pressure.

69
Consider these examples from a commercial chemical plant producing benzene

## Example 1: In the production of benzene by hydro-dealkylation of toluene, by the reaction

shown below, the reactor effluents emerge as vapour at 600 oC and 25 bar. They contain
unreacted toluene and unreacted hydrogen in addition to the products, benzene and
methane. An undesirable by-product, biphenyl, also forms in the reactor because of high
temperature and pressure conditions. The unreacted reactants, hydrogen and toluene, must
be recycled to the reactor for improving their overall conversion.

## Main Reaction: H2 + CH4

Side reaction: 2 + H2

As methane and hydrogen have low boiling points, they can be separated first from
the other components. Normal boiling points of all the components are as follows: H2,
o
C; toluene, 110.6 oC; benzene 80.1 oC; CH4, o
C; diphenyl, o
C. How
could the separation of hydrogen and toluene from the rest of the compounds be achieved?

Constraint on the separation: As unreacted methane and hydrogen are to be recycled, the
separation is to be achieved by not altering the pressure. If pressure is reduced to affect the
separation, then the separated methane and hydrogen would have to be repressurized
before they are mixed with the fresh feed to the reactor. Pressurization of gases is typically
expensive; so it is usually avoided, if possible.

Example 2: Separation of ammonia from a mixture comprising 61.5% H2, 20% N2 and the
balance 18.5% NH3, exiting ammonia synthesis reactor at 250 bar and 200 oC. Our goal is
to separate ammonia and recycle H2 and N2 to the reactor.

## Example 3: Aqueous mixtures of ethylene glycol are used as coolants in cars.

Commercially ethylene glycol is made by reacting ethylene oxide with water. Downstream
processing of reactor effluent involves separation of ethylene glycol and water. In one such
separation, a stream flowing at 100 kmol/h consists of 60 mole% water and 40 mole%
ethylene glycol. Temperature and pressure of the stream are 40 oC and 1 atm, respectively.
Normal boiling points: water, 100 oC; glycol, 197.3 oC.

## Constraint on the separation: no constraint as above.

70
Equipment Symbol Equipment Symbol

Cooler Heater

Flash chamber
Throttle valve (separates liquid
(for reducing pressure) and vapour)

Draw separation schemes for the three examples discussed in the previous pages using
above symbols. Indicate components of all streams in the schemes.

## Scheme for example 3:

71
How is flash separation accomplished for the following streams?

## Liquid stream: _____________________________________________________________

Flash Distillation

Vapour mixtures or liquid mixtures containing compounds with high relative volatility are
separated by flash distillation. The former are cooled and the latter are heated to affect the
separation; both mixtures may be depressurized also in addition to cooling and heating
operations.

Vapour mixtures
Vapour

Feed
FLASH CHAMBER
Valve for
Cooler raising
pressure Liquid

could be used

Liquid mixtures
Vapour

Feed
FLASH CHAMBER
Valve for
Heater lowering
pressure Liquid

## Both or only one of these operations

could be used

72
Let’s consider a vapour mixture for our analysis. The same analysis holds for liquid mixtures
also. A feed mixture to be separated by flash separation is flowing at kmol/h with as
composition of component . The flash separator is operated at a
temperature, , and pressure, . The operating conditions of the separator generate a
vapour phase flowing out at kmol/h and a liquid phase flowing out at kmol/h. Let the
composition of component in liquid and vapour phases produced in the separator be
and , respectively.

## Let’s derive useful relationships that allow us to solve a flash problem.

Use component balance in conjunction with overall mole balance, eliminate and then
get an equation for in terms of , and .

73
Now,

## Also, . Do this and simplify to get an equation in terms of , and .

This equation in called Rachford-Rice equation.

Can you identify two limits for the Rachford-Rice equation? Which equations are obtained
as these limits are approached? What is the significance of these limits?

## Write equations for the two limits below.

74
A stream containing 45 kmol/h hydrogen and 70 kmol/h n-hexane is flashed at 311 K and 40
bar. Find flowrates and compositions of exit streams. and .

In separation problems, we are interested not only in purity of the exit streams but also
recovery of compounds present in the feed in the exit streams. In the above example,
ideally we want the vapour stream to contain 100% pure hydrogen at 45 kmol/h. However,
this ideal can never be achieved in separations.

## Recovery of hydrogen in vapour stream

75
A four component mixture of hydrogen (1)—benzene (2)—cyclohexane (3)—n-hexane(4) is
fed to a flash separator at a total flowrate of 80 kmol/h. The feed contains 10 mol%
hydrogen, 10 mol% benzene, 60 mol% cyclohexane and 20 mol% n-hexane. At 93.3 oC and
35.4 bar, the experimentally measured values are:

## . Calculate the total flowrate, the component flowrates and the

composition of exit streams. Complete this problem in your hostel.

(Try to learn MS Excel Goal Seek feature to solve non-linear equations in one variable. This
feature could be useful to you in your professional career.)

In the commercial manufacture of acetic anhydride from acetone and acetic acid, streams
containing acetone (1) (normal boiling point = 56 oC) and acetic anhydride (2) occur (normal
boiling point = 139.5 oC). One such stream contains 30 kmol/h of acetone and 70 kmol/h of
acetic anhydride. As the boiling points differ widely, flash separation of this mixture at 105
o
C and 1 atm is recommended. and

Rachford Rice-equation: ,

kmol/h.

## The phase compositions are:

Component
Acetone 0.182 0.741
Acetic anhydride 0.818 0.259

76
Even though some separation has been accomplished by flashing, the purities obtained here
are low, far from those desired for most of the processes.

What happens to purity of acetone in vapour stream and its recovery as temperature is
varied from 95 oC to 115 oC? Plot purity and recovery of acetone, both versus temperature,
on the same graph. Check your plots with actual calculations.

We considered two problems: separation of hydrogen from its mixture with hexane and
separation of acetone from its mixture with acetic anhydride. What do you conclude about
applicability of flash separation from these problems?

In most of the chemical processes, the purities far higher than those obtained in Table above
are needed. That is, acetone is desired at, say 95% or more purity. Similarly, anhydride is
also needed at high purity. If one flash separator cannot achieve high purity, more such
separators can be added as shown below.

Vapour emerging from the first separator is cooled further, to say 100 oC, to liquefy some
anhydride and acetone. Liquid exiting this separator is heated, to say 110 oC, to vaporize
some acetone and anhydride. The vapour streams in the upper cascade of separators can
be still further cooled and the liquid stream in the lower cascade can be still further heated.

77
VT,NT, yT,NT

V=17.7 kmol/h
y=0.84

LT,NT, xT,NT
95 oC
V=19.2 kmol/h
1atm
y=0.795

L=1.5 kmol/h
V=21.2 kmol/h 100 Co x=0.27
y = 0.74 1atm

L=2 kmol/h
x=0.221
F=100 kmol/h 105 oC
1atm
z=0.3
V=5.3 kmol/h
y = 0.675
110 oC
L=78.8 kmol/h 1atm
x = 0.182
V=4.6 kmol/h
y=0.601
115 oC
L=73.5 kmol/h 1atm
X=0.146
VB,NB, yB,NB

L=68.9 kmol/h
X=0.115

LB,NB, xB,NB

78
VT,N, yT,N

LT,N, xT,N
VT,2, yT,2
LT,4, xT,4

VT,1, yT,1
LT,3, xT,3

LT,2, xT,2
F=100 kmol/h

z=0.3
VB,2, yB,2

VB,3, yB,3

LB,1, xB,1

VB,4, yB,4

LB,2, xB,2
VB,NB, yB,NB

LB,3, xB,3

## Better arrangement of flash separators to achieve high separation

(Note: Heat exchangers are not shown for convenience) LB,NB, xB,NB

79
Key points on flash distillation

##  Flash separation is used to separate mixtures containing substances with high

relative volatilities.
 Vapour streams are cooled and/or depressurized to separate constituents by flash.
 Liquid streams are heated and/or depressurized to separate constituents by flash
 The streams leaving a flash separator are assumed to be in equilibrium with each
other.
 Richford-Rice equation solves flash problems by finding fraction of feed vaporized,
which in turn helps in calculating compositions are flow rates of liquid and vapour
streams leaving flash separator.
 Rachford-Rice equation and related equations are: , ,
and .
 For more than two components, above equation can be solved by MS Excel Goal
Seek tool.

80