6P2X0: Separation technology

Evaporation and flash

distillation
Prof. dr. ir. Kitty Nijmeijer

Membrane Materials and Processes

Department of Chemical Engineering and Chemistry
Eindhoven University of Technology

Information in this lecture is taken from:

Industrial Separation Processes -
Fundamentals
André B. de Haan, Hans Bosch
2013, De Gruyter GmbH, ISBN 978-3-11-030669-9
 Maturity of separation technologies

/ Department of Chemical Engineering and Chemistry 28-02-18 PAGE 1

 State-of-the-art refineries

• Distillation: separation based

on differences in relative volatility.
• First distillation: 1st and 2nd century
• Distillation of alcohols: 15th century
• Large scale : early 20th century

• Current state: largest, most applied

separation technology worldwide.

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 State-of-the-art refineries

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 State-of-the-art refineries

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 Evaporation

• One step distillation.

• Vapor-liquid equilibrium determines selectivity.
• Both batch and continuous processes.

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 Distillation

• Most frequently applied

separation technology.
• Separation principle: difference
in volatility.
• Distillate is rich in volatile
component.
• Vaporization by heat in reboiler.
• Recovery of heat (lower
temperature) in condenser.

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 Vapor-liquid equilibrium

$%
!" =
&%

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 Txy and yx-diagrams

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 Separation factor

• Mole fraction in vapor phase: y

• Mole fraction in liquid phase: x
• Binary mixture: y1 + y2 = 1 and x1 + x2 = 1

• x1 = x, x2 = 1 - x, y1 = y en y2 = 1 – y
• x and y: fraction of the most volatile component.

• Separation factor:

/ Department of Chemical Engineering and Chemistry 28-02-18 PAGE 9

 Ideal mixtures

N
• Dalton’s law: pi = yi P P = å pi
i =1
• Raoult’s law: pi = xi Pi sat

sat
yi Pi
• Distribution coefficient: Ki = =
xi P
sat
K i Pi
• Selectivity = Relative volatility: a ij = = sat
(Depending on the temperature) K j Pj

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 Vapor pressure

• Antoine equation:

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 Example: vapor pressure

• Antoine equation:

• Example:
• Benzene: A=7.47872, B=1701.073, C=293.956
• Toluene: A=7.41946, B=1738.123, C=273.544

• Calculate the vapor pressure and the relative

volatility at 80 oC and 110 oC.
• Calculate the total pressure of a mixture with a
benzene mole fraction of 0.05 at 80 oC and 110 oC.
• What influence does the temperature have on the
relative volatility?

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 Example: vapor pressure

• The relative volatility decreases with increasing

temperature!

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 Equilibrium curve

• Relative volatility (y1 = 1-y2; x1 = 1-x2):

sat
P K1 y/x
a12 = 1
= =
P 2
sat
K 2 (1 - y ) / (1 - x )
Rewrite
• Equilibrium curve:
a12 x
y=
(a12 - 1) x + 1
= the relationship between the composition of a liquid
and the vapor with which it is in equilibrium.

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 YX-diagram

• Binary system:

n-butanol/pentane (α = 11.7)
t-butanol/n-butanol (α = 3.7)
pentane/hexane (α = 2.4)

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 Interpreting a YX-diagram

• A liquid mixture consisting of A and B (α = 4), with X

= 0.32 is in equilibrium with a vapor phase with
composition Y = 0.65.

• The vapor phase is

richer in the more
volatile component!

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 Non-ideal mixtures

N
• Dalton’s law: pi = yi P P = å pi
i =1

• Modified Raoult’s law: pi = g i xi Pi sat

yi g i Pi sat
• Distribution coefficient: Ki = =
xi P
K i g i Pi sat

• Selectivity = relative volatility: a ij = =

• (depending on temperature K j g j Pjsat
and composition!)

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 In non-ideal systems the distribution coefficients and relative volatility are de-
pendent on composition because of the composition dependence of the activity
Txy, Pxy
coefficients. When theand yx-diagrams
activity coefficient of a specific component becomes high
enough an azeotrope may be encountered, meaning that the vapor and liquid
compositions are equal and the components cannot be separated by conventional
distillation. Fig. 2.5 shows binary vapor-liquid composition (x-y), temperature-
composition
• Close(T-x) and pressure-composition
to ideal activity coefficients (P-x) diagrams
(γ ~ 1):for non-azeotrope,
• No azeotrope

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 Txy, Pxy and yx-diagrams

• Positive deviations from ideality (γ > 1):

• Minimum azeotrope
• Strong repulsive forces (dissimilar systems).

• Overhead product is azeotrope.

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 Txy, Pxy and yx-diagrams

• Negative deviations from ideality (γ < 1):

• Maximum azeotrope
• Strong attraction between the molecules.

Fig. 2.5 Types of binary (a) temperature-composition; (b) pressure-composition and (c)
• Bottom product is azeotrope.
x-y phase diagrams for vapor-liquid equilibrium.
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 Simple batch distillation

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 Example: batch distillation

• Production of liqueur from wine:

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 Continuous flash distillation

• Vapor creation by:

• Heat addition (isothermal flash)
• Pressure release (adiabatic flash)

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 Flash drum

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 Balances flash drum

• F=V+L
• Fz = Vy +Lx
• Six variables, two equations.
• The ratio y/x is physically determined (K=y/x) and
depends on temperature.
• If F and z are known, one more equation is
necessary.
• Two options:
• Specify L/V
• Specify Ptot

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 Balances flash drum

• F=V+L
• Fz = Vy +Lx
• Six variables, two equations.
• The ratio y/x is physically determined (K=y/x) and
depends on temperature.
• If F and z are known, one more equation is
necessary.
• Two options:
• Specify L/V
• Specify Ptot

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 Specifying L/V

• Overall balance:
Fill in:
• Component balance: F=L+V

Rewrite

• Result:

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 Specifying L/V

• Liquid fraction: • Vapor fraction:

Rewrite
L Fill in
F=
q
L q Rewrite V
= 1− q = q
Fill in V 1− q L

Operating line

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 Specifying L/V

• Liquid fraction:

• Operating line flash:

a12 x
• Equilibrium curve: y=
(a12 - 1) x + 1
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 Example: flash distillation of benzene

• Removal of benzene from water by

flash.
• Feed concentration of xB = 0.0005
(mole fraction).
• Isothermal flash at 70 oC
• Antoine equation parameters:
• Water: A=8.07131, B=1730.630,
C=233.426
• Benzene: A=7.47872, B=1701.073,
C=293.956
• Activity coefficient of benzene at
infinite dilution: ln(γ) = 6.43.
• What is the concentration in both the
liquid and the vapor phase if 0.5% of
the feed is evaporated?
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 Example: flash distillation of benzene

• Calculate the relative volatility at 70 oC:

pBsat = 638 mmHg
pWsat = 233 mmHg g P
¥ sat
a= B B
= 1700
g P
o sat
g B¥ = exp(6.43) = 621 w w

g w0 = 1
• Equilibrium curve:

at strong dilution
/ Department of Chemical Engineering and Chemistry 28-02-18 PAGE 31
 Example: flash distillation of benzene

• Operating line flash:

• q = 0.995
• As 0.5% is evaporated.

• Using the graph and filling in

the equation:
• x = 5.2*10-5 (about 90% stripped)
• y = 0.089

/ Department of Chemical Engineering and Chemistry 28-02-18 PAGE 32

 Balances flash drum

• F=V+L
• Fz = Vy +Lx
• Six variables, two equations.
• The ratio y/x is physically determined (K=y/x) and
depends on temperature.
• If F and z are known, one more equation is
necessary.
• Two options:
• Specify L/V
• Specify Ptot

/ Department of Chemical Engineering and Chemistry 28-02-18 PAGE 33

 Specifying Ptot

• Specifying T and P: xeq and yeq are known.

(alternatively: specifying P and x: T en y are known)
• q (=L/F) is unknown: slope of the operating line.

• Boundary conditions:
• xeq < z < yeq
• 0<q<1
• Σ xi = Σ yi = 1

/ Department of Chemical Engineering and Chemistry 28-02-18 PAGE 34

 Specifying Ptot

• Operating line: with yi = K.xi

Low concentration

• Eliminate xi from the equation of the operating line:

q zi zi
xi Ki = - xi + xi =
1- q 1- q Ki + (1 - Ki )q
Ki zi
yi = Ki xi =
Ki + (1 - Ki )q
• Boundary condition: å x - å y = 0
i i
i i
zi (1 - K i )
åi K + (1 - K )q = 0
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 Specifying Ptot

zi (1 - K i )
åi K + (1 - K )q = 0
i i
KB KA
• Solve for q: q = -z - (1 - z )
1- KB 1- KA
• Calculating q and filling it in the equation for x and y
yields every xi and yi:
zi
xi = yi = K i xi
Ki + (1 - Ki )q

1- KB
x=
K A - KB
/ Department of Chemical Engineering and Chemistry 28-02-18 PAGE 36
 Example: flash distillation of benzene

• Removal of benzene from water by

flash.
• z = 0.40
• Desired liquid mole fraction x = 0.30.
• Ptot = 1 bar (=750 mm Hg)

• Antoine equation parameters:

• Water: A=8.07131, B=1730.630,
C=233.426
• Benzene: A=7.47872, B=1701.073,
C=293.956
• Calculate the V/L-ratio in the flash
drum.

/ Department of Chemical Engineering and Chemistry 28-02-18 PAGE 37

 Example: flash distillation of benzene

• Calculate flash temperature: P = xP sat + (1 - x) P sat

B T

æ A- CB+T ö æ A- CB+T ö
750 = 0.30 × ç10 ÷ + 0.70 × ç10 ÷ T = 95.7 oC
è øB è øT
• Calculate the distribution coefficient for benzene:
B
A-
y P ( 95.7 ) 10
sat C + 95.7
KB = = tot
= B
= 1.73
x P 750
• Calculate the distribution coefficient for toluene:
B
A-
T ( 95.7 )
sat
1- y P 10 C +95.7
KT = = = = 0.687
1- x P tot
750
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 Example: flash distillation of benzene

KT KB
• Calculate q: q = -z - (1 - z )
1 - KT 1- KB
• This yields: q = 0.54

V 1
• Using q = L/F = L/(L+V): = -1
L q
• This yields V/L = 0.843

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 Stacked flash drums

Top is enriched three times

Bottom is depleted three times

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 From flash drums to a column

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 Distillation columns

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