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Gad

BY

0

Prof.Fatma K. Gad

UNIT OPERATION

Introduction:

materials are changed or separated into useful products.

ones. For example, the process used to manufacture common salts consists of

the following sequence of the unit operations, transportation’s of solids and

liquids, transfer of heat, evaporations, crystallization, drying and screening. No

chemical reaction appears in these steps. On the other hand, the cracking of

petroleum with or without the aid of a catalyst is a typical chemical reaction

conducted on an enormous scale.

Here the unit operations, transportation of fluid and solids, distillation, and

various mechanical separations are vital and the cracking reaction could not be

utilized without them.

the unit operation. some are elementary physical and chemical lows, and others

are special techniques particularly useful in chemical engineering.

The following physical and chemical lows will be used frequently later.

any process must be either accumulate or leave the process. There can be

neither loss nor gain during the process.

2. Molar units

whose mass is numerically equal to its molecular weight.

The mole is a mass unit and it can be used in material balances just like

mass in pounds or grams (mole).

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Prof.Fatma K. Gad

PV = nRT

( V1 / V2 ) = ( P2 / P1 ) * ( T1 / T2 )

4 Partial pressure

All partial pressures in a given mixture add to the total pressure. This

applies to mixtures of both ideal and non ideal gasses. A generally useful

consequence of the ideal gas low is:

For example, since air contains 79% N2 and 21% O2 by volume, 1 ft3 of air

under a pressure of P atm may be considered to be a mixture of 0.21 ft3 of

O2 , 0.79 ft3 of N2, both measured at P atm and the temperature of the

mixture.

atm, so that 0.21% of the pressure is from O2 and 0.79% from N2.

Finally 1 mole of air contains 0.21 mole of O2 and 0.79 mole of N2 at all

temperatures and pressures.

5. Equilibria

Equilibrium can not be shifted without making some change in the

conditions governing the system. Consequently the phase concept may be

defined as a homogeneous substance viewed independently of its shape

and size.

phase ) + 2.

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Prof.Fatma K. Gad

The utility of the phase concept comes from the fact that at equilibrium the

temperature pressure and concentration are independent of the geometric

shape and size of the phases.

6. Process kinetics

are that important in unit operations.

driving force or driving potential ( F).

Introduction:

components, there is a tendency for each constituent to F low in such a

direction as to reduce the concentration gradient, this process is known as mass

transfer.

the concentration gradient, the transfer is effected as a result of the random

motion of the molecules.

by eddy currents.

Mass transfer can take place in either gas, liquid or solid phases, or in both two

phases simultaneously as follow:

the gas phase to the liquid surface and the more volatile material diffuses at

an approximately equal molar rate in the opposite direction.

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Prof.Fatma K. Gad

4. In liquid extraction; the solute diffuses through the raffinate phase to the

interface and then into the extract phase.

and deposits on the solid surface.

6. Drying: Liquid water diffuses through the solid toward the surface of the

solid vaporized and diffuses as vapor into the gas.

the liquid phase is pure and no concentration gradient through it can exist.

But the vapor diffuses to or from the liquid gas interface in or out of the

gas phase.

In every case a fluid is brought into intimate contact with another phase, a

concentration gradient is established and a transfer of matter from one

phase to the other results. The concentration gradient tends to move the

component in each direction as to equalize concentration and destroys the

gradient. For example the substance moves from a phase of high

concentration to one of low concentration.

The concentration difference is thus a driving force for the mass transfer.

Diffusion can also be caused by a pressure or temperature gradients

applied over the mixture.

In all mass transfer operation, diffusion occurs in at least one phase and

often in both phase. Example in gas absorption solute diffuses through the

gas phase to the interface and through the liquid phase from the interface.

solid or liquid. It also takes place in fluid phase by physical mixing and by

the eddies or turbulent flow.

Thus we have to distinguish between two phenomena.

molecular scale in stagnant liquid.

of bulk flow.

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Prof.Fatma K. Gad

MOLECULAR DIFFUSION

be determined not only by the rate of diffusion of A but also by the behavior of

B. The molar rate of transfer of A per unit area due to molecular motion is

given by Fick’s low.

Where NA The molar rate of diffusion per unit area ( lb mole / ft2 hr).

(Equation (1) is one form of Fick’s low where NA refer to the heat flux

( q ) and D is analogous to the conductivity and concentration gradient (dC/dy)

to temperature gradient (dT/dy).

If the total pressure and hence the total molar concentration is every where

constant, (dCA/dy) and (dCB/dy) must be equal and opposite and therefore A

and B tend to diffuse in opposite directions.

In a distillation processes, where the two components have equal molar latent

heats. Condensation of one mole of the less volatile material releases just

sufficient heat for the vaporization of one mole of the more volatile component

and therefore equimolecular counter-diffusion take place with two components

diffusing at equal and opposite rate as determined by Fick’s law.

In many process B will neither remain stationary nor will it diffuse at an equal

and opposite molar rate to A. Exact calculations relating to this type of

problem are difficult. An example of this nature is the mass transfer in a

distillation column when the two components have unequal molar latent heat.

When the fluid is turbulent, Eddy diffusion takes place in addition to molecular

diffusion on the rate of diffusion is increased, so

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Prof.Fatma K. Gad

Where ED is known as the eddy diffusivity which will increase as the turbulence

is increased.

Suppose two vapors A and B are diffusing at equal and opposite rates and P A

and PB are their partial pressures at any point in the system.

PA = ( nA / V ) RT = CART = ( cA / MA ) RT (3)

PB = ( nB / V ) RT = CBRT = ( cB / MB ) RT

Where CA = PA / RT (4)

weights.

If total pressure ( P ) is constant at the system; therefore,

P = PA + PB = RT [CA + CB ] = RT [ CA /MA + CB / MB ]( 5 )

If CT = CA + CB. Therefore,

6

Prof.Fatma K. Gad

P = RT CT (6)

dPA / dy = - dPB / dy

dCA / dy = - dCB / dy

(7)

and

dCA / dy = - ( dCB / dy ) * ( MA / MB )

NA = - ( DAB / RT ) * ( dPA / dy )

system will remain constant as a result of diffusion and therefore, equal

number of molecules will diffuse in each direction.

Where NA = -NB

NA = - D * ( dCA / dy ) = - ( D / RT ) * ( dPA / dy ) ( 8 )

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Prof.Fatma K. Gad

The above equations which give the transfer rate of a point value of a

concentration or partial pressure gradient can be integrated directly. Thus if

the conditions at two different points in the system are denoted by the

suffixes 1 and 2, integration of equation (8) gives.

pressure gradient will be set up, causing A to diffuse towards and B away

from the surface. As a result a total pressure gradient will be produced

causing a bulk motion of A and B towards the surface, in addition to the

transfer by diffusion. Since there is no net motion of B, the bulk rate of flow

must exactly balance its transfer by diffusion.

NB = - D (dCA / dy)

The bulk flow of B is accompanied by bulk flow of A and since the rate of

the number of molecules of A at a point to those of B is CA/CB

Bulk flow of A

Diffusion of B

Bulk flow of B

Bulk flow of NA = - NB ( CA / CB )

8

Prof.Fatma K. Gad

NA = - D * ( dCA / dy ) * ( CA / ( CT - CA )) ( 9’’ )

diffusion and by bulk flow.

Thus, by adding equation 8 and 9’’ the total transfer N’A is given by:

N’A = - D * ( dCA / dy ) * ( CT / ( CT - CA ))

(10) between low positions 1,2.

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Prof.Fatma K. Gad

component A is small. Under these conditions C A small compared with CT.

Equation (11) gives.

N’A = D CT / (y2-y1)*[-(CA2-CA1)/(CT-CA1))–½(CA2-CA1)/(CT-CA1)2]

N’A - D / ( y2 - y1 ) * ( CA2 - CA )

the effects of bulk flow can be neglected at low concentrations

in diffusion through a stationary gas:-

NA = - D [( CA2 - CA1 )/( y2-y1 )] = + kL [ CA1 - CA2 ] = + kG [ PA1 – PA2 ]

Where

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Prof.Fatma K. Gad

kG = D / ( RT ( y2 - y1 )) * ( PT / PBM )

(13)

kL = D / ( y2 - y1 ) * ( CT / CBM )

kG

Gas diffusivities:

The value of gas diffusivity (D) for the transfer one gas in one there may not

be known and experiment determination may not be practicable. Many

attempts have been made to express D in terms of other physical properties

and the following empirical equation of Maxwell’s , modified by Gilliland,

gives satisfactory agreement with the observed figures;

D = [4.3*T1.5*((1/MA)+(1/MB))0.5]/[P*(VA1/3+VB1/3)] (15)

T absolute temp (oK)

MA & MB the molecular weight of A and B

P Total pressure in (N/m2)

VA / VB the molecular volumes of A and B.

[the vol. in m3 of 1 kmole of the material in the form of liquid at its B.P]

calculated from the following equation.

11

Prof.Fatma K. Gad

Example (1)

air, and 10% H2O vapor] assume T = 20 oC and pressure = 1 atm.

where VCO2 ,Vair and VH2O are 22.2, 29.9 and 33.3 respectively.

(0.108 cm2/sec).

Example (2)

operating at 101.3 KN/m2 and 2.95 oK. The resistance to transfer can be

regarded as lying entirely within the gas phase. At a point in the column, the

partial pressure of the ammonia is 7.0 kN/m2. The back pressure at the water

interface is negligible and the resistance to transfer can be regarded as lying

in a stationary gas filter 1 mm thick. If the diffusivity of ammonia in air is

2.36 x 10-5 m2/s; What is the transfer rate per unit area at that point in the

column? How would the rate of transfer be affected if the ammonia air

mixture were compressed to double the pressure?

Solution :

CT/CBM is essentially unaltered, and the diffusivity being inversely

proportional to the pressure equation (15).

12

Prof.Fatma K. Gad

Newton = Kg m/sec2 = 10 dyne (gm cm/sec)

Atm = (101.33) K. NEWTON (KN) / m2

The rate of diffusion of a material in the liquid phase is represented by the same

basic equation as for gas phase diffusion, i.e.

NA = -DL (CA/dy)

Simple integrated forms are available only if the total concentration (CT) and

(DL) are constant.

The integrated form of the above equation for equimolecular counter diffusion

of a material A is then of the same as for gaseous diffusion,

NA = - DL ( CA2-CA1 ) / ( y2 – y1 ) (17)

For diffusion through a stagnant liquid B

can be calculated approximately is,

T is the temperature in oK

is the viscosity in N s / m2

V is the molecular volumes

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Prof.Fatma K. Gad

The mass transfer rate between two fluid phases will depend on the physical

properties of the two phases, the concentration difference, the interfacial area

and the degree of turbulence.

region of the phase boundary. The earliest of this is the two film theory

propounded by Whitman.

Since the solute is diffusing from the gas phase into the liquid, that must be

concentrate gradient in the direction of diffusion within each phase.

In the gas phase the laminar diffusion resistance which concentrate gradient

overcomes lines lay within a thin laminar film at the interface between the two

phases. The film resistance is the same as the true molecular and eddy diffusion

resistance actually present.

A similar situation exist, while the liquid phase from the following figure.

The average concentration of A in the gas phase is P AG and this falls to PAi at

the interface due to the effective film thickness YG.

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Prof.Fatma K. Gad

In the liquid phase the concentration falls from G Ai at the interface to GAL the

average concentration in the mean bulk of the liquid..

transfer is centered in the thin films on either sides. There is no resistance to

the transfer of the diffusing solute occurs in the interface itself.

In a steady state conditions, the rate of transfer of material through the first film

will be the same as the through the second film.

Where, kG & kL are the gas film and liquid film transfer coefficients. They are

direct measure of the rate of transfer permit area of interface with a driving face

of unity.

is equilibrium curve. Point D(CL & PG) represent condition Ce in the liquid in

equilibrium with PG. Point A (Ce , PG) represent a concentration CL in the

liquid in equilibrium with (PG). Point B[Ci & Pi] represent the concentration

Pi in gas Ci in liquid in equilibrium at interfaces.

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Prof.Fatma K. Gad

Then the driving force coming transfer in the gas phase,= (PG – Pi) = DE.

and the driving force causing transfer in the liquid phase = (C i-CL) = BE.

Then PG – Pi/Ci – CL = kL/kG

And the concentrates at the interface (point B) are found by drawing a line

through D of slop; - kG /kL.

To cut the equilibrium curve in B. However the above relation has little

practical utility since it is necessary to know both, kG & kL as well as the

equilibrium relation ship between Pi and Ci in order to calculate NA.

overall driving force (P-Pe) and (Ce – CL) where Pe is the P.P of solute over a

solution of composition CL and Ce is the concentration of solution in

equilibrium with the solute partial pressure PG in the gas. Thus

NA = KG (PG – Pe)

(25)

=KL (Ce – CL)

NA = kG ( PG - Pi ) = kL ( Ci – CL ) = KG ( PG – Pe ) = KL ( Ce - CL )

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Prof.Fatma K. Gad

= 1/kG [(PG-Pi)/(PG-Pi)]+1/kG[Pi-Pe)/(PG-Pi)]

=1/kG + 1/kL [ ( Pi - Pe ) / ( Ci - CL ) ]

but (Pi - Pe) / (Ci - CL)is the average slope, slope of equilibrium curve and when

solution obeys Henry’s law, we have

H = dp / dc = ( Pi - Pe ) / ( Ci - CL )

Now for very soluble gas, the equilibrium curve lines close to the C axis and

point E approaches very close to point F. The driving force over the gas film

DE is then approximately equal to the overall driving force DF. So that k G is

approximately equal to KG.

If the gas is sparingly soluble, the equilibrium curve rises very steeply to that

the choices force EB. In the liquid film because approximately equal to the

overall driving force AD.

the film offer an appreciable resistance and the point B at the interface must be

17

Prof.Fatma K. Gad

- kL / kG = ( PG – Pi ) / ( Ci - CL )

Examples:-

at the bottom with a mixture of benzene and toluene as vapor. At the top a

condenser returns some of the product as a reflux which flows in a thin film

down the inner wall of the tube. The tube is insolated and heat losses can be

neglected. At once point in the column, the vapor contains 70 mol% B and the

adjacent liquid reflux contains 59 mol% B. The temperature at this point is

365k. Assuming the diffusion resistance to vapor layer 0.2 mm thick, calculate

the rate of interchange of benzene (B) and toluene (T) between vapor and

liquid. The molar latent heat of the two components can be taken as equal. The

vapor pressure of toluene at 365k is 54.o KN/m2 and the diffusivity of the

vapors is 0.051 cm2/sec.

Solution:

Let subscripts 1 and 2 refer to the liquid surface and vapor side of the stagnant

layer respectively. The example of equimolecular counter diffusion where,

NA = - D / R T X ( PA2 - PA1 )

P.P = (V.P) X

For Benzene:-

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Prof.Fatma K. Gad

= 6.93 * 10-5 Kmol/m2s

Example II.

A tube of small diameter was filled with acetone to 1.1 cm from the top and

maintained at a temperature of 20 oC, a gently current if air be supplied.

After 5 hr the level of acetone had fallen to 2.05 cm from top.

at 20o C, L = 0.79 gm/cm3 , M. wt = 58.

Calculate diffusivity of acetone ( R=82.06 cm3 atm / g mol ok )

Solution:-

NA = (ρL / Mwt) dL / d

= (L / Mwt) dL/d = D/RT (P/PBm) (P/L)

=[82.06*293*0.79/(58*(750/760)*Ln750/(750-180)]*(2.052)-

(1.12)/2*5*3600

= 0.101 cm2/sec

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Prof.Fatma K. Gad

Example III.

Calculate the rate of diffusion of acetic acid (A) across a film of water (B)

solution oil an thick at 17oC, when the concentration on apposite sides of the

film are respectively 9 and 3 wt %. The diffusivity of A in the solution may

be taken as 0.95 x 10-5 cm2/sec. [M wt of CH3 COOH = 60) of 9% solution

at 17oC = 1.012 gm/cm3

Solution:-

wt of acid)

(but for gasses Ptotal = PA1 + PB1 = PA2 + PB2

=0.054–0.0455/Ln0.054/0.0455=0.0497 gmole/cm3

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Prof.Fatma K. Gad

GAS OBSORPTION

This chapter deals with the mass transfer operations known as gas absorption

and stripping or desorption.

solute gas is more or less soluble, from its mixture with an inert gas. The

washing of ammonia from a mixture of ammonia and air by means of liquid

water is a typical example.

The solute is recovered from the liquid by distillation, and the absorbing liquid

can be either discarded or re used. Sometimes a solute is removed from a liquid

by bringing the liquid into contact with an inert gas, such an operation, the

reverse of gas absorption is desorption or gas stripping.

A common apparatus used in gas absorption and certain other operations is the

packed tower, Fig (4).

The device consists of a cylindrical column, or tower equipped with a gas inlet

and distributing space at the bottom; a liquid inlet and distributor at the top,

liquid and gas outlets at the bottom and top, respectively; and a supported mass

of inert solid shapes, called tower packing or tower filling. The inlet liquid may

be pure solvent or a dilute solution of solute in the solvent and is called the

weak liquor, is distributed over the top of the packing by distributor and in ideal

operation, uniformly wets the surfaces of the packing.

The solute containing gas, or rich gas, enters the distributing space below the

packing and flows upward through the interstices in the packing counter current

to the flow of the liquid. The packing provides a large area of contact between

the liquid and gas and encourages intimate contact between the phases. The

solute in the rich gas is absorbed by the fresh liquid entering the tower, and

dilute or lean gas leaves the top. The liquid is enriched in solute as it flows

down the tower, and concentrated liquid, called strong liquor, leaves the bottom

of the tower through the liquid outlet.

Many kinds of tower packing have been invented as shown in Fig (5). Packing

are divided into those which are (I) dumped at random into the tower and those

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Prof.Fatma K. Gad

I) Dumped packing consist of units ¼ to 2 inch and are used most in the

smaller columns and give high contact between liquid and gas.

II) Tthe units in stacked packing are 2 to about 8 inch in size, they are used

only in the larger towers.

2) It must be strong without excessive weight.

3) It must contain adequate passages for both streams without excessive liquid

holdup or pressure drop.

4) It must provide good contact between liquid and gas.

c)Rashing ring d)Lassing ring e)Pall ring

f)Tellerette g)Double spiral ring h)Triple spiral ring.

Thus most towers packing are made of cheap, inert light materials such as, clay,

porcelain, or graphite. Thin walled rings of steel or aluminum are some times

used. High void spaces and large passage for the fluids are achieved by making

the packing unit irregular or hollow, so that they interlock into open structures

w a porosity of 60% or more.

The requirement of good contact between liquid and gas is the hardest to meet,

especially in large towers. Ideally the liquid once distributed over the top of the

packing, flows in thin films all over the packing surface all the way down the

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Prof.Fatma K. Gad

tower. Actually the film tends to grow thicker in some places and thinner in

others, so that the liquid collects into small rivulets and flows along localized

paths through the packing. Especially at low liquid rates much of the packing

surface may be dry or, at best, covered by a stagnant film of liquid. This effect

is known as Channeling, it is the chief reason for the poor performance of large

pack towers.

Channeling is most serve in towers packed with stacked packing, less severe in

dumped packing of crushed solid, and least severe in dumped packing of

regular units such as rings.

of the tower at least 8 times the packing diameter. If the ratio of tower diameter

to packing diameter is less than 8:1, the liquid tend to flow out of the packing

and down the walls of the column.

Even in small towers filled with the packing that meet this requirement,

however, liquid distribution and channeling have a major effect on column

performance.

In toll towers filled with large packing the effect of channeling may be

pronounced, and distributors for the liquid are normally included every 10 or 15

ft in the packed section.

At low liquid rates, regardless of the initial liquid distribution, much of the

packing surface is not wetted by the flowing liquid. As the liquid rises, the

wetted fraction of the packing surface increases until at a critical liquid rate, is

usually high, the entire packing surface becomes wetted and effective. At

liquid rates higher than the critical the effect of channeling is not important.

In a tower with a definite flow of liquid, there is an upper limit to the rate of gas

flow. The gas velocity corresponding to this limits called the flooding velocity.

b) Gas flow rate.

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Prof.Fatma K. Gad

Fig (6) shows the relation between pressure drop and gas flow rate in a packed

tower. The pressure drop per unit packing depth comes from liquid friction; it

is plotted on logarithmic coordinates against the gas flow rate G y expressed in

mass of gas per hour per unit of cross sectional area, base on the empty tower.

Gy = Vsy y (1)

Where

Vsy superficial gas velocity.

When the packing is dry the line so obtained is straight and has a slope of about

1.8.

velocity Gx the relation between pressure drop and gas flow rate follows a line

such as cbde in fig (3). At low and moderate velocity, the pressure drop is

proportional to the 1.8the power of the flow rate but is greater than that in dry

packing at the same gas velocity. A gas velocity increases, the line curves

upward starting at point C in fig (3). Then at higher velocity, as shown by the

line cde, the pressure drop increases sharply at nearly constant gas velocity.

Fig. (2) Pressure drop in packed tower © loading point (e) flooding point.

The rise may follow a smooth curve, as shown by the solid line cd, or may show

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Prof.Fatma K. Gad

sharp breaks at point C and d as shown by the dotted line. As the pressure drop

increases along line bc, the amount of liquid held in the packing is constant and

independent of the gas velocity. The liquid moves downward through the

packing uninfluenced by the motion of the gas. At point C, called the

LOADING POINT, the gas flow begins to impede the downward motion of the

liquid. Local accumulations of liquid appear here and there in the packing.

As the gas rate rise further, the liquid holdup increases and the pressure drop

changes along line cde, increasing more rapidly with gas velocity than before.

At point e the FLOODING POINT, the top of the packing is covered with a

layer of liquid through with bubbles of gas issue. The liquid can no longer flow

down through the packing, and the layer grows until liquid is blown out of the

top of the tower with the gas.

The gas velocity in an operating tower must obviously be lower than the

velocity which will cause flooding. How much lower is a choice to be made by

the designer. The lower the velocity the lower the cost of power and the larger

the tower.

The higher the gas velocity, the larger the power cost and the smaller the tower.

the cost of the power and the fixed charges on the experiment.

The optimum velocity can be estimated, but it is usually taken about one-half

the flooding velocity.

Packed towers are also commonly designed on the basis of a definite pressure

drop per unit height of packing. For absorption towers the design value is

usually between 0.25 and 0.5 inch H2O per foot of packing, for distillation

columns it is in the range 0.5 to 0.8 inch H 2O per foot. In most towers packed

with rings or saddles loading usually beings at a pressure drop of about 0.5 inch

H2O per foot, and FLOODING OCCURS at a pressure drop between 2 and 3

inch H2O per foot.

Fig (7) gives corrections for estimating flooding velocities and pressure drops

in packed towers, it consists of a logarithmic plot of

Where,

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Prof.Fatma K. Gad

Gy mass velocity of gas lb/ft2 sec

Fp Packing factor Ft-1 ft-1

Px Density of liquid lb/ft3

Py Density of gas lb/ft3

x Viscosity of liquid cp.

gc Newton’s law proportionality factor, 32.174 ft/lb, S 2

Fig. (3) Generalized correlation for flooding and pressure drop in packed

column after Eckart.

Example (1)

A tower packed with 1 inch (25.4 mm) ceramic Rasching rings is to be built to

treat 25000ft3 (708m3) of entering gas/hrs (air). The ammonia content of the

entering gas is 2% by volume. Ammonia free water is used as absorbent. The

temp 20°C and pressure 1 atm. The ratio of gas flow to liquid flow is 1 lb of

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Prof.Fatma K. Gad

a) If the gas velocity is to be one half the flooding velocity, what should be the

diameter of the tower?

Solution:

x = 62.3 lb/ft3

x = 1 cp

a) The total gas flow is 25000 x 0.07465/3600 = 0.518 lb/S. If the actual

velocity is one – half the flooding velocity. The cross sectional area S of

the tower is

Gx is unchanged and the abscissa value in Fig (4) = 0.0692. The ordinate

becomes 0.19/4 = 0.0475. For these conditions the pressure drop is about

0.45 inch H2O per foot of packed height; the total pressure drop is 20 * 0.45

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Prof.Fatma K. Gad

Principle of absorption:-

depends on;

2) Their properties

3) The ratio of one stream to the other.

Where the height of the tower and hence the total volume of packing depends

on;

1) The rate of mass transfer per unit of packed volume.

2) The magnitude of the desired concentration change.

A) Material balances

B) Enthalpy balances.

C) Estimates of driving force and mass transfer coefficients.

In a differential contact plant such as the packed absorption tower, where there

is no sudden discrete change in composition. As it is known that in an

absorption process, the solute (A) in the gas phase is transferred to the liquid

phase,

Consequently a material balance for the solute “A” for a zone from bottom to

any section;

So, material balance over a differential section, where the flow rate of the two

phases through a differential length of column G, L, x and y.

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Prof.Fatma K. Gad

the column, so

Where

L moles of liquid

yA1 xA1 mole fraction of A in gas and liquid at the bottom

yA xA mole fraction of A in gas and liquid at any section

Where yA2 , xA2 mole fraction of component A at the top of the tower for gas

and liquid. The slope of equation 5

This equation is true only when G , L do not change from one section to another

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Prof.Fatma K. Gad

However, in absorption operations the flow rates of liquid and gas L , G usually

change appreciably form one point to another in the column and the operating

lines are often strongly curved specially at high concentration of solute (A)

From the figure, it is clear that for a given gas flow, a reduction in liquid flow

decreases the slope of the operating line. Consequently the maximum possible

liquor concentration and the minimum possible liquid rate are obtained when

the operating line just touches the equilibrium line as show above.

At any actual tower, the liquid rate must be greater than this minimum if the

tower to be operated.

where x* is in equilibrium with yA1.

If the liquid gas ratio is large, the average distance between the operating and

equilibrium line is also large, the concentration difference is favorable through

out the tower and the tower is short.

30

Prof.Fatma K. Gad

If on the other hand concentration costs are reduced by using less liquid, the

driving forces in the absorber are reduced and the tower become taller and more

expensive.

The optimum liquid rate is found by balancing recovery costs against fixed

costs of the equipment.

equilibrium line for economical operation.

At top driving force = yA2 – y*A2 = yA2

Where

y*A1 is in equilibrium with xA1

y*A2 is in equilibrium with xA2 as shown

31

Prof.Fatma K. Gad

Example 2:-

By mean of a plate column, Acetone is absorbed from its mixture with air in a

non-volatile absorption oil. The entering gas contains 30 mole percent acetone,

and the entering oil is acetone free. The acetone in the air 97% is to be

absorbed and the concentrated liquid at the bottom of the tower is to contain

10% acetone. Calculate the quantity of liquid (oil) used and plot the operating

line.

Solution:

Since the concentration in the entering gas is more that 10% so that there is a

change in G and L across the column and consequently are shall use mole ratio

instead mole fraction as we shall see.

= 261.9 mole ………..(1)

32

Prof.Fatma K. Gad

The operating line passes through points (0) 0.0127) and (0.1 > 0.3).

Plot the line by chose value of x and calculate the values of y from the above

equation

y 0.114 0.173 0.253 ……..(2) U.E.D

When rich gas is fed to an absorption tower, the temperature in the tower varies

appreciably from bottom to top. This temperature gradient affects the shape of

the equilibrium line. The rate of absorption is large at the gas inlet, and the heat

of condensation and solution of the absorbed constituent may be sufficient to

increase the temperature of the liquid considerably.

Since the partial pressure of the absorbed component increases with increase

the temperature, the concentration of the vapor in equilibrium of definite

composition also increases with temperature. Even if Henry’s law applies, the

equilibrium line may be strongly curved in this situation.

in Fig (11). Line “OA” is the equilibrium line for isothermal operation, and line

“OB” is that where the temp at the bottom of the tower is larger than at the top.

33

Prof.Fatma K. Gad

If the temperature effect is sufficiently great, the equilibrium line may intersect

the operating line, and the process is in operative near the bottom of the tower.

Some times cooling coils or other cooling means are installed in the tower to

reduce this heat effect.

The height of a packed tower depends on the rate of absorption which in turn is

affected by the rate of transfer of mass through the liquid and gas phases. The

following treatment has two limitations;

liquid.

2) Heat of solution is neglected.

Since the rate of solute (A) transfer from gas phase to liquid phase pass through

two diffusion resistances:

a) Gas resistance

b) liquid resistance.

Assuming that the resistance in the interface itself is Zero; consequently the gas

and liquid at the interface are in equilibrium.

34

Prof.Fatma K. Gad

concentration of the streams in term of moles of solute gas per mol of inert gas

in the gas phase, and as moles of solute gas per mol of solute free liquid in the

liquid phase as will seen later.

The actual area of interface between the two phases is not known, and the term

“a” is introduced as the interfacial area per unit volume of the column.

On this basis the general equation for mass transfer can be written as;

Where

NA mol of solute absorber / unit time and unit interfacial area.

a Surface area of interface per unit volume of column.

A Cross sectional area of column.

Z height of packed section.

Gm mole of inert gas /(unit time) (unit cross section)

Y Moles of solute gas A/moles of inert gas B in gas phase.

X moles of solute A / moles of inert solvent in liquid phase.

Consider any plane at which the molar ratios of the diffusing material in the gas

and liquid phases are Y and X. Then over a small height of Z, the moles of gas

leaving the gas phase will equal the moles taken up by the liquid as shown in

equations 8 , 9.

Gm dY = kg a [ (( Y / ( 1 + y )) - (( Yi / ( 1 + Yi )) ] dz

bottom to Y2 at the top of the column is given by;

z y1

35

Prof.Fatma K. Gad

dz = Z = Gm / kg a ( 1 + Y ) ( 1 + Yi ) dy / ( Y - Yi ) (10)

0 y2

y1

Z = G m / kg a dy / ( Y - Yi ) (11)

y2

In this analysis it has been assumed that k g is a constant throughout the column,

and provided the concentration changes are not too large.

A Lm dX = kL a ( Ci - CL ) Adz (12)

Where the concentrations C are in terms of moles of solute per unit volume

of liquor, where

CT = (mole of solute + solvent) / volume of liquid.

X = moles of solute/moles of solvent = C/(CT-C)

So C = ( X / ( 1 + X )) * CT (13)

Lm dX = kL a CT [ ( Xi / ( 1 + Xi )) – ( X / ( 1 + X ))] dz

z x1

Z = Z = Lm / kL a CT [( 1+Xi ) ( 1+X )/( Xi - X )] dx (14)

0 x2

x1

Z = Lm / kL a CT dx / ( 36Xi –X )

x2

Prof.Fatma K. Gad

(15)

If the driving force based on the gas, concentration is written as (Y-Ye) and

the overall gas transfer coefficient as KG

Y1

(16)

Z = Gm / KG a (dy) / ( Y - Ye )

Y2

And in term of liquor;

X1

Z = Lm / KL a CT dx / ( Xe – X ) (17)

X2

Xe mol ration at equilibrium with Y.

Consequently for dilute concentrations; as the mol fraction is approximately

equal to the molar ratio at dilute concentrations then considering the gas

film;

Y1

Z = Gm / Kg a dY / ( Y - Ye )

Y2

y1 (18)

Z = Gm / Kg a dy / ( y - ye )

y2

37

Prof.Fatma K. Gad

X1

Z = Lm / KL a CT dX / ( X - Xe )

X2

x1

Z = Lm / KL a CT dx / ( x - xe ) (19)

x2

X and Y are mole ratio.

line, it is permissible to use an average value of the driving force over the

column.

NA A a dz = Gm A dy = KG a A ( y - ye ) dz (20)

if y* = ye = m x + c ;

from equation 20

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Prof.Fatma K. Gad

y1 z

dy / ( y - ye ) = (( kG a ) / Gm ) dz (22)

y2 0

by substituting ye in form x

y1 y1

dy/(y-ye)= dy/{y-m[x1+(Gm/Lm)(y-y1)] – C} (23)

y2 y2

y1

dy / ( y - ye ) = ( y1 – y2 ) / ( y – ye )Lm (24)

y2

Where

39

Prof.Fatma K. Gad

In liquid term;

(molar)density) = total mol/total vol.

CA = ρm xA

Z= Lm / KL a Pm ( x1 – x2 ) / ( x )Lm (27’)

In term of mol ration equations 26, 27 and 27 will be the same, since mole

fraction equal mol ration.

Y=Y/(1+Y) (29)

40

Prof.Fatma K. Gad

A material balance taken between the bottom and some plane where the partial

pressure in the gas phase is Pg and the concentration in the liquid is X will give;

Z Pg1

dz = Gm PBm dPg / [kg a (- Pg )2 ( Pg - Pi )]

(31)

0 Pg2

= ( PB2 - PB1) / Lm ( PB2 / PB1 )

Kg has a mean value for the whole tower, but it is not constant in

this equation.

and Colburn as the number of overall gas transfer units (NOG) since as been

known.

Gm A dy = kg a A ( y - yi ) dz

y1

so dy / ( y - yi ) = ( kg a / G ) dz

y2

41

Prof.Fatma K. Gad

The group of the left hand side of this equation represents the integrated ratio of

the change in composition to the driving force tending to bring this about. This

group has been defined as the number of transfer units N G. The quantity (G / kg

a ) which is the reciprocal of right hand side, and has the dimensions, they

define as the height of transfer unit (HTU) H G and consequently the above

equation tern to;

Z = HG NG (32)

Z = HL NL (35)

a) For gas;

42

Prof.Fatma K. Gad

b) For liquid

NOL = dx / ( xe - x ) (40)

For special case where the equilibrium curve is a straight line and dilute

solution;

NOL = ( x1 - x2 ) / (x)Lm

dz / HOG = dy / ( y - ye ) , dz / HG = dy / ( y - yi ) (33')

dz / HOL = dx / ( xe - x ) , dz / HL = dx / ( xi - x ) (33'')

HOG / ( y - ye ) = HG / ( y - yi

)

43

Prof.Fatma K. Gad

HOG = HG [ 1 + ( yi - ye ) / ( y - yi )] (44)

interface.

yi - ye = m ( xi - x )

And

H0G = HG + [ m ( xi - x ) / ( y - yi ) ] HG

dz / dy = HG / ( y - yi )

dz / dx = HL / ( xi - x )

dx HL / dy Hg = dz ( xi - x ) / dz ( y - yi ).

Similarly

HOL = HL + Lm / ( m Gm HG ) (46)

By dividing

44

Prof.Fatma K. Gad

The importance of liquid and gas flow rates and slope of the equilibrium

curve:-

For a packed tower operating with dilute concentration; mol fraction = mol ratio

so

Gm ( y - y2 ) = Lm ( x1 - x2 )

For x2 = 0

x = xi = Gm / Lm ( y - y2 )

Since NOG = dy / ( y - ye )

y1

NOG = dy / [( y - m Gm / Lm) ( y - y2 )]

y2

Finally

It is shown from equation 48 that the greater mGm/Lm is the greater will be the

value of NOG for a given ratio of (y1/y2).

Example 3:-

from 0.03 k mol H2S per k mol of inert HCS gas to 1% of this value with a tri-

ethanolamine – water solvent in a counter current tower, operating at 300 k and

at 1 atm. The equilibrium relation for the solution may be taken as Ye=2X.

The solvent enters the tower free of H2S and leaves containing 0.013 k mol

H2S/kmol of solvent. If the flow of inert gas is 0.015 Kmol/Sm2 of tower cross

section, calculate;

45

Prof.Fatma K. Gad

b) The NOG required.

(Unit mol fraction driving force).

Solution:

Gm ( y1 - y2 ) A = Kg a ( y - ye )Lm AZ

or

Z = Gm / Kg a ( y1 - y2 ) / ( y )Lm

=0.00143

Example 4

A 2000 f3/min gas mixture contains 1% by vol. SO2 the rest air at 68°F. We

want to reduce the concentration to 0.01 % by vol. Using a dilute alkaline in a

packed tower. It may be assured that the P.P of SO 2 in equilibrium with solvent

is always zero and Kg equal 0.002 G0.8 where G in lb/hr. ft2 , kg in lb mol/hr atm.

Calculate the size of tower and height of packing (z). Velocity of gas phase =

46

Prof.Fatma K. Gad

Solution:-

a = 30 Ft2/ft3

v = 6.7 ft/sec

6.7 = 2000/60 A

Example 5:-

We want to scrub 2000 ft3/min air containing 0.02 by vol NH3 at 68°F in the

same previous tower using water. 98 % of the ammonia entering is to be

removed. Calculate;

47

Prof.Fatma K. Gad

NH3, Kg is = 1.2 lb mol/hr ft2 at a = 30 ft2/ft3.

Solution:-

Lm = Gm ( y1 - y2 ) / ( x1 - x2 ) = 62(0.02-0.0004)/(0.0263 – 0)

= 45 lb mol/hr ft2

M unit of air = 29

48

Prof.Fatma K. Gad

are brought together for a sufficient time to reach equilibrium and the separated.

Gas and liquid streams enter the mixer at molar flow rate Gm2 and Lm0 moles the

respectively, containing the component to be absorbed at mole fractions y2 , x01

and leave the separator at equilibrium.

The outlet composition y1e , x1e must lie on the equilibrium line.

material balance over the stage and the equilibrium relation.

Thus;

49

Prof.Fatma K. Gad

For the special case of absorption of a single component from a dilute solution

in the gas and liquid flows are changed negligibly by absorption equation 1 , 2

becomes;

Fig (11)

The composition changes until the equilibrium line is reduced a long the line

abc which has a slope equal to –Lm / Gm as required by equation (3).

It should be noted at this point that in practice complete equilibrium can never

be attained since infinite contact time would be necessary. Depending on the

prevailing mass transfer rates in the stages, the composition will move along the

line ac and stop at some point b of composition x1 , y1 short of reacting the

equilibrium line.

A stage efficiency “E” may be defined as the ratio of the composition change

actually obtained to that which would be attained at equilibrium, so;

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Prof.Fatma K. Gad

In many of the stage wise contactors used in practice stage efficiencies close to

unity can be realized.

1. Derivation of general equation.

In the previous section we used single stage contact to transfer the solute A

between the V and L phases. In order to transfer more solute from, say, the V1

stream, the single-stage contact can be repeated by again contacting the V 1

stream leaving the first stage with fresh L0. This can be repeated using multiple

stages. However, this is wasteful of the L0 stream and gives a dilute product in

the outlet L1 streams. To conserve use of the L0 stream and to get a more

concentrated product, countercurrent multiple-stage contacting is generally

used. This is somewhat similar to countercurrent heat transfer in a heat

exchanger, where the outlet heated stream approaches more closely the

temperature of the inlet hot stream.

The process flow diagram for a countercurrent stage process is shown in Fig.

1.3-4. The inlet L stream is L0 and the inlet V stream is VN+1 , instead of V2 as

for a single-stage in Fig. 1.3-3. The outlet product streams are V1 and LN and

the total number of stages is N. The component A is being exchanged between

the V and L streams.

component C. Components B and C may or may not be somewhat miscible in

each other. The two-phase system can be gas-liquid, vapor-liquid, liquid-liquid,

or other. Making a total overall balance on all stages,

51

Prof.Fatma K. Gad

(1.3-21)

where VN+1 is mol/h entering, LN is mol/h leaving the process, and M is the total

flow. Note in Fig. 1.3-4 that any two streams leaving a stage are in equilibrium

with each other. For example, in stage n, Vn and Ln are in equilibrium. For an

overall component balance on A, B, or C,

(1.3-22)

where x and y are mole fractions. Flows in kg/h (lb m/h) and mass fraction can

also be used in these equations.

(1.3-21)

(1.3-22)

(1.3-23)

relates the concentration yn+l in the V stream with xn in the L stream passing it.

The terms V1, y1, L0, and x0 are constant and usually known.

An important case where the solute A is being transferred occurs when the

solvent stream V contains components A and B with no C and the solvent

stream L contains A and C with no B. The two streams L and V are immiscible

in each other with only A being transferred. When Eq. (1.3-23) is plotted on an

xy plot (xA and yA of component A) as in Fig. 1.3-4, it is often curved, since the

slope Ln / Vn+1 of the operating line varies if the L and V streams vary from

stage to stage.

52

Prof.Fatma K. Gad

process.

In Fig. 1.3-5 is plotted the equilibrium line that relates the compositions of two

streams leaving a stage in equilibrium with each other. To determine the

number of ideal stages required to bring about a given separation or reduction

of the concentration of A from yN+1 to y1, the calculation is often done

graphically. Starting at stage l, y1 and x0 are on the operating line, Eq. (1.3-23),

plotted in the figure. The vapor y1 leaving is in equilibrium with the leaving x 1

and both compositions are on the equilibrium line. Then y2 and x1 are on the

operating line and y2 is in equilibrium with x2, and so on. Each stage is

represented by a step drawn on Fig. 1.3-5. The steps are continued on the graph

until yN+1 is reached. Alternatively, we can start at yN+l and draw the steps going

to y1.

If the streams L and V are dilute in component A, the streams are approximately

constant and the slope Ln/Vn+1 of Eq. (1.3-23) is nearly constant. Hence, the

operating line is essentially a straight line on an xy plot. In distillation, where

only components A and B are present, Eq. (1.3-23) also holds for the operating

line. Cases where A, B, and C are appreciably soluble in each other often occur

in liquid-liquid extraction.

53

Prof.Fatma K. Gad

It is desired to absorb 90% of the acetone in a gas containing 1.0 mol % acetone

in air in a countercurrent stage tower. The total inlet gas flow to the tower is

30.0 kg mol/h, and the total inlet pure water flow to be used to absorb the

acetone is 90 kg mol H2O/h. The process is to operate iso-thermally at 300 K

and a total pressure of 101.3 kPa. The equilibrium relation for the acetone (A)

in the gas-liquid is yA = 2.53 xA.

Figure 1.3-6: Theorerical stages for counter current absorption in example 1.3-

2.

Solution:

The process flow diagram is similar to Fig. 1.3-5. Given values are

yAN+1 = 0.01, xA0 = 0,

VN+l = 30.0 kg mol/h, and L0 = 90.0 kg mol/h.

Making an acetone material balance,

amount of entering acetone : yAN+1 VN+1 = 0.01 x 30 = 0.30 kg mpl / hr

entering air : (1-yAN+1) VN+1 = (1-0.01) 30 = 29.7 kg mol air / hr

54

Prof.Fatma K. Gad

acetone leaving in LN : 0.90 (0.30) = 0.27 kg mol/h

yA1 = 0.03 / 29.73 = 0.00101

LN = 90.0 + 0.27 = 90.27 kg mol water + acetone/h

xAN = 0.27 / 90.27 = 0.0030

Since the flow of liquid varies only slightly from L0 = 90.0 at the inlet to LN =

90.27 at the outlet and V from 30.0 to 29.73, the slope L n / Vn+1, of the

operating line in Eq. (1.3-23) is essentially constant. This line is plotted in Fig.

1.3-6 and the equilibrium relation yA = 2.53 xA is also plotted. Starting at point

yAl, xA0, the stages are drawn as shown. About 5.2 theoretical stages are

required.

Contact

When the flow rates V and L in a countercurrent process are essentially

constant, the operating-line equation (1.3-23) becomes straight. If the

equilibrium line is also a straight line over the concentration range, simplified

analytical expressions can be derived for the number of equilibrium stages in a

countercurrent stage process.

component A.

(1.3-24)

(1.3-25)

(1.3-26)

(1.3-27)

55

Prof.Fatma K. Gad

(1.3-28)

Ln = LN = constant = L and

Vn+l = VN+l = constant = V.

(1.3-29)

Since yn+l and xn+1 are in equilibrium, and the equilibrium line is straight,

Substituting m xn+l for yn+1 and calling A = L/mV, Eq. (1.3-29) becomes

(1.3-30)

All factors on the right-hand side of Eq. (1.3-30) are constant. This equation is a

linear first-order difference equation and can be solved by the calculus of finite-

difference methods. The final derived equations are as follows.

For transfer of solute A from phase L to V (stripping),

(1.3-31)

(1.3-32)

When A = 1,

56

Prof.Fatma K. Gad

(1.3-33)

(1.3-34)

(1.3-35)

When A = l,

Often the term A is called the absorption factor and S the stripping factor,

where S = l/A. These equations can be used with any consistent of units such as

mass flow and mass fraction or molar flow and mole fraction. Such series of

equations are often called Kremser equations and are convenient to use. If A

varies slightly from the inlet to the outlet, the geometric average of the two

values can be used, with the value of m at the dilute end being used for both

values of A

Repeat Example 1.3-2 but use the Kremser analytical equations for

countercurrent stage processes.

Solution:

V1 = 29.73 kg mol/h, yAl =0.00101,

L0 = 90.0, and xA0 = 0.

57

Prof.Fatma K. Gad

yA = 2.53 xA where m = 2.53. Then,

A1 = L / mV = L0 / m V1 = 90.0 / ( 2.53 x 29.73) = 1.20

At stage N;

VN+l = 30.0, yAN+1 = 0.01,

LN = 90.27, and xAN = 0.00300.

AN = LN / m VN+1 = 90.27 / (2.53 x 30.0) = 1.19

The geometric average A=√(A1 x AN)=√(1.2 x 1.19) = 1.195.

The acetone solute is transferred from the V to the L phase (absorption).

Substituting into Eq. (1.3-35),

N=log[{(0.01–2.53(0))/(0.00101–2.53(0))

(1–(1/1.195))}+(1/1.195)]/log(1/1.195)

=5.04 stages

This compares closely with 5.2 stages obtained using the graphical method.

desorption

This operation, also called stripping which is the reverse of absorption. And is

treated by the same methods. The only differentces are that:

1- The driving potential ∆x and ∆y are reversed and are given by ( x-xi) , (yi-y)

2-The operating line lies below the equilibrium line.

direction. Consequently the phase rates changes rapidly through the column if

an appreciable amount of material is transferred.

In absorption, the wet gas which rises through the column loses material to the

descending absorber oil but little of the relatively non available oil passes to the

gas phase. As a result, the gas phase decreases in amount as it rises and the

liquid phase increases as corresponding amount as it descends.

stripped from the oil to the gas phase to an extent described by their respective

distribution coefficients. Stripping gas normally used are essentially in soluble

in the oil phase, and little transfer of the gas to the liquid phase occurs.

58

Prof.Fatma K. Gad

Consequently, the oil phase decreases and the gas phase increases in amount as

they pass through the column.

stripping are valid only in the special case where the amount of material

transferred is so small as to have a negligible effect on the phase rates.

Besides the effect on the mass rates, the unidirectional transfer of material

creates thermal effect which must be considered. The material transferred

undergoes a phase change and the heats of vaporization or condensation are

involved along with the smaller heats of solution.

In absorption, most of the heat released as the gas components condense into

the liquid phase must appear as sensible heat in the liquid since insufficient

material is being vaporized to utilize the released heat as heat of vaporization.

Consequently the temperature of the liquid phase rises as it passes down the

column. The raise in liquid temperature occurs despite the fact that the liquid is

at its bubble point. The vaporization of only a small amount of a light

component say methane will cause a relatively large rise in the bubble point.

The amount of sensible heat required to raise the liquid temperature is large

compared with the heat required to vaporize the small amount of volatile

material

In stripping, the effect is opposite, where the heat of vaporization of the light

components as they pass from the liquid to the gas phase is supplied from the

sensible heat content of the liquid phase.

Consequently the temperature of the liquid phase decreases as it passes down

the column.

In the special case where only very small amount of material is transferred, the

temperature changes will be small and possible negligible.

columns and the resulting variation in phase rates and temperature graphical

solution methods are less useful than in the cases of binary mixture.

The change in the phase rates as they pass through the column causes the L/V

ratio to change and therefore, the operating line equation does not plot as a

straight line.

59

Prof.Fatma K. Gad

Only in special case of very small transfer will be L/V ratio remain essentially

constant.. If the temperature changes from stage to stage the distribution

coefficient K= y/x for each component changes and the equilibrium curves are

not straight lines; only in special case of an isothermal column.

If the wet gas to an absorber is very dilute in the material being absorbed, the

operation utilized only those portions of the equilibrium curve very close to the

origin and these portions often can be drawn as straight line (Henry’s holds).

operates at 100 psia and changes the following feed;

Component ye

C1 0.1

C2 0.15

C3 0.10

C4 0.05

= 1.0

Which has an Ln+1 / Vo = 2

The wet gas and the absorber oil both at 80°F and the oil is completely stripper

of light HCS to get a quick estimate of the amount absorbed.

Let us assume that L / V = Ln+1 / Vo and t = 80°F, through out the column. Both

operating and equilibrium curves will be straight lines in this case and can be

plotted as shown.

The slope of the equilibrium line for each component is the value for each

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Prof.Fatma K. Gad

The slop of all the operating lines is the same and equal 2.

equilibrium line must be such as to satisfy the known concentration in L n+1 and

Vo and also allow three stages to be stepped off between these concentrations.

Fig. (13) Graphical construction for multi-component when L/V and T are

constant.

Considering the construction for C3 as in the above fig. the point ( yo = 0.1 , x1 )

represents passing streams Vo and L1 on the operating line and it must lie some

where along the horizontal line y = 0.1

Similarly, the point (y3 , xn+1 = 0) represents passing streams V3 and Ln+1 on the

operating line and since the entering absorber oil has been completely stripped,

it must fall somewhere on the ordinate at x = 0. So, by trial and error that

positions can be formed where exactly three steps can be constructed between

the intersections of the operating line with the lines y= 0.1 and x = 0.0. Similar

trial and error construction can be made for the other components.

It can be seen that most of the methane is transferred in the top stage and by the

61

Prof.Fatma K. Gad

time the oil leaves the second stage, it is essentially saturated with methane.

Therefore, little change in methane concentration occurs across the bottom

stage and for all practical purposes the point (y0 , x1) on the operative line

coincides with the equilibrium line.

In the case of the butane most of the transfer occurs at the bottom of the column

and to construct three stages it must be assumed that (y 3 , xn+1) essentially

coincides with the origin as shown.

amount whose equilibrium curve falls most nearly parallel to the operating line

(component having a value of K most nearly equal to L/V).

Thus components heavier than the key component are absorbed nearly

completely and approach equilibrium with oil into the top if the fresh solvent

contains none of these component.

Components more volatile than the key component will approach equilibrium

with the liquid phase at the rich end (bottom) of the column.

Varying the L/V ratio clearly changes the nature of the key component. The

optimum ratio is the one which will allow substantially complete absorption of

the desired component.

The theoretical plate can be calculated by fixing the oil gas ratio and fraction of

the key component (butane) absorbed. Starting at the ordinate scale at the left

(top of the column) and counting off one step for each composition of the gas

entering and liquid leaving the top plate.

appreciable change occurs in gas composition in top plate.

It follows that the absorption of the more volatile components takes place in the

upper part of the column.

The construction for a stripping column is analogous to that shown for absorber

except that the operating lines fall below their respective equilibrium line.

the components being transferred. For all other cases a numerical solution

should be obtained.

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Prof.Fatma K. Gad

1

v1 = V1 y1 Lo = Xo lo

(1) Effective constant absorption for

Solute (n) = AE = 1.4 N

Effective constant absorption for

Solvent (k) = zero vn+1 = yn+1 Vn+1 LN=LN Xn

(3) Definition of the two functions NK and N-!K as for solute follows:

SkN = [1 - N-1K / NK] LKo + [1 – ( 1 / NK )] VkN+1 (5)

Kn

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Prof.Fatma K. Gad

n refere to the solute

k refere to the solvent

If the solvent is not present in the solvent lon = zero ( pure solvent )

Example :

Gas flow 11 mole acetone in 1 mole Lo = pure water

V

Recovery of acetone = 95 % = r

T=300 k ,

Absorption factor AE = 1.4 P=10 bar

Pressure = 10 bar

Temperature at top of the tower = 300 oK

Calculate flow rate of water.

Lw

Vn+1=10 mole/sec air

Vn+1= 1 mole/sec acetone

Solution:

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Prof.Fatma K. Gad

The flow rate of inert gas air = 10 mole /sec , acetone = 1 mole/sec

V1k =(vN+1k)/Nk+(N-1k/Nk)Lok

=(zero/1.73e6)+(1.303e5/1.93e6)0.51= 0.038

H2O in gas inlet = zero , H2O evaporate with gas outlet = 0.038

H2O oulet = 0.51 – 0.038 = 1.472

U.E.D.

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Prof.Fatma K. Gad

Humidification

1-Introduction to gas-liquid contactors. When a relatively warm liquid is

directly contacted with gas that is unsaturated, some of the liquid is vaporized.

The liquid temperature will drop mainly because of the latent heat of

evaporation. This direct contact of a gas with a pure liquid occurs most often in

contacting air with water. This is done for the following purposes: humidifying

air for control of the moisture content of air in drying or air conditioning;

dehumidifying air, where cold water condenses some water vapor from warm

air; and water cooling, where evaporation of water to the air cools warm water.

discussed. The performance and design of continuous air-water contactors is

considered. The emphasis is on cooling of water, since this is the most

important type of process in the process industries. There are many cases in

industry in which warm water is discharged from heat exchangers and

condensers when it would be more economical to cool and reuse it than to

discard it.

flows countercurrently to an air stream. Typically, the warm water enters the

top of a packed tower and cascades down through the packing, leaving at the

bottom. Air enters at the bottom of the tower and flows upward through the

descending water. The tower packing often consists of slats of wood or plastic

or of a packed bed. The water is distributed by troughs and overflows to

cascade over slat gratings or packing that provide large interfacial areas of

contact between the water and air in the form of droplets and films of water.

The flow of air upward through the tower can be induced by the buoyancy of

the warm air in the tower (natural draft) or by the action of a fan. Detailed

descriptions of towers are given in other texts.

The water cannot be cooled below the wet bulb temperature. The driving force

for the evaporation of the water is approximately the vapor pressure of the

water less the vapor pressure it would have at the wet bulb temperature. The

water can be cooled only to the wet bulb temperature, and in practice it is

66

Prof.Fatma K. Gad

cooled to about 3 K or more above this. Only a small amount of water is lost by

evaporation in cooling water. Since the latent heat of vaporization of water is

about 2300 kJ/kg, a typical change of about 8 K in water temperature

corresponds to an evaporation loss of about 1.5%. Hence, the total flow of

water is usually assumed to be constant in calculations of tower size.

and liquid phase is needed for large rates of mass transfer and heat transfer. The

gas-phase resistance controls the rate of transfer. Spray or packed towers are

used to give large interfacial areas and to promote turbulence in the gas phase.

Vapor Pressure of Water

1. Introduction. In a number of the unit operations and transport processes it

is necessary to make calculations involving the properties of mixtures of water

vapor and air. These calculations involve knowledge of the concentration of

water vapor in air under various conditions of temperature and pressure, the

thermal properties of these mixtures, and the changes occurring when this

mixture is brought into contact with water or with wet solids in drying.

Humidification involves the transfer of water from the liquid phase into a

gaseous mixture of air and water vapor. Dehumidification involves the reverse

transfer, whereby water vapor is transferred from the vapor state to the liquid

state. Humidification and dehumidification can also refer to vapor mixtures of

materials such as benzene, but most practical applications occur with water. To

better understand humidity, it is first necessary to discuss the vapor pressure of

water.

2. Vapor pressure of water and physical states. Pure water can

exist in three different physical states: solid ice, liquid, and vapor. The physical

state in which it exists depends on the pressure and temperature.

Figure illustrates the various physical states of water and the pressure-

temperature relationships at equilibrium. The regions of the solid, liquid, and

vapor states are shown. Along the line AB, the phases liquid and vapor coexist.

Along line AC, the phases ice and liquid coexist. Along line AD, ice and vapor

coexist. If ice at point (1) is heated at constant pressure, the temperature rises

and the physical condition is shown moving horizontally. As the line crosses

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Prof.Fatma K. Gad

AC, the solid melts, and on crossing AB the liquid vaporizes. Moving from

point (3) to (4), ice sublimes (vaporizes) to a vapor without becoming a liquid.

Liquid and vapor coexist in equilibrium along the line AB, which is the vapor-

pressure line of water. Boiling occurs when the vapor pressure of the water is

equal to the total pressure above the water surface. For example, at 100°C

(212°F) the vapor pressure of water is 101.3 kPa (1.0 atm), and hence it will

boil at 1 atm pressure. At 65.6°C (150°F), from the steam tables in Appendix

A.2, the vapor pressure of water is 25.7 kPa (3.72 psia). Hence, at 25.7 kPa and

65.6°C, water will boil.

pressure, the vapor pressure of water will a gain be 25.7 kPa. This

illustrates an important property of the vapor pressure of water,

which is not influenced by the presence of an inert gas suchfas air;

i.e., the vapor pressure of water is essentially independent of the

total pressure of the system.

mixture is defined as the kg of water vapor contained in 1 kg of dry

air. The humidity so defined depends only on the partial pressure pA

of water vapor in the air and on the total pressure P (assumed

throughout this chapter to be 101.325 kPa, 1.0 atm abs, or 760 mm

Hg). Using the molecular weight of water (A) as 18.02 and of air as

28.97, the humdiity H in kg H2O/kg dry air or in English units as lb

H2O/lb dry air is as follows:

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Prof.Fatma K. Gad

(1 / (28.97 kg air / kg mol air))

H = (18.02 / 28.97) (P A / (P – P A ))

liquid water at the given conditions of pressure and temperature. In

this mixture the partial pressure of the water vapor in the air -water

mixture is equal to the vapor pressure p AS of pure water at the given

temperature. Hence, the saturation humidity Hs is

H s = (18.02 / 28.97) (P AS / (P – P AS ))

100 times the actual humidity H of the air divided by the humidity

Hs if the air were saturated at the same temperature and pressure.

H P = 100 H / H S

air-water vapor mixture is also given as percentage relative

humidity HR using partial pressures.

H R = 100 (P A / P AS )

combining the first three Equations.

HP = 100 (H / H S )

= (100) (18.02/28.97) (P A /(P–P A ))/(18.02/28.97) (P AS /(P–P S ))

= (P A / P AS ) ((P – P AS ) / ( P – P A ))

EXAMPLE.

and contains water vapor with a partial pressure p A = 2.76 kPa.

Calculate the following.

Humidity, H.

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Prof.Fatma K. Gad

Percentage relative humidity, HR .

Solution:

= 3.50 kPa (0.507 psia). Also, p A = 2.76 kPa and P = 101.3 kPa

(14.7 psia).

= 0.01742 kg H 2 O / kg air

H S = (18.02/28.97) (p AS /P -p AS ))

= 18.02(3.50) / (28.97(101.3 - 3.50))

= 0.02226 kg H 2 O / kg air

which a given mixture of air and water vapor would be saturated is

called the dew-point temperature or simply the dew point. For

example, at 26.7°C (80°F), the saturation vapor pressure of water is

P A S = 3.50 kPa (0.507 psia). Hence, the dew point of a mixture

containing water vapor having a partial pressure of 3.50 kPa is

26.7°C. If an air-water vapor mixture is at 37.8°C (often called the

dry bulb temperature, since this is the actual temperature a dry

thermometer bulb would indicate in this mixture) and contains water

vapor of p A = 3.50 kPa, the mixture would not be saturated. On

cooling to 26.7°C, the air would be saturated, i.e., at the dew point.

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Prof.Fatma K. Gad

partial pressure cannot be greater than the saturation vapor pressure.

is the amount of heat in J (or kJ) required to raise the temperature of

1 kg of dry air plus the water vapor present by 1 K or 1=C. The heat

capacity of air and water vapor can be assumed constant over the

temperature ranges usually encountered at 1.005 kJ/kg dry air • K

and 1.88 kJ/kg water vapor • K, respectively. Hence, for SI and

English units,

volume vH is the total volume in m 3 of 1 kg of dry air plus the

vapor it contains at 101.325 kPa (1.0 atm) abs pressure and the

given gas temperature. Using the ideal gas law,

= (2.83 x 10 - 3 + 4.56 x 10 - 3 H)T K

= (0.0252 + 0.0405 H) T o R

saturated volume.

enthalpy of 1 kg of air plus its water vapor is Hy J/kg or kJ/kg dry

air. If T0 is the datum temperature chosen for both components, the

total enthalpy is the sensible heat of the air-water vapor mixture

plus the latent heat 0 in J/kg or kJ/kg water vapor of the water

vapor at T 0 . Note that (T - T0)°C = (T - T0) K and that this enthalpy

is referred to liquid water.

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Prof.Fatma K. Gad

(32°F), the equation for tfy becomes

chart of the properties of air-water vapor mixtures at 1.0 atm abs

pressure is the humidity chart. In this figure the humidity H is

plotted versus the actual temperature of the air-water vapor mixture

(dry bulb temperature).

The curve marked 100% running upward to the right gives the

saturation humidity tfs as a function of temperature. In the Example,

for 26.7°C Hs was calculated as 0.02226 kg H 2 O/kg air. Plotting

this point of 26.7°C (80°F) and Hs = 0.02226 on Fig. 9.3 -2, it falls

on the 100% saturated line.

Any point below the saturation line represents unsaturated air -water

vapor mixtures. The curved lines below the 100% saturation line'and

running upward to the right represent unsaturated mixtures of

definite percentage humidity HP. Going downward vertically from

the saturation line at a given temperature, the line between 100%

saturation and zero humidity H (the bottom horizontal line) is

divided evenly into 10 increments of 10% each.

humidity line Hs can be calculated from the data of vapor pressure

of water.

60°C (140°F) and a dew point of 26.1'C (80°F). Using the humidity

chart, determine the actual humidity tf, percentage humidity H P ,

humid heatcs, and the humid volume vu in SI and English units.

Solution:

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Prof.Fatma K. Gad

The dew point of 26.7°C is the temperature when the given mixture

is at 100% saturation. Starting at 26.7°C, Fig. 9.3 -2, and drawing a

vertical line until it intersects the line for 100% humidity, a

humidity of H = 0.0225 kg H 2 O/kg dry air is read off the plot. This

is the actual humidity of the air at 60°C. Stated in another way, if

air at 60°C and having a humidity H = 0.0225 is cooled, its dew

point will be 26.7°C. In English units, H = 0.0225 lb H 2 O/lb dry air.

percentage humidity H P is found to be 14%, by linear interpolation

vertically between the 10 and 20% lines. The humid heat for tf =

0.0225 is, from

c s = 1.005 + 1.88(0.0225)

= 1.047 kJ/kg dry air • K or 1.047 x 103 J/kg • K

c s = 0.24 + 0.45(0.0225)

= 0.250 btu/lb m dry air • °F (English)

v H = (2.83 x 10 - 3 + 4.56 x 10 - 3 x 0.0225) (60 + 273)

= 0.977 m3/kg dry air

In English units,

v H = (0.0252 + 0.0405 x 0.0225)(460 + 140) = 15.67 ft 3 /lbm

dry air 9.3C

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Prof.Fatma K. Gad

101.325 kPa (760 mm Hg)

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Prof.Fatma K. Gad

1. Temperature and concentration profiles at interface. In Fig. 2.5-1 the

temperature profile and the concentration profile in terms of humidity are

shown at the water-gas interface. Water vapor diffuses from the interface to the

bulk gas phase with a driving force in the gas phase of (H i - HG) kg H2O/kg dry

air. There is no driving force for mass transfer in the liquid phase, since water is

a pure liquid. The temperature driving force is T L - Ti in the liquid phase and Ti

- TG K or °C in the gas phase. Sensible heat flows from the bulk liquid to the

interface in the liquid. Sensible heat also flows from the interface to the gas

phase. Latent heat also leaves the interface in the water vapor, diffusing to the

gas phase. The sensible heat flow from the liquid to the interface equals the

sensible heat flow in the gas plus the latent heat flow in the gas.

The conditions in Fig. 2.3-1 occur at the upper part of the cooling tower. In the

lower part of the cooling tower the temperature of the bulk water is higher than

the wet bulb temperature of the air but may be below the dry bulb temperature.

Then the direction of the sensible heat flow in Fig. 2.3-1 is reversed.

Rigure 2.3.1: The conditions in the upper part of the cooling tower.

We shall consider a packed water-cooling tower with air flowing upward and

water countercurrently downward in the tower. The total interfacial area

between the air and water phases is unknown, since the surface area of the

packing is not equal to the interfacial area between the water droplets and the

air. Hence, we define a quantity a, defined as m2 of interfacial area per m3

volume of packed section, or m2/m3. This is combined with the gas-phase mass-

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Prof.Fatma K. Gad

volumetric coefficient kGa in kg mol/s ■ m3 volume • Pa or kg mol/s • m3 • atm

(lb mol/h • ft3 • atm).

The process is carried out adiabatically and the various streams and conditions

are shown in Fig. 2.3-1,

where

L = water flow, kg water/s • m2 (lbm / h • ft2)

TL = temperature of water, °C or K (°F)

G = dry air flow, kg/s • m2 (lbm / h • ft2)

TG = temperature of air, °C or K (°F)

H = humidity of air, kg water/kg dry air (lb water/lb dry air)

Hy — enthalpy of air-water vapor mixture, J/kg dry air (Btu/lbm dry air)

The enthalpy Hy is

Hy = cs(T - T0) + H λ0 = (0.24 + 0.45H) (T - 32) + 1075.4H (English)

The base temperature selected is 0°C or 273 K (32°F). Note that(T - T0)°C = (T

— T0) K.

Making a total heat balance for the dashed-line box shown in Fig. 2.5-2, an

operating line is obtained.

evaporated. The heat capacity cL of the liquid is assumed constant at 4.187 x

103 J/kg - K (1.00btu/lbm • °F). When plotted on a chart of H y versus TL, this

Eq. (3.5-1) is a straight line with a slope of L cL/G. Making an overall heat

balance over both ends of the tower,

Again making a heat balance for the dz column height and neglecting sensible

heat terms compared to the latent heat,

The total sensible heat transfer from the bulk liquid to the interface is (refer to

Fig. (2.3-1)

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Prof.Fatma K. Gad

(btu/h-ft3 ■ °F) and Ti is the interface temperature.

For adiabatic mass transfer the rate of heat transfer due to the latent heat in the

water vapor being transferred can be obtained

volumetric mass-transfer coefficient in the gas in kg mol/s - m3 • Pa, P = atm

pressure in Pa, λ0 is the latent heat of water in J/kg water, Hi, is the humidity of

the gas at the interface in kg water/kg dry air, and HG is the humidity of the gas

in the bulk gas phase in kg water/kg dry air. The rate of sensible heat transfer in

the gas is

gas in W/m3 • K.

Now from Fig. 2.3-1, Eq. (2.3-4) must equal the sum of Eqs. (2.3-5) and (2.3-6).

And hG a / MB ky a ≈ cs (2.3-8)

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Prof.Fatma K. Gad

hG a / MB P kG a ≈ cs (2.3-9)

G dHy = MB kG a P dz

[(cs Ti + λ0 Hi) - (cs TG + λ0 HG)] (2.3-10)

G dHy=MB kG a P dz (cs(Ti-T0)

+Hi λ0-[cs (TG-T0)+HG λ0] (2.3-11)

The terms inside the braces are (Hyi - Hy), and Eq. (2.3-11) becomes

(2.3-13)

Transfer Coefficients

The tower design is done using the following steps. Liquid temperature (°C)

shown in Fig. 2.3-3. This enthalpy is calculated using the saturation humidity

from the humidity chart for a given temperature, with 0°C (273 K) as a base

temperature. Calculated values are tabulated in Table 2.3-1.

2-Knowing the entering air conditions TG1 and Hl the enthalpy of this air Hyl is

calculated. The point Hyl and TL1 (desired leaving water temperature) is plotted

in Fig. 2.3-3 as one point on the operating line. The operating line is plotted

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Prof.Fatma K. Gad

with a slope LcL/G and ends at point TL2, which is the entering water

temperature. This gives Hy2 . Alternatively, Hy2 can be calculated from Eq. (2.3-

2).

3-Knowing hLa and kGa, lines with a slope of –hL a / kG a MB P are plotted as

shown in Fig. 2.3-3. From Eq. (2.3-14) point P represents Hy and TL on the

operating line, and point M represents Hyi and Ti, the interface conditions.

Hence, line MS or Hyi - Hy represents the driving force in Eq. (2.3-13).

Figure 2.3-3: Temperature – Enthalpy diagram and operating line for water

cooling tower.

4. The driving force Hyi - Hy is computed for various values of TL between TLl

andTL2-Then by plotting l/(Hyl - Hy) versus Hy from Hyl to Hy2, a graphical

integration is performed to obtain the value of the integral in Eq. (2.3-13).

Finally, the height z is calculated from Eq. (2.3-13).

Temperature)

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Prof.Fatma K. Gad

Mass-Transfer Coefficients

Often, only an overall mass-transfer coefficient KGa in kg mol/s-m3-Pa or kg

mol/s-m3 - atm is available, and Eq. (2.3-13) becomes

(2.3-15)

The value of H*y is determined by going vertically from the value of H y at point

P up to the equilibrium line to give H* y at point R, as shown in Fig. 2.3-3. In

many cases the experimental film coefficients k Ga and hLa are not available.

The few experimental data available indicate that h La is quite large and the

slope of the lines -hLal (kG a MB P) in Eq. (2.3-14) would be very large and the

value of Hyi would approach that of H*y in Fig. 2.3-3.

The tower design using the overall mass-transfer coefficient is done using the

following steps.

1-The enthalpy-temperature data from Table 2.3-1 are plotted as shown in Fig.

2.3-3.

2-The operating line is calculated as in steps 1 and 2 for the film coefficients

and plotted in Fig. 2.3-3.

3-In Fig. 2.3-3 point P represents Hy and TL on the operating line and point R

represents H*y on the equilibrium line. Hence, the vertical line RP or H* y - Hy

represents the driving force in Eq. (2.3-15).

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Prof.Fatma K. Gad

4-The driving force H*y - Hy is computed for various values of TL between TL1

and TL2. Then by plotting l/(H*y — Hy) versus Hy from Hy1 to Hy2, a graphical

integration is performed to obtain the value of the integral in Eq. (2.3-15).

Finally, the height z is obtained from Eq. (2.3-15).

height z are available, then using Eq. (2.3-15), the experimental value of KGa

can be obtained.

Coefficients

gas flow rate of G = 1.356 kg dry air/s-m2 and a

water flow rate of L = 1.356 kg water/s • m2 is to cool the water from

TL2 = 43.3°C (110°F) to

TLl = 29.4°C (85°F).

The entering air at 29.4°C has a wet bulb temperature of 23.9°C.

The mass-transfer coefficient kG a is estimated as 1.207 x 10-7 kg mol/s • m3 •

Pa and hL a / kc a MB P as 4.187 x 104 J/kg-K (10.0 btu/lbm-°F).

Calculate the height of packed tower z. The tower operates at a pressure of

1.013 x 105 Pa.

Solution:

The enthalpies from the saturated air-water vapor mixtures from Table 2.3-1 are

plotted in Fig. 2.3-4.

The inlet air at TG1 = 29.4°C has a wet bulb temperature of 23.9°C.

The humidity from the humidity chart is 77, = 0.0165 kg H20/kg dry air.

Noting that (29.4 - 0)°C = (29.4 - 0) K,

Hyl = (1.005 4- 1.88 x 0.0165)103(29.4 - 0) 4- 2.501 x 106(0.0165)

= 71.7 x 103 J/kg

The point Hyl = 71.7 x 103 and TLl = 29.4°C is plotted.

Then substituting into Eq. (2.3-2) and solving,

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Prof.Fatma K. Gad

Hy2 = 129.9 x 103 J/kg dry air (55.8 Btu/lbm. The point

Hy2 = 129.9 x 103 and

TL2 = 43.3°C is also plotted, giving the operating line.

Lines with slope –hL a /kG a MB P = -41.87 x 103 J/kg-K are plotted giving Hyi

and Hy values, which are tabulated in Table 2.3-2 along with derived values as

shown.

Table 2.3-2. Enthalpy Values for Solution to Example 2.3-1 (enthalpy in J/kg

dry air)

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Prof.Fatma K. Gad

Values of l/(Hyi — Hy) are plotted versus Hy and the area under the curve from

Hyl = 71.7 x 103 to Hy2 = 129.9 x 103 is Substituting into Eq. (2.3-13),

Often the air flow G is not fixed but must be set for the design of the cooling

tower. As shown in Fig. 3.5-5 for a minimum value of G, the operating line MN

is drawn through the point Hyi and TL) with a slope that touches the equilibrium

line at TL2, point N. If the equilibrium line is quite curved, line MN could

become tangent to the equilibrium line at a point farther down the equilibrium

line than point N. For the actual tower, a value of G greater than G min must be

used. Often, a value of G equal to 1.3 to 1.5 times Gmin is used.

Transfer Unit

Often another form of the film mass-transfer coefficient is used in Eq. (2.3-13):

(2.3-16)

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Prof.Fatma K. Gad

HG = G / MB kG a P (2.3-17)

where HG is the height of a gas enthalpy transfer unit in m and the integral term

is called the number of transfer units. The term H G is often used since it is less

dependent upon flow rates than kG a.

• Pa or kg mol/s • m3 • atm is used and Eq. (2.3-15) becomes

(2.3-18)

where HoG is the height of an overall gas enthalpy transfer unit in m. The value

of H*y is determined by going vertically from the value of Hy up to the

equilibrium line as shown in Fig. 2.3-3. This method should be used only when

the equilibrium line is almost straight over the range used. However, the H oG is

often used even if the equilibrium line is somewhat curved because of the lack

of film mass-transfer coefficient data.

The procedures outlined above do not yield any information on the changes in

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Prof.Fatma K. Gad

temperature and humidity of the air-water vapor stream through the tower. If

this information is of interest, a graphical method by Mickley is available. The

equation used for the graphical method is derived by first setting Eq. (2.3-6)

equal to Gcs dTG and combining it with Eqs. (2.3-12) and (2.3-9) to yield Eq.

(2.3-19).

For the cooling or humidification tower discussed, the operating line lies below

the equilibrium line and water is cooled and air humidified. In a

dehumidification tower cool water is used to reduce the humidity and

temperature of the air that enters. In this case the operating line is above the

equilibrium line. Similar calculation methods are used (TI).

COEFFICIENTS FOR PACKED TOWERS

The individual film mass-transfer coefficients k`ya and k`xa depend generally

upon Schmidt number, Reynolds number, and the size and shape of the packing.

The interactions among these factors are quite complex. Hence, the correlations

for mass-transfer coefficients are highly empirical. The reliability of these

correlations is not too satisfactory. Deviations of up to 25% are not uncommon.

A main difficulty arises because an overall coefficient or resistance is measured

experimentally that represents the two film resistances in series. To obtain the

single-phase film coefficient, the experiment is so arranged that the other film

resistance is negligible or can be approximately calculated.

absorption or desorption of very insoluble gases such as O 2 or CO2 in water is

used. The experiment gives K`xa, which equals k`xa, since the gas-phase

resistance is negligible.

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Prof.Fatma K. Gad

To measure the gas-phase film coefficient k`ya, we desire to use a system such

that the solute is very soluble in the liquid and the liquid-phase resistance is

negligible. Most such systems as NH3-air-water have a liquid-phase resistance

of about 10%. By subtracting this known liquid phase resistance (obtained by

correcting k`xa data for absorption of CO2 or O2 to NH3 data for k`xa) from the

overall resistance in Eq. (1.4-24), we obtain the coefficient k`ya. Details of these

are discussed elsewhere.

The experimental data for the gas film coefficient in dilute mixtures have been

correlated in terms of HG, where

HG = V / k`y a S (2.4-1)

where Gy = kg total gas/s • m2; Gx = kg total liquid/s • m2; and a, p1, and y are

constants for a packing as given in Table 2.4-1. The temperature effect, which

is small, is included in the Schmidt number μ/ρD, where μ is the viscosity of the

gas mixture in kg/m-s, ρ the density in kg/m3, and D the diffusivity of solute A

in the gas in m2/s. The coefficients k`ya and HG can be shown to be independent

of pressure.

Equation (2.4-2) can be used to correct existing data for absorption of solute A

in a gas on a specific packing to absorption of solute E in the same system and

the same mass-flow rates. This is done by Eq. (2.4-3).

The correlations for liquid film coefficients in dilute mixtures show that HL is

independent of gas rate until loading occurs, as given by the following:

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Prof.Fatma K. Gad

Data are given in Table 3.8-2 for different packings. Equation (3.8-3) can be

used to correct existing data on a given packing and solute to another solute.

Type α β γ Gy Gx

Rashing rings

9.5 mm(3/8”) 0.62 0.45 -0.47 0.271-.678 0.678-.034

25.4mm(1”) 0.557 0.32 -0.51 0.271-.814 0.678-6.1

38.1mm(1.5”) 0.83 0.38 -0.66 0.271-0.95 0.678-.034

38.1mm(1.5”) 0.689 0.38 -0.4 0.271-0.95 2.034-6.1

80.8mm(2”) 0.894 0.41 -0.45 0.271-.085 0.678-6.1

Berl saddles

12.7mm(0.5”) 0.541 0.3 -0.74 0.271-0.95 0.678-.034

12.7mm(0.5”) 0.367 0.3 -0.24 0.271-0.95 2.034-6.1

25.4mm(1”) 0.461 0.36 -0.4 0.271-.085 0.542-6.1

38.1mm(2”) 0.652 0.32 -0.45 0.271- 0.542-6.1

1.356

Predict HG, HL, and K`ya for absorption of NH3 from water in a dilute solution

in a packed tower with 25.4-mm Raschig rings at 303 K (86°F) and 101.32 kPa

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Prof.Fatma K. Gad

pressure. The flow rates are Gx = 2.543 kg/s • m2 and Gy = 0.339 kg/s • m2.

Solution:

y = 1.20x. Also, for air,

u = 1.86 x 10-5 kg/m-s. Density

= 1.168 kg/m3.

The diffusivity of NH3 in air at 273 K from Table 6.2-1 is 1.98 x 10-5

m2/s.

Correcting to 303 K by Eq. (6.2-45), DAB = 2.379 x 10-5 m2/s. Hence,

NSc = μ / ρ D = 1.86x10-5 / (1.168) (2.379x10-5) = 0.669

Substituting into Eq. (2.4-2) using data from Table 2.4-1,

HG = α Gyβ Gxγ NSc0.5 = 0.557(0.339)0.32 (2.543)-0.51 (0.669)0.5 = 0.2 m

The viscosity of water = 1.1404 x 10 -3 kg/m-s at 15°C and 0.8007 x 10-3 at

30°C. The DAB of NH3 in water at 288 K (15°C) from Table 1.3-1 is 1.77 x 10-9

m2/s. Correcting this to 303 K (30°C),

DAB = (1.1404x10-3 / 0.8007x10-3) (303 / 288) (1.77x10-9) m2 / s

Then, using ρ = 996 kg/m3 for water,

NSc μ / ρ D = 0.8007x10-3 / (996) (2.652x10-9) = 303.1

Substituting into Eq. (2.4-4), using data from Table 2.4-1,

HL = θ (Gx / μL)η NSc0.5 = (2.35x10-3) (2.543 / 0.8007x10-3)0.22 (303.1)0.5

= 0.2412 m

= 17.12 + 2.048 = 19.168

K`y a = 0.0522 kg mol/s - m3 • mol frac

Note that the percent resistance in the gas film is (17.12/19.168) (100) = 89.3%.

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Prof.Fatma K. Gad

( I ) DISTILLATION

Distillation is the most widely used method of separation of liquid mixtures into

their several components. On the engineering side, distillation column have to

be designed with a larger range in capacity than any other types of chemical

engineering equipment, with single column from 0.3 to 10 meter in diameter

and from 3 to 75 meter in height.

The demand on designers is not only to achieve the desired product quality at

minimum cost, but also to provide constant purity of product even though there

may be some variation in the feed composition.

A distillation unit must never be considered without its associated control unit

and usually it with operate in association with several other separate units.

methods of distillation and calculation of the number of stages required for both

binary and multi component systems.

The composition of the vapor in equilibrium with a liquid of given composition

is determined experimentally using an equilibrium still. The result are

conveniently shown on a temperature – composition diagram 16 - a , b, c).

In the normal case (1.a), the curve ABC shows the composition of the liquid

which boils at any given temperature and the curve ADC the corresponding

composition of the vapor at that temperature.

indicated by point D of composition y1.

In Fig (16) there is a critical composition x g where the vapor has the same

composition as the liquid, so that no change occurs on boiling, such

critical mixtures are called azeotropes, and special methods are necessary to

effect separation. it is important to note that the composition of the vapor in

equilibrium with a given liquid will change with pressure.

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Prof.Fatma K. Gad

pressure as shown in fig (17 a,b,c). It must be remembered that the temperature

varies along each of the curves.

closed in such a way that the pressure remains atm, but no material can escape.

If x of the more volatile component (B) is plotted as abscissa, and the

temperature at which the mixture boils as ordinate, then the boiling curve is

obtained as shown by ABCJ fig(18). The corresponding dew point curve ADEJ

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Prof.Fatma K. Gad

point G on the diagram, then on heating at constant P the following changes

will occur.

1. When the T reaches T2, the liquid will boil (point B), and some vapor of

composition y2 shown by point E.

2. On further heating the composition of the liquid will change, because of the

loss of the more volatile component to the vapor. The boiling point will

therefore, rise to T’. At this point (T’1) the liquid will have a composition

represented by point L and the vapor by point No. and therefore, the change

in the proportion of liquid to vapor, the ratio being ;

Liquid / Vapor = MN / ML

3. On further heating to T1, all of the liquid is vaporized to give vapor D of the

same composition y1 as the originally.

It is seen that partial vaporization of the liquid gives a vapor richer in the more

volatile component that the liquid. If the vapor initially formed, as for instant

of point E, is at once removed by condensation, the liquid of composition x 3 is

obtained, represented by point C. The step BEC may be regarded as

representing an ideal stage, since the liquid passes from composition x 2 to a

liquid of composition x3, which is a greater enrichment in the more volatile

component than can be obtained by any other degree of vaporization.

condensation will commence, and the first drop of liquid will have a

composition K. Further cooling to T’ will give liquid L and vapor N. Thus

partial condensation brings about enrichment of the vapor in the more volatile

component in the same manner as partial vaporization.

The industrial distillation column is essence a series of units in which these two

process of partial vaporization and partial condensation are affected

simultaneously.

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Prof.Fatma K. Gad

The partial pressure (PA) of component A in a mixture of vapor is the pressure

that would be exerted by component A at the same temperature, if present in the

same volumetric concentration as in the mixture.

P = PA

Then, in an ideal mixture, the partial pressure is proportional to the mol fraction

of the consistent in the vapor phase;

(1)

PA = P y1

Henry’s law:-

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Prof.Fatma K. Gad

liquid solute A in a solvent.

PA = H x1 (2)

H is Henry’s constant.

According to this law, the p. pressure is directly proportional to the mol fraction

in liquid phase (xA). It is found that this holds only for dilute solution. Where,

H is a constant depending on temperature, on the solvent and to a minor degree

on pressure.

Raoult’s law.:-

proportional to its concentration,

PA = P*A xA (3)

The above relation is usually found to be true only for high values of xA or

correspondingly law values of xB. If A is regarded as the solute and B as the

solvent, then Henry’s law applies when xA is small, and Raoult’s law when xB

is small.

graphically from a knowledge of the V.P of the two components as in figure

(19). Where OA represents the P.P of A in a mixture and CB the PP of B and

the total pressure being shown by the line BA. Thus, in a mixture of

composition D the PP of A is given by DE, PB by DE and the total pressure (P)

by DG.

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Prof.Fatma K. Gad

For a non ideal mixture fig (20), it will be found that over the range OC the

mixture follows Henry’s law and over BA it follows Raoults law.

If it is known that the mixture follows Raoult’s law, then the values of y A for

various values of xA may be calculated from the knowledge of the P (v.p) of the

true components at various temperatures thus,

PA = xA PoA , PA = P yA

Where yA + yB = 1

PoA xA / P + PoB ( 1 - xA ) / P = 1

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Prof.Fatma K. Gad

Example:-

For a mixture of nC7 (A) and Toluene at 373° k and 1 atm (101.3 KN/m2)

P°B = 73.7

yA = P°A xA / P

Log P° = A - B / (t + C) (5)

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Prof.Fatma K. Gad

curves of xA is T and yA vs the equilibrium curve which is simply a plot of x A

vs yA as shown in fig (21, 22).

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Prof.Fatma K. Gad

Example:-

The vapor pressure of B and t are shown in the following table. Assuming that

mixture of these materials follow Raoult’s law, calculate and plot the B.P and

equilibrium curve for the system at a 1 atm.

Solution:-

toluene) are chosen and the corresponding data for P° A and P°B are substituted

A equation (6) .

t°C B VP T

80.1 760 -

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Prof.Fatma K. Gad

85 877 345

90 1016 405

95 1168 475

100 1344 557

105 1532 645

110 1748 743

110.6 1800 760

The action between the composition of the vapor yA and if the liquid xA is

equilibrium can be also expressed in another way , which is particularly useful

in distillation calculations. If the ratio of the partial pressure to the mol fraction

in the liquid is defined as the volatility;

Volatility of A = PA / xA , Volatility of B = PB / xB

The ratio of these two volatilities is known as the relative volatility () given by

yA / yB = xA / xB

since yB = 1- yA , xB = 1 – xA.

yA = xA / ( 1 + ( - 1 ) x A )

(8)

(8)

xA = yA / ( - ( - 1 ) y A )

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Prof.Fatma K. Gad

unity the separation becomes much easier.

For an ideal system the volatility is numerically equal to the vapor pressure of

the pure component, thus the relative volatility () may be expressed as

In the distillation column, if the relative volatility at the top and bottom are less

than 15 percent apart an average value of must be taken over the whole

column. If they differ by more that his figure, the equilibrium curve must be

constructed incrementally by calculating the relative volatility at several point

along the column.

yA = K. xA (10)

For a binary mixture with a normal y-x fig (2-a) the vapor is always richer in

the more volatile component than the liquid from which it is formed.

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Prof.Fatma K. Gad

a) Differential distillation.

b) Flash or equilibrium distillation

c) Rectification

d) Batch distillation.

The simplest example of batch distillation is a single stage, differential

distillation, starting with a still pot, initially full, heated at constant rate. In this

process the vapor formed on boiling the liquid is removed at once from the

system. Since this vapor is richer in the more volatile component than the

liquid, it follows that the liquid remaining becomes steadily weaker in this

component. Thus, whilst the vapor formed over a short period is in equilibrium

with the liquid, the total vapor formed is not in equilibrium with the residual

liquid.

Let S be the number of moles of material in the still and x be the mol fraction of

component A. Suppose an amount of ds containing a mol fraction y of A be

vaporized. Then a material balance on component A gives

y dS = d(Sx)

= Sdx + xdS

s x

dS / S = dx / ( y - x )

s0 x0

x

Ln (S ( intial ) / S ( final )) = (dx / ( y - x ) (a-1)

x0

This equation is called Rayleigh equation. The integral on the right hand side

can be solved graphically if the equilibrium relationship between y and x is

available.

In some cases a direct integration is possible. Thus if over the range concerned

the equilibrium relationship is a straight line of the form :

y = mx+c.

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Si / So = [( y - x ) / ( yo - xo )]( 1 / ( m - 1 )) generally

( S / So )( m -1 ) = ( y - x ) / ( yo - xo ) (a-2)

Alternatively if the relative volatility may be assumed constant over the range

concerned, then :

x

Ln ( S1(intial) / So(final) ) = dx / { x / [ 1 + ( - 1 ) x ]}

xo

or equal

xo

Ln ( So / S ) = dx / [ x / ( 1 + ( - 1 ) x ) - x ]

x

xo

Ln (So/S) = [1+(-1) x] dx / [ x - x - x2 + x2 ]

x

xo

= [ ( 1 + x - x ) / ( - 1 ) ( 1 - x ) x ] dx

x

xo

Ln ( So / S ) = 1 / ( - 1 ) [ ( 1 + x - x ) / ( 1 - x ) x ]dx

x

xo

= 1 / ( - 1 ) [( 1 / x ) + ( / ( 1 - x )) ]dx

x

Also

Ln ( So / S ) – Ln ( So / S ) = Ln ( xo / x ) + Ln ( 1 - x ) / (1-xo )

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Prof.Fatma K. Gad

Ln ( S / So ) + Ln ( x / xo ) = Ln (( 1 - x ) / ( 1 - xo )+ Ln ( S / So )

for binary mixture of A and B

since xi = 1

impossible unless the relative volatility is infinite.

Example

A liquid containing 50 mol % benzene and 25 mol % toluene, 25 mol % o-

xylene is differentially distillate at 1 atm with vaporization of 32.5 mol% of the

charge. Assume Roult’s law applied compute the distillate and residue

composition.

Solution.

For benzene

Ln 100 * 0.5/67.5 * xBo = 2.49 Ln 100* 0.25/67.5 xTO (1)

= 0.285 , xxo = 0.331

Making material balance for each component.

S xi = So xio + D xid

xBd = 0.792

xTd = 0.178

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Prof.Fatma K. Gad

xxd = 0.07S

II (B) Flash or equilibrium distillation

passed into the still where part is vaporized, the vapor remaining in contact with

the liquid. The mixture of vapor and liquid leaves the still and is separated so

that the vapor is in equilibrium with the liquid.

An analysis of the process can be given as below; for a binary mixture of A and

B.

F is moles of feed of mol fraction xF of A.

S moles of liquid and x mol fraction of A.

F xF = V y + S x

F=V+S

V / F = ( xF – x ) / ( y - x )

y = ( F/V ) xF – [ ( F / V ) - 1 ] x (b-1)

= - S / V passing through the point ( x , xF )

The value of x and y required must satisfy not only the above equation

(operating line) but also the appropriate equilibrium data as shown in the

following figure.

yi in vapor (v) = Ki xi (in liquids)

Note that the richest vapor its composition will vary between its babble and

dew points depending on the relative amount of S/V.

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Prof.Fatma K. Gad

operations generally used only on mixtures of large () or in conjunction with

other distillation operation.

All the previous equations apply equally well to the use of equilibrium

condensation. Where a vapor feed is partially condensed to yield the two

products.

Where

hf ,hs , Hv are the enthalpies of feed, vapor and liquid respectively

H is heat of solution (equal zero for ideal)

Since for binary mixture of A and B

hs = [ CLA MA x + CLB MB ( 1 - x )] ( tL - to )

Where CLA , CLB are the heat capacities of component A , B

A , B are the latest heat of vaporization of A, B

MA , MB are the molecular weights of A, B

tL , tg are temp of liquid and vapor

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Prof.Fatma K. Gad

( yi )v = Ki ( xi )w

F = V+ S

S / V = ( yi – xiF ) / ( xiF – xi )

In such case S/V would have to be assumed and calculate yi , xi and the correct

value of S/V is that which gives yi = 1 or xi = 1.

Bubble point, is the temp. at the first bubble of vapor formed by heating the

mixture at constant pressure where;

yi = 1

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Prof.Fatma K. Gad

(b-6)

Dew point is the temp. at the first droplet of liquid condenses when we cool the

vapor mixture at constant pressure where;

xi = 1 (b-7)

Example

A liquid mixture containing 50 % (mol) C7 and 50% C8 at 80°F is to be

continuously flash vaporized at 1 atm to vaporize 60 mol % of the feed. What

will be the composition of the vapor and liquid, the temperature in the separator

and the heat requirement.

Vapor pressure data of C7 , C8 as follows,

MH = 100 , Mo = 114

(1) temp in the separator

(2) composition of liquid leaving the separator.

Solution

98.4 760 333 427 427 1-0 1 1

105 940 412 343 523 0.655 1.23 0.81

110 1050 984 276 566 0.487 1.38 0.674

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Prof.Fatma K. Gad

120 1350 650 110 700 0.1571 1.77 2.279

125.8 1540 760 00 780 0 2.02 0

Since yi = xiF ( 1 + ( S / V )) / (( 1 + ( S / V Ki ))

xi = xiF (( S / V ) + 1 ) / ( Ki + ( S / V ))

Hsolution = 0 , HF = 0

hS = [CLH MH x + CLO MO ( 1 - x ) ] ( t - to )

= [0.57 * 100 * 0.387 + 0.505 * 114 * 0.613][235-80]

= 8.550 BTU/lb

=00.575[0.507*100(235.9-80)+133*100]

+0.425[0.505*114(2354.80+134*114]

= 22500 BTU/lb mol.

Example 2:

Find the bubble point of the following liquid, where the pressure is 1 atom.

xi Ki Ki xi Ki Ki xi Ki Ki xi

C4 0.05 5.6 0.28 5.0 0.25 4.7 0.235

C5 0.17 2.0 0.30 1.8 2.305 1.7 0.289

C6 0.65 0.77 0.5 0.67 0.435 0.6 0.39

C7 0.1 0.29 0.029 0.24 0.24 0.22 0.022

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Prof.Fatma K. Gad

1.016 0.938

Solution

So bubble point lay between 130 and 125

Also yi at bubble point = (ki xi) (ki xi at bubble point)/(ki xi at any temp)

Example 3:

y Ki at 140°F K at 142°F

C4 0.145 5.6 5.7

C5 0.285 2.0 2.1

C6 0.530 2.0 0.8

C7 0.035 0.29 0.3

C8 0.005 0.1 0.11

Solution

Since yi / ki = xi

at 102 yi / ki = 0.988

So dew point of the mixture lies between 140 , 142 °F

So at xi = 1 = yi / ki = 140 +2 * 0.028/0.04 = 141.4°F. U.E.D

= M wt / 22.4 or M wt / 359

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Prof.Fatma K. Gad

Assume once again that feed is liquid z = x

Get dew and bubble point for Σ x , Σ y

If

Σ x > 1 system below dew point

Σ y < 1 system below bubble point

Σ x < 1 system above dew point

Σ y > 1 system below bubble point

Ln Po = C + D / T mmHg

Where

D = T1 T2 / ( T1 – T2 ) Ln ( Po2 / Po1 )

C = Ln P2 – ( D / T2 )

There are three procedures of calculation for simple phase separation unit

(flash unit) as shown in the fig.

U k f1

Ukin

Ukf2

Some definitions :-

Φ = V/F (1)

ξn = Ө / (1 + Ө) (2)

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Prof.Fatma K. Gad

Ө = kn Φ / (1 – Φ) (3)

specified. Where

Lk = (1 – ξk) fk

(6)

Lk = L , Vk = V and Fk = Lk + Vk ( 1 )

( Vk / V ) = k ( Lk / L ) (7)

So for a specified feed, the number of variables less the number of equations

equals to 2, which is the degree of freedom.

So this means that we can completely specify the condition of the flash unit by

selecting two of the variables, ( we defer specification on Q ); we will get the

following procedures;

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Prof.Fatma K. Gad

Consider the mixture with the components, flow rates, boiling point and

Antoine coefficient

t

Benzene 30 353 15.9008 2788.51 -52.34

Toluene 50 383 16.0137 3096.52 -53.67

O-xylene 40 418 16.1156 3395.57 -59.44

Solution

1/2 = 2.305 , 3/2 = 0.381

k = k/n n / ( 1 + ( k/n – 1 ) n )

Vk = fk k and Lk = ( 1 - k )fk

Yk = Vk / Vi and xk = Lk / Li

So

xi = 1.38 / ( 1.38 + 9.04 )

V2 = 50 * 0.9 = 45 L2 = 50 – 45 = 5 x2 = 0.324

V3 = 40 * 0.774 = 30.96 L3 = 40 – 30.96 = 9.04 x3 = 0.586

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Prof.Fatma K. Gad

Where ’ = i/n xI

mm Hg

The temperature at which Po3 = 380 mm Hg = 393 ok close to the suggested one.

Ln Pok = Ak – Bk / ( Ck + T )

( 3 ) Recoveries of k component:

( 4 ) Mass balance :

V2 = 50 * ( 0.91 ) = 45 L2 = 5 x2 = 0.624

V3 = 40 * ( 0.774 ) = 30.96 L3 = 9.04 x3 = 0.586

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Prof.Fatma K. Gad

So 1 = 0.902 , 3 = 0.604

L1 = 2.94 , x1 = 0.102

L2 = 10 , x2 = 0.347

L3 = 15.84 , x3 = 0.55

’ = P 3/2 / Po3 = 0.829 (close enough)

2/2 = 1.0 , k2 = 1.205

3/2 = 0.381 , k3 = 0.460

( 3 ) quantities = kn / ( 1 - ) = Vn / Ln

and n = / ( 1 + ) ( n = 2 toluene )

n = 0.828

3 = 0.647

( 5 ) Mass balance :

L1 = 2.5 , L2 = 8.6 , L3 = 14.1

x1 = 0.0999 , x2 = 0.341 , x3 = 0.560

( 6 ) ’ = k/n x2 = 0.782

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Prof.Fatma K. Gad

In these processes the whole of a batch is run into the boiler of the still and, on

heating the vapor is passed into fractionation column as indicated in fig (24).

As with continuous distillation the composition of the top product will depend

on the still composition and the number of plates in the column and on the

reflex ration used.

As the process proceeded, the liquid remaining in the still will become steadily

weaker in the M.V.C

Thus the still may be changed with S1 moles of a mixture containing xS1 of

M.V.C. Initially with reflex ration R1 the top product has a composition x d1. If

after a contain interval of time the composition of the top product starts to fall,

then if the reflex is increased to new value R 2, it will be possible to obtain the

some composition again. This method required a continuous increase in R to

maintain a constant quality of the top product.

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Prof.Fatma K. Gad

of the top product to fall.

since it is possible to obtain the different components at reasonable degree of

purity one after the other.

remaining in the still after first distillation may be added to the next batch.

EtOH and H2O. Initially there are in the still S1 moles of liquor of mol

fraction xS1 with respect to the M.V.C (EtOH). The top product is to

contain xd and this needed a R1. Suppose the distillation is to be continued

till there are S2 moles in the still with xS2. Then for the same no. of plates

the reflex ratio will be increased to R2.

Therefore, S1 – S2 = Db

S1 xS1 – S2 xS2 = Db xd

If is the intercept on the y axis for any operating line then,

= xd / ( R + 1 ) or R = ( xd / ) - 1

difference in the amount of steam used in the distillation for a given quantity D b

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Prof.Fatma K. Gad

by

R = dLp / dDp and the total reflex flowing down the column is given by

Lb R2

dLb = R dDb (2)

0 R1

to provide reflex dLb requires the removal of heat dLb in the condenser, where

is the latent heat per mol. Thus the heat to be supplied in the reboiler Q R to

provide this reflex during the total distillation in given by

Lb R2

QR = DLb = R dDb

0 R1

(III-3)

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Prof.Fatma K. Gad

the MVC in the top product will continuously fall. Over a small interval of

time dt, xd becomes xd – dxd. If in this time the amount of product obtained is

dDb ; material balance on MVC gives.

And xd dDb = - d( S xS ) = - S dxS – xS dS

But dDb = - dS , S dxS = dS ( xd - xS )

s2 xS2

And dS / S = dxS / ( xd - xS )

s1 xS1

Finally

xS1

Ln ( S1 / S2 ) = dxS / ( xd - xS ) (4)

xS2

The right hand side of this equation can be integrated by plotting (1/(x d-xS)) vs

xS. This will enable the ratio of the initial to final quantity in the still to be

found for any desired charge in xS and hence the amount of distillate Db.

QR = R Db (5)

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Prof.Fatma K. Gad

Example:(I)

A mixture of EtOH and H2O with 0.55 mol fraction of a alcohol is distilled to

give a top product of 0.75 mol fraction EtOH. The column has 4 ideal plates

and the distillation is stopped when the reflex ratio has to be increased beyond

4.0.

Find the amount of distillate and heat required / mol product.

Solution

values of the intercept and the concentration in the still as shown in the table

below.

R xS Db

0.85 0.405 0.55 0

1.0 0.375 0.50 20.0

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Prof.Fatma K. Gad

2.0 0.25 0.20 63.8

3.0 0.187 0.075 70.5

4.0 0.15 0.05 71.9

R=4

The value R dDb from the plot = 96 kmol

R=0.85

Taking and average latent heat per k mol for the EtOH – H2O mixture as 4000

kJ.

The heat to be supplied

QR = (96 * 4000)/1000 = 380 MJ

QR / Db = 380/71.4 = 5.32 MJ U.E.D

Example (ii)

If the same batch as above is distilled with constant R of 2.1. What will be the

heat required and the average composition of the distillate, if the distillation is

stopped when the composition in the still has fallen to 0.105 mol fraction of

MVC.

Solution:

The initial composition of the top product will be 0.78 as shown in the

following table and the final composition will be 0.74. values of xd, xS, xd-xS

and 1 / (xd-xS ) for various values of xS and a constant reflex ratio are given in

the following table.

xS xd xd-xS 1/(xd-xS)

0.55 0.780 0.230 4.35

0.5 0.775 0.275 3.65

0.425 0.770 0.345 2.90

0.310 0.766 0.450 2.22

0.225 0.750 0.525 1.91

0.105 0.740 0.635 1.58

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Prof.Fatma K. Gad

Fig of Example 1

0.55

For which dxS / ( xd - xS ) = 1.1

0.105

Ln ( S1 / S2 ) = 1.1 , ( S1 / S2 ) = 3.0

= 0.55*100–0.105*33.3 = 51.5 k mole.

Average composition of product is = 51.5/66.7 = 0.77 and

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Prof.Fatma K. Gad

THIELE METHOD

Rectification (fractionation) or stage distillation with reflux, from a simplified

point of view, can be considered to be a process in which a series of flash-

vaporization stages are arranged in a series in such a manner that the vapor and

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Prof.Fatma K. Gad

liquid products from each stage flow countercurrently to each other. The liquid

in a stage is conducted or flows to the stage below and the vapor from a stage

flows upward to the stage above. Hence, in each stage a vapor stream V and a

liquid stream L enter, are mixed and equilibrated, and a vapor and a liquid

stream leave in equilibrium. This process flow diagram was shown in Fig. 3.3-1

for a single stage and an example given in Example 3.2-1 for a benzene-toluene

mixture.

operating-line equation (3.2-1) was derived which relates the concentrations of

the vapor and liquid streams passing each other in each stage. In a distillation

column the stages (referred to as sieve plates or trays) in a distillation tower are

arranged vertically, as shown schematically in Fig. 3.4-1.

The feed enters the column in Fig. 3.4-1 somewhere in the middle of the

column. If the feed is liquid, it flows down to a sieve tray or stage. Vapor enters

the tray and bubbles through the liquid on this tray as the entering liquid flows

across. The vapor and liquid leaving the tray are essentially in equilibrium. The

vapor continues up to the next tray or stage, where it is again contacted with a

downflowing liquid. In this case the concentration of the more volatile

component (the lower-boiling component A) is being increased in the vapor

from each stage going upward and decreased in the liquid from each stage

going downward. The final vapor product coming overhead is condensed in a

condenser and a portion of the liquid product (distillate) is removed, which

contains a high concentration of A. The remaining liquid from the condenser is

returned (refluxed) as a liquid to the top tray.

The liquid leaving the bottom tray enters a reboiler, where it is partially

vaporized, and the remaining liquid, which is lean in A or rich in B, is

withdrawn

as liquid product. The vapor from the reboiler is sent back to the bottom stage

or

tray. Only three trays are shown in the tower of Fig. 3.4-1. In most cases the

number of trays is much greater. In the sieve tray the vapor enters through an

opening and bubbles up through the liquid to give intimate contact of the liquid

and vapor on the tray. In a theoretical tray the vapor and liquid leaving are in

equilibrium. The reboiler can be considered as a theoretical stage or tray.

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of Theoretical Stages

1. Introduction and assumptions. A mathematical-graphical method for

determining the number of theoretical trays or stages needed for a given

separation of a binary mixture of A and B has been developed by McCabe and

Thiele. The method uses material balances around certain parts of the tower,

which give operating lines, and the xy equilibrium curve for the system.

The main assumption made in the McCabe—Thiele method is that there must

be equimolar overflow through the tower between the feed inlet and the top tray

and the feed inlet and bottom tray. This can be shown in Fig. 3.4-2, where

liquid and vapor streams enter a tray, are equilibrated, and leave. A total

material balance gives

where Vn+1 is mol / h of vapor from tray n+1, Ln is mol/h liquid from tray n, yn+l

is mole fraction of A in Vn+1 and so on. The compositions yn and xn are in

equilibrium and the temperature of the tray n is T n. If Tn is taken as a datum, it

can be shown by a heat balance that the sensible heat differences in the four

streams are quite small if heats of solution are negligible. Hence, only the latent

heats in stream Vn+1 and Vn are important. Since molar latent heats for

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Prof.Fatma K. Gad

chemically similar compounds are almost the same, V n+l = Vn and Ln = Ln-1.

Therefore, we have constant molal overflow in the tower.

column is shown with feed being introduced to the column at an intermediate

point and an overhead distillate product and a bottoms product being

withdrawn. The upper part of the tower above the feed entrance is called the

enriching section, since the entering feed of binary components A and B is

enriched in. this section, so that the distillate is richer in A than the feed. The

tower is at steady state.

An overall material balance around the entire column in Fig. 3.4-3 states that

the entering feed of F mol / h must equal the distillate D in mol/h plus the

bottoms W in mol/h.

F=D+W (3.4-3)

F xF = D x D + W x w (3.4-4)

Figure 3.4-2. Vapor and liquid flows entering and leaving a tray.

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Figure 3.4-3: Distillation column showing material balance section for McCabe

thiele method.

In Fig. 3.4-4a the distillation tower section above the feed, the enriching

section, is shown schematically. The vapor from the top tray having a

composition yl passes to the condenser, where it is condensed so that the

resulting liquid is at the boiling point. The reflux stream L mol/h and distillate

D mol/h have the same composition, so yl = xD. Since equimolal overflow is

assumed, L1 = L2 = Ln and V1 = V2 = Vn = Vn+l.

Making a total material balance over the dashed-line section in Fig. 4.4-4a,

Vn+l = Ln + D (3.4-5)

Figure 3.4-4: Material balance and operating line for enriching section:

(a)Schematic of tower (b)Operating and equilibrium lines.

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Prof.Fatma K. Gad

a plot of vapor composition versus liquid composition. It relates the

compositions of two streams passing each other and is plotted in Fig. 3.4-4b.

The slope is L / Vn+l or R/(R+1), as given in Eq. (4.4-8). It intersects the y = x

line (45° diagonal line) at x = xD. The intercept of the operating line at x = 0 is y

= xD/(R+1).

The theoretical stages are determined by starting at x D and stepping off the first

plate to x1. Then y2 is the composition of the vapor passing the liquid x 1. In a

similar manner, the other theoretical trays are stepped off down the tower in the

enriching section to the feed tray.

3. Equations for stripping section. Making a total material balance over the

dashed-line section in Fig. 3.4-5a for the stripping section of the tower below

the feed entrance,

Vm+1 = Lm – W (3.4-9)

constant. Equation (3.4-11) is a straight line when plotted as y versus x in Fig.

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Prof.Fatma K. Gad

4.4-5b, with a slope of L/Vm+l. It intersects the y = x line at x = xw. The intercept

at x = 0 is y = - W xw / Vm+l.

Figure 3.4-5. Material balance and operating line for stripping section:

(a) schematic of tower, (b) operating and equilibrium lines.

Again the theoretical stages for the stripping section are determined by starting

at xw, going up to yw, and then across to the operating line, etc.

4. Effect of feed conditions. The condition of the feed stream F entering the

tower determines the relation between the vapor V m in the stripping section and

Vn in the enriching section and also between L m and Ln. If the feed is part liquid

and part vapor, the vapor will add to Vm to give Vn.

which is defined as

q= (3.4-12)

molar latent heat of vaporization of feed

If the feed enters at its boiling point, the numerator of Eq. (3.4-12), is the same

as the denominator and q = 1.0. Equation (3.4-12) can also be written in terms

of enthalpies.

q = Hv – Hf / Hv – HL (3.4-I3)

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where Hv is the enthalpy of the feed at the dew point, H L the enthalpy of the

feed at the boiling point (bubble point), and HF the enthalpy of the feed at its

entrance conditions. If the feed enters as vapor at the dew point, q = 0. For cold

liquid feed q > 1.0, for superheated vapor q < 0, and for the feed being part

liquid and part vapor, q is the fraction of feed that is liquid.

the feed plate by each mole of feed added to the tower. In Fig. 3.4-6 a diagram

shows the relationship between flows above and below the feed extrance. From

the definition of q, the following equations hold:

Lm = Ln + q F (3.4-14)

Figure 3.4-6. Relationship between flows above and below the feed entrance.

equations on an x y plot can be derived as follows. Rewriting Eqs. (3.4-6) and

(4.4-10) as follows without the tray subscripts:

Vn y = Ln x + D xD (3.4-16)

Vm y = Lm x – W xw (3.4-17)

where the y and x values are the point of intersection of the two operating lines.

Subtracting Eq. (3.4-16) from (3.4-17),

Substituting Eqs. (3.4-4), (3.4-14), and (3.4-15) into Eq. (3.4-18) and

rearranging,

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This equation is the q-line equation and is the locus of the intersection of the

two operating lines. Setting y = x in Eq. (3.4-19), the intersection of the q-line

equation with the 45° line is y = x = x f, where xF is the overall composition of

the feed.

In Fig. 3.4-7 the q line is plotted for various feed conditions given below the

figure. The slope of the q line is q/(q — 1). For example, for the liquid below

the boiling point, q > 1, and the slope is > 1.0, as shown. The enriching and

operating lines are plotted for the case of a feed of part liquid and part vapor

and the two lines intersect on the q line. A convenient way to locate the

stripping operating line is to first plot the enriching operating line and the q

line. Then draw the stripping line between the intersection of the q line and

enriching operating line and the point y = x = x w.

determine the number of theoretical trays needed in a tower, the stripping and

operating lines are drawn to intersect on the q line as shown in Fig. 3.4-8.

Starting at the top at xD,, the trays are stepped off. For trays 2 and 3, the steps

can go to the enriching operating line, as shown in Fig. 3.4-8a. At step 4 the

step goes to the stripping line. A total of about 4.6 theoretical steps are needed.

The feed enters on tray 4.

For the correct method, the shift is made on step 2 to the stripping line, as

shown in Fig. 3.4-8b. A total of only about 3.7 steps are needed with the feed

on tray 2. To keep the number of trays to a minimum, the shift from the

enriching to the stripping operating line should be made at the first opportunity

after passing the operating-line intersection.

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Liquid below boiling point (q > 1) Liquid at boiling point (q = 1)

Liquid + vapor (0 < q < 1) Saturated vapor (q = 0)

In Fig. 3.4-8b the feed is part liquid and part vapor since 0 < q < 1. Hence, in

adding the feed to tray 2, the vapor portion of the feed is separated and added

beneath plate 2 and the liquid added to the liquid from above entering tray 2. If

the feed is all liquid, it should be added to the liquid flowing to tray 2 from the

tray above. If the feed is all vapor, it should be added below tray 2 and joins the

vapor rising from the plate below.

equilibrium with xw as in Fig. 3.4-5b, the number of theoretical trays in a tower

is equal to the number of theoretical steps minus one.

101.3 kPa pressure. The feed of 100 kg mol/h is liquid and it contains 45 mol %

benzene and 55 mol % toluene and enters at 327.6 K (130°F). A distillate

containing 95 mol % benzene and 5 mol % toluene and a bottoms containing 10

mol % benzene and 90 mol % toluene are to be obtained. The reflux ratio is 4:

1. The average heat capacity of the feed is 159 kl/kg mol • K (38 btu/lb mol •

°F) and the average latent heat 32 099 kI/kg mol (13 800 btu/lb mol).

Equilibrium data for this system are given in Table 4.1-1 and in Fig. 4.1-1.

Calculate the kg moles per hour distillate, kg moles per hour bottoms, and the

number of theoretical trays needed.

Solution:

F = 100 kg mol/h,

xF = 0.45,

xD = 0.95,

xw = 0.10, and

R = L/D = 4.

For the overall material balance substituting into Eq. (3.4-3),

F=D+W (3.4-3)

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100 = D + W

F xf = D x D + W x w (3.4-4)

D = 41.2 kg mol/h W = 58.8 kg mol/h

For the enriching operating line, using Eq. (4.4-8),

Yn+1 = (R/(R+1)) xn+xD/(R+1) = (4/(4+1)) xn + 0.95/(4+1) = 0.8 xn + 0.19

FIGURE 3.4-8. Method of stepping off number of theoretical trays and location

of feed plate:[a) improper location of feed on tray 4,(b) proper location of feed

on tray 2 to give minimum number of steps.

The equilibrium data from Table 3.1-1 and the enriching operating line above

are plotted in Fig. 3.4-9.

Next, the value of q is calculated. From the boiling-point diagram, Fig. 3.1-1,

for xF = 0.45, the boiling point of the feed is 93.5°C or 366.7 K (200.3°F). From

Eq. (3.4-13),

The value of Hv — HL = latent heat = 32 099 kJ/kg mol. The numerator of Eq.

(4.4-13) is

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TB = 366.7 K (boiling point of feed), and

TF = 327.6 K (inlet feed temperature).

q = (13 800 + 38(200.3 - 130) / 13 800 = 1.195 (English)

The q line is plotted in Fig. 3.4-9 starting at the pointy = x F = 0.45 with a slope

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Prof.Fatma K. Gad

of 6.12.

with the intersection of the q line and the enriching operating line. Starting at

the point y = x = xD, the theoretical steps are drawn in as shown in Fig. 4.4-9.

The number of theoretical steps is 7.6 or 7.6 steps minus a reboiler, which gives

6.6 theoretical trays. The feed is introduced on tray 5 from the top.

Thiele Method

1. Total reflux. In distillation of a binary mixture A and B the feed conditions,

distillate composition, and bottoms composition are usually specified and the

number of theoretical trays are" to be calculated. However, the number of

theoretical trays needed depends upon the operating lines. To fix the operating

lines, the reflux ratio R = L/D at the top of the column must be set.

One of the limiting values of reflux ratio is that of total reflux, or R = ∞. Since

R = L/D and, by Eq. (3.4-5),

Vn+1 = Ln + D (3.4-5)

then Ln is very large, as is the vapor flow Vn. This means that the slope R/(R +

1) of the enriching operating line becomes 1.0 and the operating lines of both

sections of the column coincide with the 45° diagonal line, as shown in Fig.

3.4-10.

the trays from the distillate to the bottoms. This gives the minimum number of

trays that can possibly be used to obtain the given separation. In actual practice,

this condition can be realized by returning all the overhead condensed vapor V1

from the top of the tower back to the tower as reflux, i.e., total reflux. Also, all

the liquid in the bottoms is reboiled. Hence, all the products distillate and

bottoms are reduced to zero flow, as is the fresh feed to the tower.

This condition of total reflux can also be interpreted as requiring infinite sizes

of condenser, reboiler, and tower diameter for a given feed rate.

following analytical expression by Fenske can be used to calculate the

minimum number of theoretical steps Nm when a total condenser is used.

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Prof.Fatma K. Gad

For small variations in α, αav = (α1 αw)1/2, where α, is the relative volatility of the

overhead vapor and αw is the relative volatility of the bottoms liquid.

Figure 3.4-10: Total reflux and minimum number of trays by McCabe Thiele.

2. Minimum reflux ratio. The minimum reflux ratio can be defined as the

reflux ratio Rm that will require an infinite number of trays for the given

separation desired of xD and xw This corresponds to the minimum vapor flow in

the tower, and hence the minimum reboiler and condenser sizes. This case is

shown in Fig. 3.4-11. If R is decreased, the slope of the enriching operating line

R/(R + 1) is decreased, and the intersection of this line and the stripping line

with the q line moves farther from the 45° line and closer to the equilibrium

line. As a result, the number of

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Figure 3.4-11. Minimum reflux ratio and infinite number of trays by McCabe-

Thiele method.

steps required to give a fixed x D and xw increases. When the two operating lines

touch the equilibrium line, a "pinch point" at y' and x' occurs where the number

of steps required becomes infinite. The slope of the enriching operating line is

as follows from Fig. 3.4-11, since the line passes through the points x', y', and

xD (y = xD).

Fig. 3.4-12, the operating line at minimum reflux will be tangent to the

equilibrium line.

3. Operating and optimum reflux ratio. For the case of total reflux, the

number of plates is a minimum, but the tower diameter is infinite. This

corresponds to an infinite cost of tower and steam and cooling water. This is

one limit in the tower operation. Also, for minimum reflux, the number of trays

is infinite, which again gives an infinite cost. These are the two limits in

operation of the tower.

The actual operating reflux ratio to use is in between these two limits. To select

the proper value of R requires a complete economic balance on the fixed costs

of the tower and operating costs. The optimum reflux ratio to use for lowest

total cost per year is between the minimum R m and total reflux. This has been

shown for many cases to be at an operating reflux ratio between 2R m to l.5Rm.

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Prof.Fatma K. Gad

distilled to give a distillate composition of

xD = 0.95 and a bottoms composition of

xw = 0.10,

Calculate the following.

(a)Minimum reflux ratio Rm.

(b)Minimum number of theoretical plates at total reflux.

Solution:

For part (a) the equilibrium line is plotted in Fig. 3.4-13 and the q-line equation

is also shown for xF = 0.45. Using the same xD and xw as in Example 3.4-1, the

enriching operating line for minimum reflux is plotted as a dashed line and

intersects the equilibrium line at the same point at which the q line intersects.

Reading off the values of. x' = 0.49 and y' = 0.702, substituting into Eq. (3.4-

24), and solving for Rm,

Figure 3.4-12. Minimum reflux ratio and infinite number of trays when

operating line is tangent to equilibrium line.

For the case of total reflux in part (b), the theoretical steps are drawn as shown

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Prof.Fatma K. Gad

in Fig. 3.4-13. The minimum number of theoretical steps is 5.8, which gives 4.8

theoretical trays plus a reboiler.

Thiele Method

1-Stripping-column distillation. In some cases the feed to be distilled is not

supplied to an intermediate point in a column but is added to the top of the

stripping column as shown in Fig. 3.4-14a. The feed is usually a saturated

liquid at the boiling point and the overhead product VD is the vapor rising from

the top plate, which goes to a condenser with no reflux or liquid returned back

to the tower.

The bottoms product W usually has a high concentration of the less volatile

component B. Hence, the column operates as a stripping tower with the vapor

removing the more volatile A from the liquid as it flows downward. Assuming

constant molar flow rates, a material balance of the more volatile component A

around the dashed line in Fig. 3.4-14a gives, on rearrangement,

complete tower given as Eq. (3.4-11). It intersects the y = x line at x = x w, and

the slope is constant at L/Vm+l.

If the feed is saturated liquid, then Lm = F. If the feed is cold liquid below the

boiling point, the q line should be used and q > 1.

Lm = qF (3.4-26)

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FIGURE 3.4-13. Graphical solution for minimum reflux ratio Rm and total

reflux for Example

Figure 3.4-14: Material balance and operating line for stripping tower:

(a) flows in tower. (b) operating and equilibrium line.

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Prof.Fatma K. Gad

In Fig. 3.4-14 the stripping operating-line equation (3.4-25) is plotted and the q

line, Eq. (3.4-19), is also shown for q = 1.0. Starting at.x F, the steps are drawn

down the tower.

A liquid feed at the boiling point of 400 kg mol/h containing 70 mol % benzene

(A) and 30 mol % toluene (B) is fed to a stripping tower at 101.3 kPa pressure.

The bottoms product flow is to be 60 kg mol/h containing only 10 mol % A

and.the rest B. Calculate the kg mol/h overhead vapor, its composition, and the

number of theoretical steps required.

Solution:

Referring to Fig. 3.4-14a, the known values are F = 400 kg mol/h, x F = 0.70, W

= 60 kg mol/h, and xw = 0.10. The equilibrium data from Table 3.1-1 are plotted

in Fig. 3.4-15. Making an overall material balance,

F = W + VD

400 = 60 + VD

F xF = W xw + VD yD

400 (0.70) = 60 (0.10) + 340 (yD)

yD = 0.806

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Prof.Fatma K. Gad

For a saturated liquid, the q line is vertical and is plotted in Fig. 4.4-15. The

operating line is plotted through the point y = x w - 0.10 and the intersection of

yD = 0.806 with the q line. Alternatively, Eq. (3.4-25) can be used with a slope

of Lm / Vm+1 = 400 / 340. Stepping off the trays from the top, 5.3 theoretical

steps or 4.3 theoretical trays plus a reboiler are needed.

where the feed enters the bottom of the tower as a vapor. The overhead

distillate is produced in the same manner as in a complete fractionating tower

and is usually quite rich in the more volatile component A. The liquid bottoms

is usually comparable to the feed in composition, being slightly leaner in

component A. If the feed is saturated vapor, the vapor in the tower V n = F.

Enriching-line equation (3.4-7) holds, as does the q-line equation (3.4-19).

distillation tower is applied to one side of a heat exchanger (reboiler) and the

steam does not directly contact the boiling solution, as shown in Fig. 3.4-5.

However, when an aqueous solution of more volatile A and water B is being

distilled, the heat required may be provided by the use of open steam injected

directly at the bottom of the tower. The reboiler exchanger is then not needed.

The steam is injected as small bubbles into the liquid in the tower bottom, as

shown in Fig. 3.4-16a. The vapor leaving the liquid is then in equilibrium with

the liquid if sufficient contact is obtained. Making an overall balance on the

tower and a balance on-A,

F+S=D+W (3.4-27)

F xF + S ys = D x D + W x w (3.4-28)

where

ys = 0 = mole fraction of A in steam.

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Prof.Fatma K. Gad

A are as follows:

Lm + S =Vm+l + W (3.4-29)

Substituting into Eq. (3.4-31), the stripping operating line is

ym+1 = W / S xm – W / S xw (3.4-32)

When y = 0, x = xw. Hence, the stripping line passes through the point y = 0, x =

xw, as shown in Fig. 3.4-16b, and is continued to the x axis. Also, for the

intersection of the stripping line with the 45° line, when y = x in Eq. (3.4-32),x

= Wxw / (W — S).

For a given reflux ratio and overhead distillate composition, the use of open

steam rather than closed requires an extra fraction of a stage, since the bottom

step starts below the y = x line (Fig. 3.4-16b). The advantage of open steam lies

in simpler construction of the heater, which is a sparger.

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(a) schematic of tower, (b) operating and equilibrium lines.

product or side streams are removed from sections of the tower between the

distillate and the bottoms. The side stream may be vapor or liquid and may be

removed at a point above the feed entrance or below depending on the

composition desired.

The flows for a column with a liquid side stream removed above the feed inlet

are shown in Fig. 3.4-17. The top enriching operating line above the liquid side

stream and the stripping operating line below the feed are found in the usual

way. The equation of the q line is also unaffected by the side stream and is

found as before. The liquid side stream alters the liquid rate below it, and hence

the material balance or operating line in the middle portion between the feed

and liquid side stream plates.

Making a total material balance on the top portion of the tower as shown in the

dashed-line box in Fig. 3.4-17,

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where O is mol/h saturated liquid removed as a side stream. Since the liquid

side stream is saturated,

Ln = Ls + O (3.4-34)

Solving for yS+1 the operating line for the region between the side stream and

the feed is

The slope of this line is Ls / Vs+l. The line can be located as shown in Fig. 3.4-

18 by the q line, which determines the intersection of the stripping line and Eq.

(3.4-37), or it may be fixed by the specification of x D, the side-stream

composition. The step on the McCabe-Thiele diagram must actually be at the

intersection of the two operating lines at xQ in an actual tower. If this does not

occur, the reflux ratio can be altered slightly to change the steps.

Figure 3.4-17. Process flow for a rectification tower with a liquid side stream.

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Prof Fatma K. Gad

Figure 4.4-18. McCabe-Thiele plot for a tower with a liquid side stream above

the feed.

overhead distillate product as a vapor instead of a liquid. This can also occur

when the low boiling point of the distillate makes complete condensation

difficult. The liquid condensate in a partial condenser is returned to the tower as

reflux and the vapor removed as product as shown in Fig. 3.4-19.

If the time of contact between the vapor product and the liquid is sufficient, the

partial condenser is a theoretical stage. Then the composition x R of the liquid

reflux is in equilibrium with the vapor composition y D, where yD = xD. If the

cooling in the condenser is rapid and the vapor and liquid do not reach

equilibrium, only a partial stage separation is obtained.

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EFFICIENCIES

3.5A Introduction

In all the previous discussions on theoretical trays or stages in distillation, we

assumed that the vapor leaving a tray was in equilibrium with the liquid

leaving. However, if the time of contact and the degree of mixing on the tray is

insufficient, the streams will not be in equilibrium. As a result the efficiency of

the stage or tray is not 100%. This means that we must use more actual trays for

a given separation than the theoretical number of trays determined by

calculation. The discussions in this section apply to both absorption and

distillation tray towers.

Overall tray efficiency EO, Murphree tray efficiency EM, and point or local tray

efficiency EMP (sometimes called Murphree point efficiency). These will be

considered individually.

Figure 3.4-19: Partial condenser where the vapor and liquid leave in

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Prof Fatma K. Gad

equilibrium:

(a) Process flow diagram. (b) McCabe Thiele plot.

1. Overall tray efficiency. The overall tray or plate efficiency E0 concerns

the entire tower and is simple to use but is the least fundamental. It is defined as

the ratio of the number of theoretical or ideal trays needed in an entire tower to

the number of actual trays used.

For example, if eight theoretical steps are needed and the overall efficiency is

60%, the number of theoretical trays is eight minus a reboiler, or seven trays.

The actual number of trays is 7 / 0.60, or 11.7 trays.

efficiencies in commercial towers are available for standard tray designs (O1).

For hydrocarbon distillation these values range from about 50 to 85% and for

hydrocarbon absorption from about 10 to 50%. These correlations should only

be used for approximate estimates.

follows:

where yn is the average actual concentration of the mixed vapor leaving the tray

n shown in Fig. 11.5-1, yn+1 , the average actual concentration of the mixed

vapor entering tray n, and y*n the concentration of the vapor that would be in

equilibrium with the liquid of concentration x n leaving the tray to the down

comer.

The liquid entering the tray has a concentration of x n+!, and as it travels across

the tray, its concentration drops to xn at the outlet. Hence, there is a

concentration gradient in the liquid as it flows across the tray. The vapor

entering the tray contacts liquid of different concentrations, and the outlet vapor

will not be uniform in concentration.

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Prof Fatma K. Gad

shown in Fig. 3.5-1, y'n+l the concentration of the vapor entering the plate n at

the same point, and y'*n the concentration of the vapor that would be in

equilibrium with x'n at the same point. Since y'n cannot be greater than y*n, the

local efficiency cannot be greater than 1.00 or 100%.

In small-diameter towers the vapor flow sufficiently agitates the liquid so that it

is uniform on the tray. Then the concentration of the liquid leaving is the same

as that on the tray. Then yn = yn, yn+1 = yn+1, and y'*n = y*n. The point efficiency

then equals the Murphree tray efficiency or EM = EMP.

Some vapor will contact the entering liquid x n-1, which is richer in component A

than xn. This will give a richer vapor at this point than at the exit point, where x„

leaves. Hence, the tray efficiency EM will be greater than the point efficiency

EMP. The value of EM can be related to EMP by the integration of EMP over the

entire tray.

The relationship between EMP and EM can be derived mathematically if the

amount of liquid mixing is specified and the amount of vapor mixing is also set.

Derivations for three different sets of assumptions are given by Robinson and

Gilliland. However, experimental data are usually needed to obtain amounts of

mixing. Semitheoretical methods to predict EMP and EM are summarized in

detail by Van Winkle.

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Prof Fatma K. Gad

trays.

When the Murphree tray efficiency EM is known or can be predicted, the overall

tray efficiency EO can be related to EM by several methods. In the first method

an analytical expression is as follows when the slope m of the equilibrium line

is constant and also the slope L/V of the operating line:

If the equilibrium and operating lines of the tower are not straight, a graphical

method in the McCabe-Thiele diagram can be used to determine the actual

number of trays when the Murphree tray efficiency is known. In Fig. 3.5-2 a

diagram is given for an actual plate as compared with an ideal plate. The

triangle acd represents an ideal plate and the smaller triangle abe the actual

plate. For the case shown, the Murphree efficiency EM — 0.60 = ba/ca. The

dashed line going through point b is drawn so that ba/ca for each tray is 0.60.

The trays are stepped off using this efficiency, and the total number of steps

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Prof Fatma K. Gad

gives the actual number of trays needed. The reboiler is considered to be one

theoretical tray, so the true equilibrium curve is used for this tray as shown. In

Fig. 4.5-2, 6.0 actual trays plus a reboiler are obtained.

3.6.A INTRODUCTION

In chapter 8 we discussed distillation under the assumption of equimolal

overflow, i.e., vapor and liquid molar flow rates in any section of the distillation

column are the same on all trays in that section. In this chapter we will not

make that assumption. Instead, energy balances on all trays will be used to

calculate the liquid and vapor flow rates on all trays. This nonequimolal

overflow (NEMO) model of the column is more rigorous and should be used in

those columns where there are

1-Large temperature differences from the top of the column to the bottom

(where sensible heat effects are important).

The graphical calculation procedure that includes energy balances is called the

Ponchon method. The graphical solution uses an Hxy diagram on which several

A points are drawn, using the same graphical mixing rule that was used in

nonadiabatic flash calculations and in liquid-liquid extraction calculations.

McCabe-Thiele method, and the nonequimolal overflow Ponchon method so

that you can compare them directly. Both methods use VLE data and feed

conditions to calculate a minimum reflux ratio. Then component balances

(together with energy balances in the Ponchon method) are used with VLE

relationships to step up the column.

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Prof Fatma K. Gad

Design Method

1-Find the minimum reflux ratio. Usually, this is obtained from the intersection

of the feed thermal condition q line with the VLE equilibrium curve.

2-Set the actual reflux ratio. Typically, this is some preset multiple of the

minimum reflux ratio, for example 1.1 times the minimum.

3-Draw lines representing component balances. These are the straight operating

lines for each section of the column.

4-Step off stages. Use alternately the operating line and the VLE curve. Use the

stripping operating line from xB up to where it intersects the q line. Then use

the rectifying operating line.

1-Limitations: Limited to binary systems.

2-Design Procedure

(a)-Find the minimum reflux ratio. Usually, this is done by extending the VLE

tie-line on an Hxy diagram that goes through the feed point (z, hp) to a vertical

line drawn at the distillate composition xD. As shown in Figure 13-1, the

coordinates of the point of intersection are (xD,h%'n). The minimum reflux

ratio is calculated from

where

HNT = enthalpy of vapor leaving the top tray

hD = enthalpy of liquid distillate product

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Prof Fatma K. Gad

(b)-Set the actual reflux ratio. Typically, this is 1.1 times the minimum. Then

calculate the vertical coordinate hΔ of a Δ point:

(c)-Locate the Δ and ΔB points using component and energy balances. Draw a

straight line from the Δ point through the feed point to a vertical line though the

bottoms composition xB. (See Figure 3.6-2.) The point of intersection is called

the ΔB point.

operating lines in the stripping section and the VLE tie-lines for phase

equilibrium. When a VLE tie-line is used that crosses the line that joins the Δ

and ΔB points, this is the optimum feed tray. Now use the Δ point to construct

operating lines in the rectifying section.

COLUMNS

Rectifying Section

The standard simple column has one feed, a total condenser, and a partial

reboiler, and makes two products (distillate and bottoms). (See Figure 3.6-3.)

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Prof Fatma K. Gad

Consider the top part of the column. We cut the column above the nth tray, as

shown in Figure 3.6-4, and do mass, component, and energy balances around

this system.

We assume that we know Qc, D, xD, hD, Ln+1, xn+1, and hn+l. We wish to calculate

Vn, _yn, and Hn. The problem is mathematically similar to the mixing problem

discussed in chapter 11. The only difference is that one of the streams is

flowing out instead of in. This can be taken care of simply by using a negative

sign, as illustrated in Figure 3.6-5.

difference. Δ, a pseudo flow rate, is the difference between the vapor and liquid

streams passing each other in the rectifying section of the column. It is defined

by

Δ = Vn - Ln+l (3.6-3)

A total mass balance, a light component balance, and an energy balance around

the system under consideration give

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Prof Fatma K. Gad

Fgure : 3.6-3(below) Distillation column nomenclature.

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Prof Fatma K. Gad

= D (hD – (Ac / D)) (3.6-6)

The right-hand side of equation 13-6 is written in the form shown because we

want to define a pseudo enthalpy hΔ and a pseudo composition xA.

hΔ and xΔ such that they give us the three equations

Vn - Ln+l = Δ (3.6-7)

Qc

Vn

(-Ln+1) D

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Prof Fatma K. Gad

XΔ = xD (3.6-10)

hΔ = hD – (Qc / D) (3.6-11)

The graphical mixing rule tells us that if we mix the Vn and Ln+1, streams

together (with Ln+1 taken to be negative) to get the Δ stream, the coordinates of

this Δ stream will lie on a straight line joining the points Vn and Ln+1. Thus, the

Δ point can be used to do component and energy balances. The method is

similar to the use of operating lines in the McCabe-Thiele procedure to do

component balances.

Figure 3.6-6 illustrates the use of a Δ point. If we know the point Ln+1 and the Δ

point on an Hxy diagram, we can simply draw a straight line joining the two.

The intersection of this line with the saturated vapor line gives us the point Vn.

Thus, yn and Hn can be read off the graph, and then the flow rate Vn can be

calculated by means of a component balance.

The straight line that we drew can be considered an operating line. It passes

through the coordinates (xn+1, hn+1) and (yn, Hn). The Δ point permits us to relate

the compositions and enthalpies of passing streams in the column. In effect, we

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Prof Fatma K. Gad

3.6-E Condenser

Balances around the condenser and reflux drum, sketched in Figure 3.6-7, give

VNT = R + D (3.6-12)

where

R = reflux flow rate

D = distillate flow rate

Solving for R yields

Thus, the reflux ratio is the ratio of the distances a and b shown in Figure 3.6-8.

Note that the point hD lies on the saturated liquid line if there is no subcooling.

If the distillate and the reflux are subcooled, the point will lie below the

saturated liquid line.

Similar balances in the stripping section lead to the ΔB point which is used to

relate the compositions of passing streams in that section. The coordinates of

the ΔB point are

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Prof Fatma K. Gad

where

QR = heat transfer rate in the reboiler

B = bottoms product flow rate

hB = enthalpy of liquid bottoms product

Mass, component, and energy balances around the entire system as sketched in

Figure 3.6-9(a) are

Component : z F = B x B + D xD (3.6-20)

These three equations tell us that mixing a stream B with enthalpy (hB - QR / B)

and composition xB together with a stream D with enthalpy (hD — Qc / D) and

composition xD will give a stream F which has an enthalpy hF and composition

z.

Thus, a straight line from the Δ point to the ΔB point must go through the feed

point, as shown in Figure 3.6-9(b). The point Fcan lie in the two-phase region,

in the subcooled-liquid region, or in the super-heated-vapor region. This overall

balance line replaces the q line used in the McCabe-Thiele method.

Example 3.6.1.

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Prof Fatma K. Gad

atmospheric pressure. Feed flow rate is 3,000 kg/hr, and feed composition is 60

weight percent methanol. The feed enters the column at a pressure of 1

atmosphere and a temperature of 75°C. Determine the number of trays required

and the optimum feed tray to make 95 weight percent methanol distillate and 5

weight percent methanol bottoms when a reflux ratio of 0.75 is used. Assume

theoretical trays, a total condenser, a partial reboiler, and saturated reflux.

Solution:

Total mass and component balances give the product flow rates.

Total F =D + B

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Prof Fatma K. Gad

Component z F — x D D + x B B

D = 1,833 kg/hr

B = 1,167 kg/hr

Since the reflux ratio is given, the Δ point can be located on the Hxy diagram for methanol-water at atmospheric

pressure (see Figure 3.6-10) by using equation 3.6-2:

h Δ = H N T + RR(H N T - h D )

Note that the feed is partially vaporized. A straight line from the Δ point through the feed point intersects the vertical

line through x B at —500 cal/g. This is the Δ B point.

Stages are stepped off by starting at x B = 5 weight percent on the saturated liquid line in Figure 3.6-10. The vapor

leaving the base of the column has a composition y B = 31 weight percent. An operating line is drawn from y B to the Δ B

point (the dashed straight line), and the composition x 1 = 19 weight percent is read off the point of intersection with the

saturated liquid curve. Then the VLE tie-line is used to get y l = 55 weight percent.

This stepping procedure is continued for five steps (partial reboiler plus four trays). Between trays 4 and 5 the feed line is

crossed. The optimum feed tray is tray 4.

To get x 5 from y4, the Δ point is used, not the Δ B point. Stepping is continued until x D is reached. Eight trays plus the

partial reboiler are required.

In the McCabe-Thiele method, the minimum reflux ratio and the minimum

number of stages can be easily visualized and graphically calculated on an xy

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Prof Fatma K. Gad

constraints on the separation. In the Ponchon method, the same limiting

conditions can be determined with essentially the same ease, and they yield the

same useful information.

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Prof Fatma K. Gad

If we extend the VLE tie-lines to intersect with a vertical line through x D , the highest intersection point establishes the minimum

Δ point. As sketched in Figure 3.6-ll(a), the highest point usually occurs for the tie-line through the feed point. This is equivalent

to establishing the minimum reflux ratio in the McCabe-Thiele method by finding the rectifying operating line that intersects the

feed q line on the VLE curve. However, there are some systems in which the highest point of intersection on the vertical line

through x D may occur on the extension of a tie-line that is not the one that goes through the feed point.

Once the minimum Δ point is established, the minimum reflux ratio can be calculated from equation 3.6-1.

The minimum number of trays occurs at an infinite reflux ratio. If the reflux ratio is infinite, the condenser heat removal must be

infinite (or D must be zero). Therefore, the Δ point must be located at infinity. The operating lines on a Ponchon diagram are

vertical lines at an infinite reflux ratio (total reflux).

Figure 3.6—11(b) sketches the stepping-off of the minimum number of stages. Vertical operating lines and the VLE tie-lines are

used. For the system shown, four trays plus'a reboiler are required.

(a) Minimum reflux ratio. (b) Total reflux.

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Prof Fatma K. Gad

So far we have applied the Ponchon method to just the "plain vanilla" distillation column with a single feed and liquid distillate and

bottoms products. However, there are no inherent limitations to the method that would restrict us to just these simple columns.

Complex columns may have multiple feeds, multiple products, and multiple heat input or heat removal locations. The Ponchon

method becomes a little more complex, but the procedure is essentially the same. Total mass, component, and energy balances are

written around each section of the column, giving a different Δ point for each section. Several important cases will be considered.

Partial Condenser

Many columns produce a distillate product as a vapor from the reflux drum, as illustrated in Figure 3.6-12. The flow rate of this

vapor product is D, its composition is y D , and its enthalpy is H D . The D point on the Hxy diagram is located on the

saturated vapor line.

The Δ point is located at (y D , H D - Q C /D). Note that the liquid in the reflux drum is in equilibrium with the vapor

product. This liquid has a composition x R which is located at the other end of the tie-line from y D . The reflux drum gives an

additional stage of separation because of the partial condenser.

Occasionally one sees a distillation column where the product is removed as a vapor directly from the overhead vapor line, before

the condenser. In this case the condenser is a total condenser, producing liquid reflux at the same composition as the vapor product.

The reflux drum does not provide an additional stage. The Ponchon diagram looks almost the same as the liquid distillate case,

except that Q c is reduced because the distillate product is not condensed.

Other variations on the theme are also possible. For example, some columns take both vapor and liquid products. This obviously

changes the Ponchon diagram. It is instructive to sketch the diagram for this kind of system.

Dual Feeds

Many columns have more than a single feed stream. If the compositions of the two feed streams are identical, they can be

combined and fed onto a single tray. However, if the compositions are not the same (as is usual), they should be fed

onto different feed trays in order to consume the minimum amount of energy.

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Prof Fatma K. Gad

Figure 3.6-13 shows a column with feed F, introduced on a tray low in the column and

feed F 2 introduced on a tray higher in the column. The compositions are z x and z2,

where z2 is greater than z t .

The column now has three different sections: a rectifying section at the top above the

top feed, a middle section between the feed trays, and a stripping section below the

lower feed. Therefore, we need three Δ points to analyze it. Let us call these points Δ,

ΔM, and ΔB. Clearly, the Δ and ΔB points will be located at the same coordinates as in

a conventional column:

ΔB point = (x B , h B – (Q R / B))

To find the location of the A M point, we write the balance equations and rearrange them so that they have the form

Vn - L N + 1 = Δ M = D - F2 (3.6-22)

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Prof Fatma K. Gad

The pseudo flow rate A M , the pseudo composition X A M , and the pseudo enthalpy h AM define the coordinates of the A M point that

is used to step from tray to tray in the middle section of the column. The coordinates of the A M point are

x Δ M = (D x D – F 2 z 2 ) / (D – F 2 ) (3.6-25)

h Δ M = - Q c + Dh D - F 2 h F2 (D – F 2 ) (3.6-26)

This procedure is used for any complex column to locate the Δ points for each section. Remember that the coordinates of the Δ

points are pseudo compositions, so there is no restriction that they must have values between 0 and 1 only.

The procedure just described is used for each section of the column. The following

example should help to show the details of the method.

Example 3.6.2.

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Prof Fatma K. Gad

30,000 lbm/hr of feed at 80°C is fed into an atmospheric distillation column. Feed composition is 45 weight percent methanol and

55 weight percent water. The distillate product from a total condenser is 98 weight percent methanol, and the bottoms product from

the base of the column is 4 weight percent methanol. The partial reboiler in the base of the column has a heat duty of 5.65x106

Btu/hr. There is another intermediate reboiler up in the stripping seetion which uses lower pressure steam and has a heat duty of

9.13x106 Btu/hr. intermediate reboiler is located where the liquid composition on the tray is approximately 10 weight percent

methanol. Feed is introduced on the optimum feed tray. Without assuming equimolai overflow. Calculate the number of trays, the

condenser duty, and the thermal condition of the feed.

Solution:

Since equimolai ovferflow cannot be assumed, we must use a Ponchon Hxy diagram for the design of the column. The two

reboilers will result in three different column sections and three Δ points: Δ above the feed, ΔM between the feed and the

intermediate reboiler, and ΔB below the intermediate reboiler. Figure 3.6-14 shows the general layout of the column. Figure 3.6-

15 gives the Hxy diagram for methanol and water at atmospheric pressure.

The ΔB point will be located at (x B , h B — Q B /B). We first, calculate product flow rates D and B from overall total and

component balance:

F=B+D

z F = xB B + xD D 30,000 = B + D

= -106 cal/g

The ΔB point is thus located at 4 weight percent and - 106 cal/g. It is used to draw the operating lines in the lower section of the

column. The operating line connecting ΔB and y B intersects the saturated liquid line (see Figure.3.6-15) at x 1 = 12 weight

percent. Therefore, we should locate the intermediate reboiler at tray 1.

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Prof Fatma K. Gad

For the section above the intermediate reboiler, the mass, component, and energy equations are written in standard format to

determine the location of the Δ M point:

Ln + i - Vn = B = Δ M (3.6-27)

Ln +l hn +1 - V n H n = B h B - Q R - Q m = Δ M h Xu (3.6-29)

XΔ m = x B = 4 wt. % .

h Δ M = hB - (Q R + Q int ) / B

= - 405 cal/g

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Prof Fatma K. Gad

We use the Δ M point to draw operating lines on Figure 3.6-15 to get x 2 and x 3 . The optimum feed tray is tray 3, since we cross

the straight line connecting the feed point to the Δ M point.

The Δ point for the top section of the column can be calculated by determining Q c from an overall energy balance. Alternatively,

we can get the Δ point graphically by drawing a straight line from the Δ M point through the feed point at (z,h F ) to a vertical line

through x D .

Stepping is continued up the column using the Δ point. A total of six trays plus the total reboiler are needed.

The Δ point is located at an enthalpy of 830 cal/g. We can solve for Q c from

hA = hD – Qc / D

We have

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Prof Fatma K. Gad

Qc = - 18.4x106 Btu/hr

The feed is 45 weight percent methanol at 80°C and is in the two-phase region. We can read the compositions of the liquid and

vapor phases at 80°C from the ends of the VLE tie-line:

x F = 37 wt. % y F = 76 wt. %

Let F L and F v be the flow rates of the liquid and vapor feed, respectively. Then

30,000 = F L + F v

F L = 23,840 lbm/hr

EXAMPLE 3.6-3.

Example 3.4-1 except that a reflux ratio of 1.5 times the minimum reflux ratio is to be

used. The value of Rm= 1.17 from Example 3.4-2 will be used. Use enthalpy balances

to calculate the flow rates of the liquid and vapor at various points in the tower and

plot the curved operating lines. Determine the number of theoretical stages needed.

Solution:

F = 100 kg mol/h, xF = 0.45,

xD = 0.95, xw = 0.10,

R = 1.5 Rm = 1.5(1.17) = 1.755,

D = 41.2 kg mol/h, W = 58.8 kg mol/h.

The feed enters at 54.4°C and q = 1.195.

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Prof Fatma K. Gad

L / D = 1.755;

L= 1.755(41.2) = 72.3;

V1 = L + D = 72.3 + 41.2 = 113.5

The saturation temperature at the top of the tower for y1 = xD = 0.95 is 82.3°C from

Fig. 3.1-1. Using Eq. (3.6-2),

H1 = 0.95[30820+96.3(82.3-80.1)]+(1-0.95)[34224+138.2(82.3-80.1)]

= 31 206

This value of 31206 could also have been obtained from the enthalpy-concentration

plot, Fig. 3.6-1. The boiling point of the distillate D is obtained from Fig. 3.1-1 and is

81.1°C. Using Eq. (3.6-5),

Again this value could have been obtained from Fig. 3.6-1.

Following the procedure outlined for the enriching section for step 1, a value of x n

=0.55 is selected. Assuming a straight operating line for Eq. (3.6-8), an approximate

value of yn+1 is obtained.

yn+1 = 0.695, Hn+1 = 33 240.

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This calculated value of yn+1 = 0.700 is sufficiently close to the approximate value of

0.695 so that no further trials are needed.

Selecting another value for xn = 0.70 and using Eq. (3.6-8), an approximate value of

yn+I is calculated.

xn = 0.70,

hn = 1000, and for

yn+1 = 0.791,

Hn+1 = 32 500.

Vn+l = 110.8

In Fig. 3.6-3, the points for the curved operating line in the enriching section are

plotted. This line is approximately straight and is very slightly above that for constant

molal overflow.

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Prof Fatma K. Gad

Figure 3.6-3: plot of curved operating line using enthalpy concentration method for

example 4.6-2. Solid lines are for enthalpy concentration method and dashed lines for

constant molal over flow.

To obtain the reboiler duty qR, values for hw and hF are needed.

xw = 0.10,

hw = 4350.

Using Fig. 3.4-5 and making a material balance below the bottom tray and around the

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Prof Fatma K. Gad

reboiler,

Ln = W + Vw (3.6-18)

Vw Hw = (Vw+ W) hN + qR – W hw (3.6-19)

xw = 0.10,

yw = 0.207, which is the vapor composition leaving the reboiler.

For equimolal overflow in the stripping section using Eqs. (3.4-14) and (3.4-15),

is obtained.

Solving, xN = 0.174.

xN = 0.174,

yw = 0.207,

Hw = 37 000.

Vw(37 000) = (Vw+ 58.8)(3800) + 4 180 500 - 58.8(4350)

Solving, Vw = 125.0.

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Prof Fatma K. Gad

xN = 0.173

Assuming a value of ym+1 = 0.55 and using Eq. (3.6-15), an approximate value of xm

is obtained.

xm = 0.412

xm = 0.412,

hm = 2300, and for

ym+1 = 0.55,

Hm = 34 400.

Using Eq. (4.6-13),

xm = 0.407

This value of 0.407 is sufficiently close to the approximate value of 0.412 so that no

further trials are needed. The two points calculated for the stripping section are

plotted in Fig. 3.6-3. This stripping line is also approximately

straight and is very slightly above the operating line for constant molal overflow.

Using the operating line for the enthalpy balance method, the number of theoretical

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Prof Fatma K. Gad

steps is 3.4. For the equimolal method 9.9 steps are obtained. This difference would

be larger if the reflux ratio of 1.5 times Rm were decreased to, say, 1.2 or 1.3. At

larger reflux ratios, this difference in number of steps would be less.

Note that in Example 3.6-2 in the stripping section the vapor flow increases slightly

from 125.0 to 126.5 in going from the reboiler to near the feed tray. These values are

lower than the value of 133.0 obtained assuming equimolal overflow. Similar

conclusions hold for the enriching section. The enthalpy-concentration method is

useful in calculating the internal vapor and liquid flows at any point in the column.

These data are then used in sizing the trays. Also, calculations of qc and q R are used in

designing the condenser and reboiler. This method is very applicable for design using

a computer solution for binary and multicomponent mixtures to make tray to tray

mass and enthalpy balances for the whole tower. A more restrictive Ponchon-Savarit

graphical method for only binary mixtures is available (K3, T2).

In industry many of the distillation processes involve the separation of more than two

components. The general principles of design of multi*component distillation towers

are the same in many respects as those described for binary systems. There is one

mass balance for each component in the multi-component mixture. Enthalpy or heat

balances are made which are similar to those for the binary case. Equilibrium data are

used to calculate boiling points and dew points. The concepts of minimum reflux and

total reflux as limiting cases are also used.

used to separate the two components A and B into relatively pure components with A

in the overhead and B in the bottoms. However, in a multi-component mixture of n

components, n-1 fractionators will be required for separation. For example, for a

three-component system of components A, B, and C, where A is the most volatile and

C the least volatile, two columns will be needed, as shown in Fig. 3.7-1. The feed of

A, B, and C is distilled in column 1 and A and B are removed in the overhead and C

in the bottoms. Since the separation in this column is between B and C, the bottoms

containing C will contain a small amount of B and often a negligible amount of A

(often called trace component). The amount of the trace component A in the bottoms

can often be neglected if the relative volatilities are reasonably large. In column 2 the

feed of A and B is distilled with A in the distillate containing a small amount of

component B and a much smaller amount of C. The bottoms containing B will also be

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Prof Fatma K. Gad

remove A overhead with B plus C being fed to column 2 for separation of B and C. '

stages or trays are assumed in the stage-to-stage calculations. Using equilibrium data,

equilibrium calculations are used to obtain the boiling point and equilibrium vapor

composition from a given liquid composition or the dew point and liquid composition

from a given vapor composition. Material balances and heat balances similar to those

described in Section 3.6 are then used to calculate the flows to and from the adjacent

stages. These stage-to-stage design calculations involve trial-and-error calculations,

and high-speed digital computers are generally used to provide rigorous solutions.

In a design the conditions of the feed are generally known or specified (temperature,

pressure, composition, flow rate). Then, in most cases, the calculation procedure

follows either of two general methods. In the first method, the desired separation or

split between two of the components is specified and the number of theoretical trays

are calculated for a selected reflux ratio. It is clear that with more than two

components in the feed the complete compositions of the distillate and bottoms are

not then known and trial-and-error procedures must be used. In the second method,

the number of stages in the enriching section and in the stripping section and the

reflux ratio are specified or assumed and the separation of the components is

calculated using assumed liquid and vapor flows and temperatures for the first trial.

This approach is often preferred for computer calculations. In the trial-and-error

procedures, the design method of Thiele and Geddes, which is a reliable procedure, is

often used to calculate resulting distillate and bottoms compositions and tray

temperatures and compositions. Various combinations and variations of the above

rigorous calculation methods are available in the literature and are not considered

further.

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Prof Fatma K. Gad

The variables in the design of a distillation column are all interrelated, and there are

only a certain number of these which may be fixed in the design. For a more detailed

discussion of the specification of these variables, see Kwauk.

calculation methods for the approximate solution of multicomponent distillation are

considered. These methods are quite useful to study a large number of cases rapidly to

help orient the designer, to determine approximate optimum conditions, or to provide

information for a cost estimate. Before discussing these methods, equilibrium

relationships and calculation methods of bubble point, dew point, and flash

vaporization for multicomponent systems are covered.

For multicomponent systems which can be considered ideal, Raoult's law can be used

to determine the composition of the vapor in equilibrium with the liquid. For example,

for a system composed of four components, A, B, C, and D,

PA = pA xA,

PB = PB xB,

PC = PC xC,

PD = PD xD (3.7-1)

yA = pA / P = (PA / P) xA,

yB = (PB / P) xB,

yC = (PC / P) xC,

yD = (PD / P) xD (3.7-2)

represented by

yA = KA xA,

y B = KB x B ,

yC = KC xC,

y D = KD x D (3.7-3)

component A. These K values for light hydrocarbon systems (methane to decane)

have been determined semiempirically and each K is a function of temperature and

pressure. Convenient K factor charts are available by Depriester and Hadden and

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Prof Fatma K. Gad

of composition, which is sufficiently accurate for most engineering calculations. Note

that for an ideal system, KA = P/P, and so on. As an example, data for the

hydrocarbons n-butane, n-pentane, n-hexane, and n-heptane are plotted in Fig. 3.7-2

at 405.3 kPa (4.0 atm) absolute.

Figure 3.7-2. Equilibrium K values for light hydrocarbon systems at 405.3 kPa (4.0

atm) absolute.

can be defined in a manner similar to that for a binary mixture. If component C in a

mixture of A, B, C, and D is selected as the base component,

αi = Ki / KC,

αA = KA / KC ,

αB = KB / KC,

αC = KC / KC = 1,

αD = KD / KC (3.7-4)

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Prof Fatma K. Gad

The values of Ki will be a stronger function of temperature than the α i values since the

Ki lines in Fig. 3.7-2 all increase with temperature in a similar manner.

1-Boiling point. At a specified pressure, the boiling point or bubble point of a given

multicomponent mixture must satisfy the relation ∑ yi = 1.0. For a mixture of A, B, C,

and D with C as the base component,

and the values of αi are calculated from the values of Ki at this temperature. Then the

value of Kc is calculated from Kc = 1.0/αi xi. The temperature corresponding to the

calculated value of Kc = 1.0/ ∑ αi, xi. The temperature corresponding to the

calculated value of Kc is compared to the assumed temperature. If the values differ,

the calculated temperature is used for the next iteration. After the final temperature is

known, the vapor composition is calculated from

2. Dew point. For the dew point calculation, which is also trial and error,

The value of Kc is calculated from Kc = ∑ (yi / αi). After the final temperature is

known, the liquid composition is calculated from

A liquid feed to a distillation tower at 405.3 kPa abs is fed to a distillation tower. The

composition in mol fractions is as follows:

n-butane (xA = 0.40),

n-pentane (xB = 0.25),

N-hexane(xc = 0.20),

n-heptane(xD = 0.15).

Calculate the boiling point and the vapor in equilibrium with the liquid.

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Prof Fatma K. Gad

Solution:

1-First a temperature of 65°C is assumed and the values of K obtained from Fig. 3.7-

2. Using component C (n-hexane) as the base component, the following values are

calculated using Eq. (3.7-5) for.the first trial:

The calculated value of Kc is 0.2745, which corresponds to 69°C, Fig. 3.7-2. Using

69°C for trial 2, a temperature of 70°C was obtained. Using 70°C for trial 3, the

calculations shown in the table give a final calculated value of 70°C, which is the

bubble point. Values of yi are calculated from Eq. (3.7-6).

flow diagram is shown in Fig. 3.3-1. Defining/ = V/F as the fraction of the feed

vaporized and (1 - f) = L/F as the fraction of the feed remaining as liquid and making

a component / balance as in Eq. (3.3-6), the following is obtained:

yi = ((ƒ – 1) / ƒ) xi + xi F / ƒ (3.7-9)

xi in the liquid after vaporization. Also, for equilibrium, y1 = K1 x1 = Kc αi xi, where αi

= Ki / KC.Then Eq. (4.7-9) becomes

yi = Kc ai xi = ((ƒ – 1) / ƒ) xi + xi F / ƒ (3.7-10)

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Prof Fatma K. Gad

This equation is solved by trial and error by first assuming a temperature if the

fraction f vaporized has been set. When the ∑ x i values add up to 1.0, the proper

temperature has been chosen. The composition of the vapor yi can be obtained from y i

= Kc αi xi; or by a material balance.

Fractionation of a multicomponent mixture in a distillation tower will allow

separation only between two components. For a mixture of A, B, C, D, and so on, a

separation in one tower can only be made between A and B, or B and C, and so on.

The components separated are called the light key, which is the more volatile

(identified by the subscript L), and the heavy key (H). The components more volatile

than the light key are called light components and will be present in the bottoms in

small amounts. The components less volatile than the heavy key are called heavy

components and are present in the distillate in small amounts. The two key

components are present in significant amounts in both the distillate and bottoms.

1. Minimum stages for total reflux. Just as in binary distillation, the minimum

number of theoretical stages or steps, Nm, can be determined for multicomponent

distillation for total reflux. The Fenske equation (3.7-12) also applies to any two

components in a multicomponent system. When applied to the heavy key H and the

light key L, it becomes

where xLD is mole fraction of light key in distillate, xLW is mole fraction in bottoms,

x[ID is mole fraction of heavy key in distillate, and x llw is mole fraction in bottoms. The

average value of αL of the light key is calculated from the αLD at the top temperature

(dew point) of the tower and αLav at the bottoms temperature.

Note that the distillate dew-point and bottoms boiling-point estimation is partially

trial and error, since the distribution of the other components in the distillate and

bottoms is not known and can affect these values.

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Prof Fatma K. Gad

concentration of other components in the distillate and the bottoms at total reflux, Eq.

(3.7-12) can be rearranged and written for any other component i as follows:

These concentrations of the other components determined at total reflux can be used

as approximations with finite and minimum reflux ratios. More accurate methods for

finite and minimum reflux are available elsewhere.

EXAMPLE 3.7-2. Calculation of Top and Bottom Temperatures and Total Reflux

The liquid feed of 100 mol/h at the boiling point given in Example 3.7-1 is fed to a

distillation tower at 405.3 kPa and is to be fractionated so that 90% of the n-pentane

(B) is recovered in the distillate and 90% of the n-hexane (C) in the bottoms.

Calculate the following.

(a)Moles per hour and composition of distillate and bottoms.

(b)Top temperature (dew point) of distillate and boiling point of bottoms.

©Minimum stages for total reflux and distribution of other components in the

distillate and bottoms.

Solution:

(a) Material balances are made for each component, with component n-pentane (B)

being the light key (L) and n-hexane (C) the heavy key (H). For the overall balance,

F=D+W (3.7-15)

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Prof Fatma K. Gad

yCD D = 2.0.

For the first trial, it is assumed that no component D (heavier than the heavy key C) is

in the distillate and no light A in the bottoms. Hence,

moles A in distillate = yAD D = 0.40(100) = 40.0. Also,

moles D in bottoms = xDW W = 0.15(100) = 15.0.

These values are tabulated below.

(b)The dew point of the distillate (top temperature) in part (b), a value of 67°C will be

estimated for the first trial. The K values are read from Fig. 3.7-2 and the a values

calculated. Using Eqs. (3.7-7) and (3.7-8), the following values are calculated:

The calculated value of Kc is 0.2627, which corresponds very closely to 67°C, which

is the final temperature of the dew point.

For the bubble point of the bottoms, a temperature of 135°C is assumed for trial 1 and

Eqs. (3.7-5) and (3.7-6) used for the calculations. A second trial using 132°C gives

the final temperature as shown below.

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Prof Fatma K. Gad

(c) The proper a values of the light key L (n-pentane) to use in Eq. (3.7-13) are as

follows:

The distribution or compositions of the other components can be calculated using Eq.

(3.7-14). For component A, the average a value to use is

Substituting DxDA = 1017 W xwA from Eq. (3.7-14) into (3.7-18) and solving,

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Prof Fatma K. Gad

Hence, the moles of D in the distillate are quite small, as are the moles of A in the

bottoms.

Using the new distillate composition, a recalculation of the dew point assuming 67°C

gives a calculated value of Kc = 0.2637. This is very close to that of 0.2627 obtained

when the trace amount of D in the distillate was assumed as zero. Hence, the dew

point is 67°C. Repeating the bubble-point calculation for the bottoms assuming

132°C, a calculated value of Kc = 1.138, which is close to the value at 132°C. Hence,

the bubble point remains at 132°C. If either the bubble- or dew-point temperatures

had changed, the new values would then be used in a recalculation of N m.

component Distillation

As in the case for binary distillation, the minimum reflux ratio R m is that reflux ratio

that will require an infinite number of trays for the given separation of the key

components.

For binary distillation only one "pinch point" occurs where the number of steps

become infinite, and this is usually at the feed tray. For multicomponent distillation

two pinch points or zones of constant composition occur: one in the section above the

feed plate and another below the feed tray. The rigorous plate-by-plate stepwise

procedure to calculate is trial and error and can be extremely tedious for hand

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Prof Fatma K. Gad

calculations.

Underwood's shortcut method to calculate R m (Ul, U2) uses constant average a values

and also assumes constant flows in both sections of the tower. This method provides a

reasonably accurate value. The two equations to be solved to determine the minimum

reflux ratio are

The values of xiD for each component in the distillate in Eq. (3.7-20) are supposed to

be the values at the minimum reflex. However, as an approximation, the values

obtained using the Fenski total reflux equation are used. Since each a; may vary with

temperature, the average value of a; to use in the preceeding equations is

approximated by using a; at the average temperature of the top and bottom of the

tower. Some have used the average α which is used in the Fenske equation or the a at

the entering feed temperature.

To solve for Rm, the value of 9 in Eq. (3.7-19) is first obtained by trial and error. This

value of 0 lies between the α value of the light key and a value of the heavy key,

which is 1.0. Using this value of 0 in Eq. (3.7-20), the value of Rm is obtained

directly. When distributed components appear between the key components, modified

methods described by others can be used.

Reflux Ratio

number of stages for total reflux in Section 3.7E and the minimum reflux ratio in

Section 3.7F are useful for setting the allowable ranges of number of stages and flow

conditions. These ranges are helpful for selecting the particular operating conditions

for a design calculation. The relatively complex rigorous procedures for doing a

stage-by-stage calculation at any operating reflux ratio have been discussed in Section

3.7A.

for an operating reflux ratio R is the empirical correlation of Erbar and Maddox (El)

given in Fig. 3.7-3. This correlation is somewhat similar to a correlation by Gilliland

(Gl) and should be considered as an approximate method. In Fig. 3.7-3 the operating

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Prof Fatma K. Gad

reflux ratio R (for flow rates at the column top) is correlated with the minimum R m

obtained using the Underwood method, the minimum number of stages Nm obtained

by the Fenske method, and the number of stages N at the operating R.

to estimate the number of theoretical stages above and below the feed which can be

used to estimate the feed stage location. This empirical relation is as follows:

Log(Ne / Ns) =

0.206 log [ (xHF / xLF) (W / D) (xLW / xHD)2] (3.7-21)

where Ne is the number of theoretical stages above the feed plate and Ns the number

of theoretical stages below the feed plate.

EXAMPLE 3.7-3. Minimum Reflux Ratio and Number of Stages at Operating Reflux

Ratio

Using the conditions and results given in Example 3.7-2, calculate the following.

Erbar-Maddox correlation.

Solution;

The temperature to use for determining the values of αi is the average between the top

of 67°C and the bottom of 132°C and is (67 + 132)/2 or 99.5°C. The K, values

obtained from Fig. 3.7-2 and the αi values and distillate and feed compositions to use

in Eqs. (3.7-19) and (3.7-20) are as follows:

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Prof Fatma K. Gad

Figure 3.7-3: Erbar Maddox correlation between reflux ratio and number of stages

(Rm based on Underwood method).

Substituting into Eq. (3.7-19) with q = 1.0 for feed at the boiling point,

1–q=1–1=0

=(5.2 x 0.4)/(5.2–θ)

+(2.3x0.25)/(2.3–θ)+(1x0.2)/(1–θ)

+(0.467x0.15)/(0.467–θ) (3.7-22)

This is trial and error, so a value of 0 — 1.210 will be used for the first trial (0 must

be between 2.30 and 1.00). This and other trials are shown below.

The final value of θ = 1.0296 is substituted into Eq. (3.7-20) to solve for Rm.

+ (2.30(0.3489) / (2.30 - 1.2096))

+ (1.00(0.031) / (1.00 - 1.2096))

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Prof Fatma K. Gad

Solving, Rm = 0.395.

R = l.5 Rm = 1.5(0.395) = 0.593,

R/(R+1) = 0.593/(0.593 + 1.0) = 0.3723,

R/(Rm+1) = 0.395/(0.395 + 1.0) = 0.2832.

From Fig. 3.7-3, Nm/N = 0.49. Hence,

Nm/N = 0.49

From example 3.7-2, Nm = 5.40.

Solving, N = 11.0 theoretical stages in the tower.

This gives 11.0 — 1.0 (reboiler) or 10.0 theoretical trays.

(c)For the location of the feed tray in part(c) using Eq. (3.7-21),

Also, Ne = 1.184 (N – Ne)

So Ne = 6

Ne + Ns = N = 11.0 stages.

Solving, Ns — 5.0 and Ne = 6.0. This means that the feed tray is 6.0 trays from the

top.

In these processes the whole of a batch is run into the boiler of the still and, on

heating the vapor is passed into fractionation column as indicated in fig (24). As with

continuous distillation the composition of the top product will depend on the still

composition and the number of plates in the column and on the reflex ration used.

As the process proceeded, the liquid remaining in the still will become steadily

weaker in the M.V.C

Thus the still may be changed with S1 moles of a mixture containing xS1 of M.V.C.

Initially with reflex ration R1 the top product has a composition x d1. If after a contain

interval of time the composition of the top product starts to fall, then if the reflex is

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Prof Fatma K. Gad

increased to new value R2, it will be possible to obtain the some composition again.

This method required a continuous increase in R to maintain a constant quality of the

top product.

An alternative method is to work with a constant R and allow the composition of the

top product to fall.

Batch distillation is useful for handling small quantities of multi component, since it

is possible to obtain the different components at reasonable degree of purity one after

the other.

the still after first distillation may be added to the next batch.

Suppose a column of four ideal plates will be used to separate a mixture of EtOH

and H2O. Initially there are in the still S1 moles of liquor of mol fraction xS1 with

respect to the M.V.C (EtOH). The top product is to contain x d and this needed a

R1. Suppose the distillation is to be continued till there are S 2 moles in the still

with xS2. Then for the same no. of plates the reflex ratio will be increased to R2.

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Prof Fatma K. Gad

Therefore, S1 – S2 = Db

S1 xS1 – S2 xS2 = Db xd

If is the intercept on the y axis for any operating line then,

= xd / ( R + 1 ) or R = ( xd / ) - 1

the amount of steam used in the distillation for a given quantity D b

R = dLp / dDp and the total reflex flowing down the column is given by

Lb R2

dLb = R dDb

0 R1

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Prof Fatma K. Gad

to provide reflex dLb requires the removal of heat dLb in the condenser, where is

the latent heat per mol. Thus the heat to be supplied in the reboiler Q R to provide this

reflex during the total distillation in given by

Lb R2

QR = DLb = R dDb

0 R1

If the same column as before is operated at a constant R, the concentration of the

MVC in the top product will continuously fall. Over a small interval of time dt, x d

becomes xd – dxd. If in this time the amount of product obtained is dD b ; material

balance on MVC gives.

MVC in the top product = dDb [ xd - dxd / 2] = xd dDb

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Prof Fatma K. Gad

But dDb = - dS , S dxS = dS ( xd - xS )

s2 xS2

And dS / S = dxS / ( xd - xS )

s1 xS1

xS1

Ln ( S1 / S2 ) = dxS / ( xd - xS )

xS2

The right hand side of this equation can be integrated by plotting (1/(x d-xS)) vs xS.

This will enable the ratio of the initial to final quantity in the still to be found for any

desired charge in xS and hence the amount of distillate Db.

QR = R Db

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Prof Fatma K. Gad

Example:(I)

A mixture of EtOH and H2O with 0.55 mol fraction of a alcohol is distilled to give a

top product of 0.75 mol fraction EtOH. The column has 4 ideal plates and the

distillation is stopped when the reflex ratio has to be increased beyond 4.0.

Find the amount of distillate and heat required / mol product.

Solution

Assuming various values of R between 0.85 and 4, we get the corresponding values of

the intercept and the concentration in the still as shown in the table below.

R xS Db

0.85 0.405 0.55 0

1.0 0.375 0.50 20.0

1.5 0.3 0.37 47.4

2.0 0.25 0.20 63.8

3.0 0.187 0.075 70.5

4.0 0.15 0.05 71.9

R=4

The value R dDb from the plot = 96 kmol

R=0.85

Taking and average latent heat per k mol for the EtOH – H2O mixture as 4000 kJ.

QR = (96 * 4000)/1000 = 380 MJ

QR / Db = 380/71.4 = 5.32 MJ U.E.D

Example (ii)

If the same batch as above is distilled with constant R of 2.1. What will be the heat

required and the average composition of the distillate, if the distillation is stopped

when the composition in the still has fallen to 0.105 mol fraction of MVC.

Solution:

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Prof Fatma K. Gad

The initial composition of the top product will be 0.78 as shown in the following table

and the final composition will be 0.74. values of x d, xS, xd-xS and 1 / (xd-xS ) for

various values of xS and a constant reflex ratio are given in the following table.

xS xd xd-xS 1/(xd-xS)

0.55 0.780 0.230 4.35

0.5 0.775 0.275 3.65

0.425 0.770 0.345 2.90

0.310 0.766 0.450 2.22

0.225 0.750 0.525 1.91

0.105 0.740 0.635 1.58

Fig of Example 1

0.55

For which dxS / ( xd - xS ) = 1.1

0.105

Ln ( S1 / S2 ) = 1.1 , ( S1 / S2 ) = 3.0

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Prof Fatma K. Gad

= 0.55*100–0.105*33.3 = 51.5 k mole.

AZEOTROPIC DISTILLATION

In the processes so far considered, the vapor becomes steadily richer in the M.V.C on

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Prof Fatma K. Gad

successive plates.

There are two types of mixtures where this steady increase in the concentration of the

M.V.C either does not take place or else take place so slowly that an uneconomical

number of plates is required.

For instance if a mixture of EtoH and H2O is distilled, then the composition of the

alcohol steadily increases until it reaches 96% by wt, then the composition of the

vapor equals that of the liquid and no further enrichment occurs. This mixture is

called an Azeotropic and cannot be separated by straight forward distillation.

In this case the equilibrium curve crosses the diagonal, indicating the existence of an

Azeotropic.

i.e. H2O + HNO3 & H2O + HCl & H2O + many alcohol’s.

The principle of Azeotropic distillation lies in the addition of a new substance which

forms an Azeotropic with one or more of the components in the mixture, and as a

result is present on most of the plates of the column in appreciable concentration.

EXTRACTIVE DISTILLATION

When the relative volatility of a binary mixture is very low, in which case continuous

distillation of the mixture to give nearly pure components will require high (1) Reflux

ratio (2) High heat requirements (3) A tower of large cross section (4) Large No. of

trays. Examples of such mixtures;

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Prof Fatma K. Gad

The principle of Extraction Distillation lies in the addition of a substance which has

relatively less volatility compared with the components to be separated, and it is

therefore feed continuously near the top of the column. This extractive agent

(solvent) runs down the column as reflux and is present in appreciable concentration

on all the plates.

Since for a non-ideal binary mixture, the partial pressure may be expressed in the

form;

PA = A PoA xA

Consequently,

= ( PA xB ) /( PB XA ) = ( A PoA ) /( B PoA )

The solvent added to the mixture in extractive distillation differentially affects the

activities of the two components and hence ().

Such process depends upon the difference in departure from ideality between the

solvent and the components to be separated. As shown in the figure for a mixture of

Toluene – Iso Octane is seen to be very difficult to separate by adding Phenol as a

solvent 55% and 83% the relative volatility of Iso Octane increases, with as much as

83 Mol% Phenol in the liquid.

(1) Selectivity

(2) Volatility

(3) Ease of Separation from top and bottom products

(4) Its cost

Extractive distillation is usually a more desirable process than Azeotropic distillation,

since no large quantities of solvent must be vaporized. Also, a greater choice of

added component (solvent) is possible to use.

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Prof Fatma K. Gad

PLATE COLUMNS

Plate column for the most important category and their features and performance will

be considered. The number of theoretical stages required to effect a required

separation, and the corresponding rates for the liquid and vapor phases, can be

determined by the procedure described earlier. To translate these quantities to form

an actual design the following factors must be considered;

2) The vapor velocity, which is the major factor in determining the diameter of the

column.

3) The plate spacing, which is the major factor fixing the height of the column when

the number of plates is known.

TYPES OF TRAYS

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Prof Fatma K. Gad

1) The bubble cup tray as shown in Fig., which is widely used in petroleum and

chemical industries.

3) The Flexi-tray (Valve) is a recent development which has already made quite

a place for itself and appears to have a promising future.

1) The Turbo grid tray Fig. (a)

2) The Ripple tray Fig. (b) as shown in figure below.

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Prof Fatma K. Gad

Liquid level is maintained on each tray by a dynamic balance of the fluid flows.

OBJECTIONABLE PHENOMENA:

Areas of objectionable phenomena surround the region of satisfactory operation of

each tray. Changes in the design of a tray can shift the satisfactory operating range

with respect to any one or more than one of the objectionable areas.

1) CONING:

Coning occurs at low liquid rates. The vapor pushes the liquids back from the

slots or holes and passes upward with poor liquid contact. This causes poor tray

efficiency.

It occurs when the vapor rate is so small, so liquid can dump to the tray below.

3) DUMPING LIQUID:

It occurs at high liquid rates and low vapor loads.

It occurs at very high vapor rates. The vapor can literally tear holes in the liquid,

giving poor contact between phases. Excessive entrainment of large droplets and

slugs of liquid up to the tray above usually accompany blowing.

5) FLOODING:

It occurs when the pressure drop across a tray is so high that the liquid cannot

flow down the column as fast as required. Flooding is a sharp line of distinction

between satisfactory and non-operating.

The region of satisfactory operation is that range of liquid and vapor rates where;

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Prof Fatma K. Gad

2) The column is mechanically able to handle the liquid and vapor loads in a steady sate

manner.

As shown in the Figure ‘I’, areas where undesirable phenomena occur bound the

region.

Both pulsating vapor flow and dumping can be referred to jointly as weeping.

At very high vapor rate, the vapor bubbles carry Operating Region liquid as spray or

droplets to the plate above giving excessive entrainment.

Such arrangement depends largely on the ratio of liquid to vapor flow. Three layouts

are shown in the figure.

a) CROSS FLOW:

Normally, allow good length of liquid path giving good opportunity for mass

transfer.

b) REVERSE:

Down-comers much reduced in area, and very long liquid path suitable for low

liquid – vapor ration.

c) DOUBLE PASS:

Liquid flow splits into two directions, so that this system will handle high liquid.

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Prof Fatma K. Gad

Vapor ratios.

The performance of a column that can be judged in relation to two separate but related

criteria:

1) If in a column the vapor leaving a tray is in equilibrium with the liquid leaving,

this gives a theoretical tray and provides a standard of performance.

2) The relative performance of, say two column of the same diameter must be

considered in relation to their capacity for liquid and vapor flow.

2) Physical properties of vapor and liquid.

3) Extent of entrainment of liquid by rising vapor streams.

4) The hydraulics of liquid and vapor across and through the tray.

Bubble cap trays are now rarely used for new installation on account of:

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Prof Fatma K. Gad

3) The difficulties arise in large columns because of the tray hydraulic gradient,

which set up across the tray.

However Bubble cup tray are capable of dealing with very low liquid rates and are

therefore useful for operation at low reflux ratios.

TRAY SPACING:

The necessary tray spacing to avoid entrainment of the liquid by the vapor and to

enable down-comer to handle the flow, so the liquid does not rise up the down-comer.

The head of liquid in the down-comer (Z\p) is made up of the head of liquid on the

tray (hW + hoW) plus the head of the lost by the vapor (h p) plus the head lost at the

bottom of the down-comer (hd) plus the liquid gradient (hg) so;

Z\p = hp + hd + hg + hw + how

= (hrc + hr + hs) + hd + hg + hw + how

Then fore safe operation, the tray spacing is given as the following equation to

overcome the foam in down comer.

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Prof Fatma K. Gad

Zp = 2 Z\ p

Since the allowable vapor rate is a function of the densities PV and PL at tower

conditions and of constant ((K)) which is related to service and to tray spacing; so

U = k * (( L - v ) / v )0.5 ft / sec

II SIEVE TRAYS

Studies on Sieve Trays have been shown that they can offer several advantages over

the bubble cap tray.

2) The general form of the flow on sieve tray is indicated in the figure, it is seen that the

tray forms a typical cross flow system with perforations in the tray taking the place of

the more complex bubble caps.

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Prof Fatma K. Gad

Sieve tray

It is important to notice the key differences in operation between these two types of

tray; With the Sieve Tray the vapor passes vertically through the holes into the liquid

on the tray, whereas with bubble cup the vapor issues in an approximately horizontal

direction from the slots.

It is given in the same manner as bubble cup.

‘’ the aeration factor (0.8 – 0.5) depend on hw & how.

Approximation Z\p = ho + 2 (hw + how) + hd.

Zp = 2 Z\p

The Valve Tray, which may be regarded as intermediate between the bubble and the

sieve trays, offers advantages over both.

The feature of the tray is that lift able caps as variable orifices which adjust

themselves to changes in vapor flow.

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Prof Fatma K. Gad

2) A low pressure drop which, is fairly constant over a large portion of the operating

range.

3) A relatively simple construction which leads to a cost of only 20% higher than a

comparable sieve tray.

EXAMPLE-1:

lb Gasoline 3,415 lb 3415/110 = 31 Moles

lb Hot Reflux 15,000 lb 15500/110 = 141 Moles

lb Steam 567 lb567/18 = 31.5 Moles

TOTAL 19,482 lb 203.5 Moles

So the volume at the top of the tower is;

= 107600 ft3

So, PV (PL – PV) = 0.181 (42.7 – 0.181) = 7.7

‘K’ at a tray spacing of 22” = 735 Fig.(16-13) Nelson.

Mass Velocity = W / a = 735 * ( 7.7 )0.5 = 2040

Area (a) = 19582 / 2040 = 9.55

0.5

Diameter = ( 9.55 / 0.785 ) = 3.5 ft U.E.D

EXAMPLE-2:

Calculate the diameter of Vacuum Tower under the following operating condition.

Wax Distillate & Reflux 106,000 lb 331 Moles

Gas Oil 12,000 lb 49 Moles

Steam 1,400 lb 78 Moles

TOTAL 119,400 lb 459 Moles

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Prof Fatma K. Gad

v = ( 119400 / 8050000 ) = 0.0148 lb/ft 3

Assume PL = 50 lb/ft3 Fig. (5-14)

V (L – V) = 0.0148 (50 – 0.0148) = 0.74

‘K’ at 30” spacing tray = 600 Fig. (16-13)

W/a = 600 ( 0.74 ) 0.5

= 516 lb/ft2 hr.

a = 119400 / 516 = 231 ft2

CHAPTER 4

PROCESSES

In order to separate one or more of the components in a mixture, the mixture is

contacted with another phase. The two-phase pair can be gas-liquid, which was dis-

cussed in Chapter 3; vapor-liquid which was covered in Chapter 4; liquid-liquid; or

fluid-solid. In this section liquid-liquid extraction separation processes are considered

first. Alternative terms are liquid extraction or solvent extraction.

vapor. The separation of the components depends on the relative vapor pressures of

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Prof Fatma K. Gad

the substances. The vapor and liquid phases are similar chemically. In liquid-liquid

extraction the two phases are chemically quite different, which leads to a separation

of the components according to physical and chemical properties.

lation or evaporation. For example, acetic acid can be removed from water by

distillation or by solvent extraction using an organic solvent. The resulting organic

solvent-acetic acid solution is then distilled. Choice of distillation or solvent

extraction would depend on relative costs. In another example high-molecular-weight

fatty acids can be separated from vegetable oils by extraction with liquid propane or

by high-vacuum distillation, which is more expensive.

mixtures that are quite complex, and liquid extraction can be used to separate the

penicillin. Many metal separations are being done commercially by extraction of

aqueous solutions, such as copper-iron, uranium-vanadium, and tantalum-columbium.

As in the separation processes of absorption and distillation, the two phases in liquid-

liquid extraction must be brought into intimate contact with a high degree of

turbulence in order to obtain high mass-transfer rates. After this contact of the two

phases, they must be separated. In absorption and in distillation, this separation is

rapid and easy because of the large difference in density between the gas or vapor

phase and the liquid phase. In solvent extraction the density difference between the

two phases is not large and separation is more difficult.

There are two main classes of solvent-extraction equipment, vessels in which mecha-

nical agitation is provided for mixing, and vessels in which the mixing is done by the

flow of the fluids themselves. The extraction equipment can be operated batch wise or

operated continuously as in absorption and in distillation.

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Prof Fatma K. Gad

intimate contact of the two liquid phases. One phase is usually dispersed into the

other in the form of small droplets. Sufficient time of contact should be provided for

the extraction to take place. Small droplets produce large interfacial areas and faster

extraction. However, the droplets must not be so small that the subsequent settling

time in the settler is too large.

The design and power requirements of baffled agitators or mixers. In Fig. 4.2-1a a

typical mixer-settler is shown, where the mixer or agitator is entirely separate from

the settler. The feed of aqueous phase and organic phase are mixed in the mixer, and

then the mixed phases are separated in the settler. In Fig. 4.2-lb a combined mixer-

settler is shown, which is sometimes used in extraction of uranium salts or copper

salts from aqueous solutions. Both types of mixer-settlers can be used in series for

countercurrent or multiple-stage extraction.

As discussed in Section 2-3 for plate absorption and distillation towers, somewhat

similar types of devices are used for liquid-liquid contacting. A perforated-plate or

sieve-tray extraction tower is shown wherein the rising droplets of the light solvent

liquid are dispersed. The dispersed droplets coalesce below each tray and are then re-

formed on each tray by passing through the perforations. The heavy aqueous liquid

flows across each plate, where it is contacted by the rising droplets and then passes

through the down comer to the plate below.

Figure 4.2-1. Typical- mixer-settlers for extraction: (a) separate mixer-settler, (b)

combined mixer-settler.

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Prof Fatma K. Gad

(a) perforated-plate or sieve-tray tower,

(b) agitated extraction tower.

mounted on a central rotating shaft provides the agitation for the two phases. Each

agitator is separated from the next agitator by a calming section of wire mesh to

encourage coalescence of the droplets and phase separation. This apparatus is

essentially a series of mixer-settlers one above the other. Another type is the Karr

reciprocating-plate column, which contains a series of sieve trays with a large open

area of 60% where the plates are moved up and down. This is one of the few types of

extraction towers that can be scaled up with reasonable accuracy.

Packed and spray tower extractors give differential contacts, where mixing and

settling proceed continuously and simultaneously. In the plate-type towers or mixer-

settler contactors, the extraction and settling proceeds in definite stages. The heavy

liquid enters the top of the spray tower, fills the tower as the continuous phase, and

flows out through the bottom. The light liquid enters through a nozzle distributor at

the bottom which disperses or sprays the droplets upward. The light liquid coalesces

at the top and flows out. In some cases the heavy liquid is sprayed downward into a

rising light continuous phase.

A more effective type of tower is to pack the column with packing such as Raschig

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Prof Fatma K. Gad

rings or Berl saddles, which cause the droplets to coalesce and redisperse at frequent

intervals throughout the tower. Detailed discussions of flooding and construction of

packed towers are given elsewhere.

Finding the best solvent is the most critical aspect of developing a liquid-liquid

extraction process. The solvent should have a high selectivity for the extracted solute.

The selectivity p of a solvent is similar to relative volatility and is given by

where

x2s = weight fraction of component 2 in the solvent phase

x1R = weight fraction of component 1 (solute) in the raffinate phase

x2R = weight fraction of component 2 in the raffinate phase

Selectivity is thus the ratio of the compositions in the solvent phase of the two

components being separated to the ratio of the compositions in the raffinate phase of

the same components. If the ratio is high, it means that the solvent preferentially

soaks up the solute. Note that p goes to unity at the plait point.

Of course, the solvent should be easily recoverable from the extracted solute. Usually,

this is done by distillation. The solvent and raffinate phases should have as large a

density difference as possible to help settling.

without safety or pollution problems. Satisfying these last properties simultaneously

is rarely possible.

1-Phase rule. Generally in a liquid-liquid system we have three components, A, B,

and C, and two phases in equilibrium. Substituting into the phase rule, the number of

degrees of freedom is 3. The variables are temperature, pressure, and four

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Prof Fatma K. Gad

concentrations. Four concentrations occur because only two of the three mass fraction

concentrations in a phase can be specified. The third must make the total mass

fractions total to 1.0, xA + xB + xC= 1.0. If pressure and temperature are set, which is

the usual case, then, at equilibrium, setting one concentration in either phase fixes the

system.

often used to represent the equilibrium data of a three-component system, since there

are three axes. This is shown in Fig. 4.4-1. Each of the three corners represents a pure

component, A, B, or C. The point M represents a mixture of A, B, and C. The

perpendicular distance from the point M to the base AB represents the mass fraction

xc of C in the mixture at M, the distance to base C B the mass fraction xA of A, and the

distance to base AC the mass fraction xB of B. Thus,

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Prof Fatma K. Gad

A common phase diagram where a pair of components A and B are partially miscible

is shown in Fig. 4.4-2. Typical examples are methyl isobutyl ketone (A)-water (B)-

acetone (C), water (A)-chloroform (B)-acetone (C), and benzene (A)-water (B)-acetic

acid (C). Referring to Fig. 4.4-2, liquid C dissolves completely in A or in B. Liquid A

is only slightly soluble in B and B slightly soluble in A. The two-phase region is

included inside below the curved envelope. An original mixture of composition M

will separate into two phases A and B which are on the equilibrium tie line through

point M. Other tie lines are also shown. The two phases are identical at point P, the

Plait point.

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Prof Fatma K. Gad

Figure 4.4-2: Liquid – liquid phase diagram where component A and B are partially

miscible.

some disadvantages because of the special coordinates, a more useful method of

plotting the three component data is to use rectangular coordinates. This is shown in

Fig. 4.4-3 for the system acetic acid (A)-water (B)-isopropyl ether solvent (C). The

solvent pair B and C are partially miscible. The concentration of the component C is

plotted on the vertical axis and that of A on the horizontal axis. The concentration of

component B is obtained by difference from Eqs. (4.4-2) or (4.4-3).

xB = 1.0 - xA – xc (4.4-2)

The two-phase region in Fig. 4.4-3 is inside the envelope and the one-phase region

outside. A tie line gi is shown connecting the water-rich layer i, called the raffinate

layer, and the ether-rich solvent layer g, called the extract layer. The raffinate

composition is designated by x and the extract by y. Hence, the mass fraction of C is

designated as yc in the extract layer and as xc in the raffinate layer. To construct the tie

line gi using the equilibrium yA – xA plot below the phase diagram, vertical lines to g

and i are drawn.

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Prof Fatma K. Gad

Liquid – Liquid phase diagram at 293 K (20 oC).

kg of acetic acid (A), and 60 kg water (B) is equilibrated and the equilibrium phases

separated. What are the compositions of the two equilibrium phases?

Solution:

xc = 0.30,

xA = 0.10, and

xB = 0.60.

This composition of

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Prof Fatma K. Gad

xc = 0.30 and

xA = 0.10

is plotted as point h on Fig. 4.4-3.

The tie line gi is drawn through point h by trial and error.

The composition of the extract (ether) layer at g is

yA = 0.04,

yc= 0.94, and

yB = 1.00 - 0.04 - 0.94 = 0.02 mass fraction.

The raffinate (water) layer composition at i is

xA = 0.12,

xc = 0.02, and

xB= 1.00 — 0.12- 0.02 = 0.86.

Another common type of phase diagram is shown in Fig. 4.4-4, where the solvent

pairs B and C and also A and C are partially miscible. Examples are the system

styrene (A)-ethylbenzene (B)-diethylene glycol (C) and the system chlorobenzene

(A)-methyl ethyl ketone (B)-water (C).

Figure 5.4-4: Phase diagram where the solvent pairs B – C and A – C are partially

miscible.

1. Derivation of lever-arm rule for graphical addition. This will be derived for

use in the rectangular extraction-phase-diagram charts. In Fig. 4.5-1a two streams, L

kg and V kg, containing components A, B, and C, are mixed (added) to give a result-

ing mixture stream M kg total mass. Writing an overall mass balance and a balance on

A,

V + L= M (4.5-1)

V yA + L xA = M xAM (4.5-2)

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Prof Fatma K. Gad

where xAM is the mass fraction of A in the M stream. Writing a balance for component

C,

This shows that points L, M, and V must lie on a straight line. By using the properties

of similar right triangles,

This is the lever-arm rule and states that kg L / kg V is equal to the length of line VM

/ length of line LM. Also,

These same equations also hold for kg mol and mol frac, lbm, and so on.

Figure 4.5-5. Graphical addition and lever-arm rule : (a) process flow, (b) graphical

addition.

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Prof Fatma K. Gad

The compositions of the two equilibrium layers in Example 4.4-1 are for the extract

layer (V)

yA = 0.04, yB = 0.02, and

yc = 0.94,

and for the raffinate layer (L)

xA =0.12, xB = 0.86, and

xc = 0.02.

The original mixture contained 100 kg and

xAM = 0.10. Determine the amounts of V and L.

Solution:

V + L = M= 100

Alternatively, using the lever-arm rule, the distance hg in Fig. 4.5-2 is measured as

4.2 units and gi as 5.8 units. Then by Eq. ,

Solving,

L = 72.5 kg and

V = 27.5 kg,

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Prof Fatma K. Gad

in Fig. 4.5-2a, where the solvent, as stream V2, enters and also the stream LO. The

streams are mixed and equilibrated and the exit streams L 1 and V1 leave in

equilibrium with each other.

(a) process flow diagram. (b) plot on phase diagram.

The equations for this process are the same as those given for a single equilibrium

stage where y represents the composition of the V streams and x the L streams.

L0 + V2 = L1 + V1 = M (4.5-9)

equations, the equilibrium-phase diagram in Fig. 4.5-2b is used. Since the amounts

and compositions of L0 and V2 are known, we can calculate values of M, xAM, and xCM

from Eqs. (4.5-9)-(4.5-11). The points L0, V2, and M can be plotted as shown in Fig.

4.5-2b. Then using trial and error a tie line is drawn through the point M, which

locates the compositions of L1 and V1 The amounts of L1 and V1 can be determined by

substitution into Eqs. (4.5-9)—(4.5-11) or by using the lever-arm rule.

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Prof Fatma K. Gad

SOLVENT

If the process liquid stream from the first stage is fed into a second extractor and

mixed with more fresh solvent, as shown in Figure 4-6-1, we have what is called

cross-flow extraction. In cross-flow extraction, the procedure described in

Figure 4.6-2(below): Mix point for cross flow extractor.

the previous section for a single stage is simply repeated again for each stage, using

the raffinate phase from the upstream stage as the feed to each stage. The graphical

solution is sketched in Figure 4.6-1 for a three-stage cross-flow extractor. For each

stage, the point M is calculated from the flow rates of the feed and fresh solvent

streams to that particular stage.

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Prof Fatma K. Gad

EXTRACTION

Introduction

Single-stage equilibrium contact was used to transfer the solute A from one liquid to

the other liquid phase. To transfer more solute, the single-stage contact can be

repeated by contacting the exit Ll stream with fresh solvent V2 in Fig. 4.5-2. In this

way a greater percentage removal of the solute A is obtained. However, this is

wasteful of the solvent stream and also gives a dilute product of A in the outlet

solvent extract streams. In order to use less solvent and to obtain a more concentrated

exit extract stream, countercurrent multistage contacting is often used.

tification are the same or similar to those used in countercurrent extraction. Because

of the frequently high solubility of the two liquid phases in each other, the

equilibrium relationships in extraction are more complicated than in absorption and

distillation.

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Prof Fatma K. Gad

1. Countercurrent process and overall balance. The process flow for this

extraction process is the same as given previously in Fig. 3.3-2 and is shown in Fig.

4.7-1. The feed stream containing the solute A to be extracted enters at one end of the

process and the solvent stream enters at the other end. The extract and raffinate

streams flow counter-currently from stage to stage, and the final products are the

extract stream V1 leaving stage 1 and the raffinate stream LN leaving stage N.

L0 + VN+l = LN + V1 = M (4.7-1)

where M represents total kg/h (lb„yh) and is a constant,L0 the inlet feed flow rate in

kg/h, VN+l the inlet solvent flow rate in kg/h, V l the exit extract stream, and LN the exit

raffinate stream. Making an overall component balance on component C,

= [(LN xCN + V yC1)/(LN + V1)] (4.7-3)

= [(LN xAN + V yA1)/(LN + V1)] (4.7-4)

Equations (4.7-3) and (4.7-4) can be used to calculate the coordinates of point M on

the phase diagram that ties together the two entering streams L 0 and VN+1 and the two

exit streams V1 and LN. Usually, the flows and compositions of L0 and VN+l are known

and the desired exit composition x AN is set. If we plot pointsL0, VN+1, and M as in Fig.

5.7-2, a straight line must connect these three points. Then L N, M, and V1 must lie on

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Prof Fatma K. Gad

one line. Also, LN and Vl must also lie on the phase envelope, as shown. These

balances also hold for lbm and mass fraction, kg mol and mol fractions, and so on.

Pure solvent isopropyl ether at the rate of V N+1 = 600 kg/h is being used to extract an

aqueous solution of L0 = 200 kg/h containing 30 wt % acetic acid (A) by

countercurrent multistage extraction. The desired exit acetic acid concentration in the

aqueous phase is 4%. Calculate the compositions and amounts of the ether extract V 1

and the aqueous raffinate LN. Use equilibrium data from Appendix A.3.

Solution:

VN+t = 600 kg/h xA0 = 0.30

xB0 = 0.70 xC0 = 0.0 and

xAN = 0.04

and L0 are plotted.

Also, since LN is on the phase boundary, it can be plotted at xAN — 0.04. For the

mixture point M, substituting into Eqs. (4.7-3) and (4.7-4),

Figure 4.7-3: use of the mixture point M for overall material balance in countercurrent

solvent extraction.

= [(200 (0) + 600 (1.0))/(200 + 600)] = 0.75

= [(200 (0.3) + 600 (0))/(200 + 600)] = 0.075

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Prof Fatma K. Gad

Using these coordinates, the point M is plotted in Fig. 4.7-3. We locate V1 by drawing

a line from LN through M and extending it until it intersects the phase boundary.

This gives

LN = 136 kg/h and

V1 = 664 kg/h.

Figure 4.7-4: Method to perform overall material balance for example 4.7-1.

after an overall balance has been made is to go stage by stage to determine the

concentrations at each stage and the total number of stages N needed to reach LN in

Fig. 4.7-2.

L0 + V2 = Ll + Vl (4.7-5)

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Prof Fatma K. Gad

L0 - Vl = L1 - V2 = Δ (4.7-7)

= LN xN - VN +1 yN+1 = • • • (4.7-9)

[(Ln xn – Vn+l yn+l) / (Ln – Vn+1)] =

[(LN xN – VN+l yN+l) / (LN – VN+1)] (4.7-10)

Equations (5.7-7) and (5.7-8) can be written as

From Eq. (4.7-11), we see that L0 is on a line through Δ and V1, Ln is on a line

through Δ and Vn+l, and so on. This means Δ is a point common to all streams passing

each other, such as L0 and V1, Ln and Vn+l, LN and VN+l, and so on. The coordinates to

locate this Δ operating point are given for x CA and xAΔ in Eq. (4.7-10). Since the end

points VN+l, LN or V1 and L0 are known, xΔ can be calculated and point Δ located.

Alternatively, the Δ point is located graphically in Fig. 4.7-5 as the intersection of

lines L0 V1 and LN VN+l.

In order to step off the number of stages using Eq. (4.7-11) we start at L0 and draw the

line L0 Δ, which locates V1 on the phase boundary. Next a tie line through V1 locates

Ll. which is in equilibrium with V1 Then line L1 Δ is drawn giving V2. The tie line V2

L2 is drawn. This stepwise procedure is repeated until the desired raffinate

composition LN is reached. The number of stages N is obtained to perform the

extraction.

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Prof Fatma K. Gad

Figure 4.7-5. Operating point Δ and number of theoretical stages needed for

countercurrent extraction.

Pure isopropyl ether of 450 kg/h is being used to extract an aqueous solution of 150

kg/h with 30 wt % acetic acid (A) by countercurrent multistage extraction. The exit

acid concentration in the aqueous phase is 10 wt %. Calculate the number of stages

required.

Solution:

Vn+1 =450, yAN+1 =0,

yCN+1 = l.0 L0 = 150,

xA0 = 0.30, xB0 = 0.70,

xC0 = 0, and xAN = 0.10.

The points VN+l, L0, and LN are plotted in Fig. 4.7-5. For the mixture point M,

substituting into Eqs. (4.7-3) and (4.7-4),xCM = 0.75 and xAM = 0.075. The point M is

plotted and V1 is located at the intersection of line L N M with the phase boundary to

give yA1 = 0.072 and yCl = 0.895. This construction is not shown. (See Example 4.7-1

for construction of lines.)

The lines L0Vl and LNVN+l are drawn and the intersection is the operating point Δ as

shown. Alternatively, the coordinates of Δ can be calculated from Eq. (4.7-10) to

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Prof Fatma K. Gad

locate point Δ. Starting at L0 we draw line L0 Δ, which locates Vl. Then a tie line

through V1 locates Lx in equilibrium with Vt. (The tie-line data are obtained from an

enlarged plot such as the bottom of Fig. 4.5-3. Line L1 Δ is next drawn locating V2. A

tie line through V2 gives L2. A line L2 Δ gives V3. A final tie line gives L3, which has

gone beyond the desired LN. Hence, about 2.5 theoretical stages are needed.

3. Minimum solvent rate. If a solvent rate VN+1, is selected at too low a value a

limiting case will be reached with a line through A and a tie line being the same. Then

an infinite number of stages will be needed to reach the desired separation. The

minimum amount of solvent is reached. For actual operation a greater amount of

solvent must be used.

The procedure to obtain this minimum is as follows. A tie line is drawn through point

L0 (Fig. 4.7-5) to intersect the extension of line LN VN+1. Other tie lines to the left of

this tie line are drawn including one through L N to intersect the line LN VN+l. The

intersection of a tie line on line LN VN+l which is nearest to VN+l represents the Δmin

point for minimum solvent. The actual position of Δ used must be closer to V N+l than

Δmin for a finite number of stages. This means that more solvent must be used.

Usually, the tie line through L0 represents the Δmin.

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Prof Fatma K. Gad

Liquids

If the solvent stream VN+l contains components A and C and the feed stream L 0

contains A and B and components B and C are relatively immiscible in each other, the

stage calculations are made more easily. The solute A is relatively dilute and is being

transferred from L0 to VN+1.

Referring to Fig. 4.7-1 and making an overall balance for A over the whole system

and then over the first n stages,

= L` (xN / (1 – xN)) +V`(y1 / (1 – y1)) (4.7-12)

= L` (xn / (1 – xn)) +V`(y1 / (1 – y1)) (4.7-13)

where

L` = kg inert B/h,

V = kg inert C/h,

y = mass fraction A in V stream, and

x = mass fraction A in L stream.

This Eq. (4.7-13) is an operating-line equation whose slope = L/V. If y and x are quite

dilute, the line will be straight when plotted on an x y diagram.

The number of stages are stepped off as shown previously in cases in distillation and

absorption.

If the equilibrium line is relatively dilute, then since the operating line is essentially

straight, and can be used to calculate the number of stages.

An inlet water solution of 100 kg/h containing 0.010 wt fraction nicotine (A) in water

is stripped with a kerosene stream of 200 kg/h containing 0.0005 wt fraction nicotine

in a countercurrent stage tower. The water and kerosene are essentially immiscible in

each other. It is desired to reduce the concentration of the exit water to 0.0010 wt

fraction nicotine. Determine the theoretical number of stages needed. The equilibrium

data are as follows (C5), with x the weight fraction of nicotine in the water solution

and y in the kerosene.

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Prof Fatma K. Gad

6 8 2

y 0.00080 0.00195 .00045 0.0068 0.0090 0.018

6 9 4 2 4 5

Solution:

L0 = 100 kg/h, x0 =0.010,

VN+l =200 kg/h, yN+1 = 0.0005,

xN = 0.0010.

The inert streams are

Making an overall balance on A using Eq. (4.7-12) and solving, y1 = 0.00497. These

end points on the operating line are plotted in Fig. 4.7-7. Since the solutions are quite

dilute, the line is straight. The equilibrium line is also shown. The number of stages

are stepped off, giving N = 3.8 theoretical stages.

Figure 4.7-7. Solution for extraction with immiscible liquids in Example 4.7-3.

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Prof Fatma K. Gad

SOLVENTS

In this case, as illustrated in the Figure, there is no need to use Triangular diagram.

solute. Then the selective solvent to be added will be a mass B of solvent B.

X1 of solute and an extract with solvent B containing a mass ration Y 1 of solute. A

material balance on the solute gives;

Y1 / ( X1 - XF ) = - A/B

This process can be illustrated by letting the point (F) represent the feed solution and

drawing a line (FE1) of slope (- A/B), to cut the equilibrium curve in E1. This will

then give composition Y1 of the extract and X1 of the Raffinate. If a further stage is

then carried out by the addition of solvent B to the stream AX 1, then Point E2 is found

on the equilibrium curve by drawing GE2 of slope – (A/B)2.

Point E2 then gives the composition X2 and Y2 of the Final Extract and Raffinate.

This system can be used for any number of stages, any assumed variation in the

proportion of solvent B to Raffinate from stage to stage.

If the distribution law is followed, then the equilibrium curve becomes a straight line

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Prof Fatma K. Gad

of equation Y = m X.

The material balance on the solute may then be rewritten as;

and Raffinate X2 in a second stage, then.

A * X1 = A * X2 + B * m * X2 = (A + B * m)X2

X2 = [ A / ( A + B * m ) ] X1 = [ A / ( A + B * m ) ]2 * Xf

Xn = [ A / ( A + B m ) ] n * Xf

where

n = Log ( xn / xf ) / Log [ A / ( A + B * m ) ]

EXAMPLE – 4:

extracted in a single stage using MIK as solvent. The amount of solvent used is 1.745

lb solvent/lb solution (Feed). Find the composition of extract and raffinate and the

quantities of them for each lb feed

X lb Acid/lb H2O 0.5 0.1 0.15 0.2

Y lb Acid/lb Solvent 0.04 0.075 0.12 0.17

SOLUTION:

Feed Raffinate

A(X1 – X2) = B(Y2 – Y1) X1 X2

-A / B = Y2 / ( X1 – X2 ) Y1=0 Y2

Solvent extract

Where Y1 = 0 (Solvent free of solute)

Slope of operating line = - A / B = (1-0.15) / 1.745 = - 0.487

X1 mass ratio of solute (Acid) = X1 / (1 – X1) = 0.15 / (1 – 0.15) = 0.1768

Drawing a line with slope = - 0.487 and Point (X1 & Y1) = (0.178 & 0)

From the drawing we get Point (X2 & Y2) as shown

X2 = 0.074 & Y2 = 0.05

Mass Fraction X2 = X2 / (1 + X2 ) = 0.074 / (1 + 0.074) = 0.0688

Raffinate = H2O + Acid = 0.85 + (0.074 x 0.85) = 0.9129

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Prof Fatma K. Gad

Y Equilibrium line

(X2,Y2)

Operating line

(X1,Y1)

Lb acid / Lb H2O

U.E.D.

In the preceding discussion we assumed that the fresh solvent flow rate S 0 was given.

However, in the normal design situation the solvent rate must be specified by the

designer. Usually, the smaller the solvent flow rate the lower the energy costs because

less solvent must be circulated between the extractor and the stripping column and the

concentration of solute in the "fat solvent" from the extractor is higher. Hence,

separation costs are reduced.

However, the smaller the solvent flow the higher the capital costs, because more

stages are required in the liquid-liquid extractor. These engineering trade-offs

between the number of stages and the solvent flow rate are analogous to the situation

in distillation, where trade-offs must be made between the reflux ratio and the number

of trays.

A commonly used heuristic in distillation was setting the reflux ratio to 1.2 times the

minimum reflux ratio. In liquid-liquid extraction, there is similarly a minimum solvent

flow rate. Once this minimum is found, the actual solvent flow rate is set somewhat

higher. Since liquid-liquid extraction stages are usually more expensive than

distillation trays, the ratio of actual to minimum solvent flow rates is usually higher in

extraction (typically 2).

The minimum solvent flow rate S0min occurs when an LLE tie-line is coincident with

an "operating line" drawn to the Δ point. The minimum solvent rate is usually found

by extending the LLE tie-line that passes through the feed point. The intersection of

this straight line with the straight line through the points S 0 and RN gives the

minimum Δ, Δmin. As shown in Figure 4-8-1, Δmin can lie either to the left or to the

right of the phase diagram.

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Prof Fatma K. Gad

In some unusual LLE systems, there are other tie-lines (not through the feed point)

of the tie-

that intersect the S0-RN line farther to the left. The extensions

Δmin. Figure 4.8-1 illustrates this situation for

two cases: when Δmin lies to the right of the

diagram, and when it lies to the left. For both

cases, the leftmost intersection of a tie-line with

the line through the points R and gives Δmin. N

the feed point to Δmin, and a straight line is

drawn from it to the point R which has been N

intersection of this line with the straight line

connecting the points F and S . S can then be 0 0

min

and s3min of M : min

234

Prof Fatma K. Gad

Chap. 9 Liquid-

Liquid Extraction

(a) Δmin lies to the right of the phase diagram.

(b) Δmin lies to the left of the phase diagram

S0min = F (z1 – x1min) / (x1min – x1So) (4.8-1)

235

Prof Fatma K. Gad

reading. However, it is fairly straightforward once you get the basic idea. It parallels

the construction used for a single stripping or rectifying column in binary distillation.

Let us summarize the specific sequence of steps to design a countercurrent liquid-

liquid extractor for a ternary system.

1. Parameters specified.

(b) Composition of solute in the raffinate stream leaving the last stage (x 1RN).

(c) LLE data for the ternary system.

(d)Economic ratio of actual to minimum solvent flow rates (S0/ S0min).

(e) Composition of fresh solvent (x1S0, x3S0).

(b) Draw a line through the points S0 and RN.

(c) Locate S1min on the tie-line through F.

(d) Draw a line from S1min to RN.

(e) The intersection of this line with a line through F and S0 gives the point Mmin.

(f) Read off the composition (x1min) at Mmin.

(g) Calculate S0min from equation 4.8-1.

6. Locate the Δ point by drawing two lines, one through S0 and RN, and the other

through S1 and F.

7. Step off stages, alternately using the LLE tie-lines and the A point, as follows:

LLE Δ LLE A

S1 Rl S2 R2 S3 •••

Example 4.8.1.

236

Prof Fatma K. Gad

to separate acetone from methyl isobutyl ketone

(mik) using water as a solvent. The column is to

operate at 25°c.

The organic feed rate is 10,000 kg/hr, and the

composition is 45 weight percent acetone and 55

weight percent ketone. The fresh solvent is pure

water, and twice the minimum solvent rate is to

be used. The concentration of acetone in the

organic raffinate leaving the top of the extractor

is to be 2.5 weight percent acetone.

Solution:

separated from mik using water as the solvent.

Thus, component 1 is acetone and component 3

is water.

Minimum solvent rate:

solubility curve at x1RN = 2.5 weight percent

acetone. The point s0 is plotted at the right

lower corner of the diagram, since x3S0 = 100

237

Prof Fatma K. Gad

the vertical axis at z1 = 45 weight percent

acetone.

determine the points Δmin and s1min. a straight

line is drawn from rn to s1min, and another from

F to S0. The intersection of these lines is the

point Mmin, giving a composition x1min = 24

weight percent acetone. The minimum solvent

flow rate is calculated:

(100000) (0.45 – 0.24) / (0.24 – 0)

= 8750 kg / hr minimum solvent flow rate.

The actual solvent rate is twice the minimum:

M = F + S0 = 10,000 + 17,500 = 27,500 kg/hr

X1M = (F z1 + S0 x1S0) / M= [(10,000)(45) + (17,500)(0)] / 27,500

= 16.4 weight percent acetone

238

Prof Fatma K. Gad

curve. The composition of the solvent phase on stage 1 is found from Figure 4.9-2

to be x1S1 = 19 weight percent acetone.

336

Chap

. 9 Liquid-Liquid Extraction

The flow rate of S 1 can be calculated from a total mass balance and an acetone

component balance around the entire system:

F + S0 = RN + S1

10,000 + 17,500 = RN + S 1

Note that the original organic feed rate was 10,000 kg/hr, but the organic raffinate

leaving the unit is only 4,400 kg/hr. The recovery of acetone is found as follows:

= 4,390 kg/hr acetone recovered

239

Prof Fatma K. Gad

Thus, 97.6 percent of the acetone fed to the unit is captured by the solvent.

As shown in Figure 4.9-3, LLE tie-lines and the Δ point are used alternately to step

off five stages. On the fifth stage, the concentration of the raffinate phase has been

reduced to the desired value of 2.5 weight percent acetone. Thus, five equilibrium

stages are required to achieve the separation at a solvent rate twice the minimum.

The problems discussed have been design problems, i.e., problems concerned with

determining the number of stages of a system.

Just as in distillation, however, there are also many interesting rating problems in

liquid-liquid extraction. For example, we may want to find the flow rate of fresh

solvent required to attain a specified recovery of solute in a column with a fixed

number of stages.

These rating problems are usually solved iteratively. For the previous example, a fresh

solvent flow rate would be guessed, and the number of stages in the actual column

would be stepped off to see if the desired recovery was achieved. If not, a new value

of fresh solvent flow rate would be guessed. Some of the problems at the end of the

chapter are rating problems.

240

Prof Fatma K. Gad

CHAPTER 5

PROCESSES

5.1A Introduction

process industries. In this relatively new unit operation, the membrane acts as a semi-

permeable barrier and separation occurs by the membrane controlling the rate of

movement of various molecules between two liquid phases, two gas phases, or a

liquid and gas phase. The two fluid phases are usually miscible and the membrane

barrier prevents actual, ordinary hydrodynamic flow. A classification of the main

types of membrane separation is as follows.

241

Prof Fatma K. Gad

In this type a gas phase is present on both sides of the membrane, which is a micro-

porous solid. The rates of molecular diffusion of the various gas molecules depend on

the pore sizes and the molecular weights. This type of diffusion in the molecular,

transition, and Knudsen regions.

The membrane in this process is usually a polymer such as rubber, polyamide, and so

on, and is not a porous solid. The solute gas first dissolves in the membrane and then

diffuses in the solid to the other gas phase. This was discussed in detail for solutes

following Fick's law and is considered again for the case where resistances are

present.

Examples are hydrogen diffusing through rubber and helium being separated from

natural gas by permeation through a fluorocarbon polymer. Separation of a gas

mixture occurs since each type of molecule diffuses at a different rate through the

membrane.

3.Liquid permeation or dialysis.

In this case the small solutes in one liquid phase diffuse readily because of

concentration differences through a porous membrane to the second liquid phase (or

vapour phase). Passage of large molecules through the membrane is more difficult.

This membrane process has been applied in chemical processing separations such as

separation of H2S04 from nickel and copper sulfates in aqueous solutions, food

processing, and artificial kidneys and is covered in detail in Section 5.2. In electro-

dialysis, separation of ions occurs by imposing an emf difference across the

membrane.

4.Reverse osmosis.

between a solute-solvent solution and a pure solvent. The solvent diffuses into the

solution by osmosis. In reverse osmosis a reverse pressure difference is imposed

which causes the flow of solvent to reverse as in the desalination of seawater. This

process also is used to separate other low-molecular-weight solutes, such as salts,

242

Prof Fatma K. Gad

sugars, and simple acids from a solvent (usually water). This process is covered in

detail in Sections 13.9 and 13.10.

semipermeable polymeric membrane (M2). The membrane discriminates on the basis

of molecular size, shape, or chemical structure and separates relatively high molecular

weight solutes such as proteins, polymers, colloidal materials such as minerals, and so

on. The osmotic pressure is usually negligible because of the high molecular weights.

The porous gel retards diffusion of the high-molecular-weight solutes. The driving

force is concentration. This process is quite useful in analyzing complex chemical

solutions and purification of very specialized and/or valuable components.

In membrane processes with two gas phases and a solid membrane. The

equilibrium relation between the solid and gas phases is given by

(5.2-1)

relation in kg mol/m3 ■ atm. This is similar to Henry's law. The flux equations in each

phase are as follows:

(5.2-2)

243

Prof Fatma K. Gad

(5.2-3)

(5.2-4)

In the case where pure A ( p A l ) is on the left side of the membrane, there is no

diffusional resistance in the gas phase and kcl can be considered to be infinite. Note

that k G l = k c l / R T .

oxygenator for a heart-lung machine to oxygenate blood. In this biomedical appli-

cation, pure O2 gas is on one side of a thin membrane and blood is on the other side.

Oxygen diffuses through the membrane into the blood and CO2 diffuses in a reverse

direction into the gas stream.

1 . Types of membranes. Early membranes were limited in their use because of low-

selectivities in separating two gases and quite low permeation fluxes. This low-flux

problem was due to the fact that the membranes had to be relatively thick (1 mil or

1/1000 of an inch or greater) in order to avoid tiny holes which reduced the separation

by allowing viscous or Knudsen flow of the feed. Development of silicone polymers

(1 mil thickness) increased the permeability by factors of 10 to 20 or so.

Some newer asymmetric membranes include a very thin but dense skin on one side of

the membrane supported by a porous substructure (Rl). The dense skin has a thickness

of about 1000 A and the porous support thickness is about 25-100 /n.m. The flux

increase of these membranes is thousands of times higher than the 1-mil-thick original

membranes. Some typical materials of present membranes are a composite of

polysulfone coated with silicone rubber, cellulose acetate and modified cellulose

acetates, aromatic polyamides or aromatic polyimides, and silicone-polycarbonate

copolymer on a porous support.

in membranes is generally not possible, and experimental values are needed.

Experimental data for common gases in some typical membranes are given in Table

244

Prof Fatma K. Gad

5.3-1. Note that there are wide differences among the permeabilities of various gases

in a given membrane. Silicone rubber exhibits very high permeabilities for the gases

in the table.

1/T and increases with T . However, operation at high temperatures can often degrade

the membranes. When a mixture of gases is present, reductions of permability of an

individual component of up to 10% or so can often occur. In a few cases much larger

reductions have been observed (Rl). Hence, when using a mixture of gases,

experimental data should be obtained to determine if there is any interaction between

the gases. The presence of water vapor can also have similar effects on the

permeabilities and can also possibly damage the membranes.

1. Flat membranes. Flat membranes are mainly used for experimental use to

characterize the permeability of the membrane. The modules are easy to fabricate and

use and the areas of the membranes are well defined. In some cases modules are

stacked together like a multilayer sandwich or plate-and-frame filter press. The major

drawback of this type is the very small membrane area per unit separator volume.

Small commercial flat membranes are used-for producing oxygen-enriched air for

individual medical applications.

flat membranes while increasing markedly the membrane area per unit separator

volume up to 100 ft2/ft3 (328 m2/m3) while decreasing pressure drops (Rl). The

assembly consists of a sandwich of four sheets wrapped around a central core of a

perforated collecting tube. The four sheets consist of a top sheet of an open separator

grid for the feed channel, a membrane, a porous felt backing for the permeate channel,

and another membrane as shown in Fig. 5.3-1. The spiral-wound element is 100 to

200 mm in diameter and is about 1 to 1.5 m long in the axial direction. The flat sheets

before rolling are about 1 to 1.5 m by about 2 to 2.5 m. The space between the

membranes (open grid for feed) is about 1 mm and the thickness of the porous

backing (for permeate) is about 0.2 mm.

245

Prof Fatma K. Gad

The whole spiral-wound element is located inside a metal shell. The feed gas enters at

the left end of the shell, enters the feed channel, and flows through this - channel in

the axial direction of the spiral to the right end of the assembly (Fig. 5.3-1). Then the

exit residue gas leaves the shell at this point. The feed stream, which is in the feed

channel, permeates perpendicularly through the membrane. This permeate then flows

through the permeate channel in a direction perpendicular to the feed stream toward

the perforated collecting tube, where it leaves the apparatus at one end. This is

illustrated in Fig. 5.3-2, where the local gas flow paths are shown for a small element

of the assembly.

3.Hollow-fiber membranes. The membranes are in the shape of very small diameter

hollow fibers. The inside diameter of the fibers is in the range of 100 to 500 µm and

the outside 200 to 1000 µm with the length up to 3 to 5 m. The module resembles a

shell-and-tube heat exchanger. Thousands of fine tubes are bound together at each

end into a tube sheet that is surrounded by a metal shell having a diameter of 0.1 to

0.2 m, so that the membrane area per unit volume is up to 10 000 m2/m3 as in Fig. 5.3-

3.

Typically, the high-pressure feed enters into the shell side at one end and leaves at the

other end. The hollow fibers are closed at one end of the tube bundles. The permeate

gas inside the fibers flows countercurrently to the shell-side flow and is collected in a

chamber where the open ends of the fibers terminate. Then the permeate exits the

device.

246

Prof Fatma K. Gad

Figure 5.3-2: Local gas flow path for spiral wound separator.

247

Prof Fatma K. Gad

membrane and permeates normal to the membrane. The permeate leaves in a direction

normal to the membrane, accumulating on the low-pressure side. Because of the very

high diffusion coefficient in gases, concentration gradients in the gas phase in the

direction normal to the surface of the membrane are quite small. Hence, gas film

resistances compared to the membrane resistance can be neglected. This means that

the concentration in the gas phase in a direction perpendicular to the membrane is

essentially uniform whether or not the gas stream is flowing parallel to the surface or

is not flowing.

If the gas stream is flowing parallel to the membrane in essentially plug flow, a

concentration gradient occurs in this.direction. Hence, several cases can occur in the

operation of a membrane module. The permeate side of the membrane can be operated

so that the phase is completely mixed (uniform concentration) or where the phase is in

248

Prof Fatma K. Gad

plug flow. The high-pressure feed side can also be completely mixed or in plug flow.

Countercurrent or cocurrent flow can be used when both sides are in plug flow.

Hence, separate theoretical models must be derived for these different types of

operation.

conditions and negligible pressure drop in the feed stream and permeate stream are

generally assumed. It is also assumed that the effects of total pressure and/or

composition of the gas are negligible and that the permeability of each component is

constant (i.e., no interactions between different components).

Since there are a number of idealized flow patterns, the important types are

summarized in Fig. 5.3-1. In Fig. 5.3-1a complete mixing is assumed for the feed

chamber and the permeate chamber. Similar to a continuous-stirred tank, the reject or

residue and the product or permeate compositions are equal to their respective

uniform compositions in the chambers.

a)complete mixing. b) ctoss flow.

c)countercurrent flow. D)concurrent flow.

An ideal cross-flow pattern is given in Fig. 5.4-1b, where the feed stream is in plug

flow and the permeate flows in a normal direction away from the membrane without

249

mixing. Since the feed composition varies along its flow path, the local permeate

concentration also varies along the membrane path.

In Fig. 5.4-1c both the feed stream and permeate stream are in plug flow

countercurrent to each other. The composition of each stream varies along its flow

path. Cocurrent flow of the feed and permeate streams is shown in Fig. 5.4-1d.

SEPARATION BY MEMBRANES

In Fig. 5.5-1 a detailed process flow diagram is shown for complete mixing. When

a separator element is operated at a low recovery (i.e., where the permeate flow rate is

a small fraction of the entering feed rate), there is a minimal change in composition.

Then the results derived using the complete-mixing model provide reasonable esti-

mates of permeate purity. This case was derived by Weller and Steiner (W4). The

overall material balance (Fig. 5.5-1) is as follows:

qf = qo + qp (5.5-1)

where is total feed flow rate in cm3(STP)/s; q0 is outlet reject flow rate, cm3(STP)/s;

and q p is outlet permeate flow rate, cm3(STP)/s. The cut or fraction of feed

permeated, , is given as

= qp / qf (5.5-2)

below which uses cm3(STP)/s as rate of permeation rather than flux in kg mol/s • cm2.

(5.5-3)

q A is flow rate of A in permeate, cm3(STP)/s; A m is membrane area, cm2; t is

membrane thickness, c m / p h is total pressure in the high-pressure (feed) side, cm Hg;

p, is total pressure in the low-pressure or permeate side, cm Hg; x a is mole fraction of

A in reject side; x j is mole fraction of A in feed; and y p is mole fraction of A in A

similar equation can be written for component B . permeate. Note that phx0 is the

partial pressure of A in the reject gas phase.

Figure 5.5-1: Process flow for complete mixing case.

(5.5-4)

where P ' B is permeability of B , cm3(STP) • cm/(s- cm2 • cm Hg). Dividing Eq.

(5.5-3) by (5.5-4)

(5.5-5)

and the ideal separation factor * is defined as

(5.5-6)

Making an overall material balance on component A

qf xf = qo xo + qp yp (5.5-7)

(5.5-8)

Substituting q p = qf from Eq. (5.5-2) into Eq. (5.5-3) and solving for the membrane

area, Am,

(5.5-9)

For design of a system there are seven variables in the complete-mixing model

(H1), x f , x o , y p , , * , P l / p h , and A m , four of which are independent variables.

Two commonly occurring cases are considered here.

Case 1. This is the simplest case where x f , x o , * , and p l / p h are given and y p ,

, and A m are to be determined by solution of the equations. By use of the quadratic

equation formula, Eq. (5.5-5) is solved for the permeate composition y p in terms of

xQ.

(5.5-10)

Hence, to solve this case, y p is first calculated using Eq. (5.5-10). Then the fraction

of feed permeated, 9 , is calculated using Eq. (5.5-8) and the membrane area, Am from

Eq. (5.5-9).

A membrane is to be used to separate a gaseous mixture, of A and B whose feed

flow rate is q f = 1 x 10 cm3(STP)/s and feed composition of A is x f = 0.50 mole

fraction. The desired composition of the reject is x a = 0.25. The membrane thickness

t = 2.54 x 10-3 cm, the pressure on the feed side is p h = 80 cm Hg and on the permeate

side is p x = 20 cm Hg-The permeabilities are P'A = 50 x 10~10 cm3(STP) • cm/(s • cm2

• cm Hg) and P'B = 5 x 10-10. Assuming the complete-mixing model, calculate the

permeate composition, y p , the fraction permeated, 9 , and the membrane area, A m .

Solution:

Using the material balance equation (5.5-8),

Am are to be determined. Equation (5.5-5) cannot be solved f o r y p since

xo is unknown. Hence, x o from Eq. (5.5-8) is substituted into Eq. (5.5-5)

and the resulting equation solved for y p using the quadratic equation to

give

(5.5-11)

Where

After solving foryp, the value of x0 is calculated from Eq. (5.5-8) and

A m from Eq. (5.5-9).

stream using a membrane 1 mil thick with an oxygen permeability of P'A

= 500 x 10-10 cm3(STP)-cm/(s-cm2-cmHg). An * = 10 for oxygen

permeability divided by nitrogen permeability (S6) will be used. The

feed rate is q f = 1 x 106 cm3(STP)/s and the fraction cut = 0.20. The

pressure selected for use are p h = 190 cm Hg and p t = 19 cm Hg. Again,

assuming the complete-mixing model, calculate the permeate

composition, the reject composition, and the area.

Solution:

Finally, using Eq. (5.5-9) to find the area

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