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4

Flash drum

V, yi, hv

PV, TV

Heater

Liquid

feed

(a)

V, yi, hV

PV, TV

Partial

condenser

(1) PV PL

(2) TV TL

(3) yi Kixi

(4) Fzi Vyi Lxi

(5) F V L

(6) hFF Q = hVV hLL

P

P

(7) i yi " i xi 0

F, zi

hF

TF, PF

Number of

Equations

Equation

Valve

PL, TL

L, xi, hL

Vapor

feed

Partial Condensation Operations. Feed mole fractions must sum

to one.

F, zi

hF

TF, PF

Flash drum

147

PL, TL

L, xi, hL

Ki Ki{TV, PV, y, x}

hV hV{TV, PV, y}

(mechanical

equilibrium)

(thermal equilibrium)

(phase equilibrium)

(component material

balance)

(total material balance)

(energy balance)

(summations)

1

1

C

C

1

1

1

E 2C 5

hF hF {TF, PF, z}

hL hL {TL, PL, x}

(b)

(a) flash vaporization and (b) partial condensation.

vaporized in a heater and then separated into two phases.

Alternatively, a vapor feed can be cooled and partially condensed, as in Figure 4.9b, to give, after phase separation, a

liquid richer in the less-volatile components. For properly

designed systems, the streams leaving the drum will be in

phase equilibrium [4].

Unless the relative volatility, aAB, is very large, flashing

(partial vaporization) or partial condensation is not a replacement for distillation, but an auxiliary operation used to prepare streams for further processing.

Single-stage flash calculations are among the most common calculations in chemical engineering. They are used not

only for the operations in Figure 4.9, but also to determine

the phase condition of mixtures anywhere in a process, e.g.

in a pipeline.

For the single-stage operation in Figure 4.9, the 2C 5

equations listed in Table 4.3 apply. (In Figure 4.9, T and P

are given separately for the vapor and liquid products to

emphasize the need to assume mechanical and thermal equilibrium.) The equations relate the 3C 10 variables (F, V, L,

zi, yi, xi, TF, TV, TL, PF, PV, PL, Q) and leave C 5 degrees of

freedom. Assuming that C 3 feed variables F, TF, PF, and

C values of zi are known, two additional variables can be

specified for a flash calculation. The most common sets of

specifications are:

TV , P V

V/F 0, PL

V/F 1, PV

TL, V/F 0

TV, V/F 1

Q 0, PV

Q, PV

V/F, PV

Isothermal flash

Bubble-point temperature

Dew-point temperature

Bubble-point pressure

Dew-point pressure

Adiabatic flash

Nonadiabatic flash

Percent vaporization flash

If the equilibrium temperature TV (or TL) and the equilibrium

pressure PV (or PL) in the drum are specified, values of the

remaining 2C 5 variables are determined from 2C 5

equations as given in Table 4.3.

Isothermal-flash calculations are not straightforward

because Eq. (4) in Table 4.3 is a nonlinear equation in the

unknowns V, L, yi, and xi. The solution procedure of Rachford and Rice [5], widely used in process simulators and described next, is given in Table 4.4.

Equations containing only a single unknown are solved

first. Thus, Eqs. (1) and (2) in Table 4.3 are solved, respectively, for PL and TL. The unknown Q appears only in (6), so

Q is computed after all other equations have been solved.

This leaves Eqs. (3), (4), (5), and (7) in Table 4.3 to be solved

for V, L, and all values of y and x. These equations can be

partitioned to solve for the unknowns in a sequential manner

Calculations When K-Values Are Independent of Composition

Specified variables: F, TF, PF, z1, z2, . . . , zC, TV, PV

Steps

(1) TL TV

(2) PL PV

(3) Solve

C

P

zi 1 " K i

f fCg

0

1

CK i " 1

i1

for C V/F, where Ki = Ki{TV, PV}.

(4) V FC

zi

(5) xi

1 CK i " 1

zi K i

(6) yi

xi K i

1 CK i " 1

(7) L F " V

(8) Q hVV hLL " hFF

148

Chapter 4

1.0

resulting f{0} > 0, the mixture is below its bubble point (subcooled liquid). Alternatively, if f{1} < 0, the mixture is

above the dew point (superheated vapor). The Rachford

Rice procedure may fail to converge if K-values are sensitive

to composition. In that case, the method of Boston and Britt

[19] is employed in some process simulators.

0.8

f {}

0.6

0.4

0.2

0.0

0.2

0.4

EXAMPLE 4.1

0

0.2

0.4

0.6

V

=

F

0.8

A 100-kmol/h feed consisting of 10, 20, 30, and 40 mol% of propane (3), n-butane (4), n-pentane (5), and n-hexane (6), respectively,

enters a distillation column at 100 psia (689.5 kPa) and 200+ F

(366.5+ K). Assuming equilibrium, what fraction of the feed enters

as liquid, and what are the liquid and vapor compositions?

1.0

by substituting Eq. (5) into Eq. (4) to eliminate L and combining the result with Eq. (3) to obtain Eqs. (5) and (6) in

Table 4.4. Here (5) is in xi but not yi, and (6) is in yi but not

x

Pi. Summing

P these two equations and combining them with

yi

xi 0 to eliminate yi and xi gives Eq. (3) in Table

4.4, a nonlinear equation in V (or C V/F) only. Upon solving this equation numerically in an iterative manner for C

and then V, from Eq. (4), the remaining unknowns are

obtained directly from Eqs. (5) through (8) in Table 4.4.

When TF and/or PF are not specified, Eq. (6) of Table 4.3 is

not solved for Q.

Equation (3) of Table 4.4 can be solved iteratively by

guessing values of C between 0 and 1 until the function

f{C} 0. A typical function, encountered in Example 4.1, is

shown in Figure 4.10. The most widely employed procedure

for solving Eq. (3) of Table 4.4 is Newtons method [6]. A

value of the C root for iteration k 1 is computed by the

recursive relation

Ck1 Ck

f fC g

0

f fCk g

4-10

Solution

At flash conditions, from Figure 2.4, K3 4.2, K4 1.75, K5

0.74, K6 0.34, independent of compositions. Because some

K-values are greater than 1 and some less than 1, it is necessary first

to compute values of f{0} and f{1} for Eq. (3) in Table 4.4 to see if

the mixture is between the bubble and dew points.

C

X

i1

zi 1

1

0:31

1(2

1:75

1

0:74 0:41 0:34

1

1

0:21

0:128

0:11 4:2

0:21 1:75

1 4:2 1 1 1:75 1

f f1g

0:31 0:74

0:41 0:34

0:720

1 0:74 1 1 0:34 1

Since f{1} is not less than zero, the mixture is below the dew point.

Therefore, the mixture is part vapor. Using the RachfordRice procedure and substituting zi and Ki values into Eq. (3) of Table 4.4

gives

0

4-11

The iteration can be initiated by assuming C(1) 0.5. Sufficient accuracy is achieved by terminating the iterations when

jCk1 Ck j=Ck < 0:0001.

The existence of a valid root (0 * C * 1) must be checked

before employing the procedure of Table 4.4, by checking if

the equilibrium condition corresponds to subcooled liquid or

superheated vapor rather than partial vaporization or condensation. A first estimate of whether a multicomponent feed

gives a two-phase mixture is made by inspecting the Kvalues. If all K-values are > 1, the phase is superheated

vapor. If all K-values are < 1, the single phase is a subcooled

liquid. If one or more K-values are greater than 1 and one or

more K-values are less than 1, the check is made by first

4:2

Since f{0} is not more than zero, the mixture is above the bubble

point. Now compute f{1}:

0:11 4:2

0:21 1:75

1 C4:2 1 1 C1:75 1

K i 2

1 Ck K i

0:11

f f0g

of f{C}, from Eq. (3) in Table 4.4, with respect to C is

0

0:31 0:74

0:41 0:34

1 C0:74 1 1 C0:34 1

C of 0.50 gives the following iteration history:

$

$

$Ck1 Ck $

0

$

$

f fCk g

f fCk g

Ck1

k

Ck

$

$

$

$

Ck

1

2

3

4

0.5000

0.0982

0.1211

0.1219

0.2515

0.0209

0.0007

0.0000

0.6259

0.9111

0.8539

0.8521

0.0982

0.1211

0.1219

0.1219

0.8037

0.2335

0.0065

0.0000

Table 4.4, the vapor flow rate is 0.1219(100) 12.19 kmol/h, and

the liquid flow rate from Eq. (7) is (100 12.19) 87.81 kmol/h.

Liquid and vapor compositions from Eqs. (5) and (6) are

4.4

x

0.0719

0.1833

0.3098

0.4350

1.0000

Propane

n-Butane

n-Pentane

n-Hexane

Sum

149

bubble-point temperature and composition, since xi zi at

the bubble point.

Bubble- and dew-point calculations are used to determine

saturation conditions for liquid and vapor streams. Whenever

there is vaporliquid equilibrium, the vapor is at its dew point

and the liquid is at its bubble point.

y

0.3021

0.3207

0.2293

0.1479

1.0000

EXAMPLE 4.2

At the bubble point, C 0 and f{0} 0. By Eq. (3) of

Table 4.4

X

X

X

zi 1 $ K i

zi $

zi K i 0

f f0g

i

P

However, zi 1. Therefore, the bubble-point equation is

P

zi K i 1

4-12

i

Table 4.4,

X zi 1 $ K i X zi X

$

zi 0

f f 1g

Ki

Ki

i

Therefore, the dew-point equation is

P zi

1

i Ki

4-13

to find T for a specified P or to find P for a specified T.

The bubble- and dew-point equations are nonlinear in

temperature, but only moderately nonlinear in pressure,

except in the region of the convergence pressure, where

K-values of very light or very heavy species change drastically with pressure, as in Figure 2.6. Therefore, iterative procedures are required to solve for bubble- and dew-point

conditions except if Raoults law K-values are applicable.

Substitution of K i Psi =P into (4-12) allows direct calculation of bubble-point pressure:

Pbubble

C

X

zi Psi

4-14

i1

species i. Similarly, from (4-13), the dew-point pressure is

!$1

C

X

zi

4-15

Pdew

Ps

i1 i

Another exception occurs for mixtures at the bubble point

when K-values can be expressed by the modified Raoults

law, K i gi Psi =P. Substituting into (4-12)

Pbubble

C

X

i1

gi zi Psi

4-16

Bubble-Point Temperature.

In Figure 1.9, the nC4-rich bottoms product from Column C3 has the

composition given in Table 1.5. If the pressure at the bottom of the

distillation column is 100 psia (689 kPa), estimate the mixture

temperature.

Solution

The bottoms product is a liquid at its bubble point with the following composition:

kmol/h

zi xi

8.60

0.0319

215.80

0.7992

28.10

0.1041

17.50

0.0648

270.00

1.0000

The bubble-point temperature can be estimated by finding the temperature that will satisfy (4-12), using K-values from Figure 2.4. Because the bottoms product is rich in nC4, assume the K-value of nC4

is 1. From Figure 2.4, for 100 psia, T 150& F. For this temperature,

using Figure 2.4 to obtain K-values of the other three components

and substituting these values and the z-values into (4-12),

P

zi K i 0:03191:3 0:79921:0 0:10410:47

0:06480:38

0:042 0:799 0:049 0:025 0:915

Component

i-Butane

n-Butane

i-Pentane

n-Pentane

The sum is not 1.0, so another temperature is assumed and the summation repeated. To increase the sum, the K-values must increase

and, thus, the temperature must increase as well. Because the sum is

dominated by nC4, assume its K-value 1.09. This corresponds to a

temperature of 160& F, which results in a summation of 1.01. By linear interpolation, T 159& F.

EXAMPLE 4.3

Bubble-Point Pressure.

Cyclopentane is separated from cyclohexane by liquidliquid extraction with methanol at 25& C. To prevent vaporization, the mixture

must be above the bubble-point pressure. Calculate that pressure

using the following compositions, activity coefficients, and vapor

pressures:

Methanol

Vapor pressure, psia

Methanol-rich layer:

x

g

Cyclohexane-rich layer:

x

g

Cyclohexane

Cyclopentane

2.45

1.89

6.14

0.7615

1.118

0.1499

4.773

0.0886

3.467

0.1737

4.901

0.5402

1.324

0.2861

1.074

150

Chapter 4

Solution

Assume the modified Raoults law in the form of (4-16) applies for

either liquid phase. If the methanol-rich-layer data are used:

Pbubble 1:1180:76152:45 4:7730:14991:89

3:4670:08866:14

5:32 psia 36:7 kPa

A similar calculation based on the cyclohexane-rich layer gives an

1 1

identical result because the data are consistent; thus giL xi

2 2

giL xi . A pressure higher than 5.32 psia will prevent formation of

vapor at this location in the extraction process. Operation at atmospheric pressure is viable.

EXAMPLE 4.4

vapor distillate containing 90 mol% propylene. Calculate the column pressure if the partial condenser exit temperature is 100$ F

(37.8$ C), the lowest attainable temperature with cooling water. Determine the composition of the liquid reflux. In Figure 4.11, Kvalues estimated from Eq. (5) of Table 2.3, using the Redlich

Kwong equation of state for vapor fugacity, are plotted and

compared to experimental data [7] and Raoults law K-values.

on the assumption that f{P} is linear in P such that

n

o# Pk1 ' Pk $

2

Pk2 Pk1 ' f Pk1

f fPk1 g ' f fPk g

This is reasonable because, at low pressures, K-values in (2) are

almost inversely proportional to pressure. Two values of P are

required to initialize this formula. Choose 100 psia and 190 psia. At

P(1) 100 psia, K-values from the solid lines in Figure 4.11, when

substituted into Eq. (1) give,

0:90 0:10

f fPg

2:0 0:68

Similarly, for P(2) 190 psia, f{P}= +0.02. Substitution into Eq. (2)

gives P(3) 186, and so on. Iterations end when jP(k+2) ' P(k+1)j

/P(k+1) < 0.005. In this example, that occurs when k 3. Thus, the

operating pressure at the partial condenser outlet is 186 psia (1,282

kPa). The liquid reflux composition is obtained from xi zi/Ki,

using K-values at that pressure. The final results are:

Equilibrium Mole Fraction

Component

Vapor Distillate

Liquid Reflux

0.90

0.10

1.00

0.76

0.24

1.00

Propylene

1-Butene

10

Legend

K-value

Eq. (5), Table 2.3

Experimental data

When the pressure of a liquid stream is reduced adiabatically

across a valve as in Figure 4.9a, an adiabatic-flash (Q 0)

calculation is made to determine the resulting phases, temperature, compositions, and flow rates for a specified downstream pressure. The calculation is made by applying the

isothermal-flash calculation procedure of 4.4.1 in an iterative manner. First a guess is made of the flash temperature,

TV. Then C, V, x, y, and L are determined, as for an isothermal flash, from steps 3 through 7 in Table 4.4. The guessed

value of TV (equal to TL) is next checked by an energy balance obtained by combining Eqs. (7) and (8) of Table 4.4

with Q 0 to give

Propylene

1

1-Butene

f fT V g

0.1

60

80

100

120

140

160

Pressure, psia

180

200

$

Solution

The column pressure is at the dew point for the vapor distillate. The

reflux composition is that of a liquid in equilibrium with the vapor

distillate at its dew point. The method of false position [8] is used to

perform the calculations by rewriting (4-13) in the form

f fPg

C

X

zi

'1

K

i

i1

0

1; 000

4-17

Enthalpies are computed at TV TL. If the computed value

of f{TV} is not zero, the entire procedure is repeated. A plot

of f{TV} versus TV is interpolated to determine the correct

value of TV. The procedure is tedious because it involves

inner-loop iteration on C and outer-loop iteration on TV.

Outer-loop iteration on TV is successful when Eq. (3) of

Table 4.4 is not sensitive to the guess of TV. This is the case

for wide-boiling mixtures. For close-boiling mixtures, the

algorithm may fail because of sensitivity to the value of TV. In

this case, it is preferable to do the outer-loop iteration on C

and solve Eq. (3) of Table 4.4 for TV in the inner loop, using a

4.5

f fT V g

C

X

i1

zi 1 $ K i

0

1 CK i $ 1

4-18

Then, Eqs. (5) and (6) of Table 4.4 are solved for x and y.

Equation (4-17) is then solved directly for C, since

f fCg

ChV 1 $ ChL $ hF

0

1; 000

from which

C

4-19

h F $ hL

h V $ hL

4-20

used to repeat the outer loop, starting with (4-18).

Multicomponent, isothermal-flash, bubble-point, dewpoint, and adiabatic-flash calculations are tedious. Especially

for nonideal mixtures, required thermodynamic property

expressions are complex, and calculations should be made

with a process simulator.

EXAMPLE 4.5 Adiabatic Flash of the Feed to a

Distillation Column.

Equilibrium liquid from the flash drum at 120' F and 485 psia in

Example 2.6 is fed to a so-called stabilizer distillation tower to

remove the remaining hydrogen and methane. Feed-plate pressure

of the stabilizer is 165 psia (1,138 kPa). Calculate the percent molar

vaporization of the feed and compositions of the vapor and liquid if

the pressure is decreased adiabatically from 485 to 165 psia by a

valve and pipeline pressure drop.

Solution

This problem, involving a wide-boiling feed, is best solved by using a

process simulator. Using the CHEMCAD program with K-values and

enthalpies from the PR equation of state (Table 2.5), the result is:

151

case is in Figure 4.12a, where only the solute, component B,

has any appreciable solubility in either the carrier, A, or the

solvent, C, both of which have negligible (although never

zero) solubility in each other. Here, equations can be derived

for a single equilibrium stage, using the variables F, S, E, and

R to refer, respectively, to the flow rates (or amounts) of the

feed, solvent, exiting extract (C-rich), and exiting raffinate

(A-rich). By definition, the extract is the exiting liquid phase

that contains the extracted solute; the raffinate is the exiting

liquid phase that contains the portion of the solute, B, that is

not extracted. By convention, the extract is shown as leaving

from the top of the stage even though it may not have the

smaller density. If the entering solvent contains no B, it is

convenient to write material-balance and phase-equilibrium

equations for the solute, B, in terms of molar or mass flow

rates. Often, it is preferable to express compositions as mass

or mole ratios instead of fractions, as follows:

Let : F A feed rate of carrier A; S flow rate of

solvent C; X B ratio of mass or moles of solute B;

to mass or moles of the other component in the feed F;

raffinateR; or extract E:

Then, the solute material balance is

F

XB FA XB S XB FA

4-21

and the distribution of solute at equilibrium is given by

E

4-22

X B KDB X B

where K 0DB is the distribution or partition coefficient in terms

of mass or mole ratios (instead of mass or mole fractions).

E

Substituting (4-22) into (4-21) to eliminate X B ,

R

XB

XB FA

F A K 0DB S

4-23

solute B:

kmol/h

Component

Feed 120' F

485 psia

Vapor 112' F

165 psia

Liquid 112' F

165 psia

Hydrogen

Methane

Benzene

Toluene

Total

Enthalpy, kJ/h

1.0

27.9

345.1

113.4

487.4

$1,089,000

0.7

15.2

0.4

0.04

16.34

362,000

0.3

12.7

344.7

113.36

471.06

$1,451,000

EB K 0DB S=F A

4-24

Large extraction factors result from large distribution coefficients or large ratios of solvent to carrier. Substituting (4-24)

into (4-23) gives the fraction of B not extracted as

R

X B =X B

1

1 EB

4-25

predominantly H2 and CH4, is produced. The flash temperature of

112' F is 8' F below the feed temperature. The enthalpy of the feed

is equal to the sum of the vapor and liquid product enthalpies for this

adiabatic operation.

Thus, the larger the extraction factor, the smaller the fraction

of B not extracted or the larger the fraction of B extracted.

Alternatively, the fraction of B extracted is 1 minus (4-25) or

EB/(1 EB).

Mass (mole) ratios, X, are related to mass (mole) fractions,

x, by

X i xi =1 $ xi

4-26

are related to KD in terms of fractions as given in (2-20) by

!

1

1

2

xi =1 $ xi

1 $ xi

0

4-27

K Di

K Di 2

2

1

xi =1 $ xi

1 $ xi

separate liquid phases differ as to the extent of solubility of

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