Multicomponent Flash Distillation

If there are more than two components, an analytical procedure is needed. The equation used are equilibrium, mass and energy balances, and stoichiometric relations. The mass and energy balances are very similar to those used in the binary case, but the equilibrium equations are usually written of K values. i i i where in general

y !Kx

K i ! K i Tdrum , pdrum , all xi

1 These two equations are written once for each component

Fortunately, for many systems the K values are approximately independent of composition. thus,

For light hydrocarbons, the approximate K values can be determined from the monographs prepared by DePriester

The DePriester Chart

The DePriester charts have been fit to the following equation (McWilliams, 1973):

a p 2 a p3 aT 1 aT 2 ln K ! 2   aT 3  aP1 ln p  2  T T p p
Note that T is in oR and p is in psia. The constants are given in the following table. This equation is valid from 70o C (365.7o R) to 200o C (851.7o R) for pressure from 101.3 kPa (14.69 psia) to 6,000 kPa (870.1 psia) See Table 2-3 p. 33 for constants
McWilliams, M.L., An Equation to Relate K-factors to Pressure and Temperature, Chem. Eng., 80(25), 138, 1973.
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The K values are used along with the stoichiometric equations which the mole fraction in liquid and vapor phases must equal to 1.0

y
i !1

! 1.0

x
i !1

! 1.0

C is the number of components.

For ideal system Raoult s law holds

By Dalton s law of partial pressure

Combining these equations

Comparing with

yi ! K i xi

Multicomponent Flash Distillation

The mass balances,

Fzi ! Lxi  Vyi

F ! L V
and the energy balance,

FhF  Q flash ! VH V  LhL

Usually the feed, F , and the feed mole fractions z1 for C-1 of the components will be specified. If pdrum and Tdrum or one liquid or vapor composition are also specified, then a sequential procedure can be used. Suppose we have 10 components (C = 10). Then we must find 10 K s, 10 x s, 10 y s one L and one V or 32 yi ! [10 variables. To do this we must solve 32 equations K i xi C K i ! K i Tdrum from , all xi from 10 , pdrum yi ! 1.0 2 C i !1 from ! 1.0 , xi i !1 and 10 independence mass balances]

How does one solve 32 simultaneous equations? However we will restrict ourselves to ideal solution where

K i ! K i Tdrum , pdrum

Since Tdrum and pdrum are known, the 10 Ki can be determined easily (say, from the DePriester charts or using the McWilliams relation). Now there are only 22 equations to solve simultaneously.

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To simplify the solution procedure, we first use yi y ! K i xi equilibrium, to remove

Fzi ! Lxi  VK i xi

Solving for xi, we have

Fzi xi ! L  VK i
Substituting for L

Then upon rearranging we have

Fzi xi ! F  V  VK i
xi ! zi V 1  K i  1 F

i ! 1, C

(2.38)
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Then

i !1

xi !

zi V 1  K i  1 F

! 1.0

i !1

From We obtain

yi ! K i xi

yi !
and

K i zi V 1  K i  1 F
C

(2.39)

y !
i i !1 i !1

K i zi V 1  K i  1 F

! 1.0

**

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If C is greater than 3, a trial-and-error procedure or root finding technique must be used to find F . Although V the equations * and ** are both valid, they do not have the good convergence properties. That is, ifV F wrong the is chosen, the F that is chosen next may not be V better. Subtracting * from **

i !1

K i zi V 1  K i  1 F


i !1

zi V 1  K i  1 F

!0

Subtracting the sum term by term, we have

V C K i  1 zi f ! !0 F i !1 1  K  1 V i F

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 V C K i  1 zi f ! !0 F i !1 1  K  1 V i F
This equation, which is known as the Rachford-Rice equation, has excellence convergence properties.
Since the feed composition,zi are specified and i can K Tdrum be calculated when and are given, the only pdrum variable is the fraction vaporize . This equation can V F be solved by many different convergence procedures. For V F instance, the Secant method can be used by selecting two values of and calculating the values of the V F summation (it will be zero only at the correct value of ). 14

The Newton convergence procedure will converge faster. Since f V is a function of F V

F

that should have a zero

value, the equation for the Newton convergence is

df k ( F f k 1  f k ! V d F V
where f k is the value of the function for trial k and df k d  F is the value of the derivative of the function V for trial k. We desire to have f k 1 set ! 0 f k 1 equal to zero, so we

( F V and solve for

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(  F !  F k 1   F k V V V

 fk ! df k d  F V

(2-44)

This equation gives us the best next guess for the fraction vaporized. To use it, however, we need equations for both the function and derivative. For fk, use the Rachford-Rice equation. Then the derivative is df C K i  1 2 zi k !  (2-45) 2
d F V
i !1

?  K i  1 V F A 1

Substituting the Rachford-Rice equation and (2-45) into (2-44) C

K i  1 zi 1  K  1 V F V V i !1 i !  C K i  1 2 zi F k 1 F k ?1  K  1 V F A2 i !1 i

(2-46)
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Once  F k 1 is calculated the value of the Rachford-Rice V equation can be determined. If it is close enough to zero, the calculation is finished, otherwise, repeat the Newton convergence for the next trial. Once V F has been found, xi and yi 38) are calculated from (2-

and (2-39). L and V are determined from the overall mass

balances. The enthalpy hL and H V can now be calculated. For ideal solutions the enthalpies can be determined from the sum of the pure component enthalpies multiplied by the corresponding mole fractions: ~ (2-47a) HV ! yi H V Tdrum , pdrum

i !1

~ hL ! xi hLi Tdrum , pdrum

i !1

(2-47b)

~ ~ where H V and hL are enthalpies of the pure component. i i

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Example 2-2 Multicomponent Flash Distillation

A flash chamber operating at 50 oC and 200 kPa is separating 1,000 kg moles/hr of a feed that is 30 mole % propane, 10 mole % n-butane, 15 mole % n-pentane and 45 mole % n-hexane. Find the product compositions and flow rates.
V , yi , ?
F = 1,000 kg mole/hr z1 = .30 z2 = .10 z3 = .15 z4 = .45

Tdrum ! 50o C
pdrum ! 200kPa

L, xi , ?
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Since Tdrum and pdrum are given, a sequential solution can be used. We can use the Rachford-Rice equation to solve for V F and then find xi , yi , L,V Find K i from the DePriester charts (or use McWilliams equation) From the DePriester charts at 50 oC and 200 kPa we find
K1 ! 7.0 K 2 ! 2.4 K 3 ! 0.8

C3 n-C4 n-C5

K 4 ! 0.30 n-C6
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Calculate f  F from the Rachford-Rice equation V

V 4 K i  1 zi f ! F i !1 1  K  1 V i = 0.1 as first guess. F

Pick V F

7.0  1 0.3  2.4  1 0.1  0.8  1 0.15  0.3  1 0.45 f 0.1 ! 1  7.0  1 0.1 1  2.4  1 0.1 1  0.8  1 0.1 1  0.3  1 0.1
! 1.125  0.1228   0.0306   0.3387 ! 0.8785

Since f(0.1) is positive, a higher value for F is V required. Note that only term in the denominator of each term changes. Thus we can set up the equation F V so that only willF equals V change. Then

7.0  1 0.3  2.4  1 0.1  0.8  1 0.15  0.3  1 0.45 f 0.1 ! V V V V 1  7.0  1 1  2.4  1 1  0.8  1 1  0.3  1
F F F

F 20

The first derivative from (2-45)

K1  1 2 z1 df K 2  1 2 z2 d  F !  ?  K  1 V F A2  ?  K  1 V F A2 1 1 V 1 1 2

K 3  1 2 z3  K 4  1 2 z4  ?  K 3  1 V F A2 ?  K 4  1 V F A2 1 1
10.8 0.196 !   ?  6.0 V F A2 ?  1.4 V F A2 1 1 0.006 0.2205   2 2 ?  0.2 V F A ?  0.7 V F A 1 1

With V F = 0.1 this derivative is -4.631. From (2-46) the next guess for V F is
0.8785 V ! 0.29 ! 0.1  4.631 F 2
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Calculating the value of the Rachford-Rice equation, we have f 0.29 ! 0.329 . This is still positive and V/F is still too low. 2nd Trial
df d  F ! 1.891 V 2
0.329 V ! 0.46 ! 0.29  1.891 F 3
f 0.46 ! 0.066 This is closer, but V/F is still too low.

3rd Trial
df d  F ! 1.32 V 3
0.066 V ! 0.51 ! 0.46  1.32 F 3 V ! 0.51 F

f 0.51 ! 0.00173

Thus

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Now we calculate xi from (2-38) and yi from yi ! K i xi

0.30 x1 ! ! ! 0.0739 V 1  7.0  1 0.51 1  K1  1 F y1 ! K1 x1 ! 7.0 0.0739 ! 0.5172 z1

By similar calculations,
x2 ! 0.0583, x3 ! 0.1670, x4 ! 0.6998, y2 ! 0.1400 y3 ! 0.1336 y4 ! 0.2099

Since F = 1,000 and V F = 0.51

V ! 0.51F ! 510 and L ! F  V ! 1000  510 ! 490 kmol/h
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Check

and

x
i !1

! 0.999

y
i !1

! 1.0007

These are close enough.

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Simultaneous Multicomponent Convergence

If the feed rate F, the feed composition consisting of (C-1)zi values, the flash drum pressure pdrum , and the feed temperature TF are specified, the hot liquid will vaporized when its pressure is dropped. This flashing cools the liquid to provide energy to vaporize some of the liquid. The result Tdrum is unknown; thus we must use a simultaneous solution procedure.

 hF ! zi hFi TF , pF
i !1

(2-50)

For wide-boiling point feed, Tdrum cannot have much effect on V/F

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Tbp < Tdrum < Tdp

Estimate Tdrum
Calculate K

Tdrum , pdrum

Estimate V/F Solve Rachford-Rice eq. No f (V / F ) ! 0 Yes

Calculate xi, yi, L, V, H and h

Estimate Tdrum

No

Energy balance satisfied

Yes Finished

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Arranging the energy balance into the functional form

FhF  Q flash ! VH V  LhL Ek (Tdrum ) ! VHV  LhL  FhF  Q flash ! 0

(2-51)

The Newtonian procedure estimates EK+1(Tdrum) from the derivative,

(2-52) (2-53)

dEk dH v dhL !V L ! VCPV  LCPL dTdrum ,k dTdrum dTdrum

(2-54)

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Set Ek+1 =0
(2-55)

Tdrum ,k 1 ! Tdrum ,k 

Ek (Tdrum ,k ) dE dTdrum ,k

(2-56a)

Convergence when
= 0.2 or 0.01oC

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Example We have a liquid feed that is 20 mole % methane, 45 mole % n-pentane and 35 mole % n-hexane. Feed rate is 1500 kmol/h and feed temperature is 45oC and pressure is 100 psia. The flash drum operates at 30 psia and is adiabatic. Find Tdrum, V/F, xi, yi, L, V. Give I for Tdrum = 0.02 and I for V/F = 0.005
Component P (kcal/gmol) Tbp, normal, oC Methane 1.955 -161.48 n-pentane 6.160 36.08 n-hexane 6.896 68.75 Vapor heat capacities in cal/gmoloC; T in oC: CPL, cal/gmoloC 11.0 39.66 45.58

CPV , M ! 8.20  0.01307T  8.75*107 T 2  2.63*109 T 3 CPV , P ! 27.45  0.08148T  4.538*105 T 2  10.1*109 T 3 CPV , H ! 32.85  0.09763T  5.716*105 T 2  13.78*109 T 3
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V , yi , ?
F = 1,500 kg mole/hr zM = .20 zP = .45 zH = .35 TF = 45oC PF=100 psia

Tdrum ! ?o C
pdrum ! 30 psia

L, xi , ?

Answer:

Tdrum = 23.892, V/F = 0.2549

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Iterati on No. 1 2 3 4 5 6 7 8 9 10

Init Tdrum ial 15.000 27.903 21.385 25.149 23.277 24.128 23.786 23.930 23.875 23.900

Trial s to V find 16 13 14 7 3 2 2 2 2 2

V F

Ca Tdrum lc 27.903 21.385 25.149 23.277 24.128 23.786 23.930 23.875 23.900 23.892
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0.2361 0.2677 0.2496 0.2567 0.2551 0.2551 0.2550 0.2550 0.2549 0.2549