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MAY 1986

ISSN 0018-8190

Hydrocarbon

Processing

REFLUX AND SURFACE TENSION EFFECTS ON DISTILLATION

Reflux and surface tension effects on distillation

Theoretical and experimental data suggest how to set reflux ratio for the most efficient distillation separation in packed towers. Surface tension effects also are considered

T. D. Koshy and F. Rukovena, Norton Co., Akron, Ohio

EASY SEPARATION SYSTEMS (those with relative volatili- ties of approximately 2.0 or greater) are influenced signifi- cantly by reflux ratio. Theoretical relations suggest the best separation efficiency occurs when X, the ratio of the slopes of the equilibrium and operating lines (mG\{/L\), is approxi- mately 1.0. Then, experimental data are obtained to relate X to its equivalent reflux ratio.

2.0

1.5

1.0

o

0

o

a

o

° 0

More difficult separation systems (relative volatility close to 1.0) have more uniform separation efficiencies over the entire concentration range (i.e., X has a lesser influence).

A difference in surface tension can explain some differ-

ences in efficiencies. Comparing two easy separation sys- tems, one with a negative surface tension gives a lower sepa- ration efficiency than another with a positive surface tension.

Operating efficiency. The operating efficiency of packed towers is generally expressed as Height Equivalent to a The- oretical Plate (HETP) or Height of a Transfer Unit (HTU). But note, a minimum HETP or HTU represents a maxi- mum separation efficiency. The effect of reflux ratio is shown in Fig. 1, a plot of HETP versus a vapor capacity factor CY These data are for

a methanol-water binary distillation at atmospheric pres-

sure. The upper plot is for total reflux. The lower plot is for an internal reflux ratio, L\i/G\, of 0.5. The HETP is signif- icantly larger for total reflux than for partial reflux.

These data were obtained at Norton Company's Cham- berlain Laboratories in Stow, Ohio. The distillation tower

had a diameter of 381 mm and was filled with a 3,048-mm-

deep bed of No. 25 IMTP stainless steel packing. Additiona runs were made to examine the relation between HETP ana*" reflux ratio. Further, HETP measurements were conducted

at a fixed boil-up rate to eliminate the effect of Cy on HETP.

Theoretical analysis. A generalized (HTU)(X; correlation assuming a two-resistance theory1-2 is given as follows:

0.5

Total reflux Partial reflux, L/D = 1.0

0.2

\1

0.3

Cs at midpoint,ft/s -Packed tower rectification of methanol-water.

2

3

45 6

810- 1

2

3

45 6

810°

2

3

4 56

Slope ratio X Fig. 2—Relationship among variables.

(HTU)0(; = (HTU)C; + X(HTU),.

If the equilibrium curve and the operating line are as-

sumed to be straight lines over a single stage, the following relation is obtained:

HETP = (HTU)oo(ln X)/(X - 1) (2)

(1)

0.4 Then define

(3 = (HTU) L /(HTU) G

and

£ = HETP/(HTU)C;

Combining the foregoing equations gives:

(5)

£ = (l+X/3)(lnX)/(X - 1)

Fig. 2 shows a plot of £ as a function of In X for various values of /3. For a fixed (8, the minimum £ is determined by setting the first differential of Eq. 5 to zero (i.e., d£/dX = 0). This gives:

(4)

810

/3 =

(X -

1 -

X In X)/(X In X -

X2

+ X)

(6)

Substituting Eq. 6 into Eq. 5 gives:

L,,, = (lnX)2/(X -

1 -

InX)

Table 1 shows the variation of £,„,„ with j3 and X.

Finding minimum HETP. If (HTU)(, is assumed to be a con-

Reprinted from HYDROCARBON PROCESSING, May 1986

Copyright* 1986 by Gull Publishing Co., Houston, Texas. All rights reserved. Used with permission.

stant, it follows from Eq. 4 that having a minimum £ also means there is a minimum value for HETP. And since X, and to some extent /?, varies over the range of concentration for which HETP is measured, values of/? and X must be ob- tained experimentally. The righthand term of Eq. 2, (In X)/(X- 1), approaches '.0 as X approaches 1.0. Therefore, Eq. 2 suggests HETP ^approaches (HTU)OG; and it is feasible to correlate HETP as

a function of the physical properties. It is customary to use published correlations5"' to evaluate (HTU)oo using Eq. 1. Relative volatility, a, relates the vapor and liquid phase compositions of the more volatile component in a binary separation, i.e.,

y

= ax/[I

+ (a

-

l)x]

(8)

Here, a is not necessarily a constant.

is assumed to be constant over a

small range of composition, the slope of the equilibrium curve can be given as follows:

(9)

On the other hand, if a

dy/dx

= m = a/[l

+ (a

-

\)x]2

The n

whe n x

—>

1 ,

m

*•

I/a

(10

)

an

d

whe n x

—> 0 ,

m

—>

a

(11

)

and

x = 1.0, m lies betwee n

Difficult separations (those binary systems whose a. val- ues are not significantly larger than 1.0), have values of m that do not greatly differ from 1.0. This also implies the in- ternal reflux ratio, L\i/G\i, which is the slope of the operat- ing line either in the rectifying or stripping sections, for these difficult separations will not vary significantly from 1.0. This is the case because the operating line is enclosed within boundaries created by the equilibrium curve and the diago-

,nal.

Thus,

for liquid phase

compositions between

ex and

I/a .

x

= 0

As a result, X = mG\IL\, or

the ratio of the two slopes,

^emains close to 1.0 for such systems. One should not expect

X to be an important variable in the performance efficiency

of distillation towers making difficult separations. Under

such conditions HETP = (HTU)oo, and HETP is an ap- propriate design tool. Easy separations, on the other hand, where a > > 1.0,

X can have values much less than 1.0 to much greater than

1.0. Therefore, X becomes an important variable in the per- formance of a distillation tower making easy separations, es-

pecially when making very pure products.

Surface tension effects can be considered using a defini- tion given by Zuiderweg and Harmens.8 They termed distil- lation systems positive or negative on the basis of whether the surface tension of the reflux liquid increases or decreases as it flows down the column.

Experimental data. Two binary systems that can be charac- terized as easy separations were chosen in order to compare the performance of two high a systems and, at the same time, contrast the performance of a system with a positive surface tension with one having a negative surface tension. The first system was the methanol-water binary men- tioned earlier in connection with Fig. 1. The a of this system ranged from 2.6 to 8.1 and the m ranged from 0.38 to 8.1, at atmospheric pressure. This is a strongly surface-tension-pos- itive system. The second binary system was a water-di- methylformamide (DMF) system whose a varied from 3.6 to 6.8 and m varied from 0.28 to 6.8, at atmospheric pressure. This latter is a strongly surface-tension-negative system.

log X for both systems are illus-

•,—crated in Fig. 3. The HETP values were calculated using a modified McCabe-Thiele method taking into account the enthalpy difference between the components.'' Tower opera- tions were held within a narrow range of boil-up rates in or-

The data for HETP versus

2.500

2,000

.

1.500

Methanol-water •*- Water-DM F

'*«,, .,

I

I

0%

I III

 

10-'

2

3

456

7 8910° Slope ratio X

 

2

3456

7

8910

Fig. 3—Two binary systems compared.

 

E

E

Q.-200

 

10-'

2

3

4

56

810°

2

3

4

5 6

8

10'

2

3

4

56

810 2

Slope ratio X

Fig. 4—Literature data for isopropanol-water.10

TABLE 1—Variation of £mm with 0 and X

(3

0

X

00

0.1 28

5.963

0.5

0.7 1.706

0.3

2.817

1.0 1.0

3.0 0.01954

5.0 0.0936

7.0 0.0583

9.0 0.0412

oo

0

£min

0

0.469

1.003

1.373

1.660

2.0

3.219

3.836

4.250

4.560

00

der to eliminate the effect of tower loading on efficiency. For both systems, HETP goes through a minimum at a X value of approximately 1, although boil-up limitations prevented getting data for the water-DMF system at X values greater than 1.0.

Other data for an isopropanol-water system reported by

Deed, et al., are shown in Fig. 4.'° They performed atmo- spheric rectification of the binary below azeotropic condition in a 152-mm-diameter brass column with 1,194 mrn of 13-

mm ceramic Raschig Rings. These data also indicate HETP goes through a minimum.

Based on the observation that (HTU)oo increased rapidly as X was raised, Deed, et al., concluded that the principal resistance to mass transfer was in the liquid phase. This ex- planation implies that, at large values of X, /? defined by Eq. 3 increases. On the other hand, Norman, et al.,11 conclude that large variations in HETP are probably the result of poor liquid distribution over the packing and variations in the wetted area. This conclusion was based on wetted wall column data determined by other researchers in the field who found large variations in HETP in experiments with packed columns. However, based on recent experience with liquid distributors providing a widely varying number of distribution points

and liquid flowrates, there are no indications that liquid dis-

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Fig. 5—Vapor-liquid equilibrium diagram.

tribution was a limiting factor for our test data. Surface tension effects. According to Zuiderweg and Har- mens,8 a binary system is positive if the less volatile compo- nent has the higher surface tension. They demonstrated that, in apparatus where the interfacial area is mainly of the film type, mass transfer rates for positive systems(with stabi- lized film) may be much higher than for negative systems. This generalization, however, may fail when applied to negative systems, where the reduction in contact angles may result in spray formation. The interfacial surface area in such formations is not significantly affected by surface ten- sion changes. Fig. 3 illustrated that for the range of X values for which comparison can be made, the HETP for the methanol-water (positive) system is consistently lower than that for the water- DMF (negative) system. Meier, et al.,12 who performed dis- tillation at total reflux on both systems in a structured stain- less steel tower packing, found that the HETP for the water-DMF system is approximately twice that of the metha- nol-water system. For these tests, the concentration range of the methanol- water mixture was 10% methanol at the bottom and 98% methanol at the top. The range of the water-DMF system was 30% water at the bottom and 99.5% water at the top. The authors attribute the lower HETP for the methanol-wa- ter system to its good wettability. The present study, how- ever, demonstrates that wettability per se does not explain the widely differing values of HETP obtained for essentially the same range of separation at different reflux ratios. The data indicate that at X values much larger or smaller than 1.0, HETP increases dramatically. Application. The practical importance of our findings can be illustrated in Fig. 5 and the following:

X is much less than 1. The circumstances when

this happens are:

• high purity of the more volatile component, i.e., m —* I/

Case I:

a.

• reflu x ratio , i.e. , L_\ /G_\i ~*• 1.0 .

hig h

• both foregoing conditions mean X —* I/a.

Case

II.

X =

1.

The

this condition:

following situations will produce

• very low reflux ratio for high purity rectification, i.e., x

-* i.o

• very high reflux ratio for high purity stripping, i.e., x -" 0

• total reflux for a symmetric separation. Note, the term

"symmetric separation" is used here to mean that on a McCabe-Thiele diagram, the liquid phase compositions of the overhead product and bottom product are roughly equidistant from 0.5.

circumstances

Case III. X is much greater than 1. The

when this occurs are:

• high purity of bottoms products, i.e., x -» 0 and m -

• lo w L/ V approachin g tota l reflux , i.e. , LIV —* • 1. 0

• both foregoin g conditions mean that X -*• a.

NOMENCLATURE

Cs

- capacity factor V svpc/(pL ~ PG)> m/s

GM

- ga s flowrate ,

kg-moles/ h

HETP - height equivalent to a theoretical plate, m

HTU

- height of a transfer unit, m

LM

- liquid rate, kg-moles/h

m

- slope of the equilibrium line

Vs

- superficial gas flow velocity based on tower area, m/s

x

- mole fraction of the more volatile component in the liquid phase

y

- mole fraction of the more volatile component in the vapor phase

Greek symbols

a

/3

X

- relative volatility between components 1 and 2

-

- m GM/LM, ratio of the slopes of equilibrium and operating lines

- - density, kg/m3

as defined in Eq. 3

as defined

4

- - liquid phase

- moles of gas or liquid

gas phase

in Eq.

p

Subscripts

G

L

M

OG - overall gas phase

£

LITERATURE CITED

1

Lewis, W. K., and Whitman, W. G., Industrial and Engineering Chemistry, Vol. 16, p.,

1215, 1924.

 

:

Whitman. W. G., Chemical and Metallurgical Engineering, Vol. 29, p. 247, 1923.

:i

Shulman,

H.

L., Ullrich,

C.

F,

and Wells, N., AlChE Journal, Vol. 1, p

"

1955.

4

Shulman, H. L., Ullrich, C. F, Proulx, A. Z., and Zimmerman, J.

O., AlChE

Journal, Vol. 1, p. 259,

1955.

 

~~'

Shulman,

259, 1955.

H.

L., Ullrich. C.

F., Wells, N., Proulx, A. Z., AlChE Journal, Vol.

1, p.

6

Onda, K., Takeuchi, H., and Okumoto, Y.J., Chemical EngineeringJapan, Vol. 1, p.

56, 1968.

 

7

Onda, K., Mem.

Fac.

Eng., Nagoya Univ., 24 (2), p. 64, 1972.

R

Zuiderweg, F. J., and Harmens, A., Chemical Engineering Science, Vol. 9,

Nos.

2/3,

p. 89,

1958.

y

Neretnieks, I., Ericson, I., Eriksson, S., British Chemical Engineering, Vol. 14. No.

12, p. 653,

1969.

1(1 Deed, D. W., Schutz, P. W., Drew, T. B., Industrial and Engineering Chemistry, Vol.

39, No. 6, p. 766, 1947.

11 Norman, W. S., Cakaioz, T., Fresco, A. Z., Sutcliffe, D. H., Transaction of the Insti-

tution of Chemical Engineers, Vol. 41, p. 61,

1963.

1 2 Meier , W., Hunkeler , R., Stocker, D., Institution of Chemical Engineers Symposium Se-

ries No. 56, 3.3,

p.

1,

1979.

The authors

T. Dan Koshy is manager, mass transfer devel- opment, Norton Chemical Process Products, Akron, Oft/o, where he manages pilot plant re- search and data correlation. Earlier he was a design and development engineer (distillation) with Union Carbide Corp., Linde Division. He holds a BS degree from Nagpur University, In- dia, an MS degree from Wayne State University, Mich., both in chemical engineering, and an AlChE membership.

Frank Rukovena, Jr., is manager, mass transfer engineering and development, Norton Chemical Process Products, Akron, Ohio, where he man- ages mass transfer development, packed tower application and mechanical engineering. Earlier he was a research development engineer wit

Koppers Co.

with General Tire. Holder of a BS in chemical en- gineering from \bungstown University, he is a member of AlChE.

and a design and project engine*, .„.

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