June 20, 1950

w. s. HARNEY. JR. EI'AL

EX'I'RACTIVE oxsmm'r
ALCOHOL mom us:

2,511,847

0F Sscounmv Bum.
L mm. KETONE

Filed Oct. 12, 194B

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Patented June 20, _1950

2,511,841

UNITED STATES PATENT OFFICE

EXTRACTIVE msriLLArioN or SECOND
ARY BUTYL ALCOHOL mom METHYL
ETHYL KETONE

William Selby Barney, Jr., and Sidney Schneider,

Elizabeth, N. .L, asailnors to Standard Oil De
velopment Company, a corporation of Delaware
Application October 12, 194:, Serial No. 54,206 I

5 Claims. (Cl. 20239.5)

I

This invention relates to the puri?cation of

Experimental data listed in Table I show the
methyl ethyl ketone and particularly to the re
increase in relative volatilities (alpha) for the
moval of secondary butyl alcohol in its ?nal traces
system methyl ethyl ketone-secondary butanol
from methyl ethyl ketone.
in the presence of water. In the experimental
Methyl ethyl ketone is produced commercially
work, mixture of methyl ethyl ketone and second
by the catalytic dehydrogenation of secondary
ary butyl alcohol 01 various concentrations were
butyl alcohol. The crude ketone discharged from
charged to an equilibrium still and samples of
the catalytic conversion unit contains about 80
vapor in equilibrium with the liquid were taken
weight per cent methyl ethyl ketone, while the
and analyzed to determine values of "alpha for
remainder is predominantly secondary butyl al 10 this system in the dry" state. Then, water was
cohol with small amounts of acetone, isopropanol
added to the equilibrium still and samples of
and water as low concentration contaminants.
vapor and liquid were again analyzed and values
In ?nishing the crude ketone by fractional distil
of alpha were calculated for the wet state,
lation, the principal separation demanded is that
in the same way, by' the following equation:
between the methyl ethyl ketone and the second 15
ary butyl alcohol. The limitations on product
alpha =

purity are imposed by the extent to which see

ondary butyl alcohol can be removed from the

mol % SBOH in vapor

1nol% SBOH in liquid

methyl ethyl ketone. This separation and re
mol % MEK in liquid
moval of secondary butyl alcohol by fractional
distillation becomes di?lcult and expensive when
The data in Table I illustrate that due to the
?nal traces of secondary butyl alcohol are pres
increase in alpha for the system, the separation
ent.
is highly improved by conducting a fractional dis
It is an object of this invention to provide for
tillation under extractive distillation conditions
the e?lcient separation and substantially com-. 25 in
the presence of water as a solvent.
plete removal of secondary butyl alcohol from
methyl ethyl ketone by conducting the fractional
TABLE I
distillation under. extractive distillation condi
tions employing water as the distillation solvent.
E?ect of water on the relative volatility (alpha)
in the system MEK-SBOH at atmospheric pres
It is also an object of this invention to provide 30
for the efficient separation and substantially com
VALUES OF ALPHA
plete removal of secondary butyl alcohol from
methyl ethyl ketone by conducting the fractional
distillation under extractive distillation conditions
M01 per
30-35 mol
86-88 mol
employing water as the solvent at sub-atmos 35
cent
No water percent water percent water
sure

pheric

pressures.

MEK in

The effect of water in improving the separation

of methyl ethyl ketone and secondary butyl alco
hol by distillation is unexpected. In the dry
state, secondary butyl alcohol (B. P. 99.5 C.) and
methyl ethyl ketone (B. P. 79.6 C.) boil about
20 C. apart. When "wet the water present
causes binary azeotropes of both compounds to

liquid
20

:40

present

in the liquid in the liquid

phase

phase

v 2.80

____________ -_

40

2. 60

____________ __

2. 84

45

2.52

2. 58

____________ _ _

2. 85

6O
8O

2. 34
1. 86

2. 52
2. 28

2 68
2. 43

90

' l. 54

2. l 2

____________ _ _

form. The secondary butyl alcohol-water binary

It is to be observed that the e?ectiveness of
boils at 87.30 0., whilethe methyl ethyl ketone 45 water in increasing alpha is greater in the range

water binary boils at 73.4. C. This is a boiling

joint spread of about 14 C. in the wet state
as compared with a 20 C. spread in the dry
state. It would be expected that the pressure
of water would hinder the separation of the ke
tone and alcohol due to the formation of closer

ketone in commercial operation occurs in ranges

where the MEK content'is high, e. g., 80 to 100%.

boiling azeotropes. However, it has been found

- higher concentrations of MEK such as 80 to

that the effect of water on the relative volatility

of the compounds of the mixture produces the

opposite effect.

of high MEK contents. This has great practical

importance because the problem of ?nishing the

It is known that in the MEK-SBOH system the
value of alpha rapidly approaches unity at the
100%.

'

The data in Table 11 illustrate that under. giv- I

en operating conditions the MEK distillate pro

2,6l1,847

duced when water is present as the distillation

TABLE IV
solvent always contains more MEK (on a water
Effect of water and reduced pressure on the rela
free basis) than the distillate produced from an
tive volatility (alpha) in the MEK-SBOH sys
anhydrous charge. For example, at a re?ux ratio
tem
of 3 to l, the presence of 23 mol per cent water Cl
produces an increase in the strength of the dis
VALUES or ALPHA
tillate of 1.2%; that is, from 97.6 weight per cent
M9] Per 0% H2O at 30 mol per
00, B20 at
30 mol per
MEK to 98.82 weight per cent MEK, which is an

extremely sharp increase at this high purity level.

As the mol per cent water employed as the dis

cent MEK

700 mm.

in Lqiuid

Hg.

ccnt H10 at .wgomm H

760 mm. Hg.

'

cent :0 at

350 mm. Hg.

10

tillation solvent increases, even higher purity

30

2. 70

2. 9

product is obtained as indicated in the table.

50
70

2. 47
2.14

2. 6
2. 4

80

l. 86

4. l
.i 0
2. 6

3. 7
3. 3

TABLE II

Results of experiments on the continuous frac

tional distillation of synthetic crude MEK (80%
MEK-20% SBOH) at 3:1 re?ux ratio and at
mospheric pressure and in the presence of vary

Run No.

Mggtf waits Pg: Distillate Strength,

:Jharge als)
rac [V8

15 l -

lation Solvent
0
no

water and reduced pressure can be translated

into improvement and product purity according

20 to the following data.

ing concentrations of water

It has been found that the effect of increase

in relative volatilities obtained by the use of

(g-103103;? (lglElg
-

Yaw-nee has)
97.60
98.82

30.0

99.14

44.2

99. 32

'

It should be observed that the distillate strength

is reported on a water free basis. On an average

the distillate from the water extractive distilla

tion operation will contain about 11 to 12% wa
ter which, of course, would be removed in a sub

sequent simple ?nishing operation either by a

(a) 0% water at 760 mm. Hg will give 98.0 weight

per cent MEK product.
(b) 0% water at 350 mm. Hg will give 99.4 weight
per cent mol product.
25 (0) 30 mol per cent water at 350 mm. Hg will
give 99.8 weight per cent MEK product.
In carrying out the process of the invention
the crude mixture of MEK and secondary butyl
30 alcohol is subjected to a distillation operation
illustrated in the diagrammatic drawing in which
the crude feed-is introduced via line 2 to a dis

tillation tower l' equipped with trays 9 at a point

below the top, preferably at about the mid-point

35 thereof, and in which water is fed to the top of

the tower or at a point near the top thereof

via line 3 in suiiicient quantity to maintain a

combination of caustic soda dehydration and

composition between 15 and 98 mol per cent wa
fractional distillation or by azeotropic distilla
ter, preferably, 30 to 90 mol per cent water in
tion.
40 the liquid phase in the distillation column. Dur
A typical analysis of the distillate obtained
ing the distillation operation the liquid water in
from the extractive distillation operation in the
ternal re?ux passes down through the tower
presence of water is that produced in run #3 of
countercurrent to the rising vapors. The pres
Table II.
ence of water effects an increase in the relative
This analysis is as follows:
45 volatility in favor of the MEK over the secondary
butyl alcohol such that the water allows the re
TABLE III
moval overhead of MEK substantially free of sec
ondary butyl alcohol via line 4. Of course some
Composition of distillate, run #3, Table H
water distills overhead in addition to the MEK.
50 However, this water is easily removed from the
Weight per cent SBOH=0.75
Weight per cent MEK=87 .40
MEK distillate in a subsequent puri?cation step.
The overhead is condensed in condenser 5 and
Weight per cent Water=11.84
the MEK substantially free of secondary butanol
The above water extractive distillation opera
is led to a dehydration unit via line 6. Re?ux of
tions were carried out at atmospheric pressure.
the condensed overhead may be made to the tower
Data have also been obtained which show that
via line 1. The bottoms from the distillation

additional increases in relative volatility (alpha)

zone withdrawn via line 8 consist of an aqueous

can be produced by carrying out the water ex

solution of secondary butyl alcohol which may be

discarded or processed for recovery of the alcohol

tractive distillation operation at subatmospheric

pressures. Distillation in the presence of water 60 therefrom.

at reduced pressures is more advantageous than
It has been found that the presence of 15 to 98
distillation in the pressure of water at atmos
.mol per cent water in the liquid on the bulk of
pheric pressure.
the plates of the distillation tower in which the

Table IV contains data which illustrate the

effect of water and reduced pressure on the rela

tive volatility in the MEK-SBOH system. The

data illustrate that the presence of water alone
or operation under reduced pressure alone pro

separation is being effected will produce the nec

essary volatility increase to provide the separar
tion desired. However, a preferred range of oper
ation is the use of 30-90 mol per cent water.
The distillation operation may take place on an

duces a substantial increase in alpha, but that,

anhydrous feed mixture or on an aqueous feed
however, both the presence of water and distilla 70 mixture. The feed likewise may or may not be
tion under reduced pressure produces still great
pretreated for the removal of low boiling contam
er increases in alpha. This substantial increase
inants therefrom. Any low boiling contaminants
in alpha also prevails in the ranges of higher
whose volatility is not effected during the dis
MEK concentrations in which the separation by
tillation operation and which pass overhead with
distillation is most di?lcult.
75 the MEK can easily be removed in the subsequent

?nishing step.

2,511,847

The important separation, of

mixture to a fractional distillation zone at an

course, being effected during the water extractive

-distillation, is that of secondary butyl alcohol

intermediate point thereof, continuously adding

from the MEK.

When the water extractive distillation opera
tion is carried out under subatmospherie pres
sure, pressures of 100 mm. Hg to 500 mm. Hg are

tain an internal liquid re?ux having a water con

tent in the range of 15 to 98 mol per cent below

water to the fractional distillation zone substan

tially above the feed point of the mixture to main

the point of addition of the water, distilling from

preferred.

said distillation zone a vaporous mixture wherein

The temperature of the crude MEK iced to the

the distilled vaporous mixture ascends counter
distillation zone is preferably close to the tem 10 current to the liquid internal re?ux and remov
perature of the liquid on the plate at the point
ing from the distillation zone a distillate com
of introduction of the feed although it may be
prising methyl ethyl ketone substantially free of .
lower to partly condensed vapors extending to the
secondary butyl alcohol.

feed plate. For continuous e?icient operation the

2. A process according to claim 1 in which the '

water must be added continuously near the top

water is fed to the fractional distillation zone in
of the column while the crude MEK being puri
amounts su?icient to maintain 30 to 90 mol per
?ed is continuously fed into the column at a
cent water in a distillation zone below the point
lower point, preferably near the mid-point of the
of addition of water.
column, and while suf?cient heat is provided to
3. A process according to claim 1 in which
afford distillation throughout the column. The 20 the distillation is conducted at atmospheric
feed stream may be preheated to a temperature
pressure.
close to that of the internal liquid under equilib
4. A process according to claim 1 in which the
rium boiling conditions at the point of introduc
distillation is carried out at subatmospheric

tion. The preheated feed may be liquid, partly

vaporized, or completely vaporized when intro

pressure.

duced into the extractive distillation column.

Vapors of the mixture being puri?ed pass up
wardly through the distillation zone in contact
with descending internal liquid reflux under equi

WILLIAM SELBY HARNEY, JR.

SIDNEY SCHNEIDER.

librium, reboiling and re?uxing conditions.

30
Without attempting to explain the mechanism
by which the desired separation occurs in the dis
tillation column, it can be said that the process
is one of vapor-liquid extraction in which the
vapors contain a greater concentration of MEK
relative to secondary butyl alcohol than under
the normal fractional distillation conditions in
the absence of the considerable amounts of aque
ous internal reflux. It is evident from the results
obtained that the water employed within the
limits speci?ed increases the vapor pressure of
MEK in comparison with the vapor pressure of

secondary butyl alcohol, thus allowing the MEK

to pass overhead from the distillation zone more

completely free of secondary butyl alcohol.

What is claimed is:

. .

l. The method of separating methyl ethyl ke

tone from a mixture thereof with secondary butyl

alcohol which comprises continuously feeding the

'

5. A process according to claim 1 in which the

distillation is carried out at- subatmospheric
pressure of 100 to 500 mm. Hg.

REFERENCES CITED

The following references are of record'in the

?le of this patent:
Number

UNITED STATES PATENTS

Name
Date

1,929,901
2,179,991
2,290,636
2,321,748

Ricard et al _______ __ Oct.

Bright et a1 _______ __ Nov.
Deanesly ________ __v_ July
Hopkins et a1 _____ __ June

10,
14,
21,
15,

1933
1939
1942
1943

OTHER REFERENCES

Methyl Ethyl Ketone, published 1938 by Shell

Chemical Company, San Francisco, California,
45 copy in Division 25, pages 25-31.

Handbook of Chemistry and Physics, 28th

edition, published 1944 by Chemical Rubber Pub

lishing Company, 2310 Superior Avenue, N. E.
Cleveland, Ohio. Pages 6'74 and 675.