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Aug.

18, 1953

J. M. HARRISON ETAL
SEPARATION OF' ETHYL ACETATE AND ESTHANOL BY AZEOTROPIC DISTILLATION WITH METHANOL

2,649,407

Filed March 14, 1952

Patented Aug. 18, 1953

, 2,649,407

UNITED STATES PATENT OFFICE


2,649,407
SEPARATION 0F ETHYL ACETATE AND ETHAN OL BY AZEOTROPIC DISTILLA TION WITH METHANOL

James M. Harrison, Oakmont, and Allen E.

search & Development Company, Pittsburgh, Pa., a corporation of Delaware

Somers, Pittsburgh, Pa., assignors to Gulf Re

Application March 14, 1952, Serial No. 276,615 5 Claims. (Cl. 202-42)

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This invention relates to a process for sepa

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azeotropic mixture of ethyl acetate and Water is then preferably recycled to the phase separa
tion zone. The water-rich mixture of water and

rating mixtures of organic compounds in aqueous


solution and more particularly to a process for

separating a mixture of ethanol, ethyl acetate, and Water. A mixture of ethanol, ethyl acetate, and Water is produced during the separation of Fischer

ethyl acetate removed from the phase separation


zone is passed to a concentration distillation zone from which Water is removed as bottoms

Tropsch oxygenated products into components.


A mixture of ethanol, ethyl acetate, and water is diflicult to separate by distillation because the
compounds boil Within a narrow range and be

and an azeotropic mixture of ethyl acetate and water having a boiling point of 70.4 C. at 760 mm. of Hg is removed as overhead and is prefer

ably recycled to the phase separation zone. -The water-rich mixture of Water, methanol,
and ethyl acetate removed from the water ex tration zone to which the azeotrope of ethyl

cause of the existence of binary and ternary azeotropes of these compounds.


We have found that a mixture of ethanol, eth

yl acetate, and Water can be eiciently separated


vby a process which comprises introducing meth anol and the mixture into an azeotropic distil
lation zone, removing as bottoms a mixture of ethanol and Water, and as overhead an azeo tropic mixture of about 56 per cent ethyl ace tate and 44 per cent methanol, the mixture hav

acetate and methanol is introduced, is passed to a concentration distillation zone. An azeotropic


mixture of ethyl acetate and methanol having a boiling point of 62.3 C. at '760 mm. of Hg is re
moved as overhead and a mixture of methanol and water is removed as bottoms from the con centration distillation zone. The azeotropic mix

ture of ethyl acetate and methanol is passed to


a Water extraction Zone from which an ethyl

Aing a boiling point of 62.3 C. at 760 mm. of Hg.

The process further comprises introducing the azeotropic mixture of ethyl acetate and meth
anol into a water extraction Zone, and remov- '

acetate-rich and a Water-rich mixture of ethyl

acetate, methanol, and water is removed.v This


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separation can be accomplished in the same Water extraction zone as the one employed for ing an ethyl acetate-rich phase mixture of separating the azeotropic mixture of ethyl ace ethyl acetate, Water, and methanol, and a water tate and methanol removed from the azeotropic rich mixture of the same compounds from this distillation zone to which the original mixture zone. Water is preferably introduced into the upper portion of the extraction zone, the ethyl 230 of ethanol, ethyl acetate and Water is introduced. The mixture of methanol and Water is removed acetate-rich phase being removed from the top
of the Water extraction zone. The ethyl acetate-rich mixture from the ex traction zone is introduced into a concentration distillation zone. An azeotropic mixture of about 56 per cent ethyl acetate and about 44 per cent methanol and having a boiling point oi 62.3 C. at 760 mm. of Hg is removed as overhead from the concentration distillation Zone and is prefer

as bottoms from the concentration distillation


zone and can be discharged as such or it can be

separated in a stripping zone.

When it is sep

arated the Water is preferably recycled to the Water extraction zone and the methanol is pref erably recycled to the azeotropic distillation zone.
The process of our invention can best be un

ably recycled to the Water extraction zone. A mixture of ethyl acetate and Water is re moved from the bottom of the concentration
distillation zone and is then introduced into a

derstood by reference to the accompanying draw 40 ing, the single figure of which presents a simpli fied flow sheet of an apparatus suitable for car
rying out an embodiment of our invention.

Referring to the figure, a mixture of 40 parts

phase separation zone.

An ethyl acetate-rich

ethanol, 242 parts ethyl acetate, and 42 parts


7 Water is introduced by line 5 to azeotropic dis tillation still 6. A mixture of 40 parts ethanol and 42 parts Water is removed as bottoms from azeotropic distillation still 6 by line 8 and is discharged from the system. 190 parts of meth 50 anol are introduced to the azeotropic distillation still by line 1. An azeotropic mixture contain ing 242 parts of ethyl acetate and 190 parts of methanol and having a boiling point of 62.3 C. is removed as overhead from azeotropic distilla
tion still 6 by line 9. ,

mixture and a Water-rich mixture are removed

from the phase separation Zone, the ethyl ace tate-rich mixture usually being removed from the upper portion of the phase separation Zone. The ethyl acetate-rich mixture is introduced
into a concentration distillation zone, ethyl ace tate is removed as bottoms and discharged as

product, and an azeotropic mixture containing about 92 per cent ethyl acetate and about 8 per cent Water and having a boiling point of 70.4 C. -at 760 mm. of Hg is removed overhead. The

2,649,407

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An azeotropic mixture of 29 parts ethyl acetate and 23 parts methanol recycled by line I'I and an azeotropic mixture of 289 parts ethyl acetate and 227 parts methanol recycled by line 42 in
a manner .which will .be described, are .also in

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distillation still 6. 2104 parts of Water are re moved as bottoms from stripping column 46 and

recycled by lines 43, 33 and I2 into extractor II. Some mixtures of ethyl acetate and ethanol .obtained in commercial-operation do not con
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troduced into line 9, and the resulting mixture of 560 parts of ethyl acetate and 440 parts meth anol is introduced into extractor II. 2125 parts ._
of water are introduced by line I2 to extractor

tain water in admixture lWith these materials. When it is desired to treat only such a non-aque --ous mixture, azeotropic distillation still 6 need not be used and the mixture of ethanol and ethyl

II. An ethyl acetate-rich mixture containing 271 parts ethyl acetate, 21 parts Water and 23
parts methanol is removed by line I 3 and a water

acetate is introduced into the system through line


i -tc azeotrop-Lc distillation still 52. Methanol is also introduced into this still by line 53. Eth anol is removed .as bottoms from azeotropic dis ' t-llation :still 52 by line 54. An azeotropic mix ture of lethyl acetate and methanol having a boiling `point foi 62.3 C. at 760 mm. of Hg is re moved .overhead by line 56 and is passed by this line into line 9 and from this line into extractor Il. 'The azeotropic mixture is then separated in the manner previously described.
embodiment oi ~the process of our invention in which a mixture of .ethyl acetate, ethanol and water and .a mixture `of ethyl acetate and .ethanol
are separated at the same time will now .be .de

rich mixture containing 2104 ,parts Water, 417 parts methanol and 289 parts ethyl acetate is
removed by line Ill from extractor ~I I. The ethyl acetate-rich mixture from extractor I I is introduced by line I3 into concentration distillation still I6. An azeotropic mixture con

taining 29 parts ethyl acetate and 23 parts .meth


anol and having a boiling point of 62.3 C. at 760 of Hg .is recycled .by lines .I'I and .9 to ex tractor II. A mixture of 242 parts ethyl acetate and 2l parts water .is removed as bottoms vfrom

concentration .still I5 by line I8.


below are introduced into line I8.

136 parts ethyl


An azectropic

acetate and 1.2 parts Water .recycled .as >described .

mixture .of 134 parts .ethyl acetate and 12 parts water is recycled from .concentration distillation still .25 by line 2l and an .azeotropic mixture of 2 parts ethyl >acetate .and a fractional part offWa ter recycled from .concentration distillation still
B-I by lines 32 and 2 in a manner which will be described. The mixtures .are introduced into line

scribed. A mixture of 120 parte ethyl acetate, 46.9 parts ethanol, and 76 parts water is intro duced by line .l Vinto aseotropic vdistillation still
6. .94 parts methanol .are introduced into aseo

tropic distillation still l by .line l'. A mixture of 460 parts ethanol and 76 parts Water is removed
as 4bottoms by line 8. .An azeotropic mixture con

taining 120 parts `ethyl acetate and .94 par-ts methanol and having a boiling point of (5.2.3o C..
at 'Z mm. of Hg .is removed overhead .by line 9. 11.8 parts of meth-anol and Va mixture containing 1.5L` parts ethyl acetate and 520 parts ethanol are

I8 and lthe resulting .mixture of 378 parts ethyl acetate and 33 .parts water is introduced .into

phase separator 2.I.

An .ethyl acetate-rich .phase containing 376 introduced by line 5I into .azeotropic :distillation parts-ethyl acetate and 12 parts Water is removed still 52) .par-ts ethanol .are discharged as .by line 22, and .a water-rich phase containing 21 bottoms by line 54. A. mixture containing .15.0 _parts water and .2 parts ethyl acetate is removed 40 par-ts ethyl acetate and 118 parts .methanol .and .by line 23. The 4ethyl acetate-rich phase mix having a boiling point .of 62.3 C. Vat 760 mm of tureis passed by line 22 into concentration dis Hg is passed by line 56 into line 9. The resulting tillation still 26. .An azeotropic mixture con .mixture of 27.0 parts ethyl .acetate and 212 Aparts taining v134 parts ethyl acetate .and 12 parts Wa methanol is introduced into extractor l I.. The ter is removed overhead from concentration >dis- . mixture of ethyl acetate .and methanol is sepa tillation still 2.6 and is passed by lines 27 and rated in the manner previously described. 2?-0 IB into phase separator 2I. .242 parts of ethyl parts ethyl acetate .are removed .as products. acetate are removed as bottoms from concentra 118 parts methanol are recycled by line `"ITI to .tion distillation still 25 by line 29 and are dis .azeotropic distillation vsti-ll 6 and 94 parts metha charged product. The water-rich phase is in nol are passedby line ? and line 57i and then by troduced into concentration distillation still SI line 5.3 to azeotropic distillation .still .52. by line .2.3. An azeotropic mixture comprising 2 Obviously many modifications and variations ,parts ethyl acetate and a .fractional -part of Wa of thev invention as hereinbefore set forth 'may ter is removed overhead from Yconcentration dis be made without departing from the lspirit .and tillation .still .3l and is passed by llines 32y 21 and 55 Scope thereof, and therefore, only such limita .I8 into the phase separator. 21 parts of water tions should be imposed as are indicated in the are removed as bottoms from concentration still appended claims. .34. The 2.1 parts of Water together with 2104 We claim: parts of Water recycled as described below by 1. A process which comprises introducing line d8 are recycled by line 33 and line I2 t0 60 methanol and a mixture of ethanol, ethyl acetate extractor I'I. and Water into -an azeotropc distillation-zone, The `Water-rich mixture of Water, methanol removing an azeotropic mixture of ethyl acetate and ethyl acetate from extractor II is passed and methanol as overhead from the azeotropic by line I4 into concentration distillation still 4I. distillation zone, introducing the azeotropic mix An azeotropic mixture containing 289 parts ethyl 65 ture of ethyl acetate and methanol to a Water acetate and 227 parts methanol and having a extraction zone, removing an ethyl acetate-rich boiling point of 62.3 C. at 760 mm.> of Hg is re and a Water-rich mixture of ethyl acetate, meth moved as overhead from concentration distilla anol, and Water from said Water extraction zone, tion still 4I by line d2 and is introduced by line
*3 >into extractor II. A mixture of 190 parts

introducing .said ethyl acetate-rich mixture to


azeotropic mixture of ethyl acetate and metha

methanol and 2104 parts water is removed as bot toms .from concentration distillation still 4I by

a concentration distillation zone, removing an


nol as overhead and a mixture of ethyl acetate

line 43 and is passed to stripping column 4_6. and water as bottoms from said concentration 190 parts of methanol are removed overhead by .distillation zone, introducing said bottoms line 4T and are recycled by line 1 into azeotropic 75 mixture of ethyl acetate and waterto a phase

2,649,407

separation zone, removing an ethyl acetate-rich tate and Water into an azeotropic distillation and a Water-rich mixture from said phase sepa zone, removing an azeotropic mixture of ethyl ration zone, and removing ethyl acetate as bot acetate and methanol having a boiling point of toms from said ethyl `acetate-rich mixture of 62.3 C. at 760 mm. of Hg as overhead from the ethyl acetate and water in a distillation Zone.v C1 azeotropic distillation zone, introducing the azeo 2. A process which comprises introducing tropic mixture of ethyl acetate and methanol to methanol and a mixture of ethanol, ethyl acetate a Water extraction zone, removing an ethyl ace and water into an azeotropic distillation Zone, tate-rich and a water-rich mixture of ethyl ace

removing >an azeotropic mixture of ethyl acetate


and methanol as overhead from the azeotropic

tate, methanol, and Water from said Water ex traction zone, introducing said ethyl acetate
rich mixture to a concentration zone, removing an azeotropic mixture of ethyl acetate and meth anol as overhead and a mixture of ethyl acetate and Water as bottoms from said concentration distillation zone, introducing the mixture of

distillation zone, introducing the azeotropic mix


ture of ethyl acetate and methanol to a water extraction zone, removing an ethyl acetate-rich and a water-rich mixture of ethyl acetate,

methanol, and water from said water extraction Zone, introducing said ethyl acetate-rich mix
ture to a concentration zone, removing an azeo

tropic mixture of ethyl acetate and methanol as overhead and a mixture of ethyl acetate and
water as bottoms from said concentration distil

ethyl acetate and Water to a phase separation zone, removing an ethyl acetate-rich mixture and a Water-rich mixture from said phase separation

zone, introducing said ethyl acetate-rich mixture


20 of ethyl acetate and Water to a concentration

distillation zone, removing ethyl acetate as bot toms and discharging it as product, removing an removing an ethyl acetate-rich mixture and a azeotropic mixture of ethyl acetate and meth Water-rich mixture from said phase separation anol having a boiling point of 70.4 C. as over zone, introducing said ethyl acetate-rich mixture 25 head from said concentration Zone, recycling said of ethyl acetate and water to a concentration azeotropic mixture of ethyl acetate and water to distillation zone, removing ethyl acetate as bot said phase separation zone, passing the Water toms and discharging it as product, removing an rich mixture of Water, ethyl acetate and meth azeotropic mixture of ethyl acetate and Water as anol from the water extraction zone to a concen overhead from said concentration distillation tration distillation zone, removing an azeotropic zone, and recycling said azeotropic mixture of mixture of ethyl acetate and methanol having a ethyl acetate and water to said phase separation boiling point of 62.3 C. at 760 mm. of Hg as zone. overhead and a mixture of methanol and water 3. A process which comprises introducing as bottoms from said concentration zone, re methanol and a mixture of ethanol, ethyl acetate cycling the azeotropic mixture of ethyl acetate and Water into an azeotropic distillation zone, and water to the extraction zone, separating said removing an azeotropic mixture of ethyl acetate mixture of methanol and water, and recycling and methanol having a boiling point of 62.3 C. the methanol to the azeotropic distillation zone. at 760 mm. of Hg as overhead from the azeo 5. A process which comprises introducing tropic distillation zone, introducing the azeo 40 methanol and a mixture of ethanol and ethyl tropic mixture of ethyl acetate and methanol to acetate into an azeotropic distillation zone, re a Water extraction zone, removing an ethyl ace moving ethanol as bottoms and an azeotropic tate-rich and a Water-rich mixture of ethyl ace mixture of ethyl acetate and methanol having a tate, methanol, and Water from said water ex boiling point of 62.3 C. at 760 mm. of Hg as traction zone, introducing said ethyl acetate 45 overhead from the azeotropic distillation zone, rich mixture to a concentration zone, removing introducing the azeotropic mixture of ethyl ace an azeotropic mixture of ethyl acetate and meth tate and methanol to a Water separation zone, anol having a boiling point of 62.3 C. at 760 removing an ethyl acetate-rich and a water mm. of Hg as overhead and a mixture of ethyl rich mixture of ethyl acetate, methanol and wa acetate and water as bottoms from said concen 50 ter from said Water extraction zone, introducing tration distillation zone, introducing the mix said ethyl acetate-rich mixture to a concentra ture of ethyl acetate and Water to a phase sep tion Zone, removing an azeotropic mixture of aration zone, removing an ethyl acetate-rich ethyl acetate and methanol having a boiling mixture and a water-rich mixture from said point of 62.3 C. at 760 mm. of I-Ig as overhead; phase separation zone, introducing said ethyl 55 and a mixture of ethyl acetate and Water as bot acetate-rich mixture to a concentration distil toms from said concentration distillation zone, lation zone, removing ethyl acetate as bottoms introducing said bottoms mixture of ethyl acetate and discharging it as product, removing an azeo and water to a phase separation zone, removing tropic mixture of ethyl acetate and Water having an ethyl acetate-rich and a> Water-rich mixture a boiling point of 70.4 C. at '760 mm. of Hg as 60 from said phase separation zone and removing overhead from said concentration zone, recycling ethyl acetate as bottoms from said ethyl acetate said azeotropic mixture of ethyl acetate and Wa rich mixture of ethyl acetate and water. ter to said phase separation Zone, passing the JAB/IES M. HARRISON. Water-rich mixture of Water and ethyl acetate ALLEN E. SOMERS. from the phase separation zone to a concentra 65 tion zone, discharging water as bottoms and an References Cited in the le 0f this patent azeotropic mixture of ethyl acetate and water UNITED STATES PATENTS having a boiling point of 70.4 C. at 760 mm. of Hg as overhead from Isaid concentration zone and Number Name Date recycling said azeotropic mixture to said phase 70 2,099,475 Giesen et al. ..... __ Nov. 16, `1937 separation zone.

lation zone, introducing the mixture of ethyl acetate and water to a phase separation zone,

4. A process which comprises introducing

2,382,044 2,583,620

Fisher __________ __ Aug. 14, 1945 Wrightson ...... __ Jan. 29, 1952

methanol and a mixture of ethanol, ethyl ace

_2,607,719

Eliot et al. _______ __ Aug. 19, 1952