US006172258B1

(12) United States Patent

(10) Patent No.:

J awaid et al.

(45) Date of Patent:

(54)

PROCESS FOR THE PRODUCTION AND

0 706 989

PURIFICATION OF N-BUTYLACRYLATE

(75)

Inventors: Mahmood Nayyer Azam J aWaid,

Houston; Douglas Edward Schepp,

Highland Village, both of TX (Us)

9704628

US 6,172,258 B1
*J an. 9, 2001

4/1996 (EP) ............................ .. C07C/67/58

3/1998 (ZA).

* Cited by examiner

Primary ExaminerShailendra Kumar

Assistant ExaminerJ. Parsa

(73) Assignee: Celanese International Corporation,

(*) Notice:

(74) Attorney Agent Or Firm I 1' Susan Splenng

Dallas, TX (US)

(57)

Under 35 USC. 154(b), the term of this

patent shall be extended for 0 days.

A process for the production of n-butyl acrylate (BuAcA)

including the steps of esterifying acrylic acid (HAcA) With

This patent is subject to a terminal dis-

n-butanol (n-BuOH) in a reaction Zone, obtaining a conden

sate from the overhead vapors from the reaction Zone Which

claimer.

ABSTRACT

separates into organic and aqueous phases, feeding the

organic phase comprising a major portion of BuAcA and

(21) APPL NO; 09/395,410

minor portions of Bu'OH, Water and light ends impurities to

(22)
(51)

Filed?
SeP- 14, 1999
Int. c1.7 .......................... .. c07c 67/48; c07c 69/52

stream of a ?nished high purity BuAcA and an overhead

Condensate Fomprising BuAcA BuOH> Water and light

(52) US. Cl. ........................................... .. 560/218- 560/205

ends .recychng most of the Overhead iondensate frFm the

(58)

a ?nishing fractionation Zone from Which is obtained a side

Field of Search .................................... .. 560/205, 218

(56)

?nishing Zone to the reaction Zone, feeding the remainder of

Such Condensate to a purge recovery Zone, Obtaining an

References Cited

overhead condensate from the purge recovery Zone Which

[)3 PATENT DOCUMENTS

separates into organic and aqueous phases each containing a

portion of light ends produced in the reaction, recycling a
portion of the organic phase as re?uX to the purge recovery

3,868,410
4O12439
4,280,010

2/1975 Horlenko et al. .................. .. 260/486

3/1977 Erpenbach et a1
260/486
7/1981 Erpenbach 6161.
.. 560/205

5 734 074

3/1998 Dockner et aL

560005

and the entire aqueous phase of the overhead condensate of

5,877,345 *

3/1999 Bauer 6161. ....................... .. 560/218

the purge reeevery Zone has the effect of preventing or

478147493

3/1989 Dougherty et a1

__ 560005

Zone and discarding the remainder The entire aqueous phase

of the overhead condensate of the ur e recover Zone is
p g
y

discarded. The discarding of a portion of the organic phase

retarding the buildup of light ends in the system.

FOREIGN PATENT DOCUMENTS
0 733 617

3/1996 (EP) ............................ .. C07C/67/08

12 Claims, 1 Drawing Sheet

U.S. Patent

Jan. 9, 2001

US 6,172,258 B1

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US 6,172,258 B1
1

PROCESS FOR THE PRODUCTION AND

PURIFICATION OF N-BUTYL ACRYLATE

n-butanol (BuOH) are reacted in tWo reactors in series, and

BACKGROUND OF THE INVENTION

(DBE), butyl acetate (BuAc), and BuOH. Such stream is

further separated in a splitter distillation column to provide
an overhead fraction containing DBE, BuAc, and BuOH,

the product separated in tWo distillation columns to produce

a stream comprising butyl acrylate (BuAcA), dibutyl ether

1. Field of the Invention

The invention relates to an improved process for the

and a bottoms fraction containing BuAcA and heavy ends

components, e. g., loW molecular Weight polymers of HAcA,

production and puri?cation of n-butyl acrylate.

2. Background Information and Description of Related

and/or BuAcA, and Michael addition products (heavies).

Art

n-Butyl acrylate (BuAcA) is a commodity chemical use

ful for the production of acrylic resins and polymers and

10

to further distillation in the presence of Water to separate

BuOH and BuAcA from lights containing DBE and BuAc,

copolymers for paint formulations, solvent coatings, textile

and leather ?nishes and adhesives and binders. One method
of synthesizing BuAcA is to react n-butanol (BuOH) With

acrylic acid (HAcA) in the presence of an acid catalyst, e.g.,

15

a sulfonic acid, in at least one reaction Zone to produce a

mixture of BuAcA, Water and several by-product impurities,

and subjecting the product mixture to puri?cation in at least
one distillation Zone, together With any of various schemes

of re?ux and recycle streams among the reaction Zone(s) and

distillation Zone(s) to obtain a BuAcA of relatively high
purity. When any of these processes are operated, loW

Which accomplishes an adequate disposal of light ends While

keeping the loss of BuAcA and unreacted BuOH and/or the
incremental cost of energy and equipment to a minimum, is

20

by reacting acrylic acid With n-butanol in liquid phase and

BRIEF SUMMARY OF THE INVENTION

In accordance With this invention, n-butyl acrylate

(BuAcA) is produced by a process comprising reacting,
generally amounts of n-butanol (BuOH) With acrylic acid
(HAcA) in a reaction Zone from Which an overhead vapor
25

mixture is WithdraWn comprising BuAcA, BuOH, Water and

light ends Which are organic by-product impurities having

boiling points near or someWhat beloW that of BuAcA, and

composed mainly of n-butyl acetate (BuAc) and di-n-butyl

30

ether (DBE). BuAcA, BuOH, and Water are removed by a

combination of binary and ternary aZeotropes. The vapor
mixture is condensed to form a substantially organic liquid

phase comprising a major portion of BuAcA and minor

portions of BuOH, Water and light ends, and a substantially
aqueous liquid phase comprising mainly Water and a minor
35

amount of BuOH. The organic phase is fed to a ?nishing

fractionation Zone, from Which a side stream of BuAcA

very desirable.

US. Pat. No. 4,012,439, issued Mar. 15, 1977 to Erpen

bach et al., discloses a process for producing n-butyl acrylate

With the BuOH and BuAcA being recycled to either or both

reactors and the lights being sent to Waste treatment, While
the bottoms fraction from the splitter distillation is recti?ed
in a butyl acrylate distillation column to separate BuAcA
product from heavies Which are recycled to either or both
reactors.

boiling impurities produced in the reaction Zone, i.e., those

having boiling points near or beloW BuAcA, such as butyl
acetate and dibutyl ether and characteriZed as light ends,
or lights must be systematically disposed of to prevent
them from interfering With the described reaction and com
promising the purity of the BuAcA. HoWever, this is often
difficult to accomplish, eg by purging an appropriate
stream, Without also losing an unduly large amount of
BuAcA product and unreacted BuOH, and/or incurring an
unfavorably large cost in energy consumption or puri?cation
equipment to prevent such loss. Thus, any improved process,

The overhead fraction from the splitter column is subjected

40

in contact With an acid cation exchanger as a catalyst. The

process utiliZes a single reaction Zone and three distillation

product is WithdraWn. Most of the overhead stream of the

?nishing fractionation Zone composed of a major portion of
the total of BuAcA and BuOH present and minor portions of
Water and light ends, is recycled to the reaction Zone.
HoWever, to prevent an undesirable buildup of light ends in
the system, a minor portion of such overhead stream is
purged and sent to a purge recovery fractionation Zone to

effect separation of light ends from the valuable BuAcA and

Zones.

US. Pat. No. 4,280,010, issued Jul. 21, 1981 to Erpen

bach et al., discloses a continuous process for making alkyl
acrylates free from ether by reacting a C1C4-alkanol in a
molar ratio of 1:1 to 1:2 in liquid phase at 80 to 130 C.
under 100760 mmHg in the presence of a catalyst. The

45

process employs a single reaction Zone and tWo distillation

50

Zones for separating the alkyl acrylate from unreacted

alkanol and ether by-product.
US. Pat. No. 4,814,493, issued Mar. 21, 1989 to Dough

BuOH in the purge stream.

The overhead vapors from the purge recovery fraction
ation Zone are condensed to form separate organic and

aqueous liquid phases, With each phase containing a portion

of the light ends produced in the system. The majority of the
light end impurities remain in the organic phase compared to
the aqueous phase. A portion of the organic phase and the

of Which is sent to a butanol recovery toWer, and a residue

stream Which is recycled to the reactor. A butanol stream

entire aqueous phase, are discarded such that the total

amount of light ends in such discarded streams is compa
rable to the amount of light ends produced in the reaction.
The remainder of the organic phase is recycled as re?ux to
the purge recovery Zone. Alternatively the overhead vapors
are condensed and forWarded to a receiving vessel, a portion
of the resultant stream is discarded and the remainder
recycled as re?ux to the purge recovery unit. By discard
What is meant is to remove the stream, or portion thereof,
from the reaction process. The stream may be further
processed for proper disposal or further treated for recovery

from the butanol recovery toWer is recycled to the reactor,

and reuse.

erty et al., teaches a process for the production of an n-butyl

acrylate by reaction of n-butanol With acrylic acid in the

55

presence of an esteri?cation catalyst and soluble manganese

or cerium. The system for carrying out the process includes
a reactor from Which a butyl acrylate reaction product is sent
to a ?nishing toWer Wherein the reaction product is separated
into a pure butyl acrylate stream, a volatiles stream a portion

60

and a residue stream from such toWer is removed from the

system.
South African Patent No. 9704628 issued Mar. 25, 1998,
discloses a process Wherein acrylic acid (HAcA) and

65

The residue from the purge recovery Zone, containing the

bulk of the BuAcA and BuOH in the purged portion of the
condensed overhead from the ?nishing Zone, and having a
reduced light ends content is recycled to the reaction Zone.

US 6,172,258 B1
3

The process of the invention accomplishes the prevention

of a buildup of light ends in the system While minimizing the
loss of BuAcA and unreacted BuOH, and keeping the cost

operating at a temperature, e.g., of about 150 to about 250

C. and a pressure, e.g., of about 80 to about 150 psig, Where
some of the polymers are converted to monomers. See

of energy and neW equipment to accomplish this purpose, at

a relatively loW level.

Horlenko, U.S. Pat. No. 3,868,410 for further discussion

regarding heavy end components. After a residence time of,

BRIEF DESCRIPTION OF THE DRAWING

e.g., about 1 to about 50 min, most of the heat treated residue

is recycled back to the reaction vessel, With a slip stream,
e.g., of about 5 to about 20 Wt % of the heat treated residue

The draWing is a schematic representation of a preferred

embodiment of the overall process of this invention.

being removed to a heavy ends removal distillation unit,

10

DETAILED DESCRIPTION OF THE

INVENTION

In the synthesis of n-butyl acrylate (BuAcA) in accor

dance With this invention, close to equimolar amounts of
acrylic acid (HAcA) and n-butanol (BuOH) are fed to the
reaction Zone together With an acid esteri?cation catalyst,

The organic phase of the overhead condensate from the

15

e.g., about 1 to about 5 Wt % based on the Weight of total

reaction mixture. EXamples of the esteri?cation catalyst

include alkyl- or arylsulfonic acid such as methanesulfonic,
benZenesulfonic or toluenesulfonic acid. HAcA and BuOH
are fed to the reaction Zone eg about 0.85 to about 1.3
moles of BuOH per mole of HAcA. Stoichiometric eXcess of

BuOH over HAcA is preferable to minimiZe the polymer

iZable free HAcA in the system, eg about 0.85 to about 1.3
moles of BuOH per mole of HAcA. To minimiZe polymer
iZation in the process, a polymeriZation inhibitor is prefer
ably also fed to such Zone and may be miXed With the HAcA.
Those of skill in the art Will appreciate the type and amount
of inhibitor necessary to achieve non-polymeriZation, said
type and amount being based on a variety of factors. The
inhibitor may be, for example, phenothiaZine or a phenolic

20

150 C. and a pressure, e.g., of about 50 to about 400

99.0 to about 99.99 Wt % is WithdraWn as a vapor side stream

from the ?nishing toWer, and overhead vapors comprising,

25

30

35

40

the base of the column comprising primarily loW molecular

Weight polymers of HAcA and BuAcA, and catalyst and
polymeriZation inhibitor. Also, remaining in the reactor are

immiscible phases, one being predominantly BuOH Which is

butanol recovery toWer as re?uX or discarded or recycled to

55

separated into tWo phases, a substantially organic phase

60

the reaction vessel. The residue from the toWer is composed

primarily of Water containing very little BuOH and is
discarded.
The purged portion of the ?nishing toWer overhead con
densate contains an amount of light ends Which, When
discarded, is suf?cient to prevent an undesirable buildup of
light ends in the system. HoWever, to minimiZe Wastage of
BuOH and HAcA utiliZed in the process, the purge stream is
distilled in the purge recovery toWer to separate a major

portion of BuOH and BuAcA from the light ends. More

speci?cally, the purge recovery toWer operates at a

vessel.

The residue from the reaction vessel comprising mainly of

loW molecular Weight polymers of HAcA and BuAcA, some
free HAcA, BuOH, and catalyst is fed to a heat treater

reaction vessel overhead condensate may be discarded. The

vapors from the top of the toWer are primarily a binary
aZeotrope of BuOH and Water Which is condensed into tWo

recycled to the reaction vessel and the other a solution of a

50 minor amount of BuOH in Water Which is recycled to the

DBE, secondary butyl acrylate (SBuAcA) and isobutyl

having a major portion of BuAcA, reduced amounts of
BuOH and Water, and the light ends, and a substantially
aqueous phase comprising mainly Water and BuOH. The
organic phase is sent to the ?nishing fractioniZation Zone
(the ?nishing toWer) and the aqueous phase to a butanol
recovery Zone (the butanol recovery toWer) Wherein the
BuOH is separated from the Water for recycle to the reaction

the reaction vessel. Here, greater than about 0 means at

least a small quantity, Which is large enough or suf?cient to
operate the purge recovery toWer. The residue from the
?nishing toWer contains a major amount of BuAcA and is
recycled to the reaction vessel.
The aqueous phase of the reaction vessel overhead con
densate containing, e.g., about 1 to about 10 Wt % of BuOH,
and about 90 to about 99 Wt % of Water, is fed to the butanol
recovery toWer operating at a temperature, e.g., of about 70
to about 120 C. and a pressure, e.g., of greater than about

0 to about 5 psig. Alternatively, the aqueous phase of the

45

pounds having someWhat loWer boiling points than BuAcA,

such as n-butyl acetate (BuAc), n-butyl propionate (BuPr),
acrylate (IBuAcA). The overhead vapors are condensed and

toWer are condensed and a portion of the condensate, e.g.,

about 0 to about 75, preferably about 5 to about 50 Wt % is
purged and sent to a purge recovery fractionation Zone (the

purge recovery toWer) With the remainder being recycled to

In an embodiment of the invention the esteri?cation of

some quantities of free HAcA and BuAcA. The reaction

vessel operates at a temperature, e.g., in the range of about
20 to about 150 C. and a pressure in the range of about 50
to about 400 mmHgA.
The overhead vapors from the reaction vessel consist
mainly of BuAcA, loWer amounts of BuOH and Water and
a minor amount of light ends, i.e. by-product organic com

e.g., about 10 to about 80, preferably about 35 to about 70

Wt % of BuAcA, e.g., about 10 to about 80, preferably about
25 to about 70 Wt % of BuOH, and e.g., about 1 to about 10
Wt % of light ends, are WithdraWn from the top of the
?nishing toWer. The overhead vapors from the ?nishing

HAcA With BuOH to produce BuAcA takes place primarily

in the base reaction portion of the reaction vessel With the
top portion of the vessel containing fractionation stages, eg
in the form of trays and bubble caps or packing, to separate
the bulk of the BuAcA and unreacted BuOH from residue at

reaction vessel comprises a major amount, e.g., about 80 to

about 95 Wt % of BuAcA, and minor amounts, e.g., about 5
to about 15 Wt % of BuOH, about 1 to about 3 Wt % Water,
about 1 to about 10 Wt % of light ends, and about 0.001 to
about 0.05 Wt % of HAcA, is fed to the ?nishing toWer, such
toWer operating at a temperature, e.g., of about 20 to about

mmHgA. Finished BuAcA having a purity of, e.g., about

compound such as a dihydroXybenZene or a mono-loWer

alkyl dihydroXybenZene, e.g. hydroquinone or its monom

ethyl or monoethyl ether.

operating at a temperature of about 125 to about 200 C. and

a pressure of about 100 to about 700 mmHgA. The volatiles
from the heavy ends removal unit are recycled to the
reaction vessel While the residue from such unit is discarded.

65

temperature, e.g., of about 30 to about 150 C., preferably

about 65 to about 110 C., a subatmospheric pressure of,
e.g., about 50 to about 500 mmHgA, preferably about 200 to
about 350 mmHgA. The primary feed to the purge recovery
toWer is the purged portion of the ?nishing toWer overhead

US 6,172,258 B1
5

condensate, described previously. Also entering the purge

recovery toWer is a portion of the substantially organic phase

signi?cant amount of BuOH and BuAcA and lesser amounts

of Water and light ends, are fed through line 19 to condenser

of the overhead condensate of the purge recovery toWer as

20, and the residue from toWer 15 containing primarily

BuAcA is recycled through line 21 to reaction vessel 1. The

re?ux, to be described in greater detail hereinafter.

diagram indicates stream 21 forWarded to the base of vessel

1. Those of skill in the art Will appreciate that this stream
may be forWarded to any location in vessel 1 as appropriate.
Most of the condensate from condenser 20 is recycled
through line 22 to reaction vessel 1. HoWever, a minor

The overhead vapors from the purge recovery toWer are

condensed and the condensate separated into organic and

aqueous phases, With the organic phase being, e.g., about 90
to about 99 Wt % of the total overhead stream and

containing, e.g., about 10 to about 60 Wt % of BuAcA, about

30 to about 70 Wt % of BuOH, about 3 to about 20 Wt % of

light ends, and about 5 to about 15 Wt % of Water, and the

aqueous phase being the remainder of the total overhead
containing, e.g., about 85 to about 98 Wt % of Water, about
2 to about 15 Wt % of BuOH, and generally less than about
1.0 Wt % of light ends. As previously mentioned, a portion
of the condensate organic phase, e.g., about 10 to about 80
Wt %, is recycled to the purge recovery toWer as re?ux, the
remainder being discarded, With the entire condensate aque
ous phase also being discarded.
Alternatively the overheard vapors are condensed and
forWarded to a receiving vessel, a portion of the resultant
stream is discarded and the remainder is recycled as re?ux
to the purge recovery unit. The composition of the stream
coming out of the receiving vessel is about 5 to about 60 Wt
% BuAcA, about 10 to about 70 Wt % BuOH, about 3 to
about 20 Wt % light ends, and about 10 to about 50 Wt %

10

15

BuAcA and BuOH and largely stripped of light ends is

recycled through line 30 to reaction vessel 1. The condensate
from condenser 29 is fed through line 31 to separator 32

Where it separates into organic and aqueous phases. Apart of

the organic phase is recycled through line 34 to purge
recovery toWer 25 as re?ux While the remainder is With

draWn through line 35 and discarded, With the entire aqueous

phase also being discarded through line 38. The foregoing

25

The purge recovery toWer is operated such that the total

amount of the light ends in the discarded portion of the
overhead condensate organic phase and the entire discarded
aqueous phase is comparable to the amount of light ends

discarding of a portion of the organic and the entire aqueous

phase from separator 32 act to keep the light ends of the
overall system in balance.
The residue from vessel 1 comprising mainly loW molecu
lar Weight polymers of HAcA and/or BuAcA and Michael
addition products is fed through line 39 to heat treater 40
Where part of the heavies are converted to HAcA and/or
BuAcA. Most of the heat-treated stream from heat treater 40

containing increased amounts of HAcA and/or BuAcA is

recycled through line 41 to reaction vessel 1. HoWever, to
prevent a build up of heavy ends in the system, a slipstream

produced in the system, so that there is no undesirable

buildup of light ends in the system.

35

about 10 to about 80 Wt % of BuOH, as Well as relatively

smaller amounts of Water and light ends, and is recycled to

the reaction vessel.
The process of the invention may be further described
With reference to the draWing, Which is a schematic diagram
of a preferred embodiment of the inventive process.
Into reaction vessel 1 are fed n-butanol (BuOH), acrylic
acid (HAcA) and an acid esteri?cation catalyst such as

methanesulfonic acid (MSA) through lines 2, 4, and 5

respectively. A polymeriZation inhibitor is also typically
employed throughout the process, and added at appropriate

to purge recovery toWer 25. The overhead vapors from purge

recovery toWer 25 containing signi?cant amounts of BuOH,

Water, and light ends are fed through line 28 to condenser 29.
The residue of toWer 25 containing signi?cant amounts of

Water.

The residue composition from the purge recovery toWer

contains from about 10 to about 80 Wt % of BuAcA and e.g.,

portion of the condensate is purged and fed through line 24,

from the heat treater 40 is fed through line 42 to a heavy ends

removal unit 44. The vapors from unit 44 containing a
signi?cant amount of HAcA and/or BuAcA are condensed
and recycled through line 45 to reaction vessel 1 While the
residue from unit 44 is WithdraWn through line 46 and
discarded.

Aqueous phase 12 from separator 10 containing a minor

but signi?cant amount of BuOH is fed through line 48 to an

45

intermediate point of butanol recovery toWer 49. Optionally,

stream 48 may be discarded. The overhead vapors compris
ing an aZeotrope of a major portion BuOH With Water is fed
through line 50 to condenser receiver 51 Where it separates
into an organic phase comprising an increased amount of

BuOH Which is recycled to reaction vessel 1 through line 52,

and an aqueous phase comprising some BuOH Which is
either fed as re?ux to butanol recovery toWer 49 through line

locations and concentrations. Those of skill in the art Will

recogniZe appropriate locations and concentrations to uti

liZe. Conditions of temperature and pressure are maintained
in reaction vessel 1 to cause a reaction of HAcA With BuOH

54 or alternatively, is discarded. The residue containing

predominantly Water is WithdraWn through line 55 and

present in some excess to form n-butyl acrylate (BuAcA)

and Water, and small amounts of various by-products such as

discarded.
What is claimed is:

1. A process for producing n-butyl acrylate (BuAcA)

light ends including n-butyl acetate (BuAc) and di-n-butyl

ether (DBE) and heavy ends such as loW molecular Weight
polymers of HAcA and BuAcA. Vapors of the more volatile

55

comprising:
(a) esterifying acrylic acid (HAcA) With n-butanol

compounds present including BuOH, BuAcA, Water and

(BuOH) in a reaction Zone from Which an overhead

light ends rise into the fractioniZation Zone situated imme

diately above the reaction Zone of reaction vessel 1. These
vapors are forWarded through line 6 into condenser 8 from

vapor mixture is WithdraWn said mixture containing

BuAcA and BuOH, Water and light ends components,

Which the liquid condensate ?oWs through 9 into separator

10 Where the condensate is separated into immiscible sub
stantially organic phase 11 and aqueous phase 12. The

or someWhat loWer than that of BuAcA,

said light ends components having boiling points near

(b) condensing said vapor mixture to form an organic

organic phase condensate containing predominately BuAcA

is fed through line 14 to ?nishing toWer 15 from Which high
purity ?nished BuAcA is WithdraWn as a sidestream through
line 18. The overhead vapors from toWer 15 containing

65

phase containing BuAcA, BuOH, light ends, and an

aqueous phase containing predominantly Water and
BuOH,
(c) feeding said organic phase to a ?nishing fractionation
Zone,

US 6,172,258 B1
8

7
(d) WithdraWing BuAcA from said ?nishing Zone,
(e) WithdraWing and condensing the overhead vapors

about 150 C., and a pressure in the range of about 50 to

about 500 mmHgA.

7. The process of claim 6 Wherein said range of tempera

from said ?nishing Zone comprising a major portion of

the total of BuAcA and BuOH present and minor

tures in the purge recovery Zone is about 65 to about 110 C.

and said range of pressures in said Zone is about 200 to about

portions of Water and light ends,

(f) recycling a major portion of said overhead condensate

350 mmHgA.
8. The process of claim 1 Wherein said organic phase of

of the ?nishing Zone to the reaction Zone,

(g) feeding a minor portion of said overhead condensate

of the ?nishing Zone, to a purge recovery fractionation

10

Zone,

(h) condensing the overhead vapors of said purge recov

ery Zone comprising signi?cant amounts of BuOH,
BuAcA, Water and light ends to form an organic phase

containing signi?cant amounts of BuOH, BuAcA, and

the overhead condensate of the purge recovery Zone is about

90 to about 99 Wt % of the total condensate and contains
about 10 to about 60 Wt % of BuAcA, about 30 to about 70
Wt % of BuOH and about 5 to about 20 Wt % light ends, With

about 10 to about 80 Wt % of said organic phase being

recycled to said purge recovery Zone as re?uX and the
15

remainder being discarded.

lights ends and an aqueous phase containing some

9. The process of claim 8 Wherein said aqueous phase of

BuOH, BuAcA and light ends,

(i) recycling a portion of said organic phase of the

the overhead condensate of the purge recovery Zone contains

about 2 to about 15 Wt % of BuOH, and less than about 1.0

overhead condensate from the purge recovery Zone

back to said purge recovery Zone as re?uX,

Wt % of light ends, the amount of light ends in the discarded

portion of said organic phase and in the discarded aqueous

discarding the remainder of said organic phase, and

(k) discarding the entire aqueous phase of the overhead

phase of the overhead condensate of the purge recovery Zone

being such as to prevent or retard the buildup of light ends
in the system.
10. The process of claim 1 Wherein the residue from said
purge recovery Zone comprising a major amount of the total

condensate of the purge recovery Zone.

2. The process of claim 1 Wherein said overhead conden

sate from the ?nishing Zone comprises about 10 to about 80
Wt % of BuAcA, about 10 to about 80 Wt % of BuOH and
about 1 to about 10 Wt % of light ends.
3. The process of claim 2 Wherein said range of BuAcA
is about 35 to about 70 Wt % and said range of BuOH is
about 25 to about 70 Wt %.
4. The process of claim 1 Wherein from greater than about
0 to about 75 Wt % of said overhead condensate from the
?nishing Zone is fed to said purge recovery Zone With the

of BuAcA and BuOH present and largely stripped of light

ends is recycled to said reaction Zone.
11. The process of claim 1 Wherein the overhead vapors
of the purge recovery Zone are condensed and forWarded to

a receiving vessel, Wherein a portion of the resultant stream

from the receiving vessel is discarded and the remainder is
recycled as re?uX to the purge recovery Zone, Wherein the
amount to be discarded is suf?cient to prevent or retard the

remainder of said condensate being recycled to the reaction

Zone.

5. The process of claim 4 Wherein the amount of said

overhead condensate from the ?nishing Zone fed to the purge
recovery Zone is about 5 to about 50 Wt %.
6. The process of claim 1 Wherein said purge recovery
Zone operates at a temperature in the range of about 30 to

build up of light ends in the system.

35

12. The process of claim 11 Wherein the resultant stream

contains about 5 to about 60 Wt % BuAcA, about 10 to about
70 Wt % BuOH, about 3 to about 20 Wt % light ends, and
about 10 to about 50 Wt % Water.