USOO8940932B2

(12) United States Patent

(10) Patent No.:

Shimizu
(54)

(45) Date of Patent:

PROCESS FOR PRODUCING ACETIC ACID

(56)

References Cited

4,766,258 A
5,625,095 A

(73) Assignee: Daicel Corporation, Osaka-shi (JP)

Notice:

Jan. 27, 2015

US. PATENT DOCUMENTS

(75) Inventor: Masahiko Shimizu, Tokyo (JP)

(*)

US 8,940,932 B2

6,143,930 A
6,458,996 B1

Subject to any disclaimer, the term of this

patent is extended or adjusted under 35

8/1988 Komatsu et a1.

4/1997 Miura et a1.

11/2000 Singh et a1.

10/2002 Muskett

FOREIGN PATENT DOCUMENTS

U.S.C. 154(b) by 169 days.

(21) Appl. No.:

13/825,266

(22) PCT Filed:

Sep. 27, 2011

(86)

PCT/JP2011/072059

PCT No.:

EP
JP
JP
JP
JP
JP
JP
JP

2 653 458
61-267533
63-290835
4-266843
8-67650
2001-300203
2007-224040
2010-106045

A1
A
A
A
A
A
A
A

10/2013
11/1986
11/1988
9/1992
3/1996
10/2001
9/2007
5/2010

OTHER PUBLICATIONS

371 (0X1)
(2), (4) Date:

Extended European Search Report issued Sep. 11, 2014, in European

Mar. 20, 2013

Patent Application No. 118305267

(87)

Faanes, A. and S. Skogestad., Buffer Tank Design for Acceptable

Control Performance, Industrial & Engineering Chemistry
Research (Apr. 8, 2003), vol. 42, N0. 10, pp. 2198-2208.
International Search Report, issued in PCT/JP2011/072059, dated

PCT Pub. No.: WO2012/046593

PCT Pub. Date: Apr. 12, 2012

(65)

US 2013/0303800 A1

(30)

Primary Examiner * Yevegeny Valenrod

(74) Attorney, Agent, or Firm * Birch, Stewart, Kolasch &

(JP) ............................... .. 2010-226664

Int. Cl.
co 70 51/12
co 70 51/44

(52)

ability and Written Opinion issued May 16, 2013, in PCT Interna
tional Application No. PCT/JP2011/072059.

Nov. 14,2013

Foreign Application Priority Data

Oct. 6, 2010

(51)

Jan. 31, 2012.

English translation of International Preliminary Report on Patent

Prior Publication Data

(2006.01)
(2006.01)

US. Cl.
CPC ............... .. C07C 51/12 (2013.01); C07C 51/44

(2013.01)
USPC

(58)

........................................................ ..

562/519

Field of Classi?cation Search

None

See application ?le for complete search history.

Birch, LLP
(57)
ABSTRACT
A process for stably producing high purity acetic acid com
prising a condensation step for condensing and temporarily
holding the lower boiling component in a decanter and dis
charging from the decanter; and a step for separating the
lower boiling component discharged from the decanter into
acetaldehyde and a liquid residue and recycling the liquid
residue to the reaction system. In the condensation step, the
amount of the lower boiling component to be held is con
trolled based on the ?uctuating ?ow rate of the lower boiling
component to be fed to the decanter.

14 Claims, 2 Drawing Sheets

US. Patent

Jan. 27, 2015

US 8,940,932 B2

Sheet 1 0f 2

wowmm/|
(NM:2/N

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EE?F

mm?
m?

pm?

US. Patent

Jan. 27, 2015

Sheet 2 0f2

US 8,940,932 B2

2
Fag

12b

CO

met-hanol>

US 8,940,932 B2
1

PROCESS FOR PRODUCING ACETIC ACID

iodide phase. The concentration of the carbonyl impurity in

TECHNICAL FIELD

the organic stream to be recycled to the carbonylation reactor

is still high, and it is dif?cult to remove the carbonyl impurity
suf?ciently. Moreover, the process described in this patent

The present invention relates to a process for stably pro

document requires removal of the nitrogenous compound.

Japanese Patent Application Laid-Open Publication No.

ducing acetic acid by carbonylation of methanol in the pres

ence of a metal catalyst (such as a rhodium catalyst) and

8-67650 (JP-8-67650A, Patent Document 2) discloses a pro

methyl iodide.

cess for producing high-purity acetic acid, comprising allow

ing methanol to continuously react with carbon monoxide in
the presence of a rhodium catalyst, an iodide salt, and methyl

BACKGROUND ART

iodide, wherein the reaction is carried out by removing acetal

Various industrial production processes of acetic acid have

been known. Among others, an industrially excellent process
includes a process which comprises continuously allowing

dehyde from a process liquid being circulated into a reactor to

maintain the acetaldehyde concentration in the reaction mix
ture at 400 ppm or lower. This patent document forcuses
attention on that most of the impurities are formed in the
reaction system and the formation of such impurities is due to

methanol to react with carbon monoxide with the use of a

rhodium catalyst and methyl iodide in the presence of water to

give acetic acid. Moreover, recently improvement in reaction

the by-product acetaldehyde produced in the reaction system.

conditions and catalysts was investigated, and an industrial

process for producing acetic acid with a highly ef?cient pro

duction has been developed by addition of a catalyst stabilizer

20

(such as an iodide salt) and the reaction under a low water

obtained.
In addition, this patent document discloses, relating to a

content condition compared with the conventional condition.

This process enables by-products including carbon dioxide or
propionic acid to be reduced because of lowered water con

tent in the reaction mixture. In the reaction mixture, however,

there are by-products (impurities) in minor quantities other
than these components, for example, a carbonyl compound

25

product mixture containing acetic acid and an overhead con

taining methyl acetate and methyl iodide, and recirculating

30

iodide, such as ethyl iodide, butyl iodide, or hexyl iodide). As

the production of acetic acid increases, the production of the
impurities increases, which deteriorates the quality of acetic
acid. For example, in a quality test by which the very minute
amounts of the reducing impurities present in acetic acid are
checked, which is called a permanganate-reducing substance

the resulting overhead into the reactor, wherein the overhead

or a carbonyl impurity (particularly acetaldehyde) conden
sate thereof is allowed to contact with water to separate an

organic phase containing methyl acetate and methyl iodide

35

and an aqueous phase containing the carbonyl impurity, and

the organic phase is recirculated into the reactor. Moreover,
this document discloses that a concrete method for obtaining

test (permanganate time), impurities having very slight con

methyl iodide from the carbonyl impurity condensate prefer

centrations, which are hard to quantitatively determine even

with todays highly advanced instrumental analysis, can be

detected, and these impurities lead to deterioration of product

process for producing acetic acid while removing acetalde

hyde, that the process comprises separating the reaction mix
ture into a volatile phase containing acetic acid, methyl
acetate and methyl iodide and a low-volatile phase containing
the rhodium catalyst, distilling the volatile phase to obtain a

(e.g., acetaldehyde, butyraldehyde, crotonaldehyde, 2-ethyl

crotonaldehyde, and an aldol condensation product thereof),
an organic iodide (e.g., an alkyl iodide other than methyl

Therefore, the concentration of acetaldehyde in the reaction

system is reduced to decrease the carbonyl compound or the
organic iodide, and, as s result, high-purity acetic acid can be

ably includes a method which comprises separating an acetal

dehyde liquid containing methyl iodide from the process

40

liquid by distillation, and selectively extracting the resulting

quality. Moreover, some of these impurities exert a bad in?u

acetaldehyde liquid with water.

ence in connection with use of acetic acid. For example, in a

Incidentally, this document does not disclose that the ?ow

rate of the overhead is controlled in recirculating the overhead

process for producing vinyl acetate from ethylene and acetic

acid, it is known that the impurities deteriorate a palladium
series catalyst used in the process.
Unfortunately, the carbonyl compound or the alkyl iodide

into the reactor.

45

RELATED ART DOCUMENTS

is hard to remove suf?ciently by ordinary means, such as

distillation, because the boiling point of the carbonyl com

pound or the alkyl iodide is close to a boiling point of an
iodide catalyst accelerator, or other reasons.
Thus, for example, the treatment of crude acetic acid con
taining these minute impurities with ozone or an oxidiZing
agent has been developed. Because the treatment has the
limitation on the concentrations of impurities to be treated,

the carbonyl compound and the organic iodide cannot be

Patent Documents
50

Patent Document 1: JP-4-266843A (Claims)

Patent Document 2: JP-8-67650A (Claims)
SUMMARY OF THE INVENTION

55

Problems to be Solved by the Invention

removed ef?ciently.
Meanwhile, in a continuous reaction process, removal of a

It is therefore an object of the present invention to provide

a process for stably producing acetic acid while ef?ciently

carbonyl compound in a process circulation liquid is also

being attempted. For example, Japanese Patent Application

Laid-Open Publication No. 4-266843 (JP-4-266843A, Patent

removing acetaldehyde.
60

Document 1) discloses a process for removing a carbonyl

impurity, which comprises allowing a methyl iodide stream to

Another object of the present invention is to provide a

process for producing acetic acid while recycling methyl

iodide as a catalyst with a high ef?ciency.

be recycled to a carbonylation reactor to contact with an

amino compound that is allowed to react with a carbonyl

impurity to form a water-soluble nitrogenous derivative,

separating the resulting organic methyl iodide phase from the

resulting aqueous derivative phase, and distilling the methyl

Means to Solve the Problems

65

In a series of continuous acetic acid production processes

with a catalyst system containing a metal catalyst, a halide

US 8,940,932 B2
3

salt and methyl iodide, the inventor of the present invention

investigated a process for removing acetaldehyde from a

collection step for continuously feeding a distillation column

with the lower boiling point component (2A), and separating

lower boiling point component (an overhead) which is

a lower boiling point component (or an overhead or a ?rst

obtained of ter separation of a stream containing acetic acid

overhead) (3A) containing methyl iodide and by-product

and at least contains methyl iodide and acetaldehyde, collect

acetaldehyde and a stream (3B) containing acetic acid to

collect acetic acid; a condensation step for condensing (con

ing a useful component (such as methyl iodide) ef?ciently,

densing by cooling) and temporarily holding (storing) the

and recycling the useful component to the reaction system or

others. The inventor found that direct removal of acetalde
hyde from the overhead by distillation or other means actually
made it di?icult to stably operate the process.
Speci?cally, in order to remove acetaldehyde from the

lowerboiling point component (3A) (orpart of all of the lower

boiling point component (3A)) in a decanter (a decanter appa
ratus, a storage vessel) [or holding the condensed component
(condensate)] and discharging the lower boiling point com
ponent (3A) from the decanter [or discharging the lower

overhead, the following steps are required: the overhead is

condensed and temporarily retained in a decanter, and further
the condensed overhead (or overhead condensate) is fed from
the decanter to an acetaldehyde separation process (for
example, a distillation process). Through the series of con

boiling point component (3A) for feeding the component

(3A) to a separation and recycling step or subjecting the
component (3A) to acetaldehyde separation]; and a separa
tion and recycling step for separating the condensed lower

boiling point component (3A) [or the lower boiling point

tinuous production steps, the ?ow rate of the overhead fed to

the decanter usually ?uctuates with the pres sure ?uctuation in
the process. However, since the decanter has an allowable

capacity limit, direct feeding of the overhead causes the ?uc

tuation of the liquid level in the decanter with the ?ow rate
?uctuation of the overhead, and the ?uctuation of the liquid
level sometimes hinders stable operation of the process

20

component (3A) discharged from the decanter] [or a con

densed component (3A') in the lower boiling point compo
nent (3A)] into acetaldehyde and a liquid residue (or residual

liquid) and recycling (or circulating) the liquid residue, e.g.,

recycling to at least one step from the reaction step (or the
reactor or the reaction system) to the acetaldehyde-separation
step; wherein in the condensation step, the amount to be held

depending on the extent of the ?uctuation. In contrast, an

overhead so as to correspond to the ?ow rate ?uctuation

of the lower boiling point component (3A) [or the condensed

component (3A') in the lower boiling point component (3A)]

thereof for the purpose of reducing the ?uctuation of the

liquid level in the decanter cannot su?iciently ease (or
absorb s) the ?ow rate ?uctuation of the overhead fed from the

lower boiling point component (3A) [or the condensed com

ponent (3A') in the lower boiling point component (3A)] to be

attempt to feed the acetaldehyde separation process with the

decanter in the acetaldehyde separation process. Thus, the

separation of acetaldehyde is sometimes insuf?cient
(whereby the concentration of acetaldehyde in the reaction
system is increased), or an acetaldehyde separation apparatus
(such as a distillation column) sometimes fails to be operated
stably. Moreover, since the ?ow rate ?uctuation of the over
head cannot be moderated in the acetaldehyde separation

25

is adjusted or controlled based on a ?uctuating ?ow rate of the

30

fed to the decanter.

According to the production process of acetic acid, the

amount of the lower boiling point component (3A) to be fed
to the decanter signi?cantly ?uctuates in the process opera
35

tion (or throughout the whole process). For example, with

respect to the ?uctuation (or change or variation), assuming
that the average ?ow rate of the lower boiling point compo
nent (3A) to be fed to the decanter is 100 in terms of liquid

process, the liquid level in the decanter (further the pre-step)

?uctuates after all.

(condensate) volume, the ?ow rate of the lower boiling point

Accordingly, the inventor of the present invention made

intensive studies to achieve the above objects and ?nally

component (3A) to be fed to the decanter may be about 80 to

40

120 in the process operation.

A concrete method for adjusting (or controlling) the
amount of the lower boiling point component (3A) to be held
includes, for example, (1) a method in which the lower boil

45

of the amount or liquid level of the lower boiling point com

ponent (3A) to be held in the decanter may be inhibited (or
substantially kept constant) and/or (2) a method in which a
decanter having a buf fering function is used as the decanter
to ease (or diffuse) the ?uctuation of the amount of the lower

50

boiling point component (or condensate) (3A) fed inside the

found that, by (i) circulating part (a portion) of the condensed

overhead to be fed to the decanter to the reaction system

without sending to the acetaldehyde separation process or (ii)

feeding the overhead from the decanter to the acetaldehyde
separation process through the buffer tank, the amount of the

ing point component (3A) is discharged so that the ?uctuation

overhead to be stored in the decanter is adjusted or controlled

depending on the ?uctuation of the feed amount of the over
head, and then the amount of the overhead to be fed from the

decanter to the acetaldehyde separation process is adjusted or

controlled; in this manner, a series of acetic acid production

processes, comprising removing acetaldehyde and collecting

decanter.

methyl iodide, is carried out stably and ef?ciently. The

According to the method (1), for example, in the conden

sation step, assuming that each of the average liquid level (or

present invention was accomplished based on the above ?nd

ings.
That is, the present invention includes a process (a closed

average amount) and the average interface level of the lower

55

process) for producing acetic acid, which comprises the fol

lowing steps: a reaction step for continuously allowing
methanol to react with carbon monoxide in the presence of a

catalyst system comprising a metal catalyst (e.g., a rhodium

catalyst), a halide salt (e. g., an iodide salt), and methyl iodide

60

boiling point component (3A) to be held in the decanter is

100, the liquid level (or average amount) and/ or interface
level of the lower boiling point component (3A) to be held in
the decanter may be adjusted [speci?cally, the lower boiling
point component (3A) may be discharged from the decanter
to adjust the liquid level] to about 90 to 110 (for example,
about 95 to 105) in the process operation. The liquid level

in a carbonylation reactor; a ?ash evaporation step for con

tinuously feeding a ?asher (or an evaporator) with a reaction

means a height of the contact surface of the condensed lower

mixture from the reactor and separating a lower boiling point

boiling point component (3A) with gas (gas phase) in the

component (2A) (or a volatile component (2A)) containing

product acetic acid and methyl acetate and a higher boiling

point component (2B) (or a low-volatile component (2B))

containing the metal catalyst and the halide salt; an acetic acid

65

decanter. When the condensed lower boiling point compo

nent (3A) is separated into two phases (upper phase and lower
phase), the interface level means a height of the boundary
between two phases (or a height of the lower phase). Thus the

US 8,940,932 B2
5

concept of the interface level is used when the lower boiling

decanter, and the upper layer and/ or the lower layer may be

point component (3A) undergoes layer separation (phase

separation).

may be circulated as a single phase without separation of the

circulated. Further, the lower boiling point component (3A)

Moreover, according to the method (2), in the condensation

lower boiling point component (3A) into two layers.

step, a decanter having a buffering function may be used as

For the method (b), the retention time of the lower boiling

the decanter. In particular, the retention time (or holding time)

of the lower boiling point component (3A) [or the condensed
component (3A') in the lower boiling point component (3A)]

point component (3A) in the storage vessel having a buffering

function may be not less than 0.5 minutes (for example, not
less than 1 minute). Moreover, in the method (b), the total
time of the retention time of the lower boiling point compo

in such a decanter may be regulated so as to be not less than

1 minute (e.g., not less than 3 minutes). Use of the decanter

nent (3A) in the decanter and the retention time of the lower

which allows such a su?icient retention time can ef?ciently

ease the ?ow rate ?uctuation of the lower boiling point com

boiling point component (3A) in the storage vessel may be not

less than 1.5 minutes (for example, not less than 2 minutes).
For the method (c), typically, a decanter having a buffering

ponent (3A) [or the condensed component (3A') in the lower

boiling point component (3A)] in the decanter.
According to the present invention, in order to carry out the
whole process stably, in the condensation step the amount of
the lower boiling point component (3A) to be held may usu
ally be adjusted or controlled based on the ?uctuation of the
?ow rate of the lower boiling point component (3A) to be fed
to the decanter, and further the amount of the lower boiling

function is used as the decanter, and the retention time of the

lower boiling point component (3A) in the decanter may be

not less than 1 minute.
The methods (a) to (c) may be carried out alone or in

combination (for example, at least the method (a) or the

method (b)).
20

point component (3A) [or the condensed component (3A') in

the lower boiling point component (3A)] to be fed to the
separation and recycling step may be adjusted or controlled.
Speci?cally, in the condensation step, the amount of the lower
boiling point component (3A) to be fed to the separation and

25

recycling step may be adjusted so as to be constant or almost

constant (or substantially be kept constant) [for example,

assuming that the average ?ow rate of the lower boiling point
component (3A) is 100, the ?ow rate of the lower boiling
point component (3A) to be fed to the separation and recy
cling step may be adjusted to 90 to 110 (for example, 95 to

methyl iodide by distillation, and recycling the higher boiling

point component (4B) as a liquid residue [for example, at
30

least one selected from the group consisting of the reaction

least one member selected from the group consisting of the

reaction system (reactor or reaction step), the acetic acid

105) in the process operation].

Representative examples of the method for adjusting or
controlling the amount of the lower boiling point component
(3A) to be fed to the separation and recycling step include at
least one selected from the following methods (a), (b), and
(c): (a) a method for circulating part of the lower boiling point
component (3A) discharged from the decanter to a step dif
ferent from the separation and recycling step [for example, at

According to the present invention, not only removal of

acetaldehyde but also collection (recycling) of methyl iodide
is e?iciently achieved. For example, the separation and recy
cling step may comprise feeding the acetaldehyde distillation
column with the lower boiling point component (3A), sepa
rating a lower boiling point component (4A) (or a second
overhead (4A)) containing acetaldehyde and a higher boiling
point component (4B) (or a bottom stream (4B)) containing

35

collection step (or distillation column), and the acetaldehyde

removal column].
Moreover, according to the present invention, the liquid
residue separated in the separation and recycling step may be
recycled while reducing the ?uctuation of the ?ow rate of the

liquid residue. Speci?cally, in the separation and recycling

step, the liquid residue may be recycled through a storage
vessel having a buffering function.
40

The above-mentioned lower boiling point component (4A)

system (reactor or reaction step) and the acetic acid collection

sometimes contains methyl iodide which cannot be sepa

step (or distillation column), particularly at least the reaction

system (or reactor) or reaction step]; (b) a method for feeding
the separation and recycling step with the lower boiling point
component (3A) discharged from the decanter through a stor
age vessel having a buffering function; and (c) a method for
adjusting the amount of the lower boiling point component
(3A) to be discharged from the decanter to keep constant (or
almost constant, for example, assuming that the average ?ow
rate of the lower boiling point component (3A) to be dis

rated. Thus, according to the present invention, when the

45

lower boiling point component (4A) also contains methyl

iodide, in the separation and recycling step methyl iodide may
be collected from the lower boiling point component (4A) for
recycling [e.g., for recycling to a step from the reaction sys
tem to the acetaldehyde separation, for example, recycled to
at least one member selected from the group consisting of the

reaction system (reactor or reaction step), the acetic acid

50

charged from the decanter is 100, the amount of the lower

boiling point component (3A) to be discharged from the

collection step (or distillation column), and the acetaldehyde

distillation column].
Throughout this description, the term lower boiling point

decanter in the process operation is adjusted to 90 to 1 10 (for

component (3A) in the condensation step and the steps fol

example, 95 to 105)).
For the method (a), in the condensation step, the amount (or
?ow rate) of the lower boiling point component (3A) to be fed
to the separation and recycling step may be adjusted by cir
culating part of the lower boiling point component (3A) dis

lowing the condensation step means a condensed component

55

acid collection step. The condensed component sometimes

refers to as the term condensed component (3A'), conden
sate (3A') or the like to be distinguished from the lower

charged from the decanter to a step different from the sepa

ration and recycling step. In the method (a), not less than 10%,
preferably not less than 20% (for example, about 20 to 90%),
of the average ?ow rate of the lower boiling point component
(3A) to be fed to the decanter may be circulated (or recycled),
in particular, not less than 40% (for example, about 40 to
90%) of the average ?ow rate may be circulated. Moreover, in

the method (a), the lower boiling point component (3A) may
be separated into an upper layer and a lower layer in the

(a condensate or a liquid component) in the lower boiling

point component (or overhead) (3A) separated in the acetic

60

boiling point component (3A).

Effects of the Invention

65

According to the present invention, acetic acid (acetic acid

with a high purity) can stably be produced while e?iciently
removing acetaldehyde by adjusting the amount of the lower
boiling point component to be stored in the decanter in

US 8,940,932 B2
7

response to the ?uctuation of the feed amount of the lower

extraction apparatus or extractor 8 for separating acetalde

boiling point component containing methyl iodide and acetal

dehyde. Moreover, according to the present invention, since

hyde from the lower boiling point component (4A) by extrac

tion (for example, water extraction) to recycle methyl iodide;

acetaldehyde can be separated from the lower boiling point

and various lines for feeding or circulating each component to

these apparatus.
Hereinafter, the process shown in FIG. 1 will be explained

component ef?ciently and reliably, acetic acid can be pro

duced while highly e?iciently recycling the co-catalyst,

methyl iodide, separated from the lower boiling point com
ponent.

in more detail.

To the reactor 1, methanol as a liquid component is con

tinuously fed at a predetermined rate, and carbon monoxide

as a gaseous reactant is continuously fed. Moreover, to the

BRIEF DESCRIPTION OF DRAWINGS

reactor 1, a catalyst mixture (liquid catalyst mixture) contain

ing a carbonylation catalyst system [a catalyst system com

FIG. 1 is a diagram for explaining a production process (or

production apparatus) of acetic acid in accordance with an
embodiment of the present invention.
FIG. 2 is a diagram for explaining a production process (or
production apparatus) of acetic acid in accordance with
another embodiment of the present invention.

prising a main metal catalyst component (e.g., a rhodium

catalyst) and a co-catalyst (e.g., lithium iodide and methyl

iodide)] and water may be fed. Further, a stream (e. g., in the

form of liquid) containing lower boiling point component(s)

or higher boiling point component(s) from the succeeding
step(s) is fed to the reactor 1 through a line 13 and/or a line 40.

Then, inside the reactor 1, a liquid-phase reaction system

DESCRIPTION OF EMBODIMENTS
20

Hereinafter, the present invention will be explained in

containing the reactant and the higher boiling point compo

nent such as the metal catalyst component (e.g., a rhodium

detail with reference to the drawings. FIG. 1 is a diagram (a

catalyst and lithium iodide) is in equilibrium with a vapor

?ow sheet, a schematic process drawing, or a schematic plant

phase system comprising carbon monoxide, by-products by

layout drawing) for explaining a production process (or pro

duction apparatus) of acetic acid in accordance with an
embodiment of the present invention.
The embodiment of FIG. 1 shows a continuous process (or

apparatus) for producing acetic acid from a liquid reaction

medium (or reaction mixture) generated by a continuous car
bonylation reaction of methanol with carbon monoxide in the
presence of a catalyst system comprising a rhodium catalyst

the reaction (hydrogen, methane, carbon dioxide), and a

25

vaporized lower boiling point component (e.g., methyl

iodide, acetic acid as a product, and methyl acetate), and a

carbonylation reaction of methanol proceeds. In order to keep

the inner pressure of the reactor 1 (e.g., reaction pressure,

carbon monoxide partial pressure, and hydrogen partial pres

30

as a metal catalyst and a co-catalyst [lithium iodide as a halide

sure) constant, a vapor may be withdrawn and discharged

from the top of the reactor 1. Further, the vapor withdrawn
from the reactor 1 may be cooled by a heat exchanger to give

tion of methanol; a ?asher 2 for separating a lower boiling

a liquid component (containing acetic acid, methyl acetate,

methyl iodide, acetaldehyde, water, and others) and a gaseous
component (containing carbon monoxide, hydrogen, and oth
ers). The resulting liquid component may be recycled to the
reactor 1 (not shown), and the resulting gaseous component

point component or volatile phase (2A) containing product

(waste gas) may be discharged.

salt and methyl iodide], as well as acetic acid, methyl acetate,

and a ?nite amount of water.

The process (or production apparatus) comprises a reactor

(reaction system) 1 for carrying out the carbonylation reac

35

To the reactor 1, if necessary, hydrogen may be fed in order

acetic acid, methyl iodide, methyl acetate, and water and a

higher boiling point component or low-volatile phase (2B)

40

to increase the catalytic activity. Hydrogen may be fed

45

together with carbon monoxide or may be fed separately.

Moreover, since the reaction system is an exothermic reaction
system that accompanies heat generation, the reactor 1 may
be equipped with a heat-removable (or heat-removing) unit or
a cooling unit (e.g., a jacket) for controlling a reaction tem

containing the rhodium catalyst and lithium iodide from a

liquid reaction medium (or a reaction mixture or a reaction

solution) which contains acetic acid generated by the reac

tion; a splitter column 3 for separating a lower boiling point

component or overhead (a ?rst overhead) (3A) containing

methyl iodide, methyl acetate, by-product acetaldehyde,

perature.

water, and others, a stream or acetic acid phase (3B) contain

ing acetic acid as a side stream, and a higher boiling point

Components contained in the reaction mixture (crude reac

tion liquid) generated in the reactor 1 may include acetic acid,
a lower boiling point component or lower boiling point impu
rity having a boiling point lower than that of acetic acid (e. g.,

component (3C) containing acetic acid, water, propionic acid,

and others, from the lower boiling point component (2A) fed

50

to the ?asher 2; a decanter 4 for temporarily holding or storing

methyl iodide as a co-catalyst, methyl acetate as a reaction

the lower boiling point component (3A) condensed by cool

ing [or a condensed component (3A') in the lower boiling

product of acetic acid with methanol, and acetaldehyde and a

higher iodide (such as hexyl iodide) as by-products), and a

higher boiling point component or higher boiling point impu

point component (3A)]; a buffer tank 5 for temporarily stor

ing (or retaining) the lower boiling point component (3A) [or

55

rity having a boiling point higher than that of acetic acid [e.g.,

60

a metal catalyst component (e.g., a rhodium catalyst), lithium

iodide as a co-catalyst, propionic acid, and water].
In order to mainly separate the higher boiling point com
ponent (such as the metal catalyst component) from the reac
tion mixture, part of the reaction mixture is continuously

the condensed component (3A') in the lower boiling point

component (3A)] fed or discharged from the decanter 4; a

distillation column (an acetaldehyde distillation column) 6

for separating the lower boiling point component (3A) [the

condensed component (3A') in the lower boiling point com

withdrawn from the reactor 1 and introduced or fed into the

ponent (3A)] fed or discharged from the decanter 4 or the

buffer tank 5 into a lower boiling point component (4A)

containing acetaldehyde and methyl iodide and a higher boil

?asher (distillation column or catalyst separation column) 2

ing point component (4B) containing methyl iodide, methyl

acetate, water, acetic acid, and others; a buffer tank 7 for

temporarily storing (or retaining) the higher boiling point

component (4B) separated in the distillation column 6; an

65

through a feed line 11.

The amount of the reaction mixture to be fed from the
reactor 1 to the ?asher 2 is not constant and ?uctuates (or
varies) in the continuous process due to the pressure ?uctua
tion caused by sparging of carbon monoxide to be fed to the

US 8,940,932 B2
9

10

liquid phase and others. For example, assuming that the aver

side cut. Incidentally, the stream (3B) containing acetic acid

collected by side cut may usually be fed to another distillation
column (not shown) through the line 15 and then distilled for

age ?ow rate of the reaction mixture to be fed to the ?asher 2

is 100, the ?ow rate (or ?ow velocity, hereinafter, the same
applies in the ?ow rate) of the reaction mixture to be fed to the
?asher 2 is about 98 to 102 in the process operation. As
described later, for a closed process, the ?uctuation of the
feed amount affects the succeeding step(s) and is a factor that

puri?cation (not shown). The proportion of the lower boiling

point component (3A) to be separated in the splitter column 3
is about 35 to 50% by weight in the total lower boiling point
component (2A). As described later, when a process liquid
from the succeeding step(s) is circulated or recycled to the
splitter column 3, the total amount of the component to be fed
from the ?asher 12 and the component to be recycled from the

causes a ?uctuation of the feed amount of the lower boiling

point component to be fed to the decanter.

In the ?asher (?ash distillation column) 2, from the reac

succeeding step(s) is subjected to distillation in the splitter

column 3 to separate the lower boiling point component (3A).
The amount of the lower boiling point component (3A) to

tion mixture, a higher boiling point stream or higher boiling

point component or volatile product phase (2B) (mainly con
taining the metal catalyst component such as the rhodium
catalyst or lithium iodide, and others) and a lower boiling
point stream or lower boiling point component (2A) (mainly

be fed from the splitter column 3 to the decanter 4 is affected

by the ?uctuation of the amount of the reaction mixture to be
fed to the ?asher 2 and the ?uctuation of the amount of the

containing acetic acidwhich is a product and also functions as

lower boiling point component (2A) to be fed from the ?asher

a reaction solvent, methyl acetate, methyl iodide, water,

acetaldehyde, and others) are separated, and the higher boil
ing point component (2B) is withdrawn from the bottom of
the ?asher through a bottom line 13 and recycled to the

20

reactor 1, and the lower boiling point component (2A) (acetic

acid stream) is withdrawn from the column top or upper part
of the ?asher 2 through a feed line 12 and fed or introduced to

the splitter column (or distillation column) 3. Incidentally, the

higher boiling point component (2B) also contains the metal
catalyst (the rhodium catalyst) and the halide salt (lithium
iodide), and in addition components remaining without
evaporation (e.g., methyl iodide, methyl acetate, water, and a

boiling point component (3A) ?uctuates within the range of

25

about 0 to 110% by volume). The lower boiling point com

ponent (3A) is fed to the decanter 4 with such a relatively

large ?uctuation.
The lower boiling point component (3A) separated through
the line 14 is condensed by cooling, continuously fed to the

trace of acetic acid). The volume proportion of the lower

boiling point component (2A) to be separated in the ?asher 2

2 to the splitter column 3, and ?uctuates in the continuous

process. For example, assuming that the average ?ow rate of
the lower boiling point component (3A) to be fed to the
decanter 4 is 100, the ?ow rate of the lower boiling point
component (3A) to be fed to the decanter 4 is about 90 to 1 10
in the process operation (that is, the ?ow rate of the lower

30

decanter (storage vessel) 4, and temporarily held (stored) in

the decanter 4. Inside the decanter 4, the condensed lower

is about 20 to 40% in the whole reaction mixture.

Part of the lower boiling point component (2A) may be

boiling point component (condensate) (3A) is sometimes

heat-removed and recycled to the reactor. In an embodiment

separated into a water-containing upper layer (water layer or

water phase) and a lower layer (organic layer or organic

of FIG. 1, part of the vaporized lower boiling point compo

nent (2A) (for example, about 10 to 30% by volume) is fed to
a storage vessel (hold tank) and/ or heat exchanger 9 through

35

phase). When the component (3A) is separated, acetaldehyde

and methyl iodide are contained in the both layers. A larger

a line 12a and condensed by heat removal, and recycled to the

quantity of acetaldehyde is contained in the upper layer (wa

reactor 1 through a line 12b. In this manner, heat-removal of

ter layer) compared to the lower layer in many cases. In the

part of the lower boiling point component (2A) and circula

tion of the component to the reactor allows an apparatus such
as a distillation column (e.g., a splitter column) to be down

sized (or miniaturized) even for a large-sized plant. Thus

acetic acid can be produced with a high purity and a high yield
in a resource-saving and energy-saving equipment.
The amount (feed amount) of the lower boiling point com
ponent (2A) to be fed from the ?asher 2 to the splitter column

40

nent) relative to the lower layer (or lower layer component)

[the former/the latter] is, for example, about 0.5/1 to 1.5/1
(e.g., about 0.7/1 to 1.3/1 ). The ?uctuation of the feed amount
in the upper layer and the lower layer is within the same range
45

The lower boiling point component (condensate) (3A) held

6 through a feed line 17 and/ or a feed line 18. In the embodi
50

ment of FIG. 1, the storage (or the liquid level) of the lower
boiling point component (condensate) (3A) to be held in the
decanter 4 is signi?cantly restrained from ?uctuating by cir

culating (or recycling) part of the lower boiling point compo

In the splitter column 3, usually, a lower boiling point

component (or overhead) (3A) (containing methyl iodide,

as that mentioned above.

in the decanter 4 is fed to the acetaldehyde distillation column

3 also ?uctuates in the continuous process with the ?uctuation

of the amount (feed amount) of the reaction mixture to be fed
to the ?asher 2. For example, assuming that the average ?ow

rate of the lower boiling point component (2A) to be fed to the

splitter column 3 is 100, the ?ow rate of the lower boiling
point component (2A) to be fed to the splitter column 3 is
about 98 to 102 in the process operation.

lower boiling point component (3A) to be fed to the decanter

4, the volume ratio of the upper layer (or upper layer compo

55

nent (3A) to the reaction system or others through a line 17a

(sub-line 17a) branched from the line 17 or a line 18a (sub
line 18a) branched from the line 18 based on the ?ow rate

methyl acetate, acetaldehyde, water, acetic acid, and others)

?uctuation of the lower boiling point component (conden

is separated from the column top or upper part of the column

sate) (3A) to be fed to the decanter 4.

through a withdrawing line 14, and a higher boiling point

stream or higher boiling point component (3C) (a component

That is, the amount of the lower boiling point component

(3A) to be continuously fed to the decanter 4 (for example, the

containing acetic acid, water, propionic acid, and others) is

60

separated (or removed) from the bottom or lower part of the

column through a bottom line 16. The separated higher boil

tuates through the carbonylation reaction, the ?ash distilla

tion, and the recycling of the methyl iodide (for example, the

ing point component (3C) may be discharged through a line

16, or may partly or wholly be recycled to the reactor 1
through a line 40. A side stream or acetic acid phase stream

amount to be fed per unit of time) is not constant in the

continuous reaction, and as described above, the amount ?uc

65

amount of the lower boiling point component (3A) to be fed

per unit of time is increased or decreased). Accordingly, direct

(3B) (acetic acid stream) mainly containing acetic acid is

feeding of the lower boiling point component (3A) to the

collected from the splitter column 3 through a feed line 15 by

decanter 4 causes large ?uctuation of the liquid level of the

US 8,940,932 B2
11

12

lower boiling point component (condensate) (3A) condensed

?uctuation, the ?ow rate of the lower boiling point component

and stored in the decanter 4, and the operation of the process

(3A) to be fed to the line 19 is regulated to avoid (or almost

is sometimes hindered depending on the extent of the ?uc

tuation. In order to ease (or reduce) the ?uctuation, the lower

avoid) from ?uctuating [for instance, assuming that the aver

boiling point component (3A) may be fed from the decanter 4

age ?ow rate of the lower boiling point component (3A) to be

5

of the lower boiling point component (3A) is regulated (or

to the acetaldehyde distillation column 6 at a ?ow rate enough

to ease the ?uctuation of the ?ow rate. However, such feeding
causes insuf?cient process in the aldehyde distillation col

adjusted) to about 98 to 102 in the process operation, that is,

the ?uctuation of the ?ow rate is adjusted to at most about 2%

umn 6.

Then, in the embodiment of FIG. 1, the amount of the lower

fed to the line 19 is 100 in terms of liquidvolume, the ?ow rate

10

in the whole process]. Incidentally, in the embodiment of

FIG. 1, the ?ow rate ?uctuation of the lower boiling point

boiling point component (condensate) (3A) to be held in the

component (3A) to be fed to the line 19 can mainly be con

decanter 4 is adjusted or controlled by recycling part of the

trolled by adjusting the amount of the lower boiling point

component (3A) to be circulated, and additionally can further
be controlled by regulating the retention time of the lower
boiling point component (3A) in the decanter 4.

lower boiling point component (condensate) (3A) to a step (in

the embodiment of FIG. 1, the reactor 1 and/or the splitter

column 3) different from the separation and recycling step

It is su?icient that the ?ow rate of the lower boiling point

component (3A) to be fed to the line 19 is regulated by
adjusting the ?ow rate of the lower boiling point component

without feeding from the decanter 4 to the distillation column

6 based on the ?uctuation of the ?ow rate of the lower boiling
point component (3A) to be fed to the decanter 4.
Speci?cally, in the embodiment of FIG. 1, the lower boil

ing point component (condensate) (3A) is discharged from

20

(3A) to be circulated to the line 1711 and/or the line 18a. As far
as large ?uctuation of the ?ow rate to be fed to the line 19 is

the upper layer and the lower layer in the decanter 4 through
the line 17 and the line 18, respectively. The ?ow rate of the

not caused, the ?ow rate of the lower boiling point component

lower boiling point component (condensate) (3A) to be dis

kept constant (in other words, the ?ow rate of the lower
boiling point component (3A) to be fed to the line 17b or the
line 18b may ?uctuate).
Moreover, in the embodiment of FIG. 1, the lower boiling

(3A) to be circulated to the line 1711 or the line 1811 may be

charged from the decanter 4 is regulated so that each of the

liquid levels of the upper layer and the lower layer may be

25

constant (or almost constant) even under the ?uctuation of the

point component (3A) is discharged through the line 17 and

?ow rate of the lower boiling point component (3A) to be fed

to the decanter 4. That is, the decanter 4 is provided with

the line 18. The ?ow rate of the lower boiling point compo
nent (3A) to be fed to the line 19 may be regulated by dis

liquid level sensors for detecting liquid level ?uctuation (not

shown), and one of the sensors detects the liquid level ?uc
tuation of the upper layer and the other detects that of the

30

only one of the lines 17 and 18 and circulating part of the

lower boiling point component (3A). Further, without refer

lower layer. The amount of the lower boiling point component

(condensate) (3A) to be discharged from the upper layer and
the lower layer in the decanter 4 is regulated based on the
liquid level information detected by the sensors so that pre
determined liquid levels of these layers may be maintained.
More speci?cally, based on the information obtained by the

ence to the upper layer and the lower layer, the lower boiling
point component (3A) may be fed or discharged through a
35

The lower boiling point component (3A) to be fed to the

40

is increased to prevent the liquid level from raising; when the

charged is decreased. In such a way, the liquid level of the
45

decanter 4 (the liquid level of the upper layer and that of the
lower layer) is kept constant or almost constant by adjusting
(controlling) the ?ow rate in the process operation [for
instance, with respect to each of the upper layer and the lower

layer, assuming that the average liquid level is 100, the liquid

?uctuation of the ?ow rate, the lower boiling point component

(3A) is fed to the distillation column 6 through a storage
50

through a line 20. By temporarily retaining the lower boiling

Further, a portion of the lower boiling point component

55

the line 19 in the buffer tank 5 can ef?ciently be eased (or

reduced).
60

through the line 1711 and/or the line 18a in response to the

In order that the buffer tank 5 may show the function of

suf?ciently easing the ?ow rate ?uctuation, it is important for

amount of the lower boiling point component (3A) dis

charged from each of the upper layer and the lower layer in the
of the lower boiling point component (3A) to be circulated

point component (3A) in the buffer tank 5 in such a way, even

when the amount to be fed from the buffer tank 5 to the line 20

is kept constant (or almost constant), the ?uctuation of the

?ow rate of the lower boiling point component (3A) fed from

adjusting the amount of the lower boiling point component

decanter 4 ?uctuates so that the liquid level in the decanter 4

may be constant or almost constant. By changing the amount

vessel (buffer tank) 5 having a buffering function. That is, the

lower boiling point component (3A) fed to the line 19 is fed to
the buffer tank 5 and then fed to the distillation column 6

adjusted to at most about 1% in the whole process].

(3A) to be circulated through the line 1711 and/or the line 18a.
That is, in the embodiment of FIG. 1, as described above, the

point component (3A) fed to the line 19 is signi?cantly inhib

ited as described above, the boiling point component (3A)
may directly be fed to the distillation column 6. In the
embodiment of FIG. 1, in order to further ease (or reduce) the

level is regulated (or adjusted) to about 99 to 101 in the

process operation, that is, the liquid level ?uctuation is
(3A) discharged through the line 17 and the line 18 is fed to a
line 19 through the line 17b and line 18b. The ?ow rate of the
lower boiling point component (3A) to be fed to the line 19 is
adjusted (controlled) to keep constant or almost constant by

through a line 17112 and recycled (or returned) to the reactor 1,

or may be recycled through both lines 17111 and 17112. More
over, the lower boiling point component (3A) to be fed to the
line 18a is fed to the line 40 and recycled to the reactor 1.
Since the ?uctuation of the ?ow rate of the lower boiling

?ow rate to be fed to the decanter is small, the ?ow rate of the

lower boiling point component (condensate) (3A) to be dis

lower boiling point component (condensate) (3A) in the

single line.
line 1711 may be fed to a line 30 through a line 17111 and
circulated to the splitter column 3, may be fed to a line 40

liquid level sensors or other information, when the ?ow rate to

be fed to the decanter is large, the ?ow rate of the lower

boiling point component (condensate) (3A) to be discharged

charging the lower boiling point component (3A) through

the buffer tank 5 to have a capacity enough to retain the lower

boiling point component (3A) and to further ease the ?uctua

tion of the ?ow rate. The capacity depends on the extent of the
65

?ow rate ?uctuation and may generally be represented in

association with the retention time of the lower boiling point
component (3A) in the buffer tank 5. The capacity of the

US 8,940,932 B2
13

14

buffer tank to the ?ow rate can generally be adjusted so that

the line 40 while keeping the ?ow rate of the higher boiling
point component (4B) to be fed to the line 23 constant (or
almost constant). Therefore, the ?ow rate ?uctuation of the

the retention time of the lower boiling point component (3A)

may be not less than 1 minute (for example, preferably not
less than 3 minutes, and more preferably not less than 6
minutes). It is preferable that the buffer tank 5 can retain the

higher boiling point component (4B) to be recycled can be

lower boiling point component (3A) in the above-mentioned

The higher boiling point component (4B) fed to the line 40

may partly or wholly be recycled to the splitter column 3

inhibited (or reduced).

time. As described above, in the case where the ?ow rate

through a line 40a. The higher boiling point component (4B)

?uctuation of the lower boiling point component (3A) to be

fed to the line 17 is suppressed beforehand by recycling the
lower boiling point component (3A) or maintaining the suf

fed to the line 4011 may partly or wholly be fed to the distil
lation column 6 through a line 40111 as far as stable operation
of the distillation column 6 can be ensured.

?cient retention time in the decanter as described below, even

a buffer tank having a retention time shorter than the above

FIG. 2 is a diagram for explaining a production process (or

production apparatus) of acetic acid in accordance with still
another embodiment of the present invention. The process (or

range is capable of operating stably. The retention time (gen

eral retention time) can be calculated from the ?ow rate (or
?ow velocity) and the capacity of the buffer tank. For
example, assuming that the average ?ow rate of the lower
boiling point component (3A) to be fed to the buffer tank 5 is
A m3/hour and the average storage amount of the lower boil

apparatus) of FIG. 2 is the same as that of FIG. 1 except that

a decanter 4A having a buffering function is used instead of

ing point component to be held in the buffer tank 5 is B m3, the

retention time can be calculated as (B/A) hours.

20

The lower boiling point component (3A) fed to the distil

lation column 6 is separated into a lower boiling point stream
or lower boiling point component (or a second overhead)

(4A) and a higher boiling point stream or higher boiling point

component (4B) in the distillation column 6; wherein the
lower boiling point stream (4A) contains a trace of methyl
iodide, carbon monoxide, hydrogen, and others in addition to
acetaldehyde, and the higher boiling point stream (4B) con
tains methyl acetate, water, acetic acid, and others.

The separated lower boiling point component (4A) is fed

25

the decanter 4 in FIG. 1 and that the lower boiling point

component (3A) is directly fed to the distillation column 6
through the line 17.
That is, as the embodiment of FIG. 1, usually, the decanter
cannot fully ease the ?ow rate ?uctuation of the lower boiling
point component (3A) to be fed from the splitter column 3. In
contrast, in an embodiment of FIG. 2, the decanter 4A having
a large capacity enough to ease (reduce) the ?ow rate ?uc
tuation is used, and the ?ow rate to be discharged to the line 17
can be kept constant or almost constant by easing the ?ow rate

30

?uctuation inside the decanter 4A (for instance, assuming that

the average ?ow rate of the lower boiling point component
(3A) to be fed through the line 14 is 100 in terms of liquid
volume, the ?ow rate of the lower boiling point component

from the column top or upper part to an acetaldehyde extrac

(3A) to be discharged or fed to the line 17 in the process

tion apparatus (water extraction column) 8 through a line

(discharge line) 21, and acetaldehyde is extracted from the
lower boiling point component (4A) using water. The
extracted acetaldehyde (aldehyde aqueous solution) is dis
charged through a line 21b. Incidentally, part of the lower
boiling point component (4A) may be returned to the distil

operation can be regulated (or adjusted) to about 98.5 to

lation column 6 through a line 2111. Moreover, the ra?inate

containing a trace of methyl iodide, and others may be dis
charged out of the system. In the embodiment of FIG. 1, the
ra?inate discharged through a line 24 is fed to the distillation
column 6 through a line 24a, and/or is fed to a line 40 through

35

the lower boiling point component (3A) to be discharged

from the line 17 (and the line 18) is kept constant or almost
constant, whereas in the embodiment of FIG. 1, the ?ow rate

of the lower boiling point component (3A) discharged from

40

45

Moreover, the separated higher boiling point component

(4B) is fed as a liquid residue (bottom fraction or column
bottom fraction) through a line 22 to a line 40, leading to the
50

to the reaction system and others. The higher boiling point

component (4B) may directly be fed to the line 40 through the
line 22. In the embodiment of FIG. 1, the higher boiling point
component (4B) is fed to the buffer tank 7 and then to the line
40 through a line 23. That is, although the ?uctuation of the

described above (for example, not less than 1 minute, prefer

ably not less than 3 minutes, and more preferably not less than

6 minutes).
55

60

the higher boiling point component (4B). However, even if

the ?ow rate of the higher boiling point component (4B)
?uctuates, temporary retention of the higher boiling point
Thus the higher boiling point component (4B) can be fed to

(3A) may be fed as the lower layer through the line 18 as

shown in the embodiment of FIG. 1, or may be fed through
both the line 17 and the line 18. Further, without reference to

the upper layer and the lower layer, the lower boiling point
component (3A) may be fed through a single line.

and other factors sometimes cause the ?ow rate ?uctuation of

component (4B) to be fed through the line 22 in the buffer

In the embodiment of FIG. 2, the lower boiling point com

ponent (3A) is fed as the upper layer to the distillation column

6 through the line 17. The lower boiling point component

distillation column 6 as described above, recycling of the

tank 7 allows the ?uctuation in the buffer tank 7 to be eased.

embodiment of FIG. 2, the capacity of the decanter 4A is

important. The process is stably operable in many cases by
adjusting the retention time of the lower boiling point com
ponent (3A) inside of the decanter 4A to the same range as

?ow rate of the higher boiling point component (4B) to be fed

through the line 22 is inhibited with the highly controlled ?ow
rate of the lower boiling point component (3A) to be fed to the
ra?inate after the acetaldehyde extraction mentioned above,

However, use of the decanter 4A having a suf?cient capacity

allows stable operation of the process for the following rea
son: the amount of the lower boiling point component (3A) to
be held inside the decanter 4A is ?uctuated due to the ?ow rate
?uctuation while the decanter 4A has a capacity enough to
ease the ?uctuation. In this embodiment, as the same as the

reactor 1 or the splitter column 3. In such a manner, the useful

component containing methyl iodide is circulated (recycled)

the line 17 (and the line 18) is changed. When the ?ow rate is

kept constant, usually the process cannot be operated stably.

a line 24b to be recycled to the reactor 1. In such a manner, the

distillation or recycling of the ra?inate can further improve a

recovery percentage of methyl iodide.

101.5, that is, the ?uctuation of the ?ow rate can be adjusted
to at most about 1.5%) in the process operation.
Speci?cally, in the embodiment of FIG. 2, the ?ow rate of

(Reaction Step)
In the reaction step (carbonylation reaction system),
65

methanol is carbonylated with carbon monoxide in the pres

ence of the catalyst system. Incidentally, fresh methanol may
be fed to the reaction system directly or indirectly, or metha

US 8,940,932 B2
15

16

nol and/or a derivative thereof withdrawn from various dis

centration of the iodide ion in the reaction system may for

example be about 0.07 to 2.5 mol/liter and preferably about

tillation steps may be recycled and fed to the reaction system.

0.25 to 1.5 mol/liter.

The catalyst system may usually comprise a metal catalyst,

As the accelerator contained in the catalyst system, an alkyl

iodide (e.g., a Cl_4alkyl iodide such as methyl iodide, ethyl

a co-catalyst, and an accelerator. Examples of the metal cata

lyst may include a transition metal catalyst, in particular, a

iodide, or propyl iodide), particularly methyl iodide, is uti

metal catalyst containing the group 8 metal of the Periodic

lized. Since the reaction is promoted at higher concentrations

of the accelerator, an economically advantageous concentra

Table (e.g., a cobalt catalyst, a rhodium catalyst, and an iri

dium catalyst). The catalyst may be an elemental metal or
may be used in the form of a metal oxide (including a complex
metal oxide), a metal hydroxide, a metal halide (e. g., a chlo
ride, a bromide, and an iodide), a metal carboxylate (e. g., an
acetate), a metal salt of an inorganic acid (e.g., a sulfate, a
nitrate, and a phosphate), a metal complex, and others. These
metal catalysts may be used alone or in combination. The
preferred metal catalyst includes a rhodium catalyst and an

tion can suitably be selected in consideration of the recovery

of the accelerator, the plant size of a step for circulating the

recovered accelerator to the reactor, the amount of energy
necessary for the recovery or circulation, and others. In the

reaction system, the concentration of the alkyl iodide (par

ticularly methyl iodide) is, for example, about 1 to 20% by
weight, preferably about 5 to 20% by weight, and more pref
erably about 6 to 16% by weight (e.g., about 8 to 14% by
weight) in the whole liquid phase in the reactor.

iridium catalyst (particularly, a rhodium catalyst).

Moreover, it is preferred to use the metal catalyst in the
form dissolvable in a liquid reaction medium. Incidentally,
since rhodium usually exists as a complex in the liquid reac
tion medium, the form of the rhodium catalyst is not particu

The reaction is a continuous reaction, and the liquid reac

20

larly limited to a speci?c one as far as the catalyst can change

into a complex in the liquid reaction medium, and may be

tion medium contains methyl acetate. The proportion of

methyl acetate may be about 0.1 to 30% by weight, preferably
about 0.3 to 20% by weight, and more preferably about 0.5 to
10% by weight (e.g., about 0.5 to 6% by weight) in whole
liquid reaction medium.

used in various forms. As such a rhodium catalyst, a rhodium

The carbon monoxide to be fed to the reaction system may

iodide complex [for example, RhI3, [RhI2(CO)4]_, and [Rh

25 be used as a pure gas or may be used as a gas diluted with an

inactive gas (e.g., nitrogen, helium, and carbon dioxide).

Moreover, exhausted gas component(s) containing carbon

(CO)2I2]_], a rhodium carbonyl complex, or the like is par

ticularly preferred. Moreover, the catalyst may be stabilized

monoxide obtained from the succeeding step(s) may be

recycled to the reaction system. The carbon monoxide partial

in the liquidreaction medium by addition of a halide salt (e.g.,

an iodide salt) and/ or water.

The concentration of the metal catalyst is, for example,

about 10 to 5000 ppm (on the basis of weight, the same
applies hereinafter), preferably about 100 to 4000 ppm, more
preferably about 200 to 3000 ppm, and particularly about 300
to 2000 ppm (e.g., about 500 to 1500 ppm) in the whole liquid
phase in the reactor.
As the co-catalyst or the accelerator contained in the cata
lyst system, a halide salt (e.g., an iodide salt) is used. The
iodide salt is added in order to stabilize the rhodium catalyst
and inhibit side reactions, particularly, in the low water con

30

atmospheres and preferably about 4 to 15 atmospheres.

In the carbonylation reaction, hydrogen is formed (or gen

erated) by a shift reaction between carbon monoxide and
water. Hydrogen may be fed to the reaction system. The
35

ponent(s) (including hydrogen, carbonmonoxide, and others)

40

about 1 to 200 kPa, and more preferably about 5 to 150 kPa

(e.g., about 10 to 100 kPa) in terms of absolute pressure.

metal halide [for example, a metal iodide such as an alkali

45

iodide, rubidium iodide, and cesium iodide), an alkaline earth

metal iodide (e.g., beryllium iodide, magnesium iodide, and

calcium iodide), or an iodide of the group 3B metal of the

halide [for example, an organic iodide such as a phosphonium

salt of an iodide (a phosphonium iodide) (e.g., a salt with
tributylpho sphine and triphenylphosphine) or an ammonium
salt of an iodide (an ammonium iodide) (e. g., a salt of tertiary
amine, a pyridine compound, an imidazole compound, an
imide compound, or the like with an iodide), corresponding
bromide or chloride compounds]. Incidentally, the alkali
metal iodide (e.g., lithium iodide) also functions as a stabi

50

The carbon monoxide partial pressure or hydrogen partial

pressure in the reaction system may be adjusted, for example,
by suitably adjusting the amount of the carbon monoxide and
hydrogen fed and/ or recycled to the reaction system, the
amount of raw substances (e. g., methanol) fed to the reaction
system, the reaction temperature, the reaction pressure, and
others.

In the carbonylation reaction, the reaction temperature may

be, for example, about 150 to 250 C., preferably about 160 to
230 C., and more preferably about 180 to 220 C. Moreover,
55

the reaction pressure (total reactor pressure), including partial

pressures of by-products, may be, for example, about 15 to 40

atmospheres.

lizer for the carbonylation catalyst (e.g., a rhodium catalyst).

These halide salts may be used alone or in combination.
Among these halide salts, an alkali metal iodide (such as

exhausted in the succeeding distillation step(s) (distillation

column), if necessary after suitably purifying the gaseous
component(s). The hydrogen partial pressure in the reaction
system may for example be about 0.5 to 250 kPa, preferably

reaction medium. The iodide salt may include, for example, a

Periodic Table (e.g., boron iodide and aluminum iodide),

corresponding bromide or chloride compounds], an organic

hydrogen may be fed as a mixed gas with carbon monoxide as

a raw material to the reaction system. Moreover, the hydrogen

may be fed to the reaction system by recycling gaseous com

tent. The iodide salt is not particularly limited to a speci?c one

as far as the iodide salt produces an iodide ion in the liquid

metal iodide (e.g., lithium iodide, sodium iodide, potassium

pressure in the reactor may for example be about 2 to 30

60

The reaction may be carried out in the presence or absence

of a solvent. The reaction solvent is not limited to a speci?c
one as far as the reactivity, or the separation or puri?cation

ef?ciency does not decrease, and a variety of solvents may be

lithium iodide) is preferred.

used. In usual cases, acetic acid as a product may be practi

In the reaction system (liquid reaction mixture) in the reac

tor, the concentration of the halide salt (e. g., an iodide salt) is,
for example, about 1 to 25% by weight, preferably about 2 to
22% by weight, and more preferably about 3 to 20% by
weight in whole liquid phase in the reactor. Further, the con

cally utilized as a solvent.

65

The concentration of water in the reaction system is not

limited to a speci?c one, and may be a low concentration. The

concentration of water in the reaction system is, for example,

not more than 15% by weight (e.g., about 0.1 to 12% by

US 8,940,932 B2
17

18

weight), preferably not more than 10% by weight (e. g., about

?uctuation, assuming that the average ?ow rate (in terms of

liquid volume; the same applies in others unless otherwise
noted) of the reaction mixture to be fed to the ?asher is 100,

0.1 to 8% by weight), and more preferably about 0.1 to 5% by

weight and may usually be about 1 to 15% by weight (e.g.,

about 2 to 10% by weight) in the whole liquid phase of the
reaction system. The solubility of carbon monoxide in the
liquid fed to the ?asher is decreased by carrying out the

the ?ow rate of the reaction mixture to be fed to the ?asher is

about 90 to 1 10 (e.g., about 93 to 107), preferably about 95 to

105 (e.g., about 97 to 103), and more preferably about 98 to
102 (e.g., about 98.5 to 101.5) in the process operation.

reaction while maintaining a speci?ed concentration of each

The separation (?ash distillation) of the metal catalyst

component [particularly, an iodide salt (lithium iodide) and

water] in the reaction system, and the loss of carbon monox

component may be conducted by a conventional separation

ide can be reduced.

method or a conventional separation apparatus, and may usu

ally be carried out with the use of a ?ash distillation column.

In the foregoing carbonylation reaction, production of ace

tic acid is accompanied by production of an ester of the

Moreover, the metal catalyst component may be separated by

product acetic acid with methanol (methyl acetate), water

generated with the esteri?cation reaction, additionally acetal

means of ?ash distillation in combination with a mist-collect

dehyde, propionic acid, and others.

Incidentally, since acetaldehyde is separated by the after

in industrial application.

mentioned acetaldehyde separation step, the concentration of

separated into the vapor component (or vaporized stream) and

the liquid component (or liquid stream) with or without heat

acetaldehyde in the reactor is held down and is relatively low

in spite of the continuous reaction. For example, the concen
tration of acetaldehyde in the reactor (or reaction system) may

ing method or a solid-collecting method which is widely used

In the ?ash evaporation step, the reaction mixture may be

20

be not more than 1000 ppm (e.g., 0 or detection limit to 700

ppm) and preferably not more than 400 ppm (e.g., 5 to 300
ppm) in the liquid phase in the reactor in the process opera

vapor component and the liquid component with heating (and

tion.

Moreover, inside of the reactor, by-products derived from

25

acetaldehyde is also produced (for example, crotonaldehyde,

which is a reducing substance, produced by aldol condensa

?uctuation of the concentration of acetaldehyde in the reactor

is also inhibited, the combination of such inhibition and the
low acetaldehyde concentration mentioned above can signi?

1,000 kPa (e.g., about 100 to 1,000 kPa), preferably about 100
30

combination. The higher boiling point catalyst component

(metal catalyst component) separated by such step(s) may
35

Moreover, part of the lower boiling point component (2A)

may be recycled to the reactor or the reaction system, as

described above. The lower boiling point component (2A) to

40

tion of the production of by-product.

The space time yield of the objective carboxylic acid (ace
tic acid) in the reaction system may be, for example, about 5

be recycled may be heat-removed and condensed in a suitable

method (e. g., a method using a heat exchanger or a condenser)
to be recycled to the reactor. The proportion of the lower

boiling point component (2A) to be recycled may for example

45

be about 1 to 50% by volume (e.g., about 5 to 45% by

volume), preferably about 10 to 40% by volume, and more
preferably about 10 to 30% by volume.

The separated lower boiling point component (2A) con

tains product acetic acid, in addition, hydrogen iodide, a

co-catalyst (such as methyl iodide), methyl acetate, water,

cooled with a condenser, a heat exchanger or other means to

remove part of the reaction heat. The cooled vapor component

usually be recycled to the reaction system, as shown in the

embodiment of the ?gure.

concentration, and the inhibited (or decreased) acetaldehyde

mol/Lh to 50 mol/Lh, preferably about 8 mol/Lh to 40 mol/

Lh, and more preferably about 10 mol/Lh to 30 mol/Lh.
The vapor component may be withdrawn from the top of
the reactor for the purpose of the pressure control of the
reactor or others, and the withdrawn vapor component may be

to 500 kPa, and more preferably about 100 to 300 kPa.

The separation step of the catalyst may be composed of a

single step, or may be composed of a plurality of steps in

cantly decrease the formation of by-products derived from

acetaldehyde. That is, these by-products are often produced in
proportion to the second to third power of the acetaldehyde
concentration and ?uctuation can e?iciently induce inhibi

reduced pressure). The reaction mixture may be separated

into the vapor component and the liquid component by com
bining these ?ash conditions. These ?ash distillation steps
may be carried out, for example, at a temperature of about 80
to 200 C. under a pressure (absolute pressure) of about 50 to

tion of acetaldehyde; 2-ethylcrotonaldehyde produced by

aldol condensation of hydrogenated crotonaldehyde and
acetaldehyde; and hexyl iodide produced through aldol con
densation of three acetaldehyde molecules, hydrogenation,
and iodization). According to the present invention, since the

ing. For example, in adiabatic ?ash, the reaction mixture may

be separated into the vapor component and the liquid com
ponent without heating and with reduced pressure; in ther
mostatic ?ash, the reaction mixture may be separated into the

50

by-product (s) (e.g., an aldehyde such as acetaldehyde, and

may be separated into a liquid component (containing acetic

propionic acid) and others, and is fed to a distillation column

acid, methyl acetate, methyl iodide, acetaldehyde, water, and

for collecting acetic acid. The proportion of the lower boiling

point component (2A) to be fed to the acetic acid collection
step in the whole react ion mixture may for example be about
5 to 50% by weight, preferably about 8 to 40% by weight, and
more preferably about 10 to 35% by weight (e.g., about 12 to

others) and a gaseous component (containing carbon monox

ide, hydrogen, and others), and the liquid component may be

recycled to the reactor.

55

(Flash Evaporation Step)

30% by weight).
(Acetic Acid Collection Step)

In the ?ash distillation step (?asher), from the reaction

mixture fed from the reaction step or the reactor to the ?asher

(evaporator or ?ash distillation column), a higher boiling

point component (2B) containing at least a higher boiling

point catalyst component (a metal catalyst component, e.g., a

60

In the acetic acid collection step, the lower boiling point

component (2A) is fed to the distillation column (splitter
column) and separated into a lower boiling point component

rhodium catalyst and a halide salt) is separated as a liquid

(3A) containing methyl iodide and by-product acetaldehyde

(component), and a lower boiling point component (2A) con

and a stream (3B) containing acetic acid to collect acetic acid.

Speci?cally, in the distillation column, the lower boiling point

taining acetic acid and methyl iodide is separated as a vapor

(component).
As described above, the feed amount of the reaction mix
ture to the ?asher ?uctuates. With respect to the degree of the

65

component (3A) (overhead) containing methyl iodide,

methyl acetate, acetaldehyde, water, and others is separated
as a vapor from the lower boiling point component (2A)

US 8,940,932 B2
19

20

(acetic acid stream) fed from the ?asher; and the liquid stream
(3B) (side cut stream, side stream) containing acetic acid is
withdrawn by side cut. Incidentally, in the distillation col
umn, a higher boiling point component (3C) containing acetic
acid, water, propionic acid, an entrained metal catalyst com
ponent, the halide salt, and others may be separated. The

Moreover, for the plate column, the theoretical number of

plates is not particularly limited to a speci?c one, and,
depending on the species of the component to be separated, is
about 5 to 50, preferably about 7 to 35, and more preferably
about 8 to 30. Further, in order to separate acetaldehyde

highly (or with a high precision) in the distillation column, the

theoretical number of plates may be about 10 to 80, preferably

higher boiling point component (3C) may be removed (dis

about 20 to 60, and more preferably about 25 to 50. Further,

in the distillation column, the re?ux ratio may be selected

charged) from the bottom of the distillation column. Since the

higher boiling point component (3C) contains a useful com

from, for example, about 0.5 to 3,000, and preferably about

ponent such as the metal catalyst component or acetic acid

0.8 to 2,000 depending on the above-mentioned theoretical

remaining without being evaporated, the component (3C)

number of plates, or may be reduced by increasing the theo

retical number of plates.

may be recycled to the reactor (or reaction step), the ?ash

evaporation step (or distillation column), or others, as the

The separated lower boiling point component (3A) practi

embodiment of the ?gure. Incidentally, prior to recycling,

cally contains methyl iodide, acetaldehyde, and in addition

methyl acetate, water, acetic acid, and others. The proportion

propionic acid, which deteriorates the quality of acetic acid as

a ?nal product, may be removed off. The acetic acid stream

of the lower boiling point component (3A) to be fed to the

(crude acetic acid solution) is usually dehydrated in the next

condensation step or decanter may for example be about 5 to

distillation column and then introduced into an acetic acid

puri?cation column for separating higher and lower boiling

point components by distillation to give product acetic acid.

70% by volume, preferably about 10 to 65% by volume, and

20

50% by volume) in the total lower boiling point component

Moreover, as described later, the higher boiling point com

ponent (3C) to be recycled may be recycled to the reaction
system or others through a storage vessel having a buffering
function.

more preferably about 12 to 60% by volume (e. g., about 15 to

(2A).
(Condensation and Discharge Step)
In the condensation and discharge step (which may simply
25

be referred to as the condensation step), the separated lower

boiling point component (or condensate) (3A) is temporarily

As described above, the amount of the lower boiling point

component (2A) to be fed to the distillation column is also

held (or stored) in the decanter (or storage vessel) while

affected by the ?uctuation of the amount fed from the reactor

condensing, and then discharged to be subjected to at least the

and ?uctuates. With respect to the degree of the ?uctuation,

for example, assuming that the average ?ow rate of the lower
boiling point component (2A) to be fed to the distillation
column is 100, the ?ow rate of the lower boiling point com
ponent (2A) to be fed to the distillation column (2A) is about
90 to 110 (e.g., about 93 to 107), preferably about 95 to 105
(e.g., about 97 to 103), and more preferably about 98 to 102
(e.g., about 98.5 to 101.5) in the process operation.
In the distillation column (splitter column), the position of
a feed port for feeding the lower boiling point component
(2A) is not particularly limited to a speci?c one. For example,

acetaldehyde separation step. Moreover, according to the

the position of the feed port may be in an upper part, a middle

part, or a lower part of the distillation column. Moreover, in

30

point component (3A) to be discharged) in condensation and

discharge step is regulated (or controlled) in the process
operation based on the ?ow rate ?uctuation of the lower
35

40

lower boiling point component (or condensate) (3A) to be fed

45

to the decanter is 100, the ?ow rate of the lower boiling point
component (or condensate) (3A) to be fed to the decanter is
about 80 to 120 (e.g., about 85 to 115), preferably about 90 to
110 (e.g., about 93 to 107), and more preferably about 95 to
105, in the process operation. According to the present inven

50

the lower boiling point component (3A) to be held in the

decanter is adjusted.
Concrete examples of the method for adjusting (or control
ling) the amount of the lowerboiling point component (3A) to

(2A) may be fed at an upper position or a lower position

relative to a side stream port for side-cutting the acetic acid
cutting the acetic acid stream may be in an upper part, a
middle part, or a lower part of the distillation column, and

tion, in order to ease the ?ow rate ?uctuation, the amount of

usually, the position of the side stream port is preferably in a

middle part or a lower part of the distillation column.
As the distillation column, there may be used a conven

be held may include (1) a method in which the lower boiling

tional distillation column, for example, a plate column, a

packed column, and a ?ash distillation column. A distillation

point component (3A) is discharged so that the ?uctuation of

the amount or liquid level of the lower boiling point compo

column such as a plate column or a packed column may be

usually employed. Incidentally, the material of (or for form

ing) the distillation column is not limited to a speci?c one, and

55

a glass, a metal, a ceramic, or others can be used. In usual, a

distillation column made of a metal is used practically.

The distillation temperature and pressure in the distillation
column may suitably be selected depending on the condition
such as the species of the distillation column, or the main

60

subject (target) for removal selected from the lower boiling

point component and the higher boiling point component. For

example, in the distillation column, the inner temperature of
the column (usually, the temperature of the column top) may
be adjusted by adjusting the inner pressure of the column, and
may be, for example, about 20 to 180 C., preferably about 50
to 150 C., and more preferably about 100 to 140 C.

boiling point component (3A) to be fed to the decanter.

That is, as described above, the amount of the lowerboiling
point component (3A) to be fed to the decanter widely ?uc
tuates through a series of steps. For example, the ?uctuation is
large as follows: assuming that the average ?ow rate of the

the distillation column, the lower boiling point component

stream. Further, the position of the side stream port for side

present invention, the amount of the lower boiling point com

ponent (3A) to be held (or the amount of the lower boiling

65

nent (3A) to be held in the decanter may be reduced (e.g., a

method shown in FIG. 1) and (2) a method in which a decanter
having a buffering function is used as the decanter to ease the

?uctuation of the feed amount of the lower boiling point

component (3A) in the decanter (e. g., a method shown in FIG.
2). These methods may be combined.
According to the method (1), the discharge amount of the
lower boiling point component (3A) is adjusted so as to
correspond to the ?uctuation of the lower boiling point com
ponent (3A) to be fed to the decanter. In this method, for
example, assuming that the average liquid level of the lower
boiling point component (3A) to be held to the decanter is

100, the liquid level of the lower boiling point component

(3A) to be held to the decanter may be adjusted to about 80 to

US 8,940,932 B2
21

22

120 (e.g., about 85 to 115), preferably about 90 to 110 (e.g.,

about 93 to 107), and more preferably about 95 to 105 (e.g.,
about 98 to 102) in the process operation (or the discharge
amount of the lower boiling point component (3A) may be
adjusted). Moreover, in the case where the lower boiling point
component (3A) to be held to the decanter is phase-separated

upper layer or the lower layer or both upper and lower layers.
In the lower boiling point component (3A) to be fed to the
decanter, the volume ratio of the upper layer relative to the
lower layer may be selected from the range of about 0.2/1 to
5/1 (e.g., about 0.3/1 to 3/1) as a ratio ofthe former/the latter,

(or is separated into two layers (or two phases)), assuming

0.6/1 to 1.4/1, and more preferably about 0.7/1 to 1.3/1 as a

that the average interface level is 100, the interface level of the

ratio of the former/the latter. In the upper layer and the lower

lower boiling point component (3A) to be held to the decanter

(for example, the liquid level of the lower layer) may be
adjusted to about 80 to 120 (e.g., about 85 to 115), preferably

layer, the feed amount ?uctuation is in the same range as

boiling point component (3A) is separated into the upper

about 90 to 110 (e.g., about 93 to 107), and more preferably

about 95 to 105 (e. g., about 98 to 102) in the process operation

layer and the lower layer, it is su?icient to reduce the ?uctua

tion of the liquid level (or the holding amount) as a whole so

(or the discharge amount of the lower boiling point compo

nent (3A) may be adjusted).
Moreover, according to the method (1), assuming that the
average amount of the lower boiling point component (3A) to

as to fall within the above-mentioned range. The ?uctuation

and for example be about 0.5/1 to 1.5/1, preferably about

described above. Moreover, in the method (1 ), when the lower

of the liquid level (or the holding amount) of each of both

layers may be reduced so as to fall within the above-men
tioned range. For example, as the embodiment of FIG. 1

be held to the decanter is 100 on the basis of liquid volume,

the amount of the lower boiling point component (3A) to be

held to the decanter may be adjusted to constant or almost or

20

substantially constant [for example, about 80 to 120 (e.g.,

about 85 to 115), preferably about 90 to 110 (e.g., about 93 to
107), and more preferably about 95 to 105 (e.g., about 98 to

component (3A) to be fed to the decanter.

The lower boiling point component (3A) discharged from

102)] in the process operation.

In the method (1), the liquid level or the like may be
adjusted using the above-mentioned sensor (liquid level sen
sor) or other means or may be adjusted by equipping the

25

point component (3A) is directly fed without adjustment of

boiling point component (3A) when the liquid level reaches a

inhibited under the in?uence of the ?uctuation of the amount

30

In the method (2), it is su?icient that the decanter having a

buffering function has a capacity enough to ease the feed

amount ?uctuation of the lower boiling point component

(3A). As described above, the decanter can generally be
selected based on, as an index, the range enough to keep at the

35

retention time of the lower boiling point component (3A) in

the decanter, for example, the retention time (or average
retention time) of not less than 1 minute [e.g., not less than 2
minutes (e.g., about 2.5 minutes to 3 hours), preferably not
less than 3 minutes [e.g., not less than 4 minutes (e.g., about
5 to 60 minutes)], more preferably not less than 6 minutes
(e. g., about 8 to 50 minutes), and particularly not less than 12
minutes (e.g., about 15 to 40 minutes)]. Even when the feed

40

45

stable operation of the process. As described later, in the case

where the lower boiling point component (3A) is separated

into an upper layer and a lower layer, it is suf?cient that the
retention time of the whole layer is in the above-mentioned
range. Moreover, the retention time of the upper layer is not

of the lower boiling point component (3A) to be fed to the

decanter. Thus, according to the present invention, the
amount of the lower boiling point component (3A) to be fed
to the separation and recycling step in addition to the amount
of the lower boiling point component (3A) to be held to the
decanter may be adjusted.
Speci?cally, assuming that the average ?ow rate of the
lower boiling point component (3A) to be fed to the separa
tion and recycling step is 100, the ?ow rate of the lower

boiling point component (3A) to be fed to the separation and

recycling step may be adjusted (that is, substantially be sta
bilized) so as to be constant or almost constant [for example,

amount of the lower boiling point component (3A) ?uctuates,

use of the decanter ensuring the su?icient retention time can
ease the ?uctuation inside the decanter, which enables the

the decanter is fed to the acetaldehyde separation step (or

acetaldehyde distillation column). When the lower boiling
the ?ow rate, stabilized acetaldehyde separation is sometimes

decanter with a suitable means for discharging the lower

predetermined liquid level.

described above, the liquid level ?uctuation of both the upper

layer and the lower layer can be reduced by changing the ?ow
rate of the lower boiling point component (3A) to be dis
charged from each of the upper layer and the lower layer in
response to the ?ow rate ?uctuation of the lower boiling point

50

about 90 to 1 10 (e.g., about 93 to 107), preferably about 95 to

105 (e.g., about 97 to 103), more preferably about 98 to 102,
and particularly about 98.5 to 101.5] in the process operation.
The method for adjusting or controlling the amount of the
lower boiling point component (3A) to be fed to the separa

tion and recycling step may include, for example, (a) a

method for circulating part of the lower boiling point com
ponent (3A) discharged from the decanter to a step different
from the separation and recycling step (particularly, at least
the reactor or reaction step) (e.g., the embodiment shown in

FIG. 1), (b) a method for feeding the separation and recycling

necessarily needed to be the same as the retention time of the

lower layer. The retention time of one of these layers may be

step with the lower boiling point component (3A) discharged

lengthened (or shortened).

from the decanter through a storage vessel having a buffering

function (e.g., the embodiment shown in FIG. 1), and (c) a
method for adjusting the amount of the lower boiling point
component (3A) to be discharged from the decanter to keep
constant (or almost constant) (e.g., the embodiment shown in
FIG. 2). These methods may be combined.

In the method (1), the retention time of the lower boiling

point component (3A) in the decanter is not particularly lim

55

ited to a speci?c one, and may for example be not less than 5

seconds (e.g., not less than 10 seconds), preferably not less

than 15 seconds (e.g., not less than 20 seconds), and more
preferably not less than 30 seconds. Moreover, in the method
(1), a decanter having a buffering function available for the
method (2) may be used to keep at the suf?cient retention
time.

The lower boiling point component (3A) is sometimes

separated into the upper layer and the lower layer in the

60

For the method (a), part of the discharged lower boiling

point component (3A) is circulated (recycled) in response to
the ?uctuation of the lower boiling point component (3A) to
be fed to the decanter without subjecting to the separation and

65

recycling step, and thus the amount of the lower boiling point
component (3A) to be fed to the separation and recycling step

decanter, as described above. In this case, the lower boiling

can be adjusted so as to be constant or almost constant.

point component (3A) may be discharged from either the

Speci?cally, in the case where the amount of the lower boiling

US 8,940,932 B2
23

24

point component (3A) to be discharged from the decanter

?uctuates, the ?uctuation of the lower boiling point compo

upper layer to be recycled relative to the lower boiling point

component (3A) of the lower layer to be recycled may be

nent (3A) to be fed to the separation and recycling step can be

reduced at a high level by changing the amount of the lower

preferably about 90/ 10 to 10/90 as a ratio of the former/the

about 99/1 to 1/99, preferably about 95/5 to 5/95, and more

boiling point component (3A) to be circulated. The step (or

apparatus) for recycling the lower boiling point component

latter. Moreover, for recycling of part of the upper layer, the

proportion of the lower boiling point component (3A) to be
recycled in the total lower boiling point component (3A) of
the upper layer may be, for example, about 3 to 90% by
volume, preferably about 5 to 80% by volume (e.g., about 10

(3A) is not particularly limited to a speci?c one as far as the

step (or apparatus) is not a separation and recycling step (or

acetaldehyde separation column). The step (or apparatus) for

recycling the lower boiling point component (3A) may be the
reactor (or reaction step), the acetic acid collection step (or

to 75% by volume), and more preferably about 15 to 65% by

volume (e.g., about 20 to 60% by volume). Further, for recy
cling of part of the lower layer, the proportion of the lower
boiling point component (3A) to be recycled in the total lower

distillation column), or others. The lower boiling point com

ponent (3A) may be recycled to a plurality of steps. In par

ticular, the lower boiling point component (3A) may be

boiling point component (3A) of the lower layer may be, for

recycled to at least the reaction step.

In the method (a), the amount to be circulated may be
selected depending on the throughput of the acetaldehyde

example, about 5 to 95% by volume, preferably about 10 to

90% by volume (e.g., about 15 to 85% by volume), and more
preferably 20 to 80% by volume (e.g., about 25 to 75% by

separation column, the degree of the ?uctuation of the lower

boiling point component (3A), or others. For example, the
amount to be circulated may be not less than 2% (e.g., about

3 to 99%), preferably not less than 5% (e.g., about 7 to 95%),

more preferably not less than 10% (e.g., about 12 to 90%),
and particularly not less than 20% (e.g., about 20 to 90%) of
the average ?ow rate of the lower boiling point component
(3A) to be fed to the decanter. In particular, the circulation of
a relatively large amount [for example, not less than 40%
(e.g., about 40 to 90%), preferably about 50 to 90% (e.g.,
about 55 to 85%), more preferably about 60 to 80%, and
usually about 55 to 90% (e.g., about 65 to 85%) of the average
?ow rate of the lower boiling point component (3A) to be fed

to the decanter] of the lower boiling point component (3A)

e?iciently achieves both stable operation of the process and
removal of acetaldehyde.
The proportion of the lower boiling point component (3A)
(or the average ?ow rate of the lower boiling point component

volume).
20

a conventional method (for example, the after-mentioned

extraction) for separation of acetaldehyde and then circulated

to the reaction system or others.
25

For the method (b), before the lower boiling point compo
nent (3A) discharged from the decanter is fed to the separa

tion and recycling step, the lower boiling point component

(3A) is retained in a storage vessel (such as a buffer tank)

having a buffering function. The temporal retention of lower

30

boiling point component (3A) in the storage vessel further

eases the ?ow rate ?uctuation in the storage vessel and allows

the lower boiling point component (3A) to be fed to the

separation and recycling step at a constant or almost constant
35

(3A)) to be circulated to the reaction system (or reaction step

or reactor) in the total lower boiling point component (3A) to
be circulated may be about 5 to 100% by volume, preferably
about 10 to 90% by volume, more preferably about 15 to 80%

by volume, and particularly about 20 to 75% by volume (for

If necessary, the lower boiling point component (3A) to be

circulated to the reaction system or others may be subjected to

?ow rate, and thus the stable operation of the process is

achievable.
The storage vessel having a buffering function can be
selected based on the degree of the ?ow rate ?uctuation or
others, as the same as described above, or may be selected

40

according to the retention time of the lower boiling point

component (3A). In the storage vessel, the retention time of

example, about 25 to 70% by volume). Moreover, in the case

where the lower boiling point component (3A) is circulated to

the lower boiling point component (3A) is not particularly

the reactor and the acetic acid collection step (or distillation

0.5 minutes [for example, not less than 1 minute (e.g., about
1.5 minutes to 3 hours)], preferably not less than 2 minutes
[for example, not less than 3 minutes (e.g., about 4 to 60
minutes)], more preferably not less than 6 minutes (e.g.,
about 8 to 50 minutes), and particularly not less than 12
minutes (e.g., about 15 to 40 minutes).
When the ?ow rate ?uctuation of the lower boiling point
component (3A) can be eased in the decanter in some degree,
the retention time of the lower boiling point component (3A)

limited to a speci?c one, and may for example be not less than

column), the ratio (volume ratio) of the component (3A) to be

circulated to the reactor relative to that to be circulated to the

45

acetic acid collection step may be about 95/5 to 5/95 (e.g.,

about 90/10 to 10/90), preferably about 85/15 to 15/85 (e.g.,
about 80/20 to 20/80), more preferably about 75/25 to 25/75
(e.g., about 70/30 to 30/70), and particularly about 65/35 to
35/65 (e.g., about 60/40 to 40/60) as a ratio ofthe former/the

50

latter. Further, the ratio (volume ratio) of the lower boiling

point component (3A) (or the average ?ow rate thereof) to be
circulated to the reactor relative to the lower boiling point
component (3A) (or the average ?ow rate thereof) to be fed to
the separation and recycling step may be about 95/ 5 to 10/ 90
(e.g., about 90/10 to 15/85), preferably about 85/15 to 20/80
(e.g., about 80/20 to 25/75), more preferably about 75/25 to

in the storage vessel can also be shortened. Thus, the retention

time of the lower boiling point component (3A) in the storage

vessel may be determined in connection with the retention
55

decanter. For example, the storage vessel may be selected so

that the total time of the retention time of the lower boiling

point component (3A) in the decanter and the retention time

of the lower boiling point component (3A) in the storage

35/65 (e.g., about 70/30 to 40/60), and particularly about

70/30 to 45/55 (e.g., about 65/35 to 50/50) as a ratio ofthe
former/the latter.

In the case where the lower boiling point component (3A)

is separated into an upper layer and a lower layer inside the
decanter, either the upper layer (part of all of the upper layer)
or the lower layer (part of all of the lower layer) may be
recycled. In particular, the both layers may be recycled to the
reaction system. When the both layers are recycled, the vol
ume ratio of the lower boiling point component (3A) of the

time of the lower boiling point component (3A) in the

60

65

vessel may ne not less than 1 minute [for example, not less

than 1.5 minutes (e.g., about 2 minutes to 3 hours)], prefer

ably not less than 3 minutes [for example, not less than 4
minutes (e.g., about 5 to 60 minutes)], more preferably not
less than 6 minutes (e.g., about 8 to 50 minutes), and particu
larly not less than 12 minutes (e.g., about 15 to 40 minutes).
It is su?icient that the storage vessel having a buffering
function is provided (or installed) in a step prior to the sepa

US 8,940,932 B2
25

26

ration and recycling step. The storage vessel may be provided

(or installed) in a bottom of the after-mentioned acetaldehyde

hyde and metaldehyde may be positively produced by modi

fying the distillation conditions so that acetaldehyde can be
separated and removed in the form of paraldehyde or metal
dehyde from the bottom of the distillation column. In this

separation column.
For the method (c), the amount of the lower boiling point
component (3A) to be discharged from the decanter is kept

case, clogging due to crystallization of metaldehyde may be

reduced by adding a solvent for dissolving metaldehyde (e. g.,

constant (or almost constant) in itself [for example, assuming

that the average ?ow rate of the lower boiling point compo
nent (3A) to be discharged from the decanter is 100, the
amount of the lower boiling point component (3A) to be
discharged from the decanter in the process operation is regu
lated to about 90 to 100 (e.g., about 95 to 105), preferably
about 98 to 102, and more preferably about 98.5 to 101.5].
Since the amount of the lower boiling point component (3A)
to be discharged from the decanter is substantially kept con
stant, the method (c) may preferably be combined with a
method for easing the ?ow rate ?uctuation inside the decanter
(for example, the method (2)) in order to operate the process

methanol) to the column.

The liquid residue, which is the residue after separation of

acetaldehyde by distillation, is usually separated as a liquid

residue (higher boiling point component (4B)) containing

methyl iodide which is a useful component and is recycled.
Prior to the separation of acetaldehyde, an off gas component
may be removed beforehand by using a condenser, a cooler, or
others.
As the acetaldehyde separation column, a conventional
distillation column, for example, a plate column, a packed
column, and a ?ash distillation column, may be used. A

stably.

distillation column such as a plate column or a packed column

The position (the position of an outlet) for discharging the

lower boiling point component (3A) from the decanter is not

may usually be employed.

The temperature (the temperature of the column top) and

20

particularly limited to a speci?c one. The position of the outlet

the pressure (the pressure of the column top) in the acetalde

hyde separation column may be selected depending on the
boiling point of acetaldehyde and that of methyl iodide as
well as the types of the distillation column and others, and is

may be in an upper part, a middle part, a lower part or a bottom

part of the decanter. A plurality of these parts may be com

bined to provide a plurality of outlets. Moreover, in the case

where the lower boiling point component (3A) is separated

25

not particularly limited to a speci?c one as far as the lower

30

boiling point component (4A) containing at least acetalde

hyde is separable from the lower boiling point component
(3A) by utiliZing difference between acetaldehyde and other
components (particularly methyl iodide) in boiling point. For
example, for the plate column, the column top pressure is

into an upper layer and a lower layer inside the decanter, the

lower boiling point component (3A) may be discharged from

a position corresponding to the upper layer, a position corre
sponding to the lower layer, or both.

(Separation and Recycling Step)

In the separation and recycling step, the lower boiling point

about 10 to 1000 kPa, preferably about 10 to 700 kPa, and

more preferably about 100 to 500 kPa in terms of absolute
pressure. The inner temperature of the column (the column

component (3A) discharged or fed in a condensed state (liq

uid state) by the condensation step is separated into acetalde
hyde and a liquid residue (or residual liquid), and the liquid
residue is recycled to a step from the reaction system to the

top temperature) is, for example, about 10 to 80 C., prefer

35

acetaldehyde separation.
The discharged lower boiling point component (3A) may
further contain a vapor component withdrawn from the top of

the reactor, a higher boiling point component (3C), or others.

The lower boiling point component (3A) to be subjected to

ably about 20 to 70 C., and more preferably about 40 to 60

C. The number (theoretical number) of plates of the distilla

tion column may for example be about 5 to 80, preferably
about 8 to 60, and more preferably about 10 to 50.

In the acetaldehyde separation column, the re?ux ratio may

separation contains acetaldehyde, methyl iodide, and in addi

tion, methyl acetate, water, other carbonyl impurities (e.g.,

be selected from about 1 to 1000, preferably about 10 to 800,

and more preferably about 50 to 600 (e.g., about 100 to 600)
depending on the above-mentioned theoretical number of

crotonaldehyde and butyraldehyde) in many cases. In the

plates.

40

The recycling of the liquid residue (or higher boiling point

lower boiling point component (3A), the proportion of acetal

dehyde may be about 0.05 to 50% by weight, the proportion
of methyl iodide may be about 0.5 to 90% by weight, the
proportion of methyl acetate may be about 0 to 15% by

45

reaction step (or reactor), the ?ash distillation step (or ?ash
distillation column), and the acetic acid collection step (or

weight, the proportion of acetic acid may be about 0 to 80%

by weight, and the proportion of water may be about 0.1 to

40% by weight.

component (4B)) is not particularly limited to a speci?c step

as far as the recycling step is placed from the reaction system
to the acetaldehyde separation. The step may be any of the

50

distillation column). As in the embodiment of the ?gure, the

The method for separating acetaldehyde is not particularly

higher boiling point component (4B) may be recycled to the

limited to a speci?c one as far as the liquid residue can be

acetaldehyde distillation column, or may be recycled to a

obtained. As the separation method, a conventional method

combination of these steps. The liquid residue (or higher

[for example, extraction, distillation (e.g., separation and dis

boiling point component (4B)) after acetaldehyde separation

tillation of a process liquid containing acetaldehyde using one

55

is usually recycled to at least the reactor.

or a plurality of distillation columns), a combination thereof,

The liquid residue (or higher boiling point component

and extractive distillation] may be used.

Representatively, a preferably usable method includes a

(4B)) may be recycled directly or recycled through a storage

vessel having a buffering function (e.g., a buffer tank). Use of

method which comprises feeding the lower boiling point

component (3A) to the distillation column (acetaldehyde

60

the storage vessel having a buffering function eases the ?ow

rate ?uctuation in the storage vessel and allows easy recycling

65

of the liquid residue at a constant or almost constant ?ow rate,

even if the ?ow rate of the liquid residue ?uctuates. Thus the
storage vessel can reduce the in?uence of the ?ow rate ?uc
tuation on the recycling step.
With respect to the ?ow rate ?uctuation of the liquid resi

separation column) and separating the lower boiling point

component (3A) by distillation into a lower boiling point
component (4A) containing acetaldehyde and a liquidresidue
(bottom fraction or column bottom fraction). The production
of paraldehyde and/ or metaldehyde may be decreased by
feeding water to the distillation column and increasing the
pressure or/ and the distillation temperature. Further, paralde

due (higher boiling point component (4B)), for example,

assuming that the average ?ow rate of the liquid residue is

US 8,940,932 B2
27

28

100, the ?ow rate of the liquid residue may be about 85 to 1 15

decanter, an RDC (rotated disk contactor), a Karr column, a

(e.g., about 90 to 110), preferably about 93 to 107 (e.g., about

spray column, a packed column, a perforated plate column, a

baf?ed column, a pulse column, and others.

94 to 106), and more preferably about 95 to 105 in the process

operation.

The recycling of methyl iodide (or a component containing

The storage vessel having a buffering function may be

selected based on the degree of the ?ow rate ?uctuation, in the

methyl iodide) is not particularly limited to a speci?c step as

far as the recycle step is placed from the reaction system to the

same manner as in the condensation step, and may be selected

acetaldehyde separation. Methyl iodide may be recycled to

any of the reaction step (or reactor), the ?ash distillation step
(or ?ash distillation column), and the acetic acid collection
step (or distillation column).As the embodiment of the ?gure,
methyl iodide may be recycled (recycled as the higher boiling
point component (4B)) to the acetaldehyde-separating col

based on the desired retention time of the liquid residue. In the

storage vessel, the retention time of the liquid residue is not

particularly limited to a speci?c one, and may for example be
not less than 1 minutes (e.g., about 2 minutes to 3 hours),
preferably not less than 3 minutes (e.g., about 4 to 60 min
utes), and more preferably not less than 12 minutes (e.g.,
about 15 to 40 minutes).

umn, or may be recycled to a combination of these steps.

When the liquid residue is recycled through the storage

EXAMPLES

vessel having a buffering function, the ?uctuation of the ?ow

rate of the liquid residue (higher boiling point component

The following examples are intended to describe this

(4B)) can be decreased. For example, assuming that the aver

age ?ow rate of the liquid residue is 100, the ?ow rate of the
liquid residue may be about 90 to 110 (e.g., about 93 to 107),
preferably about 95 to 105, and more preferably about 96 to
104 (e.g., about 97 to 103) in the process operation.

invention in further detail and should by no means be inter

preted as de?ning the scope of the invention.

20

Example 1

For recycling the liquid residue (higher boiling point com

ponent (4B)) to the acetaldehyde separation column, in order
to reduce the ?ow rate ?uctuation in the separation column at

In the apparatus (or process) of FIG. 1, acetic acid produc

tion process was carried out continuously as shown in FIG. 1
25

average ?ow rate of the liquid residue is 100, the ?ow rate of
the liquid residue to be recycled to the separation column may

the buffer tank 5. The detail of the process will be described

below.

A liquid reaction medium had the following composition

30

be about 95 to 105, preferably about 97 to 103, and more

preferably about 98 to 102 (e.g., about 99 to 101) in the

process operation].
The separated lower boiling point component (4A) con
taining acetaldehyde may be discharged as it is. Since the
lower boiling point component (4A) sometimes contains a
useful component such as methyl iodide, methyl iodide (or a

(or formulation): methyl iodide (13% by weight), water (8%

by weight), methyl acetate (1.3% by weight), acetic acid
(73.6% by weight), lithium iodide (5% by weight), and
rhodium (800 ppm by weight). The liquid reaction medium

35

was fed to the reactor 1, and the process was started. Through
out the process, the variation in the ?ow rate of the liquid
reaction medium fed from the reactor 1 to the ?asher 2 was in
the range of about 11.6% relative to the average ?ow rate. In

the ?asher 2, about 27% by weight of the total liquid reaction

component containing methyl iodide, for example, a compo

nent containing methyl iodide, methyl acetate, and others)
may be collected from the lower boiling point component

except that the lower boiling point component (3A) was fed to

the acetaldehyde separation column 6 without going through

a high level, the ?ow rate of the higher boiling point compo
nent (4B) to be recycled to the separation column may be
constant or almost constant [for example, assuming that the

medium was fed to the splitter column 3 as the lower boiling

40

(4A) and recycled.

point component (2A) (the variation in the ?ow rate was in the
range of 1 1 % relative to the average ?ow rate); the remaining

The method for separating each of acetaldehyde and

higher boiling point component (2B) was recycled to the

methyl iodide (or a component containing methyl iodide)

from the lower boiling point component (4A) is not particu

reactor 1 without any treatment. Part (about 19% by volume)

of the volatilized lowerboiling point component (2A) was fed
to the hold tank 9 for removal of heat, and recycled to the

larly limited to a speci?c one, and may include a conventional

45

method (for example, extraction, distillation). Representative

reactor 1.

In the splitter column 3, the volatile component (2A) was

examples of the method may include (i) a method for sepa

rating each of methyl iodide and acetaldehyde by distilling

the lower boiling point component (4A), (ii) a method for
separating each of methyl iodide and acetaldehyde by water
extraction, which takes advantage of the miscibility of acetal
dehyde with water and the immiscibility of methyl iodide
with water. From the viewpoint of the inhibition of produc
tion of metaldehyde or others, the water extraction (ii) is
preferred. According to the method, since the increase in
hydrogen ion concentration in the distillation solution due to
ester degradation or others inhibits production of paraldehyde
and metaldehyde, acetaldehyde can ef?ciently be condensed
to a high level and removed.
The extraction temperature and the extraction time are not

50

separated by distillation into the lower boiling point compo

nent (3A) (about 50% by volume), the acetic acid-containing
stream (3B), and the higher boiling point component (3C).
The acetic acid-containing stream (3B) was withdrawn by

side cut, and the higher boiling point component (3C) was
directly recycled to the reactor. In the splitter column 3, the
55

total amount of a component fed through the line 12 and a

component fed through the after-mentioned line 30 was dis
tilled, and the volatilized component was separated as the

lower boiling point component (3A).

Meanwhile, when the lower boiling point component (3A)
60

was fed to the decanter 4, the variation in the ?ow rate was in
the range of 15% relative to the average ?ow rate (48.5

particularly limited to speci?c ones. For example, the extrac

m3/hour). The lower boiling point component (3A) has the

tion may be carried out at a temperature of 00 C. to 100 C. for

about 1 second to 1 hour. The extraction pressure is not

following composition (or formulation): methyl iodide (61%

by weight), methyl acetate (6% by weight), acetic acid (6% by
weight), water (24% by weight), and acetaldehyde (0.27% by

particularly limited to a speci?c one, and an advantageous

condition can be selected based on costs, and others. As the
extractor, for example, there may be used a combination of a
mixer with a settler, a combination of a static mixer with a

65

weight).
In the decanter 4, the lowerboilingpoint component (3A)
was separated into an upper layer and a lower layer (the

US 8,940,932 B2
29

30

former/the latter (volume ratio):l .l/l). The lower boiling

point component (3A) was discharged through the line 17 and

volume of the whole upper layer) of the total lower boiling

point component (3A) fed to the decanter 4 was recycled to
the splitter column 3.

the line 18 such that the liquid level and the interface level of

the lower boiling point component (3A) to be held in the

The composition of the lower boiling point component

decanter 4 were maintained substantially constant (such that

the ?uctuation of the liquid level was about 11% relative to
the average liquid level and the ?uctuation of the interface
level (or the liquid level of the lower layer) was about 11%
relative to the average interface level). That is, the liquid level

(3A) to be fed to the distillation column 6 was as follows:

methyl iodide (46% by weight), methyl acetate (6% by

weight), acetic acid (10% by weight), water (37% by weight),
acetaldehyde (0.3% by weight), and hydrogen iodide (0.01%

by weight).
In the distillation column 6 (a distillation column having 80

and the interface level of the lower boiling point component

(3A) in the decanter 4 were maintained substantially constant

plates, re?ux ratio: 170, feeding plate: the 70th plate from the

by changing the ?ow rate of the lower boiling point compo

nent (3A) to be discharged through the line 17 and the line 18

perature: 820 C.), 0.3% by volume of the lower boiling point

top, column top temperature: 54 C., column bottom tem

component (3A) was withdrawn as the lower boiling point
component (4A) from the column top, and the whole amount
of the residue was recycled as the higher boiling point com
ponent (4B) to the reactor 1 from the column bottom without
going through the buffer tank 7. The composition of the lower

so as to correspond to the ?ow rate ?uctuation of the lower

boiling point component (3A) to be fed to the decanter 4 and

by adjusting the retention time of the lower boiling point

component (3A) in the decanter 4.
The discharged lower boiling point component (3A) was
fed to the line 19 (or the line 20) such that the ?ow rate thereof

boiling point component (4A) withdrawn from the column

20

was substantially constant (the ?uctuation of the ?ow rate was

(2% by weight), and acetaldehyde (56% by weight).

about 11.5% relative to the average ?ow rate) by partly recy

Moreover, the lower boiling point component (4A) with

cling the lowerboiling point component (3A) through the line

17a and the line 18a, and fed to the distillation column 6
without any treatment. The ?ow rate of the lower boiling point
component (3A) to be fed to the line 19 was adjusted by

drawn from the column top was subjected to water extraction

in the extractor 8, so that acetaldehyde was removed, and a
25

directly recycled to the bottom (10th plate) of the distillation

the line 17a and the line 18a and by adjusting the retention
decanter 4. In the decanter 4, the retention time of the upper
layer was 13 minutes and the retention time of the lower layer
was 6 minutes. That is, the amount of the lower boiling point
component (3A) to be fed to each of the line 17b and the line

18b was successfully maintained substantially constant by

30

35

The above-mentioned process was carried out continu

ously, and the process was successfully operated stably. After

boiling point component (3A) to be discharged from the

40

lower boiling point component (3A) to be fed to the line 1811

was in the range of about 110%. Thus, the ?ow rate of the

the operation was carried out for a predetermined time (200

hours), the acetaldehyde concentration measured in the reac
tor was 390 ppm. This revealed that both the stable operation
and the removal of acetaldehyde at a high level were achieved

successfully. It was found that the resulting product acetic

acid had a permanganate time of 240 minutes.
45

Example 2

the upper layer, the proportion of the lower boiling point

component (3A) fed to the line 19 (or the line 17b) was 13.5%
by volume (corresponding to 25% by volume of the whole

(34 kg/hr) withdrawn from the column top of the above

mentioned distillation column having 80 plates. In this way,
59% of the acetaldehyde (32 kg/hr) produced in the reactor
was successfully removed.

so as to correspond to the ?ow rate ?uctuation of the lower

lower boiling point component (3A) to be fed to the line 19

(further the ?ow rate of the lower boiling point component
(3A) to be fed to the distillation column 6) was successfully
maintained substantially constant.
With respect to the lower boiling point component (3A) of

column 6 and the other was directly recycled to the reactor 1.

The amount to be recycled to the distillation column 6 was set
to constant. The acetaldehyde extraction rate of the lower

boiling point component (4A) was 98%. Acetaldehyde (l9

kg/hr) was successfully removed by treating the whole liquid

changing the ?ow rate of each of the line 17a and the line 1811

decanter 4. For example, the variation in the ?ow rate of the

ra?inate containing methyl iodide was separated. Then the

ra?inate was divided into two fractions; one fraction was

changing the amount of the lower boiling point component

(3A) to be circulated to the reaction system (reactor) through

time of the lower boiling point component (3A) in the

top was as follows: methyl iodide (42% by weight), water

Example 2 was conducted in the same manner as in

Example 1 except that part of the lower boiling point compo

50

nent (3A) discharged from the decanter 4 was recycled and

upper layer) in the total lower boiling point component (3A)

that the rest was fed to the distillation column 6 in the process

fed to the decanter 4; with respect to the lower boiling point

component (3A) of the lower layer, the proportion of the
lower boiling point component (3A) fed to the line 19 (or the
line 18b) was 13.5% by volume (corresponding to 28% by
volume of the whole lower layer) in the total lower boiling
point component (3A) fed to the decanter 4.
That is, 27% by volume of the total lower boiling point

as described later.

55

component (3A) fed to the decanter 4 was fed to the line 19 (or
the distillation column 6), and 73% by volume of the total
lower boiling point component (3A) fed to the decanter 4 was

60

With respect to the lower boiling point component (3A) of

the upper layer, the proportion of the lower boiling point

to the line 19 or the line 17b); with respect to the lower boiling

recycled. The breakdown of the recycle was as follows: 34%

by volume [0% by volume from the upper layer, 34% by

volume from the lower layer (corresponding to 72% by vol
ume of the whole lower layer)] of the total lower boiling point
component (3A) fed to the decanter 4 was recycled to the
reactor 1, and 39% by volume (corresponding to 75% by

component (3A) fed to the line 19 (or the line 17b) was 0% by
volume in the total lower boiling point component (3A) fed to
the decanter 4 (that is, the lower boiling point component
(3A) of the upper layer is wholly recycled without being fed

65

point component (3A) of the lower layer, the proportion of the

lower boiling point component (3A) fed to the line 19 (or the
line 18b) was 27% by volume (corresponding to 57% by
volume of the whole lower layer) in the total lower boiling
point component (3A) fed to the decanter 4.
That is, 27% by volume of the total lower boiling point
component (3A) fed to the decanter 4 was fed to the line 19 (or
the distillation column 6), and 73% by volume of the total

US 8,940,932 B2
31

32

lower boiling point component (3A) fed to the decanter 4 was

The above-mentioned process was carried out continu

recycled. The breakdown of the recycle was as follows: 34%

ously, and the process was successfully operated stably. After

by volume [13% by volume from the upper layer (corre

the operation was carried out for a predetermined time (210

hours), the acetaldehyde concentration measured in the reac
tor was 375 ppm. This revealed that both the stable operation
and the removal of acetaldehyde at a high level were achieved

sponding to 25% by volume of the whole upper layer), 21%

by volume from the lower layer (corresponding to 43% by
volume of the whole lower layer)] of the total lower boiling

successfully. It was found that the resulting product acetic

point component (3A) fed to the decanter 4 was recycled to

the reactor 1, and 39% by volume (corresponding to 75% by
volume of the whole upper layer) of the total lower boiling
point component (3A) fed to the decanter 4 was recycled to
the splitter column 3.

acid had a permanganate time of 260 minutes.

Example 3
Example 3 was conducted in the same manner as in

According to the above-mentioned step, the discharged

lower boiling point component (3A) was fed to the line 19 (or

Example 1 except that part of the lower boiling point compo

the line 20) such that the ?ow rate thereof was substantially
constant (the ?uctuation of the ?ow rate was about 12.5%

that the rest was fed to the distillation column 6 in the process

nent (3A) discharged from the decanter 4 was recycled and

relative to the average ?ow rate) by partly recycling the lower

boiling point component (3A) through the line 18a, and fed to

as described later.

the distillation column 6 without any treatment. The ?ow rate

point component (3A) was discharged from an upper part of

the decanter 4 (a position corresponding to the upper layer)
through the line 17 such that the liquid level and the interface
level of the lower boiling point component (3A) to be held in
the decanter 4 were maintained substantially constant (such

In the same manner as in Example 1, the lower boiling

of the lower boiling point component (3A) to be fed to the line

19 was adjusted by changing the amount of the lower boiling
point component (3A) to be circulated to the reaction system
(reactor) through the line 18a. That is, the amount of the lower
boiling point component (3A) to be fed to the line 18b was

20

successfully maintained substantially constant by changing

25

the ?ow rate of the line 1811 so as to correspond to the ?ow rate

?uctuation of the lower boiling point component (3A) to be

discharged from the decanter 4 (the variation in the ?ow rate
of the lower boiling point component (3A) to be fed to the line
1811 was in the range of about 117%). Thus, the ?ow rate of the

30

lower boiling point component (3A) to be fed to the line 19

(further the ?ow rate of the lower boiling point component

(3A) to be fed to the distillation column 6) was successfully
maintained substantially constant.

The composition of the lower boiling point component

35

(3A) to be fed to the distillation column 6 was as follows:

methyl iodide (91% by weight), methyl acetate (7% by

weight), acetic acid (1% by weight), water (0.3% by weight),
acetaldehyde (0.1% by weight), and hydrogen iodide

(0.001% by weight).

that the ?uctuation of the liquid level was about 11% relative
to the average liquid level and the ?uctuation of the interface

level (or the liquid level of the lower layer) was about 11%
relative to the average interface level). That is, the liquid level
and the interface level of the lower boiling point component
(3A) in the decanter 4 were maintained substantially constant
by changing the ?ow rate of the lower boiling point compo
nent (3A) to be discharged through the line 17 along with the
?ow rate ?uctuation of the lower boiling point component
(3A) to be fed to the decanter 4.
The ?ow rate to be fed to the line 19 was successfully
relatively reduced by changing the ?ow rate to be fed to the
line 1711 (about 11.5% relative to the average ?ow rate).

With respect to the lower boiling point component (3A) of

the upper layer, the proportion of the lower boiling point
40

component (3A) fed to the line 19 (or the line 17b) was 27%
by volume (corresponding to 51% by volume of the whole

In the distillation column 6 (a distillation column having 80

upper layer) in the total lower boiling point component (3A)

plates, re?ux ratio: 170, feeding plate: the 70th plate from the

fed to the decanter 4; with respect to the lower boiling point

component (3A) of the lower layer, the proportion of the
lower boiling point component (3A) fed to the line 19 (or the
line 18b) was 0% by volume in the total lower boiling point

top, column top temperature: 54 C., column bottom tem

perature: 820 C.), 0.3% by volume of the lower boiling point

component (3A) was withdrawn as the lower boiling point
component (4A) from the column top, and the whole amount
of the residue was recycled as the higher boiling point com
ponent (4B) to the reactor 1 from the column bottom without
going through the buffer tank 7. The composition of the lower

45

boiling point component (4A) withdrawn from the column

50

component (3A) fed to the decanter 4 (corresponding to 0%

by volume of the whole lower layer, that is, the lower boiling
point component (3A) of the lower layer was wholly recycled
without being fed to the line 19 or the line 18b).

top was as follows: methyl iodide (43% by weight), water

(1% by weight), and acetaldehyde (56% by weight).

Moreover, the lower boiling point component (4A) with
drawn from the column top was subjected to water extraction
in the extractor 8, so that acetaldehyde was removed, and a

55

ra?inate containing methyl iodide was separated. Then the

ra?inate was divided into two fractions; one fraction was

directly recycled to the bottom (10th plate) of the distillation

column 6 and the other was directly recycled to the reactor 1.
The amount to be recycled to the distillation column 6 was set
to constant. The acetaldehyde extraction rate of the lower

60

boiling point component (4A) was 98%. Acetaldehyde (20

kg/hr) was successfully removed by treating the whole liquid
(34 kg/hr) withdrawn from the column top of the above
mentioned distillation column having 80 plates. In this way,
63% of the acetaldehyde (32 kg/hr) produced in the reactor
was successfully removed.

That is, 27% by volume of the total lower boiling point

component (3A) fed to the decanter 4 was fed to the line 19 (or
the distillation column 6), and 73% by volume of the total
lower boiling point component (3A) fed to the decanter 4 was
recycled. The breakdown of the recycle was as follows: 47%

by volume [0% by volume from the upper layer, 47% by

volume from the lower layer (corresponding to 100% by
volume of the whole lower layer)] of the total lower boiling
point component (3A) fed to the decanter 4 was recycled to
the reactor 1, and 39% by volume (corresponding to 75% by
volume of the whole upper layer) of the total lower boiling
point component (3A) fed to the decanter 4 was recycled to
the splitter column 3.

Then, the discharged lower boiling point component (3A)

65

was fed to the buffer tank 5 and retained at a retention time of

3 minutes to ease the ?uctuation of the ?ow rate in the buffer

tank 5, and the lower boiling point component (3A) was fed at
a constant ?ow rate to the distillation column 6.

US 8,940,932 B2
33

34

The composition of the lower boiling point component

The above-mentioned process was carried out continu

ously, and the process was successfully operated stably.

(3A) to be fed to the distillation column 6 was as follows:

methyl iodide (3% by weight), methyl acetate (4% by

weight), acetic acid. (19% by weight), water (73% by
weight), acetaldehyde (0.5% by weight), and hydrogen
iodide (0.01% by weight).

Comparative Example 1
5

The process was conducted in the same manner as in

Moreover, the total amount of the higher boiling point

Example 2 except that the lower boiling point component

component (4B) separated in the distillation column 6 was

recycled to the splitter column 3 through the buffer tank 7.
Although the variation in the ?ow rate of the higher boiling

(3A) of the lower layer was wholly fed to the distillation

column 6 through the lines 18b to 19 and that the total amount

point component (4B) separated from the distillation column

the reactor 1 without going through the buffer tank 7. The

liquid level of the lower layer of the decanter 4 or the ?ow rate
of the lower boiling point component (3A) to be fed to the

of the higher boiling point component (4B) was recycled to

6 was about 14%, the ?ow rate of the higher boiling point
component (4B) to be recycled through the line 23 was suc

distillation column 6 ?uctuated largely, and it was di?icult to

cessfully maintained substantially constant by recycling the

component (4B) through buffer tank 7.

continue the stable operation in the splitter column 3 and the

distillation column 6. Accordingly, the operation had to be
discontinued.

The above-mentioned process was carried out continu

ously, and the process was successfully operated stably.

Example 4

Comparative Example 2
20

The process was conducted in the same manner as in

The acetic acid production process was carried out con

Example 3 except that the lower boiling point component

tinuously as shown in the apparatus (or process) of FIG. 1.

The conditions including the charging amounts were the
same as those of Example 2 except that the process was

25

conducted via buffer tank 5.

In the same manner as in Example 2, the lower boiling

point component (3A) was discharged from a lower part of the

decanter 4 (a position corresponding to the lower layer)

through the line 18 such that the liquid level and the interface
level of the lower boiling point component (3A) to be held in
the decanter 4 were maintained substantially constant (such
that the ?uctuation of the liquid level was about 11% relative
to the average liquid level and the ?uctuation of the interface

level (or the liquid level of the lower layer) was about 11%
relative to the average interface level). That is, the liquid level
and the interface level of the lower boiling point component
(3A) in the decanter 4 were maintained substantially constant
by changing the ?ow rate of the lower boiling point compo
nent (3A) discharged through the line 18 along with the ?ow
rate ?uctuation of the lower boiling point component (3A) to
be fed to the decanter 4. Then, the discharged lower boiling
point component (3A) was fed to the buffer tank 5 and

30

35

(3A) of the upper layer was wholly fed to the distillation

column 6 through the lines 17b to 19 without going through
the buffer tank 5 and that the higher boiling point component
(4B) was recycled without going through the buffer tank 7
(about 10% by volume thereof was recycled to the reactor 1,
about 20% by volume thereof was recycled to the distillation
column 6, and the rest was recycled to the splitter column 3).
The liquid level of the upper layer of the decanter 4 or the ?ow
rate of the lower boiling point component (3A) to be fed to the
distillation column 6 ?uctuated largely, and it was di?icult to
continue the stable operation in the splitter column 3 and the
distillation column 6. Accordingly, the operation had to be
discontinued.

Comparative Example 3
40

The acetic acid production process was carried out in the

same manner as in Example 2 except that 57% by volume of

the lower boiling point component (3A) of the lower layer

was fed to the line 19 (or the line 18b) without changing the
?ow rate of the line 18a in response to the ?ow rate ?uctuation

of the lower boiling point component (3A) to be discharged

retained at a retention time of 3 minutes to ease the ?uctuation

from the decanter 4. The variation in the ?ow rate of the lower

of the ?ow rate in the buffer tank 5, and the lower boiling point

boiling point component (3A) fed to the line 19 was in the

range of 57:5% by volume.
In the distillation column 6 (a distillation column having 80

component (3A) was fed at a constant ?ow rate to the distil

lation column 6.

The composition of the lower boiling point component

(3A) to be fed to the distillation column 6 was as follows:

plates, re?ux ratio: 170, feeding plate: the 70th plate from the
50

methyl iodide (91% by weight), methyl acetate (7% by

weight), acetic acid (1% by weight), water (0.3% by weight),
acetaldehyde (0.1% by weight), and hydrogen iodide

(0.001% by weight).
Moreover, about 80% by volume of the higher boiling
point component (4B) separated in the distillation column 6

55

column top was as follows: methyl iodide (37 to 49% by

60

distillation column 6 was constant. Moreover, although the

variation in the ?ow rate of the higher boiling point compo

ra?inate containing methyl iodide was separated. Then the

14%, the ?ow rate of the higherboiling point component (4B)

tained substantially constant by recycling the component

(4B) through buffer tank 7.

weight), water (about 1% by weight), and acetaldehyde (50 to

62% by weight).
Moreover, the lower boiling point component (4A) with
drawn from the column top was subjected to water extraction
in the extractor 8, so that acetaldehyde was removed, and a

nent (4B) separated from the distillation column 6 was about

to be recycled through the line 23 was successfully main

point component (3A) was withdrawn as the lower boiling

point component (4A) from the column top, and the whole
amount of the residue was recycled as the higher boiling point
component (4B) to the reactor 1 from the column bottom
without going through the buffer tank 7. The composition of

the lower boiling point component (4A) withdrawn from the

was recycled to the reactor 1 through the buffer tank 7, and

about 20% by volume of thereof was recycled to the distilla
tion column 6 through the buffer tank 7. The ?ow rate of the

higher boiling point component (4B) to be recycled to the

top, column top temperature: 53 to 55 C., column bottom

temperature: 820 C.), 0.3% by volume of the lower boiling

65

ra?inate was divided into two fractions; one fraction was

directly recycled to the bottom (10th plate) of the distillation

column 6 and the other was directly recycled to the reactor 1.