Us 20180201562 A 1

MAIN TEH ETA AUTOMAT ETA MATKALLA
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(19) Amerika Serikat

(12) aplikasi paten publikasi (10) Pub.MATAN
Tidak. : US
US 201820180201562A1
/ 0201562 A1 SHIMIZU et al. Juli. 19, 2018
(43) pub. Tanggal:
(54) METODE UNTUK MENGHASILKAN ASAM ASETAT B01D 3700 (2006. 01)
B01D 3 / 14
(71) pemohon: DAICEL CORPORATION, Osaka - shi, Osaka (JP) BOID 15 / 36 (2006. 01) (2006. 01)
(52) U. S. CI.
(72) penemu: Masahiko SHIMIZU, Himeji - shi (JP); BPK............ C07C 51 / 12 (2013. 01); C07C 51 / 445
GODA Susumu, Himeji - shi 15 / 361 (2013. 01); BOID 3 / 143 (2013. 01); B01D
(JP); Hiroyuki MIURA, Himeji - shi (JP)
(73) diberi tugas: DAICEL CORPORATION, Osaka - shi, Osaka (JP)
(57) ABSTRAK
(21) Appl. Tidak. : 15 / 540, 172
Hal ini dimaksudkan untuk memberikan metode produksi asam asetat yang mampu
(22) PCT Filed: PCT 25 Mei 2017 industri advantageously memisahkan dan menghapus oleh - produk asetaldehida di
(86) tidak. : PCT / JP2017 / 019573 langkah pemisahan memisahkan aliran proses menjadi fase berair dan organik.
$ 371 (c) (1), Dalam penemuan hadir, langkah pemisahan memenuhi, sebagai contoh, kondisi
(2) tanggal: Jun. 27, 2017
(30) Asing aplikasi prioritas Data berikut (vi) sampai dengan (viii), dan setidaknya sebagian dari fasa air
diperlakukan di langkah pemisahan dan penghapusan asetaldehida: konsentrasi
Jan. 18, 2017 (JP)............................. . 2017 - 006645
Mar. 2, 2017 asetaldehida (vi) di t Ia berair dan / atau organik fase yang tidak lebih dari
(JP)................................. 2017 - 039389
Publikasi Klasifikasi 28. 1% massa dan tidak lebih dari 24. 8 massa %, masing-masing; (vii) suhu pemisahan adalah tidak lebih da
(51) Int. Cl.
C07C 51 / 12 (2006. 01)
CO7C 51 / 44 (2006. 01)
Aplikasi paten publikasi Juli. 19, 2018 lembar 1 dari 6 U.S. 2018 / 0201562 Al
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US 2018 / 0201562 A1 Jul . 19 , 2018
METHOD FOR PRODUCING ACETIC ACIDin the case of distilling an organic phase ( methyl iodide phase ) in an acetaldehyde removal column as
mentioned later is necessary for the separation of methyl iodide and
TECHNICAL FIELD
[ 0001 ] The present invention relates to a method for to the separation of water .
The present application claims the priorities
[ 0005 ] On the other hand , ofa Japanese
method ofPatent Application
distilling , in Noan. 2017 - 006645
filed in Japan on Jan . 18 , 2017 and Japanese Patent Appli cation No . 2017 phase
- 039389
of the two phases separated using the decanter in the lower boiling
filed in Japan on Mar . 2 , 2017 , the contents of which are incorporated hereincolumn
by , and subjecting a conden sate of an over
reference in their entirety . separate and remove acetaldehyde is also known .
BACKGROUND ART
[ 0002 ] A carbonylation process of a methanol method is small because the main component of the organic phase is
evaporation , and the corrosion problem is also less likely to arise as compared with th
industrial method for producing acetic acid . In this process , for example , methanol and
phase . However , as described above , according to the studies of the present
carbon monoxide are reacted in the presence of a catalyst in a reaction vessel
disadvantage that separation efficiency is generall
separated
produce aceticinacidan. The
evaporator into amixture
obtained reaction vaporisphase containing acetic acid
concentration than that of the aqueous phase . residual liquid phase
and lower boiling point components and a
containing acetic acid and the catalyst , to the acetaldehyde removalandtreatment and thephase
the vapor methodisof separated
acetaldehyde removal
by distillation in a distil lation column ( lower boiling pointtreatment have advantages and disadvantages .
10006 ] Thus , an object of the present invention is to
component removal column ) into an overhead stream containing lower
provide a method capable of industrially advantageously
boiling point components and an acetic acid separating stream . The acetic
and removing a by - product acetaldehyde in con
acid stream is further purified to obtain productsideration acetic acid . In
of the advantages and disadvantages of the
this process , acetaldehyde is produced as a by - product
method of subjecting the aqueous phase to the
during the reaction , and this acetaldehyde is responsible for
acetaldehyde removal treatment and the method of
reducing the quality of the product acetic acid . Therefore , for
subjecting the organic phase toexample , in
the acetaldehyde
Patent Literature 1 , a condensate of the over head streamremoval of the Solution to Problem tion ste
treatment in the separa
lower boiling point CITATION component removal [
ahave
0007
process
] In order to
stream onintoan the
attain the
column object
aqueous
, the present inventors
is separated into an aqueous
LIST focused acetaldehyde distribution phase and the
phase and an organic phase using a decanter phase . Of them , the aqueous
in the carbonylation( process phase is
acetaldehyde of concentration in the
Patent Literature coefficient
distilled in an acetaldehyde removal column , and a condenaqueous phase / acetalde hyde concentrationsate in (tP
[ 0003 ] Patent Literature 1 : National Publication of Inter national
containing overhead stream
Application No . acetaldehyde
2001 - 508405 and methyl iodide ) of an organic phase ) under various conditions in
thereof is subjected to extraction
SUMMARY OF INVENTION with water to thereby separate and remove
separation step , and conducted a liquid
acetaldehyde . Technical Problem equilibrium experiment simulating the condensate
[ 0004 ] According to the studies of the present inventors , a composition of an overhead stream of a lower boiling metho
, in an acetaldehyde removal column , an point component aqueous phase of two phases
removal separated. using
column As aa result , the
a lower inboiling point component removal column as
decanter present inven tors have found that described
therein Patent
existsLiterature
the 1 ment
generally tends to have high separation efficiency because the aqueous given correlation of acetaldehyde concentrations in an
that of the organic phase . However , in this method , treatment aqueous phase and an organic phase obtained by separation energy is i
containing a large amount of water having large latent heat of evaporation
using a decanter in the . In lower boiling point component
method in the case where the acetaldehyde
made of an expensive material havingremoval
very high corrosion
columnresistance ,is necessary
a liquid is temperature
distribution coefficient high to atsome the
hydrolysis of methyl iodide contained in a extent small amount
time of(in thethe aqueous
in thephasecase where
separation , andacet methyl acetate aldehyde is
Since a considerable concentrations
the aqueous phase , theinin atherelatively
amount of methyl iodide is present indistributed aqueous phase and amount
large the organic
in
column equivalent to that phase
the with the distribution coefficient of acetaldehyde
aqueous phase ) , to adopt the latter
method
. As men in the case
tionedwhere
above the
, theacetaldehyde
method of subjecting
distribution coefficient is low to some the acetaldehyde removal
the aqueous phase to
extent ( in
treatment and the method ofthe case where acetaldehyde is distributed
subjecting i
the organic
US 2018 / 0201562 A1 Jul . 19 , 2018
ticularly , for adopting the method of subjecting the aqueous phase monoxide to the in the presence of a catalyst system
acetaldehyde removal treatment , it is necessary comprising a metal catalyst andtomethyl use an expensive
iodide apparatus
, or
equipment having high [ 0023. Therefore
acetic
corrosion resistance ] acid
a separation it step
,, methyl ofacetate
is necessaryseparatingto, a process stream containing at and water
strictly determine the acetaldehyde distribution coefficient . Theleast water , acetic acid , methyl iodide , and present inventio
on[ 0008
these] findings and discussions
Specifically , the present invention provides a aqueous
[ 0024 ] phasean and andhasanbeenorganic
acetaldehyde completed
separation phaseandthrough
; removalfurther
step forstudies .
method for producing acetic acid , comprising : the acetaldehyde derived from the process stream , wherein
[ 0009 ] a carbonylation reaction step of reacting methanol
a catalyst system comprising a metal catalyst and methyl[ 0025 iodide] ,theacetic
separation
acid , step satisfies at least one of the
conditions ( i ) to ( v ) , and at least a portion of the
water in a reaction vessel to produce acetic acid ;
acetaldehyde separation and removal step ( hereinafter , this method is a
[ 0010 ] an evaporation step of separating the reaction mix ture obtained in the
the[ 0026 ] ( i ) an acetaldehyde concentration in the aqueous
production method 2 of the present invention " ) :
carbonylation reaction step into a vapor less than 0 . 045 % by mass , and / or an acetalde stream and a residual liquid
[ 0011 ] a lower boiling point component removal step of
stream in an evaporator ; phase is not less than 0 . 013 % by mass ;
vapor stream by distillation into an overhead [ 0027 ] ( ii ) a temperature at the time of the separation is not stream rich in at least one
lower boiling point component 5° C ]. ;( selected
[-0028
from methyl iodide and acetaldehyde and an acetic
iii ) a methyl acetate concentration in the aqueous
[acid0012stream
] a separation step ofacidseparating
rich in acetic ; a process stream less than 1 . 2 % by mass , and / or a methyl acetate
water , acetic acid , methyl iodide , and acetaldehyde into an aqueous phase and an mass , and / or the sum of the methyl
not less than 2 . 2 % by
organic and
[ 0013 ] phase ;
an acetaldehyde separation and removal step for aqueous phase and the methyl acetate concentration in
separating an
[by0029
mass ]; ( iv ) an acetaldehyde distribution coefficient [ { acet
removing the acetaldehyde derived from the process stream , wherein
[ 0014 ] the separation step satisfies at least one of the concentration ( % by mass ) of the aqueous phase }/
( i ) to ( v ) , and at least a portion of the concentration ( % by mass ) of the organic
[ 0030 ] ( v ) a methyl acetate organic phase iscoefficient
distribution treated in the
acetaldehyde separation and and removal step
concentration ( % (byhereinafter
mass ) of the, this
aqueousmethod is also
referred
[ 0015 ]to (asi ) an acetaldehyde concentration the “inproduction method 1 of the present( %invention
the aqueous by mass ”) )of: the organic phase } ] is not more than 0 . 53 .
[ 0031 ] In the production method 2 of the present inven
less than 0 . 045 % by mass , and / or an acetalde hyde concentration in the organic
catalyst system may further comprise an ionic
phase is not less than 0 . 013 % by mass ; [ 0032 ] In the production method 2 of the present inven
0016 ] ( ii ) a temperature at the time of the separation is not
less than - 5° C . ; preferred that the separation step should satisfy all
[ 0017 ] ( iii ) a methyl acetate concentration in the aqueous 10033 ] ) ,The present invention further provides a method phase
methyl acetate ) , ( iii
concentration in the organic phase is not less than 2 . 2 % by
( iv ) , and ( v ) .
acetate concentration in
for producing
the aqueous phase [and0034the ]methyl
a carbonylationacetic
reaction
acetate concentration
acid , comprising :
in step of reacting methanol
catalyst system comprising a metal catalyst and methyl iodide , acetic acid , methyl ace
. 4 % by mass ;
[ 0018 ] ( iv ) an acetaldehyde distribution coefficient [ { acet reaction vessel to produce acetic acid ;
by mass ) of the aqueous phase } [ 0035 ] an evaporation step of separatingconcentration
{ acetaldehyde the reaction(mix% by mass ) of the
organic phase } ] is not more than 4 . 1 ; and carbonylation reaction step into a vapor
[ 0019 ] ( v ) a methyl acetate distribution coefficient [ { methyl acetate [ in0036an] evaporator
a lower boiling
; point component removal step of
concentration ( % by mass ) of the aqueous phase } / { methyl acetate concentration stream by( %distillation into an overhead
by[ 0020
mass] ) Inof the
the production method 1 of the present inven organic phase } ] is notcomponent
more than 0 . 53 . selected from methyl iodide and acetaldehyde and an acetic tion , the cata
10037 ]
in acetic acid ; a separation step of separating
iodide . a process
system may further comprise an ionic
[ 0021 ] In the production method 1 of the present inven stream containing at least water , acetic acid , methyl tion , i
and
iodide , and
that the separation step should satisfy all
[ 0038 ] an acetaldehydeof separation acetaldehyde
the conditions ( i )step, ( foriiinto
and removal ) , ( an aqueous phase and an
[ 0022 ] The present invention also provides a method for the acetaldehyde derived from the produci
process stre
iii ) , ( iv ) , and ( v
acid by reacting methanol with carbon
) .
US 2018 / 0201562 A1 Jul . 19 , 2018
[ 0039 ] the separation step satisfies at least one of the following { acetaldehyde concentration ( % by mass ) of the organic
phase } ] is not less than 1 . 1 ; and
conditions ( vi ) to ( x ) , and at least a portion of the [ 0055 ] ( x ) a methyl acetate distribution coefficient aqueous phase is treat
the acetaldehyde separation and removal step
concentration ( % (byhereinafter
mass ) of the, thisaqueous
method is also
referred
10040 ]to as( vi ) an acetaldehyde concentration the production method
in the3 of the present (invention
% by mass” )) of: the organic phase } ] is not less than 0 . 25 .
aqueous [ 0056 ] In the production method 4 of the present inven
phase is not more than 28 . 1 % by mass
,[ 0041and] ( /vii or system may further
hyde concentration in the comprise an ionic
) a an acetalde
temperature at the time of the separation is 10057 ] In the production method 4 of the present not more th
organic phase is not more than 24
inven . 8 % by mass ;
[ 0042 ] ( viii ) a methyl acetate concentration in the aqueous tion , it is preferred that the
[separation
0058 ] The productionstep methodsshould
1 to 4 ofsatisfy
the present all of the conditions ( vi ) ,
or a methyl acetate concentration in the organic phase is not more than
a scrubber step of separating offgas from the process into a
acetate concentration in the aqueous phase and the methyl acetate concentration in the org
and a stream rich in acetic acid by absorption treat
than 59 . 6 % by mass ;
containing at least acetic acid .
[ 0043 ] ( ix ) an acetaldehyde distribution coefficient [ { acet
Advantageous Effects of Invention
concentration ( % by mass ) of the aqueous phase } / [ 00591 . According to the present invention , in the separa { acetaldehyde
concentration ( % by mass ) of the organic
[ 0044 ] ( x ) a methyl acetate distribution coefficient process stream into an aqueous phase } ] is not lessphasethanand 1an.organic
1 phase , an objec
%; and
by mass ) of the aqueous removal
phase }treatment is determined
/ { methyl acetateonconcentration
the basis ( % by mass ) of the
organic phase } ] is not less than 0 . 25 . aqueous phase , an acetaldehyde concentration in the organic phase , a tempera
[ 0045 ] In the production method 3 of the present inven tion , the
time of the separation , a methyl acetate concen iodide .
catalyst system may further comprise an ionic
[ 0046 ] In the production method 3 of the present inven methyl acetate concentra tion in the organic phase , etc . Th
acetaldehyde produced as a by - product in the carbonylation process of the
preferred that the separation step should satisfy all of the conditions ( vi ) , ( vii ) ,
[( viii
0047 )] , (Theix )present
, and (invention
x ) . further provides a method removed industrially advanta geously and efficiently .
for producing
monoxide in the presence of a catalyst system comprising a BRIEF DESCRIPTION OF DRAWINGSmetal catalyst and methyl iodide , acetic a
acetate , and water , comprising [ 0060 ] FIG . 1 is an acetic acid production flow diagram
embodiment of the present invention .
10048 ] a separation step of separating a process stream[ 0061 ] FIG . 2 is a schematic flow diagram showing one
containing at least water , acetic acid , methyl iodide acetaldehyde separation and removal system .
diagram showing
acetaldehyde into an aqueous phase and an organic another example of the acetaldehyde separation and removal system .
, and
[ 0049 ] an acetaldehyde separation and removal step for separating and removing the
phase ; and [ 0063 ] FIG . 4 is a schematic flow diagram showing a
acetaldehyde derived from the process stream , wherein
0050 ] the separation step satisfies at least one alternative example of the acetaldehyde separation
[ 0064 ] FIG . 5 is a schematic flow diagram showing a
of the following conditions ( vi ) to ( x ) , and alternative at example of the acetaldehyde separation
least a portion of the aqueous phase[ 0065is) treated
FIG . 6 is ainschematic diagram of a liquid - liquid
[ the
0051 ] acetaldehyde
( vi ) an acetaldehydeseparation
concentration in and
the aqueous pha
measurement apparatusremoval step (of the
used in Examples
28 . 1 % by mass , ,and this
hereinafter / or an method
acetalde is also referred to as hyde concentrationthe in the" organic phase is notmethod 4 of the prese
production
24 . 8 % by mass ; DESCRIPTION OF EMBODIMENTS
more than
[ 0052 ] ( vii ) a temperature at the time of the separation is [ 0066 ] FIG . 1 is an acetic acid production flow diagram
than0053
70° C ]. ; ( viii ) a methyl acetate concentration in the embodimentaqueous
of the present invention . An acetic
production flow has a reaction vessel 1 , an evaporator 2 , a
phase is not more than 12 . 0 % by mass , and acetic / oracida
methyl acetate concentration in the organic , a phase
decanter 4 ,isa distillation
not column 5 ,
more than 47 . 6 % by mass , and / or theresinsumcolumn of 7 , athe methyl scrubber system 8 , an acetaldehyde separation and removal
mass
acetate ; concentration in the aqueous phase and condensers
the lamethyl, 2a , 3a , 5a , and 6a , a heat
[ 0054 ] ( ix ) an acetaldehyde distribution coefficient [ { acet a pump 57 and is configured to be capable of continuously
acetate concentration in the organic phase is not , and 6bmore, linesthan
11 to5956 ., and6 % by
concentration ( % by mass ) of the aqueous phase } the method for producing acetic
US 2018 / 0201562 A1 Jul . 19 , 2018
acid according to the present embodiment , a reaction step , ( particularly , an ionic metal iodide ) and can exhibit the effect
an evaporation step ( flash step ) , a first stabilizing the catalyst mentioned above and the effect of
distillation step , a second distillation stepof, thea ionic
reaction . Examples thirdiodide
distillation step , and an adsorptiveiodide
removal
, sodiumstep are performed iodide , and potassium iodide . The concentration of the ionic
in the reaction vessel 1 , the reaction
evaporator 2 example
mixture is , for , the, 1 to 25 % by
distillation column 3 , the distillation respect to the whole columnliquid5 ,phasetheof the reaction mixture . In addition , when an
distillation column 6 , and the ion exchange or the like is used , for example , a ruthenium resin column 7 ,
respectively . The first distillation step is also co - catalyst . The amount of these compounds to be used as
referred to as a lower boiling point component removal step , metal ) , p
010071
. 1 to ]30 moles
Water( inintermsthe
of reaction mixture is a component
the second distillation step is also referred to as a dehydra based acid in
acetic theofreaction nism of the m
on 1 mole iridium in mecha
terms of metal ) .
tion step , and the third distillation step is also also a component necessary for solubilizing a water - soluble com
[ 0067 ] The reaction vessel 1 is a unit for performing the
referred to as
is a step for continuously a higher boiling point component
producing
reaction removal
aceticsystem
acid through a reaction
. The ( methanol carboof water in
concentration
step . Also , a separation step andexample an acetaldehyde
, 0 . 1 to 15 % by mass , given below . In a steady operation stateprefera
of the a
represented by the chemical formula ( 1 )
separation and removal ( acetaldehyde removal treatment ) step
acid production apparatus , for example , a reaction mixture under preferably 1 to 6 % by mass , particularly preferablystirr1
are performed in the decanter 4 andrespect the acetaldehyde
reaction mixture contains
the reaction vessel 1 . The to methanol
the andwhole
carbon monoxide
liquid phase of the reaction mixture . The wat
separation and removal system 9 , respectively . In the
catalyst , a co - catalyst , water , a production target acetic acid , and various by
concentration is preferably not more than 15 % by mass for
present invention , the steps are not limited to those described
liquid phase and a gaseous phase are in equilibrium . efficient acetic acid production by reducing energy
above and may exclude , particularly , equipment of the
CH3OH + CO - CH2COOH ( 1 ) removal waterdistillation
[ 0072 ] Theofacetic acidin in the column
the reaction
course of 5purifica
mixture , distilacetic acid fed in
includes
[ 0068 ] The raw materials in the reaction mixture are advance
controlinto thethereaction
watervessel 1 before
concentra tion , water ma
methanol in a liquid state and carbon monoxide in apredetermined gaseous
apparatus , and aceticflow acid generated as
rate to the reaction vessel a main product of the methanol
1 . carb
state . Methanol is continuously fed at a predetermined reaction . Such acetic acid can function as a solvent
flow rate to the reaction vessel 1 from a methanol
concentrationreservoir (
of the acetic acid in the reactio
not shown ) through the line 11 . Carbon monoxide is continu ously fed at
% by mass , preferably 60 to 80 % by mass , with respect to the whole
a predetermined flow rate to the reaction vessel [ 0073 ] Examples of the main by - products contained1 infrom
the a carbon
phase of the reaction mixture .
include methyl acetate . This methyl acetate
monoxide reservoir ( not shown ) through the line 12 . The
acetic acid and methanol . The concentration of the methyl acetate in the reaction mixture is ,
carbon monoxide is not necessarily required to be pure carbon
[ 0069 ] The metal catalyst in the reaction mixture promotes for example , 0 . 1 to 30 % by mass , prefera
monoxide other gases such as nitrogen
methanol , and ,and may contain
for example ,a , for example ,
rhodium catalyst or an iridium catalyst
to the whole can ofbe theusedreaction
liquid phase . For mixture . Another example of the
, hydrogen , carbon dioxide , and oxygen , in a small amount ( e . g
, a rhodium complex represented by the chemical contained in the reaction mixture includes formula [ Rh ( CO ) 212 ] - can be used as the
. , not more than 5 % by mass , preferably not
For example , an iridium complex represented by the chemi more than 1 % by
rhodium catalyst . inevitably gener ated under the reaction mechanism of the methanol carbo
,mass
1 - can)be .used as the iridium cata in the case where the catalyst lystor.theA metal complex catalyst is preferred as the metal
catalyst . The concentration ( in terms of the metal ) of the the hydrogen iodide in the reactioncatalyst
mixture isin, for
theexample
reaction
, mixtur
concentration of
example , 200 to 5000 ppm by mass , preferably 400 to 2000 ppm by mass , with by mass with respect to the whole liquid phase
whole
0070liquid
] phase
The ofcothe-reaction mixtureis. an iodide for assisting of the by - products
catalyst include hydrogen , methane , carbon dioxide , aceta
the action of the catalyst mentioned above , and , crotonaldehyde , 2 - ethyl crotonaldehyde , dimethyl ether ,
for example , methyl iodide or an ionic propionic acidiodide
, and alkyl iodides such as hexyl io
is used . The methyl iodide can exhibit the reaction mixture may contain a metal , such as iron , nickel , chromium ,
effect of promoting the catalytic effect of
man ganese , or molybdenum , generated by the corrosion of the
the catalyst mentioned above . The concentration
hereinafter , also referred to as a " corroded
of the methyl iodide is , for example , 1 to
such as cobalt , zinc , and copper .
US 2018 / 0201562 A1 Jul . 19 , 2018
[ 0074 ] In the reaction vessel 1 where the reaction mixture as described above is The reaction mixture containing such acetic acid is
present , the reaction temperature is set to , for example , 150 to 250° C . The continu ously withdrawn at a predetermined flow
reaction pressure as the total pressure
rateis setfrom
to , for the
example , 2 . 0 to 3 . 5 MPa ( reaction vessel 1 and introduced to the
absolute
[ 0078 ] The evaporator 2 is a unit for performing the
pressure ) , and the carbon monoxide partial pressure is setnext
to , evaporator 2
( flash step ) . This evaporation step is a step through the line 16 .
[example
0075 ], 0The. 4vaporto of1 .a 8 MPa ( absolute
gaseous pressure in) , preferably
phase portion the reac 0 . 6 to 1 . continuously introduced to the evaporator 2 through the line 16 ( reaction m
5 MPa ( absolute
operation containspressure
, for ) . example , carbon monoxide , hydrogen , methane , carbon
line ) , into a vapor stream ( volatile phase ) and a residual
oxygen , methyl iodide , hydrogen iodide , water , methyl acetate , acetic acid , dimethyl ether , methanol ,
low volatile phase ) by partial evaporation .
acetaldehyde , formic acid , and propionic acid . This vapor can b
reducing the pressure
13 . The internal pressure of the reaction vessel 1 can be
without heating the reaction mixture
vessel 1 through the line be caused by reducing the pressure while heating the reac
the adjustment of the amount of the vapor may withdrawn , and , for example , the internal pressure of the
vessel 1 is kept constant . The vapor withdrawn from evaporation step , the temperature of the the reaction vessel 1 is introduced to the conde
. , preferably 120 to 200° C . , and the temperature of the residual liquid stream
.
[ 0076 ] The condenser la separates the vapor from the example , 80 to 200° C . , preferably 100 to 180° C . The
and a gaseous portion by cooling and partial condensationevaporator
. The condensate
is , for example , 50 to
, methyl iodide , hydrogen iodide , water , methyl acetate , acetic acid , dimethyl ether ,
between the vapor stream and the residual liquid stream to be separat
acetaldehyde , formic acid , and propionic acid and is introduced to the reaction
evaporation step is , for example , 10 / 90 to 50 / 50 ( vapor
through the line 14 and recycled . The gaseous portion contains , for ex
stream ) in terms of a mass ratio . The
meth ane , carbon dioxide , nitrogen , oxygen , methyl iodide , hydro example , methyl iodide , hydrogen iodide , water , methyl acetate , acetic acid ,
acetic acid , dimethyl ether , methanol , acetaldehyde , and formic acid and is fed to
dimethyl ether , methanol , acetaldehyde , formic acid , and
from the condenser la through the line 15 . In the scrubber system 8 , useful components ( e . g . ,
is continuously withdrawn to the line 17
, water , methyl acetate , and acetic acid ) are mass ) , further preferablyseparated 50 toand 75 recovered
% byfrom mass
the gaseous
portion of(theportion from
evapor.stream the, 55from
g .withdrawn
the evaporator 2 . A
1a . In this separation and recovery , a wet method by mass ) , a methyl iodide concentration of , for example , 2
continuously introduced to the condenser 2a , and that is performed using an absorbing liquid for captu
useful components in the gaseous portion is utilized in the mass
stream is( continuously
preferably intro 5 to 30 % by mass ) , a waterducedpresent to theembodiment
next distill.
containing at least acetic acid and / or methanol is preferredfor
as the absorb
. example , 0 . 2 to 20 % by mass ( prefer
The vapor stream has an acetic acid concentration of , for
contain methyl acetate . For example , a )condensate portion methyl
of a vapor fromacetate
the
85,% and
by massa( preferably 50 to 85 % by concentration o
later can be used as the absorbing
50 liquid
% by. Inmass the separation and recovery , a2pressure
( preferably to 30 % by
method may be used . The separated and stream generated in this step
recovered useful components ( e . g . , methyl iodide ) are contains
intro , for
the reaction vessel 1 from the scrubber system 8 catalyst and the co - catalyst ( methyl through the recycle line 48 and,recycled
iodide lithi .A
capturing of the useful components is discarded through the iodide , etc . ) contained in the reaction line 49 . The g
used as a CO source to be introduced to the bottom part of the methyl acetate , acetic acid , formic acid ,
residual liquid stream recycle lines 18 and 19 . As without
remaining for treatment inbeing
the scrubbervolatilized in this
the reaction vessel 1 and discarding , continuously
the same holds true for gaseous portions
introduced to the heat
to the scrubber system 8 from the other
It condensers
is preferred. For2totheconnect
[ 0079 ]evaporator productiona carbon
through methodthe
ofmonoxide
theline
present 18
it is preferred to have a scrubber step of separat heat exchanger
introduction 2b cools
line 54 for introducing the monoxide
a carbon - containing gasingto offgas
residual from ofthetheprocess intoliquid
the bottom a stream richsti
monoxide and a stream rich in acetic acid by absorption evaporator
evaporator 2 2 . The cooled residual
and / or the residual treatment
liquid streamwithrecycle
an absorption
lines ( solvent
line 18containing
and / orat lea
acid . continuously
line 19 ) . Carbon monoxideintroduced
is introduced to a to
residualthe
liquidreaction
exchanger 2b through
part of the evaporator the line 19 and
2 or to a residual recy
[ 0077 ] In the reaction vessel 1 during apparatus operation , as mentioned
line
residual 19liquidarestream
collectively referred recycle lines 18 to
and partiab
19 (as
acetic acid is continuously produced .
torecycle
thereby lines . increase Thethe amount
acetic acid
of carbon monoxide dissolved in the
residual liquid stream is , for
stream . Thus , the stability of the catalyst is example ,
US 2018 / 0201562 A1 Jul . 19 , 2018
enhanced , and the precipitation or accumulation of thedenotes catalysta reboiler . From the height position between the
can be prevented . The content of the carbon mon column top and the column bottom of the distillation oxide in the carbon
monoxide - containing gas to be intro columnduced is , for 3 , example
the acetic, acidnot less streamthan( first
10 acetic acid stream ;
% by mass , preferably not less than liquid [ 0083 ]
20 % ) by The vapor withdrawn
as mass , further from the column top of the
a side stream is continuously withdrawn through t
contains a larger amount of compo nents hav
[preferably not less
0080 ] The condenser thanthe vapor stream from the evaporator 2 into40 a %condensate
2a separates by mass portion, andparticularly preferably
components ) than that of acetic acid as compared with the
anotgaseous
lessportion 60 % andbypartial condensation . The condensate mass .boiling point
thanby cooling
and the side stream from the distillation
methyl iodide , hydrogen iodide , water , methyl acetate , acetic acid , dimethyl ether ,
methyl iodide , hydro gen iodide , water , methyl acetate , dimethyl ether ,
, formic acid , and propionic acid and is introduced to the reaction vessel 1 from the condenser 2a
methanol , acetaldehyde , and formic acid . This vapor also contains
the lines 22 and 23 and recycled . The gaseous portion contains , for exampleSuch,a carbon monoxide ,
vapor is continuously introduced to the
hydrogen , methane , carbon dioxide , nitrogen , oxygen , methyl iodide[ 0084
, ] The condenser 3a separates the vapor from the
acetic acid , dimethyl 24column
. 3 into, anda condensate
ether , methanol , acetaldehyde formic acid portion
and is fedandtoa gaseous
from the condenser 2a through the condensation . The condensatelines 20 and 15 . Since the reaction to produce acetic acidportion in contains , for
reaction step mentioned above is an exothermic reaction , hydrogen iodide , water , methyl acetate , acetic acid , dimethyl ether , of heat accumulated in the
a portion
is transferred to the vapor generated from the reaction mixture methanol , acetaldehyde , and formic acid and is continuously in the evaporation step
condensate portion decanter 4 from the condenser
generated by the cooling of this vapor in the condenser 2a 3a through
vessel 1 . Specifically , in this acetic The aqueous
portion introducedphase contains water
to the and , for
acid production example
apparatus , heat,generated
methyl through decanter
the 4 is
methanol carbonylation reaction is efficiently removed in the condenser 2a . hydrogen
upper phase ) iodide , methyl acetate , acetic acid , dim
and an organic phase ( methyl iodide phase ; lower phase ) .
acetaldehyde , and formic acid . The orga
[ 0081 ] The distillation column 3 is a unit for performing the first distillation step and example , hydrogen iodide ,
methyl iodide and boiling , forpoint component removal column in the present embodiment . The first
serves as the so - called lower acetic acid , dimethyl ether , methanol , acetaldehyde , and formic
distillation step is the step of sub jecting the vapor stream continuously introduced to the
In the present embodiment , a portion of the aqueous
3 to distillation treatment to separate and remove lower boiling point components . More specifically ,
distillation column 3 through the line 29 , and a
in the first distillation step , the vapor stream is separated by
phase is introduced to the reaction vessel 1 through th
at least one lower boiling point component selected from methyl iodide and
23 and recycled . A portion of the organic phase is introduced to t
rich in acetic acid . The distillation column 3 consists of , for example , a distil lation column such as a plate column or a
reaction vessel 1 through the lines 31 and 23 and recycled . Another portion of the
packed column . In the case of adopting a plate column as the[ 0085
distillation
] In the present invention , in the separation step ( e . g . ,
organic phase and / or a remaining portion of t
thereof is , for example , 5 to 50 , and the reflux ratio is separation
, for examplein ,the0 .decanter
5 to 4 ) of separating a process stream
the acetalde hyde separation and removal system 9 through the lines 31
theoretical number of plates . In the , acetic acid ( AC ) , methyl iodide inside of the distillation column 3 , the column top pressure
and / oran the
example , 80 to 160 kPa ( gauge pressure ) , and the column bottom pressure is higher thanphasetheandcolumn top
lines 30 and 51organic . phase , a phase to be subjected to the acetaldehyde
pressure and is set to , for example , 85 to 180 kPa ( gauge removal step is determined on the basis of an pressure ) . In t
column 3 , the column top temperature is , for aqueous
example ,phasea temperature
, an acetof aldehyde concentration in the
acetic acid at the set column top pressure
acetate and is setinto the90 aqueous
concentration to 130°phase
C . ,, and the column
a methyl acetate
example , a temperature of not less phase , the sum of the methylthan the boiling point of acetic acid at the set columnacetate
bottom concentration in the aqueou
and is set to 120 to 160° C . acetate concentration in the organic phase , a temperature ( liquid temperature ) at the time
10082 ] The vapor stream from the evaporator 2 is of the separation , an acet aldehyde distribution coefficient (
continu cient ) determined according to the expression given below ,
ously introduced to the distillation column
3 through the line distribution
21 . From the column top ofcoefficient
the ( MA distribution
to the below . In another aspect , a preferre
distillation column 3 , a vapor as expression
the overheadgiven stream
is continuously withdrawn to the line subjecting the organic phase24to .theFrom acetaldehyde
the separation
column bottom of the distillation column 3 , a a preferred separation condition for subjecting withdr
the aqueo
bottom fraction is continuously
US 2018 / 0201562 A1 Jul . 19 , 2018
7
separation
AD distribution coefficient = { AD concentration
by mass ) of the aqueous phase } / { AD
(% and removal step because the AD distribution
concentra coefficient
tion ( % by mass ) of the organic phase is , for example , more than 4 . 3 .
MA distribution coefficient = { MA concentration ( %
[ 0094 ] In} the condition ( iii ) , the methyl acetate concen
by mass ) of the aqueous phase } / { MA ,1.2 to 15 % by mass , preferably 2 . 5 to 12 % by mass , further preferably 6 . 0
concen tration ( % by mass ) of the organic phase }
[ 0086 ] In the production methods 1 and 2 of the present methyl acetate concentration in the organic phase
separation step satisfies at least one of the mass , further preferably 19 to 42 % following conditions ( i ) to ( v ) , and at by mas
least a portion of the organic phase is treated aqueous
in the phase
acetaldehyde
should be separation
not less and than 1 . 2 % by mass , and th
[ 0087 ]step( :i ) an acetaldehyde concentration in the aqueous
removal than 2 . 2 % by mass . Also , the sum of the methyl acetate
less than 0 . 045 % by mass , and / or an acetalde hyde concentration in the organic phase is not
the methyl acetate concen tration ( % by mass ) in
less than 0 . 013 % by mass ;
[ 0088 ] ( ii ) a temperature at the time of the separation is not . 3 to 60 % by mass ( e . g . , 10 to
5° C . ;
100891 . ( iii ) a methyl acetate concentration in the aqueous
condition ( iii ) , a methyl acetate concentration in phase is
not less than 1 . 2 % by mass , and / or a methyl acetate
the decanter 4 ) is , for example , 2 . 0 to 50 % by mass ,
concentration in the organic phase is not less than 2 . 2 % by
preferably 15 to 31 % by mass . In the case where the methyl acetate
mass , and / or the sum of the methyl acetate concentration in the aqueous
mass , in the case
[ 0090 ]and( ivthe ) methyl
phase an acetaldehyde
acetatedistribution coefficient in
concentration [ { acet the organic phase isacetate concentration in the organic phas
where the methyl
concentration
not ( % by mass
less than 3 .) of4 the
% aqueous phase ;} /
by mass case where the sum of { acetaldehyde
the methyl acetate concentration (%
by mass ) of the organic massphase
) in }the] organic
is notphase
more isthanless4 than
. 1 ;3 .and4 % by mass , it is low
[ 0091 ] ( v ) a methyl acetate distribution coefficient
acetate concentration ( % by mass ) of the aqueous acetaldehyde separation and removalphase
step }because the ADacetate
/ { methyl distribution
concentration ( % by mass ) of the
[ 0092 ] In the condition ( i ) , the acetaldehyde concentration [ 0095 ] In theorganic phase (} iv] is) not, themoreADthandistribution
condition 0 . 53 . coefficient
phase is , for example , 0 . 045 to 35 % by mass , than 4 . 1 ( e . g . , 0 . 5 to 4 . 1 ) , preferably not more than 3 . 35 ( e . g preferably 0 . 15 to
2by.mass0 % , byfurther
mass preferably
. Also , 0the. 2acetaldehyde
to concentration in the . , 0 . 6 to 3 . 35 ) , more preferably less than 1 . 5 organic ph
example , 0 . 013 to 30 % by mass , preferably 0 . 05 to 5 . 0 % by mass , further preferably
7 and less than 1 . 5 ) , further preferably
01..1 0 to% by mass . In the condition ( i ) , it is preferred that the case where the A
8 and less than 1 . 1 ) . In the
0 . 045 % by mass , and the acetaldehyde con 1, centration in the organic phase should be not less than
it is very low advantageous to treat the organic phase in the
condition ( i ) , an acetaldehyde
acetaldehydeconcentration in a liquid
separation and removal to bethesubjected
step because acet to the separation
" separation step feeding liquid ” ; e . g . , a liquid to be fed to the decanter 4 ) is , for
organic phase is very low . A method for attaining the AD distribution
by mass ( e . g . , 0 . 026 to 32 % by mass ) , preferably 0 . 10 to 8 . 0 % by mass , further prefer
coefficient ( less than 1 . 1 ) most preferred for the acetaldehyde removal
the case where the acetalde hyde concentration in theincludes
the organic phase aqueous, phase is less, than
for example setting0 .the045 %
concentration in the organic phase is less than 0 . 013 % aqueous
by massphase, ittoismorevery than 28 . 1 % by mass , setting the acetaldehyde co
acetal dehyde separation and removal step because the AD distri bution coefficient is a large value .
the organic phase to more than 24 . 8 % by mass , setting the
concentration in the separation step feeding
setting the temperature at the time of the separation to more t
[ 0093 ] In the condition ( ii ) , the temperature ( liquid tem [ 0096 ] In the condition ( v ) , the MA distribution coefficient
methyl acetate concentration in the aqueous phase to more
the separation is not less than - 5° C . g . , 0 . 15 to 0 . 53 () ,e preferably
. g . , not- 5°moreC . to 90° C . ) , preferably not less than 0° C
tion in the orga
. (e.g., 0 to 90° C . ) , further preferably notthe lessmethyl
further than acetate
preferably concentra
10° Cless
. ( ethan. g . , 10 to 0 . 25 ( e . g .
setting the methyl acetate concentration in the separation
90° C . ) , particularly preferably a temperature of higher 0 . 25 ) . The rates of distribution of methyl acetate ( MA ) to t
than 38 . 2 %
the organic phaseCvary by mass .
than 70° C . and not more than 90° . )depending
. In theon acase
temperature and temperature ( liquid
where the
temperature ) at the time of the separation is less than - 5° acetic
C . , itacidis inveryaddition
low to water and methyl iodide ) , and this also serves as
organic phase in the acetaldehyde acetaldehyde distribution coefficient control .
US 2018 / 0201562 A1 Jul . 19 , 2018
[ 0097 ] In the production methods 1 and 2 of the present liquid to be fed to the decanter 4 ) is , for example , not more
( i ) to ( v ) , but may satisfy not less than 2 of the than 26 . 0 % by mass ( e . g . , 0 . 026 to 26 . 0 % by massconditions
) , prefat the same time . Examples of
preferably satisfied at the same timeerably
include combinations
0 . 057 toof the10 conditions
% by mass( i ,) and
further preferably 0 . 057 to
( iv ) , the conditions ( i ) and ( v ) , the conditions ( ii ) mass
and ( ,iiiparticularly
) , the preferably 0 . 057 to 1 . 0 % by mass
, the conditions ( iii ) and ( iv ) , the conditions ( iii ) and to( v 0) ., 42the% by mass ) . In the case where the
) , the conditions ( i ) , ( ii ) , and ( iv ) , the conditions ( i ) , ( theii )aqueous , and (phase
v ) is, more than 28 . 1 % by mass or in the case
i ) , ( 111 ) , and ( v ) , the conditions ( i ) , ( iv ) ,acetaldehyde
and ( v ) , the conditions ( ii ) , ( iii )concentration , in the organic phase is more than 24 . 8 % by
( v ) , the conditions ( ii ) , ( iv ,) ,itandis( vvery
mass ) , thelowconditions ( iii ) to, ( treat
advantageous iv ) , and
the( aqueous
v ) , the conditions
phase
, the conditions ( i ) , ( ii ) , ( iii ) , and ( v ) , the acetaldehyde
[ 0105 ] In separation
the conditionand( viiremoval) , thesteptemperature
by weighing ( liquid tem conditions ( i ) , (
v ) , and the conditions ( i ) , ( ii ) , ( iii ) , ( iv ) , and ( v ) . Among atacetaldehyde the time ofrecovered and the isneed, for
the separation of using
example , - 5° C .
conditions ( i ) , ( ii ) , and ( iii ) at the same time , to satisfy at 5°highC . tocorrosion
51° C . resis
, further preferably - 5° tance , because the AD distributionleast
coefficient
the con
satisfy all of the conditions ( i ) , ( ii ) , ( iii ) , ( iv ) , and ( v ) at .g to. , 31° C . ) . less In thethancase1 where
. 1 )the.
time of the separa tion is more than 70° C . , it is very low advantage
small
treat . the aqueous phase in the acetaldehyde separation and
[ 0098 ] On the other hand , in the production methods 3 and [ 0106 ] In the condition
AD distribution coefficient is very ( viii ) , the methyl acetate concen
invention , the separation step satisfies at . 0 % by mass , preferably least 2 . 0onetoof 12the .following
0 % by conditions
mass , further
( vi ) preferably
to ( x ) , and at least a portion of the aqueous12 phase
. 0 %is bytreated
mass )in. Also , the
the acetaldehyde methyl acet
separation preferably 5 . 0 to 42 % by mass , further pre
[ 0099 ] and( removal
vi ) anstepacetaldehyde
: concentration in the aqueous
mass , and / or an acetalde hyde concentration in the organic phase is not more than ) , it is preferred that the methyl acetate concentration in
acetate concentration in the organic phase should be not more than
[ 0100 ] ( vii ) a temperature at the time of the separation is % by mass ) in the aqueous phase and the methyl
C[ .0101; ] ( viii ) a methyl acetate concentration in the aqueous phase
59 . 6 % by mass ( e . g . , 4 . 2 to 59 . is6 no%
/ or a methyl acetate concentration in the organic phase is not
massmore
( e than
. g . , 16 to 42 % by mass ) . In
or the sum of the methyl acetate concentration in the aqueous phase and the methyl acetate
liquid ( e . g . , a liquid to be fed to the
organic phase is not more than 59 . 6 % by mass ;
38 . 2 % by mass ) , preferably 5 . 0 to 31 % by mass ,
[ 0102 ] ( ix ) an acetaldehyde distribution coefficient [ { acet acetate concentration in the aqueous phase is more
mass ) of the aqueous phase } | the organic phase is more{ acetaldehyde
than 47 . 6 % concentration
by ( % by mass ) of the
organic
[ 0103 ] ( x ) a methyl acetate phase } ]distribution
is not less than 1 . 1 ; and
coefficient
the aqueous phase and the methyl acetate concentration ( % by mass ) in
acetate concentration ( % by mass ) of the aqueous geous to treat the aqueous phase in the acetaldehyde sepa phase } / { methyl acetate
concentration ( % by mass ) of the distribution coefficient is , for organic
example , phase
less } ] is not less than 0 . 25 .
[ 0104 ] In the condition ( vi ) , the acetaldehyde concentra
, preferably 0 . 098 to 10 % by mass , further preferably
% by mass ( e . g . , 0 . 15 to 0 . 9 % by mass ) . Also , the acetaldehyde
. 8 % by mass , preferably 0 . 030 to 2 . 0 % by mass , further preferab
[ 0107 ] In the condition ( ix ) , the AD distribution coefficient
030 to 0 . 24 % by mass . In the condition ( vi ) , it is preferred
. 1 to 8 . 0 , preferably 1 . 5 to 6 . 0 , further
more than 28 . 1 % by mass , and the acetalde the case where the AD distribution hyde concentration in the organic phase should be not more
coefficient is less th
condition ( vi ) , an acetaldehyde concentration in a separation step feeding liquid ( e . g . , a
very disadvan tageous to perform the acetaldehyde removal treatment of
phase which requires large energy and easily
acetaldehyde concentra tion in the aqueous phase is low . However
US 2018 / 0201562 A1 Jul . 19 , 2018
distribution coefficient is not less than 1 . 1 ( preferably not water concentration , the catalyst concentration , and
further preferably not less than 1 . 9 ) , improve the lithium iodide concentration ment inin acetaldehyde
the separation and remov
efficiency is highly advantageous even if an apparatus reaction havingsystem
high cor
and to be decreased with i
resistance is used .
[ 0108 ] In the condition ( x ) , the MA distribution coefficient in each of the CO partial pressure and
acetate
preferably not less than 0 . 26 ( e . g . , 0 . 26 to 0 . 65 ) , further preferably not less concentration
than ( see Japanese Patent
Open No . 2006 - 182691 ) . Since methyl acetate is
0 . 60 ) . As mentioned above , the rates of distribution of methyl acetate ( MA ) to the
vary depending on a temperature and throughcomposition
the containing
esterification
components such as reaction
acetic acid in between
addition to wateracetic
and methyl iodide ) , and this also serves as
a guideline for acetaldehyde distribution coefficient control . [ 0109 ] In theacid and methanol
production methods 3 and, 4theof the methyl
presentacetate concentration
in the reaction mixture is increased with increase in
invention , the separation step can satisfy at least one of the
each of the acetic acid concentration and the methanol
of the conditions at the same time . Examples of the combination of
[concentration
0111 ] In the acetaldehyde in separation and removal stepthe reaction system and decreased with
same time include combinations of the conditions ( vi ) and ( vii
increase in the water concentration . Thus , the
and ( ix ) , the conditions ( vi ) and ( x ) , the conditions ( viiseparation ) and and removal system 9 , the
composition of the separation step feedi
conditions ( vii ) and ( x ) , the conditionsand (least
viiibythe) water
and , ( theix )acetic
, acidconditions
the ( AC ) , the( viii
extension , the acetaldehyde concen
methyl )iodide
and ( x ) , the conditions (
ix ) and ( x ) , the conditions ( vi ) , ( vii ) , and acetaldehyde ( AD ) is separated and removed . ( viii ) , th
and the methyl acetate concentrations in the aqueous
( vii ) , and ( x ) , the conditions ( vi ) , ( viii ) , and ( ix ) , the con a method for separating and removing acetaldehyde . Acetaldehyde is
and the organic phase can be adjusted by adjusting
conditions ( vi ) , ( ix ) , and ( x ) , the conditions ( vii ) , ( viii ) , and reaction removed
( ix ) by, ,the for conditions
example ,for
conditions distillation , extracvessel , and operating conditions in the e
( viithe) ,reaction
) , and ( x ) , the conditions ( vii ) , ( ix ) , and ( x ) , the condi thereof . The separated acetaldehyde istio
( viii ) , and ( ix ) , the conditions ( vi ) , ( vii the) , line( viii ) , and ( x ) ,53the. Theconditions
useful components ( e . g . , methyl iodide ) contained in the
x ) , the conditions ( vii ) , ( viii ) , ( ix ) , and organic phase and / or the aqueous phase are recycled to the reaction vessel( x1 )through, and the conditions ( vi ) , ( vi
Among them , it is particularly preferred to satisfy at least the the lines 52 and 23 and reused . [ 0112 ] F
time , to satisfy at least the conditionsdiagram
( vi ) ,showing
( vii ) one
, ( viii ) , and ( ix ) at the same example of the acetaldehyde separation and removal s
( vi ) , ( vii ) , ( viii ) , ( ix ) , this flow , in the case of treating
and ( x, )foratexample
the same, time .
separation and removal step , the organic phase is fed to a distillation
[ 0110 ] The acetaldehyde concentrations and the methyl acetaldehyde removal column ) 91 through a acetate
phase and the organic phase are determinedoverhead
by the composition
stream rich ofin theacetaldehyde
separation( line 102 ) and a residual liquid
temperature at the time of the iodideseparation
( line 103 ) .. AsThe the separation
overhead stream step feeding liquid has a higher
acetaldehyde concentration , the acetaldehyde concentrations condensate is refluxed to the column top of the distillation columnin91 the aqueous phase and the or
higher . As the separation step feeding liquid has a remaining
higher methyl
portion ofacetate
the condensate is fed to an
concentrations in the aque ous phase and condensate
the organicfed phase
to are higher . As shown in the extraction column 92 is subjected to extraction treatment
temperature at the time of the sepa ration , the rate of distribution
introduced from a line 109 . The extract obtained of acetaldehyde to the organic
phase is relatively higher . Furthermore , the acetaldehyde distillation column ( second acetaldehyde removal column ) 93 through a line
concentration in the separation step distillation
feeding liquidinto an can
overheadbe stream
controlled by , for ric
reaction conditions for the reaction vessel 1 , liquid stream rich in water ( line 113 ) . Then , the overhead stream rich in an
evaporation conditions for the evaporator 2 ,
distillation conditions for the distillation column 3 . In general , when isthecondensed in a condenser 93a . A portion of the condensate is refluxed to the
acetaldehyde
acetaldehyde concentration and methylcolumn
acetate
top ofconcentration
the distilla , the acetaldehyde concen tion column 93 ( line 114 ) , and the rem
acetate concentration in the separation step feeding liquid are
condensate is discharged to the outside of therespectively higher . The acetaldehyde
system ( line
concentration in the reaction mixture tends to be increased with increase in each of the reaction temperatu
liquid stream rich in methyl iodide , which
hydro gen partial pressure , the methyl iodide concentration , theremoval column 91 , a raffinate rich in methyl iodide ( line 108 ) obtained in the
extraction column 92 , and the residual liquid stream rich in
US 2018 / 0201562 A1 Jul . 19 , 2018
column 91 through a line 110 . The liquid from theForline example 113 , a unit ( chimney tray , etc . ) that
is usually discharged to the outside as water discharge . Acangasreceive the liquid ( extract ) dropped from the that
not been condensed in the condenser 91a or 93a concentration zone is ( line 106 or 116disposed ) is in this distillati
[subjected
0113 ] Accordingto to absorption treatment
the flow of FIG . 2 , in inthe case
theof column so that a liquid ( extractscrubber ) system 8 or
acetaldehyde
discarded separation
. and removal step , forunit
examplecan, thebe aqueous phase isasfed ato side stream . The
withdrawn
first acetaldehyde removal column ) solvent introduction 91 throughposition
the line 101 and
is separated by distillation
preferably supeinto an
stream rich in acetaldehyde ( line 102 ) and a to the charging mixture feeding position , more prefer residual liquid stream rich in water
overhead stream is condensed in the condenser 91a . A portion of the the column top . The side stream withdrawal
the distillation column 91 ( line 104 ) , and the remaining portionlower
of the than the extraction solvent
preferably
extraction column 92 ( line 105 ) . The condensate fed to the extraction column 92 is subjected to
introduction position and higher than the charging
with water introduced from the line 109 . The extract obtained by the extraction treatment is fed
mixture feeding position , in the height direction
distillation column ( second acetaldehyde removal column ) 93 through the line 107 and separated by d
of the column . According to this method , acetaldehyde can be
into an overhead stream rich in acetaldehyde ( line 112 ) and a residu
extracted with a high concentration from a concentrate
line 113 ) . Then , the overhead stream rich in acetaldehyde is condensed in the
of methyl iodidecolumnand
of the condensate is refluxed to the top of the acetaldehyde
the distillation using
column 93 ( line 114 ) , an
and the
remaining portion of the condensate is discharged to the outside of the system ( extraction
line 115 ) . The solvent ( usually , water ) . In additi
residual liquid stream rich in water ,,which
theis region
a bottom between
fraction of the the extrac tion
first acetal solvent
a raffinate rich in methyl iodide (introduction sitein and
line 108 ) obtained the the side column
extraction cut site
92 , andis used as
the
stream rich in water , which is a bottom fraction of the second acetaldehyde removal column 93 extraction
are zone . Therefore , acetaldehyde can be effi
reaction vessel 1 through the lines 103 , 111 , extracted with a small amount of and the113extraction
, respectively , or recycled to an appropriate are
of the process and reused . For example , the raffinate rich in Therefore , for example , the number of plates in the methyl io
can be recycled to the distillation column 91 through the line 110 . distillation column can be drastically decreased Th
discharged to the outside as water discharge . A gas as
that hascompared
not been con densed in the condenser 91awith
or 93a ( alinemethod
106 or of withdrawing an extract by
116 ) is subjected to absorption treatment in the scrubber system 8 or extractive distillation from the column bottom of the discarded .
distillation col umn ( extractive distillation column
[ 0114 ] The acetaldehyde derived from the process stream ) . In addition , steam load can alsoco
acetic acid ( AC ) , the methyl iodide ( Mel ) ,, andthethe ratio
acetaldehyde
Furthermore of (methyl
AD ) can also be sepa
iodide
removed by use of extractive distillation , in addition
( MeI / AD ratio ) in a water extract can tobethe method described above . For example ,
the organic phase and / or the aqueous phase ( charging mixture ) as compared with a method of combining the
process stream is fed to a distillation columndistillation
( extractive distillation
removing of FIG . column ) . Inwater
2 with addi
an extraction solvent ( usually , water ) is introduced to a concentration zone ( e . g . , space from t
using a small amount of an extraction solvent .
column top to the charging mixture feeding position ) where methyl iodide and
Therefore , acetaldehyde can be removed under
distillation column are concentrated . A liquid ( extract ) dropped from the concentration zone
conditions that can suppress a loss of methyl iodide to the
is withdrawn as a side stream ( side cut stream ) . This side stream is separated into
outside of the system . The acetaldehyde concentration in the
and an organic phase . The aqueous phase can be distilled to thereby dis
side stream is where a much
relativelyhigher thanof the
large amount water isacetaldehyde
present in the
to the outside of the system . In the case
distillation column , the liquid dropped from the concentra concentration in the
[ 0115 ] The theoretical number of plates of the distillation charging mixture and
tion the botb
zone may
stream without thefraction
introducing the extraction solvent to distillation column(column
distillation )column bottom
is ., for example , 1 to fraction ) . The
acetaldehyde to methyl iodide in the
US 2018 / 0201562 A1 Jul . 19 , 2018
100 , preferably 2 to 50 , further preferably 3 to 30the, particu

decanter 96 are recycled to the distillation column 94
preferably 5 to 20 . Acetaldehyde can be efficiently through lines 213 and 210 and lines 214 and 210 , respec sepa
removed by a smaller number of plates than , but may not be recycled . A portion of the aqueous 80 to 100 plates in a
distillation column or an extractive decanter 95 may be utilized as an extraction
distillation column for use in
conventional acetaldehyde ) in the. distillation
removal The mass ratiocolumn
between94 the
. A flow
portionrateof ofthe
the extraction solvent and the flow rate of the chargingaqueous
mixturephase of the decanter 96 may be recycled to the ( the
and / or the aqueous phase obtained by the distillation column 94 through the line 210 . In some cases
separation of the process stream ) (
former / latter ) may be selected from the range of 0 .the0001case/ 100
wheretomethyl
100 acetate is contained in the
/ 100 and is usually 0 . 0001 / 100 to 20 mixture
/ 100 , ) preferably
, a solvent0 (. acetic acid to, ethyl acetate , etc .
001 / 100
) miscible with the components ( e . g . , methyl acetate ) consti
10 / 100 , more preferably 0 . 01 / 100 to 8 / 100 , further prefer
tuting the organic phase obtained by the separation of the
. 1 / 100 to 5 / 100 . The column top temperature of the distillation column
process stream may be fed to the distillation column 94
extractive distillation column ) is , for example , 15 to 120° C . ,
a line 215 to thereby improve distillation efficiency .
preferably 20 to 90° C . , more preferably 20 to 80° C . , further
[ 0116 ] FIG . 3 is a schematic flow diagram showing position of the miscible solvent to the distilla
preferably
separation and removal25 to 70° C . The system using the extractive to thecolumn
distillation
is superior described abovetop
charging . In pressure
mixture feeding is , on the order of
, for 0 . 5 MPa inmixture terms of absolute pressure
of the .process
Other conditions
phase and /example
or the aqueous, phase
0 . 1 to line 201( )charging
and inferior) obtained by thejunction
to the separation
for the part (distillation
position between column
the column( extractive distillation column ) may bottom fraction of the distillation be the
middle top andcolumnthe column bottom ) toof thea distillation
94 is recycled reaction column 94 same as
forthrough
a distillation column
a feed line 201 , while water or an extractive
is introduced thereto system . A vapor at the distillation column for
columnusetop innearthethedistillation
from of column top through a li9
column
conventional extractive
that acetaldehyde
distillation isremoval
performed in .the distillation column 94 ( extractive distillation
led to column ) . A chimney tray
a condenser 94a through a line 203 and condensed . Th
200 for [ 0117methyl] iodide
receiving a liquid ( extract ) dropped from a concentration zone where FIG .and4acetaldehyde
is a schematic flow diagram showing a
condensate is separated in a decanter 99 . The organic phase is
in the column are concentrated is disposed superior to the charging mixture
alternative example of the acetaldehyde separation
refluxed to the column top of the distillation column 94 through a line
extractive distillation described above . In this example , a condensate of
column 94 . In this extrac tive distillation ,206preferably
, whilethethewhole amountphase
aqueous , of theis liquid
led to the decanter 95
the column top of the distillation column 94 is led to
200 is withdrawn , introduced to a line 207 . A bottomdecanter fraction95 through
( watera lineis208a , main
and separated . The aqueous
whole amount thereof is refluxed to duced to a cooler 95a through
phase ( containing acetaldehyde ) in the decanter 95 is intro of
line the distillation
206 . The othercolumn 97 theandsamea asbottom
points are in the example of FIG .
that methyl iodide dissolved in the aqueous phase is separated [containing 0118 ] FIGa . small 5 is amounta schematic flow diagram
of acetaldehyde ) showing a
aqueous phase in the alternative
decanter 96 is fed to a distillation
columncolumn9897example of the acetaldehyde
(( extractive
acetaldehyde separation
distillation column )
216 and distilled . The vapor extractive
at the column
outsidetop ofisdistillation
led tosystema condenser
the through97alinesthrough
218 a line described above . In this exampleand, the22
condensed . A portion of the condensate ( mainly , liquid
recycledon tothethechimneyreaction traysystem
200 is. Awithdrawn , directly acetaldehyde and methyl iodide ) is refluxed to theh
gas that
column top of the distillation column 97 , and the remaining portioncooler 95a through94athe, 97a
the condenser line, 208 without the or 98a ( line 211 , 221 , or 227 )
distillation column 98 ( extractive the[ 0119
decanter] In FIG distillation 96 . The
column ) other
throughpoints
a are
line
. 1 described above , the gaseous portion the
220 . same asisinintroduced
Water thetreatment
example of in
FIG the
. scrubber
subjected to absorption
thereto from near the column top of the distillation column ,3a orcontains , for example
discarded . , carbon 98 through a line 222 , f
distillation . The vapor at the column top is led to a condenser 98a
methyl iodide , hydrogen iodide , water , methyl acetate , acetic acid , dimethyl ether , through a
of the conden sate ( mainly , methyl iodide ) is refluxed to the column top , and formic acid and is
methanol , acetaldehyde ,
to the reaction system through a linethrough
226 , thebut lines
may be32 discharged
and 15 . For toexample
the outside
, of
Preferably the whole amount , of the organic acid , dimethyl ether , methanol , acetaldehyde , and formic phase ( methyl iodide phase ) in the decanter 95 is
recycled to below the position of the chimney tray 200 of the the scrubber
distillation system 8 are absorbed to an absorbing liquid in the scrubber
and 210 . A portion of the aqueousiodidephasegenerates
of the methyl
decanteriodide
95 and the organic phase of through reaction with
Then , a liquid portion containing useful
US 2018 / 0201562 A1 Jul . 19 , 2018
components such as the methyl iodide is recycled to appropriate site where hydrogen iodide is present . The
the reaction vessel 1 from the scrubber system potassium hydroxide added during the process also reacts
8[ 0120through
] The bottom
the fraction
recyclewithdrawn
linesfrom48 the
andcolumn
23 and reused . with [ 0123acetic
] Theacid distillation
to formcolumn 5 is a acetate
potassium unit for. performing
contains a larger amount of components having a higher boiling point ( higher boiling distillation step and serves as the so - called
that of acetic acid as compared with present embodiment . The second
the overhead stream and the side stream from the distillation distillation step is a step for
and contains , for example , propionic acid , and the entrained catalyst and co - catalyst mentioned above
acid. byThis bottom the distillation treatment of the first acetic acid stream
fraction also contains , for example , acetic acid , methyl iodide , methyl acetate , and water . Inintroduced
the presentto the distillation column 5 . The
of ,2 forthrough
embodiment , a portion of such a bottom fraction is continu ously introduced to the evaporator examplethe ,lines
a distillation column such as
25 and 26 and recycled , and another portion of the bottom fraction case of adopting a plate column as the distillation column 5 ,
the reaction vessel 1 through of plates thereof25 isand, for
the lines 23 andexample , 5 to.
recycled
[ 0121 ] The first acetic acid stream continuously with 0 . 2 to 3000 according to the theoretical number of plates . In th
more enriched with acetic acid than the vapor stream continuously distillation column 5 in the second distillation step , the introduced to the distillatio
acetic acid concentration of the first acetic acid stream is is set to , for example , 150 to 250 kPa higher t
acetic acid concentration of the first acetic acid stream bottom pressure is higher than the, 90columnto top99 pr.
is , for example
to 99 % by mass . Also , the first acetic acid stream may contain160, in to 290 kPa ( gauge pressure ) . In the inside of the distillation
iodide , hydro gen iodide , water , methyl acetate , dimethyl ether , methanol , second distillation step , the column top
propionic acid . The first higher than aceticthe acid stream has a methyl iodide concentration boiling point
of , forof water and lower than the boiling point of acetic a
[ 0124 ] A vapor as an overhead stream is continuously
g . , 0 . 1 to 8 % by at the330 set
mass ) , preferably
line 2 column
. from to the5 top%column
bypressure
masstop ,andofa the
is setconcentration
water to 130 dist
8 % by mass ( e . g . , 0 . 1 to 8 % temperature
continuously is , for by mass ) , preferably withdrawn0to. 2theto line example
5 % 34by from , a temperature
mass ,theandcolumn
a methyl of the distillationth
of
bottomacetate not less than
, for example , not more than 8 % by mass liquid or5 .gas5bacetic
of(column beacid
) maydenotes aat( reboiler
ethe. withdrawn
continuously gset. column bottom
., A0to.side 834pressure
1 tolinestream
the % by massand )is, set to 0 . 2 to 5 % by mass . The
preferably
connection position of the line 27 to the distillation column column top and the column bottom of the distillation column3 may5 . be , as shown in the dr
[ 0125 ] The vapor withdrawn from the column top of the
nection position of the line 21 to the distillation columncontains
3 in a larger amount of compo
height direction of the distillation column 3 , but may be boiling point components ) than that of acetic acid as compared with the bottom lower
fraction from
thanthe t
connection position of the line 21 to the distillation column 5 and contains , for example , methyl iodide , hydrogen column
distillation iodide , water3 ,ormethyl
may be
the same as the connection position of theacidline, dimethyl
acetate , acetic 21 to ether
the ,distillation column 3, .
methanol , acetaldehyde
The first acetic acid stream from the distillation column
0126 ]3is isThecontinuously
a[ vapor continu introduced to the condenser 5a through the line 33 .
condenser 5a separates the vapor from the
introduced at a predetermined flow rate to the next distillation column 5
into a condensate portion and a gaseous
through the line 27 . The first acetic acid stream withdrawn as a side
The condensate portion contains , for example , water and acetic acid .
stream from the distillation column 3 , column bottom fraction of the
A portion of the condensate portion is continuously refluxed to
distillation column 3 , or condensate of the vapor in the column bottom of
[ 0122 ] To distillation
the first acetic columnacid3 stream flowing through
may be directly used astheproduct acetic
5 from the condenser 5a through the
the acid , or may be
hydroxide can be fed or added through portion is con the line 55 ( potassium hydroxide introduction lineintroduced
tinuously ). to the reaction vessel 1 fr
directly introduced into the distillation column 6 without using the
The potassium hydroxide can be fed or added , for example , as a condenser 5a through the lines 35 , 36 , and 23 and recycled . solution such as an aqueous
distillation column 5 .
solution . Hydrogen iodide in the the condenser first
5a containsacetic
, acid stream can be decreased by the for example , carbon monoxide , hydrogen
feed or addition of potassium hydroxide to the first acetic acid stream . dioxide , nitrogen , oxygen , methyl iodide , hydrogen iodide ,
Specifically , the hydrogen iodide reacts with the acetic acid , dimethyl ether , methanol , potassium hydroxide to form
potassium iodide and water . This can reduce the corrosion of an apparatus such as a
fed to the scrubber system 8 from the condenser 5a through the lines
distillation column ascribable to hydrogen iodide . In this process , the potassium hydroxide can be
Hydrogen iodide in the gaseous portion that has entered the
fed or added to an
an absorbing liquid in the scrubber system 8 . Methyl iodide is generated through the
US 2018 / 0201562 A1 Jul . 19 , 2018
acetate in the absorbing liquid . Then , a liquid portion and is set to 50 to 150° C . , and the column bottom
containing useful components such as the methyl iodide is tem perature is , for example , a temperature of
recycled to the reaction vessel 1 from the scrubber system 8 boiling point ofthrough
acetic acid at the set column
[ 0127 ] The bottom fraction ( or the side stream ) withdrawn higher
[ 0131 ] Athan vapor theas an overhead stream is continuously
the recycle lines 48 and 23 and reused . bottom pressure
line 38 a from and is set boiling
to 70point
to 160° C . dist
distillation column 5 contains largerthe amount
column top of the having
of components a higher
boiling point components ) than that of acetic acid as continuously withdrawn to the line 39 from the column bottom
compared ofwiththethe overhead s
distillation distillation
, potasor gascolumn) is6 .continuously
( liquid
column 5 and contains , for example , propionic acid 6b denotes awithdrawn
reboilerto. theA side
line stream
46 from
potassium hydroxide to the line 27 , etc . ) , andthethe distillation
entrained catalyst columnand6 co. -Thecatalyst
connection position
bottom fraction may also contain acetic acid . Such a bottom fraction is continuously intro drawing , higher than the connection position of the
second acetic acid stream to the next distillation column 6 , but may be distillation
lower than the concolumn 6 through the line 34 .
[ 0128 ] The second acetic acid stream is more enriched the same as the connection position of the line 34 to
first acetic acid stream continuously introduced to the distillation column 5 . Specifically
, the acetic acid concentration of the second acetic acid stream is [ 0132 ] The vapor withdrawn from the column top of the distillation column higher than the
concentration of the first acetic 6 contains a larger amount of compo
acid stream . The acetic acid concentration of the second
acetic acid stream is , for example , 99 . 1 to 99 . 99 % by mass boiling point components ) than that of acetic acid as compared with the
than the acetic acid concentration of bottom fraction from the distillation column 6 and contains ,
the first acetic acid stream . Also , the second acetic
acid stream may contain , as described above , in addition to acetic acid , for example , methyl iodide ,
acid and hydrogen iodide . In dimethyl ]ether
the present
[ 0133 ,condenser ,6ain separates
The embodiment vapor fromamethanol
the case ofthewithdrawing sidethe , and formic acid . Such a vapor is continuously
withdrawal position of the side stream from the introduced to theportion
into a condensate condenserand6aa through
gaseous the line 38 . distillation column 5 is lower than the introduction
position distillation column 5 in condensation . The condensate portion contains , in
[ 0129 ] To the secondof acetic
the firstacid
aceticstream
acid stream
flowingto thethrough
the
can bedistillation
fed or added column 5 . methyl iodide , hydrogen iodide , water , methyl acetate , dim
through the line 56 ( potassium hydroxide introduction line ) .
hydroxide can be fed or added , for example , and formic acid . At least a portion of
as a solution such as an aqueous solution . Hydrogen iodide
tillation column 6 from the condenser 6a through the line 40 . or addition of potassium hydroxide to the second
second acetic acid stream can be decreased by the feed
the condensate portion may be recycled to the first acetic
stream . Specifically , the hydrogen iodide reacts with the potassium hy
before introduction to the distillation column 5 from the condenser
and water . This can reduce the corrosion of an apparatus lines
such 40as, 41a , and 42 . Together with this or
ascribable to hydrogen
[ 0130 ] The iodidecolumn
distillation . 6 is a unit for performing of the condensate portion may be recycled to the vapor stream in
the so - called higher to theremoval
boiling point component distillation
columncolumn 3 frompresent
in the the condenser
step for further Also , atreatment
purifying acetic acid by the purification portion (ofdistil
the late ) of the condensate portion
continuously introduced to the vessel 1 from the condenser
distillationba through
column 6 the. Thelines 40 , column 6 consists of
distillation
distillation column such as a plate column or above , a portion of the distillate from the condenser ba may be feda packed
to the column . In the case of adopting a plate column as t
distillation column 6 , the theoretical number of plates and used as an absorbing liquid in this thereof is , for example , 5 to 50 , and the reflu
example , 0 . 2 to 3000 according to the theoretical number of after absorption of a useful portion is discharged to the outside of plates . In the i
the third distillation step , the column top pressure is set to , fora liquid portion containing the useful
and the column 1 from the scrubber system 8 through the recycle lines 48
bottom pressure is higher than the column top pressure and
addition , a portion of the distillate fro
kPa ( gauge pressure ) . In the inside of the distillation column 6 in the third distillation
shown ) operated in the apparatus , through lines ( not shown )
temperature is , for example , a tempera ture of higher than the boiling point of water and lower than
these pumps . In addition , a portion of the distillate from the condenser 6a may be
point of acetic acid at the set column top pressure
steadily withdrawn to the outside of the apparatus through a
to the line 40 , or may be non steadily withdrawn to the outs
needed . In the case where a portion ( distillate ) of the
US 2018 / 0201562 A1 Jul . 19 , 2018
14
ment system in the distillation column 6 , thea amount

portion of leaving
of the protons in an exchange group such as a sulfonic acid
distillate ( ratio of the distillate ) is , forgroupexample
, a carboxyl,group
0 ., or a phosphonic acid
01 to 30 % by mass , preferably 0 . 1 to 10 % by mass ,. more
such as silver or copper In the adsorptive removal ste
preferably 0 . 3 to 5 % by mass , moreacetic acid stream (0liquid
preferably . 5) flows
to through
3 % the inside of the ion exchange
by mass , of the condensate generated resin
in column
the7 packed with such an 6a
condenser ion exchange
. On resin , and in the course of this
flow , impurities such ascondenser
the alkyl iodides in t
the other hand , the gaseous portion generated in the
adsorbed to the ion exchange resin and removed from the third acetic
6a contains , for example , carbon monoxide , hydrogen , meth
ane
[ 0134, ] carbon
The bottomdioxide
fraction ,withdrawn
nitrogen column , methyl iodide ,In[ the
from ,theoxygen thethroughput
hydro ion exchange resin acid
of acetic column per7 min resin
the volume ( m3 / h ) ]
gen bottom of the
temperature is , for example , 18 to 100° C . , and the rate of the acetic a
aiodide
larger amount, ofwater components, having
methyla higheracetate , acetic acid example , 3 to 15 m / h · m ( resin volume ) .
fourth acetic acid stream is continuously led to boiling point ( higher boiling point components
[ 0137 ] ,A dimethyl
ether
compared , methanol
with the overhead stream from the , acetaldehyde , and formicfromacid the lowerand
end of isthe iondistillation
exchange resincolumn 6 and contains , for example , propionic
fed feeding potassium the scrubber system 8 from the condenser
the case ofto hydroxide ba through the lines
fourthtoacetic
the line 34 , etc . ) . Also acid , thestream
bottomis fraction
higher than the acetic acid concentration of the third
45 and 15 .
of the distillation col umn 6 through theacetic
line acid streamcontains
39 also . Specifically , the fourth
, for example , a acetic acid
and released from enriched this
the inside wall of a member constituting with acetic
acetic acid
acid than the third acetic
derived from corrosive iodine and the corroded metal , etc . In the introduced to the ion exchange resin column 7 .
of the fourth acetic acid stream is , for example , 99 . 9 to 99 . 999 % by mass
discharged to the outside of the acetic acid production apparatus .
not less than this range as long as being higher than the
[third0138acetic] acid
In this
streamacetic
. In acid production apparatus , a so - called this production method , this fourth
[ 0135 ] The side stream continuously withdrawn to the line column
introduced as a third acetic acid stream to the next ion exchange resin retainedor infinishing
a productcolumn whichshownis) a. distillation
tank ( not colum
purification unit for further purifying the fourth
enriched with acetic acid than the second acetic acid streamthecontinuously exchange resin column 7 . In the case where such a product
ion
column 6 . Specifically , the acetic acid concentration of the third acetic acid stream is higher than the acetic acid
product column consists of , for
concentration of the second acetic a acid stream
packed. The
columnacetic
. Inacidthe concentration of thea plate
case of adopting third column
acetic as the
. 8 to 99 . 999 % by mass as long as being higher
theoretical numberthanof plates
the acetic acid concentration
thereof is , of the
present embodiment , the withdrawal position of the
, forside stream, 0 .from
example 5 the distillation column 6 is higher than the according to the theoretical number of plates . In t
to 3000
introduction position of the thesecond
productaceticcolumn
acid stream
in theto purification
the distillation step
column, 6 inthethe
distillation column 6 . In another for example , - 195 to 150 kPa embodiment , the withdrawal position of the side stream ( gauge pressure
column 6 is the same as or lower than pressure is higher the introduction position of the second aceticthanacidthestream
columntotop pressure and is set to , for example
6 in the height direction of the kPa ( gauge pressuredistillation
) . In the inside
columnof the6 .product
A simple distillator ( evaporator ) may
used in place of the distillation column 6 . Also , the distillation column 6 can be omitted as long astemperature
the removal is , for example , a tem
in the distillation column 5 is adequately lower than the boiling point of acetic acid at the set column performed .
set to 50 to 150° C . , and the column
[ 0139 ] In the case of disposing the product column , the
of higher
[ 0136 ] . The ion exchange resin column 7 is a purification than the boiling point of acetic acid at the set column bottom
of the fourth acetic acid stream ( liquid ) from the ion exchange resin column 7 is
removal step . This adsorptive removal step continuously
isseta step
to for70 further
to 160°purifying acetic introduced
C . A simple distillatorto the product column . A vapor as an overhead
of , mainly , alkyl iodides place
( hexyl iodide of the product
, decyla iodide column or the finishing column .
containing very ,smalletcamount
. ) contained in a very small
of lower boiling
the third acetic acid stream continuously intro
methyl iodide , water , methyl duced to the ion exchange resin column 7 . In the ion acetat
exchange resin column 7 , an ion exchange resin having the acetaldehyde , and ability towithdrawn
formic acid ) is continuously adsorb alkyl
fromiodides
the
to establish an ion exchange resin bed . Examples of such an ion of such a product column . This vapor is separated into a
exchange resins in which portion in a predetermined condenser . A portion of the condensate po
ously refluxed to the product column , and another portion of
US 2018 / 0201562 A1 Jul . 19 , 2018
15
the condensate portion may be recycled to the reaction lower phase withdrawal tube , 304 denotes an upper phase1 or discarded
vessel
to the outside of the system , or both . withdrawal tube , 305 denotes a thermometer
The gaseous portion is ,fed306 to
the scrubber system 8 . A bottomdenotes
fraction a containing a very small denotes a water bath ,
magnet stirrer , 307
308 denotes a temperature controller , 309 denotes a
amount of higher boiling point components is continuously withdrawn
thermometer , 310 denotes a lower phase sampling tube , fracti
from the column bottom of the product column . This bottom
311 denotes an upper phase sampling tube , 312 denotes a
stream in the line 34 before
recycled to , for example , the second acetic acid
pressure gauge , 313 denotes a pressure regulating
introduction to the distillation column 6 . A side stream ( liquid ) is
valve , 314 , 315 , 316 , and 317 each denote
continuously withdrawn as a fifth acetic acid stream from
318 denotes a safety valve , 319 denotes the height a low
position between the column top and the[ column
0142 ] ADbottom
, Mel , and waterproduct
of the were fed in amounts shown in
withdrawal line , 320 denotes an upper phase
. The withdrawal position of the side stream from the feed amount ” ofline
withdrawal Table, 1 321
to thedenotes
pressure a nitrogen gas introduction product column is lower
than , for example , the introduction chip 302 was placed
line , 322 denotes positiona pressure of the fourth discharge therein
acetic
line, and, the
andcontainer was covered with
acid stream to the product After
323 denotes column purginginof thetheinside with nitrogen
anheight , the temperature
direction
exhaust line .of The was adjusted
the dotted lineas shown in the a li
represents
product column . The fifth acetic acid stream is more enrichedcolumnwith“ Temperature
acetic acid” of Table 1 using the water ba
than the fourth acetic acid stream continuously introducedfor to30 minutes
the . After stopping of the stirring , the container was
product column . Specifically , the acetic acid concentration minutes for complete separation . Then , the of the fifth acetic acid
stream is higher than the acetic acid phase ( methyl iodide phase )
concentration of the fourth acetic acid were sampled into
stream . The acetic acid concentration of the , respecfifth acetic acidtivelystream , and their
is ,respective AD , Mel , and water concentra
for . 9 to 99 . 999 % by mass or not less than measured
example , 99EXAMPLES this range Examples
, while the AD distribution coefficient 11 to 15
as long
[being
0140 ] higher
Hereinafter than
, the present invention willacid
the acetic concentration of shown
be described [ 0143 ] In
in Table 1 . Examples 11 to 15 , experiments were conducted the fourth acetic acidi
to examine each component concentration in an aqueous
.stream
However. ,This
the fifth acetic acid stream is retained in , foris not
present invention example , a toproduct
intended
distribution tankby( these
becoeffilimited cient when an AD concentration in a charging mixture was
acetaldehyde
not shown ), .“ Mel
The” ion
represents exchange resin column temperature 7 may be( liquid placedmethyl iodide
downstream , “
temperature ) in the MA ”
of represents
the methyl acetate , and “ AC ”
product
acetic acidcolumn instead of of( each
. The measurements or incompoaddition to its placement nent concentrationdownstream
in an aqueous phase
of theand an or
distillation [ 0144 ] The amounts of AD , Mel , and water fed to the pressure - ponents except for wa
were performed bycolumn
using 6gastochromatography
treat the acetic
for the com acid stream from the product column
water determination apparatus for water . The AD distribution resistant glass container 301 and the temperature
. coefficient between th
Table 1 . The experiments according to the aqueous
same procedures
organic phase , and the MA distribution coefficient between the phase ana
were performed to measure each component concentration
determined according to the following expressions : 10
the organic phase and to determine the AD distr
AD distribution coefficient = { AD concentration ( %
by mass ) of the aqueous phase } / { AD are shown in Examples 16Tableto 1 21.
concentra tion ( % by mass ) of the organic phase }
MA distribution coefficient = { MA[ 0145 ] In Examples 16 to (21 ,%experiments were conducted
concentration
by mass ) of the aqueous phase } / { to examine each component concentration in an aqueous
MA concen tration ( % by mass ) of the organic phase }
organic phase , an AD distribution coefficient ,
Examples 1 to 10 distribution coefficient when an AD concentration
[ 0141 ] Examples 1 to 10 employed a liquid - liquid equi
300 adaptable to a pressur ized concentration
system shown
10146
in. 6 , aand charging
] inTheFIG amounts experiments
of AD were
mixture were kepteach
con ducted
, Mel , MAto, examine
and water fed to
component concentration in an a temperature ( liquid temperature ) in the sepa
aqueous
the phasepressure
and an organic
step was changed phase and anglass
. - resistant AD distribution
container 301 and
coefficient by changing an AD concentration in a charging the temperature were set to the values shownmixture
in toTable
be subjected t
step ( separation step feeding liquid ) . In FIG2. .6 The
, 301experiments
denotes a pressure according to the same procedures
container ( internal volume : 100 cc ) , 302 as in Examples 1 to 10 denotes a were
stirrerperformed
chip ( rugbytoballmeasure
-
shaped ) , 303each
denotescomponent
a concentration in the aqueous pha
and the organic phase and to determine t
US 2018 / 0201562 A1 Jul . 19 , 2018
16
Examples 22 to 26 Reference Examples 1 and 2

[ 0147 ] In Examples 22 to 26 , experiments were conducted [ 0149 ] In Reference Examples 1 and 2 , experiments were
component concentration in an aqueous each component concentration in anphase and an organic phase and an AD aqueous p
distribution coeffi in a charging mixture . cient and an MA distributiondistribution
coefficient bycoefficient
changing an MAby changing an AC concentration in a charging
concentration
[ 0148 ] The amounts of AD , Mel , MA , and water fed to the [ 0150. ]
mixture The amounts of AD , Mel , water , and AC fed to the pressu
glass container 301 and the temperature resistant glasswerecontainer
set to 301theandvalues
the temperature
shown in Table 2 . The
experiments according to the same procedures as in Examples 1 to2 . 10The experiments according to the same procedures as in Examples 1 to 1
measure each component concentration performed to measure each component concentration
in the aqueous phase and the organic phase
and to determine organic phase and to determine
the AD distribution coefficient and the MA distribution the AD distribution
shown in TABLE Table
1 2.
coefficient . The results are shown in Table 2 .
Example Example Example Example Example Example Example Example
Example 1 2 3 4 5 6 7 8
Actual feed AD 0 . 05 0 . 11 0 . 20 0 . 39 0 . 81 1 . 62 5 . 63 21 . 20
amount Mel 132 . 15 132 . 02 132 . 10 132 . 95 131 . 91 132 . 05 128 . 04 .115 . 06
[g] MA
H20 60 . 09 60 . 09 60 . 11 60 . 23 59 . 85 60 . 15 54 . 01 41 . 05
AC
total 192 . 29 192 . 22 192 . 41 193 . 57 192 . 57 193 . 82 187 . 68 177 . 31
Temperature [ °C ] 40 40 . 2 40 . 1 40 . 2 40 . 2 40 . 2 40 . 1 40 . 1
Pressure [ MPaG ] 0 . 05 AD0 . 05 0 0 . 05 0 0 . 05 0 . 05 0 0 . 05 0 0 . 05 0 . 07
Actual feed Mel [ . 026 % 68 . 057 % 68 0 68
. 104 % . 201 % 68 . 42 % 68 0 . 84 % 3 . 0 % 12 . 0 %
.7% 68 . 1 %68 . 2 %
wt % ] MA .7% .7% .7% .5% 64 . 9 %
H2O 31 . 2 % 31 . 3 %31 . 2 % 31 . 1 % 31 . 1 % 31 . 0 % 28 . 8 % 23 . 2 %
AC
total 100 . 0 % 100 . 0 %100 . 0 %100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 100 . 0 %

Aqueous AD 0 . 045 % 0 . 098 % 0 . 190 % 0 . 371 % 0 . 76 % 1 . 539 % 16 . 78 %
phase Mel 2 . 45 % 2 . 45 % 2 . 45 % 2 . 46 % 2 . 47 % 2 . 49 % % 5 . 3 . 09 %
[ wt % ] MA
H2O 97 . 50 % 97 . 45 % 97 . 36 % 97 . 17 % 96 . 7722%% 95 . 972 .% 5392 %. 24 % 80 . 14 %
AC
total 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 %

Organic AD
0 . 013 0%99. 030 % 0 . 240 % 0 . 495 % 1 . 95 % 9 . 48 %
phase Mel . 47 % 0 . 058 %% 0 .99 . 26 %
[ wt % ] MA 99 . 49 % 99 . 44 115
% % 99 . 3999% . 01 % 97 . 18 % 90 . 06 %
H20 0 . 50 % 0 . 50 % 0 . 50 % 0 . 50 % 0 . 50 % 0 . 50 % 0 . 87 % 0 . 46 %
AC
total 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 %
AD 3 . 35 3 . 30 3 . 26 3 . 22 3 . 17 3 . 11 2 . 68 1.8
distrib
( aqueous
ution phase /
coefficient
organic phase )
Example Example Example Example Example Example Example

Example 10 11 12 13 14 15
9
Actual feed
amount
[g]
MA
AD
Mei
AC
24 . 80 35 . 210 . 41
1 - 2921 0 . 39
101 . 12 66 . 04 104 . 03104 . 03 111 . 33 112 . 87 114 . 12
29 . 01 33 . 99 37 . 00 37 . 00 39 . 42 39 . 90 40 . 41
0 . 41 0 . 39 0 . 42
H2O
total 154 . 93 135 . 24 141 . 44 141 . 42 151 . 16 153 . 16 154 . 95
Temperature
Pressure
Actual feed AD
[ wt % ] MA
[ ° C . ] 40 . 2 4 0 . 2
[ MPa ] 0 . 08
16Mel .
65 . 3 %
29394 19341
0 . 10
70 . 0 50 . 0 30 . 6
0 . 13 0 . 13
0 % 26 . 0 % 730 .. 36 %% . 3 %
48 . 8 % .6%
20 . 6
0 . 07 0 0 . 03
0 . 3 % 73 . 3 %
73 . 7 %
.7%
11 . 1
0 . 01 0
0 . 3 % 73
73 . 6 %
US 2018 / 0201562 A1 Jul . 19 , 2018
17
TABLE 1 - continued
H2O 18 . 7 % 25 . 1 % 26 . 2 % 26 . 2 % 26 . 1 % 26 . 1 % 26 . 1 %
AC
total 100 . 0 % 100 . 0 %100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 %

Aqueous AD 20 . 64 % 28 . 10 % 0 . 44 % 0 . 51 % 0 . 54 % 0 . 50 % 0 . 60 %
phase MeI 3 . 98 % 5 . 43 % 2 . 47 % 2 . 46 % 3 . 37 % 2 . 40 % 2 . 30 %
[ wt % ] MA
H20 75 . 37 % 66 . 47 % 97 . 09 % 97 . 03 % 96
. 09 % 97 . 10 % 97 . 10 % AC
total 100 . 0 %100 . 0 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 %
Organic AD 14 . 06 % 24 0.. 230 % 0 . 181 % 0 . 153 % 0 . 122 % 0 . 143 %
phase 85 . 18 % % 99 . 13 % 99 . 18 %99 . 45 % 99 . 56 % 99 . 57 %
[ wt % ] Mel 80 % 73 . 34 %
MA 0 . 77 % 1 . 86 % 0 . 64 % 0 . 64 % 0 . 40 % 0 . 32 % 0 . 28 %
H2O
total 100 . 0 % 100 . 0 % 100 . 0 %100 . 0 % 100 . 0 % 100 . 0 %100 . 0 %
AD AC 1.5 1.1 1.9 2.8 3.5 4.1 4.2
distributio
n( aqueous
coefficient phase /
organic phase )
TABLE 2
Refer - Refer
ence ence
Ex Ex - Ex - Ex - Ex - Ex Ex - Ex - Ex Ex - Ex - Ex Ex
Example ample ample ample
16 17 18
ample ample ample
19 20 22 21
23 ata
41 - 1993 24 ample
25
ample ample
26
ample ample ample
ample
461 0 . 41 46 0 . 40
Actual feed
amount
AD 0 . 40 0 . 41
88 . 49 . 68
0 . 41 89 0 . 39 0 . 40 0 . 44
94 . 94 98 . 18 101 . 08
0 . 42
* * * | 19
0 . 40 0 . 43 0 . 42 78 0 . 42
113 . 01 92 . 02
11 =ata2889 20181386493999999
Mel 105 . 53 8 . 127 . 09 . 43 109 . 12 3 . . 01 8 . 23. 03. 03 .3903 .
[g] MA
7 . 43 77 .. 9855 8 . 21 8 56 . 00
34 . 21 34 . 66 36 . 72 37 . 59 5539 . 01 40 . 50 805 9 . 01 6855 . 97 50 . 01 03 44 . 02 44 . 02 58 . 00 57 . 00
H2O
AC 9 . 01 17 . 02
total 130 . 53 132 . 30 140 . 05 144 . 37 149 . 04 154 . 90 190 . 32 174 . 17 151 . 48 129 . 50 146 . 47 180 . 43 166 . 44
Temperature [ °C . ] 50 . 3 4 0 . 6 30 . 5 21 . 0 11 . 3 -5.1 40 . 3 40 . 3 40 . 3 40 . 5 40 . 5 40 . 0 40 . 0
Pressure [ MPaG ] AD 0 . 14 0 . 310 . 11 0 . 07 0 . 290 . 05 0 . 270 . 02 0 0 . 02 0 0 . 06 0 . 06 0 . 06 0
19941993 1234849 Dag 1909

0 . 06 0 . 06 0 . 0 . 06 0 . 06 0
Actual feed [ MeI MA 0 . 31 % 50 ..722. %8 68% . 62
0 . 23 % 0 . 32 % 0 . 25 %
% H2O67 .678 % . 8 %% 67 .% 85 .% 75 68 ..027% % . 528. %7 67 66 . 7 % 28 % 51 . 5
35 5. 5 % 31 . 4 % . 23 % . 24 % 62 55
wt % ] AC % 26 . 2. % 7 % % 26 26. %. 2 % 26 . 0. %58 .% 7 % 1265% .. 14 %% 312 . .0 %0 % . 0 % % 3215 .. 23034% .. 10 %% 38 .2% .343 %. 2 %
30 . 1 % .326 %. 1 %
Aqueous
phase
total
Mel
. 72AC% 2 . 83 % 2 .. 62 %
2%
* 19933 19348
2 2. 58 % 2 .
2
0 . 54 %
26 . 2 %
1 33%. 0 %
100 . 0AD % 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 %100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 %
0 MA. 55 % 0 . 60 % 0 . 613 % 0 . 55 % 0 . 56 % 0 . 46 % 02 . 42 % 0 . 41 % 0 . 37 % 0 . 301 % 0 . 140 % 0 . 139 %
. 882 % 2 . 31 % 2 . 23 % . 68 % . 45 % 6 . 20 % 10 . 3 . 09 %12 . 3 . 37 %
5.0% 10 . 2 %
[ wt % ] H20 94 2 . 97 % 21 . 21 %2 . 2 . 56 %
9328 .% 45 % . 18 % 25 % 94. 30. 57%94 %. 9451 .% 05 % 96 . 03 % 94 . 79 %01 % 87
36 %.9182. %00 % 84 . 9086 .% 73 . 89 %
. 40 % . 48 % 94 11 . 61 % 22 . 35 %
53 % 90 % 50 %
100 . 0 %100 . 0 % 100 . 0 % 100 . 0 % 100 .. 001%100 % . 0 % 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 100 . 0 100 . 0 % 100 . 0 %
1 949
total
Organic AD 0 . 190 % 0 . 194 % 0 . 17993 %. 00 0 . 14593 .% 16 0 . 132 % 0 . 124 % 0 . 134 % 0 . 136 % 950 .. 2171 % % 93 .050. %29 0 . 028. 127 % 0 . 125 %
phase 5 . 94% % 5 . 92935% . .96 %250 .%9387 . 45 0%. 93 5 5 2 . 29
[ wt % ] Mel % 73 . 47 % 93 . 60 % % % 5 . 8179% . 341 .%8741 % . 56
98 . 88 %98 . 75 %
080 ..%%5563 % 49 .
MA 0 %. 60 % . 92 % . 99 % 0 . 5 . 90 % 0 . 019%. 88. %57 % 2 . 00 % 153 .% 00 % 0 .4724 .% 57 0% . 28 %
% %
AC
H20 48 % 42 %0 . 38 % 0 . 75 % 0 . 85 %
total 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 %1 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 %
AD 22 . .9 9 33 ..1 1 33 . .4 4 33 ..8 8 44 .. 11 44 ..5 5 33 . .4 4 33 ..1 1 11 ..9 9 11 ..3 3 11 . .1 1 33 ..1 1 33 ..1 1
distribution
coefficient
( aqueous
phase /
organic
phase )
Aqueous phase MA 8 . 22 % 8 . 01 % 8 . 21 % 8 . 22 % 8 . 47 % 8 . 41 % 3 . 50 % 8 . 37 % 25 . 58 % 51 . 44 59% . 57 %
concentration +
organic phase MA
concentration ( wt % ]
US 2018 / 0201562 A1 Jul . 19 , 2018
TABLE 2 - continued
Refer - Refer
ence ence
Ex - Ex
Ex Ex
Ex - Ex - Ex
Ex Ex Ex
Ex - Ex
Ex Ex
Ex - Ex - Ex
Ex Ex Ex - Ex
Ex Ex - Ex
Ex
ample ample ample ample ample ample ample ample ample ample ample ample ample
Example 16
16 17
17 18 19 20 21
21 22 23
23 24 25
25 26 1
MA distribution
0 . 38 0 . 37 0 . 38 0 . 39 0 . 41 0 . 43
coefficient ( aqueous
0 . 53 0 . 44 0 . 31 0 . 25 0 . 25
phase / organic phase )
[ 0151 ] [ Discussion on Results ] tration conditions , at a higher temperature at the time of the
[ 0152 ] From the results of Examples 1 to 10 , it is evident separation , the AD distribution coefficient is smaller , and
AD concentration and the aqueous phase and the organic phase have higher AD
coefficient is smaller so
where methyl acetate is present , at a higher temperature ,
that the rate of distribution of AD to the organic phase tends
the rate of distribution of AD to the organic
. Specifically , from the viewpoint of acetaldehyde removal efficiency , the AD removal treatment
relatively higher . Specifically , from the
is highly advantageous in the case where the AD concentrations in the aqueous phase and the
acetaldehyde removal efficiency , the AD
whereas the AD removal treatment of the organic phase is low advantageous in geous
phase is highly advanta the casein where
the case where the temperature at the
concentrations in the aqueous phase and the organic
the separation is high , whereas the AD removal treatmenthandof, the
phase are low . On the other the AD removal treatment
the aqueous phase is highly advantageous in the case where the AD concentrations in the aqueous phase and
organic phase is low advantageous in the case where the
organic phase are low , whereas the AD removal treatment of the aqueous phase is low ad
the time of the separation is low . On the other
where the AD concentrations in the aqueous phase and the organic where methyl acetate is present , the AD
in the case of using a step or equipment for the AD removal treatment of the advantageous in the case where the temperature at the time
phase is highly
increase the AD concentra tion in the aqueous the
phaseseparation
and / or theis organic phase in the
low , whereas the AD removal treatment
adjusting , for example , reaction condi tions for a reaction vessel , evaporation conditions for an
is low advantageous in the case where
evaporator , and distillation conditions for a vapor stream obtained i
separation is high . From another viewpoint , in the case
of using a step or equipment for the AD removal treatment of the aqueous phase , it is preferred to decrease
[step the results of Examples 22 to 26 , 4 , and 17 , for the AD removal treatment of the organic pha
0155 ]orFromequipment
the AD concen trations in the aqueous phase and / or the organic phase in the
as the charging mixture
preferred to sethasthe
a higher
liquidMA temperature at the time of the
reaction condi tions for a reaction vessel , evaporation conditions for an
separation
organic phase in the separation step have
to higher
a highMA concentrations
temperature ,, the AD distribution coeffi
conditions for a vapor stream obtained in the evaporation step . the presence
so that or absence
the rate of methyl acetate
of distribution of AD to. the Al
orhigher
equipment for the, AD
. Specifically removal
from treatment of theof aqueous
the viewpoint phaseremoval
acetaldehyde , it
10153 ] From the results of Examples 11 to 15 , it is evident that
set the liquid
removal treatment temperature
of the organic phase is athighly
the advan
time of the separation in the
under the constant AD concentration condition , at a higher
separation
concentrationsstep
in theto a low temperature . aqueous phase and the organic phase are high , whe
temperature at the time of the separation , the AD
removal treatment of the organic phase is low advan
distribution coefficient is smaller so that the rate of aqueous pha
the MA concentrations in the
distri bution of AD to the organic phaseother tends to hand , the AD removal treatment of the aqueous phase is
be relatively higher . Specifically , from the viewpoint of
case where the MA concentra tions in the aqueous phase and the or
acetaldehyde removal efficiency , the AD removal whereas the AD removal treatment of the aqueous phase is
low ,
treatment of the organic phase is highly advantageous
case where the MA concentrations in the aqueous p
in the case where the tem perature at the time of
another viewpoint , in the case of using a step or equipment
high . From
the separation is high , whereas the AD removal treatment of the organic phase , it isremoval
10154 ] Fromofthethe
treatment results of Examples
organic phase 16istolow
21 ,advantageous
it is
in phase and / o
evident that under the constant AD concentration concentration in the aqueous
and MA concen
the case where the temperature at the time of by the adjusting , for example , reaction conditions for a reaction
sepa ration is low . On the other handconditions , the for an AD
evaporator , and distil
US 2018 / 0201562 A1 Jul . 19 , 2018
the AD removal treatment of the aqueous phase , it is preferred { acetaldehyde

to concentration ( % by mass ) of the organic
decrease the MA concentrations in the aqueous phase and the organic [more0169than] (4 v. )1 (ae .methyl
g . , 0acetate
. 5 to 4distribution
. 1 ) ; and coefficient [ { methyl
phase in the separation step by acetate concentration (adjusting % by mass ), offortheexample
aqueous ,
reaction conditions for a reaction concentration ( % by mass ) of the vessel , evaporation conditions organic p
for an evaporator , and distil lation conditions
. g . , 0 . 15 to 0 . 53 ) . for a vapor stream [ 0170 ] Appe
obtained in the evapo ration step acetic
. From the results of Examples
evident that as the
0171 acid
[ charging according
] Appendix
mixture
3 has to Appendix
: The
a
method
higher
forMA1 producing
, whereinacetic
the catalyst
acid system further
22 to 26 , it is comprises an ionicin iodide . (i),
or 2 , wherein the condition phase have higher MA
concentration and the aqueous phase and / or the organic
[ 0156 ] From the results of Reference Examples 1 and 2 , it is not less than 0 . 045 % by mass , and the acetaldehyde concentra
concentrations , not only
distribution coefficient is notthemuch
AD distribution coefficient changed
but theby theMAACdistribution
concentrations of the charging mixture ,
phase is not less than 0 . 013 % by mass . [ 0172 ] Appendix 4 : The method for
coefficient smaller, .from
aqueous phase ,isand the organic phase . Specifically
producing acetic acid according to any onetheofviewpoint
concentration is not much significant for comparing the advantages of
appendixesof 1acetald
to 3
removal efficiency , the AC condition ( i ) , the acetaldehyde concentration in the aqueous
the method of the AD removal treatment of the organic phase and the method of the AD removal
the aqueous phase . [by0173
mass ]( preferably
Appendix 0 5. :15Theto method
10 % byfor producing acetic acid
massof) .appendixes 1 to 4 , wherein in the
one
0157 ] The configurations according to the present inven
tion and variations or modifications thereof will be listed in the organic phase is 0 . 013 to 30 % below
by mass ( preferably 0 . 05 to 5 . 0 % by
as[ 0158
a summary
] Appendixof 1the: Aabove
method description . acid ,
for producing acetic co
[ 0174 preferably
further ] Appendix0 .6 1: toThe1 method
. 0 % byformass
producing
) . acetic acid
101591 a carbonylation reaction step of reacting methanol of appendixes 1 to 5 , wherein in the with c
carbon monoxide in the presence of a catalyst system acetaldehyde concen tration in a liquid
comprising a to be subjected to t
metal catalyst and methyl iodide , acetic acid , methyl not less than 0 . 026 % by mass ( e . g . , 0 . 026 to 32 % by mass , prefer
[ 0160 ] an,evaporation
acetate and water step ofinseparating the reaction
a reaction mix to produce ably
vessel [ 01750 ]. 10Appendix
to 8 . 07 %: The
by mass
method, further preferablyacetic
for producing to 1 . 8 % by massacetic
0 . 15acid ).
carbonylation
acid ; reaction step into a vapor of appendixes 1 to 6 ,stream wherein inandthea residual liquid stream in an c
[evaporator
0161 ] a; lower boiling point component removal step of the separation separating
is not less than 0° C . ( e . g . , 0 to 90° C . , further preferably no
by distillation into an overhead stream rich in at least one lower boiling point component
less than 10° C . ( e . g . , 10 to 90° C . ) , particularly preferably
selected from methyl iodide and acetaldehyde and an acetic acid stream rich in
temperature
[ 0176 ] of higher8than
Appendix : 70°method
The C . ( efor. gproducing
. , more than 70°acid
acetic C . and not more than
acid
[ 0162; ] a separation step of separating a process stream containing
appendixes
90° C . ) 1 to 7 , wherein in the condition ( iii ) ,
acetic acid , methyl iodide , and acetaldehyde into an aqueous phase and an organic phase ;
in the aque ous phase is not less than 1 . 2 % by mass , and the methyl
[ 0163 ] an acetaldehyde separation and removal step for acetate concentration in the organic phase is not less than sepa
removing the acetaldehyde derived from the [ 0177 ] Appendix 9 : The method for producing acetic acid according
process stream , wherein to
[ 0164 ] the separation step satisfies at least one of the any one of appendixes 1 to 8 , wherein in the
) , and at least a portion of the acetate concentration
organic inphasethe isaquetreated in the acetaldehyde separation and ous phase
removal 2[ .01785 to] 12Appendix
% by mass
10 : ,Thefurther
methodpreferably 6 . 0 toacetic
for producing 11 % by mass ) .
[ 0165 ] step
( i ): an acetaldehyde concentration in the aqueous phase is not less than
one of appendixes 1 to 9 , wherein in
by mass , and / or an acetalde hyde concentration
concentrationin inthetheorganic phase is not less organic phase is 2 . 2 to 60 % by mass ( prefe
than 0 . 013 % by mass ;
[ 0166 ] ( ii ) a temperature at the time of the separation is not [by0179
mass ], further
Appendixpreferably
11 : The19methodto 42 for
% byproducing
mass ) . acetic acid
[- 0167
5° C .] ( (e .iiig .) ,a-methyl
5° C . acetate
to 90° Cconcentration
.) in the aqueous one of Appendix 1 to 10 , wherein in the phase
methyl acetate concentration in the organic phase is not acetate
less thanconcentration
2 . 2 % by in the aqueous phase and the methyl acetate conc
methyl acetate concentration in the organic phasetheisaqueous
3 . 4 tophase75 and
% bythemassmethyl
( preferably
acetate8 concentration
. 3 to in
than 3 . 4 % by mass ; ,[100180to ]40Appendix
% by mass12 ): ,Thefurther
method preferably
for producing acetic
[ 0168 ] ( iv ) an acetaldehyde distribution coefficient [ { acet one of appendixes 1 to 11 , wherein in
concentration ( % by mass ) of the aqueous phase } , a methyl acetate
US 2018 / 0201562 A1 Jul . 19 , 2018
20
concentration in the liquid to be subjected to the ( 0193 ] ( iii ) a methyl acetate concentration in the aqueous phase is not less than 1 .
separation is 2 . 0 to 50 % by mass ( preferably2 % by5 mass . 0, and / or a methyl acetate
[to018138] %Appendix 13 The method for producing acetic acid mass , and) /.or the sum of the methyl acetate concentration in according
by mass , further preferably. 2 15 % by to 31 % by mass
in the condition ( iv ) , the acetaldehyde distribution coefficientthe ismethyl acetate concentration in the organic phase i
3 . 35 , more preferably less than 1 . ;5[ 0194
( e .]g .( ,ivnot) less
an acetaldehyde distribution
than 0 . 7 and less than 1coefficient [ { acet
. 5 ) , further
less than 1 . 1 ( e . g . , not less than 0 . 8 and less than concentration ( % by mass ) of the aqueous phase } /
[ 0182 ] Appendix 14 : The method for producing acetic acid according to appendix [% 0195by13mass ()v of) the
], wherein organic
a methyl acetate distribution coefficient phase } ] is not
the acetaldehyde . than
5 to1 concentration
distribution coefficient is set to lessacetate .41 .by1not) less
; and(than% by mass ) of the aqueous
group consisting of setting the concentration acetaldehyde
( % by massconcentration
) of the in the aqueous phase to more organic p
by mass , setting the acetaldehyde concentration in the organic phase to more than 24 . 8 % by mass ,
g . , 0 . 15 to 0 . 53 ) . [ 0196 ] Appendix 20 : The method for
setting the acetaldehyde concentration in the liquid to be subjected to
producing
[ 0197 ] Appendixacetic 21 : The method for producing aceticacid according to appendix 19 , wherein the catalyst s
0 % by mass , setting the temperature at the time of the separation to more than 70° C . ,
comprises19 anor ionic
appendix iodidein .the condi
20 , wherein tion
methyl acetate concentration in the aqueous phase to more than 12 .is0 not
% bylessmassthan, setting the methyl
the aqueous phase 0 . 045 % by mass , and the ac
acetate concentration in the organic phase to more than 47 . 6 % by mass , and setting the methyl
concentration
mass . in the organic phase is not less than 0 . 013 % by
concentration
in the liquid to be subjected to the separation to more than [ 0198 ] Appendix 22 : The method for producing acetic 38 . 2 % by mass .
one of appendixes 19 to 21 , wherein in the
[ 0183 ] Appendix 15 : The method for producing acetic aci
concentration in the aqueous phase is 0 . 045 to 35 % by mass ( prefera
any one of appendixes 1 to 14 , wherein in the condition ( v ) , the methyl acetate
distribution coefficient is not more than10[ 00199
%. 44by]( emass
Appendix0 . 2320 to: preferably
. g .,, further The
0 . 44method 0 for. 2 toproducing
, further 2 . 0 acetic
% by mass ) .
preferably
any one of appendixes 19 to 22 , wherein
less than 0 . 25 ( e . g . , not less than 0 . 20 and lessconcentration
than 0 . 25in ) the)
organic phase is 0 . 013 to 30 % by mass ( prefera
. [ 0184 ] Appendix 16 : The method for producing acetic to[ 0200
5 . ]0 %Appendix
by mass ,24further
: The preferably
method for 0 producing
. 1 to 1 .acetic
0 % by mass ) .
according
[ 0185 ] toAppendix
any one 17of :appendixes
The method1 to for15 ,producing
wherein theacetic separation step satisfies
acid according t
atof appendixes
least the 1conditions ( i )the, ( ii ) , and
to 16 , wherein ( iii ) at the same time .
) , an acetaldehydeseparation step satisfies at least the conditionsconcentration in a liquid to be subjected to the separa
( i ) , ( ii ) , ( iii ) , and than
( iv 0) .at026the%sameby mass
time .( e . g . , 0 . 026 to 32 % by mass ,
[ 0186 ] Appendix 18 : The method for producing acetic acid accordin
17 , wherein the separation step satisfies all .
of0 %
the by mass
conditions ,( further
i ) , ( preferably
ii ) , ( iii 0
) .
,
[ 0201 ] Appendix 25 : The method for producing acetic 15 to
). any one of appendixes 19 to 24 , wherein
[ 0187 ] Appendix 19 : A method for producing acetic acid by rea
the time of the separation is not less than 0° C . ( e . g . , 0 to 90° C . , furthe
in the presence of a catalyst system comprising a metal catalyst and methyl
preferably not less than 10° C . ( e . g . , 10 to 90° C . ) , particu
methyl
[ 0188 ]acetate , and water
a separation step of, comprising
separating a: process stream containing
temperature
[ 0202 ] ofAppendix
higher than26 70°: CThe. (method
e . g .for, producing acetic
acetic acid , methyl iodide , and acetaldehyde into an aqueous phase and an organic phase ;
.any) one of appendixes 19 to 25 , wherein in the condition ( iii ) , the methyl acetate
[ 0189 ] an acetaldehyde separation and removal step for concentration in the aqueous phase is not less than 1 . 2 % by ma
separating and removing the acetaldehyde derived from the
methyl acetate concentration in the organic phase is not less than
process stream , wherein
[ 0190 ] the separation step satisfies at least one of the [ 0203 ] Appendix 27 : The method for producing acetic
) , and at least a portion of the one of appendixesorganic
19 to 26phase
, wherein
is treated in the acetaldehyde separation and in the condition ( i
removal step : concentration in the aqueous phase is 1 . 2 to 15 % by mass ( prefera
[ 0191 ] ( i ) an acetaldehyde concentration in the aqueous
%[ 0204 ]by Appendix
mass , further
28 : preferably
The method6 for. 0 toproducing
11 % by mass
acetic) .
less than 0 . 045 % by mass , and / or an acetalde hyde concentration in the
organic
[ 019 ] phase
( ii ) aistemperature
not lessatthan
the time of the separation is not 0 . 013 % by mass ;
acetate concentration in the organic phase is 2 .less
2 to
e . g . , - 5° C . to 90° C . ) to 48 % by mass , further preferably 19 to 42 % by mass ) .
US 2018 / 0201562 A1 Jul . 19 , 2018
[ 0205 ] Appendix 29 : The method for producing acetic 10216 ] a lower boiling point component removal step of
appendixes 19 to 28 , wherein separating the invapor the condition
stream ( byiii )distillation
, the sum of the into
methyl acetate
an concen
tration in the aqueous phase and the methyl acetate concen overhead stream rich in at least one lower boilingtration pointin the organi
by mass ( prefer [. 0217
g . ,] 10ato separation
ably 8 . 3 to 60 % by mass ( ecomponent 40 % by massstep)selected
, offurther
separating
from amethyl
processiodide
stream and acetaldehyde and
least water , acetic acid , methyl
an acetic acidiodide
stream
, andrich in acetic acid ;
53[ 0206
% by] Appendix
mass ) . 30 : The method for producing acetic acid accordin
organic phase ; and step
one of appendixes 19 to 29 , wherein [ 0218 ] an acetaldehydein separation
the case ofandsatisfying
removal the condition
for ( iii ) ,
the methyl acetate concentration in the liquid to beacetaldehyde
subjected toderived
the separation
from the process stream , wherein
2[ .02070 ]toAppendix
50 % by31 mass ( 0219 ] the separation step satisfies at least one of the
: The( method
preferably 5 . 0 acetic
for producing to 38 % by mass , acid according to
preferably 15 to 31 % by mass ) . ) to ( x ) , and at least a portion of the
one of appendixes 19 to 30 , wherein in the condition ( iv ) , the acetaldehyde
acetaldehyde separation and removal step :
distribution coeffi cient is not more than 3 . 35 ([e0220
. g ]. ,( 0vi. )6 toan 3 acetaldehyde
. 35 , more concentration in the aqueous phase is not more than 28 . 1
preferably % by 1mass. 5 ,) and, / or an acetalde
less than 1 . 5 ( e . g . , not less than 0 . 7 and less than hyde concentrati
further
[ 0208 ] Appendix 32 : The preferably
method forlessproducing 1 ( e . g . , not less than 0 . 8 andthan
than 1 . acetic less24 than
0221 .]8 % (by vii mass ; ) a temperature at the time of the separation acid according
is t
1.1)). not more
distribution than 70° C . ;
wherein the acetaldehyde 0222 ] coefficient ( viiiis set) toa less than 1 .acetate
methyl 1 by not lessconcentration
than in
selected from the group consisting of setting the the aqueous phase is not more than 12 . 0 %concentration acetaldehyde by in the aqueou
more than 28 . 1 % by mass , setting the acetaldehyde concentration mass , and / or a methyl acetate concentration in
24 . 8 % by mass , setting the acetaldehyde concentration
the organic phase is not more thanin the liquid to be subjected to 47 . 6
more than 26 . 0 % by mass , setting the mass
mass ; temperature at the time of the separation to more than 70° C . ,
0223 ,] and ( ix/ )oranthe sum of the
acetaldehyde methyl acetate
distribution
setting the methyl acetate concentration in the aqueous concentration in the aqueous phase and the methyl acetate phase to more than 12 .
coefficient [ { acet aldehyde concentration ( %
0 % by mass , setting the methyl acetate concentration in the organic phase to
by mass ) of the aqueous phase } / {
more than 47 . 6 % by mass , and setting the methyl acetate [acetaldehyde
0224concentration
] ( x ) a methyl acetate distribution coefficient
concentration ( % by mass ) of the organic
liquid to be subjected to the separation to more than acetate concentration ( % by mass ) of the aqueous phase } / { methyl acetate 38 . 2 % by
[ 0209 ] Appendix 33 : The method for producing acetic concentration ( % by mass ) of the acid according to
mass . [ 0225 ] Appendix 38 : The method for producing acetic
one of appendixes 19 to 32 , wherein e . g . , 0 . 25 to 0 . 70 ) . in the condition ( v ) , the methyl acetate
distribution coeffi cient is not more thanappendix
0 . 44 37( e, .wherein
g . , 0the. 20catalyst
0 .system
[ 0226 ] Appendix 39 : Thetomethod for producing acetic
44 , further preferably less than 0 . 25 ( e . g . , not less than 0 . 20 and less
[ 0210 ] Appendix 34 : The method for producing acetic appendix 37 or 38 , wherein in the condi acid
than 0 . 25 ) ) . aqueous phase is not more than the 28 .separation
1 % by mass step
, and satisfies
the acetaldehyde
any one of appendixes 19 to 33 , wherein at least
the the organic phaseandis not more thanthe24 .same 8 % time
by .
[ 0211conditions
] Appendix( i35) :, The( iimethod
) , for producing acetic acid
[ 0227 ] Appendix (40iii: )Theat method for producing acetic according to a
appendixes 19 to 34 , wherein the any one of appendixes separation
37 to 39step satisfies at least the
, wherein
conditions ( i ) , ( 36ii ): , The ( iiimethod
) , for producing acetic concentration in the and ( iv ) at the same time . aqueous phase is 0 . 045 to 28 . 1 % by mass ( pref
[ 0212 ] Appendix acid
any one of appendixes 19 to 35 , wherein 098 to 10 % by mass , further preferably 0 . 098 to 3 . 0 % by mass ,
the separation step satisfies all of the
conditions ( i ) , ( ii ) , ( iii ) , preferably 0 . (098iv41to) :,1 and
[ 0228 ] Appendix .The0 (%method
v by) .massfor( producing
e . g . , acetic
0 . 15 to 0 . 9 % by
[ 0213 ] Appendix 37 : A method for producing acetic acid ,
any
massone) )of.appendixes 37 to 40 , wherein
[ 0214 ] a carbonylation reaction step of reacting methanol acetaldehyde concentration in the or
of a catalyst system comprising a metal catalyst
preferablyand0methyl
. 030 iodide , acetic acid , to 2 . 0 % by mass , further preferably 0 . 030 to 0 . 50
and water in a reaction vessel to produce [
,
0229 ] Appendix 42 : The method for producing
acetic acid ; acetic
particularly preferably 0 . 030 to 0 . 24 % by mass ).
[ 0215 ] an evaporation step of separating the reaction mix any one of appendixes 37 to 41 , wherein in the case of satisfying the condition ture obtained in the
carbonylation reaction step into a vapor ( vi ) , an acetaldehyde stream and a residual liquid stream in concentration in a liquid
separation is not more than 26 . 0 % by mass ( e . g . , 0 . 026 to 26 . 0 % by
an evaporator ;
mass ,
US 2018 / 0201562 A1 Jul . 19 , 2018
preferably 0 . 057 to 10 % by mass , further preferably 0 . 057ofto a3 catalyst system comprising a metal catalyst
. 0 % by mass , particularly preferably 0 . 057 to 1 . 0 % by[and 0242 ] methyl
mass a separation iodide , acetic
step of separating acid , methyl acetate , and water , comp
a process stream
[( 0230 ] Appendix 43 : The method for
e . g . , 0 . 057 to 0 . 42 % by mass ) ) . producing acetic acid , methyl iodide , and acetaldehyde into an aqueous phase and an organ
any one of appendixes 37 to 42 , wherein and in the condition ( vii ) , the
separation is - 5°
temperature at the time of theC . to 70° C . ( preferably - 5° C . to [
51° 0243 C ]. an
, acetaldehyde separation and removal step for
further preferably - 5° C . to 41° C . ( e . g . , - 5° C . toremoving 31° theC .acetaldehyde
) derived from the
). [ 0231 ] Appendix 44 : The method for producing acetic acid [ 0244 ] the separation step satisfies at least one of the
according to any one of appendixes 37 to 43 , wherein conditions ( vi ) to ( x ) , and at least a portion of the in the conditi
( viii ) , the methyl acetate concentration in in[ 0245the] acetaldehyde separationconcentration
( vi ) an acetaldehyde and the in theaqueous
aqueous phase is not more
[ 0232 ] 12Appendix
than . 0 %45 by: Themassmethod, and
for producing
the acetic methyl acetate concentration in the acid acco
. 1 % by mass , and / or an acetalde
appendixes 37 to 44is ,notwherein in the condition ( viii ) ,more
organic phase the methyl
than 47acetate
. 6 %concentration
by. 8 mass
24( 0246 . ;
% (byviimass
in the aqueous phase is 1 . 2 to 12 . 0 % by mass ( preferably 2 . 0 ] ) a temperature at the time of the separation is
further preferably 5 . 0 to 12 . 0 % by mass ;[ 02471 ( viii ) a methyl acetate concentration in the aqueous ( e . g . , 6 . 0 to 12 . 0 % by mass )
[ 0233 ] Appendix 46 : The method for producing acetic acid according to any one of appendixes 37 to 45 , wherein in the
12 . 0 % by mass , and / or a methyl
condition ( viii ) , the methyl acetate concentration in the organic
more than 47 . 6 % by mass , and / or the sum of the methyl acetate
% by mass , further preferably 8 . 0 to 35 % by mass ( e . g . , in the aqueous phase and the methyl acetate
mass ;
[ 0234 ] Appendix 47 : The method for producing acetic .[ 60248
% by] ( ix ) an acetaldehyde distribution coefficient [ { acet
acid according to any one of appendixes 37 to 46 , wherein in the condition
concentration ( % by mass ) of the aqueous phase } /
( viii ) , the sum of the methyl acetate con centration in the aqueous phase and
by mass] ) (ofx the organic acetate distribution coefficient phase } ] is not less tha
the methyl acetate concentration in the organic[ 0249
phase is ) 4a . methyl
2 to 59 . 6 %
by mass ( preferably 10 to 54 % by mass , further preferably acetate concentration
14 to 47( %% by mass ) of the aqueous
[ 0235 ] Appendix 48 : The method for producing acetic ( % by mass ) of the acid accordin
mass ( e . g . , 16 to 42 % by mass ) ) . [ 0250 ] Appendix 55 : The method for producing organic
acetic phase } ] is not less than 0 . 25 ( e . g .
37 to 47 , wherein in the case of satisfying the condition
to 0 . 7054() viii
appendix
) , a methyl acetate
,. wherein the catalyst system
concentration in the liquid to be subjected to the separation [ 0251 ] Appendix 56 : The method for producing acetic
by mass ( e . g . , 2 . 0 to 38 . 2 % by mass , appendix 54 or 55 , wherein in the condi tion ( vi ) , the acetaldehyde concentration inpreferably 5 . 0 to 31 % by
[further
0236 ]preferably
Appendix 1049 : toThe25method
% for producing acetic the aqueous by mass )phase. is not more than 28 . 1 % by mass , and the acetaldehyde acid
any one of appendixes 37 to 48 , wherein in the condition ( ix ) , the
in the .organic phase is not more than 24 . 8 % by
mass
acetaldehyde distribution coeffi [ 0252 ] cient Appendix
is 157. :1 toThe 8method . 0 ( for producing1 .acetic
preferably 5
[to02376 .] 0 Appendix
, further50preferably
: The method for producing acetic any one of appendixes 54 to 56 ,
1 . 9 to 5 . 0 ) . wherein acid ac
any one of appendixes 37 to 49 , wherein in the aqueous phase is 0in. 045the tocondition 28 . 1 %( byx )mass, the( preferably
methyl 0 . 098 to
acetate distribution coeffi 10cient
% byis massnot,less further
thanpreferably
0 . 26 ( 0e .. 098g .to, 03 .. 0 % by mass ,
[260238to ]0 .Appendix 51 : Thenotmethod for producing acetic acid according toparticularly
65 , preferably any one
[ 0253 of preferably
] Appendix appendixes
58less:0than.The0980 method
. to28 (1e.for
. 0g %. producing
, by0 .mass
28 to( acetic
0e ..60g ). ), 0 . 15 to
37. to 50 , wherein the separation step satisfies at least the conditions ( vi 9any)%,oneby( ofvii massappendixes
)) ,) . 54 to 57 , wherein
) at the same time . concentration in the organic phase is 0 . 013 to 24 . 8 % by mass ( preferably 0
[ 0239 ] Appendix 52 : The method for producing acetic
any one of appendix 37 to 51 , wherein the . 030 to 2 . 0 % by mass , furthersteppreferably satisfies 0at. least
030 tothe0 . 50 % by mass ,
[ 0254 ] Appendix 59 : The method separation for producing acetic
conditions ( vi ) , 53( vii particularly( viiipreferably
) , and ( ix0 ).at030the tosame 0time. 24. % by mass ) .
[ 0240 ] Appendix : The) ,method for producing acetic one of appendixes 54 to 58 , wherein acid according to a
one of appendixes 37 to 52 , wherein , an acetaldehyde the separation step satisfies all of the concentration in a liquid to be subjected to the separat
conditions ( vi )54, :( Aviimethod
) , for producing acetic acid not more than( viii26 . )0 ,% (byixmass) ,( ande . g( .x ,) 0. . 026 to 26 . 0 % by mass ,
[ 0241 ] Appendix by reacting methanol with
to 10 % by mass , further preferably 0 . 057 to
carbon monoxide in the presence
preferably 0 . 057 to 1 . 0 % by mass
).
US 2018 / 0201562 A1 Jul . 19 , 2018
23
[ 0255 ] Appendix 60 : The method for producing acetic rich in acetic acid by absorption treatment with an absorp tion
to 59 , wherein in the condition ( vii ) , thesolvent containing
temperature at theat time
leastofacetic
the acid .
. to 70° C . ( preferably - 5° C . to 51° C . , INDUSTRIAL APPLICABILITY further preferably - 5° C . to 41
5° C . to 31° C . ) ) .
[ 0267 ] The method for producing acetic acid of the present
used as industrial method for producing in the condition ( vii
according to any one of appendixes 54 to 60 , wherein
concentration in
methanol method ( acetic acid process of a methanol method ) .
the aqueous phase is not more than 12 . 0 % by mass , and the
REFERENCE SIGNS LIST
in the organic phase is not more than 47 . 6 % by mass .
[ 0257 ] Appendix 62 : The method for producing acetic 10268 ] 1 : reaction vessel
[ 0269in ] the2condition
: evaporator
appendixes 54 to 61 , wherein 10270 ] 3 , 5 , and 6the: methyl
( viii ) ,
acetate concentration in
distillation
phase is 1 . 2 to 12 . 0 % by mass ( preferably 2 . 0 column to 12 . 0 % by mass
[ 0272 ] 7 : ion [exchange
0271resin] column
4 : decanter
5 . 0 to 12 . 0 % by mass ( e . g . , 6 . 0 to 12 . 0 % by mass ) ) .
[ 0258 ] Appendix 63 : The method for producing acetic 80274
: scrubber
] 9 system
: acetaldehyde separation and removal system
in the condition ( viii ) , the methyl acetate concentration in [ 0275 ] 16 : reaction mixture feed line
0276 ] 17 : vapor stream discharge line the organic phase
to 42 % by mass , further preferably 8 . 0 to 35 % by mass ( e . g . , [ 0277 ] 18 and 19 : residual liquid stream recycle line
[ 0278 ] 54 : carbon monoxide - containing gas introduc
[ 0259 ] Appendix 64 : The method for producing acetic acid according to any[ 0279 one ] 55 and 56 : potassium hydroxide introduction
of appendixes 54 to 63 , wherein in the condition ( viii ) , the sum of the [methyl 0280 ] 57 : catalyst circulating pump
acetate con [ 0281
centration in the aqueous phase and the methyl acetate ] 91 : distillation column ( first acetaldehyde
organic phase is 4 . 2 to 59 . 6 % by mass 10282 ] 92 : extraction column ( preferably 10 to 54 % by mass , further
preferably [ 0283 ] 93 : distillation column ( second acetaldehyde
[ 0260 ] 14Appendix
to 47 % 65 : The method for producing acetic by mass ( e . g . , 16 to 42 % by mass ) ) .
one of appendixes 54 to 64 , wherein [ 0284 ] 94 : distillation columnin (theextractive distillation
case of satisfying the condition ( viii ) ,
a methyl acetate concentration in the liquid to be [subjected
0285 ] 95to :thedecanter
separation
[ 0286 ] 96 : decanter
more than 38 . 2 % by mass ( e . g . , 2 . 0 to 38 . 2 % by mass , [ 0287 ] 97 : distillation column ( acetaldehyde removal
preferably
[ 0261 ] 5Appendix
. 0 to 3166% :by The massmethod
, furtherforpreferably
producing10 acetic
to 25 % [ 0288 ] 98 : distillation column ( extractive distillation
65 , wherein in the condition ( ix ) , the acetaldehyde10289 distribution
) 99 :coeffi decanter
preferably 1 . 5 to 6 . 0 , further preferably [ 0290 ] 200 : chimney tray 1 . 9 to 5 . 0 ) . apparatus
[ 0291 ) 300 : liquid - liquid equilibrium n measurement
54 to 66 , wherein in the condition ( x 1) ,- 3the. (methyl
canceled
acetate) distribution coeffi
4 . A method for producing acetic acid by reacting metha
than 0 . 26 ( e . g . , 0 . 26 to 0 . 65 , preferably not monoxide in the presence of a catalyst
0[ 0263
. 60 ]) )Appendix
. 68 : The method for producing acetic a
methyl aiodide , aceticstep of separating a process stream contain
separation acid , methyl acetate , and water
any one of appendixes 54 to 67 , wherein the separation step satisfies at least
acetic acid , methyl
and (iodide
viii ), at andthe same time . acetaldehy
the conditions ( vi ) , ( vii ) ,
[ 0264 ] Appendix 69 : The method for producing acetic organic phase ; and
an acetaldehyde separation and removal thestep for step
separation separat
satisfies at least
to any one of appendixes 54 to 68 , wherein
ing and removing the acetaldehyde derived from
the conditions ( vi ) , ( vii ) , ( viii ) , and ( ix )stepatstream
thesatisfies
same, time . at least one of the following
[ 0265 ] Appendix 70 : The method for producing acetic thethe separation process wherein acid according to
one of appendixes 54 to 69 , wherein conditions ( i ) to (thev separation ) , and step at least
satisfiesaallportion
of the of the
conditions ( vi ) , ( 71vii: ) ,The method for producing acetic organic
( i( )viii , and (phase
) , ( ix )concentration x )in. theisaqueoustreated
phase is in the acetaldehyde acid a
[ 0266 ] Appendix an acetaldehyde
any one of appendixes 1 to 70 , further comprising a scrubber step of separating separation
not less than and 0 . removal
045 % step
by :
mass , and / or an
process into a stream rich in carbon monoxide acetaldehyde
and a stream concentration in the organic phase is
offgas from the
not less than 0 . 013 % by mass ;
US 2018 / 0201562 A1 Jul . 19 , 2018
24
( ii ) a temperature at the time of the separation is not less { acetaldehyde concentration ( % by mass ) of the than - 5° C . ;
( iii ) a methyl acetate concentration in the aqueous phase is( xnot) less than acetate
a methyl 1 . 1 ; anddistribution coefficient [ { methyl is not
methyl acetate concentration in the organic phase is not less than%2 .by2 mass
% by )massof, the
and /aqueous
or the sum of the methyl acetate phase } / { methy
concen tration in the aqueous phase and the methyl acetate the organic phase } ] is not less than 0 . 25 .
.4% by mass ; 8 . The method for producing acetic acid according to
wherein the catalyst system further comprises an
( iv ) an acetaldehyde distribution coefficient [ facetalde 9 . The method for producing acetic acid according to claim 7 ,
concentration
{ acetaldehyde( % byconcentration
mass ) of the( % aqueous
by massphase
) of} the wherein the separation step satisfies all of the conditions ( vi ) , ( organic phase } ]
is( vnot) amoremethyl
than acetate
4 . 1 ; and
distribution coefficient [ { methyl vii 10) ,.( viii
A method
) , ( ixfor
) , andproducing
( x ) . acetic acid by reacting
methanol with carbon monoxide in the presence of a catalyst phase } | { methyl acetate concentra
concentration ( % by mass ) of the aqueous
( % by mass ) of comprising a metal catalyst and methyl iodide , acetic
5 . The method for producing acetic acid according to the organic phase } ] ismethylnot more than 0 . 53step. of separating a process stream contain
a separation
acetate claim 4 , wherein the
acetic acid ,, methyl
and water
iodide ,, and
comprising
ionic iodide .
catalyst system further comprises an organic
6 . The method for producing acetic acid according to phase ; and claim 4 , wher
an acetaldehyde separation and removal step for separat
separation step satisfies all of the conditions ( i ) , ( ii ) , ( iii ) , ( iv ) , and ( v ) .
ing and removing the acetaldehyde derived from the
7 . A method for producing acetic acid , comprising : the separation
a carbonylation reaction step of reacting methanol with stream , wherein step satisfies at least one of the following carbon monoxide in
a catalyst system conditions ( vi ) to ( x ) , and at least a portion of the
comprising a metal catalyst and methyl iodide , acetic
acetate , and water in a reaction vessel to treated in the acetaldehyde separation acid ;
( vi ) an acetaldehyde concentration inproducethe acetic
aqueous phase is
an evaporation step of separating the reaction mixture not more than 28 . 1 % by mass , and / or an
obtained in the carbonylation reaction step into a acetaldehyde concentration in the organic phase is
a lower boiling point component removal step of sepa ( vii ) amoretemperature at the time of the separation is not
vapor stream and a residual liquid stream not in an than evaporator ; 24 . 8 % by mass ; rating the vapor stream
distillation into an overhead ( viii ) a methyl acetate stream concentration
rich in at least in onetheloweraqueous
boilingphase
point compo
nent selected from methyl iodide and acetaldehyde and , and / or a methyl an aceticinacidthestream
acetate concentration organicrichphasein ai
a separation
acid ; step of separating a process stream contain and / or the sum of the methyl acetate concentr
water , acetic acid , methyl iodide , and concentration in the organic phase is not acetaldehyde into an aqueous phase and
an organic phase ; and
an acetaldehyde separation and removal step for separat ( ix ) an acetaldehyde distribution coefficient [ { acetalde
ing and removing the acetaldehyde derived from the ) of the aqueous phase } / process { acetaldehyde concen
the separation
stream , wherein step satisfies at least one of the following phase } ] is not less than 1 . 1 ; and
conditions ( vi ) to ( x ) , and at least a portion of the ( x ) a methyl acetate distribution coefficient [ { methyl acetate concentration aqueous (%
by mass ) of the aqueous and removalphase } / { methyl
( viphase is treated
) an acetaldehyde in thein acetaldehyde
concentration the aqueous phase separation
is
not
step more : than 28 . 1 % by mass , and / or an acetaldehyde 11 organic phase for} ] producing
. The method is not less aceticthanacid0 .according
25 . to claim 10 ,
concentration in the organic phase is not more thanwherein the catalyst system further comprises an
( vii24 ) . a 8 temperature
% by mass at the; time of the separation is not 12 . The method for producing acetic acid according to
70°( Cviii. ; ) a methyl acetate concentration in the aqueous phase claim 10 , wherein the separation step satisfies all of the is not more than 12 . 0
and / or a methyl 13 in. theThe(organic
conditions
acetate concentration vimethod
)phase for
not )moreproducing
, ( isvii , (thanviii47 ). 6, acetic
%( byixmass) ,,acid
and /( according
and x). to
or the sum of the methyl comprising ina thescrubber
acetate concentration aqueous step
phase andof separating
the
concentration in the organic phase is not in carbon mon more than oxide
59 . 6 %andbyamassstream
; rich in acetic acid by
( ix ) an acetaldehyde distribution coefficient [ { acetalde anacid .
absorption solvent containing at least acetic
hyde concentration ( % by mass ) of the aqueous phase } / * * * * *

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MAIN TEH ETA AUTOMAT ETA MATKALLA

(19) Amerika Serikat

116 93A 115

7205 99 208 2094 210

100 , preferably 2 to 50 , further preferably 3 to 30the, particu

ment system in the distillation column 6 , thea amount

Examples 22 to 26 Reference Examples 1 and 2

total 100 . 0 % 100 . 0 %100 . 0 %100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 100 . 0 %

total 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 %

Example Example Example Example Example Example Example

total 100 . 0 % 100 . 0 %100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 % 100 . 0 %

19941993 1234849 Dag 1909

the AD removal treatment of the aqueous phase , it is preferred { acetaldehyde

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