United States Patent £19J
`Smith et al.
`
`[11] Patent Number:
`[45] Date of Patent:
`
`5,001,259
`Mar. 19, 1991
`
`[54] METHANOL CARBONYLATION PROCESS
`
`[75]
`
`Inventors: Brad L. Smith, Portland; G. Paull
`Torrence, Corpus Christi; Adolfo
`Aguilo', Corpus Christi; James S.
`Alder, Corpus Christi, all of Tex.
`
`[73] Assignee: Hoechst Celanese Corporation,
`Somerville, N.J.
`
`[21] Appl. No.: 870,267
`
`[22] Filed:
`
`Jun. 3, 1986
`
`Related U.S. Application Data
`[63] Continuation-in-part of Ser. No. 699,525, Feb. 8, 1985,
`abandoned, which is a continuation-in-part of Ser. No.
`606,730, May 3, 1984, abandoned.
`
`Int. CJ.5 ....................... C07C 51!12; C07C 53/08
`[51]
`[52] U.S. CI ...................................... 562/519; 562/607
`[58] Field of Search ......................................... 562/519
`
`[56]
`
`References Cited
`U.S. PATENT DOCUMENTS
`3,769,329 10/1973 Paulik et al. ........................ 560/232
`
`FOREIGN PATENT DOCUMENTS
`90443 10/1983 European Pat. Off ............. 562/579
`55618 4/1985 European Pat. Off.
`6054334 9/1983 Japan .
`Primary Examiner-Vivian Garner
`Attorney, Agent, or Firm-Ralph M. Pritchett; Donald
`R. Cassady
`
`ABSTRACf
`[57]
`An alcohol such as methanol is reacted with carbon
`monoxide in a liquid reaction medium containing a
`rhodium catalyst stabilized with an iodide salt, espe(cid:173)
`cially lithium iodide, along with alkyl iodide such as
`methyl iodide and alkyl acetate such as methyl acetate
`in specified proportions. With a finite concentration of
`water in the reaction medium the product is the carbox(cid:173)
`ylic acid instead of, for example, the anhydride. The
`present reaction system not only provides an acid prod(cid:173)
`uct of unusually low water content at unexpectedly
`favorable reaction rates but also, whether the water
`content is low or, as in the case of prior-art acetic acid
`technology, relatively high, is characterized by unex(cid:173)
`pectedly high catalyst stability; i.e., it is resistant to
`catalyst precipitation out of the reaction medium.
`
`4 Claims, 25 Drawing Sheets
`
`CE Ex. 2038
`Daicel v. Celanese
`IPR2015-00171
`
`001
`
`

`
`FIG.I
`
`Water Dependence for Methanol Carbony1ation
`190 oc, 28.2 atm. abs. total pressure
`
`26
`
`22
`
`18
`
`14
`
`10
`
`J.l
`.c:
`.......
`H
`.......
`Ill
`QJ
`rl
`~
`>t
`f-1
`Ul
`
`~
`
`0
`~
`0
`:X::
`
`6
`
`2
`
`•
`•
`
`• A
`8
`
`A
`cJI
`
`0
`
`•
`•
`
`0
`
`{ •l
`!
`
`20 wt% u2o
`
`•
`
`• •
`
`~
`
`Continuous Unit
`•
`400 ppm Rh
`4-6 wt\ MeOAc
`15-20 wt\ Lii
`14 wt\ Mel
`Balance HOAc
`
`Batch Autoclave
`A 400 ppm Rh
`4-6 wt\ MeOAc
`18-20 wt\ Lii
`14 wt\ Mel
`Balance HOAc
`
`0 400 ppm Rh
`10-ll wt\ MeOAc
`15-20 wt\ Lil
`14 wt\ Mel
`Balance HOAc
`
`2
`
`4
`
`6
`
`8
`
`1120,
`
`wt\
`
`~ •
`00
`•
`
`~ a tD =
`
`f""t--
`
`~
`~
`~ :;c
`
`~
`
`~
`
`~
`
`r:n =(cid:173)~
`~ .....
`
`~
`
`0 .....
`N
`01
`
`01
`....
`0
`0
`1-l
`....
`~
`01
`\0
`
`002
`
`

`
`FIG.2
`
`Lil Dependence for Methanol Carbonylation- Batch Autoclave
`
`21 l
`
`19 t
`
`~ 17
`.c.:
`.......
`.:I
`.......
`Ul
`Q)
`
`...... 15 a
`' ><
`8 13~
`Ill
`u
`~
`0
`:I:
`
`11
`
`I
`
`9 J
`
`7 ~
`
`412 ppm Rh
`27 wt\ HeOAc
`14 wt\ Hel
`Balance IIOAc
`190 •c
`28.2 atm. aha. total pressure
`
`•
`
`0
`
`•
`
`• •
`
`• •
`
`•
`
`0
`
`•
`
`0
`
`•
`
`•
`
`0
`
`••
`
`0 14 wt\ 11 20
`
`• 8 wt\ 11 20
`• 2 Wt\ 11 20
`
`2
`
`4
`
`6
`
`8
`
`10
`
`12
`
`14
`
`16
`
`18
`
`20
`
`22
`
`Lil,
`
`wt%
`
`~ •
`rJl
`•
`1-d
`= f""t-
`=
`
`f""t-
`
`('I)
`
`s=
`~
`"""" ~le
`""""
`~
`""""
`
`~
`
`en
`=-
`~ .....
`N
`0 .....
`N
`til
`
`01
`,..
`0
`0
`~ ,..
`N
`01
`\0
`
`003
`
`

`
`FIG.3
`MeOAc Dependence for Methanol Carbonylation- Batch Autoclave
`
`----
`
`8 . - - - - - - - - - - - - - -
`
`d
`
`, ,t
`
`I
`I
`I
`I
`I
`
`•
`
`• 236 PPIII Rh
`20 wU LU
`14 wt' Mel
`8 wU H20
`Balance HOAc
`190 •c, 28.2 atm. abs.
`total pressure
`
`• 236 ppm Rh
`no Lil
`14 wU H~O
`14 wU M I
`Balance HOAc
`190 •c, 28.2 atm. abs.
`total pressure
`
`lH
`
`.J
`
`10
`
`~
`.d
`......
`H
`......
`Ul
`Ql
`.-I
`
`~
`'
`:><
`E-t
`tJ)
`u
`~
`0
`:r:
`
`8
`
`6
`
`•
`' I
`I
`.
`•
`HI -,
`
`2LI
`
`I
`
`10
`
`20
`
`30
`
`40
`
`HeOAc, wt\
`
`~ •
`00.
`•
`~
`~ ......
`tD = ......
`
`~
`~
`I-'
`.. ~e
`I-'
`IC
`IC
`I-'
`
`00 =-t'D
`.....
`t'D
`w
`0 ....
`
`N
`01
`
`'>61
`
`U1
`0
`0
`1-l
`l-..J
`U1
`\0
`
`'>61
`
`004
`
`

`
`U.S. Patent
`
`Mar. 19, 1991
`
`Sheet 4 of 25
`
`5,001,259
`
`16
`
`14
`
`12
`
`10
`
`8
`
`6
`
`4
`
`2
`
`~
`..c:
`......
`..;;
`......
`Ill
`QJ
`.....
`0
`e
`' ><
`E-<
`Cll
`
`0 < 0
`
`:t:
`
`FIG.4
`Mei Dependence for Methanol Carbonylation - Batch Autoclave
`
`472 ppm Rh
`27 wtt MeOAc
`2 wtt a o
`Balance2BOAc
`190 •c
`28.2 atm. abs.
`
`• 11 wt% Lii
`• 2. 5 wt% Lil
`
`0
`
`ro Lii
`
`2
`
`4
`
`6
`
`8
`
`10
`
`12
`
`14
`
`16
`
`18
`
`20
`
`22
`
`24
`
`Mel:, wtt
`
`005
`
`

`
`/ .
`
`FIG.5
`
`Rh Dependence for Methanol Carbonylation-- Batch Autoclave
`
`H
`.c:
`......
`H
`......
`Ill
`41
`r-1
`~
`'
`><
`E-t
`{I)
`u
`,.:(
`0 :z:
`
`35 l
`
`30 I
`
`25
`
`20
`
`14 wtl Mel
`27 wU MeOAc
`2 wtl u2o
`Balance HOAc
`190 .. c
`28.2 atm. abs. total pressure
`
`• 14 wU Lil
`• 2.5 Wt\ Lil
`
`•
`
`15 L
`
`0
`
`no Lil
`
`- /
`
`10 t
`
`5
`
`•
`
`----
`
`•
`
`200
`
`400
`
`600
`
`800
`
`1000
`
`Rh,
`
`ppm
`
`~ •
`00
`•
`"'C
`~
`.......
`=
`n>
`.......
`
`s::
`~
`:;.o
`"""'
`"""'
`1.0
`1.0
`"""'
`
`t'D
`
`rJ). =-t'D
`.....
`til
`0 .....
`N
`til
`
`...
`01
`0
`0
`...
`~
`N
`01
`\0
`
`006
`
`

`
`Effect of Water on the Rate of Rh Precipitation -- Batch Glass Vessel
`
`FIG.6
`
`fl•t-
`
`~
`..£:
`
`....... a 0.
`~
`0
`r-i
`-'=
`~
`
`200
`
`160
`
`I
`
`120
`
`80
`
`40
`
`1332 ppm/hr
`0.2 wt\ H2o
`
`e 1000 ppm Rh
`• 1000 ppm Rh
`3.5 wt\ HI
`3.5 wt\ HI
`3.5 wt\ Lil
`no Lil
`balance HOAc
`balance UOAc
`130 °C
`130 °C
`N
`sparge, 2 atm. abs. N2 sparge, 2 atm.
`total pressure
`total pressure
`
`2
`
`abs.
`
`•
`
`•
`
`•
`
`•
`
`•
`
`•
`
`•
`
`·2
`
`4
`
`6
`
`8
`
`10
`12
`u2o , wt%
`
`1 4
`
`16
`
`18
`
`20
`
`L! • '{JJ
`
`•
`~
`~
`f""t(cid:173)
`
`('D = f""t-
`
`~
`~
`J-l
`:;c
`1-'
`IC
`IC
`1-'
`
`rJl =-tD
`tD ....
`
`0'1
`0 .....
`N
`01
`
`...
`U1
`0
`0
`~ ...
`~
`U1
`\0
`
`007
`
`

`
`U.S. Patent
`
`Mar. 19, 1991
`
`Sheet 7 of 25
`
`5,001,259 -
`
`FIG.7
`
`Rate of Rh Precipitation in the Presence of Lii
`(Batch Glass Vessel)
`
`1000
`
`• 3.5 wt\ HI
`
`3 Wt\ H 0
`1000 !?!?~ Rh
`Balance HOAc
`N2 sparge
`2 atm. abs. total press
`150°C
`
`0 same as above
`except at 130 •c
`
`900
`
`800
`
`700
`
`600
`
`500
`
`400
`
`300
`
`200
`
`100
`
`1-1 .c
`...... = a.
`a. -al
`
`en
`0
`.....
`.c
`0::
`
`5
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`2o
`Base case, 15 wt\ H
`600 ppm Rh
`
`Lii,
`
`wtl
`
`008
`
`

`
`FIG.B
`Rate ol Rh Precipitation in the Absence of Lil
`(Bate~ Glass Ve~~el)
`
`•
`
`900l •
`
`800
`
`700
`
`600
`
`I
`,..I
`400 J
`
`a p.
`
`'
`I':
`0
`·.-I
`-1-1
`::I
`.--1
`0
`Ill
`
`I':
`·.-I
`.a
`~
`
`•
`• •
`
`•
`
`1000 ppm Rh initially
`3.5 wt\ III
`8 wt\ u2o
`no Lil
`Balance HOAc
`110 •c
`2 atm. abs. total pressure
`
`~ • rL1 •
`"'tl a ('D = f"'t-
`
`a:
`~
`""""
`~I.C
`"""" ~
`""""
`
`rJJ. =(cid:173)til
`.....
`til
`00
`0
`
`"*' N
`
`tl1
`
`2
`
`]
`
`4
`
`5
`
`6
`
`7
`
`8
`
`9
`
`Time,
`
`II ours
`
`...
`01
`0
`0
`~ ...
`~
`01
`\0
`
`009
`
`

`
`260
`
`220
`
`1801
`
`.....
`
`H
`..c::
`
`...... a n.
`
`Ul
`Ul
`0
`.-1
`
`~
`
`140
`
`100
`
`60
`
`20 ..
`
`0
`
`•
`
`....
`
`0. 1
`
`FIG.9
`
`Rate of Rh Precipitation in the Presence of 1- Additives
`CBatch Autoclave)•
`
`..A. Lil
`
`Q Nal • KI
`
`0 HI
`
`8 wt\ u2o
`627 ppm Rh
`Balance HOAc
`120 °C
`1.5 atm. abs. total press. (N
`
`)
`
`2
`
`0
`.A
`I
`0.2
`
`<>~ I
`
`0.3
`
`11-1, molar
`
`~
`0.4
`
`'
`0.5
`
`~ • 00 •
`1-C a (1) a
`
`a:
`~
`""" ~
`"""
`"""
`
`I,Q
`I,Q
`
`rJ) =(cid:173)~ a
`
`I,Q
`
`0 .....
`N
`01
`
`...
`Ut
`0
`0
`...
`""""
`~
`Ut
`\0
`
`010
`
`

`
`).j .a
`I
`...:l
`.......
`Ul
`41
`r-i
`~
`
`;..
`E-<
`Ul
`u
`;3
`:z:
`
`25
`
`20
`
`15
`
`10
`
`5
`
`0
`
`FIG.IO
`
`Water Dependence for Methanol Carbonylation - Continuous Unit
`(lt-15 wt\ Hel, tOO p(lll Rh, I!JO"C, 28.2 atm. abs. Total Pressure)
`(MeOAc, Lii, and Water as shown, Balance HOAc)
`
`•
`
`D
`
`~rP
`
`Legend
`
`• 4 wt% MeOAc, 16-21% Lii
`
`D 1 wt% MeOAc, 0-2.5% Lii
`
`I
`0
`
`I
`2
`
`I
`
`4
`
`I
`
`6
`
`I
`
`8
`
`I
`
`10
`
`.
`
`I
`
`14
`
`I
`
`12
`
`I
`
`16
`
`Reactor u
`
`o, wt%
`
`2
`
`~ •
`rJ1 •
`""0 a
`~ f"t-
`
`a:: = !""
`
`.....
`~\0
`.....
`\0
`\0
`.....
`
`r./'1 =-tD
`tD
`......
`.....
`0 .....
`N
`OJ
`
`Q
`
`...
`U1
`0
`0
`...
`1-4
`~
`U1
`\0
`
`011
`
`

`
`FIG. II
`Wate~ Dependence for Methanol Carbonylation - Continuous Unit
`(14-15 wt' Hel, 400 PPII Rh, Jgo•c, 28.2 atm. abs. Total Pressure)
`(MeOAc, Lil, and Water as Shown, Balance HOAc)
`
`. . . • • • • . . • • •
`
`:
`•
`
`0
`.
`.
`.
`.
`•
`•
`•
`•
`.•.............•. : ....•••••...•.... ~ .........•.•••... ; ....•••.•.••..... : .••....•.••...••.
`.
`.
`.
`i
`i
`i
`0 ~
`.
`.
`.
`: 0
`:
`:
`.
`- ai~
`•
`•
`• . •
`•
`•
`=
`.... . ...•.••.•...••.•. : :·················
`~--~----
`~......... :
`. . ... .... .. .. . ... io/--
`i
`• . •
`.
`.
`: .................• · ..
`.
`.
`.
`.
`:
`:
`.............. .
`......
`········•·········
`!
`.
`....
`•
`•
`• ••••••• t
`.
`•
`•••••••• t
`.
`. . Legend
`i
`
`: 0 3-6 wt%
`... ..• .. .. .
`:
`•••••••••••• :
`16-21 M:!OAc
`wt% Lii
`··············!············
`•
`:
`
`-
`
`-
`
`• • . .
`
`• 10-13 wt% M:!OAc
`16-21 wt% Lii
`
`25
`
`20
`
`15
`
`10
`
`5
`
`H
`.!!
`I
`...:!
`......
`~
`Q
`><
`E-<
`Ul
`u
`1':1;
`0 :z:
`
`o F
`
`I
`
`0
`
`•
`I
`
`2
`
`I
`
`:
`i
`'
`'
`4
`
`I
`
`i
`6
`
`I
`
`2o, wt%
`Reactor H
`
`-,j-----·
`
`I
`
`8
`
`I
`10
`
`~ •
`'00 •
`
`1-C a (1) a
`
`~
`~ ....
`~IC ....
`....
`
`IC
`IC
`
`rJ1 =(cid:173)
`('!) a
`....
`....
`0 .....
`N
`Ul
`
`...
`01
`0
`0
`...
`lo-o&
`~
`01
`\0
`
`012
`
`

`
`1-l
`;:::
`I
`H
`........
`Ul
`4l
`.-I
`~
`
`><
`E-<
`Ul
`u
`(3
`:X:
`
`20
`
`16
`
`12
`
`8
`
`4
`
`0
`
`. . . . . . : . . .
`
`I
`I
`
`.
`.
`.
`.
`.
`.
`.
`.
`.
`
`.
`
`t
`
`.
`.
`
`I
`I
`
`I
`I
`
`.
`.
`.
`.
`.
`.
`.
`.
`. . . .
`.
`
`.
`. . . . .
`.
`.
`. . .
`
`FIG .12
`Lil Dependence for Methanol Carbonylation -
`continuous Unit
`(14-15 wt\ Mel, 4 wt\ H20, 4 wt\ MeOAc, Lil as Shown, Balance HOAc)
`400 ppm Rh, 190"C, 28.2 atm. abs. Total Pressure)
`
`·················!·················~······················
`
`.
`.
`
`.
`
`. . . . .
`.
`
`• •
`. ...... -~ ..•.............
`
`····················································•·················•·················
`
`·················t·················t·················t·················l·················
`
`............................ - ............................... t ......... "' ........................................................... .......... ..
`I
`I
`I
`I
`
`.
`
`.
`.
`.
`
`.
`.
`.
`
`0
`
`5
`
`10
`
`15
`
`20
`
`25
`
`Reactor Lii, wt%
`
`...
`OJ
`0
`0
`~ ...
`~
`01
`\0
`
`L! • '(Jj
`•
`~ e;.
`t1) = pot.
`
`~
`~
`
`1-l
`~\&:)
`
`1-l
`~
`1-l
`
`00 =(cid:173)
`(D a
`
`1-l
`N
`
`0 ....
`
`N
`OJ
`
`013
`
`

`
`20-r----------~----------r----------,-----------r----------,
`
`t
`
`•
`
`I
`
`t
`
`I
`0
`
`0
`0
`
`:
`.
`
`I
`
`I
`
`0
`I
`
`I
`I
`
`:
`•
`
`I
`
`t
`
`I
`t
`
`0
`0
`
`•••••••••••••••••Jl••••LLA
`
`•
`
`oii••••••••••••••••••••••••••••••••••••~•••l•••••••••••••••••
`
`1-l
`~
`I
`....:!
`.......
`Ul
`Q)
`rl
`
`~
`><
`E-<
`Ul
`u
`~
`0 :r:
`
`-
`16-
`
`12-
`
`8-
`
`4 -
`
`FIG.I3
`Lil Dependence for Methanol Carbonylation - Continuous Unit
`(14-15 wt\ Mel, 8 wt\ H2o, 1 wt\ MeOAc, Lii as Shown, Balance HOAc,
`400 ppm Rh, 190"C, 28.2 atm. abs. Total Pressure)
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`•
`•
`.
`.
`•
`•
`.
`.
`.
`.
`•
`•
`.
`.
`.
`.
`.
`.
`.
`..............•..•................. , ••......•...•....•................. , .............••..
`.
`.
`.
`.
`.
`.
`.....
`•=
`:
`:
`:
`T
`.
`.
`.
`.
`.
`i
`.
`.
`:
`'!'
`:
`.
`.
`.
`.
`.
`.
`•
`.
`.
`•
`•
`•
`.
`.
`'
`.
`.
`.
`.
`.
`.
`·················t·················t·················t·················i·················
`.
`.
`: . . . • . . .
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.................•.................•.................•.................•.................
`.
`.
`. . . . . . . .
`
`I
`
`I
`I
`
`I
`
`t
`
`I
`
`I
`I
`
`0
`0
`0
`
`I
`
`I
`
`I
`
`I
`1
`
`I
`I
`I
`
`I
`
`I
`
`I
`I
`
`0
`0
`0
`
`I
`
`0
`
`I
`0
`
`I
`
`I
`5
`
`I
`
`I
`10
`
`I
`
`I
`15
`
`I
`
`I
`20
`
`I
`
`I
`25
`
`Reactor Lii, wt%
`
`~ •
`rJ'J.
`•
`
`""d a t'D = """"
`
`~
`~
`1-4
`~\C
`1-4
`
`~
`
`1-4
`
`rJJ =(cid:173)~
`~ ......
`1-4 w
`0 ....
`
`N
`01
`
`(JJ
`....
`0
`0
`~ ....
`N
`(JJ
`\0
`
`014
`
`

`
`Fl G.l4
`HeOAc Dependence for Hethanol Carbonyl at ion - Continuous Unit
`(14-15 wt\ Mel, 4 wt\ H2o, 400 ppm Rh, Lii and HeOAc as Shown, Balance HOAc
`190•c, 28.2 atm. abs. Total Pressure)
`
`20
`
`16
`
`12
`
`8
`
`4
`
`H .a
`I
`...:I
`' Ul
`
`Q)
`rl
`
`~
`
`~
`E-1
`Ul
`u
`-t:
`0
`:X:
`
`.
`.
`.
`:
`I .
`.
`.
`.
`. . . I . I
`.
`.
`.
`.••..•... , .........•......... , ...
`.
`
`o
`I
`
`1
`
`I
`
`I
`I
`
`I
`
`I
`
`I
`I
`I
`I
`
`t
`I
`I
`
`1
`I
`I
`
`I
`I
`I
`
`.
`.
`.
`.
`.
`
`. . . I : . .
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.•.......•.........•.........•..•......•.........•........••.........
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`·t·········t·········t·········t·········t·········t·········t·········t·········
`.
`.
`.
`.
`.
`.
`.
`.
`. .
`.
`.
`
`I
`I
`I
`I
`I
`• • • • • • • • • I • • • • • • • • • I • • • • • • • • • I • • • • • • • • • I • • • • • • • • • I • • •
`
`.
`.
`.
`
`1
`I
`
`I
`
`0
`
`0
`
`0
`I
`
`o
`
`•
`
`•
`
`0
`
`I
`
`I
`
`I
`I
`I
`I
`
`I
`
`I
`I
`t
`
`I
`I
`I
`
`.
`.
`.
`.
`.
`.
`.
`. I . . . .
`.
`.
`.
`
`I
`
`I
`
`I
`I
`I
`I
`
`I
`
`I
`I
`I
`
`I
`I
`I
`
`.
`.
`
`I
`
`I
`
`I
`I
`I
`I
`
`I
`
`I
`I
`I
`
`I
`I
`e
`
`I
`
`I
`
`I
`I
`I
`I
`
`I
`
`I
`I
`I
`
`I
`I
`
`I
`
`I
`
`I
`I
`I
`I
`
`I
`
`I
`I
`I
`
`I
`I
`'
`
`Legend
`
`0 20 wt% Lii
`•
`10 wt% Lii
`
`c::
`• 00.
`•
`
`""d a tD = f"'t-
`
`~
`~
`......
`~
`......
`~ ......
`
`00. =(cid:173)(t)
`"* ......
`0 ....
`
`(t)
`
`~
`
`N
`OJ
`
`I
`
`0
`
`I
`0
`
`I
`
`I
`1
`
`I
`2
`
`I
`
`I
`
`I
`3
`
`I
`4
`
`I
`
`I
`
`I
`
`')
`
`I
`
`I
`6
`
`I
`7
`
`I
`
`I
`
`I
`8
`
`I
`9
`
`Reactor MeOAc, wt%
`
`...
`01
`0
`0
`...
`1--6
`N
`01
`\0
`
`015
`
`

`
`FIG.I5
`
`KeOAc Dependence fo~ Methanol Carbonylatlon - Continuous Unit
`(14-15 wt' Hei, 15-23 wt' Lii, 400 ppm Rh, Water and HeOAc as Shown,
`Balance HOAc, 190°C, 28.2 atm. abs. Total Pressure)
`
`•
`
`I
`I
`
`I
`I
`
`I
`I
`
`t
`
`I
`I
`
`I
`I
`
`I
`I
`
`I
`I
`
`I
`
`I
`I
`
`I
`I
`
`I : I
`.
`.
`.
`r
`•
`•
`•
`•
`···········•·····•······•··········•··············•··•···•·······•·····•····•············
`:
`:.
`:
`:
`.
`•
`•
`•
`:
`:
`!
`
`!
`
`-:
`
`·o· ....... -: ............ -
`,
`
`I
`I
`I
`I
`I
`I
`I
`I
`I
`
`o-o
`
`I
`I
`I
`
`I
`I
`
`·········•·················•·················•·················•·················
`
`I
`I
`I
`
`I
`I
`I
`I
`I
`
`I
`I
`I
`I
`I
`
`I
`I
`I
`I
`I
`
`I
`I
`I
`I
`I
`
`I
`
`I
`I
`
`I
`
`I
`I
`
`·················t·················t·················t·················t·················
`
`•
`.
`•
`.
`•
`•
`Legend
`······••••••••!•••••••••••••••••! .. ••••••••••••••· 0 4 wt% Hp
`•
`Hp
`8 wt%
`•
`•
`.
`.
`.
`.
`.
`.
`.
`.
`
`I
`I
`I
`I
`I
`I
`I
`I
`I
`
`I
`
`t
`
`I
`I
`t
`I
`I
`
`.
`.
`.
`.
`
`I
`I
`I
`I
`I
`I
`I
`I
`t
`
`I
`
`.
`.
`.
`.
`
`I
`
`I
`I
`I
`I
`I
`
`t
`
`I
`I
`I
`I
`I
`
`I
`
`I
`I
`I
`I
`I
`
`.
`I
`I
`I
`
`I
`
`I
`I
`
`I
`
`0
`
`3
`
`6
`
`9
`
`12
`
`15
`
`Reactor MeOAc, wt%
`
`11
`I
`..:I
`' Ill
`
`41
`r-i
`~
`
`><'
`E-<
`(/)
`u
`(3
`:I:
`
`24
`
`20
`
`16
`
`12
`
`8
`
`4
`
`0
`
`L! •
`rJ1
`•
`
`1-C a tD = f"t-
`
`~
`~
`.....
`~1,0
`.....
`:8
`.....
`
`en =(cid:173)
`I'D a
`.....
`0 .....
`N
`OJ
`
`OJ
`
`...
`01
`0
`0
`~ ...
`t-.J
`01
`\0
`
`016
`
`

`
`Fl G.l6
`Mel Dependence for Methanol Carbonylation - Continuous Unit
`(10 wt\ Lil, Mel as Shown, 4 wt\ H2o, 4 wt\ H2o, 4 wt\ HeOAc, Balance HOAc,
`400 ppm Rh, 190"C, 28.2 atm. abs. Total Pressure)
`
`I
`I
`
`t
`
`I
`
`I
`
`I
`
`I
`I
`
`I
`I
`
`I
`
`I
`
`I
`
`I
`I
`
`I
`I
`
`I
`
`I
`
`I
`
`I
`
`I
`I
`
`I
`I
`
`I
`
`I
`
`I
`
`I
`
`I
`I
`
`I
`
`I
`
`I
`I
`I
`
`20
`
`16
`
`12
`
`8
`
`4
`
`l!
`I
`..:I
`.......
`
`=·
`.-1 a
`~ Cl)
`~
`
`: .
`• • . • • . . . . • •
`.
`.
`.
`................. , .••.....••...•.•• ; .................•.......•..•...... : ....... .
`.
`.
`.
`.
`•
`•
`•
`•
`.
`.
`.
`.
`.
`.
`.
`.
`.
`•
`•
`•
`•
`•
`.
`.
`•
`.
`.
`.
`.
`.
`•
`•
`•
`.
`.
`.
`.
`•
`•
`•
`.
`.
`.
`...... .. . .. .. ... . ......... ... ..... ..•.. .. . ............................................ .
`.
`•
`•
`•
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`i
`•
`•
`•
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`• •
`.
`.
`.
`.
`•
`•
`•
`.
`.
`.
`.
`.
`.
`·················•······· ·········t·················i·················t·················
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`i
`i
`16
`8
`
`........•........•.••..............•................. .•....••.........•.................
`•
`•
`
`t
`
`I
`
`t
`t
`t
`
`0 I
`0
`
`I
`
`I
`
`'
`
`i
`4
`
`I
`
`I
`
`I
`
`I
`
`I
`
`I
`
`I
`
`I
`
`I
`
`12
`
`Reactor Mel, wt%
`
`I
`
`I
`
`I
`
`I
`20
`
`~ •
`00. •
`"'C a
`m
`
`pot.
`
`a::
`~
`"""
`:;.c
`""" ~
`"""
`
`en =(cid:173)~
`~ ......
`""" 0'1
`0 .....
`N
`01
`
`01
`....
`0
`0
`~ ....
`~
`01
`\0
`
`017
`
`

`
`Fl G.l7
`Rh Dependence for Methanol Carbonylation - Continuous
`Lil, 12 wt\ HeOAc, 4 wt'l H20, 4 wt'l MeOAc, Rh as Shown, Balance
`28.2 atm. abs. Total Pressure)
`
`(10 wt'l
`
`Unit
`HOAc, 190"C,
`
`30
`
`25
`
`20
`
`15
`
`1-1
`.t:
`I
`..:I
`.......
`Ul
`~
`...-I
`
`~
`
`I
`
`I
`I
`I
`1
`
`I
`I
`
`I
`
`I
`
`I
`
`I
`
`I
`I
`I
`I
`
`I
`I
`
`I
`
`I
`
`I
`
`I
`
`I
`I
`I
`t
`
`I
`I
`
`I
`
`I
`
`I
`
`I
`
`I
`I
`I
`I
`
`I
`I
`
`I
`
`I
`
`I
`
`I
`
`I
`I
`I
`I
`
`I
`I
`
`I
`
`I
`
`I
`I
`
`I
`
`I
`I
`t
`
`•
`•
`J
`:
`·············-····
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`I
`I
`t
`I
`·······························~·····
`
`•
`
`•
`
`I
`
`,
`
`'·
`
`I
`
`I
`
`I
`I
`
`I
`
`I
`
`I
`I
`
`I
`
`I
`
`I
`I
`
`I
`
`I
`
`I
`I
`
`~ •
`00.
`•
`
`""d a ('!) = .....
`
`~
`~
`
`~
`~II:)
`
`~
`
`~
`
`~
`
`.
`.
`.
`. .
`. • •
`. , .
`.
`. , .
`•
`•
`.
`•
`•
`.
`.
`. . • .
`.
`.
`. , .
`.
`.
`:
`:
`.
`.
`.
`.
`.
`:
`:
`,
`.
`.
`.
`.
`········:········t········:········t········:········:········· .. ···
`,' .
`:
`,t'
`:
`•
`•
`•
`•
`•
`•
`:
`:
`:
`:
`.
`.
`•
`•
`•
`•
`•
`•
`.
`.
`.
`.
`.
`.
`.
`•
`.
`•
`•
`•
`.
`•
`.
`.
`.
`.
`.
`.
`.
`.
`•
`•
`•
`•
`•
`........•........•........•........•........•.....
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`•
`•
`•
`•
`.
`.
`•
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`........ , ........ : ........ , ........ •
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`..... i ........ : ........ & ........ i ........ & ....... .
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`•
`•
`•
`•
`.
`.
`.
`•
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`• • . • . •
`.
`.
`········l········l······
`········1········1········1········1········1········1········
`.
`.
`.
`.
`.
`•
`•
`•
`•
`•
`•
`•
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`····i········t········i········i········i········t········i········i········
`
`I
`I
`
`I
`
`I
`
`I
`
`I
`I
`
`I
`I
`I
`I
`I
`I
`I
`I
`1
`I
`I
`
`I
`I
`
`I
`
`I
`
`t
`
`I
`I
`
`I
`I
`I
`I
`I
`I
`I
`I
`1
`I
`I
`
`I
`I
`
`I
`
`I
`
`I
`
`I
`I
`
`I
`1
`I
`1
`I
`I
`1
`
`I
`I
`
`I
`
`I
`
`I
`
`I
`I
`
`I
`I
`I
`I
`I
`I
`I
`
`I
`I
`
`I
`
`I
`
`I
`
`I
`I
`
`1
`I
`I
`I
`I
`I
`I
`
`00 =(cid:173)(t)
`~
`~
`-.....1
`0
`M>
`N
`01
`
`(.II
`....
`0
`0
`~ ....
`~
`(.II
`\0
`
`0
`
`100
`
`200
`
`300
`
`400
`
`500
`
`600
`
`700
`
`BOO
`
`900
`
`1000
`
`Reactor Rh,
`
`ppm
`
`><
`~
`Ul
`
`~ ::r:
`
`10
`
`5
`
`0
`
`I
`
`I
`
`I
`
`I
`I
`
`I
`I
`I
`I
`I
`I
`I
`I
`1
`I
`1
`
`I
`I
`
`I
`I
`I
`I
`I
`I
`I
`I
`I
`I
`I
`
`I
`
`I
`
`I
`
`.
`.
`.
`.
`
`I
`
`I
`I
`
`I
`I
`I
`I
`I
`I
`I
`I
`I
`I
`I
`
`018
`
`

`
`FIG. IS
`Water: Dependence for: Methanol Car:bonylatlon - Continuous Unit
`I so•c, 28.2 atm. · abs. Total Pressure)
`( 14- I 5 wtl Mel, •00 PPII Rh,
`(HeOAc, Lil, and Water as Shown, Balance HOAc)
`
`2.5
`
`2
`
`1.5
`
`•
`
`c • 00
`~ a a
`
`~
`~
`.....
`"'\C
`.....
`\C
`.....
`\C
`
`><
`E-<
`Ul
`
`u < 0
`
`:X:
`4-4
`0
`
`<If'
`
`.
`
`><
`E-<
`Ul
`
`N
`
`0 u
`
`1
`
`0.5
`
`0
`
`•
`
`...
`
`-- .
`
`Legend
`
`0
`e
`
`1 wt% MeOAc, 0-2.5 wt% .Lii
`
`4 wt% MeOAc, 16-21 wt% Lii
`
`0
`
`2
`
`4
`
`6
`
`8
`10
`Reactor u2o, wt%
`
`12
`
`14
`
`16
`
`00 =(cid:173)ttl
`
`ttl -.....
`
`00
`0 .....
`N
`01
`
`...
`01
`0
`0
`...
`1-L
`~
`01
`\0
`
`019
`
`

`
`0.7
`
`0.6
`
`0. 5.--
`
`"'
`
`:I:
`
`....
`
`~ ···t
`0 0. 3 -. tJ
`··t
`
`FIG. 19
`Lii Dependence for Methanol Carbonylation - Continuous Unit
`(14-15 wt\ Mei, 4 wt\ H 0, 4 wt\ HeOAc, Lii as Shown, Balance HOAc, 400 ppm Rh,
`190•c, ~8.2 ata. abs. Total Pressure)
`
`•
`~
`
`....
`
`•
`
`5
`
`10
`Reactor Lii, wt\
`
`15
`
`20
`
`•
`
`c:: • 00.
`~ a ('D = .....
`
`s=
`~
`~
`~I.e
`
`~
`I.e
`I.e
`~
`
`rFl =-ttl
`.....
`ttl
`
`~
`I.e
`0 .....
`N
`01
`
`...
`(.JJ
`0
`0
`...
`""""
`N
`(.JJ
`\0
`
`020
`
`

`
`FIG.20
`Lil Dependence for Methanol Carbonylation - Continuous Unit
`(14-15 wt\ Mel, 8 ~~~o~~o;8~2w::m~e~~~: ~~!a~sp~:~::;e~alance HOAc, 400 ppm Rh,
`. . I
`I . I
`I . . I . I
`
`2
`
`~
`
`•
`
`I
`I
`I
`
`I
`I
`
`><
`f;
`ttl
`u
`o<(
`0
`:X:
`....
`0
`
`<JP
`
`><
`f;
`ttl
`
`N
`
`0 u
`
`1.5
`
`1
`
`0.5
`
`0.20
`
`0.15
`
`~ •
`rLl
`•
`
`1-C a tD = .....
`
`~
`~
`.....
`~
`.....
`::g
`.....
`
`00 =(cid:173)ttl
`.....
`ttl
`N
`Q
`
`0 ....
`
`N
`OJ
`
`.......... , ....•........•....•.................. ~ .....••.•...••••.
`
`•••••••••••••••••~r••••••••••••••
`
`.
`
`I
`I
`I
`I
`I
`I
`I
`I
`I
`I
`I
`I
`I
`
`<JP
`
`~
`
`H
`:X:
`1-l
`0
`-1.1 u
`Ill
`QJ
`!:>:
`
`0.10
`
`0.05
`
`.................... -~ ..................... .
`
`. I . .
`. . . . .
`
`0
`
`0
`
`5
`
`10
`
`15
`
`20
`
`Reactor Lil, wt%
`
`0.00
`
`25
`
`...
`01
`0
`0
`...
`1-A
`~
`01
`\0
`
`021
`
`

`
`FIG.21
`Continuous Unit
`HeOAc Dependence for Hethanol Carbonylation
`(14-15 wt\ Mel, 4 wt\ H20, MeOAc and Lil as Shown, Balance HOAc 190°C, 400 ppm Rh, 28.2 atm. abs.
`Total Pressure)
`
`0.6-r-----,------r-----,------r-----,------r-----,------r----~
`
`• • • • • • • • •
`.
`
`:
`
`I
`I
`I
`
`I
`I
`I
`I
`I
`I
`I
`I
`
`I
`
`I
`I
`I
`
`.
`
`I
`I
`I
`I
`I
`I
`I
`I
`
`I
`
`I
`I
`I
`
`.
`
`I
`I
`I
`I
`I
`I
`I
`I
`
`I
`
`I
`I
`I
`
`.
`
`I
`I
`I
`I
`t
`I
`I
`I
`
`t
`
`.
`
`I
`I
`I
`f
`I
`I
`I
`I
`I
`I
`I
`
`t
`
`I
`I
`I
`
`.
`
`I
`I
`I
`I
`t
`I
`I
`I
`
`t
`
`I
`I
`I
`
`.
`
`I
`I
`I
`I
`t
`I
`I
`I
`
`0.5
`
`0.4
`
`Ill
`
`f:
`~ :t:
`....
`
`0
`
`dP
`
`0.3
`
`•
`
`.
`
`I
`I
`I
`
`I
`I
`
`I
`
`I
`I
`I
`I
`
`I
`I
`I
`I
`I
`
`•·······•·•·•·•·••··•··••·•···•·········••··•·····•·••····•·•···•···•••·•·····•·
`
`......•..• ··•·•···••··•••·••••··•·····•···•·••··•·········•··•··•••·•·•·•··••·•••····•··
`•
`•
`•
`•
`•
`•
`•
`•
`
`I
`I
`I
`I
`
`I
`I
`I
`I
`I
`
`.
`
`I
`I
`I
`I
`
`I
`I
`I
`I
`I
`
`I
`I
`I
`I
`
`I
`I
`I
`I
`I
`
`I
`I
`I
`I
`
`I
`I
`I
`I
`I
`
`I
`I
`I
`I
`
`I
`I
`I
`I
`I
`
`I
`t
`I
`I
`
`I
`I
`I
`I
`I
`
`I
`I
`I
`I
`
`I
`I
`I
`I
`I
`
`I
`I
`
`I
`I
`
`I
`I
`
`I
`
`I"
`I
`
`I
`I
`
`I
`I
`
`I
`
`~ •
`rJ1
`•
`
`~ a ('D = f"'to-
`
`~
`~
`""'"'
`~1.0
`
`""'"' 1.0
`1.0
`~
`
`.
`.
`.
`.
`.
`.
`'
`......... , ....... :.Jil .....•......... : .........•......... : .........•.........•.........
`: .... :
`.
`.
`.
`.
`.
`.
`.
`l
`:e
`:
`:
`.
`:
`:
`:
`.
`.
`I
`.
`.
`.
`.
`• •
`:
`:
`:
`:
`·········•·········•·········1'········ ••
`····t·········•·········l·········•·········
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`
`I
`
`t
`I
`
`I
`I
`
`• •
`I
`
`I
`I
`
`I
`
`I
`I
`
`I
`I
`
`I
`
`I
`
`I
`I
`
`I
`
`I
`I
`
`I
`I
`
`I
`
`I
`I
`
`I
`I
`
`I
`
`I
`I
`
`I .
`I
`
`I•
`I
`I
`
`fl)
`
`N
`
`en =(cid:173)
`fl) ....
`""'"' 0 .....
`
`N
`01
`
`I
`I
`•
`·•·········
`I
`:
`
`.
`.
`.
`
`I
`
`:
`i
`8
`
`I
`
`I
`9
`
`~
`
`U1
`0
`0
`~
`~
`U1
`\0
`
`~
`
`><
`E-<
`Ill
`
`N
`
`0 u
`
`0.2
`
`0.1
`
`I
`I
`I
`I
`I
`I
`I
`I
`I
`I
`I
`t
`t
`I
`I
`I
`I
`I
`I
`I
`I
`I
`t
`I
`•
`•
`•
`•
`•
`·········t·········t·········t·········t·········t··
`I
`I
`I
`I
`t
`:
`:
`:
`:
`:
`
`.
`
`I
`
`0.0 I
`0
`
`I
`
`I
`
`i
`1
`
`I
`
`.
`.
`.
`:
`i
`2
`
`I
`
`.
`.
`.
`:
`i
`3
`
`I
`
`I
`
`.
`.
`.
`
`I
`
`:
`
`;
`
`4
`
`I
`
`•
`
`•
`
`I
`
`Legend
`
`10 wt% Li I
`
`20 wt% Lii
`i
`i
`7
`6
`
`I
`
`I
`
`.
`.
`.
`
`I
`
`:
`i
`5
`
`Reactor MeOAc, wt%
`
`022
`
`

`
`Mel Dependence fo~ Methanol Ca~bonylation - Continuous Unit
`0, 4 wt\ MeOAc, Balance HOAc, 400 ppm Rh,
`(10 wt\ Lil, Mel as Shown, 4 wt\ H
`2
`190°C, 28.2 atm. abs. Total Pressure)
`
`Fl G. 22
`
`. • • . : . . • . • • : • .
`
`:
`-
`
`. :
`
`.
`.
`.
`.
`
`.
`
`>< E-<
`
`Ul
`
`0
`~
`0
`0::
`
`'H
`0
`
`dP
`
`-><
`
`E-<
`Ul
`
`"'
`0 u
`
`0.4
`
`0.3
`
`0.2
`
`0.1
`
`0.0
`
`.
`.
`.
`.
`.
`.
`.
`·················i·-···············i················-i·-···············1·····
`.
`:
`..
`. . . . . . .
`.
`.................•................. , .••..•.•.•....... , ..... •
`.
`. . . . . . . . . . . . . . . . . . .. . . .. . . . . . .. . . . . . .. . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . ..
`
`0
`
`4
`
`B
`
`12
`
`16
`
`20
`
`Reactor Mel, wt%
`
`•
`
`~ • 00.
`~ a tD = f"'t.
`
`~ ....
`....
`~ ....
`
`"'IC
`
`rJ).
`:::r
`(I) a
`
`N
`N
`0 .....
`N.
`01
`
`01
`,..,
`0
`0
`,..,
`""'""'
`~
`01
`\0
`
`023
`
`

`
`FIG.23
`H2o Dependence for the Lil/LiOAc Equilibrium - Continuous Unit
`(1 wt\ Li (equivalent to 20 wt\ Lil],
`14-15 wt\ Mei, LiOAc, MeOAc, and Water as Shown, Balance HOAc, 190°C, 300-400 ppm Rh, 28.2 atm. abs.
`Total Pressure)
`
`~ •
`rJ:1
`•
`
`~ e. ('t) = f"'t-
`
`I
`
`I
`
`~
`I
`
`I
`
`I
`
`I
`
`·····•·········1·········1·········1·········1·········1·········1·········
`
`• I • • • • .
`.
`
`I
`
`I
`I
`
`I
`
`I
`
`4.0
`
`3.5
`
`3.0
`
`2.5
`
`I
`
`. .
`
`I
`
`..•.•••..•......•..•.•....••••..•...••.•.•.••..•.••.••..•..•....•....•.......•.•......••.
`•
`•
`•
`•
`•
`•
`•
`•
`:
`:
`I
`:
`:
`:
`:
`I
`t
`
`I
`I
`
`I
`
`.
`
`I
`
`I
`I
`
`I
`
`.
`
`I
`
`I
`I
`
`I
`
`.
`
`I
`
`I
`I
`
`I
`
`.
`
`I
`
`I
`I
`
`I
`
`.
`
`I
`
`I
`I
`
`.
`
`I
`I
`I
`I
`I
`
`I
`I
`I
`I
`I
`I
`I
`I
`
`I
`I
`I
`I
`I
`I
`I
`I
`
`I
`I
`I
`I
`I
`I
`I
`I
`
`I
`I
`I
`I
`I
`I
`I
`I
`
`I
`1
`I
`I
`I
`I
`I
`I
`
`I
`I
`I
`I
`I
`I
`I
`I
`
`•
`·········•···
`•
`•
`•
`•
`•
`• •
`.
`.
`.•.......•......... ········•·········•···•··•··•·········•····•····•··•······•·········
`.
`.
`.
`•
`.
`•
`•
`•
`......... , ......... , ...... . . ........ , ....•.••.•......
`•
`•
`•
`•
`•
`- :
`•
`.
`.
`•
`•
`•
`. .
`. . . • . • .
`•
`•
`•
`•
`•
`•
`I • .
`·········t·········•·········:·······
`·········•······
`.
`~
`.
`.
`.
`.
`.
`.
`.
`.
`I •
`.........•....•....•
`······•·········•·········•·········••
`.
`.
`• • • •
`•
`.
`.
`.
`.
`i
`'
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`......... i··· ...... i ......... i ......... i ......... , ... ......._, ......... , .......... Jt"'
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`.
`-
`.
`-
`.
`.
`.
`.
`.
`.
`.
`.
`.
`
`I
`I
`I
`I
`I
`I
`I
`I
`
`I
`I
`I
`I
`
`I
`I
`
`I
`I
`t
`I
`I
`I
`I
`I
`
`I
`
`I
`I
`I
`I
`I
`I
`I
`I
`
`I
`I
`I
`I
`
`I
`I
`
`I
`
`I
`I
`I
`I
`I
`
`•
`•
`
`I
`
`I
`
`o
`
`I
`
`I
`
`I
`
`01'
`.j..l
`)
`
`u
`(§
`·.-I
`..:I
`H
`0
`.j..l
`u
`Ill
`~
`
`2.0
`
`1.5
`
`1.0
`
`0.5
`
`0.0
`
`•
`
`•
`
`•
`
`•
`
`•
`
`-
`
`0
`
`1
`
`2
`
`3
`
`4
`
`5
`
`6
`
`7
`
`8
`
`9
`
`Reactor H20, wt%
`
`I
`I
`I
`I
`•
`
`I
`I
`I
`t
`•
`
`Legend
`
`12 wt% MeOAc
`
`. . . . . . • .
`
`4 wt% MeOAc
`·-·~-········
`
`•
`•
`·••·•···•··•··•·•·•·····
`
`~
`~
`"'"" ~\C
`"'""
`\C
`\C
`"'""
`
`rJj =(cid:173)(b
`(b
`......
`N w
`0 .....
`N
`Ul
`
`...
`01
`0
`0
`...
`1-l
`N
`01
`\0
`
`024
`
`

`
`Fl G. 24
`Rate of Ahodiu. Loss in the Presence of Lil - Continuous Unit
`(14-15 wt\ Mel, Lii, n2o, and HeOAc as Shown, 300-600 ppm Rh,
`28.2 atm. abs. Total Pressure)
`
`3 ,
`
`2.5 ~
`
`.•.............•••......••...
`
`Legend
`
`.......•.........•.•....•...•.
`
`I
`I
`I
`
`I
`
`I
`I
`I
`
`I
`
`I
`I
`I
`
`I
`
`t
`t
`f
`
`I
`
`• • • • • • • • • • •
`• • • • • • • • • • • •
`• •
`14 wtl H2o, 1 wt% MeOAc, 2.4 atm. ab. flash
`8 wt% H20, 1 wt% MeOAc, 2.4 atm. ab. flash
`• 4 wti H
`• • • • • • • •
`2o, 4 wt% MeOAc, 2.4 atm. ab. flash
`2o, 4 wt% MeOAc, 1.1 atm. ab. flash
`:
`0
`4 wt% H
`~
`·················•·················•·················i···································
`•
`•
`•
`•
`•
`•
`•
`•
`
`I
`I
`I
`I
`I
`
`.
`
`I
`
`I
`I
`
`-
`
`25
`
`1-1
`.d
`.......
`[
`0..
`
`Ill
`Ill
`0
`H
`~
`
`2 -
`
`1.5 -
`
`1
`
`-
`
`0. 5
`
`-
`
`0
`
`•
`
`I
`I
`I
`I
`I
`
`.
`
`I
`
`I
`I
`
`I
`I
`I
`I
`I
`
`.
`
`I
`
`I
`I
`
`I
`I
`I
`I
`I
`
`.
`
`I
`
`I
`I
`
`..
`
`I
`10
`
`Reactor Lii, wt%
`
`0
`
`I
`5
`
`·················t·················t·················t·················l·················
`•
`•
`•
`•
`•
`•
`•
`•
`A:
`:
`:
`:
`I
`I
`t
`t
`I
`I
`I
`I
`················Ol·················t·················t·················J·················
`I
`•
`'
`'
`I
`I
`I
`I
`.
`.
`I
`I
`I
`I
`.
`.
`:
`:
`.
`.
`.
`.
`m
`~
`.
`.
`:
`:
`I
`I
`20
`15
`
`~ •
`rJ'J. •
`
`~ a tD = ......
`
`~
`~
`,.....
`~IC
`,.....
`IC
`,.....
`IC
`
`'Jl =(cid:173)
`(D a
`
`N
`~
`0 .....
`N
`OJ
`
`~
`
`01
`0
`
`0 ..... ~
`
`~
`01
`\0
`
`025
`
`

`
`2
`
`1.6
`
`1.2
`
`0.8
`
`0.4
`
`l! .......
`[
`0.
`' Ill
`Ill
`3
`iil
`
`t
`
`t
`t
`
`-;._
`I - - -
`
`I
`I
`
`t
`t
`
`:
`:
`~---
`··································•·····················
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`•
`..... ~ ...........•.................•.................•.....
`•
`•
`•
`•
`•
`•
`.
`.
`.
`•
`•
`•
`•
`•
`•
`•
`•
`•
`.
`.
`. • • • •
`•
`•
`•
`•
`•
`•
`•
`•
`•
`
`Effect of Water on the Rate of Ahodiu. Loss - Continuous Unit
`(20 wt' Lii, 14-15 wt' Hei, HeOAc, and Water as Shown, Balance HOAc, 300-400 ppm Rh,
`190•c, 28.2 atm. abs. Total Pressure)
`
`Fl G. 25
`
`I
`
`t
`
`t
`
`I
`
`t
`
`• • • • • • • • • • • •
`• • • • • • • . • • • • • •
`....••..••.•...•.•.•.••..•...•••.•. : ........•........ ................. , ......•........•.
`. ---- :
`•
`•
`• • I
`f!-
`i
`I • I • • • •
`.
`~
`• . • • • • :
`~~···············
`
`t
`
`I
`
`t
`
`Legend
`
`• 12 wt% MeOAc
`
`• 4 wt% MeOAc
`. • •
`• • • • • • • • :
`
`...•...........•••...••.••.•••.••.•
`
`0
`
`0
`
`2
`
`4
`
`6
`
`8
`
`10
`
`2o, wt%
`Reactor H
`
`L: •
`00
`•
`""d e.
`tD = .....
`
`~ .... :;c
`
`....
`....
`
`\C
`\C
`
`rJ1 =(cid:173)to
`to ....
`
`N
`01
`0 .....
`N
`01
`
`)
`
`(.1)
`....
`0
`0
`1--l
`....
`~
`(.1)
`\0
`
`026
`
`

`
`METHANOL CARBONYLATION PROCESS
`
`RELATED APPLICATIONS
`This is a continuation-in-part of copending U.S. Pat.
`Application Ser. No. 699,525, flied Feb. 8, 1985, which
`is a continuation-in-part of U.S. Pat. Application Ser
`. No. 606,730, filed May 3, 1984, both now abandoned.
`
`THE DRAWINGS
`FIGS. 1-25 show interactions among the several
`reaction medium components, which interactions are at
`the heart of the present invention.
`
`BACKGROUND OF THE INVENTION AND
`PERTINENT PRIOR ART
`Among currently-employed processes for synthesiz(cid:173)
`ing acetic acid one of the most useful commercially is
`the carbonylation of methanol with carbon monoxide as
`taught in U.S. Pat. No. 3,769,329 issued to Paulik et al. 20
`on Oct. 30, 1973. The catalyst comprises rhodium, ei(cid:173)
`ther dissolved or otherwise dispersed in the liquid reac(cid:173)
`tion medium or else supported on an inert solid, along
`with a halogen-containing catalyst promoter as exem(cid:173)
`plified by, for example, methyl iodide. The rhodium can 25
`be introduced into the reaction system in any of many
`forms, and it is not relevant, if indeed it is possible, to
`identify the exact nature of the rhodium moiety within
`the active catalyst complex. Likewise, the nature of the
`halide promoter is not critical. The patentees disclose a 30
`very large number of suitable promoters, most of which
`are organic iodides. These compounds are employed as
`promoters, not stabilizers. Most typically and usefully,
`the reaction is conducted with the catalyst being dis(cid:173)
`solved in a liquid reaction medium through which car- 35
`bon monoxide gas is continuously bubbled.
`Paulik et al. teach that the liquid reaction medium can
`be any solvent compatible with the catalyst system and
`that it may comprise, for example, the pure alcohol
`which is being reacted, or mixtures thereof with the 40
`desired carboxylic acid end product and/or esters of
`these two compounds. However, the patentees teach
`further that the preferred solvent and liquid reaction
`medium for the process is the desired carboxylic acid
`itself, i.e., acetic acid when methanol is being car- 45
`bonylated to produce acetic acid.
`An important aspect of the teachings of Paulik et a!.
`is that water should also be present in the reaction mix(cid:173)
`ture in order to attain a satisfactorily high reaction rate.
`The patentees exemplify a large number of reaction 50
`systems including a large number of applicable liquid
`reaction media. The general thrust of their teachings is,
`however, that a substantial quantity of water helps in
`attaining an adequately high reaction rate. The paten(cid:173)
`tees teach furthermore that reducing the water content 55
`leads to the production of ester product as opposed to
`carboxylic acid. Considering specifically the carbonyla(cid:173)
`tion of methanol to acetic acid in a solvent comprising
`predominantly acetic acid and using the promoted cata(cid:173)
`lyst taught by Paulik et a!., it is taught in European 60
`Patent Application No. 0055 618 that typically about
`14-15 wt% water is present in the reaction medium of
`a typical acetic acid plant using this technology. It will
`be seen that in recovering acetic acid in anhydrous or
`nearly anhydrous form from such a reaction solvent, 65
`separating the acetic acid from this appreciable quantity
`of water, involves substantial expenditure of energy in
`distillation and/or additional processing steps such as
`
`1
`
`5,001,259
`
`2
`solvent extraction, as well as enlarging some of the
`process equipment as compared with that used in han(cid:173)
`dling drier materials. Also Hjortkjaer and Jensen [Ind.
`Eng. Chern., Prod. Res. Dev. 16, 281-285 (1977)] have
`5 shown that increasing the water from 0 to 14 wt %
`water increases the reaction rate of methanol carbony(cid:173)
`lation. Above 14 wt % water the reaction rate is un(cid:173)
`changed .
`In addition, as will be further explai