US009302974B1

(12) United States Patent (10) Patent No.: US 9,302,974 B1

Shaver et al. (45) Date of Patent: Apr. 5, 2016

(54) PROCESS FOR PRODUCING ACETIC ACID 5,731,252 A 3, 1998 Warner et al.
5,877,347 A 3, 1999 Ditzel et al.
5,877,348 A 3, 1999 Ditzel et al.
(71) Applicant: State stational Corporation, 5,880,311 A * 3/1999 Uemura ................... BO1J 8/OO7
rving, TX (US) 560,231
5,883,295 A 3/1999 Sunley et al.
(72) Inventors: Ronald D. Shaver, Houston, TX (US); 5,932,764 A 8, 1999 Morris et al.
Yaw-Haw Liu, Missouri City, TX (US); 5,942.460 A 8, 1999 Garland et al.
Mark O. Scates, Houston, TX (US) 6,143,930 A 1 1/2000 Singh et al.
6,225.498 B1 5/2001 Blay et al.
6,339,171 B1 1/2002 Singh et al.
(73) Assignee. CELANESE INTERNATIONAL 6,458.996 B1 10/2002 Muskett
CORPORATION, Irving, TX (US) 6,552,221 B1 * 4/2003 Hallinan .............. B01J 19,0006
562/517
(*) Notice: Subject to any disclaimer, the term of this 376 R: 39. RSet al. 1
luckman et al.
past its, G adjusted under 35 7,005,541 B2 2/2006 Cheung et al.
.S.C. 154(b) by 0 days. 7,223,883 B2 5/2007 Picard et al.
(21) Appl. No.: 14/788,928 (Continued)
(22) Filed: Jul. 1, 2015 FOREIGN PATENT DOCUMENTS
JP 4489487 B2 6, 2010
(51) E-14 (2006.01) WO 2014/11582.6 A1 T 2014
C07C5L/09 (2006.01) OTHER PUBLICATIONS
(52) is C. C07C 51/44 (2013.01); C07C51/09 Zhu, Y. et al. (Apr. 2009). "Techno-economic Analysis for the
- ------ --- ------- • u. fs (2013.01) Thermochemical Conversion of Lignocellulosic Biomass to Ethanol
via Acetic Acid Synthesis,” prepared for U.S. Department of Energy,
(58) Field of Classification search C 51/44: CO7C 51/09 PNNL-18483, Pacific Northwest National Laboratory, Richland,
- -- - - -- - - s WA, 79
USPC .......................................................... 562/608 , 9 pages
See application file for complete search history. Primary Examiner — Jafar Parsa
(56) References Cited Assistant Examiner — Amy C Bonaparte
(74) Attorney, Agent, or Firm — Kilpatrick Townsend &
U.S. PATENT DOCUMENTS Stockton LLP
3,769,329 A 10, 1973 Paulik et ai. (57) ABSTRACT
3,791935 A 2f1974 Eubanks et al.
4,008, 131 A 2, 1977 Price A process for producing acetic acid is disclosed in which the
4,615,806 A 10, 1986 Hilton water concentration is controlled in the side stream between
5,001,259 A 3, 1991 Smith et al. two columns. Controlling the water concentration by a
5,026,908 A 6, 1991 Smith et al. recycle rate of the light liquid phase maintains the hydrogen
5,144,068 A 9, 1992 Smith et al.
5,416.237 A 5/1995 Aubigne et al. iodide concentration in the side stream to be up to 50 wppm.
5,653,853. A 8/1997 Kagotani et al.
5,696.284 A 12/1997 Baker et al. 19 Claims, 1 Drawing Sheet

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 US 9,302,974 B1
Page 2

(56) References Cited 9,006,483 B2 4/2015 Shimizu et al.

2002fO151746 A1* 10, 2002 Scates ..................... CO7C 51/12
U.S. PATENT DOCUMENTS 562,519
2006, OO11462 A1 1/2006 Horiguchi et al.
7,223,886 B2 5, 2007 Scates et al. 2012/0090981 A1 4/2012 Torrence et al.
wa. W all 2013/0261334 A1 10, 2013 Shimizu et al.
7,855,306 B2 12/2010 Zinobile et al. 2013/0264186 A1 10, 2013 Shimizu et al.
7,884,237 B2 2/2011 Shaver 2013/0281735 A1 10, 2013 Shimizu et al.
7,884.241 B2 2/2011 Miura et al.
8.318,977 B2 11/2012 Zinobile etal 2013/0303800 A1 11, 2013 Shimizu
8,697,908 B2 4/2014 Torrence et al. 2013/0310603 A1 11/2013 Shimizu et al.
8,889,904 B2 11/2014 Shaver et al. * cited by examiner
U.S. Patent Apr. 5, 2016 US 9,302,974 B1

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 US 9,302,974 B1
1. 2
PROCESS FOR PRODUCING ACETIC ACID to 8% by weight) as the mixture to the distillation column and
distilling the mixture. In the Zone having a high water con
FIELD OF THE INVENTION centration, hydrogen iodide is allowed to react with methyl
acetate to produce methyl iodide and acetic acid.
This invention relates to processes for producing acetic U.S. Pat. No. 7,884.241 discloses a mixture containing
acid and, in particular, to improved processes for controlling hydrogen iodide and water and having a water content of not
the water concentration and the hydrogen iodide concentra more than 5% by weight (particularly not more than 3% by
tion fed to the drying column. weight) in a distillation system is distilled to prevent conden
sation of hydrogen iodide in the distillation system. The mix
BACKGROUND OF THE INVENTION 10 ture may comprise hydrogen iodide, water, methanol, methyl
iodide, acetic acid, and methyl acetate. Even when the mix
Among currently employed processes for synthesizing ture contains hydrogen iodide at a concentration of 1 to 3000
acetic acid, one of the most useful commercially is the cata ppm on the basis of weight, an acetic acid product having a
lyzed carbonylation of methanol with carbon monoxide as concentration of hydrogen iodide of not more than 50 ppm
taught in U.S. Pat. No. 3,769,329, which is incorporated 15 can be obtained by withdrawing a fraction containing hydro
herein by reference in its entirety. The carbonylation catalyst gen iodide from the top of the column, and withdrawing
contains a metal catalyst, such as rhodium, which is either acetic acid as a side-cut stream or a stream from the bottom of
dissolved or otherwise dispersed in a liquid reaction medium the column. This distillation process can inhibit condensation
or Supported on an inert Solid, along with a halogen-contain of hydrogen iodide in the distillation system and corrosion in
ing catalyst promoter as exemplified by methyl iodide. The the distillation system with a large energy penalty. To keep
reaction is conducted by continuously bubbling carbon mon water concentrations low, this process requires a large reflux
oxide gas through a liquid reaction medium in which the of 2.35, which is energy intensive.
catalyst is dissolved. U.S. Pat. No. 6,657,078 discloses a low energy process for
Methanol and carbon monoxide are fed to a reactor as producing acetic acid by the carbonylation of methanol. The
feedstocks. A portion of the reaction medium is continuously 25 process involves a rhodium-catalyzed system operated at less
withdrawn and provided to a flash vessel where the product is than about 14 wt.% water utilizing up to 2 distillation col
flashed and sent as a vapor to a purification train. The purifi S.
cation train includes a light ends column which removes U.S. Pat. No. 4,008,131 discloses a method for removal of
“light' or low boiling components as an overhead and pro excess water which tends to build up in recycle streams and
vides a side stream for further purification. The purification 30 reduces the rate of pure acid production during operation of a
train may further include columns to dehydrate the side distillation system for purification of crude acetic acid con
stream or for removing "heavy or high boiling components, taining water and methyl iodide. The crude acid is introduced
Such as propionic acid, from the side stream. It is desirable in into the upper half of a distillation Zone. The methyl iodide, a
a carbonylation process for making acetic acid to minimize major proportion of water and an equivalent amount of acid
the number of distillation operations to minimize energy 35 are removed overhead from the Zone. A minor proportion of
usage in the process. the water containing a small amount of acetic acid is removed
U.S. Pat. No. 5,416.237 discloses a process for the produc as a liquid sidedraw at a point near the top of the distillation
tion of acetic acid by carbonylation of methanol in the pres Zone. A product acid stream essentially dry and Substantially
ence of a rhodium catalyst, methyl iodide, and an iodide Salt free of methyl iodide is removed from the bottom of the
stabilizer. The improvement according to the 237 patent 40 distillation Zone. The overhead stream can be stored, disposed
resides in maintaining a finite concentration of water up to of or preferably recycled to the acid-producing step. The
about 10 wt.% and a methyl acetate concentration of at least liquid water sidedraw may either be discarded or subjected to
2 wt.% in the liquid reaction composition and recovering the rectification for recovery of acid values.
acetic acid product bypassing the liquid reaction composition U.S. Pat. No. 3,791.935 discloses a process by introducing
through a flash Zone to produce a vapor fraction which is 45 a monocarboxylic acid stream containing water and the halo
passed to a single distillation column from which the acetic gen contaminant into the upper half of a distillation column,
acid product is removed. The drawback of eliminating distil removing an overhead fraction consisting primarily of the
lation stages is that the level of purity of the product suffers. water and alkyl halide charged to said column, removing a
In particular, the distillation columns tend to remove high stream from the middle portion of said column containing a
boiling iodides as well as aldehyde contamination products. 50 major proportion of hydrogen halide present in said column,
Both of these impurities impact the commercial desirability and removing a product acid stream from at or near the
of the final product. bottom of said column, the product acid stream being essen
U.S. Pat. No. 9,006,483 discloses a production process of tially dry and Substantially free of the halogen contaminants
acetic acid that seeks to inhibit the concentration of hydrogen charged to said column. The method is particularly applicable
iodide and provides a liquid-liquid separation of an overhead 55 to the removal of water and iodine-containing compounds
from a distillation column. Acetic acid is produced by distill from acetic and propionic acids. In the examples, the bottoms
ing a mixture containing hydrogen iodide, water, acetic acid product that contains acetic acid is reported to contain from
and methyl acetate in a first distillation column (3) to forman 83 to 132 wppm water and 0.083 wippm to 0.3 wppm hydro
overhead and a side cut stream or bottom stream containing gen iodide.
acetic acid, cooling and condensing the overhead in a con 60 In view of the foregoing, the need exists for an improved
denser to form separated upper and lower phases in a decanter acetic acid production process to control recovery of acetic
(4). According to this process, a Zone having a high water acid.
concentration is formed in the distillation column above the
feed position of the mixture by feeding a mixture having a SUMMARY OF THE INVENTION
water concentration of not less than an effective amount to not 65
more than 5% by weight (e.g., 0.5 to 4.5% by weight) and a In one embodiment the present invention relates to a pro
methyl acetate concentration of 0.5 to 9% by weight (e.g., 0.5 cess for producing acetic acid comprising providing a reac
 US 9,302,974 B1
3 4
tion system comprising a reactor and a flash vessel; forming ing a reaction medium in the reactor; separating the reaction
a reaction medium in the reactor; separating a reaction medium in the flash vessel into a liquid recycle stream and a
medium in the flash vessel into a liquid recycle stream and a vapor product stream; distilling at least a portion of the vapor
vapor product stream, distilling at least a portion of the vapor product stream in a first column to obtain a low boiling
product stream in a first column to obtain a side stream and a 5 overhead vapor stream and a side stream comprising water in
low boiling overhead vapor stream comprising more than 5 an amount from 1 to 3 wt.%, one or more C-C alkyl iodides
wt.% water, condensing and biphasically separating at least a in an amount from 0.1 to 6 wt.%, and hydrogen iodide in an
portion of the low boiling overhead stream to form a heavy amount up to 50wppm, e.g., from 1 to 50wppm, distilling at
liquid phase and a light liquid phase, controlling a recycle rate least a portion of the side stream in a second column to obtain
of the light liquid phase to the reaction system to maintain a 10 a purified acetic acid product; and contacting the purified
water concentration in the side stream from 1 to 3 wt.% water, acetic acid product with a guard bed when total iodide con
e.g., preferably from 1.1 to 2.5 wt.% water, and a hydrogen centration of the purified acetic acid product is up to 5 wppm.
iodide (HI) concentration up to 50 wppm, e.g., preferably
from 0.1 to 50 wppm, and distilling at least a portion of the BRIEF DESCRIPTION OF THE DRAWING
side stream in a second column to obtain a purified acetic acid 15
product. In one embodiment, the side stream further com The present invention will be better understood in view of
prises one or more C-C alkyl iodides in an amount from 0.1 the appended non-limiting FIGURE, wherein:
to 6 wt.%, and methyl acetate in an amount from 0.1 to 6 wt. FIG. 1 is a schematic drawing for producing acetic acid in
%. The light liquid phase optionally comprises from 40 to 80 accordance with the present invention.
wt.% water. The reaction medium may comprise from 0.5 to 20
30 wt.% methylacetate, from 0.1 to 14 wt.% water, from 200 DETAILED DESCRIPTION OF THE INVENTION
to 3000 wppm metal catalyst, from 1 to 25 wt.% iodide salt,
and from 1 to 25 wt.% methyl iodide. The reaction medium Introduction
may also comprise acetic acid and methanol. In addition to Acetic acid recovery processes typically involve distilling
the recycle of the light liquid phase, a portion of the light 25 a crude acetic acid product in a first column to form a side
liquid phase may also be refluxed to the first column. In one stream, and distilling the side stream in a second column to
embodiment, the first column is operated with a reflux ratio form a purified acetic acid product. The side stream com
from 0.05 to 0.4. In some embodiments, another portion of the prises acetic acid, water, and various minor impurities, such
light liquid phase may be directed to a PRC removal system as, hydrogen iodide. The first column also forms a low boiling
for removal of acetaldehyde and/or other permanganate 30 overhead vapor stream, which is typically condensed and
reducing compounds. In other embodiments, a portion of the biphasically separated into a light liquid phase and a heavy
heavy liquid phase may be refluxed to the first column alone liquid phase.
or as a mixture with the reflux of the light liquid phase. The present invention provides methods for controlling the
Hydrogen iodide concentration in the side stream may be water concentration and, indirectly, the hydrogen iodide con
determined by potentiometric titration using lithium acetate 35 centration of the side stream. The water concentration of the
as the titrating agent. In response to the measured hydrogen side stream may be advantageously maintained within the
iodide concentration(s), the recycle rate of the light liquid desired range by controlling a recycle rate of the light liquid
phase may be increased when the measured hydrogen iodide phase recovered from the first column to the reaction system,
concentration exceeds a determined threshold, e.g., is greater which comprises the reactor and flash vessel. In one embodi
than 50 wppm. In one embodiment, additional steps may be 40 ment, from 0 to 20% of the total light liquid phase condensed
taken to further reduce the iodide concentration of the purified from the low boiling overhead stream is recycled and the
acetic acid product that is withdrawn at or near the bottom of remainder may be used as a reflux on the first column or fed
the second column. For example, the present invention may to a PRC removal system. In some embodiments, the recycle
further comprise contacting the purified acetic acid product rate of the light liquid phase may be 0% indicating that there
with a guard bed when the total iodide concentration of the 45 is no recycle to the reaction system and the light liquid phase
purified acetic acid product is up to 5 wppm, e.g., up to 1 used as a reflux on the first column or fed to a PRC removal
wppm, to remove residual iodide contaminants. system. Because the light liquid phase may be refluxed to the
In another embodiment, the present invention relates to a first column, a change in the reflux ratio also affects recycle
process for producing acetic acid comprising providing a rate to the reactor, and ultimately the water and hydrogen
reaction system comprising a reactor and a flash vessel; form- 50 iodide content of the side stream. Reducing the hydrogen
ing a reaction medium in the reactor; separating the reaction iodide content of the side stream reduces the total iodide
medium in the flash vessel into a liquid recycle stream and a content in the second column and ultimately the purified
vapor product stream; distilling at least a portion of the vapor acetic acid product. Having a low total iodide concentration,
product stream in a first column to obtain a side stream and a e.g., up to 5 wppm, e.g., up to 1 wppm, in the purified acetic
low boiling overhead vapor stream; condensing and biphasi- 55 acid product allows for the efficient removal of any residual
cally separating at least a portion of the low boiling overhead iodide contaminants using a guard bed. This greatly improves
stream to form a heavy liquid phase and a light liquid phase; the quality of the purified acetic acid product.
measuring hydrogen iodide concentration in the side stream; In one embodiment, the present invention relates to a pro
controlling a recycle rate of the light liquid phase to the cess for producing acetic acid comprising providing a reac
reaction system in response to the measured hydrogen iodide 60 tion system comprising a reactor and a flash vessel; forming
to maintain up to 50wppm hydrogeniodide in the side stream, a reaction medium in the reactor, separating the reaction
e.g., preferably from 0.1 to 50 wppm; and distilling at least a medium in the flash vessel into a liquid recycle stream and a
portion of the side stream in a second column to obtain a vapor product stream; distilling at least a portion of the vapor
purified acetic acid product. product stream in a first column to obtain a side stream and a
In yet another embodiment, the present invention relates to 65 low boiling overhead vapor stream comprising more than 5
a process for producing acetic acid comprising providing a wt.% water, condensing and biphasically separating at least
reaction system comprising a reactor and a flash vessel; form a portion of the low boiling overhead stream to form a heavy
 US 9,302,974 B1
5 6
liquid phase and a light liquid phase; controlling a recycle rate feed that is sent to the first column. In addition, the process
of the light liquid phase to the reaction system to maintain a described in U.S. Pat. No. 9,006,483 does not involve con
water concentration in the side stream from 1 to 3 wt.% water trolling the light liquid phase recycle to the reaction system,
and hydrogen iodide concentration in the side stream of up to and thus does not independently allow for the control the
50wppm, and distilling at least a portion of the side stream in water and hydrogen iodide concentrations of the side stream.
a second column to obtain a purified acetic acid product. The major component in the side stream is acetic acid, and
In another embodiment, the present invention relates to a the side stream preferably comprises more than 90 wt.%
process for producing acetic acid comprising providing a acetic acid, e.g., more than 94 wt.% or more than 96 wt.%. In
reaction system comprising a reactor and a flash vessel; form terms of ranges, the side stream may comprise acetic acid in
ing a reaction medium in the reactor; separating the reaction 10 an amount from 90 to 99 wt.%, e.g., from 91 to 98 wt.%. Such
medium in the flash vessel into a liquid recycle stream and a concentrations allow a majority of the acetic acid that is fed to
vapor product stream; distilling at least a portion of the vapor the first column to be withdrawn in the side stream for further
product stream in a first column to obtain a side stream and a purification in the second column. Preferably, acetic acid is
low boiling overhead vapor stream; condensing and biphasi not recovered in the low-boiling vapor stream or high boiling
cally separating at least a portion of the low boiling overhead 15 residue stream of the first column.
stream to form a heavy liquid phase and a light liquid phase; In addition to acetic acid and water, the side stream may
measuring hydrogen iodide concentration in the side stream; also comprise one or more C-C alkyl iodides in an amount
controlling a recycle rate of the light liquid phase to the from 0.1 to 6 wt.%, and in particular methyl iodide. Other
reaction system in response to the measured hydrogen iodide alkyl iodides, such as hexyl iodide, may also be formed from
to maintain up to 50wppm hydrogeniodide in the side stream, carbonyl impurities such as acetaldehyde. More preferably,
e.g., preferably from 0.1 to 50 wppm; and distilling at least a the side stream comprises one or more C-C alkyl iodides in
portion of the side stream in a second column to obtain a an amount from 0.5 to 3 wt.%. Due to the presence of water,
purified acetic acid product. the side stream may also contain methyl acetate in an amount
In yet another embodiment, the present invention relates to from 0.1 to 6 wt.%, e.g., from 0.5 to 3 wt.%.
a process for producing acetic acid comprising providing a 25 Hydrogen iodide concentration of the side stream is deter
reaction system comprising a reactor and a flash vessel; form mined by potentiometric titration using lithium acetate as the
ing a reaction medium in the reactor; separating the reaction titrating agent. Others have determined hydrogen iodide con
medium in the flash vessel into a liquid recycle stream and a tent indirectly by calculation. U.S. Pub. No. 2013/0310603,
vapor product stream; distilling at least a portion of the vapor for example, indicates that iodide ion concentration may be
product stream in a first column to obtain a low boiling 30 calculated by Subtracting the iodide ion concentration derived
overhead vapor stream and a side stream comprising water in from the iodide salt form (including iodides derived from
an amount from 1 to 3 wt.%, one or more C-C alkyl iodides co-catalysts and metal iodide) from the total concentration of
in an amount from 0.1 to 6 wt.%, and hydrogen iodide in an iodide ion (I). Such indirect calculation techniques are typi
amount up to 50 wppm, e.g., from 1 to 50 wppm, distilling at cally inaccurate, resulting in a poor indication of actual
least a portion of the side stream in a second column to obtain 35 hydrogen iodide concentration owing largely to the inaccu
a purified acetic acid product; and contacting the purified racies of the underlying ion measurement methods. In addi
acetic acid product with a guard bed when total iodide con tion, this indirect calculation technique fails to account for
centration of the purified acetic acid product is up to 5 wppm. other iodide forms because metal cations are measured and
By controlling the recycle of the light liquid phase, the incorrectly assumed to be completely associated only with
water concentration in the side stream between two columns 40 iodide anions while, in fact, the metal cations may be associ
may be maintained within certain concentration limits. The ated with otheranions. Such as acetate and catalyst anions. In
side stream may comprise water in an amount from 1 to 3 wt. contrast, the direct measurement of hydrogen iodide concen
%, e.g., from 1 to 2.5 wt.% and more preferably from 1.1 to tration according to the present invention advantageously
2.1 wt.%. A water concentration within this range has been reflects the actual hydrogen iodide concentration in the sys
discovered to maintain a hydrogen iodide concentration of up 45 tem, and can result in accuracy as low as 0.01%.
to 50 wppm in the side stream, e.g., from 0.1 to 50 wppm By detecting the hydrogen iodide concentration of the side
hydrogen iodide, or from 5 to 30 wppm hydrogen iodide. stream, the recycle rate of the light liquid phase may be
Hydrogen iodide is soluble in acetic acid-water mixtures controlled. For example, when the hydrogen iodide concen
containing water in an amount from 3 to 8 wt.%, and the tration exceeds a pre-determined threshold, Such as 50wppm,
solubility of hydrogen iodide decreases as the water concen 50 the recycle rate of the light liquid phase may be increased.
tration decreases. This correlation results in making hydrogen Once the hydrogen iodide concentration is below the deter
iodide more volatile and thus less hydrogen iodide will be mined threshold, such as 10 wippm, the recycle rate of the
collected in the overhead of the column. Although hydrogen light liquid phase may be decreased. As described herein, the
iodide may be corrosive under certain circumstances, some recycle rate of the light liquid phase is the percent being
amounts of hydrogen iodide under certain conditions may 55 recycled as compared to the total amount of light liquid phase
beneficially act as a catalyst, Such as a catalyst for forming condensed from the first column overhead. The light liquid
dimethyl ether as described in U.S. Pat. No. 7,223,883 (de phase may be recycled to the reaction system.
scribing the benefits of dimethyl ether formation in certain Reaction Step
acetic acid separation processes), the entirety of which is An exemplary reaction and acetic acid recovery system
incorporated herein by reference. 60 100 is shown in FIG.1. As shown, methanol-containing feed
The control of the recycle rate of the light liquid phase to stream 101 and carbon monoxide-containing feed stream 102
the reaction system is an improvement over other processes are directed to liquid phase carbonylation reactor 105, in
for controlling hydrogen iodide content, Such as those which the carbonylation reaction occurs to form acetic acid.
described in U.S. Pat. No. 9,006,483, since the present inven Methanol-containing feed stream 101 may comprise at
tion advantageously allows for hydrogen iodide control with 65 least one member selected from the group consisting of
out introducing additional components into the first column methanol, dimethyl ether, and methyl acetate. Methanol-con
and/or maintaining certain concentrations in a vapor product taining feed stream 101 may be derived in part from a fresh
 US 9,302,974 B1
7 8
feed or may be recycled from the system. At least some of the to 3000 wppm, e.g., from 800 to 3000 wppm, or from 900 to
methanol and/or reactive derivative thereof will be converted 1500 wppm. The concentration of water in the reaction
to methyl acetate in the liquid medium by esterification reac medium is maintained to be less than 14 wt.%, e.g., from 0.1
tion with acetic acid. wt.% to 14 wt.%, from 0.2 wt.% to 10 wt.% or from 0.25 wt.
Typical reaction temperatures for carbonylation will be % to 5 wt.%. Preferably, the reaction is conducted under low
from 150 to 250° C., with the temperature range of 180 to water conditions and the reaction medium contains 0.1 to 4.1
225°C. being a preferred range. The carbon monoxide partial wt.% water, e.g., from 0.1 to 3.1 wt.% or from 0.5 to 2.8 wt.
pressure in the reactor may vary widely but is typically from %. The concentration of methyl iodide in the reaction
2 to 30 atm, e.g., from 3 to 10 atm. The hydrogen partial medium is maintained to be from 1 to 25 wt.%, e.g., from 5
pressure in the reactor is typically from 0.05 to 2 atm, e.g., 10 to 20 wt.%, from 4 to 13.9 wt.% or from 4 to 7 wt.%. The
from 0.25 to 1.9 atm. Because of the partial pressure of concentration of iodide salt, e.g., lithium iodide, in the reac
by-products and the vapor pressure of the contained liquids, tion medium is maintained to be from 1 to 25 wt.%, e.g., from
the total reactor pressure will range from 15 to 40 atm. The 2 to 20 wt.%, from 3 to 20 wt.%. The concentration of methyl
production rate of acetic acid may be from 5 to 50 mol/L. h. acetate in the reaction medium is maintained to be from 0.5 to
e.g., from 10 to 40 mol/Lh, and preferably about 15 to 35 15 30 wt.%, e.g., from 0.3 to 20 wt.%, from 0.6 to 4.1 wt.%. The
mol/L. h. following amounts are based on the total weight of the reac
Carbonylation reactor 105 is preferably either a stirred tion medium. The concentration of acetic acid in the reaction
vessel or bubble-column type vessel, with or without an agi medium is generally more than 30 wt.%, e.g. more than 40
tator, within which the reacting liquid or slurry contents are wt.% or more than 50 wt.%.
maintained, preferably automatically, a predetermined level. In some embodiments, the desired reaction rates are
which preferably remains Substantially constant during nor obtained even at low water concentrations by maintaining an
mal operation. Into carbonylation reactor 105, fresh metha ester concentration in the reaction medium of the desired
nol, carbon monoxide, and Sufficient water are continuously carboxylic acid and an alcohol, desirably the alcohol used in
introduced as needed to maintain Suitable concentrations in the carbonylation, and an additional iodide ion that is over and
the reaction medium. 25 above the iodide ion that is present as hydrogen iodide. A
The metal catalyst may comprise a Group VIII metal. Suit desired ester is methyl acetate. The additional iodide ion is
able Group VIII catalysts include rhodium and/or iridium desirably an iodide salt, with lithium iodide (LiI) being pre
catalysts. When a rhodium catalyst is used, the rhodium cata ferred. It has been found that under low water concentrations,
lyst may be added in any suitable form such that rhodium is in methyl acetate and lithium iodide act as rate promoters only
the catalyst Solution as an equilibrium mixture including Rh 30 when relatively high concentrations of each of these compo
(CO)I-anion, as is well known in the art. Iodide Salts nents are present and that the promotion is higher when both
optionally maintained in the reaction mixtures of the pro of these components are present simultaneously.
cesses described herein may be in the form of a soluble salt of The carbonylation reaction of methanol to acetic acid prod
an alkali metal or alkaline earth metal, quaternary ammo uct may be carried out by contacting the methanol feed with
nium, phosphonium salt or mixtures thereof. In certain 35 gaseous carbon monoxide bubbled through an acetic acid
embodiments, the catalyst co-promoter is lithium iodide, Solvent reaction medium containing the rhodium catalyst,
lithium acetate, or mixtures thereof. The salt co-promoter methyl iodide (Mel) promoter, methyl acetate (MeAc), and
may be added as a non-iodide salt that will generate an iodide additional soluble iodide salt, at conditions of temperature
salt. The iodide catalyst stabilizer may be introduced directly and pressure suitable to form the carbonylation product. It
into the reaction system. Alternatively, the iodide salt may be 40 will be generally recognized that it is the concentration of
generated in-situ Since under the operating conditions of the iodide ion in the catalyst system that is important and not the
reaction system, a wide range of non-iodide salt precursors cation associated with the iodide, and that at a given molar
will react with methyl iodide or hydroiodic acid in the reac concentration of iodide the nature of the cation is not as
tion medium to generate the corresponding co-promoter significant as the effect of the iodide concentration. Any metal
iodide salt stabilizer. For additional detail regarding rhodium 45 iodide salt, or any iodide salt of any organic cation, or other
catalysis and iodide salt generation, see U.S. Pat. Nos. 5,001, cations such as those based on amine or phosphine com
259; 5,026,908; 5,144,068 and 7,005,541, which are incor pounds (optionally, ternary or quaternary cations), can be
porated herein by reference in their entireties. The carbony maintained in the reaction medium provided that the salt is
lation of methanol utilizing iridium catalyst is well known sufficiently soluble in the reaction medium to provide the
and is generally described in U.S. Pat. Nos. 5,942.460, 5,932, 50 desired level of the iodide. When the iodide is a metal salt,
764, 5,883,295, 5,877,348, 5,877,347 and 5,696,284, which preferably it is an iodide salt of a member of the group
are incorporated herein by reference in their entireties. consisting of the metals of Group IA and Group IIA of the
The halogen-containing catalyst promoter of the catalyst periodic table as set forth in the “Handbook of Chemistry and
system consists of a halogen compound comprising an Physics” published by CRC Press, Cleveland, Ohio, 2002-03
organic halide. Thus, alkyl, aryl, and Substituted alkyl or aryl 55 (83rd edition). In particular, alkali metal iodides are useful,
halides can be used. Preferably, the halogen-containing cata with lithium iodide being particularly suitable. In the low
lyst promoter is present in the form of an alkyl halide. Even water carbonylation process, the additional iodide ion over
more preferably, the halogen-containing catalyst promoter is and above the iodide ion present as hydrogen iodide is gen
present in the form of an alkylhalide in which the alkyl radical erally present in the catalyst Solution in amounts such that the
corresponds to the alkyl radical of the feed alcohol, which is 60 total iodide ion concentration is from 1 to 25 wt.% and the
being carbonylated. Thus, in the carbonylation of methanol to methyl acetate is generally present in amounts from 0.5 to 30
acetic acid, the halide promoter will include methyl halide, wt.%, and the methyl iodide is generally present in amounts
and more preferably methyl iodide. from 1 to 25 wt.%. The rhodium catalyst is generally present
The components of the reaction medium are maintained in amounts from 200 to 3000 ppm.
within defined limits to ensure sufficient production of acetic 65 In a typical carbonylation process, carbon monoxide is
acid. The reaction medium contains a concentration of the continuously introduced into the carbonylation reactor, desir
metal catalyst, e.g. rhodium catalyst, in an amount from 200 ably below the agitator, which may be used to stir the con
 US 9,302,974 B1
10
tents. The gaseous feed preferably is thoroughly dispersed 110 comprise a portion of the carbon monoxide and may also
through the reacting liquid by this stirring means. Gaseous contain gaseous by-products such as methane, hydrogen, and
purge stream 106 desirably is vented from the reactor 105 to carbon dioxide. Such dissolved gases exit flash vessel 110 as
prevent buildup of gaseous by-products and to maintain a set part of the vapor product stream 112. In one embodiment,
carbon monoxide partial pressure at a given total reactor carbon monoxide in gaseous purge stream 106 may be fed to
pressure. The temperature of the reactor may be controlled the base of flash vessel 110 to enhance rhodium stability.
and the carbon monoxide feed is introduced at a rate sufficient Recovery of Acetic Acid
to maintain the desired total reactor pressure. Stream 113 The distillation and recovery of acetic acid is not particu
comprising the liquid reaction medium exits reactor 105. larly limited for the purposes of the present invention. As
The acetic acid production system preferably includes 10
shown in FIG. 1, vapor product stream 112 is directed to a first
separation system 108 employed to recover the acetic acid column 120, also referred to as a light ends column. In one
and recycle metal catalyst, methyl iodide, methyl acetate, and embodiment, vapor product stream 112 may comprise acetic
other system components within the process. One or more of acid, methyl acetate, water, methyl iodide, and acetaldehyde,
the recycle streams may be combined prior to being intro
duced into the reactor. The separation system also preferably 15 along with other impurities such as hydrogen iodide and
controls water and acetic acid content in the carbonylation crotonaldehyde, and byproducts such as propionic acid. Dis
reactor, as well as throughout the system, and facilitates per tillation yields a low-boiling overhead vapor stream 122, a
manganate reducing compound (PRC) removal. PRC's purified acetic acid product that preferably is removed via a
may include acetaldehyde, acetone, methyl ethyl ketone, side stream 123, and a high boiling residue stream 121. A
butylaldehyde, crotonaldehyde, 2-ethyl crotonaldehyde, majority of the acetic acid is removed in side stream 123 and
2-ethylbutyraldehyde, and the aldol condensation products preferably little or no acetic acid is recovered from high
thereof. boiling residue stream 121.
The reaction medium is drawn off from the carbonylation In one embodiment, low-boiling overhead vapor stream
reactor 105 at a rate sufficient to maintain a constant level 122 comprises more than 5 wt.% water, e.g., more than 10 wt.
therein and is provided to flash vessel 110 via stream 113. 25 % water, or more than 25 wt.% water. The amount of water
Reactor 105 and flash vessel 110, along with the associated may be up to 80 wt.%. In terms of ranges, water may be from
pumps, vents, pipes, and values, comprise the reaction sys 5 wt.% to 80 wt.%, e.g., from 10 wt.% to 70 wt.% or from
tem. The flash separation may be carried out at a temperature 25 wt.% to 60 wt.%. Reducing water concentration to less
from 80° C. to 280° C., under an absolute pressure from 0.25 than 5 wt.% is not advantageous because this results in a large
to 10 atm, and more preferably from 100° C. to 260° C. and 30 recycle of acetic acid back to the reaction system which then
from 0.3 to 10 atm. In flash vessel 110, the reaction medium sets up a large recycle through the entire purification system.
is separated in a flash separation step to obtain a vapor product In addition to water, low-boiling overhead vapor stream 122
stream 112 comprising acetic acid and liquid recycle stream may also comprise methyl acetate, methyl iodide, and carbo
111 comprising a catalyst-containing solution. nyl impurities, such as PRC's, which are preferably concen
Liquid recycle stream 111 comprises acetic acid, the metal 35 trated in the overhead to be removed from acetic acid in side
catalyst, corrosion metals, as well as other various com stream 123.
pounds. In one embodiment, liquid recycle stream comprises As shown, low-boiling overhead vapor stream 122 prefer
from 60 to 90 wt.% acetic acid, from 0.01 to 0.5 wt.% metal ably is condensed and directed to an overhead phase separa
catalyst; from 10 to 2500wppm corrosion metals (e.g., nickel, tion unit, as shown by overhead decanter 124. Conditions are
iron and chromium); from 5 to 20 wt.% lithium iodide; from 40 desirably maintained such that the condensed low-boiling
0.5 to 5 wt.% methyl iodide; from 0.1 to 5 wt.% methyl overhead vapor stream 122, once in decanter 124, will bipha
acetate; from 0.1 to 8 wt.% water; up to 1 wt.% acetaldehyde sically separate into a light liquid phase 133, also referred to
(e.g., from 0.0001 to 1 wt.% acetaldehyde); and up to 0.5 wt. as an aqueous phase, and a heavy liquid phase 134, also
% hydrogen iodide (e.g., from 0.0001 to 0.5 wt.% hydrogen referred to as an organic phase. An offgas component may be
iodide). 45 vented via line 132 from decanter 124. Although the specific
The respective flow rates of vapor product stream 112 and compositions of light liquid phase 133 may vary widely, some
liquid recycle stream 111 may vary, and in one exemplary preferred compositions are provided below in Table 1.
embodiment 15% to 55% of the flow into flash vessel 110 is
removed as vapor product stream 112 and 45% to 85% of the TABLE 1
flow is removed as liquid recycle stream 111. The catalyst 50
Exemplary Light Liquid Phase Compositions
containing solution may be predominantly acetic acid con
taining the rhodium and the iodide salt along with lesser conc. (Wt. %) conc. (Wt. %) conc. (Wt.%)
quantities of methyl acetate, methyl iodide, and water and is Water 40-80 SO-80 60-75
recycled to the reactor, as discussed above. Prior to returning Methyl Acetate 1-SO 1-2S 1-10
a liquid recycle stream to the reactor, a slip stream may pass 55 Acetic Acid 1-40 1-2S 15-25
through a corrosion metal removal bed. Such as an ion PRC's Up to 5 Up to 3 O.1-0.7
exchange bed, to remove any entrained corrosion metals, Methyl Iodide Up to 10 Up to 5 1-5
HI Up to 1 Up to 0.5 O.OO1-0.5
Such as nickel, iron and chromium, as described in U.S. Pat.
No. 5,731,252, which is incorporated herein by reference in
their entirety. Also, the corrosion metal removal bed may be 60 The concentration of water and hydrogen iodide in side
used to remove nitrogen compounds, such as amines, as stream 123 is controlled by the recycle rate of light liquid
described in U.S. Pat. No. 8,697.908, which is incorporated phase 133 to the reaction system via line 136. The reflux ratio
herein by reference in their entirety. (the mass flow rate of the reflux divided by the total mass flow
In addition to acetic acid, vapor product stream 112 also exiting the top of the column 120, including both heavy liquid
comprises methyl iodide, methyl acetate, water, hydrogen 65 phase 134, which may or may not be fully recycled, and the
iodide, and PRC's, e.g., acetaldehyde and crotonaldehyde. light liquid phase 133) to the first column of the light liquid
Dissolved gases exiting reactor 105 and entering flash vessel phase 133 via line 135 preferably is from 0.05 to 0.4, e.g.,
 US 9,302,974 B1
11 12
from 0.1 to 0.35 or from 0.15 to 0.3. In one embodiment, to trolled so as to provide the desired balance of water and
reduce the reflux ratio, the number of theoretical trays above hydrogen iodide in side stream 123 and water recycle to the
between the side stream and top of first column may be reactOr.
greater than 5, e.g., preferably greater than 10. In some embodiments, all or a portion of heavy liquid
In one embodiment, the recycle of light liquid phase in line phase 134, which contains more methyl acetate and methyl
136 to the reaction system is up to about 20%, e.g., up to about iodide than light liquid phase 133, may also be recycled to
10%, of the total light liquid phase 133 condensed from the reactor 105 and/or refluxed to first column 120. Additional
first column overhead. In terms of ranges, the recycle of light carbonyl impurities may be removed from heavy liquid phase
liquid phase in line 136 may be from 0 to 20%, e.g., from 0.5 134 using a similar process as described hereinforlight liquid
to 20% or from 1 to 10%, of the total light liquid phase 133 10 phase 133.
condensed from the column overhead. The remaining portion In one embodiment, hydrogen iodide concentration in side
may be used as a reflux on the light ends column or fed to a stream 123 may be determined by feeding a sample stream
PRC removal system. As shown in FIG. 1, recycle in line 136 141 to an on-line analyzer 142. On-line analyzer 142 may
may be combined with liquid recycle stream 111 and be provide real-time or near real-time measurements. In one
returned to reactor 105. In one embodiment, recycle in line 15 embodiment, any Suitable analyzer may be used, such as, but
136 may be combined with another stream that is being not limited to, chromatography-mass spectrometry, selected
recycled to the reaction system, e.g., reactor 105 or flash ion monitoring, mass spectrometry, infrared spectroscopy,
vessel 110. When condensed overhead stream 138 from dry resonant frequency analyzers or ultrasonic concentration ana
ing column 125 is phased into an aqueous phase and an lyZers.
organic phase, the recycle in line 136 may be preferably Acetic acid removed via side stream 123 preferably is
combined with the aqueous phase. Alternatively, recycle in Subjected to further purification, Such as in a second column
line 136 may be combined, or at least partially combined, 125, also referred to as a drying column, and separates side
with the heavy liquid phase 134 and/or the organic phase from stream 123 into overhead stream 126 comprised primarily of
the overhead stream 138. water and bottoms stream 127 comprised primarily of acetic
For purposes of the present invention, a flow valve (not 25 acid and may be referred to as the acetic acid product stream.
shown) and/or flow monitor (not shown) may be used to Acetic acid may also be recovered as a side stream near the
control the reflux in line 135 and recycle in line 136. In one bottom of second column 125. Overhead stream 126 may
embodiment, the controls for the reflux in line 135 and comprise 50 to 75 wt.% water. Methyl acetate and methyl
recycle in line 136 may be in communication with on-line iodide are also removed from the side stream and concen
analyzer 142 that may provide feedback information to con 30 trated in the overhead stream. Drying column bottoms stream
trol the respective reflux ratio and recycle to reactor. Chang 127 preferably comprises or consists essentially of acetic
ing the reflux ratio may impact the amount of water that is acid. In preferred embodiments, drying column bottoms
recycled to the reactor. In some embodiments, the amount stream 127 comprises acetic acidinan amount greater than 90
may be changed so that there is no recycle of the light liquid wt.%, e.g., greater than 95 wt.% or greater than 98 wt.%.
phase 133 to the reactor. Reducing the reflux (and increasing 35 Drying column bottoms stream 127 may be further processed,
the recycle to the reactor) decreases the side stream water e.g. by passing through an ion exchange resin, prior to being
content. Increasing the reflux increases the water concentra stored or transported for commercial use.
tion in the side stream and decreases the water recycled to the Similarly, overhead stream 126 from second column 125
reactor. Increasing the reflux ratio above 0.4 increases the contains a reaction component, Such as methyl iodide, methyl
water concentration to greater than 3 wt.% in side stream, 40 acetate, and water, and it is preferable to retain these reaction
which makes separation in the second column difficult for components within the process. As shown, overhead stream
removing water, methyl acetate, and methyl iodide from the 126 is condensed by a heat exchanger into stream 138, which
acetic acid. As a result, the acetic acid in the second column is recycled to reactor 105 and/or refluxed second column 125.
bottoms stream may contain a total iodide concentration that An offgas component may be vented via line 137 from con
is too high for efficient handling by guard beds. 45 densed low-boiling overhead vapor stream 126. Similar to the
Although not shown, a portion (preferably an aliquot por condensed low-boiling overhead vapor stream from first col
tion) of light liquid phase 133 may be separated and directed umn 120, condensed overhead stream 138 may also be sepa
to PRC removal system to recover methyl iodide and methyl rated into an aqueous phase and an organic phase, and these
acetate. As shown in Table 1, light liquid phase 133 contains phases may be recycled or refluxed as needed to maintain the
PRC's, and the process may include removing carbonyl 50 desired concentrations in the reaction medium.
impurities, such as acetaldehyde, that compromise the quality To recover residue liquids from the vent stream, in particu
of the acetic acid product and may be removed in suitable lar lines 106, 132, and 137, these lines may be fed to a
impurity removal columns and absorbers as described in U.S. scrubber that operates with cooled methanol and/or acetic
Pat. Nos. 6,143,930; 6,339,171; 7,223,883; 7,223,886; 7,855, acid to remove methyl acetate and methyl iodide. A suitable
306; 7,884,237; 8,889,904; and US Pub. Nos. 2006/0011462, 55 scrubber is described in U.S. Pat. No. 8,318,977, which is
which are incorporated herein by reference in their entireties. incorporated herein by reference in its entirety.
Carbonyl impurities, such as acetaldehyde, may react with The distillation columns of the present invention may be
iodide catalyst promoters to form alkyl iodides, e.g., ethyl conventional distillation column, e.g., a plate column, a
iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl packed column, and others. The material of the distillation
iodide, etc. Also, because many impurities originate with 60 column is not limited and may include a glass, a metal, a
acetaldehyde, it is desirable to remove carbonyl impurities ceramic, or other Suitable material can be used. For a plate
from the light liquid phase. column, the theoretical number of plates may depend on the
Thus, although not shown in FIG. 1, all or a portion of light component to be separated, and may include up to 50 plates,
liquid phase 133 and/or heavy liquid phase 134 may be e.g., from 5 to 50, or from 7 to 35.
directed to a PRC removal system as described above. Pref 65 Guard Bed
erably the portion(s) directed to the PRC removal system as Carboxylic acid streams, e.g., acetic acid streams, that are
well as the reflux rate of light liquid phase 133 may be con contaminated with a halides and/or corrosion metals may be
 US 9,302,974 B1
13 14
contacted with the inventive ion exchange resin composition BV/hr means that a quantity of organic liquid equal to the
under a wide range of operating conditions. Preferably, the volume occupied by the resinbed passes through the resinbed
ion exchange resin composition is provided in a guard bed. in a one hour time period.
The use of guard beds to purify contaminated carboxylic acid To avoid exhausting the resin with a purified acetic acid
streams is described, for example, in U.S. Pat. Nos. 4,615, 5 product that is high in total iodide concentration, in one
806; 5,653,853; 5,731,252; and 6.225,498, which are hereby embodiment the purified acetic acid product in bottoms
incorporated by reference in their entireties. Generally, a stream 127 is contacted with a guard bed when total iodide
contaminated liquid carboxylic acid stream is contacted with concentration of the purified acetic acid product is up to 5
the inventive ion exchange resin composition, which is pref wppm, e.g. preferably up to 1 wppm. In one exemplary
erably disposed in the guard bed. The halide contaminants, 10
embodiment, the total iodide concentration of the purified
e.g., iodide contaminants, react with the metal to form metal acetic acid product may be from 0.01 wppm to 5 wppm, e.g.,
iodides. In some embodiments, hydrocarbon moieties, e.g., from 0.01 wppm to 1 wppm. Concentrations of iodide above
methyl groups, that may be associated with the iodide may 5 wppm may require re-processing the off-spec acetic acid.
esterify the carboxylic acid. For example, in the case of acetic
acid contaminated with methyl iodide, methyl acetate would 15 Total iodide concentration includes iodide from both organic,
be produced as a byproduct of the iodide removal. The for C to Calkyl iodides, and inorganic sources, such as hydro
mation of this esterification product typically does not have a gen iodide. A purified acetic acid composition is obtained as
deleterious effect on the treated carboxylic acid stream. a result of the guard bed treatment. The purified acetic acid
The pressure during the contacting step is limited only by composition, in one embodiment, comprises less than 100
the physical strength of the resin. In one embodiment, the wppb, iodides, e.g., less than 90 wppb, less than 50 wppb, or
contacting is conducted at pressures ranging from 0.1 MPa to less than 25 wppb. In one embodiment, the purified acetic
1 MPa, e.g., from 0.1 MPa to 0.8 MPa or from 0.1 MPa to 0.5 acid composition comprises less than 100 wppb corrosion
MPa. For convenience, however, both pressure and tempera metals, e.g., less than 750 wppb, less than 500 wppb, or less
ture preferably may be established so that the contaminated than 250 wppb. In terms of ranges, the purified acetic acid
carboxylic acid stream is processed as a liquid. Thus, for 25 composition may comprise from 0 to 100 wppb iodides, e.g.,
example, when operating at atmospheric pressure, which is from 1 to 50 wppb; and/or from 0 to 1000 wppb corrosion
generally preferred based on economic considerations, the metals, e.g., from 1 to 500 wppb. In other embodiments, the
temperature may range from 17° C. (the freezing point of guard bed removes at least 25 wt.% of the iodides from the
acetic acid) to 118°C. (the boiling point of acetic acid). It is crude acetic acid product, e.g., at least 50 wt.% or at least 75
within the purview of those skilled in the art to determine 30
wt.%. In one embodiment, the guard bed removes at least 25
analogous ranges for product streams comprising other car wt.% of the corrosion metals from the crude acetic acid
boxylic acid compounds. The temperature of the contacting product, e.g., at least 50 wt.% or at least 75 wt.%.
step preferably is kept relatively low to minimize resin deg While the invention has been described in detail, modifi
radation. In one embodiment, the contacting is conducted at a cations within the spirit and scope of the invention will be
temperature ranging from 25°C. to 120° C. e.g., from 25°C. 35 readily apparent to those of skill in the art. In view of the
to 100° C. or from 50° C. to 100° C. Some cationic macrore foregoing discussion, relevant knowledge in the art and ref
ticular resins typically begin degrading (via the mechanism of erences discussed above in connection with the Background
acid-catalyzed aromatic desulfonation) at temperatures of and Detailed Description, the disclosures of which are all
150° C. Carboxylic acids having up to 5 carbonatoms, e.g., up incorporated herein by reference. In addition, it should be
to 3 carbon atoms, remain liquid at these temperatures. Thus, 40 understood that aspects of the invention and portions of vari
the temperature during the contacting should be maintained ous embodiments and various features recited below and/or in
below the degradation temperature of the resin utilized. In the appended claims may be combined or interchanged either
Some embodiments, the operating temperature is kept below in whole or in part. In the foregoing descriptions of the vari
temperature limit of the resin, consistent with liquid phase ous embodiments, those embodiments which refer to another
operation and the desired kinetics for halide removal. 45 embodiment may be appropriately combined with other
The configuration of the guard bed within an acetic acid embodiments as will be appreciated by one of skill in the art.
purification train may vary widely. For example, the guard Furthermore, those of ordinary skill in the art will appreciate
bed may be configured after a drying column for treating the that the foregoing description is by way of example only, and
acetic acid product. Additionally or alternatively, the guard be is not intended to limit the invention.
may be configured after a heavy ends removal column or 50
finishing column. Preferably the guard bed is configured in a EXAMPLES
position wherein the temperature acetic acid product stream
is low, e.g., less than 120° C. or less than 100° C. Aside from The present invention will be better understood in view of
the advantages discussed above, lower temperature operation the following non-limiting examples.
provides for less corrosion as compared to higher temperature 55
operation. Lower temperature operation provides for less for Comparative Example 1
mation of corrosion metal contaminants, which, as discussed
above, may decrease overall resin life. Also, because lower No Light Liquid Phase Recycle
operating temperatures result in less corrosion, Vessels
advantageously need not be made from expensive corrosion 60 A typical example of the HI concentration in side stream
resistant metals, and lower grade metals, e.g., standard stain was determined by titrating 0.2 g of side stream sample with
less steel, may be used. 0.01 M lithium acetate solution in 50 ml acetone. A pH
In one embodiment, the flow rate through the guard bed electrode was used with Metrohm 716 DMS Titrino to deter
ranges from 0.1 bed volumes per hour (“BV/hr) to 50 BV/hr, mine the end point at Dynamic Equivalence-point Titration
e.g., 1 BV/hr to 20 BV/hr or from 6 BV/hr to 10 BV/hr. Abed 65 mode. HI concentration in wt.% was calculated based on the
Volume of organic medium is a Volume of the medium equal consumption of lithium acetate titrating agent as depicted in
to the volume occupied by the resin bed. A flow rate of 1 following equation.
 US 9,302,974 B1
15 16
HI wt.% =(ml of LiOAc)(0.01 M)(128 g/mole)x
100/(g sample) (1000 ml/L)
9. The process of claim 1, wherein the recycle rate is
increased when hydrogen iodide concentration exceeds a
A sample side stream composition having about 1.9 wt.% determined threshold.
water was tested using this HI titration method. The HI con 10. The process of claim 1, wherein the first column is
centrations varied from 50wppm to 300wppm. No portion of 5 operated with a reflux ratio from 0.05 to 0.4.
the light liquid phase from the overheadlight ends is recycled 11. The process of claim 1, further comprising refluxing the
to the reactor. Without light liquid phase recycle, the HI heavy liquid phase, the light liquid phase, or a mixture thereof
concentrations tend to be higher. to the first column.
12. The process of claim 1, wherein the light liquid phase
Example 1 10 comprises from 40 to 80 wt.% water.
13. The process of claim 1, further comprising contacting
Light Liquid Phase Recycle the purified acetic acid product with a guard bed when total
iodide concentration of the purified acetic acid product is up
A portion of light liquid phase from the overheadlight ends to 5 wppm.
is recycled to the reactor to reduce the water content in the 15 14. A process for producing acetic acid comprising:
side stream. The side stream comprises 1.5 wt.% water with providing a reaction system comprising a reactor and a
less than 25 wppm HI, and the balance comprising acetic acid, flash vessel;
methyl acetate and methyl iodide. HI concentrations were too forming a reaction medium in the reactor;
low to measure directly with titration. There are other cations separating the reaction medium in the flash vessel into a
present that makes directly measuring HI difficult. The mea liquid recycle stream and a vapor product stream;
sure of total inorganic iodide, i.e. total possible maximize HI, distilling at least a portion of the vapor product stream in a
is done directly. These other inorganic iodides may include first column to obtain a side stream and a low boiling
lithium iodide, as well as corrosion metal iodide. overhead vapor stream;
What is claimed is: condensing and biphasically separating at least a portion of
1. A process for producing acetic acid comprising: 25 the low boiling overhead stream to form a heavy liquid
providing a reaction system comprising a reactor and a phase and a light liquid phase;
flash vessel; measuring hydrogen iodide concentration in the side
forming a reaction medium in the reactor; stream;
separating the reaction medium in the flash vessel into a controlling a recycle rate of the light liquid phase to the
liquid recycle stream and a vapor product stream; 30 reaction system in response to the measured hydrogen
distilling at least a portion of the vapor product stream in a iodide to maintain a water concentration in the side
first column to obtain a side stream and a low boiling stream from 1 to 3 wt % and a hydrogen iodide concen
overhead vapor stream comprising more than 5 wt.% tration in the side stream of up to 50 wppm; and
water; distilling at least a portion of the side stream in a second
condensing and biphasically separating at least a portion of 35 column to obtain a purified acetic acid product.
the low boiling overhead stream to form a heavy liquid 15. The process of claim 14, wherein the hydrogen iodide
phase and a light liquid phase; concentration in the side stream is measured by potentiomet
controlling a recycle rate of the light liquid phase to the ric titration using lithium acetate as the titrating agent.
reaction system to maintain a water concentration in the 16. The process of claim 14, wherein the first column is
side stream from 1 to 3 wt.% water and hydrogen iodide 40 operated with a reflux ratio from 0.05 to 0.4.
concentration in the side stream of up to 50 wppm; and 17. The process of claim 14, wherein the hydrogen iodide
distilling at least a portion of the side stream in a second is maintained in the side stream from 0.1 to 50 wppm.
column to obtain a purified acetic acid product. 18. A process for producing acetic acid comprising:
2. The process of claim 1, wherein the reaction medium providing a reaction system comprising a reactor and a
comprises methyl acetate, water, a metal catalyst, an iodide 45 flash vessel;
salt and methyl iodide. forming a reaction medium in the reactor;
3. The process of claim 1, wherein the reaction medium separating the reaction medium in the flash vessel into a
comprises from 0.5 to 30 wt.% methyl acetate, from 0.1 to 14 liquid recycle stream and a vapor product stream:
wt.% water, from 200 to 3000 wppm metal catalyst, from 1 to distilling at least a portion of the vapor product stream in a
25 wt.% iodide salt, and from 1 to 25 wt.% methyl iodide. 50 first column to obtain a low boiling overhead vapor
4. The process of claim 1, wherein the water concentration stream and a side stream comprising water in an amount
is maintained in the side stream from 1.1 to 2.5 wt.%. from 1 to 3 wt.%, one or more C-C alkyl iodides in an
5. The process of claim 1, wherein the hydrogen iodide is amount from 0.1 to 6 wt.%, and hydrogen iodide in an
maintained in the side stream from 0.1 to 50 wppm. amount up to 50 wppm;
6. The process of claim 1, wherein the side stream further 55 distilling at least a portion of the side stream in a second
comprises one or more C-C alkyl iodides in an amount column to obtain a purified acetic acid product; and
from 0.1 to 6 wt.%. contacting the purified acetic acid product with a guard bed
7. The process of claim 1, wherein the side stream further when total iodide concentration of the purified acetic
comprises methyl acetate in an amount from 0.1 to 6 wt.%. acid product is up to 5 wppm.
8. The process of claim 1, wherein the hydrogen iodide 60 19. The process of claim 18, wherein the hydrogen iodide
concentration in the side stream is determined by potentio is maintained in the side stream from 0.1 to 50 wppm.
metric titration using lithium acetate as the titrating agent. ck ck ck ck ck