Technology Profile
Acetic Acid Production from Methanol
By Intratec Solutions
A
cetic acid (also known as
ethanoic acid) is a carboxylic
acid found as dilute solutions
in plant and animal systems.
Industrially, the chemical is widely
used in organic processes, primarily in
the production of vinyl acetate mono-
mer and acetic anhydride.
The process
The following paragraphs describe
a process for producing acetic acid
from methanol and carbon monoxide,
based on rhodium-catalyzed carbon-
ylation. Figure 1 presents a simplified
flow diagram of the process.
Catalyst preparation. Initially, re-
cycled rhodium catalyst is treated
to recover the rhodium. The treated
catalyst is mixed with fresh catalyst, a
promoter (methyl iodide) and a stabi-
lizer (iodide salt). The mixture is then
dissolved in hot acetic acid under
pressurized carbon monoxide.
Carbonylation. The reactor is fed with
the catalyst solution, methanol and
carbon monoxide, along with recycle
streams. The reaction occurs in the
liquid phase, where dissolved carbon
monoxide combines with methanol to
yield acetic acid. Gases vented from
the reactor are cooled to recover un-
reacted methanol, methyl iodide and
methyl acetate. Uncondensable spe-
cies are sent to the methanol scrub-
ber, to prevent the loss of low-boiling
components, such as methyl iodide.
Liquid product is drawn off from the
reactor at a rate sufficient to maintain
a constant level, and is fed to a flash
vessel, where the catalyst solution is
withdrawn as a base stream and re-
cycled to the catalyst preparation. The
Fresh catalyst
make-up
CHW
1 4. Methanol scrubber
Carbon dioxide
2 3
5 ST
FIGURE 1. The diagram shows a typical rhodium-catalyzed carbonylation process for acetic acid production
24
Acetaldehyde Oxidation
Butane or Liquid-phase
naphtha oxidation
Ethanol Fermentation
n Raw material n Pathway n Main product
FIGURE 2. Methanol carbonylation is one of several possible pathways for the production of acetic acid
product overhead of the flash vessel
an acetic acid stream containing
methyl iodide, methyl acetate and wa-
ter is purified in distillation columns.
Purification. In the crude acetic acid
column, a gaseous stream from the
overhead, containing water, methyl io-
dide, methyl acetate and some acetic
acid, is condensed and recycled to the
carbonylation stage. A crude acetic
acid liquid stream, withdrawn as a side
draw, is routed to the drying column.
The bottom product, containing dis-
solved catalyst, is recycled to the flash.
In the drying column, water, methyl
iodide and methyl acetate are re-
moved from the crude acetic acid as
an overhead distillate, which is further
recycled to the carbonylation unit. The
column bottom stream, containing
acetic acid, is fed to a finishing col-
umn, where heavy ends are removed.
The acetic acid stream is finally passed
through ion-exchange resin beds to
remove iodide contaminants. Heavy-
ends from the finishing column are
sent to the acetic acid stripper, where
residual acetic acid is recovered as
overhead product and recycled to the
finishing column, while the bottom
product is discarded as waste acid.
Off-gas
4 3. Carbonylation reactor
Fresh methanol
CW
CW 10 Acetic acid
6 7 8 9
ST
Waste
acid
CHEMICAL ENGINEERING
Carbonylation Methanol
Acetic acid Oxidation Ethane
Anaerobic
Glucose
fermentation
Production pathways
Currently, the most important produc-
tion routes for acetic acid are based
on methanol carbonylation and oxida-
tion of acetaldehyde or light hydrocar-
bons. Figure 2 presents different path-
ways for acetic acid production.
Economic performance
The total operating cost (raw materials,
utilities, fixed costs and depreciation
costs) estimated to produce acetic acid
is about $560/ton of acetic acid. The
analysis is based on data from the sec-
ond quarter of 2013 using a plant with
capacity to produce 650,000 metric ton
per year of acetic acid.
This column is based on Ace-
tic Acid Production from Methanol
Cost Analysis, a report published
by Intratec. It can be found at: www.
intratec.us/analysis/acetic-acid-pro-
duction-cost. n
Edited by Scott Jenkins
Editors note: The content for this column is supplied by In-
tratec Solutions LLC (Houston; www.intratec.us) and edited by
Chemical Engineering. The analyses and models presented
are prepared on the basis of publicly available and non-
confidential information. The content represents the opinions
of Intratec only. More information about the methodology for
preparing analysis can be found, along with terms of use, at
www.intratec.us/che.
1. Catalyst preparation
2. Carbon monoxide compressor
5. Flash vessel
6. Crude acetic acid column
7. Drying column
8. Finishing column
9. Acetic acid stripper
10. Ion exchange resins
11. Steam boiler
12. Cooling tower
11 13. Chilled water unit
CW 12
ST Steam
CHW 13 CW Cooling water
CHW Chilled water
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