ACETIC ACID

1.1.1. INTRODUCTION
 Acetic acid – important raw material used for the production of vinyl acetate, acetic anhydride,
polymer-grade terephthalic acid (PTA), etc.
 Production of PTA – the most important and leading reason for the increase of demand of acetic acid;
growth rate in per capita consumption of acetic acid in Asia is typically 7 to 8 percent per annum
 Methanol carbonylation process – world's leading acetic acid production process, synthesis from
methanol and carbon monoxide
 Other methods:
 Oxidation of acetaldehyde
 Direct oxidation of ethylene, etc.
 Chiyoda ACETICA® - developed and owned by Chiyoda, to produce acetic acid by the carbonylation
of methanol and carbon monoxide.
 The ACETICA process for producing acetic acid is based on the presence of a proprietary
heterogeneous rhodium catalyst in the active rhodium complex that is chemically immobilized on a
polyvinylpyridine resin. To minimize attrition of the solid catalyst material, a bubble column reactor
is employed.

This immobilized catalyst system has the following advantages over the conventional liquid rhodium
catalyst:
 Handling of the catalyst is easy because it need not be recovered by separating the rhodium
from the reaction liquid.
 A high level of reactor productivity can be obtained because the concentration of rhodium
can be increased without the limitations imposed by solubility.
 The formation of by-products can be suppressed because operation is conducted under a
low water concentration.
 The corrosive environment is moderated because the concentration of hydrogen iodide is
decreased.

CHIYODA ACETIC ACID PROCESS ACETICA

The methanol carbonylation reaction between methanol and carbon monoxide is conducted at
moderate temperatures (170 to 190°C) and pressures (3.0 to 4.5 MPa). The usual acetic acid yields
based on methanol and CO consumption are greater than 99 and 92 percent, respectively.

The principal reactions:

Carbonylation:

Esterification:

Etherification:

The process consists of the following units:

 Feed/absorption/reaction unit
 Distillation unit
 Product-treating unit
 Methyl iodide (MI)–generation unit
 Iodide-removal unit Waste-treating unit

The basic chemistry of carbonylation is similar to that of a homogeneous catalyst in the

conventional processes. The net reaction in the carbonylation of methanol is
Carbonylation:
ACETICA requires no additional water to stabilize the active rhodium complex. Therefore, the reaction
solution contains less than 8 percent water according to the following equilibrium reactions:
Esterification:

Etherification:

Hydrogen iodide is formed in the reaction solution by hydrolysis of the metal iodide:

Certain amounts of methanol and acetic acid may react with the methyl iodide as shown below:

The detailed pathway of the Rh complex catalyst supported on solid resin can be depicted as two
interacting cycles, as shown in Fig. 1.1.1.

Methyl iodide is added oxidatively to the rhodium-dicarbonyl-diiodide

complex [RhI2(CO)2](A) to generate a rhodium-methyl complex (B).
This rhodium-methyl complex rapidly undergoes a methyl migration to
a neighboring carbonyl group in the acetyl form (CH 3CO) and reacts
with CO to generate the rhodium-acetyl complex (D). Reductive
elimination of the acetyl iodide (CH3COI) then liberates the original
rhodium complex (A). The hydration of acetyl iodide is very rapid in
the presence of water and results in the formation of acetic acid and
Figure 1.1.1. Catalytic Cycle for rhodium carbonylation.
hydrogen iodide to complete the cycle.
The figure indicates that the concentrations of dissolved CO, CH 3I,
catalyst, and H2O affect the reaction rate of carbonylation and catalyst stability.

1.1.2.2.Catalyst Preparation Reactions

Promoter (CH3I): The ACETICA process uses methyl iodide as the promoter for the carbonylation
reaction, as described earlier. The method of producing CH3I in a methyl iodide generator is

Heterogeneous Catalyst (Rhodium Immobilized on Resin): The ACETICA process is based on a

heterogeneous rhodium catalyst. The nitrogen atoms of the resin pyridine groups become positively
charged after quaternization with methyl iodide.

The active rhodium complex, [Rh(CO)2I2], is immobilized by the ion exchange on the
quaternizedpolyvinylpyridine resin.
Because the ion-exchange equilibrium favors the solid
phase, almost all Rh in the reaction mixture is immobilized
on the resin support.

1.1.2.3. By-Product Formations

Gaseous By-Products (CO2, H2, CH4). Gaseous by-product formation reactions, such as water-gas shift
and methane formation, also occur in the carbonylation reactor, but losses of CO and methanol by these
reactions amount to less than 1 percent of the total feed:
Water-gas shift reaction:
Methanation:

Liquid By-Products. Very small amounts of liquid by-products are produced at the initial stage of plant
operation, and their concentrations come to equilibrium,except for some heavy by-products such as
propionic acid. These heavy by-products are eliminated with small purges from the purification unit.

1.1.2.4. Iodide-Removal ReactionTo minimize iodide loss, most of the iodide compounds in the crude
product are recovered and returned to the synthesis section from the distillation section. Small amounts
of iodide compounds remain in the distilled product, and these are removed by a proprietary adsorbent.

1.1.3. PROCESS FEATURES

In comparison with conventional systems, the key features of the Chiyoda ACETICA process are
 Higher productivity. Unlike homogeneous catalyst systems, the concentration of Rh is not
restricted by solubility limitations of a liquid catalyst. With ACETICA, the Rh concentration can be
increased, enabling higher reaction levels.
 Few mechanical problems. The ACETICA process employs a unique bubble-column reactor that
has no mechanical agitator, meaning fewer problems with leakage and maintenance.
 Moderate corrosive system. The heterogeneous catalyst system enables the use of less water in
the system, resulting in a lower concentration of hydrogen iodide, which is the leading contributor
to corrosion. Zr is used in the reactor system. However, Ti or hastelloy is acceptable for use in
the rest of the system, thereby reducing investment costs.
 Higher product purity and lower by-product formation. The high degree of catalyst activity under
a low water concentration suppresses the formation of by-products, resulting in higher product
purity.
 Competitive economics. A moderate corrosive system environment enables the use of lower-
grade materials. In addition, the higher yield of acetic acid and the recovery of the reaction heat
in the reactor system reduce operating costs.
 More flexible for large-scale capacity. Because there are no moving parts or mechanical
equipment in the reactor, ACETICA offers more flexible application to larger plants having an
annual capacity such as 200,000 to 500,000 tons.
 Easy catalyst handling. There is no need to recover the rhodium by separating it from the
reaction liquid.
 Open licensing policy. Chiyoda offers ACETICA technology based on an open license policy.
 Chiyoda's full service as EPC contractor. Not only as a technology supplier but also as an EPC
contractor, Chiyoda can supply all its accumulated expertise, including the design, procurement,
and construction details of an actual acetic acid plant, as well as the license and the basic
process package.

1.1.4. PROCESS DESCRIPTION

A simplified diagram of the process flow of the ACETICA process is shown in Fig. 1.1.2.
Figure 1.1.2. Simplified process flow diagram.

1.1.4.1. Feed/Absorption/Reaction Unit

 The CO compressor compresses carbon monoxide received by pipeline at the battery limit to the
reaction level. After the moisture is removed, the CO is sparged into the carbonylation reactor.
 Fresh methanol is split into two streams, each of which is fed to a separate countercurrent high-
pressure (HP) absorber and low-pressure (LP) absorber.
 Part of the methanol feed contacts the reactor offgas in the HP absorber, which mostly contains
unconverted CO, methyl iodide, methyl acetate, and so on. The other part of the methanol feed
stream contacts the light gases in the LP absorber, which were released at low pressure from the
distillation unit. The main purpose of this absorption system is to maximize recovery of valuable
methyl acetate and methyl iodide, which otherwise would exit the system with the vented gas,
resulting in unnecessarily high chemical consumption and yield loss. The methanol feed streams
exiting the absorbers are recombined and mixed with the recycled liquid from the recycle vessel
and makeup methyl iodide from the MI generator unit. The combined and recycled stream is then
charged to the bottom of the carbonylation reactor riser section.
 The carbonylation reactor, using a three-phase bubble-column system, consists of a riser,
separator, downcomer, and reactor cooler.
 Methanol, CO, and recycled liquid from the distillation unit are introduced at the bottom of the
carbonylation reactor riser section. The compressed CO is fed through a sparger for even
distribution. These feeds and catalyst, together with the circulation, flow from the downcomer and
up the riser, where almost all the CO and methanol are converted into acetic acid by
carbonylation. The difference in density between the gaseous CO-rich riser and CO-depleted
downcomer drives the circulation. The agitation provided by the high velocities of the liquid and
gaseous reactants rapidly dissolves the CO into a liquid phase that reacts with methanol so that
the system is not mass-transfer controlled.
 Unreacted CO and other gaseous by-products are vented from the top of the separator to the HP
absorber. A portion of the reactor liquid effluent (crude acetic acid) is disengaged by gravity from
the solids in the recycle slurry atthe separator and sent to the downstream distillation unit. The
remaining catalyst-liquid mixture is routed through the reactor downcomer, cooled by the reactor
cooler to remove the large heat of reaction, and returned to the bottom of reactor riser to maintain
circulation. The reactor cooler generates the low-pressure steam by recovering the reaction heat,
which is used as a heat source of the distillation unit. Catalyst
retention in the reactor is almost 100 percent.
A drawing of the bubble-column reactor is shown inFig. 1.1.3.

1.1.4.2. Distillation Unit

The purposes of the distillation unit are
 Production of purified acetic acid from crude acetic acid by
purification
 Maintenance of the stable condition in terms of water content and
impurities
 Recovery of valuable hydrocarbons, including methyl iodide
Discharged liquid from the carbonylation reactor, containing crude acetic
acid product, methyl acetate, water, carbon monoxide, etc., is flashed and
vaporized in the flasher to separate vapor and liquid streams. A major portion
Figure 1.1.3. Drawing of bubble-column reactor.
of the acetic acid, unreacted methanol, methyl acetate, methyl iodide, water,
and some heavy impurities such as propionic acid are flashed into the vapor
phase and fed to the dehydration column. At the same time, some heavy
impurities are recycled from the bottom liquid stream containing acetic acid to
the carbonylation reactor.
The vapor stream from the flasher is sent to the dehydration column to remove dissolved gases, light
organic components, and water. The overhead stream is condensed and passed to the dehydration
column receiver. In the receiver, uncondensed volatile materials consisting mainly of CO with minor
amounts of vaporized methyl iodide are sent to the LP absorber for recovery and to prevent yield loss. A
part of the condensed liquid is sent to the excess water column. The remainder of this stream is returned
to the carbonylation reactor.
The side stream containing hydrogen iodide, water, and acetic acid is withdrawn from the column. The
dehydrated acetic acid from the bottom of the column is sent to the finishing column.
A part of the stream from the dehydration column receiver is fed to the excess water column to remove
excess waterand some of the accumulated impurities and to maintain a constant concentration of water
and impurities in the reactor. The overhead vapor is cooled, and any uncondensed vapor is fed to the LP
absorber for recovery. The water from the bottom of the column is also returned to the carbonylation
reactor.
The dehydrated acetic acid is fed to the finishing column, where the heavy by-products (predominantly
propionic acid) are removed with small amounts of acetic acid in the bottom draw-off and sent to the
incinerator. The purified product acetic acid drawn from the middle of the upper distillation section is
cooled and sent to the product-treating unit. The overhead acetic acid, containing small amounts of water
and light organic compounds, is returned as a recycle stream. Small amounts of uncondensed light
gaseous components containing traces of thermally cracked byproducts are removed as vent gas to the
waste-treating unit.

1.1.4.3. Iodide-Removal Unit

Product acetic acid still contains traces of iodide compounds, which might harm the catalyst in a vinyl
acetate plant. In this section, any remaining traces of iodide compounds are adsorbed by a proprietary
adsorbent to reduce the level of the iodide contents to less than 3 ppb.