Acetic acid

Industrial Chemistry
Methods to produce acetic acid
Acetic acid is one of the major commoditiy chemicals, with a current (2008)
word production of ca. 9 Mt/a.

History of CH3COOH production:

Vinegar (5–10 % CH3COOH in H2O) as food additive since time immemorial.

Not suitable to pruduce glacial CH3COOH, because water removal is
extremely energy demanding.

Destructive distillation of wood gives methanol, acetone, and some acetic acid,
not used anymore.

Oxidation of acetaldehyde (from ethanol oxidation now superseded by Wacker

oxidation of ethene in water)
 Carbonylation of methanol
Most important industrial processes are based on carbonylation:

CH3OH + CO → CH3COOH ΔG = –86 kJ/mol

Cost Advantages of Methanol Carbonylation

– Highly selective process

– Syngas is the only feedstock, as methanol is made from syngas by heterogeneous catalysis:

CO + 2 H2 → CH3OH

If natural gas is used as the feedstock for syngas production, the conversion to acetic acid can be
represented in three steps based only upon methane and water as reagents:

CH4 + H2O → CO + 3 H2 | CO + 2 H2 → CH3OH | CH3OH + CO → CH3COOH

The overall stoichiometry is:

2 CH4 + 2 H2O → CH3COOH + 4 H2

The excess H2 produced can be used in other processes: An integrated chemical plant might
produce acetic acid and use the hydrogen to make ammonia: N2 + 3 H2 → 2 NH3
Monsanto’s Acetic Acid Process
First large-scale industrial application of homogeneous catalysis

The global annual manufacturing capacity for acetic acid is ca. 9 million tons, about
80 % of which is based on methanol carbonylation technology

Catalyst: Rhodium + iodide as promoter

Rh catalyst, I –
CH3OH + CO ! !!!!!!!! → CH3COOH (99 %)
180°C, 30 – 40 atm

Any source of rhodium or of iodide may be introduced as precatalysts. These are

converted into [RhI2(CO)2]– and CH3I under reaction conditions

Review Article: C. M. Thomas, G. Süss-Fink, Coord. Chem. Rev. 2003, 243, 125.
Role of iodide
For all catalysts – cobalt, rhodium, iridium (see below) – the actual substrate of
carbonylation is methyl iodide.

CH3OH must be converted to CH3I, otherwise methanol would insert CO into the O–H
bond (to give methyl formate) and not into the C–O bond (to give acetic acid).

The rhodium-catalyzed reaction depends on iodide, which is simultaneously a good

nucleophile, a very weak base, a good leaving group, and an effective ligand for
rhodium. No alternative to iodide has been found yet.

Drawbacks:

– Hydrogen iodide is corrosive → major engineering problem.

– A substantial amount of water (up to 15 wt.%) is required to achieve high catalyst

activity and stability. H2O assists the reductive elimination of CH3C(O)I, which
becomes rate-determining at lower [H2O]. As Rh also catalyzes the WGSR, the
presence of water is a serious problem.
Mechanism
Rate determining is the oxidative addition of MeI to
[RhI2(CO)2]– (see rate law below: the active form of
iodide is methyl iodide).

Remember:

(a) Iodide is a good leaving group, speeds up

oxidative addition.

(b) Iodide is the best σ-donor among the halides →

increases the electron density at rhodium.

After the r.d.s., migratory insertion and reductive

elimination occur. They are fast and therefore not rate-
limiting here. The reductive elimination has been
observed in a model reaction.

Finally, methyl is a special alkyl group, as it undergoes

the fastest oxidative addition and the resulting alkyl
complex is incapable of β-hydride elimination .

rate = k [Rh]1[I–]1[CH3OH]0[CO]0
Commercial Plant
Process details
– Continuous CO / MeOH feed into the reactor

– "Flash tank" where the pressure is released to separate most of the volatiles (including CH3COOH).
The catalyst remains dissolved in the liquid phase and is recycled back to the reactor vessel.

– The distillation train is fed with the product stream from the flash tank. MeI is removed and recycled in
the first column, water is the second, and heavier by-products (such as propionic acid) are removed in the
third one.

Besides being the product, CH3COOH also acts as the major solvent component. Therefore, the methanol
feedstock is largely esterified into methyl acetate under process conditions:

MeOH + MeCO2H → MeCO2Me + H2O

As well as the water produced by esterification, quite a high concentration of water (ca. 10 M) is required to
maintain high rates and prevent deactivation by precipitation of the rhodium catalyst as insoluble Rh(III)
iodides. Indeed, water promotes reduction of Rh(III) to Rh(I) via the water-gas shift reaction (WGSR), then
Rh(I) reacts with CO and forms soluble carbonyl complexes.

Low water content is desirable: 1) Separation of water by distillation is expensive (energy!).

2) H2O causes significant loss of CO as CO2 by the WGSR.

The Cativa™ Process
Iridium catalyst + iodide + Lewis-acidic promoter → higher activity and
selectivity.

Commercialized in 1996 by BP-Amoco. Operated in four plants worldwide

(stand 2004).

Advantages: Higher catalyst stability and activity (allows lower water content),
higher solubility.

Mechanistically more complicated than rhodium, as neutral intermediates are

involved, too.
 Mechanism
The oxidative addition of CH3I to iridium is ca. 100
times faster than to rhodium (why?) → is not rate-
– determining!
I CO
Ir
I CO Resting state of the catalyst:
1

CH3COI CH3I
fac,cis-[IrI3(CH3)(CO)2]– (2)
H3 C O –
C HI CH3 –
I CO I CO (with water content ≥ ca. 5% w/w. Observed by in
Ir H2O Ir situ IR spect.)
I CO I CO
I I
6 CH3COOH CH3OH 2 R.d.s.: Substitution of an iodo ligand by CO (2 →
+
mer,trans CO 4)
isomer I–
CH3
I CO The promoter accelerates this step by abstracting
Ir an iodo ligand from 2. (why is this step slow?)
I CO I–
CO 4
Why is step 2 → 4 needed?

Migratory CO insertion is ca. 700 times faster for 4

than for 2 because of decreased π–back-donation
to the CO ligands in 4 as compared to 2. (Why?)
Role of the promoter

Promoters are (a) carbonyl complexes of W, Re, Ru, and Os, or (b) simple
iodides of Zn, Cd, Hg, Ga, and In:

[RuI2(CO)3]2, [RuI2(CO)2]n, InI3, GaI3, and ZnI2.

None of the promoters show any detectable activity in the absence of the
iridium catalyst. Typical promoter : iridium ratios are between 1 and 10. Soluble
iodide salts (LiI and (Bu4N)I) are catalyst poisons.

The ability to accept an iodo ligand is a key property of the promoter!

Uses of acetic acid

Esters are used:

- to produce polymers - Polyvinylacetate (PVA)

- for the manufacture of artificial silk - Cellulose acetate

- As solvents fo paints and resins – alkyl acetates

Metal salts are used as additives for textiles, dye and medicine industries

Chloroacetic acids, ketenes, acetic anhydride are used as synthetic

intermediates

Acetic acid is also used as solvent