Lecture 19

Chemical Process Technology

(CHE F419)_Dr Smita R
BITS Pilani
Pilani Campus

Examples of Homogenous catalysis: Acetic acid

production
Direct liquid phase oxidation of acetaldehyde was
once preferred route to acetic acid coz of low cost of
these hydrocarbons
Reaction mechanism is based on radicals
It follows the typical initiation, propagation &
termination steps
But D/A is that; around 50% of feed goes in
production of by products (formic acid,
aldehydes, higher acids)

Preferred route for acetic acid .

Carbonylation of methanol which dates back to 1925
But the commercial plant came in 1963 when a new
cobalt/iodide catalyst system was developed (BASF
technology)
In 1968; Monsanto Chemical Co. introduced a new
carbonylation process using a novel highly selective
catalysts (rhodium iodide) which was commercialized
2 yrs later

Preferred route for acetic acid .

Preferred route for acetic acid .

Key to success is very active catalyst system which
allows operation at much less severe conditions than
BASF process
Important part of catalyst system is iodide which is
supplied as hydrogen iodide which is very corrosive

Methanol equilibrium conversion is almost complete at the

reaction conditions employed.
Indeed, at the temperatures employed the conversion is even
nearly complete at atmospheric pressure.

What is the reason????

But rxn is carried out at elevated pressure,
however, in order to keep the reaction mixture in
the liquid phase and
To generate and maintain the catalyst in its active
form; the catalyst complex is not stable at low
carbon monoxide pressure

Preferred route for acetic acid .

Important part of catalyst system is iodide which is
supplied as hydrogen iodide which is very corrosive
Rxn is
CH3OH HI CH3I H 2O

H -53.1 kJ/mol

Formation of methyl iodide is start of catalytic cycle

Preferred route for acetic acid .

Formation of methyl iodide is start of catalytic cycle
Addition of methyl iodide to rhodium complex has
been found to be rate determining step;
In fact rxn rate is independent of two reactants
methanol & CO

Rate eqn is: rCH COOH k[Rh][CH3I]

3

Preferred route for acetic acid .

Consequence of zero order dependence of rxn
mixture on concentrations is that at any conversion
level, production rate is same
Hence, high conversions can be obtained even in
_____________

So a question can be..

Recall design eqn of CSTR & show that only in the
case of 0th order reactions, complete conversion can
be attained in a reactor of finite volume.

Preferred route for acetic acid .

Also methanol is diluted with water to suppress
formation of methyl acetate & dimethyl ether
Addition of water increases methanol conversion to
acetic acid but leads to water gas shift rxn as well
(CO2 gets formed)

Flow sheet for Monsanto process

Monsanto process
CO & methanol are fed to CSTR containing the
catalyst
Reaction takes place in liquid phase under relatively
mild conditions
Liquid reactor effluent is de pressurized in a flash
vessel which results in gas & liquid phase
Liquid phase is send to light ends column

Monsanto process
Overhead is combined with gases from flash vessel &
scrubbed with methanol to recover methyl iodide
Off gases from scrubber are flared
Bottom stream of light ends column (containing
catalyst complex, water & AA) is recycled to reactor
Wet AA is taken as a side stream from light ends
column & fed to drying column

Monsanto process
Dry AA is removed as bottom pdt
Overheads containing a mixture of AA (35%
concentration) & water are recycled to reactor
Fixed amt of water & AA is continuously circulating in
plant
Dry AA is fed to products column from which heavy
byproducts are removed as bottoms

Monsanto process
Overheads from product column is sent to finishing
column from which ultra pure AA is obtained as a
side stream
Both overhead & bottoms from this column are
recycled to process

Key points: Monsanto process

Imp requirement is small amt of water
Requires large no. of trays

Catalyst complex must be recovered with an extreme

efficiency & returned to reactor as rhodium is
harmful metal & is quite expensive
Nearly complete recovery of rhodium is effected in
light ends column

Key points: Monsanto process

Volatile & toxic methyl iodide has to be retained in
system
This is achieved by methanol scrubber
Overhead gases from all the columns are send to this
scrubber

Homogenous catalysis
In homogeneous catalysis, soluble catalysts are
applied

Homogenous catalysis
S No.

Homogeneous catalyst

Heterogeneous catalyst

1.

Soluble catalysts are applied

Solid catalyst are used

2.

Reaction mixture contains catalysts

complex in solution: meaning that all
metal is exposed to reaction mixture

Metal is applied on a carrier

material as a porous metal
sponge type material & only
surface atoms are active

3.

In terms of activity per metal center,

homogeneous catalyst are more active

Less active

4.

One poison molecule only deactivates

one metal complex

Poison molecule can block a

pore containing many active
sites

5.

Capable of being more selective; as

there is only one type of active site

Less selective as contain many

different types of active sites

6.

As carried out in liquid phase, temp.

control is relatively easy

Temp. control is not that easy

Homogenous catalysis
If so many advantages, then why homogeneous
catalysis is not used in every reactions?
High specificity is not always called for
For example: in many refinery processes; especially;
complex feeds & products do not justify use of highly
selective catalysts

Homogenous catalysis: Certain disadvantages

Separation of catalysts & products is difficult
Feasible for only low M Wt products
Use of solvents add an additional separation step

Complex are not often resistant to high temp.

Often precious metals are used & hence recovery is
needed which may not be the case always

Homogenous catalysis
Hence developments needs the working together of
chemists & chemical engineers
Hence organometallic chemistry deals with
development of catalysts
Mild reaction conditions are advantage for
homogeneous reactions